JP2008163364A - Chemical conversion-treated steel sheet having excellent coating film adhesive strength and film adhesion after forming - Google Patents
Chemical conversion-treated steel sheet having excellent coating film adhesive strength and film adhesion after forming Download PDFInfo
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本発明は、加工後の塗膜密着性およびフィルム接着性に優れた皮膜が形成された化成処理鋼板に関する。 The present invention relates to a chemical conversion treated steel sheet on which a film having excellent coating film adhesion and film adhesion after processing is formed.
化成処理としてクロメート処理を施した亜鉛めっき鋼板（以下、クロメート皮膜処理亜鉛めっき鋼板とも記載する。）は、耐食性，塗膜密着性，フィルム接着性に優れる。そのため、クロメート皮膜処理亜鉛めっき鋼板表面に塗装やフィルムラミネートした鋼板は、例えば、冷蔵庫外板、家電製品などの用途に使用されている。 A galvanized steel sheet subjected to chromate treatment as a chemical conversion treatment (hereinafter also referred to as chromate film-treated galvanized steel sheet) is excellent in corrosion resistance, coating film adhesion, and film adhesion. Therefore, steel plates that have been coated or film-laminated on the surface of a chromate film-treated galvanized steel plate are used for applications such as refrigerator outer plates and home appliances.
クロメート処理は公害規制物質である６価クロムを使用するものであるが、この６価クロムは処理工程においてクローズドシステムで処理されること、また、その上層に形成する有機皮膜によるシーリング作用によってクロメート皮膜中からのクロム溶出もほぼゼロにできることから、実質的には６価クロムによって人体や環境が汚染されることはない。しかしながら、近年の地球環境問題に対する高まりと共に、製造業者では、６価クロムを用いない化成処理に切り替える動きがある。 The chromate treatment uses hexavalent chromium which is a pollution control substance. This hexavalent chromium is treated with a closed system in the treatment process, and the chromate film is formed by the sealing action by the organic film formed on the upper layer. Since the elution of chromium from the inside can be made almost zero, the human body and the environment are not substantially polluted by hexavalent chromium. However, with the recent increase in global environmental problems, manufacturers have moved to switch to chemical conversion treatment that does not use hexavalent chromium.
塗装やフィルムラミネートした鋼板についても、６価クロムを用いない化成処理皮膜を有する亜鉛めっき鋼板への切り替えが検討されている。６価クロムを使用しない化成処理として、リン酸あるいはリン酸化合物を含有した処理液をめっき皮膜と接触させてめっき皮膜と処理液との反応によって、めっき表面にリン酸塩皮膜を形成するリン酸塩処理がある（例えば特許文献１）。
リン酸塩皮膜を形成させた化成処理鋼板は、通常、鉄鋼メーカ側でリン酸塩処理され、ユーザー側で製品形状に成形加工されている。成形加工に際し、従来のリン酸塩皮膜では皮膜構成成分である無機質のリン酸塩が硬質で延性がないため、亀裂，剥離等の皮膜欠陥が起こりやすい。皮膜欠陥は腐食発生の起点となり、化成皮膜の耐食性改善作用や塗膜密着性およびフィルム接着性が極端に低下する。 The chemical conversion treated steel sheet on which the phosphate film is formed is usually subjected to phosphate treatment on the steel manufacturer side and molded into a product shape on the user side. In the molding process, in the conventional phosphate film, the inorganic phosphate, which is a film component, is hard and not ductile, so that film defects such as cracking and peeling are likely to occur. A film defect becomes a starting point of corrosion occurrence, and the corrosion resistance improving action, coating film adhesion and film adhesion of the chemical conversion film are extremely lowered.
特許文献２にはめっき層／リン酸塩皮膜の密着性を改善するため、リン酸塩処理した亜鉛めっき鋼板の表面粗さを調整する方法が開示され、特許文献３には表面粗さに加えてリン酸塩皮膜の膜厚を調整する方法等が開示されている。また、特許文献４には環境負荷物質である６価クロムを含むこと無く加工後耐食性，加工後の塗膜密着性およびフィルム接着性に優れた化成処理鋼板として、微細な〔Ａｌ／Ｚｎ／Ｚｎ２Ｍｇの三元共晶組織〕をもつめっき層が形成された溶融Ｚｎ―Ａｌ―Ｍｇ合金めっき鋼板を基材に用い，リン酸塩皮膜，クロムフリー化成皮膜が基材表面に形成させる技術が提案されている。しかし，従来技術では依然としてユーザー側での加工後の塗膜密着性およびフィルム接着性を十分に満足させるに至っていない。
本発明は、亜鉛めっき鋼板または亜鉛合金めっき鋼板を基材とし，クロムフリー系の化成処理皮膜を形成し、加工後の塗膜密着性およびフィルム接着性に優れた化成処理鋼板を提供することを目的とする。 The present invention provides a chemical conversion-treated steel sheet which is formed of a galvanized steel sheet or a zinc alloy-plated steel sheet and forms a chromium-free chemical conversion coating film, and is excellent in coating film adhesion and film adhesion after processing. Objective.
本発明の化成処理鋼板は、亜鉛めっき鋼板または亜鉛合金めっき鋼板を基材とし，めっき鋼板表面に、酸化物が高い絶縁抵抗を示すバルブメタルの酸化物または水酸化物およびフッ化物と多価フェノール樹脂からなる化成処理皮膜の膜厚が０．０１〜０．５μｍで形成されていることを特徴とする。さらに，化成処理皮膜は、リン酸またはリン酸化合物を含むことができる。 The chemical conversion treated steel sheet of the present invention comprises a zinc-plated steel sheet or a zinc alloy-plated steel sheet as a base material, and a valve metal oxide or hydroxide and a fluoride and a polyhydric phenol exhibiting high insulation resistance on the surface of the plated steel sheet. The chemical conversion film made of resin is formed with a film thickness of 0.01 to 0.5 μm. Furthermore, the chemical conversion treatment film may contain phosphoric acid or a phosphoric acid compound.
本発明の化成処理鋼板は、多価フェノール樹脂とバルブメタルの酸化物または水酸化物およびフッ化物を共存させている。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、Ｔｉ，Ｚｒ，Ｈｆ，Ｖ，Ｎｂ，Ｔａ，Ｍｏ，Ｗの１種または２種以上が使用される。バルブメタルの酸化物または水酸化物およびフッ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り，バルブメタルの酸化物または水酸化物およびフッ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。 In the chemical conversion treated steel sheet of the present invention, the polyhydric phenol resin and the valve metal oxide or hydroxide and fluoride coexist. The valve metal refers to a metal whose oxide exhibits high insulation resistance, and one or more of Ti, Zr, Hf, V, Nb, Ta, Mo, and W are used. A film made of valve metal oxide or hydroxide and fluoride acts as a resistance to electron movement, reducing the reduction reaction (oxidation reaction with the underlying steel) due to dissolved oxygen contained in the moisture in the atmosphere. It is done. As a result, elution (corrosion) of metal components from the base steel is prevented. Among these, tetravalent compounds of Group IV A elements such as Ti, Zr, and Hf are stable compounds, and are suitable film components because they form excellent films, and include valve metal oxides or hydroxides and When fluoride is formed on the steel sheet surface as a continuous film, it effectively acts as a resistor against electron transfer.
しかし，バルブメタルの酸化物または水酸化物およびフッ化物のみの化成処理皮膜の場合，硬質で延性に乏しいためバルブメタルの酸化物または水酸化物およびフッ化物の連続皮膜は成型加工する際，鋼板の伸びに追従できず、クラックや剥離等の欠陥が化成処理皮膜に生じる。その結果，化成処理皮膜上に後塗装やフィルム接着後，成形加工すると塗膜剥離またはフィルムの接着性が低下する。 However, in the case of chemical conversion coatings consisting only of valve metal oxides or hydroxides and fluorides, the continuous coatings of valve metal oxides or hydroxides and fluorides are not suitable for forming because they are hard and poorly ductile. Inability to follow the elongation of the film, defects such as cracks and peeling occur in the chemical conversion film. As a result, when the film is formed after post-coating or film adhesion on the chemical conversion film, the coating film peeling or the film adhesiveness decreases.
化成処理皮膜に柔軟性を付与できれば成型加工による化成処理皮膜の剥離を抑えられ、加工後の塗膜やフィルムの密着性が向上することが予想される。本発明においてバルブメタルの酸化物または水酸化物およびフッ化物と多価フェノール樹脂を組合せることにより，化成処理皮膜に柔軟性と腐食因子に対するバリア機能を付与し，さらに鋼板と塗膜の密着性またはフィルムとの接着性を向上させることができる。 If flexibility can be imparted to the chemical conversion coating, it is expected that peeling of the chemical conversion coating due to molding will be suppressed, and the adhesion of the processed coating film and film will be improved. In the present invention, a combination of valve metal oxide or hydroxide and fluoride and a polyhydric phenol resin gives the chemical conversion coating a flexibility and a barrier function against corrosion factors, and further provides adhesion between the steel plate and the coating. Or the adhesiveness with a film can be improved.
バルブメタルの酸化物または水酸化物およびフッ化物と多価フェノール樹脂を組合せることにより，一分子中に多く存在するＯＨ基がバルブメタルの酸化物または水酸化物およびフッ化物に吸着し三次元網目構造を形成し，残存しているＯＨ基がめっき鋼板表面と塗膜やフィルムに吸着することで密着性または接着性が向上するものと推察され、後述の実施例でも支持されている。特に化成処理される原板にＡｌを含むめっき鋼板を使用し，また、化成処理皮膜中にフッ素を含む場合，めっき鋼板と化成処理皮膜の界面にＡｌ−Ｆの反応層が形成されることで皮膜の密着性がさらに向上する。 By combining valve metal oxides or hydroxides and fluorides with polyhydric phenol resins, OH groups present in many molecules are adsorbed on the valve metal oxides or hydroxides and fluorides in three dimensions. A network structure is formed, and the remaining OH groups are presumed to be adsorbed on the surface of the plated steel sheet and the coating film or film, so that adhesion or adhesion is improved, which is also supported in Examples described later. In particular, if a plated steel sheet containing Al is used as the raw sheet to be chemically treated, and if the chemical conversion film contains fluorine, a film is formed by forming an Al-F reaction layer at the interface between the plated steel sheet and the chemical conversion film. The adhesion is further improved.
さらに化成処理皮膜のバリア機能を向上させるためには、化成処理皮膜中にリン酸またはリン酸化合物を含ませるとよい。
リン酸またはリン酸化合物は、Ｚｎめっき層表面をエッチングする作用があり、エッチングによって活性化しためっき層とバルブメタルの酸化物または水酸化物およびフッ化物の反応を促進させる。その結果、生成した化成処理皮膜のめっき層に対する密着性が向上する。また、めっき層から溶出したＺｎやＡｌおよび未反応のバルブメタルの酸化物または水酸化物およびフッ化物がリン酸と反応し、バリア機能の高い化成処理皮膜を形成する。
Furthermore, in order to improve the barrier function of the chemical conversion coating, phosphoric acid or a phosphoric acid compound may be included in the chemical conversion coating.
The phosphoric acid or phosphoric acid compound has an action of etching the surface of the Zn plating layer, and promotes the reaction between the plating layer activated by the etching and the oxide or hydroxide and fluoride of the valve metal. As a result, the adhesion of the generated chemical conversion coating to the plating layer is improved. In addition, Zn and Al eluted from the plating layer and unreacted valve metal oxide or hydroxide and fluoride react with phosphoric acid to form a chemical conversion film having a high barrier function.
本発明の化成処理鋼板は、亜鉛めっき鋼板または亜鉛合金めっき鋼板表面に、バルブメタルの酸化物または水酸化物およびフッ化物と多価フェノール樹脂からなる化成処理皮膜を形成させることにより、化成処理皮膜にバリア機能を高めて耐食性を向上し，さらに柔軟性を付与して成型加工による化成処理皮膜の剥離等を抑制し，多価フェノール樹脂の優れた塗膜密着性およびフィルム接着性を活用し，しかも環境に悪影響をおよぼしかねない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。本発明の化成処理皮膜は、優れた柔軟性と塗膜密着性およびフィルム接着性を示すため塗装やフィルムラミネートした後で曲げ加工などを行ってもリン酸塩皮膜等のような凝集破壊による密着性低下は見られない。さらに，化成処理皮膜中にリン酸またはリン酸化合物を含ませると著しく耐食性が向上する。 The chemical conversion treatment steel sheet of the present invention is formed by forming a chemical conversion treatment film comprising a valve metal oxide or hydroxide and fluoride and a polyhydric phenol resin on the surface of a galvanized steel sheet or a zinc alloy plated steel sheet. In order to improve the corrosion resistance by improving the barrier function, to suppress the exfoliation of the chemical conversion film by molding process, and to take advantage of the excellent coating adhesion and film adhesion of polyhydric phenol resin, In addition, since it is a chemical conversion coating that does not contain Cr, which may adversely affect the environment, it is used in a wide range of fields as an alternative to conventional chromate-treated steel sheets. The chemical conversion film of the present invention exhibits excellent flexibility, coating film adhesion and film adhesion, and adhesion due to cohesive failure such as phosphate film even after bending such as coating or film lamination There is no decline in sex. Furthermore, when phosphoric acid or a phosphoric acid compound is included in the chemical conversion film, the corrosion resistance is remarkably improved.
化成処理される原板としては、電気めっき法，溶融めっき法，蒸着めっき法で製造された亜鉛または亜鉛合金めっき鋼板が使用される。亜鉛合金めっき鋼板には、Ｚｎ−Ａｌ，Ｚｎ−Ｍｇ，Ｚｎ−Ｎｉ，Ｚｎ−Ａｌ−Ｍｇ等がある。
その中で，溶融Ｚｎ−Ａｌ−Ｍｇ合金めっきは、Ａｌ：２.５〜１５質量％，Ｍｇ：２.０〜４.０質量％を含み残部が実質的にＺｎの合金めっき浴を用いた溶融めっき法で製造される。また、外観及び耐食性に悪影響を与えるＺｎ１１Ｍｇ２相の生成・成長を抑制するためＴｉ，Ｂ，Ｔｉ―Ｂ合金又はＴｉ，Ｂ含有化合物をめっき浴に添加することが有益である。めっき浴に対する添加量は、Ｔｉ：０.００１〜０.１質量％，Ｂ：０.００１〜０.０４５質量％の範囲で定めることが好ましい。過剰なＴｉ，Ｂの添加はめっき層に析出物を成長させる原因であり、リン酸塩処理性を阻害することがある。さらに、加工時のめっき密着性を向上させるため、めっき層と素地鋼との界面におけるＡｌ―Ｆｅ合金層の成長を抑制する作用のあるＳｉを０.００５〜０.５質量％の範囲で添加することもできる。
なお，溶融めっきした後で合金化処理を施した合金化亜鉛めっき鋼板も化成処理用原板として使用できる。
As an original plate to be subjected to chemical conversion treatment, a zinc or zinc alloy plated steel plate manufactured by electroplating, hot dipping, or vapor deposition is used. Examples of zinc alloy-plated steel sheets include Zn—Al, Zn—Mg, Zn—Ni, and Zn—Al—Mg.
Among them, the molten Zn—Al—Mg alloy plating used an alloy plating bath containing Al: 2.5-15 mass%, Mg: 2.0-4.0 mass%, and the balance being substantially Zn. Manufactured by hot dipping method. In addition, it is beneficial to add a Ti, B, Ti—B alloy or a Ti, B-containing compound to the plating bath in order to suppress the formation / growth of the Zn 11 Mg 2 phase, which adversely affects the appearance and corrosion resistance. The addition amount to the plating bath is preferably determined in the range of Ti: 0.001 to 0.1% by mass and B: 0.001 to 0.045% by mass. Excessive addition of Ti and B causes the growth of precipitates in the plating layer, and may impair phosphate treatment properties. Further, in order to improve the plating adhesion during processing, Si having an action of suppressing the growth of the Al—Fe alloy layer at the interface between the plating layer and the base steel is added in the range of 0.005 to 0.5 mass%. You can also
An alloyed galvanized steel sheet that has been subjected to alloying treatment after hot dipping can also be used as a raw sheet for chemical conversion treatment.
本発明で使用する化成処理液について，以下の説明では、バルブメタルの酸化物および水酸化物またはフッ化物としてＴｉを例に採っているが、Ｔｉ以外のバルブメタルの酸化物および水酸化物またはフッ化物を使用する場合も同様である。また、化成処理液は金属イオンを基準として次のように定めることが好ましく，所定の化成処理皮膜をめっき鋼板上に形成させるためには、化成処理皮膜中の成分比率と同じ比率で各成分を添加した化成処理液とすればよい。なお，以下の比率は全て重量比で示す。 In the following description of the chemical conversion solution used in the present invention, Ti is taken as an example of valve metal oxides and hydroxides or fluorides, but valve metal oxides and hydroxides other than Ti or hydroxides or The same applies to the case of using fluoride. Further, the chemical conversion treatment liquid is preferably determined as follows based on metal ions. In order to form a predetermined chemical conversion treatment film on the plated steel sheet, each component is added at the same ratio as the component ratio in the chemical conversion treatment film. What is necessary is just to set it as the added chemical conversion liquid. The following ratios are all expressed by weight.
水溶性チタン化合物としては、水酸化チタン，フッ化チタンアンモニウム，フッ化チタンカリウム、弗化チタンナトリウム，硫酸チタン，硝酸チタン，蓚酸チタン等が使用される。なかでも、Ｚｎめっき層をエッチングする作用のあるフッ素を含むフッ化チタン塩が好ましい。 As the water-soluble titanium compound, titanium hydroxide, ammonium fluoride titanium, potassium titanium fluoride, sodium titanium fluoride, titanium sulfate, titanium nitrate, titanium oxalate and the like are used. Especially, the titanium fluoride salt containing the fluorine which has the effect | action which etches a Zn plating layer is preferable.
多価フェノール樹脂の種類としてはウルシオール，タンニン酸や市販品としては、例えば、ＣＫＥ−２３７０，ＢＲＬ−１２０Ｚ（以上、いずれも昭和高分子製）；ＰＲ−ＮＩＳ−１，ＰＲ−５５３１７（以上、いずれも住友ベークライト製）などを挙げることができる。 Examples of the polyhydric phenol resin include urushiol, tannic acid, and commercially available products such as CKE-2370, BRL-120Z (all of which are manufactured by Showa Polymer Co., Ltd.); PR-NIS-1, PR-55317 (and above). , Both of which are manufactured by Sumitomo Bakelite).
多価フェノール樹脂は、化成処理皮膜に柔軟性を付与するだけでなく，後塗装後の塗膜やフィルムとの密着性向上成分であり，多価フェノール樹脂／金属イオン＝１以下では、十分な塗膜密着性が得られず、多価フェノール樹脂／金属イオン＝２０以上になると亜鉛めっき鋼板と未反応の多価フェノール樹脂が過剰となり塗膜密着性およびフィルム接着性が低下する。 The polyhydric phenol resin not only gives flexibility to the chemical conversion coating, but is also a component for improving adhesion to a coating film and a film after post-coating. The polyhydric phenol resin / metal ion = 1 or less is sufficient. When the coating film adhesion cannot be obtained and the polyhydric phenol resin / metal ion = 20 or more, the galvanized steel sheet and the unreacted polyhydric phenol resin are excessive, and the coating film adhesion and the film adhesion are deteriorated.
リン酸またはリン酸化合物としては、リン酸，ポリリン酸，リン酸２水素アンモニウム，リン酸２水素ナトリウム，リン酸マグネシウム等が使用される。 Examples of phosphoric acid or phosphoric acid compounds include phosphoric acid, polyphosphoric acid, ammonium dihydrogen phosphate, sodium dihydrogen phosphate, magnesium phosphate, and the like.
リン酸またはリン酸化合物は、Ｚｎめっき層をエッチングする成分であると共に、難溶性リン酸塩の生成に消費される。Ｐ／金属イオン＝０．１以上になると、めっき層を活性化するエッチング作用が十分に得られ、塗膜密着性およびフィルム接着性を低下させることなく耐食性にも優れた化成処理皮膜形成に適した表面状態にめっき層表面が改質される。しかし、Ｐ／金属イオン＝５．０を超える過剰のリン酸が含まれるとエッチング作用が強くなりすぎ、化成処理液の安定性も低下する。 Phosphoric acid or a phosphoric acid compound is a component that etches the Zn plating layer and is consumed in the production of a poorly soluble phosphate. When P / metal ion = 0.1 or more, an etching action that activates the plating layer is sufficiently obtained, and it is suitable for forming a chemical conversion film having excellent corrosion resistance without deteriorating coating film adhesion and film adhesion. The surface of the plating layer is modified to the surface state. However, if an excessive amount of phosphoric acid exceeding P / metal ion = 5.0 is contained, the etching action becomes too strong, and the stability of the chemical conversion treatment liquid also decreases.
本発明の化成処理皮膜を亜鉛めっき鋼板または亜鉛合金めっき鋼板上に形成させるための化成処理液は、必須成分としてバルブメタルの酸化物および水酸化物またはフッ化物と多価フェノール樹脂を化成処理皮膜の所定組成に対応するように，多価フェノール樹脂／金属イオン＝１〜２０となるように配合し，めっき鋼板上に塗布することで加工後の塗膜密着性およびフィルム接着性に優れた化成処理皮膜を形成できる。さらに、リン酸およびリン酸化合物をＰ／金属イオン＝０．１〜５．０添加してもかまわないが，良好な特性の化成処理皮膜を形成する上で化成処理液のpHを好ましくはｐＨ０．５〜４．０に調整される。０．５未満のｐＨ値ではエッチング過多になり処理液寿命が短くなり，４．０を超えるｐＨ値では液安定性が極端に悪くなる。 The chemical conversion treatment liquid for forming the chemical conversion treatment film of the present invention on a galvanized steel sheet or a zinc alloy plated steel sheet contains a chemical conversion treatment film comprising a valve metal oxide and hydroxide or fluoride and a polyhydric phenol resin as essential components. In order to correspond to the predetermined composition, a polyphenol resin / metal ion is blended so as to be 1 to 20, and it is applied on a plated steel sheet to form a coating film having excellent adhesion and film adhesion after processing. A treatment film can be formed. Further, phosphoric acid and a phosphoric acid compound may be added at P / metal ion = 0.1 to 5.0, but the pH of the chemical conversion treatment solution is preferably pH 0 for forming a chemical conversion treatment film having good characteristics. Adjusted to .5 to 4.0. If the pH value is less than 0.5, the etching is excessive and the life of the processing solution is shortened. If the pH value exceeds 4.0, the liquid stability becomes extremely poor.
十分な耐食性および塗膜密着性を得るためには化成処理皮膜の膜厚を０．０１〜０．５μｍの範囲に調整することが好ましい。０．０１μｍ未満の付着量では塗膜密着性が十分に向上せず、逆に０．５μｍを超える付着量では，加工時に化成処理皮膜が凝集破壊し塗膜密着性およびフィルム接着性が低下する。 In order to obtain sufficient corrosion resistance and coating film adhesion, it is preferable to adjust the film thickness of the chemical conversion coating to a range of 0.01 to 0.5 μm. If the adhesion amount is less than 0.01 μm, the adhesion of the coating film is not sufficiently improved. Conversely, if the adhesion amount exceeds 0.5 μm, the chemical conversion coating film cohesively breaks down during processing, and the adhesion of the coating film and the film adhesion deteriorate. .
所定組成に調整された化成処理液をロールコート法，スプレー法等によって亜鉛系めっき鋼板に塗布した後、水洗せずに乾燥することによって所定性能をもつ化成処理皮膜がめっき層の表面に生成する。化成処理皮膜は常温でも乾燥可能であるが、連続操業を考慮すると５０℃以上の温度に保持して乾燥時間を短縮することが好ましい。しかし、２００℃を超える乾燥温度では、化成処理皮膜に含まれる多価フェノール樹脂の加熱分解により化成処理皮膜の耐食性が低下する虞がある。 After the chemical conversion treatment liquid adjusted to the prescribed composition is applied to the galvanized steel sheet by the roll coat method, spray method, etc., the chemical conversion treatment film having the prescribed performance is formed on the surface of the plating layer by drying without washing with water. . The chemical conversion film can be dried at room temperature, but considering continuous operation, it is preferable to maintain the temperature at 50 ° C. or higher to shorten the drying time. However, at a drying temperature exceeding 200 ° C., the corrosion resistance of the chemical conversion coating film may be reduced due to thermal decomposition of the polyphenol resin contained in the chemical conversion coating film.
化成処理皮膜は、０．０１〜０．５μｍの薄膜になるように化成処理液の塗布条件などを調整して形成される。 The chemical conversion treatment film is formed by adjusting the application conditions of the chemical conversion treatment solution so as to be a thin film of 0.01 to 0.5 μm.
化成処理原板としては、板厚０．５ｍｍ，片面当りめっき付着量２０ｇ／ｍ２の電気亜鉛めっき鋼板および板厚が０．５ｍｍで片面当りめっき付着量５０ｇ／ｍ２のＺｎ-６質量％Ａｌ―３質量％Ｍｇの合金めっき層が形成された溶融めっき鋼板を使用した。なお，Ｚｎ-６質量％Ａｌ―３質量％Ｍｇの合金めっき層中には微量元素として、Ｔｉ：０.００１〜０.１質量％，Ｂ：０.００１〜０.０４５質量％，Ｓｉ：０.００５〜０.５質量％含まれる。
各めっき鋼板を脱脂，酸洗することにより化成処理原板を用意した。表１の化成処理液を亜鉛めっき鋼板に塗布し，水洗することなく電気オーブンに装入し，板温８０℃で加熱乾燥した。
As the chemical conversion raw plate, an electrogalvanized steel sheet having a plate thickness of 0.5 mm and a plating adhesion amount of 20 g / m 2 on one side, and a Zn-6 mass% Al having a plate thickness of 0.5 mm and a plating adhesion amount of 50 g / m 2 on one side. -A hot-dip plated steel sheet on which an alloy plating layer of 3% by mass Mg was formed was used. In the alloy plating layer of Zn-6 mass% Al-3 mass% Mg, Ti: 0.001 to 0.1 mass%, B: 0.001 to 0.045 mass%, Si: 0.005 to 0.5 mass% is contained.
A chemical conversion treatment original plate was prepared by degreasing and pickling each plated steel plate. The chemical conversion treatment liquid shown in Table 1 was applied to a galvanized steel sheet, charged into an electric oven without being washed with water, and dried by heating at a plate temperature of 80 ° C.
比較材としてリン酸塩処理液（リン酸：０．１５ｍｏｌ／ｌ、Ｚｎ：０．０８ｍｏｌ／ｌ、Ｍｎ：０．０６ｍｏｌ／ｌ、硝酸：０．２０ｍｏｌ／ｌ、フッ化物：０．０１ｍｏｌ／ｌ）を用いて各めっき鋼板をリン酸塩処理した後、クロムフリー化成処理液（Ｔｉ水溶液；Ｔｉ濃度［ＴｉＳＯ4］：１０ｇ／ｌ）を塗布し乾燥することによりリン酸塩皮膜をクロムフリー化成皮膜（Ｔｉ付着量：２０ｍｇ／ｍ２）でシーリングした。また，市販のクロメート処理液（ＺＭ−３３８７：日本パーカライジング株式会社製）を各めっき鋼板に塗布し乾燥した。 Phosphate treatment solution (phosphoric acid: 0.15 mol / l, Zn: 0.08 mol / l, Mn: 0.06 mol / l, nitric acid: 0.20 mol / l, fluoride: 0.01 mol / l as a comparative material The chrome-free chemical conversion film is coated with a chromium-free chemical conversion treatment solution (Ti aqueous solution; Ti concentration [TiSO4]: 10 g / l) and dried. Sealing was performed with (Ti adhesion amount: 20 mg / m 2 ). Further, a commercially available chromate treatment solution (ZM-3387: manufactured by Nippon Parkerizing Co., Ltd.) was applied to each plated steel sheet and dried.
作成した化成処理鋼板から試験片を切り出し、平坦部腐食試験および加工後の塗膜密着性およびフィルム接着性を調査した。調査結果を表２に示す。 A test piece was cut out from the prepared chemical conversion treated steel sheet, and the flat part corrosion test and the coating film adhesion and film adhesion after processing were investigated. The survey results are shown in Table 2.
〔平坦部腐食試験〕
試験片の端面をシールし、ＪＩＳ Ｚ ２３７１ に準拠して３５℃の５％ＮａＣｌ水溶液を試験片表面に噴霧した。塩水噴霧を８時間又は２４時間継続した後、試験片表面を観察し白錆発生状況を調査した。試験片表面に占める白錆の面積占有率が１０面積％未満を◎，１０以上〜２０面積％未満を○，２０以上〜５０面積％未満を△，５０面積％以上を×として平坦部耐食性を評価した。
[Flat corrosion test]
The end face of the test piece was sealed, and a 5% NaCl aqueous solution at 35 ° C. was sprayed on the surface of the test piece in accordance with JIS Z 2371. After spraying salt water for 8 hours or 24 hours, the surface of the test piece was observed to investigate the occurrence of white rust. Corrosion resistance of the flat part is defined as ◎ when the area occupancy ratio of white rust on the surface of the test piece is less than 10 area%, ◯ when 10 or more and less than 20 area%, △ when 20 or more but less than 50 area%, and x when 50 area% or more. evaluated.
〔塗膜密着性〕
メラミンアルキット塗料を用いて試験片に膜厚３０μｍの塗膜を形成し、エリクセン６ｍｍ張出し加工した後、ＪＩＳ Ｋ５４００の碁盤目法に準拠した試験で残存率：９０％以上の塗膜を◎，９０未満〜８０％以上を○，８０未満〜６０％以上を△，６０％未満を×として塗膜密着性を評価した。
[Coating film adhesion]
After forming a 30 μm thick coating on the test piece using melamine alkit paint and overhanging Erichsen 6 mm, a coating with a residual rate of 90% or more was tested in accordance with the cross-cut method of JIS K5400. The coating film adhesion was evaluated by assuming that less than 90 to 80% or more was ◯, less than 80 to 60% or more was Δ, and less than 60% was x.
〔フィルム接着性〕
エポキシ系接着剤を用いてＰＥＴフィルムを試験片にラミネートした後、荷重２００ｋｇｆのドロービード摺動変形試験後にフィルムの先端を強制的に引き剥がす引張り試験によって剥離強度を測定した。剥離強度が１００（Ｎ／４０ｍｍ）以上を◎，１００未満〜８０（Ｎ／４０ｍｍ）以上を○，８０未満〜６０（Ｎ／４０ｍｍ）以上を△，６０（Ｎ／４０ｍｍ）未満を×として評価した。
[Film adhesion]
After laminating a PET film on a test piece using an epoxy adhesive, the peel strength was measured by a tensile test in which the tip of the film was forcibly peeled after a draw bead sliding deformation test with a load of 200 kgf. Peel strength of 100 (N / 40 mm) or more is evaluated as ◎, less than 100 to 80 (N / 40 mm) or more is evaluated as ○, less than 80 to 60 (N / 40 mm) or more is evaluated as Δ, and less than 60 (N / 40 mm) is evaluated as ×. did.
表２の調査結果にみられるように、各めっき鋼板上に多価フェノール樹脂とチタン化合物からなる化成処理皮膜を形成させた試験Ｎｏ.１〜１６の試料は、平坦部耐食性，塗膜密着性，フィルム接着性のいずれにも優れた特性を示した。なかでも、化成処理皮膜中にリン酸またはリン酸化合物を添加した場合，耐食性が格段と向上している。 As can be seen from the survey results in Table 2, the samples of Test Nos. 1 to 16 in which a chemical conversion treatment film composed of a polyhydric phenol resin and a titanium compound is formed on each plated steel plate are flat portion corrosion resistance and coating film adhesion. The film showed excellent properties in both film adhesion. Especially, when phosphoric acid or a phosphoric acid compound is added in the chemical conversion film, the corrosion resistance is remarkably improved.
他方，多価フェノール樹脂以外の有機樹脂を配合した試験Ｎｏ.１７〜１９、適正な化成処理膜厚でない試験Ｎｏ.２０，２１、多価フェノール樹脂を含まない試験Ｎｏ．２３、従来のリン酸塩処理の試験Ｎｏ.２４やクロメート処理の試験Ｎｏ.２５では、塗膜密着性やフィルム接着性が劣る。また、化成処理皮膜中にバルブメタルの酸化物または水酸化物およびフッ化物を含まない試験Ｎｏ.２２では、平坦部の白錆発生率が劣る。 On the other hand, Test Nos. 17 to 19 containing an organic resin other than the polyhydric phenol resin, Test Nos. 20 and 21 that do not have an appropriate chemical conversion treatment film thickness, and Test Nos. 23. In conventional phosphate treatment test No. 24 and chromate treatment test No. 25, coating film adhesion and film adhesion are inferior. Moreover, in test No. 22 in which the valve metal oxide or hydroxide and fluoride are not contained in the chemical conversion treatment film, the white rust occurrence rate of the flat portion is inferior.
以上説明したように、本発明による加工後の塗膜密着性およびフィルム接着性に優れた化成処理鋼板は、亜鉛系めっき鋼板表面に形成された柔軟性のあるクロムフリー系化成処理皮膜のため，後塗装またはフィルムラミネートし，成形加工しても良好な密着性または接着性を呈する。これは、ユーザー側での加工後の塗膜密着性やフィルム接着性を十分に満足させるものであり、利用価値は高い。
As explained above, the chemical conversion-treated steel sheet having excellent coating adhesion and film adhesion after processing according to the present invention is a flexible chromium-free chemical conversion film formed on the surface of a zinc-based plated steel sheet. Good adhesion or adhesion even after post-coating or film lamination and molding. This sufficiently satisfies the coating film adhesion and film adhesion after processing on the user side, and has high utility value.
Claims (4)
The coating film adhesion and film adhesion after processing according to claims 1 to 3, wherein the chemical conversion coating is polyphenol resin / metal ions = 1 to 20 and P / metal ions = 0.1 to 5.0 by weight ratio. Chemically treated steel sheet with excellent properties.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102560491A (en) * | 2010-12-30 | 2012-07-11 | 鸿富锦精密工业（深圳）有限公司 | Aluminium and aluminium alloy surface antiseptic treatment method and product prepared by same |
| US10125424B2 (en) | 2012-08-29 | 2018-11-13 | Ppg Industries Ohio, Inc. | Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates |
| US10400337B2 (en) | 2012-08-29 | 2019-09-03 | Ppg Industries Ohio, Inc. | Zirconium pretreatment compositions containing lithium, associated methods for treating metal substrates, and related coated metal substrates |
| US11518960B2 (en) | 2016-08-24 | 2022-12-06 | Ppg Industries Ohio, Inc. | Alkaline molybdenum cation and phosphonate-containing cleaning composition |
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2006
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102560491A (en) * | 2010-12-30 | 2012-07-11 | 鸿富锦精密工业（深圳）有限公司 | Aluminium and aluminium alloy surface antiseptic treatment method and product prepared by same |
| US10125424B2 (en) | 2012-08-29 | 2018-11-13 | Ppg Industries Ohio, Inc. | Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates |
| US10400337B2 (en) | 2012-08-29 | 2019-09-03 | Ppg Industries Ohio, Inc. | Zirconium pretreatment compositions containing lithium, associated methods for treating metal substrates, and related coated metal substrates |
| US10920324B2 (en) | 2012-08-29 | 2021-02-16 | Ppg Industries Ohio, Inc. | Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates |
| US11518960B2 (en) | 2016-08-24 | 2022-12-06 | Ppg Industries Ohio, Inc. | Alkaline molybdenum cation and phosphonate-containing cleaning composition |
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