JP2003268518A - Original sheet for coating having excellent workability - Google Patents
Original sheet for coating having excellent workabilityInfo
- Publication number
- JP2003268518A JP2003268518A JP2002075044A JP2002075044A JP2003268518A JP 2003268518 A JP2003268518 A JP 2003268518A JP 2002075044 A JP2002075044 A JP 2002075044A JP 2002075044 A JP2002075044 A JP 2002075044A JP 2003268518 A JP2003268518 A JP 2003268518A
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- JP
- Japan
- Prior art keywords
- hot
- dip
- coating
- layer
- alloy
- 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.)
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、耐食性に優れたＺｎ−
Ａｌ合金めっき鋼板を基材とし、加工性が改善された塗
装原板に関する。BACKGROUND OF THE INVENTION The present invention relates to a Zn-based alloy having excellent corrosion resistance.
The present invention relates to a coated original plate having an Al alloy plated steel sheet as a base material and having improved workability.
【０００２】[0002]
【従来の技術】内装建材，外装建材等では、耐食性の良
好な溶融亜鉛めっき鋼板等が塗装原板として従来から使
用されている。しかし、大気汚染の進行に伴ってイオウ
酸化物，窒素酸化物等による大気や雨水の酸性化が著し
い昨今、塗装鋼板の平坦部，切断端面，塗膜疵付き部等
の塗膜下で溶融亜鉛溶融めっき層の腐食が促進されるこ
とから内装建材，外装建材等としての耐久性が懸念され
る状況になってきている。たとえば、平坦部の腐食は、
Ｃ１イオン等の腐食性イオンが塗膜を透過して溶融亜鉛
溶融めっき層の腐食を促進させ、体積膨張した亜鉛系腐
食生成物によって塗膜が押し上げられ、塗膜フクレとし
て観察される。2. Description of the Related Art In interior building materials, exterior building materials, etc., hot-dip galvanized steel sheets and the like having good corrosion resistance have been conventionally used as original coating plates. However, due to the remarkable acidification of the atmosphere and rainwater due to sulfur oxides, nitrogen oxides, etc., along with the progress of air pollution, molten zinc under the coating such as flat parts, cut edges, and film flaws of coated steel sheets. Since the corrosion of the hot-dip galvanized layer is promoted, there is a concern about its durability as interior building materials and exterior building materials. For example, flat part corrosion is
Corrosive ions such as C1 ions permeate the coating film to accelerate the corrosion of the hot dip galvanized layer, and the coating film is pushed up by the volume-expanded zinc-based corrosion product and observed as coating film blisters.
【０００３】環境悪化に対応するため、溶融亜鉛めっき
鋼板よりも優れた耐食性を呈する塗装原板として、溶融
Ｚｎ−Ａｌ合金めっき鋼板の使用が進められている。溶
融Ｚｎ−Ａｌ合金めっき鋼板は、Ｚｎ−Ａｌ合金溶融め
っき層のＡｌ含有量が増加するに従って平坦部や塗膜疵
付き部の耐食性が向上する。しかし、Ａｌ含有量の増加
に伴い溶融めっき層の加工性が低下する。たとえば、塗
装溶融Ｚｎ−５５％Ａｌ合金めっき鋼板の折り曲げ加工
部では溶融めっき層に大きな加工割れが発生し、加工割
れは溶融めっき層上の塗膜にも伝播する。目視観察でも
検出できる程度に塗膜割れが大きくなると、成形加工品
の意匠性が低下する。また、溶融めっき層，塗膜に生じ
た加工割れを介して腐食性イオンが侵入する。腐食性イ
オンは溶融めっき層中のＺｎと選択的に反応してＺｎの
犠牲防食作用によって下地鋼が防食されるが、腐食反応
にＺｎが消尽されると下地鋼の腐食が開始される。下地
鋼の腐食は、赤錆となって現れ、成形加工品の外観を著
しく劣化させる。In order to cope with environmental degradation, use of a hot dip Zn-Al alloy-plated steel sheet has been promoted as a coating base plate exhibiting better corrosion resistance than the hot-dip galvanized steel sheet. In the hot-dip Zn-Al alloy-plated steel sheet, the corrosion resistance of the flat portion and coating film flawed portion improves as the Al content of the Zn-Al alloy hot-dip coating layer increases. However, the workability of the hot-dip plated layer decreases as the Al content increases. For example, a large work crack occurs in the hot-dip coating layer at the bent portion of the coated hot-dip Zn-55% Al alloy-coated steel sheet, and the work crack propagates to the coating film on the hot-dip coating layer. If the coating film cracks become large enough to be detected by visual observation, the design of the molded product deteriorates. In addition, corrosive ions penetrate through the work cracks generated in the hot-dip layer and the coating film. The corrosive ions selectively react with Zn in the hot-dip plated layer to protect the base steel by the sacrificial anticorrosion action of Zn, but when Zn is exhausted by the corrosion reaction, corrosion of the base steel starts. Corrosion of the base steel appears as red rust and significantly deteriorates the appearance of the molded product.
【０００４】[0004]
【発明が解決しようとする課題】溶融Ｚｎ−Ａｌ合金め
っき鋼板の加工性を改善するため、約９３〜４２７℃の
後加熱で溶融めっき層を軟質化する方法が特開昭５６−
８７６５４号公報で紹介されている。後加熱した溶融Ｚ
ｎ−Ａｌ合金めっき鋼板は、溶融めっき層の軟質化によ
って折り曲げ加工部の加工性が向上するが、塗装原板に
要求される溶融めっき層の加工性が未だ十分でない。そ
のため、後加熱の条件によっては溶融めっき層が十分に
軟質化されず、折り曲げ加工で溶融めっき層，塗膜に無
数の割れが発生し、加工部の外観劣化が依然として解消
されないことがある。In order to improve the workability of hot-dip Zn-Al alloy-plated steel sheet, a method of softening the hot-dip coating layer by post-heating at about 93 to 427 ° C is disclosed in JP-A-56-.
87654. Post-heated molten Z
In the n-Al alloy-plated steel sheet, the workability of the bent portion is improved due to the softening of the hot-dip coating layer, but the workability of the hot-dip coating layer required for the original coating sheet is still insufficient. Therefore, depending on the post-heating conditions, the hot-dip coating layer may not be sufficiently softened, and numerous bending cracks may occur in the hot-dip coating layer and the coating film, and the appearance deterioration of the processed portion may not be eliminated.
【０００５】[0005]
【課題を解決するための手段】本発明は、溶融めっき層
の軟質化に及ぼす後加熱の影響を調査・検討する過程で
見出された知見に基づいて案出されたものであり、Ｚｎ
−Ａｌ合金溶融めっき層に晶出しているＡｌリッチのデ
ンドライト相のＺｎ濃度を規制することによって、Ｚｎ
−Ａｌ合金溶融めっき層の軟質化状態を安定化させ、高
度の折り曲げ加工を施しても加工割れがない耐食性，加
工性に優れた塗装原板を提供することを目的とする。The present invention was devised based on the findings found in the process of investigating and examining the effect of post-heating on the softening of the hot-dip plated layer.
By controlling the Zn concentration of the Al-rich dendrite phase crystallized in the Al alloy hot-dip layer,
-It is an object of the present invention to provide a coating base plate which stabilizes the softened state of an Al alloy hot-dip layer and has no corrosion cracking even when subjected to a high degree of bending work and which is excellent in workability.
【０００６】本発明の塗装原板は、その目的を達成する
ため、５０〜６０質量％のＡｌを含むＺｎ−Ａｌ合金溶
融めっき層が鋼板表面に形成されており、Ｚｎ−Ａｌ合
金溶融めっき層に晶出しているＡｌリッチのデンドライ
ト相のＺｎ濃度が１０質量％以下に抑えられていること
を特徴とする。Ｚｎ−Ａｌ合金溶融めっき層は、更に３
質量％以下のＳｉを含むことができる。In order to achieve the object of the coated original sheet of the present invention, a Zn-Al alloy hot-dip coating layer containing 50 to 60% by mass of Al is formed on the steel sheet surface. The Zn concentration of the crystallized Al-rich dendrite phase is suppressed to 10 mass% or less. The Zn-Al alloy hot-dip layer is further 3
It can contain Si in an amount of not more than mass%.
【０００７】[0007]
【作用】Ｚｎ−Ａｌ合金めっき鋼板は、還元加熱しため
っき原板を所定組成のＺｎ−Ａｌめっき浴に導入し、Ｚ
ｎ−Ａｌめっき浴から引き上げられためっき原板に付着
している溶融めっき金属の付着量を調整した後、急冷す
ることによって製造されている。溶融めっき金属の急冷
凝固によって溶融めっき層が形成されるため、溶融めっ
き層に無数の熱歪が導入されており、溶融めっき層に晶
出しているＡｌリッチのデンドライト相も過飽和状態の
Ｚｎが固溶している。Ｚｎ−Ａｌ合金めっき鋼板を後加
熱すると熱歪が解放されるため溶融めっき層が軟質化す
るが、熱歪に解放程度によっては軟質化が不十分な場合
がある。[Function] For the Zn-Al alloy plated steel sheet, the reduction-heated original plate is introduced into a Zn-Al plating bath having a predetermined composition, and Z
It is manufactured by adjusting the adhesion amount of the hot-dip plated metal adhering to the plating original plate pulled up from the n-Al plating bath, and then quenching. Since the hot-dip coating layer is formed by rapid solidification of the hot-dip metal, a myriad of thermal strains are introduced into the hot-dip layer, and the Al-rich dendrite phase crystallized in the hot-dip layer also contains Zn in the supersaturated state. It's melting. When the Zn—Al alloy-plated steel sheet is post-heated, thermal strain is released and the hot-dip coating layer is softened. However, depending on the degree of thermal strain released, the softening may be insufficient.
【０００８】Ｚｎ−Ａｌ合金溶融めっき層は、過飽和状
態でＺｎが固溶している硬質のＡｌリッチのデンドライ
ト相とＺｎリッチの軟質マトリックスからなる組織をも
っている。Ａｌリッチのデンドライト相とＺｎリッチの
マトリックスとの間に大きな硬度差があるため、折り曲
げ加工等によって導入された応力がデンドライト相／マ
トリックスの界面に集中し、デンドライト相／マトリッ
クスの界面を起点として亀裂が発生・伝播する。亀裂の
発生・伝播機構を考慮するとき、デンドライト相の硬度
を下げてマトリックスに近づけることが必要といえる。The Zn-Al alloy hot-dip plated layer has a structure composed of a hard Al-rich dendrite phase in which Zn is solid-soluted in a supersaturated state and a Zn-rich soft matrix. Since there is a large hardness difference between the Al-rich dendrite phase and the Zn-rich matrix, the stress introduced by the bending process concentrates on the interface of the dendrite phase / matrix, and cracks originate from the interface of the dendrite phase / matrix. Occurs and propagates. Considering the mechanism of crack initiation and propagation, it can be said that it is necessary to lower the hardness of the dendrite phase and bring it closer to the matrix.
【０００９】Ａｌリッチのデンドライト相の硬さにはデ
ンドライト相に固溶しているＺｎ濃度が大きく影響して
おり、固溶Ｚｎが少ないほどデンドライト相が軟質にな
る。溶融めっき層の軟質化と後加熱との関係を調査・検
討する過程で意外にも１３０〜２７０℃の低温加熱でＡ
ｌリッチのデンドライト相のＺｎ濃度が低下することを
見出した。低温加熱によるＺｎの濃度低下は、デンドラ
イト相に不安定な過飽和状態で固溶Ｚｎが含まれ、しか
も無数の熱歪がデンドライト相に導入されているため、
低温域でもＺｎの固溶拡散が進行することによるものと
推察される。The hardness of the Al-rich dendrite phase is greatly affected by the concentration of Zn dissolved in the dendrite phase, and the smaller the amount of dissolved Zn, the softer the dendrite phase. Surprisingly in the process of investigating and examining the relationship between softening of the hot-dip layer and post-heating
It has been found that the Zn concentration in the l-rich dendrite phase decreases. The decrease in Zn concentration due to low temperature heating is because the dendrite phase contains solid solution Zn in an unstable supersaturated state, and innumerable thermal strains are introduced into the dendrite phase.
It is speculated that this is due to the progress of solid solution diffusion of Zn even in the low temperature region.
【００１０】Ａｌリッチのデンドライト相のＺｎ濃度と
硬さとの関係を調査したところ、Ｚｎ濃度を１０質量％
以下に低下させるときデンドライト相の硬さが９０ＨＶ
以下になり、加工時の応力集中に起因する割れ発生がな
い程度にまでＺｎリッチのデンドライト間隙相との硬度
差が減少する。Ａｌリッチのデンドライト相のＺｎ濃度
は、ＥＤＸでのスポット分析によって測定できる。分析
では、ＡＩリッチのデンドライト相中に存在するＺｎ析
出箇所を外した測定点を設定することが好ましい。When the relationship between the Zn concentration in the Al-rich dendrite phase and the hardness was investigated, the Zn concentration was 10% by mass.
When the hardness is decreased below, the hardness of dendrite phase is 90 HV
Below, the hardness difference with the Zn-rich dendrite interphase is reduced to the extent that cracking due to stress concentration during processing does not occur. The Zn concentration in the Al-rich dendrite phase can be measured by spot analysis with EDX. In the analysis, it is preferable to set a measurement point excluding the Zn precipitation portion existing in the AI-rich dendrite phase.
【００１１】Ｚｎ濃度１０質量％以下は、１３０〜２７
０℃の低温域で０.５〜２４時間均熱処理した後、１℃
／分以下の冷却速度で室温まで徐冷することにより達成
される。均熱処理後の徐冷には、たとえば炉冷が採用さ
れるが、徐冷中にもＡｌリッチのデンドライト相のＺｎ
濃度が低下する。１３０〜２７０℃の低温加熱は、固溶
拡散によるデンドライト相のＺｎ濃度低下に留まらず、
溶融めっき時の急冷凝固で溶融めっき層に導入された熱
歪の開放にも有利である。その結果、折り曲げ加工時に
Ａｌリッチのデンドライト相／Ｚｎリッチのマトリック
スの界面に過度の応力が集中することなく、加工割れの
発生が抑えられる。また、溶融めっき層の加工割れの発
生が抑えられるため、Ｚｎ−Ａｌ合金溶融めっき層本来
の優れた耐食性が加工部においても維持される。If the Zn concentration is 10% by mass or less, 130 to 27
After soaking for 0.5 to 24 hours in the low temperature range of 0 ℃, 1 ℃
This is achieved by gradually cooling to room temperature at a cooling rate of not more than 1 minute. Furnace cooling, for example, is used for slow cooling after soaking, but during the slow cooling, Zn in the Al-rich dendrite phase is also used.
The concentration decreases. The low temperature heating of 130 to 270 ° C. is not limited to the reduction of Zn concentration in the dendrite phase due to solid solution diffusion,
It is also advantageous for releasing thermal strain introduced into the hot-dip coating layer by rapid solidification during hot-dip coating. As a result, during bending, excessive stress is not concentrated on the interface of the Al-rich dendrite phase / Zn-rich matrix, and the occurrence of work cracks is suppressed. Further, since the occurrence of work cracks in the hot-dip plated layer is suppressed, the original excellent corrosion resistance of the Zn-Al alloy hot-dip plated layer is maintained even in the worked portion.
【００１２】[0012]
【発明の実施の態様】本発明の塗装原板は、溶融めっき
層が５０〜６０質量％のＡｌと３質量％以下のＳｉを含
み、溶融５５％Ａｌ−Ｚｎ系合金めっき鋼板に代表され
るめっき鋼板である。熱間圧延後に酸洗脱スケールした
熱延鋼板、或いは熱延鋼板を更に冷間圧延した冷延鋼板
をめっき原板に使用し、還元加熱雰囲気中で鋼板を焼鈍
すると共に鋼板表面を活性化した後、約６００℃に保持
された溶融Ｚｎ−Ａｌ−Ｓｉ溶融めっき浴に導入し、溶
融めっき浴から引き上げられた鋼板表面に不活性ガスを
吹き付けてめっき付着量を調整した後、常法により溶融
めっき層を冷却凝固することによりＺｎ−Ａｌ系合金溶
融めっき層が鋼板表面に形成される。BEST MODE FOR CARRYING OUT THE INVENTION In the coated original sheet of the present invention, the hot-dip coating layer contains 50-60 mass% of Al and 3 mass% or less of Si, and is represented by hot-dip 55% Al-Zn alloy plated steel sheet. It is a steel plate. After the hot-rolled steel sheet that has been pickled and descaled after hot-rolling or the cold-rolled steel sheet that has been further cold-rolled is used as the original plating plate, after annealing the steel sheet in a reducing heating atmosphere and activating the steel sheet surface Introduced into a hot-dip Zn-Al-Si hot-dip galvanizing bath maintained at about 600 ° C, and spraying an inert gas onto the surface of the steel sheet pulled up from the hot-dip galvanizing bath to adjust the amount of plating applied, and then hot-dip galvanizing by a conventional method. By cooling and solidifying the layer, a Zn-Al alloy hot-dip plated layer is formed on the surface of the steel sheet.
【００１３】溶融Ｚｎ−Ａｌ系合金めっき鋼板のＺｎ−
Ａｌ合金溶融めっき層の構造は、主に過飽和状態でＺｎ
が固溶している硬質のＡｌリッチのデンドライト相とＺ
ｎリッチの軟質マトリックス及び鋼板との界面に形成さ
れたＦｅ−Ａｌ−Ｓｉ系の合金層（金属間化合物層）か
らなる組織をもっている。溶融Ｚｎ−Ａｌ系合金めっき
鋼板に厳しい折り曲げ加工を施すと、硬質の合金層に無
数の加工割れが発生し、加工割れが溶融めっき層に伝播
することによって溶融めっき層自体に加工割れが生じ
る。Zn- of hot-dip Zn-Al alloy plated steel sheet
The structure of the Al alloy hot-dip plated layer is mainly Zn in the supersaturated state.
Hard Al-rich dendrite phase and Z
It has a structure including an n-rich soft matrix and an Fe-Al-Si based alloy layer (intermetallic compound layer) formed at the interface with the steel sheet. When the hot-dip Zn-Al alloy-plated steel sheet is subjected to severe bending, innumerable work cracks occur in the hard alloy layer, and the work cracks propagate to the hot-dip plating layer, causing work cracks in the hot-dip plated layer itself.
【００１４】従来法で製造された溶融Ｚｎ−ＡＩ系合金
めっき鋼板の溶融めっき層は、Ａｌリッチのデンドライ
ト相とＺｎリッチのマトリックスとの間に大きな硬度差
があるため、折り曲げ加工を施すと合金層の割れがＡｌ
リッチのデンドライト相／Ｚｎリッチのマトリックスの
界面に集中してしまい、デンドライト相／マトリックス
の界面を起点とした亀裂が発生・伝播する。この結果、
個々の割れの開口幅と開口長さが大きくなり、加工部の
溶融めっき層の表面の外観が損なわれるのみならず、塗
装原板として使用すると、溶融めっき層の割れが塗膜に
も発生・伝播して、塗装溶融Ｚｎ−Ａｌ合金めっき鋼板
の加工部の外観及び耐食性が損なわれる。Since the hot-dip coating layer of the hot-dip Zn-AI alloy-plated steel sheet produced by the conventional method has a large hardness difference between the Al-rich dendrite phase and the Zn-rich matrix, it is alloyed by bending. Layer crack is Al
It concentrates on the interface of the rich dendrite phase / Zn rich matrix, and cracks are generated and propagated starting from the interface of the dendrite phase / matrix. As a result,
Not only does the opening width and opening length of each crack increase and the surface appearance of the hot-dip coating layer in the processed part is impaired, but when used as a coating base plate, cracks in the hot-dip coating layer also occur and propagate in the coating film. As a result, the appearance and corrosion resistance of the processed part of the coated hot-dip Zn-Al alloy plated steel sheet are impaired.
【００１５】このような問題に対して本発明では、溶融
めっき後、溶融めっき層が急冷凝固した後の溶融Ｚｎ−
Ａｌ合金めっき鋼板を１３０〜２７０℃の低温域で０.
５〜２４時間均熱加熱した後、１℃／分以下の冷却速度
で室温まで均熱徐冷処理を施す。後加熱により溶融めっ
き層中にあるＡｌリッチのデンドライト相の固溶Ｚｎ濃
度が１０質量％以下にまで低下し、デンドライト相が硬
さ９０ＨＶ以下の軟質相になる.溶融Ｚｎ−Ａｌ合金め
っき鋼板を後加熱する温度域は１３０〜２７０℃の任意
の温度域でよい。１３０℃に達しない均熱加熱温度で
は、Ａｌリッチのデンドライト相が９０Ｈ以下にならず
溶融めっき層の軟質化が不十分で、溶融めっき層の加工
性が十分に改善されない。逆に、２７０℃を超える温度
で均熱加熱しても軟質化効果が飽和し、不経済である。
Ａｌリッチのデンドライト相の軟質化とＦｅ−Ａｌ−Ｓ
ｉ系合金層の成長を防止する観点から、１５０〜２５０
℃の温度域で均熱加熱することが特に好ましい。In the present invention, in order to solve such a problem, molten Zn-after the hot dip coating is rapidly solidified after hot dipping
Al alloy plated steel sheet at a low temperature range of 130 to 270 ° C.
After soaking and heating for 5 to 24 hours, soaking and gradual cooling treatment is performed to room temperature at a cooling rate of 1 ° C./minute or less. The post-heating reduces the solid solution Zn concentration of the Al-rich dendrite phase in the hot-dip coating layer to 10 mass% or less, and the dendrite phase becomes a soft phase having a hardness of 90 HV or less. The temperature range for post-heating may be any temperature range of 130 to 270 ° C. At a soaking and heating temperature which does not reach 130 ° C., the Al-rich dendrite phase does not become 90 H or less, the softening of the hot-dip coating layer is insufficient, and the workability of the hot-dip coating layer is not sufficiently improved. On the contrary, even if it is uniformly heated at a temperature of more than 270 ° C., the softening effect is saturated and it is uneconomical.
Softening of Al-rich dendrite phase and Fe-Al-S
From the viewpoint of preventing the growth of the i-based alloy layer, 150 to 250
It is particularly preferable to carry out soaking heating in the temperature range of ° C.
【００１６】均熱加熱は、１３０〜２７０℃の低温域で
０.５〜２４時間実施する。均熱保持時間が０.５時間未
満では、Ａｌリッチのデンドライト相の硬さが９０ＨＶ
以下にならず、溶融めっき層の軟質化が不十分で加工性
が十分に改善されず、逆に２４時間を越えて長時間均熱
加熱しても軟質化効果が飽和するため不経済である。Ａ
ｌリッチのデンドライト相中の固溶Ｚｎ濃度を低下させ
てデンドライト相を十分に軟質化するためには、１時間
以上の均熱加熱が好ましい。The soaking heating is carried out in a low temperature range of 130 to 270 ° C. for 0.5 to 24 hours. If the soaking time is less than 0.5 hours, the hardness of the Al-rich dendrite phase is 90 HV.
It does not become the following, the softening of the hot-dip coating layer is insufficient and the workability is not sufficiently improved, and conversely, the softening effect is saturated even after soaking and heating for a long time exceeding 24 hours, which is uneconomical. . A
In order to lower the solid solution Zn concentration in the l-rich dendrite phase and to sufficiently soften the dendrite phase, soaking and heating for 1 hour or longer is preferable.
【００１７】均熱加熱後の冷却は、１℃／分以下の冷却
速度で室温まで均熱徐冷処理を施す。均熱徐冷速度が１
℃／分以上では、デンドライト相中の固溶Ｚｎ濃度が十
分に低下せず、デンドライト相の硬さが９０ＨＶ以下に
ならず、溶融めっき層の軟質化が不十分で加工性改善効
果が十分に得られない。Ａｌリッチのデンドライト相中
の固溶Ｚｎ濃度を低下させてデンドライト相を十分に軟
質化する上では、０.５℃／分以下の冷却速度が特に好
ましい。For cooling after soaking and heating, soaking and slow cooling treatment is performed to room temperature at a cooling rate of 1 ° C./minute or less. Soaking and slow cooling rate is 1
At a temperature of ℃ / min or more, the solid solution Zn concentration in the dendrite phase does not sufficiently decrease, the hardness of the dendrite phase does not fall below 90 HV, the softening of the hot-dip coating layer is insufficient, and the workability improving effect is sufficient. I can't get it. A cooling rate of 0.5 ° C./min or less is particularly preferable in order to sufficiently soften the dendrite phase by lowering the concentration of solid solution Zn in the Al-rich dendrite phase.
【００１８】Ａｌリッチのデンドライト相中のＺｎ濃度
を１０質量％以下に低下させると、デンドライト相の硬
さが９０ＨＶ以下になり、デンドライト相とＺｎリッチ
のマトリックスとの硬度差が減少する。その結果、折り
曲げ加工時に鋼板との界面に形成された合金層（金属間
化合物層）に無数の微細な加工割れが発生しても、デン
ドライト相／マトリックスの界面に過度の応力が集中す
ることがなく、溶融めっき層に無数で微細な割れが生じ
るため、目視上観察されない程度に加工割れの発生が抑
えられる。When the Zn concentration in the Al-rich dendrite phase is reduced to 10% by mass or less, the hardness of the dendrite phase becomes 90 HV or less, and the difference in hardness between the dendrite phase and the Zn-rich matrix decreases. As a result, even if numerous minute work cracks occur in the alloy layer (intermetallic compound layer) formed at the interface with the steel sheet during bending, excessive stress may be concentrated at the dendrite phase / matrix interface. Since, innumerable and minute cracks occur in the hot-dip plated layer, the occurrence of work cracks is suppressed to the extent not visually observed.
【００１９】溶融めっき後に均熱加熱・均熱徐冷した溶
融Ｚｎ−Ａｌ合金めっき鋼板は、従来の溶融Ｚｎ−Ａｌ
合金めっき鋼板と同様に連続塗装ラインで塗装される
が、塗装に先立って溶融めっき層表面が塗装前処理され
る。塗装前処理では、先ず塗装原板の溶融めっき層の濡
れ性を良くし、均一な化成処理皮膜を形成させるための
表面調整処理としての脱脂処理が施される。脱脂処理剤
には主にアルカリ脱脂液が使用され、塗装原板表面にス
プレーされ、或いは処理液中に塗装原板が浸漬される。The hot-dip Zn-Al alloy-plated steel sheet which has been soaked and heated and soaked and cooled after the hot dip coating is
Like the alloy-plated steel sheet, it is coated on a continuous coating line, but the surface of the hot-dip coating layer is pre-treated prior to coating. In the coating pretreatment, first, a degreasing treatment is performed as a surface conditioning treatment for improving the wettability of the hot-dip coating layer of the coating original plate and forming a uniform chemical conversion treatment film. Alkaline degreasing liquid is mainly used as a degreasing treatment agent, and it is sprayed on the surface of the original coating plate or the original coating plate is immersed in the treatment liquid.
【００２０】表面調整された塗装原板に従来と同様なク
ロメート系皮膜や非クロメート系化成処理皮膜を形成す
ることにより、塗膜密着性を向上させる。たとえば、ク
ロメート系皮膜は、耐食性及び塗膜密着性を確保するた
めにＣｒ換算付着量５〜１００ｍｇ／ｍ2の割合で形成
することが好ましい。５〜１００ｍｇ／ｍ2のＣｒ付着
量は、水溶性又は水分散性の樹脂やシリカを含有するク
ロメート皮膜や、リン酸−クロム酸系処理液により形成
されるクロメート皮膜でも同様である。非クロメート系
皮膜は、有機樹脂，チタン化合物，フッ素化合物，ジル
コニウム化合物等を含む有機−無機複合皮膜であり、耐
食性及び塗膜密着性を確保するため皮膜量２〜５００ｍ
ｇ／ｍ2の割合で形成することが好ましい。By forming a chromate-based coating or a non-chromate-based chemical conversion coating similar to the conventional one on the surface-coated coated original plate, the coating adhesion is improved. For example, it is preferable to form the chromate-based film at a rate of 5-100 mg / m 2 in terms of Cr equivalent in order to secure corrosion resistance and coating adhesion. The Cr deposition amount of 5 to 100 mg / m 2 is the same for a chromate film containing a water-soluble or water-dispersible resin or silica or a chromate film formed by a phosphoric acid-chromic acid-based treatment liquid. The non-chromate coating is an organic-inorganic composite coating containing an organic resin, a titanium compound, a fluorine compound, a zirconium compound, etc., and the coating amount is 2 to 500 m in order to secure corrosion resistance and coating adhesion.
It is preferably formed at a rate of g / m 2 .
【００２１】化成処理皮膜が形成された塗装原板の表面
には、従来と同様の樹脂塗膜を従来と同様の方法で形成
する。下塗り塗料には、エポキシ系，エポキシ・ウレタ
ン系，ポリエステル系，アクリル系，エポキシ変性ポリ
エステル系，フェノキシ系等の樹脂が使用される。下塗
り塗膜の膜厚は、従来と同様の３〜１０μｍの範囲とす
る。下塗り塗料には、クロム酸ストロンチウム，クロム
酸カルシウム，クロム酸バリウム，クロム酸亜鉛等のク
ロム酸系防錆顔料や変性シリカ系防錆顔料，トリポリリ
ン酸二水素アルミニウム，リン酸亜鉛，リン酸カルシウ
ム，シリカ−カルシウム系等の非クロム酸系防錆顔料
を、単独であるいは２種以上組み合わせて添加しても良
い。防錆顔料の他に酸化チタン等の着色顔料，炭酸カル
シウム，硫酸バリウム等の体質顔料や各種の有機樹脂ビ
ーズ，有機樹脂粉末，無機骨材等の添加剤を下塗り塗料
に配合してもよい。下塗り塗料樹脂の分子量，ガラス転
移温度，顔料，骨材等の添加量は、塗装鋼板の用途に応
じて適宜調整される。On the surface of the coated original plate on which the chemical conversion coating has been formed, a resin coating film similar to the conventional one is formed by a conventional method. For the undercoat paint, resins such as epoxy type, epoxy-urethane type, polyester type, acrylic type, epoxy modified polyester type, and phenoxy type resin are used. The film thickness of the undercoat coating film is in the range of 3 to 10 μm as in the conventional case. The undercoat paint includes strontium chromate, calcium chromate, barium chromate, zinc chromate, and other chromic acid-based rust-preventive pigments and modified silica-based rust-preventive pigments, aluminum tripolyphosphate dihydrogen phosphate, zinc phosphate, calcium phosphate, silica- You may add non-chromic acid type | mold rust preventive pigments, such as calcium type, individually or in combination of 2 or more types. In addition to the rust preventive pigment, a coloring pigment such as titanium oxide, an extender pigment such as calcium carbonate and barium sulfate, and various organic resin beads, organic resin powders, additives such as inorganic aggregates may be added to the undercoat paint. The molecular weight of the undercoat resin, the glass transition temperature, the amount of pigment, aggregate, etc. added is appropriately adjusted according to the application of the coated steel sheet.
【００２２】下塗り塗膜の上に上塗り塗膜が形成され
る。上塗り塗料には、ポリエステル系，ウレタン系，ア
クリル系，シリコーン変性ポリエステル系，シリコーン
アクリル系，ポリ塩化ビニル系，ポリフッ化ビニリデン
−アクリル系等、熱硬化性樹脂又は熱可塑性樹脂が使用
される。必要に応じ有機系骨材，無機系骨材，メタリッ
ク粉末，潤滑剤，汚れ防止剤，防かび剤，紫外線吸収
剤，光安定剤（酸化防止剤），光触媒粒子，艶消し剤
等、各種粉末が下塗り塗料に配合される。塗装方法は特
に制限はなく、従来一般に実施されているロールコータ
ー法，カーテンフローコーター法，スプレー法等が適用
できる。An overcoat film is formed on the undercoat film. As the top coating material, a thermosetting resin or a thermoplastic resin such as polyester, urethane, acrylic, silicone modified polyester, silicone acrylic, polyvinyl chloride, polyvinylidene fluoride-acrylic is used. Various powders such as organic aggregates, inorganic aggregates, metallic powders, lubricants, antifouling agents, antifungal agents, ultraviolet absorbers, light stabilizers (antioxidants), photocatalyst particles, matting agents, etc. Is blended in the undercoat paint. The coating method is not particularly limited, and a roll coater method, a curtain flow coater method, a spray method, etc., which have been generally practiced conventionally, can be applied.
【００２３】このように、溶融めっき後に溶融Ｚｎ−Ａ
ｌ合金めっき鋼板を１３０〜２７０℃の低温域で０.５
〜２４時間均熱加熱した後、１℃／分以下の冷却速度で
室温まで均熱徐冷処理を施すと、塗装原板として連続塗
装ラインで塗装しても、Ａｌリッチのデンドライト相中
のＺｎ濃度は１０質量％以下で、硬さも９０ＨＶ以下に
軟質化された状態が保持される。この塗装溶融Ｚｎ−Ａ
ｌ合金めっき鋼板を折り曲げ加工した場合、鋼板との界
面に形成された合金層（金属間化合物層）に無数の微細
な加工割れが発生しても、デンドライト相／マトリック
スの界面に過度の応力が集中することがなく、溶融めっ
き層に無数で微細な割れが生じるため、目視上観察され
ない程度に加工割れが分散して大きな加工割れの発生が
抑えられる。その結果、加工割れが溶融めっき層上の塗
膜に伝播することが大幅に抑制され、塗膜割れ部からの
腐食性イオンの侵入が塗膜によって抑制されるため、Ｚ
ｎ−Ａｌ合金溶融めっき層本来の優れた耐食性が加工部
においても維持される。Thus, after the hot dip plating, the hot dip Zn-A
l alloy-plated steel sheet at a low temperature range of 130 to 270 ° C of 0.5
After soaking and heating for ~ 24 hours, soaking and gradual cooling treatment to room temperature at a cooling rate of 1 ° C / min or less allows Zn concentration in the Al-rich dendrite phase even when applied as a coating original plate in a continuous coating line. Is 10% by mass or less, and the hardness is maintained at 90 HV or less. This coating melt Zn-A
l When an alloy-plated steel sheet is bent, even if numerous minute work cracks occur in the alloy layer (intermetallic compound layer) formed at the interface with the steel sheet, excessive stress is generated at the dendrite phase / matrix interface. Since there is no concentration and numerous countless fine cracks occur in the hot-dip plated layer, the work cracks are dispersed to the extent that they cannot be visually observed, and the occurrence of large work cracks is suppressed. As a result, the propagation of work cracks to the coating film on the hot-dip coating layer is significantly suppressed, and the penetration of corrosive ions from the cracked portion of the coating film is suppressed by the coating film.
The original excellent corrosion resistance of the n-Al alloy hot-dip plated layer is maintained even in the processed portion.
【００２４】これに対し、従来の条件で製造された塗装
原板及び本発明の範囲外の条件で後加熱処理された塗装
原板を用いると、Ａｌリッチのデンドライト相中のＺｎ
濃度が１０質量％以下には低下せず、硬さも９０ＨＶ以
下に軟質化された状態にならない場合があるため、折り
曲げ加工で鋼板との界面に形成された合金層（金属間化
合物層）に無数の微細な加工割れが発生すると、デンド
ライト相／マトリックスの界面に過度の応力が集中し、
溶融めっき層に開口幅と開口長の大きい割れが生じ、溶
融めっき層の割れが塗膜にも伝播して大きな塗膜割れが
生じる。その結果、塗膜割れ部から容易に腐食性イオン
が侵入するため、加工部においてはＺｎ−Ａｌ合金溶融
めっき層本来の優れた耐食性が維持することが困難とな
る。On the other hand, when the coating base plate manufactured under the conventional conditions and the coating base plate post-heat-treated under the conditions outside the scope of the present invention are used, Zn in the Al-rich dendrite phase is used.
Since the concentration does not decrease below 10 mass% and the hardness may not be softened below 90 HV, there are countless alloy layers (intermetallic compound layers) formed at the interface with the steel sheet during bending. When microscopic work cracking occurs, excessive stress concentrates on the dendrite phase / matrix interface,
A crack with a large opening width and a large opening length occurs in the hot-dip coating layer, and the crack in the hot-dip coating layer propagates to the coating film, causing a large coating film crack. As a result, corrosive ions easily enter from the cracked portion of the coating film, making it difficult to maintain the original excellent corrosion resistance of the Zn-Al alloy hot-dip coating layer in the processed portion.
【００２５】[0025]
【実施例】板厚０.３５ｍｍの普通冷延鋼板をめっき原
板に使用し、還元・加熱によって鋼板表面を活性化した
後、ラインスピード１７０ｍ／分で浴温６０.５℃のＺ
ｎ−５５％Ａｌ溶融めっき浴に導入した。溶融めっき浴
から引き上げられた鋼板に不活性ガスを吹き付けて片面
めっき付着量を７５ｇ／ｍ2に調整した後、溶融めっき
層を冷却速度２０℃／秒で冷却凝固することによりＺｎ
−Ａｌ合金溶融めっき層を鋼板表面に形成した。製造さ
れた溶融Ｚｎ−５５％Ａｌ合金めっき鋼板について、Ｚ
ｎ−Ａｌ合金溶融めっき層に晶出しているＡｌリッチの
デンドライト相のＺｎ濃度を測定したところ、１８〜２
５質量％のＺｎ濃度であった。なお、Ｚｎ濃度の測定
は、ＥＤＸによるスポット分析に依った。また、Ｚｎ−
Ａｌ合金溶融めっき層の硬さをマイクロビッカース硬度
計で測定したところ、Ａｌリッチのデンドライト相が１
２０〜１５０ＨＶ，Ｚｎリッチのマトリックスが２０〜
４０ＨＶであり、デンドライト相とマトリックスとの間
に大きな硬度差があった。[Example] A normal cold-rolled steel sheet having a plate thickness of 0.35 mm is used as a plating base sheet, and after activating the steel sheet surface by reduction and heating, a line speed of 170 m / min and a bath temperature of 60.5 ° C. are applied.
It was introduced into an n-55% Al hot dip bath. After the inert gas was blown onto the steel plate pulled up from the hot dip coating bath to adjust the coating amount on one side to 75 g / m 2 , the hot dip layer was cooled and solidified at a cooling rate of 20 ° C./sec to obtain Zn.
-Al alloy hot dip coating layer was formed on the steel plate surface. Regarding the manufactured hot dip Zn-55% Al alloy plated steel sheet, Z
When the Zn concentration of the Al-rich dendrite phase crystallized in the n-Al alloy hot-dip layer was measured, it was 18 to 2
The Zn concentration was 5% by mass. The Zn concentration was measured by spot analysis by EDX. In addition, Zn-
When the hardness of the Al alloy hot-dip layer was measured with a micro Vickers hardness meter, the Al-rich dendrite phase was 1
20-150 HV, Zn-rich matrix is 20-
It was 40 HV, and there was a large hardness difference between the dendrite phase and the matrix.
【００２６】デンドライト相のＺｎ濃度を低下させるた
め、１３０〜２７０℃，０.５〜２４時間の条件下で後
加熱し、加熱条件の調整によってデンドライト相のＺｎ
濃度を種々のレベルに低下させたＺｎ−Ａｌ合金溶融め
っき層に改質した。後加熱された溶融Ｚｎ−５５％Ａｌ
合金めっき鋼板を塗装原板に使用し、クロメート皮膜の
上に、クロム酸ストロンチウムを不揮発分に対して２５
質量％を配合し、その他に着色顔料として酸化チタン，
体質顔料として硫酸バリウム及びシリカ粉末を配合した
エポキシ樹脂の下塗り塗料を塗布し、２１５℃で乾燥し
て乾燥膜厚５μｍの下塗り塗膜を形成した。次いで、ポ
リエステル系樹脂に有機樹脂と無機骨材を配合した艶消
し上塗り塗料を塗布し、同様に２１５℃で乾燥して乾燥
膜厚１５μｍの上塗り塗膜を形成した。In order to lower the Zn concentration in the dendrite phase, post-heating is performed under the conditions of 130 to 270 ° C. and 0.5 to 24 hours, and the Zn in the dendrite phase is adjusted by adjusting the heating conditions.
The Zn-Al alloy hot-dip galvanized layer having various concentrations was modified. Post-heated molten Zn-55% Al
Using alloy-plated steel sheet as the coating base plate, strontium chromate was added to the non-volatile content on the chromate film.
In addition to this, titanium oxide is added as a coloring pigment.
An undercoat paint of an epoxy resin containing barium sulfate and silica powder as an extender pigment was applied and dried at 215 ° C. to form an undercoat paint film having a dry film thickness of 5 μm. Then, a matte topcoat paint prepared by blending an organic resin and an inorganic aggregate was applied to the polyester resin, and similarly dried at 215 ° C. to form a topcoat film having a dry film thickness of 15 μm.
【００２７】塗装された溶融Ｚｎ−５５％Ａｌ合金めっ
き鋼板から４０×５０ｍｍの試験片を１００個切り出
し、折り曲げ加工試験に供した。折り曲げ加工試験で
は、２０℃に調整された室内で加工試験片と同じ塗装鋼
板を４枚間に挟んで試験片を１８０度折り曲げした後、
曲げ部外側の塗膜表面を目視観察し、塗膜に亀裂が発生
した試験片の個数で加工性を評価した。更に、促進耐食
性試験では、１２５サイクルの酸性雨複合腐食試験［１
サイクル：０.１％ＮａＣ１腐食液噴霧（３５℃×１時
間，硫酸でｐＨ４に調整）→乾燥（５０℃×４時間）→
湿潤（５０℃×３時間，相対湿度９８％）］後に、４ｔ
加工部の表面を観察し、試験対象部の面積１００に対す
る白さび発生率（％）で加工部耐食性を評価した。100 pieces of 40 × 50 mm test pieces were cut out from the coated hot dip Zn-55% Al alloy plated steel sheet and subjected to a bending test. In the bending test, after bending the test piece 180 degrees by sandwiching the same coated steel plate as the processed test piece between 4 sheets in a room adjusted to 20 ° C.,
The coating film surface outside the bent portion was visually observed, and the workability was evaluated by the number of test pieces having cracks in the coating film. Furthermore, in the accelerated corrosion resistance test, 125 cycles of acid rain complex corrosion test [1
Cycle: 0.1% NaC1 corrosive solution spray (35 ° C x 1 hour, pH adjusted to 4 with sulfuric acid) → drying (50 ° C x 4 hours) →
Wetness (50 ° C x 3 hours, relative humidity 98%)], then 4t
The surface of the processed portion was observed, and the corrosion resistance of the processed portion was evaluated by the white rust occurrence rate (%) with respect to the area 100 of the test target portion.
【００２８】試験結果を示す表１にみられるように、加
工割れの発生や加工部耐食性が溶融めっき層に晶出して
いるデンドライト相のＺｎ濃度と密接に関係していた。
すなわち、デンドライト相のＺｎ濃度を１０質量％以下
に改質した溶融Ｚｎ−Ａｌ合金めっき鋼板を塗装原板に
するとき、折り曲げ加工部の溶融めっき層や塗膜に加工
割れが発生しておらず、Ｚｎ−Ａｌ合金溶融めっき層が
健全な状態に保たれたため良好な耐食性を呈した。塗膜
の外観も、加工割れや腐食がないことから曲げ加工前の
塗膜表面とほとんど変わらない良好な状態に維持されて
いた。他方、デンドライト相のＺｎ濃度が１０質量％を
超えるＺｎ−Ａｌ合金溶融めっき層をもつ塗装原板で
は、折り曲げ加工部に無数の割れが検出され、割れを起
点とする腐食が進行していた。また、加工割れや腐食に
より曲げ加工部の塗膜外観が著しく劣化していた。As shown in Table 1 showing the test results, the occurrence of work cracks and the corrosion resistance of the worked part were closely related to the Zn concentration of the dendrite phase crystallized in the hot dip layer.
That is, when a hot-dip Zn-Al alloy-plated steel sheet having a Zn concentration in the dendrite phase modified to 10 mass% or less is used as a coating original plate, no work cracks are generated in the hot-dip coating layer or coating film in the bent portion, Since the Zn-Al alloy hot-dip layer was kept in a healthy state, it exhibited good corrosion resistance. The appearance of the coating film was maintained in a good state, which was almost the same as the surface of the coating film before bending because there was no work cracking or corrosion. On the other hand, in the coating base plate having the Zn—Al alloy hot-dip coating layer in which the Zn concentration in the dendrite phase exceeds 10% by mass, innumerable cracks were detected in the bent portion, and corrosion starting from the cracks proceeded. Further, the appearance of the coating film in the bent portion was significantly deteriorated due to work cracking and corrosion.
【００２９】 [0029]
【００３０】[0030]
【発明の効果】以上に説明したように、本発明の塗装原
板は、Ｚｎ−Ａｌ合金溶融めっき層に晶出しているデン
ドライト相のＺｎ濃度を１０質量％以下にしているので
Ｚｎ−Ａｌ合金溶融めっき層が十分に軟質化された状態
にある。そのため、塗膜成形後の溶融Ｚｎ−Ａｌ合金め
っき鋼板に高度の加工を施してもＺｎ−Ａｌ合金溶融め
っき層の加工割れが抑制され、Ｚｎ−Ａｌ合金溶融めっ
き層本来の優れた耐食性が加工部においても発現され、
良好な外観をもつ塗膜性状が維持される。As described above, in the coating base plate of the present invention, the Zn concentration of the dendrite phase crystallized in the Zn-Al alloy hot-dip layer is 10% by mass or less. The plating layer is in a sufficiently softened state. Therefore, the work crack of the Zn-Al alloy hot-dip coating layer is suppressed even when the hot-dip Zn-Al alloy-plated steel sheet after the coating film is formed is subjected to a high degree of work, and the excellent corrosion resistance inherent to the Zn-Al alloy hot-dip coating layer is processed. Is also expressed in the department,
The coating properties with good appearance are maintained.
フロントページの続き (72)発明者 服部 保徳 大阪府堺市石津西町５番地 日新製鋼株式 会社技術研究所内 (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 会社技術研究所内 (72)発明者 圓谷 浩 千葉県市川市高谷新町７番１号 日新製鋼 株式会社技術研究所内 Ｆターム(参考） 4K027 AA02 AA22 AB02 AB05 AB09 AB32 AB44 AB48 AC72 AD25 AE03 AE12 AE18 AE21 Continued front page (72) Inventor Yasunori Hattori No. 5 Ishizu Nishimachi, Sakai City, Osaka Prefecture Nisshin Steel Co., Ltd. Company Technology Research Center (72) Inventor Tadaaki Miono No. 5 Ishizu Nishimachi, Sakai City, Osaka Prefecture Nisshin Steel Co., Ltd. Company Technology Research Center (72) Inventor Hiroshi Enya 7-1 Takaya Shinmachi, Ichikawa City, Chiba Prefecture Nisshin Steel Technical Research Institute Co., Ltd. F-term (reference) 4K027 AA02 AA22 AB02 AB05 AB09 AB32 AB44 AB48 AC72 AD25 AE03 AE12 AE18 AE21
Claims (2)
ｌ合金溶融めっき層が鋼板表面に形成されており、Ｚｎ
−Ａｌ合金溶融めっき層に晶出しているＡｌリッチのデ
ンドライト相のＺｎ濃度が１０質量％以下に抑えられて
いることを特徴とする加工性に優れた塗装原板。1. Zn-A containing 50-60 mass% Al.
l hot-dip galvanized layer is formed on the surface of the steel sheet.
A coated original plate having excellent workability, characterized in that the Zn concentration of the Al-rich dendrite phase crystallized in the Al alloy hot-dip layer is suppressed to 10% by mass or less.
量％以下のＳｉを含んでいる請求項１記載の塗装原板。2. The coated original plate according to claim 1, wherein the Zn-Al alloy hot-dip plated layer further contains 3 mass% or less of Si.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002075044A JP2003268518A (en) | 2002-03-18 | 2002-03-18 | Original sheet for coating having excellent workability |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002075044A JP2003268518A (en) | 2002-03-18 | 2002-03-18 | Original sheet for coating having excellent workability |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2003268518A true JP2003268518A (en) | 2003-09-25 |
Family
ID=29204272
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002075044A Withdrawn JP2003268518A (en) | 2002-03-18 | 2002-03-18 | Original sheet for coating having excellent workability |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2003268518A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012528244A (en) * | 2009-05-28 | 2012-11-12 | ブルースコープ・スティール・リミテッド | Metal coated steel strip |
| JP2013245355A (en) * | 2012-05-23 | 2013-12-09 | Yodogawa Steel Works Ltd | METHOD FOR MANUFACTURING Al-Zn ALLOY PLATED STEEL SHEET |
| JP2014237887A (en) * | 2013-05-08 | 2014-12-18 | 株式会社神戸製鋼所 | HOT DIP GALVANIZED STEEL SHEET OR HOT DIP GALVANNEALED STEEL SHEET HAVING TENSILE STRENGTH OF 1,180 MPa OR HIGHER AND EXCELLENT IN BALANCE OF STRENGTH-BENDABILITY |
| JP2021031759A (en) * | 2019-08-29 | 2021-03-01 | Ｊｆｅ鋼板株式会社 | FUSION Al-Zn BASED ALLOY PLATING STEEL SHEET EXCELLENT IN PROCESSING PART CORROSION RESISTANCE AND PRODUCTION METHOD FOR THE SAME |
| JP7291860B1 (en) | 2022-03-24 | 2023-06-15 | Ｊｆｅ鋼板株式会社 | Hot-dip Al-Zn-based plated steel sheet and manufacturing method thereof |
| WO2023181427A1 (en) * | 2022-03-24 | 2023-09-28 | Ｊｆｅ鋼板株式会社 | Molten al-zn-plated steel sheet and method for producing same |
-
2002
- 2002-03-18 JP JP2002075044A patent/JP2003268518A/en not_active Withdrawn
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012528244A (en) * | 2009-05-28 | 2012-11-12 | ブルースコープ・スティール・リミテッド | Metal coated steel strip |
| JP2013245355A (en) * | 2012-05-23 | 2013-12-09 | Yodogawa Steel Works Ltd | METHOD FOR MANUFACTURING Al-Zn ALLOY PLATED STEEL SHEET |
| JP2014237887A (en) * | 2013-05-08 | 2014-12-18 | 株式会社神戸製鋼所 | HOT DIP GALVANIZED STEEL SHEET OR HOT DIP GALVANNEALED STEEL SHEET HAVING TENSILE STRENGTH OF 1,180 MPa OR HIGHER AND EXCELLENT IN BALANCE OF STRENGTH-BENDABILITY |
| JP2021031759A (en) * | 2019-08-29 | 2021-03-01 | Ｊｆｅ鋼板株式会社 | FUSION Al-Zn BASED ALLOY PLATING STEEL SHEET EXCELLENT IN PROCESSING PART CORROSION RESISTANCE AND PRODUCTION METHOD FOR THE SAME |
| JP7291860B1 (en) | 2022-03-24 | 2023-06-15 | Ｊｆｅ鋼板株式会社 | Hot-dip Al-Zn-based plated steel sheet and manufacturing method thereof |
| WO2023181427A1 (en) * | 2022-03-24 | 2023-09-28 | Ｊｆｅ鋼板株式会社 | Molten al-zn-plated steel sheet and method for producing same |
| WO2023181426A1 (en) * | 2022-03-24 | 2023-09-28 | Ｊｆｅ鋼板株式会社 | Hot-dip al-zn-based plated steel sheet and method for manufacturing same |
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