JP3302676B2 - Chemical treated steel sheet with excellent corrosion resistance - Google Patents
Chemical treated steel sheet with excellent corrosion resistanceInfo
- Publication number
- JP3302676B2 JP3302676B2 JP2000338515A JP2000338515A JP3302676B2 JP 3302676 B2 JP3302676 B2 JP 3302676B2 JP 2000338515 A JP2000338515 A JP 2000338515A JP 2000338515 A JP2000338515 A JP 2000338515A JP 3302676 B2 JP3302676 B2 JP 3302676B2
- Authority
- JP
- Japan
- Prior art keywords
- chemical conversion
- steel sheet
- film
- treated steel
- conversion treatment
- 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.)
- Expired - Lifetime
Links
Description
【０００１】[0001]
【産業上の利用分野】本発明は、Ａｌ−Ｓｉ合金めっき
層の上に耐食性に優れた皮膜が形成された化成処理鋼板
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a chemical conversion treated steel sheet having a coating having excellent corrosion resistance formed on an Al--Si alloy plating layer.
【０００２】[0002]
【従来の技術】耐食性の良好な鋼材としてアルミニウム
系めっき鋼板が多用されているが、湿潤雰囲気，排ガス
雰囲気，海塩粒子飛散雰囲気等にアルミニウム系めっき
鋼板を長期間放置すると、鋼板表面に白錆が発生し外観
が劣化する。白錆の発生はアルミニウム系めっき鋼板を
クロメート処理することにより防止できるが、Ｃｒイオ
ンを含む排液の処理に多大な負担がかかる。そこで、チ
タン系，ジルコニウム系，モリブデン系，リン酸塩系等
の薬液を使用したＣｒフリーの化成処理方法が検討され
ており、アルミニウム材料ではＤＩ缶等への適用を主目
的として多数の提案がある。たとえば、チタン系では、
チタン化合物，燐酸イオン，フッ化物，促進剤を含む水
溶液をアルミニウム含有金属材料に接触させ、水洗・乾
燥することにより化成処理皮膜を形成する方法が特開平
９−２０９８４号公報で紹介されている。2. Description of the Related Art Aluminum-plated steel sheets are often used as a steel material having good corrosion resistance. And the appearance deteriorates. Although the generation of white rust can be prevented by subjecting the aluminum-based plated steel sheet to chromate treatment, a large burden is imposed on the treatment of the effluent containing Cr ions. Accordingly, Cr-free chemical conversion treatment methods using chemicals such as titanium-based, zirconium-based, molybdenum-based, and phosphate-based chemicals are being studied. For aluminum materials, many proposals have been made mainly for application to DI cans and the like. is there. For example, in the titanium series,
Japanese Patent Application Laid-Open No. 9-20984 discloses a method of forming a chemical conversion coating by bringing an aqueous solution containing a titanium compound, a phosphate ion, a fluoride and an accelerator into contact with an aluminum-containing metal material, washing with water and drying.
【０００３】[0003]
【発明が解決しようとする課題】クロム系皮膜は、三価
Ｃｒ及び六価Ｃｒが複合した酸化物，水酸化物からなる
皮膜である。難溶性の三価Ｃｒ化合物Ｃｒ2Ｏ3等は、環
境遮断機能を呈し、基材の腐食を防止する。他方、六価
Ｃｒ化合物は、Ｃｒ2Ｏ7 2-等の酸素酸アニオンとなって
化成処理皮膜から溶出し、加工等で生じた鋼板露出部と
還元反応し難溶性の三価Ｃｒ化合物として再析出する。
三価Ｃｒ化合物の析出により化成処理皮膜が自己修復さ
れ、優れた防食作用が発現される。The chromium-based film is a film composed of an oxide or hydroxide in which trivalent Cr and hexavalent Cr are combined. The hardly soluble trivalent Cr compound Cr 2 O 3 or the like exhibits an environmental barrier function and prevents corrosion of the base material. On the other hand, the hexavalent Cr compound is converted into an oxygen acid anion such as Cr 2 O 7 2- and elutes from the chemical conversion coating, and undergoes a reduction reaction with the exposed portion of the steel sheet formed by processing or the like, and is converted into a hardly soluble trivalent Cr compound. Precipitates.
The chemical conversion coating is self-repaired by the precipitation of the trivalent Cr compound, and an excellent anticorrosion action is exhibited.
【０００４】ところが、クロム系皮膜に代わるものとし
て提案されているチタン系，ジルコニウム系，リン酸塩
系等の皮膜では、クロム系皮膜にみられるような優れた
自己修復作用が得られていない。たとえば、チタン系皮
膜は、クロム系皮膜と同様にバリア作用のある酸化物や
水酸化物からなる連続皮膜として形成されるが、クロム
系皮膜と異なり難溶性であることから自己修復作用を呈
さない。そのため、化成処理時や成形加工等の際に生じ
た皮膜欠陥部を起点とする腐食の抑制には有効でない。
他のＣｒフリー皮膜も、チタン系皮膜と同様に自己修復
作用が弱く、腐食抑制効果が不充分である。However, titanium-based, zirconium-based and phosphate-based coatings proposed as alternatives to chromium-based coatings do not provide the excellent self-healing effect found in chromium-based coatings. For example, a titanium-based film is formed as a continuous film made of an oxide or hydroxide having a barrier function, like a chromium-based film, but does not exhibit a self-healing effect because it is hardly soluble unlike a chromium-based film. . For this reason, it is not effective in suppressing corrosion originating from a film defect portion generated during chemical conversion treatment or molding.
Other Cr-free coatings, like the titanium-based coatings, also have a weak self-healing effect, and their corrosion inhibitory effect is insufficient.
【０００５】また、アルミニウム系めっき鋼板に化成処
理液をロールコート法，スプレーリンガー法等で従来の
Ｃｒフリー処理液を塗布する場合、皮膜量が少ないとア
ルミニウムめっき層が露出する部分が生じることがあ
る。めっき層露出部は腐食の起点やプレス加工時のカジ
リの起点になりやすく、化成処理皮膜やめっき層が剥離
してしまう。逆にめっき層表面を完全に被覆するために
皮膜量を多くすると、プレス成形時の鋼板の変形に追従
できない化成処理皮膜にクラック等の欠陥が発生しやす
く、耐食性が低下する。[0005] When a conventional Cr-free treatment solution is applied to an aluminum-based plated steel sheet by a roll coating method, a spray ringer method, or the like, a portion of the aluminum plating layer is exposed if the coating amount is small. is there. The exposed portion of the plating layer easily becomes a starting point of corrosion or a starting point of galling at the time of press working, and the chemical conversion treatment film and the plating layer are peeled off. Conversely, if the coating amount is increased to completely cover the plating layer surface, defects such as cracks are likely to occur in the chemical conversion coating which cannot follow the deformation of the steel sheet during press forming, and the corrosion resistance is reduced.
【０００６】[0006]
【課題を解決するための手段】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、Ａｌ−Ｓｉ合金
めっき鋼板を基材とし、バルブメタルの酸化物又は水酸
化物とフッ化物が共存した化成処理皮膜をＡｌ−Ｓｉ合
金めっき層の上に形成することにより、耐食性が格段に
改善された化成処理鋼板を提供することを目的とする。
本発明の化成処理鋼板は、その目的を達成するため、Ａ
ｌ−Ｓｉ合金めっき鋼板を基材とし、酸化物が高い絶縁
抵抗を示すバルブメタルの酸化物又は水酸化物とフッ化
物とが共存する化成処理皮膜が基材表面に形成されてい
ることを特徴とする。基材のＡｌ−Ｓｉ合金めっき鋼板
には、めっき層全体でのＳｉ含有量が５〜１３質量％，
表層のＳｉ含有量が７〜８０質量％のＡｌ−Ｓｉ合金め
っき層が形成されている。SUMMARY OF THE INVENTION The present invention has been devised to solve such a problem. It is based on an Al--Si alloy plated steel sheet as a base material, and contains an oxide or hydroxide of a valve metal. An object of the present invention is to provide a chemical conversion treated steel sheet having significantly improved corrosion resistance by forming a chemical conversion treatment film in which fluoride coexists on an Al-Si alloy plating layer.
The chemical conversion treated steel sheet of the present invention has a
A chemical conversion treatment film in which an oxide or a hydroxide of a valve metal having a high insulation resistance and a fluoride coexist is formed on the surface of the base material using an l-Si alloy plated steel sheet as a base material. And In the base material Al-Si alloy plated steel sheet, the Si content in the entire plating layer is 5 to 13% by mass,
An Al—Si alloy plating layer having a surface Si content of 7 to 80% by mass is formed.
【０００７】バルブメタルとしては、Ｔｉ，Ｚｒ，Ｈ
ｆ，Ｖ，Ｎｂ，Ｔａ，Ｍｏ，Ｗ等がある。化成処理皮膜
に含まれるＯ及びＦの濃度比Ｆ／Ｏが原子比率で１／１
００以上となるようにフッ化物を含ませるとき、フッ化
物起因の自己修復作用が顕著になる。化成処理皮膜には
有機系又は無機系の潤滑剤を添加することもできる。化
成処理皮膜は、更に可溶性又は難溶性の金属リン酸塩又
は複合リン酸塩を含むことができる。可溶性の金属リン
酸塩又は複合リン酸塩としては、アルカリ金属，アルカ
リ土類金属，Ｍｎ等の塩がある。難溶性の金属リン酸塩
又は複合リン酸塩としては、Ａｌ，Ｔｉ，Ｚｒ，Ｈｆ，
Ｚｎ等の塩がある。[0007] As the valve metal, Ti, Zr, H
f, V, Nb, Ta, Mo, W and the like. The concentration ratio F / O of O and F contained in the chemical conversion coating is 1/1 by atomic ratio.
When fluoride is contained so as to be not less than 00, the self-healing action caused by the fluoride becomes remarkable. An organic or inorganic lubricant may be added to the chemical conversion coating. The chemical conversion coating may further include a soluble or poorly soluble metal phosphate or composite phosphate. Examples of the soluble metal phosphate or composite phosphate include salts of alkali metals, alkaline earth metals, Mn, and the like. Examples of poorly soluble metal phosphates or complex phosphates include Al, Ti, Zr, Hf,
There are salts such as Zn.
【０００８】[0008]
【作用】本発明の化成処理鋼板は、バルブメタルの酸化
物又は水酸化物とフッ化物とを共存させている。バルブ
メタルは、酸化物が高い絶縁抵抗を示す金属を指し、Ｔ
ｉ，Ｚｒ，Ｈｆ，Ｖ，Ｎｂ，Ｔａ，Ｍｏ，Ｗの１種又は
２種以上が使用される。バルブメタルの酸化物又は水酸
化物からなる皮膜は、電子の移動に対する抵抗体として
働き、雰囲気中の水分に含まれている溶存酸素による還
元反応（下地鋼との酸化反応）が抑えられる。その結
果、下地鋼からの金属成分の溶出（腐食）が防止され
る。なかでも、Ｔｉ，Ｚｒ，Ｈｆ等のＩＶ族Ａ元素の４
価化合物は安定な化合物であり、優れた皮膜を形成する
ことから好適な皮膜成分である。The chemical conversion-treated steel sheet according to the present invention contains an oxide or hydroxide of a valve metal and a fluoride. Valve metal refers to a metal in which an oxide has high insulation resistance, and T
One or more of i, Zr, Hf, V, Nb, Ta, Mo, and W are used. The coating made of the oxide or hydroxide of the valve metal acts as a resistor against the transfer of electrons, and suppresses the reduction reaction (oxidation reaction with the underlying steel) due to dissolved oxygen contained in the moisture in the atmosphere. As a result, elution (corrosion) of the metal component from the base steel is prevented. Among them, 4 of Group IV A elements such as Ti, Zr and Hf
The valent compound is a stable compound and is a suitable film component because it forms an excellent film.
【０００９】バルブメタルの酸化物又は水酸化物が連続
皮膜として鋼板表面に形成されている場合、電子移動に
対する抵抗体として有効に作用するが、実際の化成処理
皮膜では化成処理時や成形加工時における皮膜欠陥の発
生が避けられない。皮膜欠陥部では下地鋼が露出するた
め、所期の腐食抑制作用が期待できない。そこで、本発
明においては、バルブメタルの可溶性フッ化物を共存さ
せることによって化成処理皮膜に自己修復作用を付与し
ている。バルブメタルのフッ化物は、雰囲気中の水分に
溶け出した後、皮膜欠陥部から露出している下地鋼の表
面に難溶性酸化物又は水酸化物となって再析出し、皮膜
欠陥部を埋める自己修復作用を呈する。When the oxide or hydroxide of the valve metal is formed as a continuous film on the surface of the steel sheet, it effectively acts as a resistor against electron transfer. Unavoidable film defects in Since the underlying steel is exposed at the film defect, the expected corrosion inhibiting action cannot be expected. Therefore, in the present invention, a self-repairing action is imparted to the chemical conversion treatment film by allowing the soluble fluoride of the valve metal to coexist. The fluoride of the valve metal dissolves in the moisture in the atmosphere and then re-precipitates as a hardly soluble oxide or hydroxide on the surface of the base steel exposed from the defective film portion, thereby filling the defective film portion. Exhibits self-healing action.
【００１０】たとえば、めっき鋼板表面に形成されたチ
タン系皮膜は、酸化物〔ＴｉＯ2］や水酸化物［Ｔｉ(Ｏ
Ｈ)4］が複合した皮膜である。ミクロ的にみて皮膜厚み
が極端に不足する部分やピンホール等の皮膜欠陥部では
下地鋼が露出し、腐食の起点になりやすい。この点、従
来のクロム系皮膜では可溶性の六価Ｃｒが皮膜欠陥部に
難溶性三価Ｃｒ化合物として析出することにより自己修
復作用が発現するが、チタン系皮膜では自己修復作用を
期待できない。皮膜厚みを増加することによって皮膜欠
陥部を少なくできるが、硬質で延性に乏しいチタン系皮
膜は化成処理された鋼板を成形加工する際に鋼板の伸び
に追従できず、クラック，カジリ等の欠陥が化成処理皮
膜に生じやすくなる。[0010] For example, a titanium-based film formed on the surface of a plated steel sheet includes oxide [TiO 2 ] or hydroxide [Ti (O
H) 4 ] is a composite film. Microscopically, the base steel is exposed at portions where the film thickness is extremely insufficient or at film defects such as pinholes, and is likely to be a starting point of corrosion. In this regard, in the conventional chromium-based coating, self-healing action is exhibited by soluble hexavalent Cr precipitated as a poorly soluble trivalent Cr compound in the coating defect portion, but the self-healing action cannot be expected in the titanium-based coating. Increasing the film thickness can reduce the number of film defects, but the hard and poorly ductile titanium film cannot follow the elongation of the steel sheet when forming a chemically treated steel sheet, and defects such as cracks and galling can occur. It is likely to occur in chemical conversion coatings.
【００１１】これに対し、ＸnＴｉＦ6（Ｘ：アルカリ金
属，アルカリ土類金属又はＮＨ4，ｎ＝１又は２），Ｔ
ｉＦ4等のフッ化物を共存させると、フッ化物が化成処
理皮膜から溶出し、ＴｉＦ6 2-＋４Ｈ2Ｏ→Ｔｉ(ＯＨ)4
＋６Ｆ-等の反応によって難溶性の酸化物又は水酸化物
となって皮膜欠陥部に再析出し、自己修復作用を呈す
る。フッ化物としては、酸化物又は水酸化物となる金属
と同種又は異種の何れであってもよい。また、バルブメ
タルとしてＭｏ又はＷを選択するとき、これら六価酸素
酸塩の中には可溶性を示す塩も存在し、自己修復作用を
呈するものもある。そのため、化成処理皮膜に含ませる
フッ化物に加わる制約が緩和される。On the other hand, X n TiF 6 (X: alkali metal, alkaline earth metal or NH 4 , n = 1 or 2), T
Coexistence fluorides iF 4 etc., fluorides are eluted from the chemical conversion coating, TiF 6 2- + 4H 2 O → Ti (OH) 4
Due to the reaction of + 6F - or the like, it becomes a hardly soluble oxide or hydroxide and is reprecipitated at a film defect portion to exhibit a self-healing action. The fluoride may be the same or different from the metal to be an oxide or hydroxide. In addition, when Mo or W is selected as a valve metal, some of these hexavalent oxyacid salts have a solubility, and some exhibit a self-healing action. Therefore, restrictions on the fluoride contained in the chemical conversion coating are reduced.
【００１２】更に、Ａｌ−Ｓｉ合金めっき層のＳｉ含有
量を規制するとき、化成処理皮膜量が少ない場合でもＡ
ｌの露出を防止できる。Ａｌ−Ｓｉ合金めっき層のＳｉ
含有量がＡｌ露出の如何に及ぼす影響は次のように推察
される。めっき層の表層にＳｉをある程度濃化させたＡ
ｌ−Ｓｉ合金めっき鋼板を基材として化成処理すると、
めっき層表面のＡｌが選択的にエッチング除去され、金
属Ｓｉ主体の凸部及びＡｌリッチの凹部をもつ表面にな
る。凹部に化成処理液が溜まりやすいので、チタンの酸
化物又は水酸化物及びフッ化物からなる複合皮膜でＡｌ
リッチな凹部が優先的に被覆される。Further, when regulating the Si content of the Al—Si alloy plating layer, even when the amount of the chemical conversion coating is small, A
1 can be prevented. Si of Al-Si alloy plating layer
The effect of the content on the Al exposure is presumed as follows. A in which Si is concentrated to some extent on the surface of the plating layer
When a chemical conversion treatment is performed using an l-Si alloy plated steel sheet as a base material,
Al on the surface of the plating layer is selectively removed by etching to form a surface having a convex portion mainly composed of metal Si and a concave portion rich in Al. Since the chemical conversion treatment liquid easily accumulates in the recesses, the composite coating composed of titanium oxide or hydroxide and fluoride has a
The rich recess is preferentially covered.
【００１３】この方法で化成処理皮膜を形成することに
より、めっき層表層は金属Ｓｉ及びチタンの複合化合物
皮膜で覆われて硬質化すると共に、凹凸の形成で金型と
の接触面積が低減することから、プレス成形時に摺動抵
抗が軽減され、加工性が向上する。また、めっき層表層
にＡｌリッチな部位が露出していないため、抵抗溶接時
には電極へのＡｌのピックアップが低減され、電極寿命
も長くなる。めっき層表層に形成された凹凸は、アンカ
ー効果を呈し、後工程で形成される塗膜の密着性を向上
させる上でも有効である。By forming the chemical conversion coating by this method, the surface layer of the plating layer is hardened by being covered with the composite compound film of metal Si and titanium, and the contact area with the mold is reduced by forming irregularities. Therefore, the sliding resistance during press molding is reduced, and workability is improved. Further, since the Al-rich portion is not exposed on the surface layer of the plating layer, the pickup of Al to the electrode during resistance welding is reduced, and the life of the electrode is prolonged. The irregularities formed on the surface layer of the plating layer exhibit an anchor effect, and are also effective in improving the adhesion of a coating film formed in a later step.
【００１４】以上のように、Ｓｉ含有量が特定されたＡ
ｌ−Ｓｉ合金めっき層をもつめっき鋼板を基材とし、チ
タンの酸化物又は水酸化物及びフッ化物からなる複合皮
膜をめっき層の上に設けることにより、皮膜量が少なく
てもＡｌリッチな部位の露出が防止されるため良好な平
坦部が得られ、プレス成形時に鋼板の塑性変形に化成処
理皮膜が追従しないことに起因するクラック等の欠陥が
化成処理皮膜に発生しても自己修復作用によって優れた
加工部耐食性が得られる。As described above, A with the specified Si content is
By using a plated steel sheet having an l-Si alloy plating layer as a base material and providing a composite coating composed of an oxide or hydroxide of titanium and fluoride on the plating layer, an Al-rich portion can be obtained even if the coating amount is small. A good flat part is obtained because the exposure of the chemical conversion coating does not follow the plastic deformation of the steel sheet during press forming. Excellent corrosion resistance in the processed part.
【００１５】[0015]
【実施の形態】下地鋼としては、低炭素鋼，中炭素鋼，
高炭素鋼，合金鋼等が使用される。なかでも、良好なプ
レス成形性が要求される用途では、低炭素Ｔｉ添加鋼，
低炭素Ｎｂ添加鋼等の深絞り用鋼板が好ましい。下地鋼
は、常法に従って溶融アルミニウムめっきされるが、Ａ
ｌ−Ｓｉ合金めっき層のＳｉ含有量を５〜１３質量％の
範囲に調整することが好ましい。Ｓｉ含有量を５質量％
以上とすることにより、めっき層表層にＳｉが濃化しや
すくなると共に、下地鋼とめっき層との界面に生じ加工
性に有害な合金層の成長が抑制される。しかし、１３質
量％を超える過剰量のＳｉが含まれると、溶融めっき後
の冷却過程で初晶Ｓｉがめっき層に晶出し、加工性が著
しく劣化する。DESCRIPTION OF THE PREFERRED EMBODIMENTS Low-carbon steel, medium-carbon steel,
High carbon steel, alloy steel, etc. are used. In particular, in applications where good press formability is required, low carbon Ti-added steel,
A deep drawing steel plate such as a low carbon Nb added steel is preferable. The base steel is hot-dip aluminum plated according to the usual method.
It is preferable to adjust the Si content of the l-Si alloy plating layer in the range of 5 to 13% by mass. 5% by mass Si content
By doing so, Si is easily concentrated in the surface layer of the plating layer, and the growth of an alloy layer which occurs at the interface between the base steel and the plating layer and is harmful to the workability is suppressed. However, when an excessive amount of Si exceeding 13% by mass is contained, primary crystal Si is crystallized in the plating layer in a cooling process after hot-dip plating, and workability is significantly deteriorated.
【００１６】Ｓｉ含有量を５〜１３質量％に調整したＡ
ｌ−Ｓｉ合金めっき鋼板を溶融めっき浴から引き上げ、
冷却速度等を調整することによって予めめっき層の表層
にＳｉを濃化させた後、酸洗，アルカリ洗浄等を施すこ
とにより金属Ｓｉ主体の凸部及びＡｌリッチの凹部がめ
っき層の表層に形成される。酸洗，アルカリ洗浄等で金
属Ｓｉ主体の凸部及びＡｌリッチの凹部を形成する場
合、水洗，乾燥工程を必要とする。他方、Ａｌに対して
エッチング作用のある化成処理液を使用する場合、化成
処理液をめっき層に塗布して乾燥させる化成処理皮膜の
生成過程で表層のＡｌが選択的にエッチング除去され、
Ａｌリッチの凹部が形成される。A with the Si content adjusted to 5 to 13% by mass
Pull up l-Si alloy plated steel sheet from hot-dip bath,
After concentrating Si in the surface layer of the plating layer in advance by adjusting the cooling rate and the like, a convex portion mainly composed of metal Si and an Al-rich concave portion are formed in the surface layer of the plating layer by performing pickling, alkali cleaning, and the like. Is done. When a convex portion mainly composed of metal Si and a concave portion rich in Al are formed by pickling, alkali cleaning, or the like, a water washing and drying step is required. On the other hand, in the case of using a chemical conversion treatment solution having an etching effect on Al, the surface Al is selectively removed by etching in the process of forming a chemical conversion treatment film in which the chemical conversion treatment solution is applied to the plating layer and dried.
An Al-rich recess is formed.
【００１７】金属Ｓｉ主体の凸部及びＡｌリッチの凹部
がめっき層の表層に分散している状況は、ＡＥＳ分析法
を用いて１０００μｍ四方のエリアを走査・分析し、同
様にＡｒスパッタで表層から１００ｎｍの深さまで繰返
し分析することにより確認できる。本発明者等による実
験結果からすると、めっき層の表層から１００ｎｍまで
の深さにおけるＳｉ濃度を７質量％以上にするとき、目
標とする平坦部耐食性及び加工部耐食性が得られること
が判った。しかし、表層のＳｉ濃度が８０質量％を超え
るまでＡｌがエッチング除去されると、めっき層の表層
が脆くなり、プレス加工時等の際に鋼板が変形すると化
成処理皮膜が脱落しやすくなる。The situation where the convex portion mainly composed of metal Si and the Al-rich concave portion are dispersed in the surface layer of the plating layer is obtained by scanning and analyzing an area of 1000 μm square using the AES analysis method, and similarly, from the surface layer by Ar sputtering. It can be confirmed by repeatedly analyzing to a depth of 100 nm. From the experimental results by the present inventors, it was found that when the Si concentration at a depth of 100 nm from the surface layer of the plating layer was 7% by mass or more, the target flat portion corrosion resistance and processed portion corrosion resistance were obtained. However, if Al is removed by etching until the Si concentration of the surface layer exceeds 80% by mass, the surface layer of the plating layer becomes brittle, and if the steel sheet is deformed at the time of press working or the like, the chemical conversion treatment film tends to fall off.
【００１８】化成処理は塗布型又は反応型の何れであっ
てもよいが、反応型化成処理では処理液の安定性を維持
する上からｐＨを若干低く調整する。以下の説明では、
バルブメタルとしてＴｉを例に採っているが、Ｔｉ以外
のバルブメタルを使用する場合も同様である。The chemical conversion treatment may be either a coating type or a reaction type. In the reaction type chemical conversion treatment, the pH is adjusted to be slightly lower in order to maintain the stability of the processing solution. In the following description,
Although Ti is taken as an example of the valve metal, the same applies when a valve metal other than Ti is used.
【００１９】化成処理液は、Ｔｉソースとして可溶性の
ハロゲン化物や酸素酸塩を含む。Ｔｉのフッ化物はＴｉ
ソース及びＦソースとしても有効であるが、(ＮＨ4)Ｆ
等の可溶性フッ化物をＦソースとして化成処理液に別途
添加する場合もある。具体的なＴｉソースとしては、Ｘ
nＴｉＦ6（Ｘ：アルカリ金属又はアルカリ土類金属，
ｎ：１又は２），Ｋ2[ＴｉＯ(ＣＯＯ)2]，(ＮＨ4)2Ｔｉ
Ｆ6，ＴｉＣｌ4，ＴｉＯＳＯ4，Ｔｉ(ＳＯ4)2，Ｔｉ(Ｏ
Ｈ)4等がある。これらＴｉソースは、化成処理液を塗布
した後で乾燥・焼付けするときに所定組成の酸化物又は
水酸化物とフッ化物からなる化成処理皮膜が形成される
ように各成分の配合比率が選定される。The chemical conversion treatment solution contains a soluble halide or oxyacid salt as a Ti source. Ti fluoride is Ti
Although it is effective as a source and an F source, (NH 4 ) F
In some cases, such a soluble fluoride as F source is separately added to the chemical conversion treatment solution. As a specific Ti source, X
n TiF 6 (X: alkali metal or alkaline earth metal,
n: 1 or 2), K 2 [TiO (COO) 2 ], (NH 4 ) 2 Ti
F 6 , TiCl 4 , TiOSO 4 , Ti (SO 4 ) 2 , Ti (O
H) Fourth magnitude. The mixing ratio of each component of the Ti source is selected so that a chemical conversion coating composed of an oxide or hydroxide and a fluoride having a predetermined composition is formed when the titanium source is dried and baked after applying the chemical conversion treatment liquid. You.
【００２０】Ｔｉソースを化成処理液中にイオンとして
安定的に維持する上で、キレート作用のある有機酸を添
加することが好ましい。有機酸を添加する場合、金属イ
オンをキレート化して化成処理液を安定させることか
ら、有機酸／金属イオンのモル比が０．０２以上となる
添加量に定められる。有機酸としては、酒石酸，タンニ
ン酸，クエン酸，蓚酸，マロン酸，乳酸，酢酸等が挙げ
られる。なかでも、酒石酸等のオキシカルボン酸やタン
ニン酸等の多価フェノール類は、処理液を安定化させる
と共に、フッ化物の自己修復作用を補完する作用も呈
し、塗膜密着性の向上にも有効である。可溶性又は難溶
性の金属リン酸塩又は複合リン酸塩を化成処理皮膜に含
ませるため、各種金属のオルソリン酸塩やポリリン酸塩
を添加してもよい。In order to stably maintain the Ti source as ions in the chemical conversion treatment solution, it is preferable to add an organic acid having a chelating action. When an organic acid is added, the molar ratio of organic acid / metal ion is determined to be 0.02 or more, since the chemical conversion treatment solution is stabilized by chelating metal ions. Examples of the organic acid include tartaric acid, tannic acid, citric acid, oxalic acid, malonic acid, lactic acid, and acetic acid. Among them, oxycarboxylic acids such as tartaric acid and polyhydric phenols such as tannic acid stabilize the processing solution and also exhibit the function of complementing the self-healing action of fluoride, which is also effective in improving coating film adhesion. It is. Orthophosphates or polyphosphates of various metals may be added in order to include soluble or hardly soluble metal phosphates or composite phosphates in the chemical conversion coating.
【００２１】化成処理皮膜に含まれるフッ化物による自
己修復作用を発現させるためには、化成処理皮膜中のＯ
とＦとの原子数比Ｆ／Ｏを１／１００以上に調整するこ
とが好ましい。化成処理皮膜中のＦ，Ｏは蛍光Ｘ線，Ｅ
ＳＣＡ等を用いて分析できる。原子数比Ｆ／Ｏが１／１
００未満では、フッ化物の加水分解による自己修復作用
が不充分で、化成処理皮膜の欠陥部や成形加工時の疵部
を起点とする腐食が進行することがある。In order for the fluoride contained in the chemical conversion treatment film to exhibit a self-healing effect, O
It is preferable to adjust the atomic ratio F / O between F and F to 1/100 or more. F and O in chemical conversion coating are fluorescent X-ray, E
It can be analyzed using SCA or the like. Atomic ratio F / O is 1/1
If it is less than 00, the self-healing effect due to the hydrolysis of the fluoride is insufficient, and corrosion starting from a defective portion of the chemical conversion coating or a flaw at the time of molding may progress.
【００２２】可溶性の金属リン酸塩又は複合リン酸塩
は、化成処理皮膜から溶出して皮膜欠陥部に溶出し、下
地鋼のＡｌ等と反応して不溶性リン酸塩を析出すること
によって、チタンフッ化物の自己修復作用を補完する。
また、可溶性リン酸塩が解離する際に雰囲気が若干酸性
化するため、チタンフッ化物の加水分解、ひいては難溶
性チタン酸化物又は水酸化物の生成が促進される。可溶
性リン酸塩又は複合リン酸塩を生成する金属にはアルカ
リ金属，アルカリ土類金属，Ｍｎ等があり、各種金属リ
ン酸塩又は各種金属塩と燐酸，ポリ燐酸，リン酸塩とし
て化成処理液に添加される。難溶性の金属リン酸塩又は
複合リン酸塩は、化成処理皮膜に分散し、皮膜欠陥を解
消すると共に皮膜強度を向上させる。難溶性リン酸塩又
は複合リン酸塩を形成する金属にはＡｌ，Ｔｉ，Ｚｒ，
Ｈｆ，Ｚｎ等があり、各種金属リン酸塩又は各種金属塩
と燐酸，ポリ燐酸，リン酸塩として化成処理液に添加さ
れる。The soluble metal phosphate or composite phosphate elutes from the chemical conversion treatment film and elutes at the defect of the film, reacts with Al and the like of the base steel to precipitate insoluble phosphate, thereby producing titanium phosphate. Complements the self-healing action of the compound.
Further, since the atmosphere is slightly acidified when the soluble phosphate dissociates, the hydrolysis of titanium fluoride and, consequently, the formation of poorly soluble titanium oxide or hydroxide are promoted. Metals that form soluble phosphates or complex phosphates include alkali metals, alkaline earth metals, Mn, and the like, and are formed from various metal phosphates or various metal salts and phosphoric acid, polyphosphoric acid, and phosphates. Is added to The poorly soluble metal phosphate or composite phosphate disperses in the chemical conversion treatment film to eliminate film defects and improve film strength. Al, Ti, Zr,
Hf, Zn, etc. are added to the chemical conversion treatment liquid as various metal phosphates or various metal salts and phosphoric acid, polyphosphoric acid, and phosphate.
【００２３】化成処理液には、潤滑性の向上に有効なワ
ックスを化成処理皮膜に含ませるため、フッ素系，ポリ
エチレン系，スチレン系等の有機ワックスやシリカ，二
硫化モリブデン，タルク等の無機質潤滑剤等を添加する
こともできる。低融点の有機ワックスは、皮膜乾燥時に
表面にブリードし、潤滑性を発現すると考えられる。高
融点有機ワックスや無機系潤滑剤は、皮膜中に分散状態
で存在するが，処理皮膜の最表層では島状分布で皮膜表
面に露出することによって潤滑性が発現するものと考え
られる。In the chemical conversion treatment liquid, a wax effective for improving lubricity is contained in the chemical conversion treatment film, so that a fluorine-based, polyethylene-based or styrene-based organic wax or an inorganic lubricant such as silica, molybdenum disulfide, or talc is used. Agents and the like can also be added. It is considered that the organic wax having a low melting point bleeds on the surface when the film is dried, and exhibits lubricity. The high melting point organic wax and the inorganic lubricant are present in a dispersed state in the film, but it is considered that lubricity is exhibited by being exposed on the surface of the film in an island-like distribution on the outermost layer of the treated film.
【００２４】調製された化成処理液をロールコート法，
スピンコート法，スプレー法等でＡｌ−Ｓｉ合金めっき
鋼板に塗布し、水洗することなく乾燥することによっ
て、耐食性に優れた化成処理皮膜がＡｌ−Ｓｉ合金めっ
き層の表層に形成される。化成処理液の塗布量は、十分
な耐食性を確保するため１ｍｇ／ｍ2以上のチタン付着
量となるように調整することが好ましい。化成処理皮膜
は、常温で乾燥することもできるが、連続操業を考慮す
ると５０℃以上に保持して乾燥時間を短縮することが好
ましい。ただし、２００℃を超える乾燥温度では、化成
処理被膜に含まれている有機成分が熱分解し、有機成分
で付与された特性が損なわれることがある。The prepared chemical conversion treatment solution is roll-coated,
A chemical conversion coating film having excellent corrosion resistance is formed on the surface of the Al-Si alloy plating layer by applying the composition to the Al-Si alloy plating steel sheet by spin coating, spraying, or the like, and drying the coating without washing with water. The application amount of the chemical conversion treatment liquid is preferably adjusted so that the titanium adhesion amount is 1 mg / m 2 or more in order to secure sufficient corrosion resistance. The chemical conversion coating can be dried at room temperature, but in consideration of continuous operation, it is preferable to keep the temperature at 50 ° C. or higher to shorten the drying time. However, if the drying temperature exceeds 200 ° C., the organic components contained in the chemical conversion treatment film may be thermally decomposed and the properties imparted by the organic components may be impaired.
【００２５】化成処理皮膜を形成した後、更に耐食性に
優れた有機皮膜を形成することもできる。この種の皮膜
として、たとえばウレタン系樹脂，エポキシ樹脂，ポリ
エチレン、ポリプロピレン，エチレン−アクリル酸共重
合体等のオレフィン系樹脂，ポリスチレン等のスチレン
系樹脂，ポリエステル，或いはこれらの共重合物又は変
性物，アクリル系樹脂等の樹脂皮膜を膜厚０．１〜５μ
ｍで化成処理皮膜の上に設けると、クロメート皮膜を凌
駕する高耐食性が得られる。After the formation of the chemical conversion coating, an organic coating having further excellent corrosion resistance can be formed. Examples of this type of film include urethane-based resins, epoxy resins, olefin-based resins such as polyethylene, polypropylene, and ethylene-acrylic acid copolymer, styrene-based resins such as polystyrene, polyesters, and copolymers or modified products thereof. Resin film such as acrylic resin film thickness 0.1-5μ
When provided on the chemical conversion treatment film with m, high corrosion resistance surpassing that of the chromate film can be obtained.
【００２６】有機樹脂皮膜に有機系又は無機系潤滑剤を
添加してプレス成形時の潤滑性を確保し、或いは無機ゾ
ルを添加して抵抗溶接性を改善することも可能である。
樹脂皮膜としては、アルカリ洗浄で容易に除去できるア
ルカリ可溶タイプ又は非可溶タイプの何れであってもよ
い。アルカリに対する溶解性は樹脂皮膜に含まれるアク
リル酸量によって調整でき、アクリル酸量を多くすると
アルカリ可溶性に、少なくすると非可溶性になる。この
種の樹脂皮膜は、ロールコート法や静電霧化によって形
成できる。It is also possible to add an organic or inorganic lubricant to the organic resin film to ensure lubricity during press molding, or to add an inorganic sol to improve resistance weldability.
The resin film may be either an alkali-soluble type or a non-soluble type that can be easily removed by alkali washing. The solubility in alkali can be adjusted by the amount of acrylic acid contained in the resin film. The higher the amount of acrylic acid, the more alkali-soluble, and the lower the amount, the more insoluble. This type of resin film can be formed by a roll coating method or electrostatic atomization.
【００２７】[0027]
【実施例】Ｔｉソース及びＦソースを配合し、場合によ
っては各種金属化合物，有機酸，リン酸塩を添加し、表
１の組成をもつ化成処理液を調合した。EXAMPLE A chemical conversion treatment solution having the composition shown in Table 1 was prepared by blending a Ti source and an F source, optionally adding various metal compounds, organic acids, and phosphates.
【００２８】 [0028]
【００２９】板厚０．８ｍｍの極低炭素Ｔｉ添加冷延鋼
板を連続溶融めっきラインに通板し、Ｓｉ：６〜１１質
量％のＡｌ−Ｓｉ合金めっき層をめっき付着量３５ｇ／
ｍ2（平均層厚１３μｍ）で形成させた。このＡｌ−Ｓ
ｉ合金めっき鋼板を化成処理用原板とし、表１の組成を
もつ化成処理液をロールコート法で塗布した後、水洗す
ることなくオーブンに装入し、到達板温１２０℃で乾燥
することにより化成処理皮膜を形成した。形成された化
成処理皮膜を蛍光Ｘ線，ＡＥＳ及びＥＳＣＡで分析し，
めっき層表面から深さ１００ｎｍまでの表層部における
Ｓｉ含有量及び化成処理皮膜の各成分濃度を求めた。調
査結果を表２に示す。A very low carbon Ti-added cold-rolled steel sheet having a thickness of 0.8 mm is passed through a continuous hot-dip galvanizing line, and an Al—Si alloy plating layer having a Si content of 6 to 11% by mass is coated with a coating weight of 35 g /
m 2 (average layer thickness: 13 μm). This Al-S
An i-alloy-plated steel sheet was used as a base plate for chemical conversion treatment. A chemical conversion treatment solution having the composition shown in Table 1 was applied by a roll coating method, and then charged into an oven without washing with water, and dried at an ultimate plate temperature of 120 ° C. A treated film was formed. The formed chemical conversion film is analyzed by X-ray fluorescence, AES and ESCA,
The Si content in the surface layer from the surface of the plating layer to a depth of 100 nm and the concentration of each component of the chemical conversion coating were determined. Table 2 shows the survey results.
【００３０】 [0030]
【００３１】化成処理されたＡｌ−Ｓｉ合金めっき鋼板
から試験片を切り出し、平坦部腐食試験，加工部腐食試
験及び抵抗溶接性試験に供した。平坦部腐食試験では、
試験片の端面をシールし、ＪＩＳ Ｚ２３７１に準拠し
て３５℃の５％ＮａＣｌ水溶液を噴霧した。塩水噴霧を
２４，７２，１２０時間継続した後、試験片表面に発生
した白錆を観察した。試験片表面に占める白錆の面積率
が５％以下を◎，５〜１０％を○，１０〜３０％を△，
３０〜５０％を▲，５０％以上を×として平坦部の耐食
性を評価した。A test piece was cut out from the chemical conversion-treated Al—Si alloy plated steel sheet and subjected to a flat portion corrosion test, a processed portion corrosion test, and a resistance weldability test. In the flat part corrosion test,
The end face of the test piece was sealed, and a 5% NaCl aqueous solution at 35 ° C. was sprayed according to JIS Z2371. After salt spraying was continued for 24, 72 and 120 hours, white rust generated on the surface of the test piece was observed. The area ratio of white rust occupying 5% or less of the surface of the test piece was evaluated as ◎, 5-10% as ○, 10-30% as
The corrosion resistance of the flat portion was evaluated by setting ▲ to 30 to 50% and × to 50% or more.
【００３２】加工部腐食試験では、３５ｍｍ×２００ｍ
ｍの試験片をビード高さ：４ｍｍ，ビード先端Ｒ：４ｍ
ｍ，加圧力：４．９ｋＮの条件でドロービード試験し、
同様な塩水噴霧試験を所定時間継続した後、試験片加工
部の表面を観察し白錆の面積率を測定した。そして、平
坦部耐食性と同じ基準で白錆面積率から加工部耐食性を
評価した。抵抗溶接性試験では、Ｃｒ−Ｃｕ合金電極を
用い、重ね合わせた２枚の試験片をスポット溶接した。
溶接条件は、各試験片ごとに適正電流及び適正荷重を予
め求めておき、一定打点ごとに一定比率で溶接電流を増
加させる方法を採用した。そして、溶接打点数が５００
〜１０００打点を○，５００打点以下を×として抵抗溶
接性を評価した。In the processed part corrosion test, 35 mm × 200 m
m test piece, bead height: 4 mm, bead tip R: 4 m
m, applied pressure: 4.9 kN
After the similar salt spray test was continued for a predetermined time, the surface of the processed part of the test piece was observed, and the area ratio of white rust was measured. Then, the corrosion resistance of the processed portion was evaluated from the white rust area ratio on the same basis as the corrosion resistance of the flat portion. In the resistance weldability test, two superposed test pieces were spot-welded using a Cr-Cu alloy electrode.
As the welding conditions, a method was adopted in which an appropriate current and an appropriate load were obtained in advance for each test piece, and the welding current was increased at a fixed rate at each fixed point. And the number of welding points is 500
The resistance welding property was evaluated by setting ○ to 1000 spots as ， and 500 points or less as ×.
【００３３】表３の調査結果にみられるように、本発明
に従って化成処理皮膜が形成された試験番号１〜６は、
何れも良好な平坦部耐食性，加工部耐食性，抵抗溶接性
を示した。これに対し、可溶性チタンフッ化物を含まな
い化成処理皮膜を形成した試験番号７（比較例）は、自
己修復効果が不充分なため皮膜欠陥部を起点とする腐食
が観察された。チタン化合物を含まない化成処理皮膜を
形成した試験番号８（比較例）では、バリア効果に乏し
く平坦部耐食性，加工部耐食性共に劣っていた。同じ化
成処理液を使用した場合でも、Ｓｉを含まないアルミニ
ウムめっき鋼板を化成処理液Ｎｏ．１で化成処理した試
験番号９（比較例）では、Ａｌリッチ部位が一部露出し
てしまい、目標とする品質性能が得られなかった。As can be seen from the survey results in Table 3, the test numbers 1 to 6 in which the chemical conversion coating was formed according to the present invention were:
All exhibited good flat section corrosion resistance, processed section corrosion resistance, and resistance weldability. On the other hand, in Test No. 7 (Comparative Example) in which a chemical conversion treatment film containing no soluble titanium fluoride was formed, the self-healing effect was insufficient, so that corrosion starting from a film defect portion was observed. In Test No. 8 (Comparative Example) in which a chemical conversion film containing no titanium compound was formed, the barrier effect was poor and both the flat portion corrosion resistance and the processed portion corrosion resistance were poor. Even when the same chemical conversion solution was used, an aluminum-plated steel sheet containing no Si was converted to the chemical conversion solution No. In Test No. 9 (Comparative Example) subjected to the chemical conversion treatment in No. 1, the Al-rich portion was partially exposed, and the target quality performance was not obtained.
【００３４】 [0034]
【００３５】[0035]
【実施例２】Ｔｉ以外のバルブメタルソース及びＦソー
スを配合し、場合によっては各種金属化合物，有機酸，
リン酸を添加し、表４の組成をもつ化成処理液を調合し
た。各化成処理液をロールコート法でＡｌ−Ｓｉ合金め
っき鋼板に塗布した後，水洗することなくオーブンに装
入し、到達板温１６０℃で乾燥することにより化成処理
皮膜を形成した。Example 2 A valve metal source other than Ti and an F source were blended, and in some cases, various metal compounds, organic acids,
Phosphoric acid was added, and a chemical conversion treatment solution having the composition shown in Table 4 was prepared. Each of the chemical conversion treatment solutions was applied to an Al—Si alloy plated steel plate by a roll coating method, then charged into an oven without washing with water, and dried at a reaching plate temperature of 160 ° C. to form a chemical conversion treatment film.
【００３６】 [0036]
【００３７】化成処理皮膜が形成された各Ａｌ−Ｓｉ合
金めっき鋼板について、実施例１と同様にめっき層表面
から深さ１００ｎｍまでの表層部におけるＳｉ含有量及
び化成処理皮膜の各成分濃度を求めた。調査結果を表５
に示す。For each of the Al—Si alloy plated steel sheets on which the chemical conversion coating was formed, the Si content and the concentration of each component in the surface layer from the surface of the plating layer to a depth of 100 nm were determined in the same manner as in Example 1. Was. Table 5 shows the survey results
Shown in
【００３８】 [0038]
【００３９】次いで、化成処理された各Ａｌ−Ｓｉ合金
めっき鋼板から試験片を切り出し、実施例１と同様の方
法で平坦部腐食試験，加工部腐食試験及び抵抗溶接性試
験に供した。表６の調査結果にみられるように、本発明
に従って化成処理皮膜が形成された試験番号１〜６は、
平坦部耐食性，加工部耐食性及び抵抗溶接性の何れにも
優れていた。Next, test pieces were cut out from each of the chemical conversion-treated Al—Si alloy plated steel sheets and subjected to a flat portion corrosion test, a processed portion corrosion test and a resistance weldability test in the same manner as in Example 1. As can be seen from the survey results in Table 6, Test Nos. 1 to 6 in which the chemical conversion coating was formed according to the present invention were:
Excellent in corrosion resistance in flat part, corrosion resistance in processed part, and resistance weldability.
【００４０】 [0040]
【００４１】[0041]
【発明の効果】以上に説明したように、本発明の化成処
理鋼板は、Ｓｉ含有量が特定されたＡｌ−Ｓｉ合金めっ
き層が形成されたＡｌ−Ｓｉ合金めっき鋼板を基材と
し、金属の酸化物又は水酸化物及びフッ化物が共存した
化成処理皮膜で基材表面が覆われているため、難溶性の
金属酸化物又は水酸化物が環境遮断機能を呈し下地鋼の
腐食を防止すると共に、可溶性のフッ化物が自己修復作
用を呈する。そのため、成形加工等で欠陥が導入された
化成処理皮膜であっても溶出したフッ化物の再析出によ
って自己修復されるため、皮膜欠陥部を介して下地鋼が
露出することがなくなり、優れた耐食性が維持される。
更に、リン酸塩又は複合リン酸塩を含ませることにより
耐食性が一層向上し、従来のクロメート皮膜に匹敵する
優れた耐食性を呈する。しかも、環境に悪影響を及ぼし
かねないＣｒを含まない化成処理皮膜であることから、
従来のクロメート処理鋼板に代わる材料として広範な分
野で使用される。As described above, the chemical conversion treated steel sheet of the present invention is based on an Al—Si alloy plated steel sheet having an Al—Si alloy plated layer having a specified Si content as a base material, Since the surface of the base material is covered with a chemical conversion coating in which oxides or hydroxides and fluorides coexist, the hardly soluble metal oxides or hydroxides exhibit an environmental barrier function and prevent corrosion of the underlying steel. In addition, soluble fluoride exhibits a self-healing effect. As a result, even if the chemical conversion coating has defects introduced by molding or the like, it will be self-repaired by re-precipitation of the eluted fluoride, so that the base steel will not be exposed through the coating defects and excellent corrosion resistance Is maintained.
Further, by including a phosphate or a composite phosphate, corrosion resistance is further improved, and excellent corrosion resistance comparable to a conventional chromate film is exhibited. In addition, since it is a chemical conversion treatment film that does not contain Cr, which may have an adverse effect on the environment,
It is used in a wide range of fields as a material that replaces conventional chromate treated steel sheets.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 古川 伸也 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 武津 博文 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 (56)参考文献 特開2000−104021（ＪＰ，Ａ) 特開 平９−228066（ＪＰ，Ａ) 特開 平９−20984（ＪＰ，Ａ) 特開2000−265283（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C23C 22/00 - 22/86 C23C 28/00 B32B 9/00,15/04,15/18 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Shinya Furukawa 5th Ishizu Nishimachi, Sakai City, Osaka Prefecture Nisshin Steel Co., Ltd. Technical Research Laboratory (72) Inventor Hirofumi Takezu 5th Ishizu Nishimachi 5th Sakai City, Osaka Prefecture (56) References JP 2000-104021 (JP, A) JP 9-228066 (JP, A) JP 9-20984 (JP, A) JP 2000-265283 (JP) , A) (58) Fields investigated (Int. Cl. 7 , DB name) C23C 22/00-22/86 C23C 28/00 B32B 9/00, 15/04, 15/18
Claims (6)
化物が高い絶縁抵抗を示すバルブメタルの酸化物又は水
酸化物、及びフッ化物が共存する化成処理皮膜が基材表
面に形成されていることを特徴とする耐食性に優れた化
成処理鋼板。1. A The Al-Si alloy coated steel sheet as a base material, an oxide or hydroxide of the valve metal showing an oxide high insulation resistance, and the chemical conversion coating fluoride coexist is formed on the substrate surface Chemical conversion treated steel sheet with excellent corrosion resistance.
１３質量％，表層のＳｉ含有量が７〜８０質量％のＡｌ
−Ｓｉ合金めっき層が形成されているめっき鋼板を基材
とする請求項１記載の化成処理鋼板。2. The Si content of the plating layer as a whole is 5 to 5.
13% by mass, Al whose surface Si content is 7 to 80% by mass
The chemical conversion treated steel sheet according to claim 1, wherein the base material is a plated steel sheet having a -Si alloy plating layer formed thereon.
Ｎｂ，Ｔａ，Ｍｏ，Ｗから選ばれた１種又は２種以上で
ある請求項１記載の化成処理鋼板。3. The valve metal is Ti, Zr, Hf, V,
The chemical conversion treated steel sheet according to claim 1, wherein the steel sheet is one or more kinds selected from Nb, Ta, Mo, and W.
比Ｆ／Ｏが原子比率で１／１００以上である請求項１記
載の化成処理鋼板。4. The chemical conversion treated steel sheet according to claim 1, wherein the concentration ratio F / O of O and F contained in the chemical conversion treatment film is 1/100 or more in atomic ratio.
性又は不溶性金属のリン酸塩又は複合リン酸塩を含む化
成処理鋼板。5. A chemical conversion treated steel sheet, wherein the chemical conversion treatment film according to claim 1 further contains a phosphate or a composite phosphate of a soluble or insoluble metal.
剤を含む化成処理鋼板。6. A chemical conversion treated steel sheet, wherein the chemical conversion treatment film according to claim 1 further contains a lubricant.
Priority Applications (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000338515A JP3302676B2 (en) | 2000-11-07 | 2000-11-07 | Chemical treated steel sheet with excellent corrosion resistance |
| DE60127793T DE60127793T2 (en) | 2000-11-07 | 2001-10-29 | Chemically processed steel sheet with excellent corrosion resistance |
| MYPI20014995A MY126690A (en) | 2000-11-07 | 2001-10-29 | A chemically processed steel sheet excellent in corrosion resistance |
| EP01125363A EP1205579B1 (en) | 2000-11-07 | 2001-10-29 | A chemically processed steel sheet excellent in corrosion resistance |
| TW090127272A TW527437B (en) | 2000-11-07 | 2001-11-02 | A chemically processed steel sheet excellent in corrosion resistance |
| KR1020010068500A KR100792182B1 (en) | 2000-11-07 | 2001-11-05 | A chemically processed steel sheet excellent in corrosion resistance |
| CNB011344873A CN1201031C (en) | 2000-11-07 | 2001-11-06 | Chemical treatment steel board with good corrosion-resisting property |
| US09/992,962 US6730414B2 (en) | 2000-11-07 | 2001-11-06 | Chemically processed steel sheet excellent in corrosion resistance |
| AU89255/01A AU781710B2 (en) | 2000-11-07 | 2001-11-07 | A chemically processed steel sheet excellent in corrosion resistance |
| US10/829,678 US7147934B2 (en) | 2000-11-07 | 2004-04-22 | Chemically processed steel sheet excellent in corrosion resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000338515A JP3302676B2 (en) | 2000-11-07 | 2000-11-07 | Chemical treated steel sheet with excellent corrosion resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002146551A JP2002146551A (en) | 2002-05-22 |
| JP3302676B2 true JP3302676B2 (en) | 2002-07-15 |
Family
ID=18813716
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000338515A Expired - Lifetime JP3302676B2 (en) | 2000-11-07 | 2000-11-07 | Chemical treated steel sheet with excellent corrosion resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3302676B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022185840A1 (en) | 2021-03-01 | 2022-09-09 | 日本製鉄株式会社 | Battery unit |
| WO2022244568A1 (en) | 2021-05-20 | 2022-11-24 | 日本製鉄株式会社 | Cooling structure, battery unit, and manufacturing method for cooling structure |
| WO2022244570A1 (en) | 2021-05-20 | 2022-11-24 | 日本製鉄株式会社 | Cooling structure, battery unit, and cooling structure manufacturing method |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7147934B2 (en) * | 2000-11-07 | 2006-12-12 | Nisshin Steel Co., Ltd. | Chemically processed steel sheet excellent in corrosion resistance |
| JP4777705B2 (en) * | 2005-07-05 | 2011-09-21 | 日新製鋼株式会社 | Heat-resistant pre-coated steel sheet |
| JP5005254B2 (en) * | 2006-05-15 | 2012-08-22 | 新日本製鐵株式会社 | Al-plated steel for hot pressing with excellent temperature rise characteristics, workability, and post-coating corrosion resistance |
-
2000
- 2000-11-07 JP JP2000338515A patent/JP3302676B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022185840A1 (en) | 2021-03-01 | 2022-09-09 | 日本製鉄株式会社 | Battery unit |
| WO2022244568A1 (en) | 2021-05-20 | 2022-11-24 | 日本製鉄株式会社 | Cooling structure, battery unit, and manufacturing method for cooling structure |
| WO2022244570A1 (en) | 2021-05-20 | 2022-11-24 | 日本製鉄株式会社 | Cooling structure, battery unit, and cooling structure manufacturing method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2002146551A (en) | 2002-05-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4845951B2 (en) | Manufacturing method of surface-treated steel sheet, surface-treated steel sheet, and resin-coated surface-treated steel sheet obtained by coating surface-treated steel sheet with organic resin | |
| CA2600996C (en) | Surface treated metal material | |
| JP3305703B2 (en) | Chemical treated steel sheet with excellent corrosion resistance | |
| JP3302684B2 (en) | Chemical treated steel sheet with excellent corrosion resistance | |
| JP4615807B2 (en) | Manufacturing method of surface-treated steel sheet, surface-treated steel sheet, and resin-coated surface-treated steel sheet | |
| EP1526190B1 (en) | Corrosion resistant steel sheet with a chemically modified zinc coating | |
| JP3868243B2 (en) | Chromate-free treated hot dip zinc-aluminum alloy plated steel sheet with excellent weldability and corrosion resistance | |
| JP3302676B2 (en) | Chemical treated steel sheet with excellent corrosion resistance | |
| JP3305702B2 (en) | Aluminum plated steel sheet for fuel tank | |
| JP2003213458A (en) | Cr-FREE CHEMICAL CONVERSION-TREATED ALUMINUM-BASED PLATED STEEL SHEET | |
| JP3302680B2 (en) | Steel plate with excellent corrosion resistance | |
| JP2003221660A (en) | Fuel tank for vehicle made from hot-dip aluminized stainless steel sheet | |
| JP3219453B2 (en) | Manufacturing method of galvanized steel sheet with excellent blackening resistance | |
| JP2007023309A (en) | Hot-dip zinc alloy plated steel sheet having excellent corrosion resistance | |
| JP4795647B2 (en) | Galvanized steel sheet with excellent corrosion resistance, paintability and adhesion | |
| JP3261378B1 (en) | Aluminum plated steel sheet for fuel tank | |
| KR100792182B1 (en) | A chemically processed steel sheet excellent in corrosion resistance | |
| JP3302679B2 (en) | Steel structure with excellent corrosion resistance | |
| JP2005105321A (en) | Method for manufacturing surface treated steel sheet of excellent appearance, surface treated steel sheet, film-covered surface-treated steel sheet | |
| JP4179527B2 (en) | Manufacturing method of surface-treated steel sheet, surface-treated steel sheet, and resin-coated surface-treated steel sheet obtained by coating surface-treated steel sheet with organic resin | |
| JP2003293168A (en) | PRECOATED Al-Si ALLOY PLATED STEEL SHEET HAVING EXCELLENT CORROSION RESISTANCE | |
| JP3886913B2 (en) | Chemically treated steel plate with excellent corrosion resistance | |
| JP3261377B1 (en) | Chemical treated steel sheet with excellent corrosion resistance | |
| US7147934B2 (en) | Chemically processed steel sheet excellent in corrosion resistance | |
| JP2003306777A (en) | Zn-Al ALLOY PLATED STEEL SHEET HAVING IMPROVED CORROSION RESISTANCE |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20020416 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 3302676 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080426 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090426 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090426 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100426 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100426 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110426 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110426 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120426 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130426 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140426 Year of fee payment: 12 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |