JP2010053424A - Surface-treated metal plate having superior adhesiveness to coating, and method for producing the same - Google Patents
Surface-treated metal plate having superior adhesiveness to coating, and method for producing the same Download PDFInfo
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Abstract
Description
本発明は、環境負荷性の高い６価クロムを含まず、かつ高い塗装後の皮膜密着性を有し、耐食性に優れた表面処理金属板、及びその製造方法に関するものである。 The present invention relates to a surface-treated metal plate which does not contain hexavalent chromium having high environmental impact, has high coating adhesion after coating, and has excellent corrosion resistance, and a method for producing the same.
家庭電化製品、自動車、建築材料等の各分野において、防錆性あるいは上層との塗料密着性の付与を目的として、鋼板や表面処理鋼板にクロメート処理を施すのが一般的である。しかし、通常クロメート処理皮膜は環境負荷性の高い６価クロムを含有することから、近年この６価クロムのフリー化に対する要望が高まっており、一部では既に全廃に向けて動き出している業界もある。 In various fields such as home appliances, automobiles, and building materials, it is common to perform chromate treatment on steel sheets and surface-treated steel sheets for the purpose of imparting rust prevention or paint adhesion to the upper layer. However, since the chromate-treated film usually contains hexavalent chromium, which has a high environmental impact, there has been a growing demand for the free use of hexavalent chromium in recent years, and some industries have already started moving toward complete elimination. .
これらの流れに対し、クロムを含まない表面処理方法が各種考案されている。例えば、無機化合物皮膜や有機化合物を主体とした皮膜、あるいはそれらの複合皮膜が各種考案されており、その中で無機化合物皮膜は一次防錆機能とその後の塗装密着性を目的として使用されつつある。 For these flows, various surface treatment methods not containing chromium have been devised. For example, various inorganic compound films, organic compound-based films, or composite films thereof have been devised, among which inorganic compound films are being used for the purpose of primary rust prevention and subsequent coating adhesion. .
その無機系皮膜を形成する方法として、スパッタリング法やＣＶＤ法等の気相法とゾルゲル法等の液相法があるが、以下のような制約を有していた。 As a method for forming the inorganic film, there are a gas phase method such as a sputtering method and a CVD method, and a liquid phase method such as a sol-gel method, which have the following limitations.
気相法は、気相において基材上に成膜を行うものであり、真空系を得るための高価な設備が必要である。さらに、成膜にあたって、あらかじめ基材を加熱するため、その手段も必要となる。また、凹凸や曲面を有する基材に成膜することは困難である。 The vapor phase method forms a film on a substrate in the gas phase, and requires expensive equipment for obtaining a vacuum system. Further, since the substrate is heated in advance during film formation, the means is also necessary. Further, it is difficult to form a film on a substrate having irregularities or curved surfaces.
一方、液相法であるゾルゲル法は、塗布後焼成が必要であり、そのためクラックの発生や基材からの金属の拡散の影響を受ける。また、揮発分があるため、緻密な皮膜の形成が困難である。 On the other hand, the sol-gel method, which is a liquid phase method, requires baking after coating, and is therefore affected by the occurrence of cracks and the diffusion of metal from the substrate. In addition, since there is a volatile component, it is difficult to form a dense film.
ここで、液相法の一つであるフルオロ錯イオン等を含むフッ素化合物水溶液を用いる液相析出法においては、上記のような真空を得るための高価な設備は必要とせず、基材を高温度に加熱しなくても成膜でき、更にはさまざまな形状の基材にも皮膜を形成することができる。しかしながら、これらの溶液は腐食性があるため、主にガラスや高分子材料、セラミックス等の非金属材料を基材として行われてきた。金属材料を基材とする方法として、例えば、特開昭６４−８２９６号公報では、金属、合金、半導体基材、等の少なくとも表面の一部に導電性を有する基材表面に、二酸化珪素被膜を製造する方法が提案されている。しかし、基材への影響については、本文中に「該処理液にホウ酸、アルミニウムなどを加えてエッチングされないようにしておくことも可能である」とあるのみで、これでは不十分である。また、液相法の一つであるフルオロ錯イオン等のフッ素化合物水溶液を用いる液相析出法においては、特許第２８２８３５９号等の実施例に記されているように、成膜には数十時間の長時間を要し、成膜速度が低いことが問題であった。 Here, in the liquid phase deposition method using a fluorine compound aqueous solution containing a fluoro complex ion or the like, which is one of the liquid phase methods, expensive equipment for obtaining a vacuum as described above is not required, and the substrate is made high. A film can be formed without heating to a temperature, and a film can be formed on a substrate having various shapes. However, since these solutions are corrosive, they have been mainly used with non-metallic materials such as glass, polymer materials, and ceramics as base materials. As a method using a metal material as a base material, for example, in Japanese Patent Application Laid-Open No. 64-8296, a silicon dioxide film is formed on the surface of a base material having conductivity on at least a part of the surface of a metal, an alloy, a semiconductor base material, etc. There has been proposed a method of manufacturing. However, as for the influence on the base material, there is only a statement in the text that “it is possible to prevent etching by adding boric acid, aluminum or the like to the treatment solution”, and this is insufficient. Further, in the liquid phase deposition method using a fluorine compound aqueous solution such as a fluoro complex ion, which is one of the liquid phase methods, as described in Examples of Japanese Patent No. 2828359 and the like, film formation takes several tens of hours. It took a long time, and the film formation rate was low.
これに対し、電解処理を行うことで表面に各種の無機系化合物皮膜を施す方法もいくつか開示されている。例えば、特開２００５−１０５３２１号公報には、４価Ｖ化合物の１種以上とｐＨ調整剤を含有する水溶液、またはさらにＰ化合物、Ｍｏ化合物、Ｔｉ化合物、Ｚｒ化合物、Ａｌ化合物、Ｍｇ化合物の１種以上を加えた水溶液中で電解処理を行い皮膜を形成する技術、特開２００３−２１３４５９号公報には、Ａｌ，Ｔｉ，Ｚｒ，Ｌａ，Ｍｇ，Ｍｏの１種または２種以上を１０〜１０００モル／ｌの金属イオン濃度を含むｐＨ１〜５の処理液中でカソード電解処理することにより、Ａｌ，Ｔｉ，Ｚｒ，Ｌａ，Ｍｇ，Ｍｏの１種または２種以上を含む金属酸化物皮膜を形成する技術が開示されている。しかし、これらはいずれも皮膜の密着性と耐食性との相関において十分に技術的検討がなされておらず、最適な皮膜組成や表面形態の要件が不明確であり、密着性発現要素が不安定である懸念があった。また、本発明者らも従来国際公開第２００３／０４８４１６号パンフレットにおいて、フルオロ錯イオンを主体とする溶液にて電解処理を行い、基体に酸化物皮膜及び／又は水酸化物皮膜を短時間形成する技術を開示しているが、同様に密着性発現における最適な皮膜組成や表面形態の検討が不足していたため、安定した密着性確保のための課題を残していた。 On the other hand, several methods for applying various inorganic compound films on the surface by performing electrolytic treatment are also disclosed. For example, Japanese Patent Application Laid-Open No. 2005-105321 discloses an aqueous solution containing one or more tetravalent V compounds and a pH adjuster, or a P compound, a Mo compound, a Ti compound, a Zr compound, an Al compound, or an Mg compound. Japanese Patent Application Laid-Open No. 2003-213659 discloses a technique for forming a film by performing an electrolytic treatment in an aqueous solution to which more than one species is added, and describes that one or more of Al, Ti, Zr, La, Mg, and Mo is 10 to 1000. Forming a metal oxide film containing one or more of Al, Ti, Zr, La, Mg, and Mo by cathodic electrolysis in a treatment solution of pH 1-5 containing a metal ion concentration of mol / l. Techniques to do this are disclosed. However, none of these has been sufficiently technically examined in the correlation between the adhesion and corrosion resistance of the film, the requirements for the optimal film composition and surface morphology are unclear, and the adhesiveness development factors are unstable. There was some concern. In addition, in the conventional pamphlet of International Publication No. 2003/048416, the present inventors also perform electrolytic treatment with a solution mainly composed of a fluoro complex ion to form an oxide film and / or a hydroxide film on a substrate for a short time. Although the technology is disclosed, the examination of the optimal film composition and surface form in the adhesion expression is similarly insufficient, and therefore there remains a problem for ensuring stable adhesion.
本発明では、上記の課題に着目し、その上層との皮膜密着性に優れ、かつ優れた耐食性を発現する酸化物及び／又は水酸化物皮膜を施した表面処理金属板の提供、及びその製造方法の提供を目的とする。 In the present invention, focusing on the above-mentioned problems, a surface-treated metal sheet provided with an oxide and / or hydroxide film that is excellent in film adhesion to the upper layer and that exhibits excellent corrosion resistance, and production thereof are provided. The purpose is to provide a method.
本発明者らは、上記目的を達成するために鋭意検討を重ね、以下のことを見出した。
本発明では、フルオロ錯イオン等を含むフッ素化合物水溶液で金属材料を陰極電解処理することにより、ある特定の皮膜組成と、特定の大きさの皮膜形態を有する金属酸化物系皮膜及び／又は金属水酸化物系皮膜を形成することを特徴としている。
The inventors of the present invention have made extensive studies in order to achieve the above object, and have found the following.
In the present invention, a metal material is subjected to cathodic electrolytic treatment with a fluorine compound aqueous solution containing a fluoro complex ion or the like, whereby a metal oxide film and / or metal water having a specific film composition and a film form of a specific size. It is characterized by forming an oxide-based film.
フルオロ錯イオン等を含むフッ素化合物水溶液の処理液中では、フッ素イオンの消費、水素イオンの還元により、金属イオンが酸化物及び／又は水酸化物になる反応が進むと考えられる。例えば、フルオロ錯イオン等を含むフッ素化合物水溶液に金属材料を浸漬した場合、その表面上で局部セルが形成され、金属溶出反応と水素発生反応が起こる。溶出した金属イオンによるフッ素イオンの消費と、水素イオンの還元が起こるので、金属イオンの酸化物及び／又は水酸化物が金属基材表面に析出する。この場合、ほぼ基材の表面に沿って均一にエピタキシャル成長が起こるため、平らな皮膜が形成され、基材の表面と同様の形態の皮膜が形成される。 In a treatment solution of an aqueous solution of a fluorine compound containing a fluoro complex ion or the like, it is considered that a reaction in which metal ions are converted into oxides and / or hydroxides proceeds due to consumption of fluorine ions and reduction of hydrogen ions. For example, when a metal material is immersed in a fluorine compound aqueous solution containing a fluoro complex ion or the like, a local cell is formed on the surface, and a metal elution reaction and a hydrogen generation reaction occur. Since fluorine ions are consumed by the eluted metal ions and hydrogen ions are reduced, oxides and / or hydroxides of the metal ions are deposited on the surface of the metal substrate. In this case, since epitaxial growth occurs substantially along the surface of the substrate, a flat film is formed, and a film having the same form as the surface of the substrate is formed.
水溶液中での陰極電解処理で形成される皮膜は、理論的には金属酸化物で構成されるはずであるが、ほとんどの場合、反応物の金属の一部が水と反応して生成した金属水酸化物を含む。場合によっては、金属水酸化物が一様に分布して、あたかも金属水酸化物の皮膜であるかのように見えることもある。そのため、本発明では、金属板表面に陰極電解処理により形成した皮膜を、「金属酸化物系皮膜及び／又は金属水酸化物系皮膜」と呼ぶことにする。 The film formed by cathodic electrolysis in an aqueous solution should theoretically be composed of a metal oxide, but in most cases, a metal formed by reacting part of the reactant metal with water. Contains hydroxide. In some cases, the metal hydroxide is uniformly distributed and may appear as if it is a metal hydroxide film. Therefore, in the present invention, a film formed on the surface of the metal plate by cathodic electrolysis is referred to as a “metal oxide film and / or metal hydroxide film”.
このような酸化物系皮膜及び／又は水酸化物系皮膜の場合、一般的に表面における水酸基などの官能基の数が十分でない場合が多く、上層にさらに皮膜を塗装する場合の密着性が不足する傾向にある。諸性能を確保するためには密着性の確保が必要なため、密着性を安定して発現させるために、皮膜組成の選定と表面の皮膜形態の制御に着目して検討を行った。その結果、ある特定の金属の酸化物及び／又は水酸化物皮膜を、陰極電解処理を用いてある特定の大きさの粒状析出物を金属材料表面に生じさせて形成することにより、塗装後の密着性が大幅に向上することを見出した。これは、粒状析出物を金属材料表面に配置することで界面の表面積を増加させ密着力を増加させると共に、表面の凹凸を増やすことでアンカー効果による密着性向上への寄与を得たためであると考えられる。ここで、粒状析出物とは、電気亜鉛めっき鋼板のＳＥＭ写真である図１に示すように、金属材料表面に形成した長径１０〜２００ｎｍ程度のさまざまな形態を持つ析出物を指す。図２には、粒状析出物無しの電気亜鉛めっき鋼板のＳＥＭ写真を示す。 In the case of such an oxide-based film and / or hydroxide-based film, in general, the number of functional groups such as hydroxyl groups on the surface is often insufficient, and the adhesion when further coating the upper layer is insufficient. Tend to. In order to secure various performances, it is necessary to ensure adhesion. Therefore, in order to stably develop adhesion, studies were made focusing on the selection of the coating composition and the control of the coating form on the surface. As a result, an oxide and / or hydroxide film of a specific metal is formed by forming a granular precipitate of a specific size on the surface of the metal material by using cathodic electrolysis. It has been found that the adhesion is greatly improved. This is because the arrangement of the granular precipitate on the surface of the metal material increases the surface area of the interface and increases the adhesive force, and the contribution to the improvement in adhesion due to the anchor effect is obtained by increasing the unevenness of the surface. Conceivable. Here, as shown in FIG. 1 which is a SEM photograph of the electrogalvanized steel sheet, the granular precipitate refers to a precipitate having various forms having a major axis of about 10 to 200 nm formed on the surface of the metal material. In FIG. 2, the SEM photograph of the electrogalvanized steel plate without a granular deposit is shown.
さらに、所定の条件、方法で陰極電解処理を行うことによりその効果が高まることを見出した。これは、前述した特定の大きさの析出物を表面に形成させる手段や、析出物の層構造や形態を確保する手段を見出したものであると共に、皮膜表面における適度な水酸基などの官能基濃度確保に作用しているためであると推察している。その手法としては、二段階以上に工程を分離し、始めの電解処理で比較的低い電流密度で電解し、その後それより高い電流密度で電解処理することにより、下地となる金属材料との密着性に優れた均一で緻密な皮膜を形成した後、その上部に目的とする大きさ、形態の析出物を形成することにより、より一層良好な性能を発現させることができる。 Furthermore, it has been found that the effect is enhanced by carrying out cathodic electrolysis under predetermined conditions and methods. This is a means for forming the above-mentioned precipitates of a specific size on the surface, and a means for ensuring the layer structure and form of the precipitates, and the concentration of functional groups such as appropriate hydroxyl groups on the film surface. It is assumed that this is due to the fact that it acts on securing. As the method, the process is separated into two or more stages, electrolysis is performed at a relatively low current density in the first electrolytic treatment, and then the electrolytic treatment is performed at a higher current density, so that adhesion to the underlying metal material is achieved. After forming a uniform and dense film excellent in the above, a precipitate having a desired size and shape is formed on the upper part, whereby even better performance can be exhibited.
また、本発明は導電性を有する金属材料であれば適用可能であるが、金属酸化物系皮膜及び／又は水酸化物系皮膜を施す基体として、Ｚｎを含有するめっきで表面処理した鋼板を用いると著しい効果を発現する。これは、本発明にて選定したＳｉ、Ｔｉ、Ｚｒ、Ｖ、Ｎｂ、Ｔａ、Ｐ、Ｗを少なくとも一種含有する金属酸化物系皮膜及び／又は金属水酸化物系皮膜が、前述した上塗り塗料との密着性を発揮する一方で、Ｚｎの過剰な犠牲防食作用を抑制できるためと考えている。 In addition, the present invention can be applied to any conductive metal material, but a steel plate surface-treated with Zn-containing plating is used as a substrate on which a metal oxide film and / or hydroxide film is applied. And a significant effect. This is because the metal oxide film and / or metal hydroxide film containing at least one of Si, Ti, Zr, V, Nb, Ta, P, and W selected in the present invention is the above-described topcoat paint. It is considered that the excessive sacrificial anticorrosive action of Zn can be suppressed while exhibiting the adhesiveness.
さらに、その上層にある特定の官能基を有する有機樹脂系皮膜を施すことで、複層構造による機能分担により、密着性以外のさまざまな諸性能を担保できることも見出した。これは、本発明にて選定したＳｉ、Ｔｉ、Ｚｒ、Ｖ、Ｎｂ、Ｔａ、Ｐ、Ｗを少なくとも一種含有する金属酸化物系皮膜及び／又は金属水酸化物系皮膜と、樹脂皮膜の官能基が最適な密着力を発揮する組み合わせであるためと考えられる。 Furthermore, it has also been found that by applying an organic resin-based film having a specific functional group on the upper layer, various functions other than adhesion can be ensured by function sharing by a multilayer structure. This is a metal oxide film and / or metal hydroxide film containing at least one of Si, Ti, Zr, V, Nb, Ta, P, and W selected in the present invention, and a functional group of the resin film. Is considered to be the combination that exhibits the optimum adhesion.
すなわち、本発明の主旨とするところは、
（１）金属材料の少なくとも片面に、Ｓｉ、Ｔｉ、Ｚｒ、Ｖ、Ｎｂ、Ｔａ、Ｐ、Ｗを少なくとも一種含有する金属酸化物系皮膜及び／又は金属水酸化物系皮膜を陰極電解処理にて形成した表面処理金属板であって、その金属酸化物系皮膜及び／又は金属水酸化物系皮膜が、当該陰極電解処理により形成した、独立した粒状析出物もしくは隣どうし接触した粒状析出物であって、その１個あたりの長径が５ｎｍ以上３００ｎｍ以下であり、かつ１×１０-12ｍ2に１０個以上存在している粒状析出物で構成されていることを特徴とする塗装密着性に優れた表面処理金属板、
（２）前記金属材料がＺｎを含有するめっきで表面処理した鋼板であることを特徴とする（１）記載の塗装密着性に優れた表面処理金属板、
（３）前記金属酸化物系皮膜及び／又は金属水酸化物系皮膜の上層に、さらにカルボキシル基、水酸基、スルホン酸基の少なくとも一種を有する有機樹脂系皮膜を０．１μｍ〜５．０μｍの膜厚で施したことを特徴とする（１）または（２）記載の塗装密着性に優れた表面処理金属板、
（４）前記金属酸化物系皮膜及び／又は金属水酸化物系皮膜を、フルオロ金属化合物を主体とし、Ｓｉ、Ｔｉ、Ｚｒ、Ｖ、Ｎｂ、Ｔａ、Ｐ、Ｗのうちの少なくとも一種を金属種として含む処理浴中で、電流密度０．５〜３０×１０2Ａ／ｍ2、温度２０℃〜６０℃で金属材料を陰極電解処理して形成することを特徴とする（１）〜（３）の一つに記載の塗装密着性に優れた表面処理金属板の製造方法、
（５）前記金属酸化物系皮膜及び／又は金属水酸化物系皮膜を、フルオロ金属化合物を主体とし、Ｓｉ、Ｔｉ、Ｚｒ、Ｖ、Ｎｂ、Ｔａ、Ｐ、Ｗのうちの少なくとも一種を金属種として含む処理浴中で、０．１秒までの電圧印加初期の電流密度が０．５〜５×１０2Ａ／ｍ2、０．１秒以降の電流密度が１〜３０×１０2Ａ／ｍ2にて金属材料を陰極電解処理して形成することを特徴とする（１）〜（３）の一つに記載の塗装密着性に優れた表面処理金属板の製造方法、
（６）前記金属酸化物系皮膜及び／又は金属水酸化物系皮膜を、フルオロ金属化合物を主体とし、Ｓｉ、Ｔｉ、Ｚｒ、Ｖ、Ｎｂ、Ｔａ、Ｐ、Ｗのうちの少なくとも一種を金属種として含む処理浴中で、金属材料を電流密度０．５〜２０×１０2Ａ／ｍ2で陰極電解処理した後、電流密度３〜３０×１０2Ａ／ｍ2でさらに陰極電解処理する２段階の電解処理にて形成することを特徴とする（１）〜（３）の一つに記載の塗装密着性に優れた表面処理金属板の製造方法、
である。
That is, the main point of the present invention is that
(1) Cathodic electrolytic treatment of a metal oxide film and / or metal hydroxide film containing at least one of Si, Ti, Zr, V, Nb, Ta, P, and W on at least one surface of a metal material The formed surface-treated metal plate, wherein the metal oxide film and / or metal hydroxide film is an independent granular deposit formed by the cathodic electrolytic treatment or a granular deposit in contact with each other. In addition, the long diameter per one is 5 nm or more and 300 nm or less, and it is composed of granular precipitates present at 10 or more in 1 × 10 −12 m 2 , and has excellent paint adhesion. Surface treatment metal plate,
(2) The surface-treated metal plate excellent in coating adhesion according to (1), wherein the metal material is a steel sheet surface-treated with plating containing Zn,
(3) An organic resin film having at least one of a carboxyl group, a hydroxyl group, and a sulfonic acid group is formed on the metal oxide film and / or metal hydroxide film, and the film has a thickness of 0.1 μm to 5.0 μm. (1) or (2) a surface-treated metal plate excellent in coating adhesion, characterized by being applied in a thickness;
(4) The metal oxide film and / or metal hydroxide film is mainly composed of a fluoro metal compound, and at least one of Si, Ti, Zr, V, Nb, Ta, P, and W is a metal species. (1) to (3), wherein the metal material is formed by cathodic electrolysis at a current density of 0.5 to 30 × 10 2 A / m 2 and a temperature of 20 ° C. to 60 ° C. ), A method for producing a surface-treated metal sheet having excellent paint adhesion,
(5) The metal oxide film and / or metal hydroxide film is mainly composed of a fluoro metal compound, and at least one of Si, Ti, Zr, V, Nb, Ta, P, and W is a metal species. In the treatment bath included, the current density at the initial voltage application up to 0.1 second is 0.5 to 5 × 10 2 A / m 2 , and the current density after 0.1 second is 1 to 30 × 10 2 A / m. The method for producing a surface-treated metal plate excellent in coating adhesion according to any one of (1) to (3), wherein the metal material is formed by cathodic electrolysis at m 2
(6) The metal oxide film and / or metal hydroxide film is mainly composed of a fluoro metal compound, and at least one of Si, Ti, Zr, V, Nb, Ta, P, and W is a metal species. in the processing bath containing as, after cathodic electrolytic treatment of metal materials at a current density of 0.5~20 × 10 2 a / m 2 , further cathodic electrolysis at a current density of 3~30 × 10 2 a / m 2 2 The method for producing a surface-treated metal sheet having excellent coating adhesion according to any one of (1) to (3), characterized in that it is formed by electrolytic treatment in a stage,
It is.
本発明は、環境負荷の高い６価クロムを含まず、優れた塗装後の皮膜密着性を有し、かつ高い耐食性能を有する表面処理金属板を提供するもので、今後の環境対応の材料として非常に有望であり、各産業分野への寄与も大きい。 The present invention provides a surface-treated metal plate that does not contain hexavalent chromium, which has a high environmental impact, has excellent coating adhesion after coating, and has high corrosion resistance. It is very promising and contributes greatly to various industrial fields.
本発明では、金属材料の少なくとも片面に、Ｓｉ、Ｔｉ、Ｚｒ、Ｖ、Ｎｂ、Ｔａ、Ｐ、Ｗを少なくとも一種含有する金属酸化物系皮膜及び／又は金属水酸化物系皮膜を、フルオロ錯イオン等を含むフッ素化合物水溶液中での金属材料の陰極電解処理にて生じさせた、粒状の形態である特定の大きさ、個数の析出物であって、独立したものとして、もしくは隣どうしで接触したものとして形成した析出物により構成したことを特徴とする。Ｓｉ、Ｔｉ、Ｚｒ、Ｖ、Ｎｂ、Ｔａ、Ｐ、Ｗを少なくとも一種含有する金属酸化物系皮膜及び／又は金属水酸化物系皮膜は、不可避的に混入する不純物を含んでいても構わない。 In the present invention, a metal oxide film and / or a metal hydroxide film containing at least one of Si, Ti, Zr, V, Nb, Ta, P, and W is provided on at least one surface of a metal material. A specific size and number of precipitates in the form of particles, produced by cathodic electrolysis of a metal material in an aqueous solution of a fluorine compound containing, etc., in contact with each other as independent or adjacent to each other It is characterized by comprising the precipitate formed as a thing. The metal oxide film and / or metal hydroxide film containing at least one of Si, Ti, Zr, V, Nb, Ta, P, and W may contain impurities that are inevitably mixed.
本発明におけるフルオロ金属化合物を主体とする処理浴は、金属イオンとフッ素イオンが共存する水溶液、及び／又は、金属とフッ酸でなる錯イオンを含む水溶液であり、ここでのフルオロ金属化合物における金属種は、金属材料の表面の析出物により構成される金属酸化物皮膜及び／又は金属水酸化物皮膜における金属種（Ｓｉ、Ｔｉ、Ｚｒ、Ｖ、Ｎｂ、Ｔａ、Ｐ、Ｗのうちの少なくとも一種）と同じである。金属イオンとフッ素イオンが共存する水溶液におけるフッ素イオンは、金属に対して４倍以上のモル比で存在するのが好ましい。また、金属とフッ酸でなる錯イオンを含む水溶液におけるフッ酸は、金属に対して４倍以上のモル比で存在するのが好ましい。このような水溶液（処理液）中では、フッ素イオンが関与した金属イオンと酸化物及び／または水酸化物との平衡反応がある。フッ素イオンの消費、水素イオンの還元により、金属イオンが酸化物及び／又は水酸化物になる反応が進むと考えている。析出させたい基材を処理液に浸漬させることだけでは、きわめてゆっくりとした析出しか起こらないのに対し、不溶性電極を浸漬して、析出させたい基材に数ｍＶ以上のカソード過電圧を印加すると、析出反応が飛躍的に増大する。この際、電流密度０．５〜３０×１０2Ａ／ｍ2、温度２０℃〜６０℃で陰極電解処理を施すと、基材表面に粒状析出物が形成される。電流密度が０．５〜３０×１０2Ａ／ｍ2の範囲を外れた場合でも、処理浴の組成によっては粒状析出物が形成されることがあるが、形状が小さく、あるいは大きくなりすぎたり、分布が少ない、あるいは多すぎたりして密着性に寄与しないことが多い。電流密度の好ましい範囲は１〜２０×１０2Ａ／ｍ2、より好ましい範囲は２〜１５×１０2Ａ／ｍ2である。処理浴温度が２０℃未満では、温度低下による反応性の低下が成膜を阻害する場合があり、また反応により固形物（析出物）が生成しやすくなる懸念がある。６０℃を超えると、処理浴の蒸発が激しくなり、また温度差による処理むらが生じやすくなるため安定した連続操業には不適となる。より好ましい範囲は３０℃〜６０℃である。 The treatment bath mainly composed of a fluoro metal compound in the present invention is an aqueous solution in which metal ions and fluorine ions coexist and / or an aqueous solution containing complex ions composed of metal and hydrofluoric acid, and the metal in the fluoro metal compound here The seed is a metal species (at least one of Si, Ti, Zr, V, Nb, Ta, P, and W in a metal oxide film and / or a metal hydroxide film constituted by precipitates on the surface of a metal material. ). Fluorine ions in an aqueous solution in which metal ions and fluorine ions coexist are preferably present in a molar ratio of 4 times or more with respect to the metal. Moreover, it is preferable that the hydrofluoric acid in the aqueous solution containing a complex ion composed of a metal and hydrofluoric acid is present in a molar ratio of 4 times or more with respect to the metal. In such an aqueous solution (treatment liquid), there is an equilibrium reaction between metal ions involving oxides and / or oxides and / or hydroxides. It is considered that the reaction of metal ions to oxides and / or hydroxides proceeds by consumption of fluorine ions and reduction of hydrogen ions. By immersing the substrate to be deposited in the treatment solution, only very slow precipitation occurs, whereas when an insoluble electrode is immersed and a cathode overvoltage of several mV or more is applied to the substrate to be deposited, The precipitation reaction increases dramatically. At this time, when a cathode electrolytic treatment is performed at a current density of 0.5 to 30 × 10 2 A / m 2 and a temperature of 20 ° C. to 60 ° C., granular precipitates are formed on the surface of the substrate. Even when the current density is out of the range of 0.5 to 30 × 10 2 A / m 2, a granular precipitate may be formed depending on the composition of the treatment bath, but the shape is too small or too large. Often, the distribution is small or too large and does not contribute to adhesion. A preferable range of the current density is 1 to 20 × 10 2 A / m 2 , and a more preferable range is 2 to 15 × 10 2 A / m 2 . When the treatment bath temperature is less than 20 ° C., a decrease in reactivity due to a decrease in temperature may inhibit film formation, and there is a concern that a solid (precipitate) is likely to be generated by the reaction. When it exceeds 60 ° C., the evaporation of the treatment bath becomes violent and the treatment unevenness due to the temperature difference is likely to occur, so that it is not suitable for stable continuous operation. A more preferable range is 30 ° C to 60 ° C.
金属酸化物皮膜及び／又は金属水酸化物皮膜の粒状析出物について、本発明にて見出した好ましい条件は、粒状析出物の１個あたりの長径が５ｎｍ以上３００ｎｍ以下であり、かつ１×１０-12ｍ2に１０個以上形成すること、である。ここで長径とは、粒状析出物を真上から見たときの最も長い径の長さを示す。粒子１個あたりの長径が５ｎｍ未満では、塗装密着性に対する寄与が小さく効果が得られない。１個あたりの長径が３００ｎｍを超える粒子があると、その数にもよるが、塗装密着性を低下させるため好ましくない。これは、粒子があまり大きく成長しすぎると球状形状に近くなり、表面から脱離しやすくなるためと考えられる。したがって、析出物の高さは特に規定していないが、あまり高すぎるものは好ましくない。粒状析出物１個あたりの好ましい長径は１０〜２００ｎｍ、より好ましくは１０〜１５０ｎｍである。また、析出物が１×１０-12ｍ2に１０個未満しか形成されていない状態では、塗装密着性に対する寄与が小さく効果が得られない。一方、析出物が極端に多くなると、表面処理金属板とその上に形成する有機樹脂皮膜との接触面積が少なくなって、アンカー効果を含む総合的な密着性に影響する。そのため、１×１０-12ｍ2あたりの析出物の個数の上限は４００個程度である。従って、１×１０-12ｍ2あたりの析出物の個数は、好ましくは１０〜４００個であり、より好ましくは５０〜３００個である。 Regarding the granular precipitates of the metal oxide film and / or metal hydroxide film, the preferred conditions found in the present invention are that the major axis per granular precipitate is 5 nm or more and 300 nm or less, and 1 × 10 − Forming 10 or more in 12 m 2 . Here, the long diameter indicates the length of the longest diameter when the granular precipitate is viewed from directly above. If the major axis per particle is less than 5 nm, the contribution to the coating adhesion is small and the effect cannot be obtained. If there is a particle having a major axis exceeding 300 nm per particle, although it depends on the number, it is not preferable because the coating adhesion is lowered. This is presumably because when the particles grow too large, they become close to a spherical shape and are easily detached from the surface. Therefore, the height of the precipitate is not particularly specified, but too high is not preferable. The preferred major axis per granular precipitate is 10 to 200 nm, more preferably 10 to 150 nm. Moreover, in the state in which only 10 precipitates are formed in 1 × 10 −12 m 2 , the contribution to the coating adhesion is small and the effect cannot be obtained. On the other hand, when the amount of precipitates is extremely large, the contact area between the surface-treated metal plate and the organic resin film formed thereon is reduced, which affects the overall adhesion including the anchor effect. Therefore, the upper limit of the number of precipitates per 1 × 10 −12 m 2 is about 400. Therefore, the number of precipitates per 1 × 10 −12 m 2 is preferably 10 to 400, and more preferably 50 to 300.
粒状析出物の大きさ、形態、数量は、ＳＥＭ（走査型電子顕微鏡）、ＴＥＭ（透過型電子顕微鏡）、ＡＦＭ（原子間力顕微鏡）、ＳＴＭ（走査型トンネル電子顕微鏡）など、表面の形態を観察する分析機器を適用することにより容易に測定できる。粒状析出物の形態に関しては様々なものが観察され、例えば図１の電気亜鉛めっき鋼板上に形成した析出物のＳＥＭ写真に示すように、概ね粒状の形態を示し、一部台形状の形態などが観察される。 The size, shape, and quantity of the granular precipitates are the same as the surface morphology such as SEM (Scanning Electron Microscope), TEM (Transmission Electron Microscope), AFM (Atomic Force Microscope), STM (Scanning Tunnel Electron Microscope). It can be easily measured by applying an analytical instrument to be observed. Various forms of granular precipitates are observed. For example, as shown in the SEM photograph of the precipitates formed on the electrogalvanized steel sheet in FIG. Is observed.
また、さらに段階的に電流密度を変化させることで、電圧印加初期の核発生をより均一化し、結果として均一な粒状析出物の皮膜が得られ、塗装後の密着性をより向上させることができる。その好ましい方法として、フルオロ金属化合物を主体とする処理浴中で、０．１秒までの電圧印加初期の電流密度が０．５〜５×１０2Ａ／ｍ2、その後の電流密度が１〜３０×１０2Ａ／ｍ2にて陰極電解処理して酸化物系皮膜及び／又は水酸化物系皮膜を形成する方法（この場合、電圧印加初期の電流密度としては、好ましくは０．５〜３×１０2Ａ／ｍ2であり、その後の電流密度は好ましくは１〜２０×１０2Ａ／ｍ2である）、フルオロ金属化合物を主体とする処理浴中で、電流密度０．５〜２０×１０2Ａ／ｍ2で陰極電解処理した後電流密度３〜３０×１０2Ａ／ｍ2で陰極電解処理する２段階の電解処理にて酸化物系皮膜及び／又は水酸化物系皮膜を形成する方法（この場合、１段目の電流密度は、好ましくは１〜１０×１０2Ａ／ｍ2であり、２段目の電流密度は、好ましくは３〜２０×１０2Ａ／ｍ2である）が挙げられる。これら以外にも、初期にパルス通電により核生成させる方法も適用可能である。 Further, by changing the current density in a stepwise manner, nucleation at the initial stage of voltage application can be made more uniform, and as a result, a film of uniform granular precipitates can be obtained and adhesion after coating can be further improved. . As a preferable method, in a treatment bath mainly composed of a fluoro metal compound, the current density at the initial stage of voltage application up to 0.1 second is 0.5 to 5 × 10 2 A / m 2 , and the current density thereafter is 1 to 1. A method of forming an oxide film and / or a hydroxide film by cathodic electrolysis at 30 × 10 2 A / m 2 (in this case, the current density at the initial stage of voltage application is preferably 0.5 to 3 × 10 2 A / m 2 , and the subsequent current density is preferably 1 to 20 × 10 2 A / m 2 ). In a treatment bath mainly composed of a fluoro metal compound, the current density is 0.5 to Oxide-based film and / or hydroxide-based film in a two-stage electrolytic process in which cathode electrolysis is performed at 20 × 10 2 A / m 2 followed by cathodic electrolysis at a current density of 3 to 30 × 10 2 A / m 2 method of forming (in this case, the current density of the first stage is preferably 1~10 × 10 2 a / 2, the current density of the second stage is preferably from 3~20 × 10 2 A / m 2 ) and the like. In addition to these, a method of generating nuclei by pulse energization in the initial stage is also applicable.
本発明において用いられるフルオロ金属化合物を主体とする処理浴の構成成分である、フルオロ錯イオン等を含むフッ素化合物としては、ヘキサフルオロチタン酸、ヘキサフルオロジルコニウム酸、ヘキサフルオロケイ酸、ヘキサフルオロニオブ酸、ヘキサフルオロタンタル酸など、あるいはこれらの塩、例えばアンモニウム塩、カリウム塩、ナトリウム塩などを用いることができ、これらに関しては特に制約は無い。この錯イオンは、金属イオンと該金属イオンに対してモル比４倍以上のフッ素を含有する化合物が少なくとも結合した錯イオンでもよい。すなわち、金属とフッ素以外の元素が錯イオン中に含まれていてもよい。塩を用いる場合はそのカチオン種によって飽和溶解度が異なるため、成膜濃度範囲を考慮して選定しなければならない場合がある。 Fluorine compounds containing fluoro complex ions and the like, which are constituents of a treatment bath mainly composed of a fluoro metal compound used in the present invention, include hexafluorotitanic acid, hexafluorozirconic acid, hexafluorosilicic acid, hexafluoroniobic acid. , Hexafluorotantalic acid and the like, or salts thereof such as ammonium salt, potassium salt, sodium salt and the like can be used, and there are no particular restrictions on these. This complex ion may be a complex ion in which a metal ion and a compound containing fluorine having a molar ratio of 4 times or more with respect to the metal ion are bonded. That is, elements other than metals and fluorine may be contained in the complex ions. When a salt is used, the saturation solubility varies depending on the cation species, and therefore, it may be necessary to select a salt concentration range.
また、陰極電解処理において、フルオロ錯イオン等を含むフッ素化合物とともに、それと併用可能な別の化合物を用いて複合酸化物系皮膜及び／又は水酸化物系皮膜を形成することが可能である。フルオロ錯イオン等と同程度のｐＨを有するカチオンを含有する化合物であればよく、例えば、バナジン酸、メタバナジン酸、硫酸バナジル、硫酸バナジウム、リン酸バナジウム、重リン酸バナジウムなどのバナジウム化合物、また、例えば、リン酸、リン酸三アンモニウム、リン酸水素二アンモニウム、リン酸二水素アンモニウム、リン酸カリウム、リン酸二水素カリウム、リン酸ナトリウム、リン酸水素二ナトリウム、リン酸二水素ナトリウム、リン酸二水素カルシウム、リン酸水素マグネシウム、リン酸二水素マグネシウム等のリン酸化合物、そしてタングステン酸アンモニウム、タングステン酸ナトリウムなどのタングステン酸塩、硝酸酸化ジルコニウム、硫酸ジルコニウムなどのジルコニウム化合物、が挙げられる。これらは、一種もしくは二種以上を複合して用いることも可能である。 In the cathode electrolytic treatment, it is possible to form a composite oxide film and / or a hydroxide film using a fluorine compound containing a fluoro complex ion or the like and another compound that can be used in combination therewith. Any compound containing a cation having a pH comparable to that of a fluoro complex ion, for example, vanadium compounds such as vanadic acid, metavanadic acid, vanadyl sulfate, vanadium sulfate, vanadium phosphate, and vanadium biphosphate, For example, phosphoric acid, triammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium phosphate, potassium dihydrogen phosphate, sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, phosphoric acid Examples thereof include phosphoric acid compounds such as calcium dihydrogen phosphate, magnesium hydrogen phosphate and magnesium dihydrogen phosphate, and tungstates such as ammonium tungstate and sodium tungstate, and zirconium compounds such as zirconium nitrate and zirconium sulfate. These can be used alone or in combination of two or more.
また本発明において用いられるフッ素イオンは、フッ化水素酸あるいはその塩、例えば、アンモニウム塩、カリウム塩、ナトリウム塩などにより供給することができる。本発明で用いるフッ素イオン源に関しては特に制約は無いが、塩を用いる場合はそのカチオン種によって飽和溶解度が異なるため、成膜濃度範囲を考慮して選定しなければならない場合がある。 The fluorine ion used in the present invention can be supplied by hydrofluoric acid or a salt thereof, for example, ammonium salt, potassium salt, sodium salt, or the like. The fluorine ion source used in the present invention is not particularly limited. However, when a salt is used, the saturation solubility differs depending on the cation species, so that it may be necessary to select a film concentration range.
また、金属の酸化物系皮膜及び／又は水酸化物系皮膜析出を促進させるために、同時反応である水素ガス生成反応を促進する方法があるが、水素ガス発生を促進すべく処理液ｐＨをより低くすると、皮膜が形成されなかったり、不均一な、あるいは密着力の乏しい皮膜が形成されたりしてしまう。そのため、処理液ｐＨに着目して検討した結果、処理液ｐＨは２〜７が好ましいことを見出した。より好ましくは３〜４であった。処理液ｐＨが２未満では水素発生による皮膜の阻害が起こりやすく、健全な皮膜形成のための電位制御が難しい。一方７より大きい場合は液が不安定であるし、また凝集したものが析出する場合があり、密着力が不十分であった。 Further, in order to promote the deposition of metal oxide film and / or hydroxide film, there is a method of promoting a hydrogen gas generation reaction which is a simultaneous reaction. If it is lower, a film is not formed, or a film that is uneven or has poor adhesion is formed. Therefore, as a result of examining the treatment solution pH, it was found that the treatment solution pH is preferably 2 to 7. More preferably, it was 3-4. If the treatment solution pH is less than 2, the coating is likely to be inhibited by the generation of hydrogen, and it is difficult to control the potential for forming a healthy coating. On the other hand, when it is larger than 7, the liquid is unstable, and agglomerated material may be precipitated, resulting in insufficient adhesion.
また、塩濃度、温度を管理し、あるいは基材表面上での水素発生反応抑制・促進を目的とした有機物を添加することにより、析出速度を制御することも可能である。 It is also possible to control the deposition rate by controlling the salt concentration and temperature, or adding an organic substance for the purpose of suppressing or promoting the hydrogen generation reaction on the substrate surface.
本発明で用いる金属材料としては、導電性材料であれば適用できるため特に限定しないが、Ｚｎを含有するめっきで表面処理した鋼板を用いた場合に著しい効果が得られる。鋼材の被覆層として、特にＺｎめっきもしくはＺｎ−Ｎｉ、Ｚｎ−Ｆｅ、Ｚｎ−Ｍｇ、Ｚｎ−Ａｌ−Ｍｇ−Ｓｉ等のＺｎ系合金めっきを施したものが最も優れた特性を示し、クロメート皮膜代替可能である。また、ＡｌもしくはＡｌとＳｉ、Ｚｎ、Ｍｇの少なくとも１種からなる合金、例えばＡｌ−Ｓｉ系合金、Ａｌ−Ｚｎ系合金、Ａｌ−Ｓｉ−Ｍｇ合金等のＡｌ系めっき、もしくはＳｎとＺｎの合金めっき等にも適用可能である。その他、Ａｌキルド鋼板、Ｔｉ、Ｎｂ等を添加した極低炭素鋼板、及びこれらにＰ、Ｓｉ、Ｍｎ等の強化元素を添加した高強度鋼板、及びそれらに各種めっきを施した材料、ステンレス鋼に代表されるＣｒ含有鋼等種々のものが適用できる。また、その他の金属Ａｌ及びＡｌ系合金材料、金属Ｔｉ及びＴｉ系合金材料、Ｍｇ系合金材料等、Ｆｅ系以外の金属材料に適用することが可能である。また、基材に導電性があれば成膜可能であるが、導電率が０．１Ｓ／ｃｍ以上あることが好ましい。これ未満の導電率では抵抗が大きいため析出効率が低い。 The metal material used in the present invention is not particularly limited because it can be applied as long as it is a conductive material, but a remarkable effect can be obtained when a steel sheet surface-treated with plating containing Zn is used. As the steel coating layer, Zn plating or Zn-based alloy plating such as Zn-Ni, Zn-Fe, Zn-Mg, Zn-Al-Mg-Si, etc. shows the most excellent characteristics, and it replaces the chromate film. Is possible. In addition, Al or an alloy composed of at least one of Al and Si, Zn, and Mg, for example, Al-based plating such as Al-Si alloy, Al-Zn alloy, Al-Si-Mg alloy, or Sn and Zn alloy It can also be applied to plating. In addition, Al killed steel plates, ultra-low carbon steel plates to which Ti, Nb, etc. are added, high-strength steel plates to which reinforcing elements such as P, Si, Mn are added, and materials obtained by applying various platings to them, stainless steel Various types such as a typical Cr-containing steel can be applied. Further, the present invention can be applied to metal materials other than Fe, such as other metal Al and Al alloy materials, metal Ti and Ti alloy materials, and Mg alloy materials. A film can be formed if the substrate has conductivity, but the conductivity is preferably 0.1 S / cm or more. If the conductivity is less than this, the resistance is large, so the deposition efficiency is low.
また、金属酸化物系皮膜及び／又は金属水酸化物系皮膜を陰極電解処理にて形成した後、その上層にさらにカルボキシル基、水酸基、スルホン酸基、の少なくとも一種を有する有機樹脂系皮膜を０．１μｍ〜５．０μｍの膜厚で施すことにより、耐食性と塗装密着性のみならず、加工性や耐傷付性、耐結露性、耐洗浄液性など種々の特性を付与することができる。一般の有機系樹脂皮膜でかまわないが、カルボキシル基、水酸基、スルホン酸基の少なくとも一種を含有する樹脂を主体とする皮膜を使用することにより、特に酸化物皮膜系との相性がよく、高い密着性が得られるため性能が良好である。この樹脂系皮膜には、シリカや防錆顔料が含まれているとさらに良好な特性を示す。 Moreover, after forming a metal oxide film and / or a metal hydroxide film by cathodic electrolysis, an organic resin film having at least one of a carboxyl group, a hydroxyl group, and a sulfonic acid group is further formed on the upper layer. By applying with a film thickness of 1 μm to 5.0 μm, not only corrosion resistance and paint adhesion, but also various properties such as workability, scratch resistance, condensation resistance, and washing liquid resistance can be imparted. A general organic resin film may be used, but by using a film mainly composed of a resin containing at least one of a carboxyl group, a hydroxyl group, and a sulfonic acid group, the compatibility with the oxide film system is particularly good and high adhesion is achieved. Therefore, the performance is good. If this resin-based film contains silica or a rust-preventive pigment, even better properties are exhibited.
本発明の有機樹脂系皮膜の厚みは、通常の用途では０．１μｍ以上５．０μｍ以下が好ましい。０．１μｍ未満では耐食性に対する寄与が少ない。５．０μｍ以上では効果が飽和し不経済である。有機樹脂系皮膜の厚みは、好ましくは０．１μｍ以上３．０μｍ以下である。 The thickness of the organic resin film of the present invention is preferably 0.1 μm or more and 5.0 μm or less for normal use. If it is less than 0.1 μm, the contribution to the corrosion resistance is small. If it is 5.0 μm or more, the effect is saturated and uneconomical. The thickness of the organic resin film is preferably 0.1 μm or more and 3.0 μm or less.
以上の金属酸化物系皮膜及び／または金属水酸化物系皮膜を被覆した金属板、及びその上層に有機樹脂系皮膜を施した金属板の用途としては、家電製品、自動車、建材等に使用される、耐食性の向上した種々の鋼板や、上塗り塗膜との密着性の向上したラミネート板や樹脂貼り付け板が挙げられる。 The metal plate coated with the above metal oxide film and / or metal hydroxide film and the metal plate coated with an organic resin film on the upper layer are used for home appliances, automobiles, building materials, etc. And various steel plates with improved corrosion resistance, laminate plates with improved adhesion to the top coat film, and resin pasting plates.
次いで、電解処理設備の一例を示す。
図３に、片側もしくは両面の表面が導電性である金属材料に連続して金属酸化物系皮膜及び／または金属水酸化物系皮膜を成膜する設備の構成図を示す。主たる構成は、連続して搬送される金属材料１の表面に接触したコンダクターロール１１，１２と金属材料１の導電面と相対向して配置された電極４の間に電解液３を充填し、コンダクターロール１１，１２と電極６の間に、コンダクターロール側を（−）極、電極側を（＋）極として、直流電源装置６を配置している。片面処理の場合には、片側に電解マスクを配置した構成とし、同じ側のコンダクターロール及び電極を切ればよい。直流電源装置６とコンダクターロール１１，１２の間には、開閉器７が設置されており、この開閉器７を閉にすることにより、コンダクターロール１１，１２と電極４の間に電圧を印加する。また開閉器７を開とすることにより電圧印加を中断する。直流電源装置６は、アップスロープ型電圧印加方式のものやパルス型電圧印加方式のタイプであってもかまわない。また、電解液３には液を均一に電極表面に供給するため、槽内循環を加える場合がある。また、導電性材料１の搬送ロールとして、電解槽２の入出側には、リンガーロール（図示省略）が設置され、電解液３の槽外への流出を抑制しており、槽内には、シンクロール１３、１４が設置され、電極４と導電性材料１の距離を一定に保持している。これらの装置系は縦型であっても構わない。
Next, an example of electrolytic treatment equipment is shown.
FIG. 3 shows a configuration diagram of equipment for continuously forming a metal oxide film and / or a metal hydroxide film on a metal material whose one or both surfaces are conductive. The main configuration is that the electrolyte roll 3 is filled between the conductor rolls 11 and 12 that are in contact with the surface of the metal material 1 that is continuously conveyed and the electrode 4 that is disposed opposite to the conductive surface of the metal material 1. Between the conductor rolls 11 and 12 and the electrode 6, the DC power supply device 6 is arranged with the conductor roll side as the (−) pole and the electrode side as the (+) pole. In the case of single-sided treatment, an electrolytic mask is arranged on one side, and the conductor roll and electrode on the same side may be cut. A switch 7 is installed between the DC power supply device 6 and the conductor rolls 11 and 12, and a voltage is applied between the conductor rolls 11 and 12 and the electrode 4 by closing the switch 7. . The voltage application is interrupted by opening the switch 7. The DC power supply device 6 may be an up-slope type voltage application type or a pulse type voltage application type. Further, in order to supply the electrolyte 3 uniformly to the electrode surface, circulation in the tank may be added. In addition, as a transport roll for the conductive material 1, a ringer roll (not shown) is installed on the entry / exit side of the electrolytic cell 2 to suppress the outflow of the electrolytic solution 3 to the outside of the cell. Sink rolls 13 and 14 are installed to keep the distance between the electrode 4 and the conductive material 1 constant. These apparatus systems may be vertical.
図４に、片側もしくは両面の表面が導電性である金属材料に、異なる電流密度で段階的に金属酸化物系皮膜及び／または金属水酸化物系皮膜を成膜する設備の構成図を示す。主たる構成は連続して搬送される金属材料１の導電面と相対向して、金属材料１の進行方向に、電源装置の異なる電極４、電極５を順次設置し、金属材料１と電極４、電極５の間に電解液３を充填し、金属材料１側を（−）極、電極４、電極５側を（＋）極として、直流電源装置６から並列に接続し、電極との間にトランス９、１０を配置している。トランス９、１０により電圧を任意に変化させ、異なる電流密度で段階的に電解処理を行うことができる。片面処理の場合には、片側に電解マスクを配置した構成とし、同じ側のコンダクターロール及び電極を切ればよい。直流電源装置６と電極４、５の間には、開閉器７、８が配置されており、この開閉器７、８を閉にすることにより、電極４、電極５の間に異なる電圧を印加している。また、開閉器７、８を開とすることにより、電圧印加を中断する。直流電源装置６は、アップスロープ型電圧印加方式のものやパルス型電圧印加方式のタイプであってもかまわない。また、金属材料１の搬送ロールとして、電解槽２の入出側には、リンガーロール（図示省略）が設置され、電解液３の槽外への流出を抑制しており、槽内には、シンクロール１３、１４が設置され、電極４、電極５と金属材料１の距離を一定に保持している。 これらの装置系は縦型であっても構わない。 FIG. 4 shows a configuration diagram of equipment for forming a metal oxide film and / or a metal hydroxide film in stages at different current densities on a metal material whose one or both surfaces are conductive. The main structure is such that the electrodes 4 and 5 of the power supply device are sequentially installed in the advancing direction of the metal material 1 in opposition to the conductive surface of the metal material 1 that is continuously conveyed. The electrolyte solution 3 is filled between the electrodes 5, the metal material 1 side is set as the (−) electrode, the electrode 4, and the electrode 5 side is set as the (+) electrode, and is connected in parallel from the DC power supply device 6. Transformers 9 and 10 are arranged. The voltage can be arbitrarily changed by the transformers 9 and 10, and the electrolytic treatment can be performed step by step at different current densities. In the case of single-sided treatment, an electrolytic mask is arranged on one side, and the conductor roll and electrode on the same side may be cut. Switches 7 and 8 are arranged between the DC power supply 6 and the electrodes 4 and 5, and different voltages are applied between the electrodes 4 and 5 by closing the switches 7 and 8. is doing. Moreover, voltage application is interrupted by opening the switches 7 and 8. The DC power supply device 6 may be an up-slope type voltage application type or a pulse type voltage application type. In addition, a ringer roll (not shown) is installed on the entrance / exit side of the electrolytic cell 2 as a transport roll for the metal material 1 to suppress the outflow of the electrolytic solution 3 to the outside of the cell. Rolls 13 and 14 are installed to keep the distance between the electrodes 4 and 5 and the metal material 1 constant. These apparatus systems may be vertical.
本発明においては、金属酸化物系皮膜及び／又は金属水酸化物系皮膜の上層に有機樹脂系皮膜を施す前、もしくは塗料を塗装する前に、リン酸塩処理等の化成処理を加えることにより、あるいは同様のクロムフリー皮膜の更なる複層化処理により、必要に応じてさらに耐食性向上や機能付与を図ることが可能である。また、めっき後の処理として、化成処理以前に、溶融めっき後の外観均一処理であるゼロスパングル処理、めっき層の改質処理である焼鈍処理、表面状態、材質調整のための調質圧延等があり得るが、本発明においては、特にこれらを限定せず、適用することも可能である。 In the present invention, by applying a chemical conversion treatment such as a phosphate treatment before applying an organic resin film on the metal oxide film and / or metal hydroxide film or before applying a paint. Alternatively, by further multilayering treatment of the same chromium-free coating, it is possible to further improve the corrosion resistance and impart functions as necessary. In addition, as post-plating treatment, before chemical conversion treatment, there are zero spangle treatment that is uniform appearance after hot dipping, annealing treatment that is modification treatment of plating layer, surface condition, temper rolling for material adjustment, etc. However, in the present invention, these are not particularly limited and can be applied.
以下に、本発明を実施例により具体的に説明する。 Hereinafter, the present invention will be specifically described by way of examples.
〔実施例１〕
表１に示す各種処理液を用い、表２に示す電解条件にて、白金を対極としたカソード電解により各種金属材料に金属酸化物皮膜及び／又は金属水酸化物皮膜を成膜後、水洗、乾燥して供試材とした。表面の皮膜析出状態は、走査型電子顕微鏡を用い３００００倍で観察し、粒状析出物の大きさ、個数を測定した。
[Example 1]
Using various treatment liquids shown in Table 1 and forming metal oxide films and / or metal hydroxide films on various metal materials by cathode electrolysis using platinum as a counter electrode under the electrolysis conditions shown in Table 2, washing with water, It dried and it was set as the test material. The surface film deposition state was observed at 30000 times using a scanning electron microscope, and the size and number of granular precipitates were measured.
金属板として、以下の金属材料を使用した。
ＥＧ：電気亜鉛めっき鋼板；板厚１．０ｍｍ、めっき付着量２０ｇ／ｍ2
ＺＬ：電気亜鉛−Ｎｉ合金めっき鋼板；板厚０．８ｍｍ、めっき付着量２０ｇ／ｍ2
ＧＩ：溶融亜鉛めっき鋼板；板厚０．９ｍｍ、めっき付着量５０ｇ／ｍ2
ＧＡ：溶融亜鉛−鉄合金めっき鋼板；板厚０．８ｍｍ、めっき付着量４５ｇ／ｍ2
ＳＵＳ：ステンレス鋼板；板厚０．５ｍｍ、フェライト系ステンレス鋼板、
鋼成分：Ｃ ０．００８質量％、Ｓｉ ０．０７質量％、Ｍｎ ０．１５質量％、Ｐ ０．０１１質量％、Ｓ ０．００９質量％、Ａｌ ０．０６７質量％、Ｃｒ １７．３質量％、Ｍｏ １．５１質量％、Ｎ ０．００５１質量％、Ｔｉ ０．２２質量％、残部Ｆｅ及び不可避的不純物
The following metal materials were used as the metal plate.
EG: electrogalvanized steel sheet; plate thickness 1.0 mm, plating adhesion 20 g / m 2
ZL: electrogalvanized-Ni alloy plated steel sheet; plate thickness 0.8 mm, plating adhesion 20 g / m 2
GI: hot dip galvanized steel sheet; plate thickness 0.9 mm, plating adhesion 50 g / m 2
GA: hot dip zinc-iron alloy plated steel sheet; plate thickness 0.8 mm, plating adhesion 45 g / m 2
SUS: stainless steel plate; plate thickness 0.5 mm, ferritic stainless steel plate,
Steel composition: C 0.008 mass%, Si 0.07 mass%, Mn 0.15 mass%, P 0.011 mass%, S 0.009 mass%, Al 0.067 mass%, Cr 17.3 mass %, Mo 1.51 mass%, N 0.0051 mass%, Ti 0.22 mass%, balance Fe and inevitable impurities
作製した供試材に対して、以下の塗装後密着性の評価を行った。その結果を表３に示す。 The following post-coating adhesion evaluation was performed on the prepared test materials. The results are shown in Table 3.
（１）塗装密着性
一次塗料密着性は、バーコーターを用いてメラミンアルキッド樹脂塗料（関西ペイント（株）製、アミラック＃１０００）を乾燥膜厚３０μｍになるように塗布し、炉温１３０℃で２０分間焼き付けた。次に、一晩放置した後、７ｍｍのエリクセン加工を施した。その加工部に粘着テープ（ニチバン（株）：商品名セロテープ（登録商標））を張り付け、速やかに斜め４５°の方向に引っ張って剥離させて、剥離面積率により、以下の評価を行った。
５：剥離面積率０％
４：剥離面積率５％未満
３：剥離面積率５％以上、１０％未満
２：剥離面積率１０％以上、５０％未満
１：剥離面積率５０％以上
(1) Paint adhesion The primary paint adhesion was applied by applying a melamine alkyd resin paint (Amirac # 1000, manufactured by Kansai Paint Co., Ltd.) to a dry film thickness of 30 μm using a bar coater at a furnace temperature of 130 ° C. Baked for 20 minutes. Next, after leaving overnight, 7 mm Erichsen processing was performed. A pressure-sensitive adhesive tape (Nichiban Co., Ltd .: trade name cello tape (registered trademark)) was attached to the processed part, and was immediately pulled in an oblique 45 ° direction for peeling, and the following evaluation was performed based on the peeled area ratio.
5: peeling area ratio 0%
4: Peel area ratio less than 5% 3: Peel area ratio 5% or more and less than 10% 2: Peel area ratio 10% or more and less than 50% 1: Peel area ratio 50% or more
二次塗料密着性は一次塗料密着性と同様、メラミンアルキッド塗料を塗装し、一晩放置した後、沸騰水に３０分浸漬した。その後、７ｍｍのエリクセン加工を施し、その加工部に粘着テープ（ニチバン（株）：商品名セロテープ（登録商標））を張り付け、速やかに斜め４５°の方向に引っ張って剥離させて、剥離面積率により、以下の評価を行った。
５：剥離面積率０％
４：剥離面積率５％未満
３：剥離面積率５％以上、１０％未満
２：剥離面積率１０％以上、５０％未満
１：剥離面積率５０％以上
Similar to the primary paint adhesion, the secondary paint adhesion was applied with a melamine alkyd paint, allowed to stand overnight, and then immersed in boiling water for 30 minutes. After that, 7mm Eriksen processing is applied, and adhesive tape (Nichiban Co., Ltd .: trade name cello tape (registered trademark)) is pasted on the processed part, and it is quickly pulled obliquely at a 45 ° angle and peeled off. The following evaluation was performed.
5: peeling area ratio 0%
4: Peel area ratio less than 5% 3: Peel area ratio 5% or more and less than 10% 2: Peel area ratio 10% or more and less than 50% 1: Peel area ratio 50% or more
Ｎｏ．２３〜２５は、粒状の析出物が無く、塗装二次密着性に劣る。Ｎｏ．２６は、粒状析出物が少ない、もしくは出方が不均一で、大きな析出物が見られ、塗装密着性に劣る。
Ｎｏ．１〜２２の本発明例の皮膜構成を用いることにより、良好な塗装後密着性を得ることができる。
No. No. 23 to 25 have no granular precipitates and are inferior in coating secondary adhesion. No. No. 26 has a small amount of granular precipitates or is uneven in appearance, shows large precipitates, and has poor coating adhesion.
No. Good post-coating adhesion can be obtained by using the coating composition of Examples 1 to 22 of the present invention.
〔実施例２〕
実施例１の表１、２の条件にて作製した電解処理皮膜の上に、更に表４に示す有機樹脂皮膜をバーコーターにて塗布し、熱風乾燥炉にて到達板温度１４０℃〜１６０℃で焼き付けた後、水冷、乾燥し、複層皮膜を形成した。その複層皮膜系について、以下に示す各種性能を試験した。その結果を表５に示す。
[Example 2]
The organic resin film shown in Table 4 was further applied with a bar coater on the electrolytic treatment film produced under the conditions shown in Tables 1 and 2 of Example 1, and the ultimate plate temperature was 140 ° C to 160 ° C in a hot air drying furnace. After being baked in, it was cooled with water and dried to form a multilayer film. Various performances shown below were tested for the multilayer coating system. The results are shown in Table 5.
（１）塗料密着性
実施例１と同様の方法にて評価した。
(1) Paint adhesion The evaluation was performed in the same manner as in Example 1.
（２）耐食性
（ｉ）平板
端面・裏面をシールした平板試験片について、ＪＩＳ Ｚ ２３７１に規定されている塩水噴霧試験（ＳＳＴ）を実施し、２４０時間後の白錆の発生率で評価した。耐食性評価基準を以下に示す。
５：白錆発生無し
４：白錆発生率１％未満
３：白錆発生率１％以上、５％未満
２：白錆発生率５％以上、２０％未満
１：白錆発生率２０％以上
(2) Corrosion resistance (i) Flat plate About the flat plate test piece which sealed the end surface and the back surface, the salt spray test (SST) prescribed | regulated to JISZ2371 was implemented, and it evaluated by the incidence rate of the white rust 240 hours afterward. Corrosion resistance evaluation criteria are shown below.
5: No white rust generation 4: White rust generation rate of less than 1% 3: White rust generation rate of 1% or more, less than 5% 2: White rust generation rate of 5% or more, less than 20% 1: White rust generation rate of 20% or more
（ｉｉ）加工材：
端面・裏面をシールした平板試験片について、中央部に７ｍｍエリクセン加工を施した後、ＪＩＳ Ｚ ２３７１に規定されている塩水噴霧試験（ＳＳＴ）を実施し、１２０時間後のエリクセン部の白錆発生率で評価した。耐食性評価基準を以下に示す。
５：白錆発生無し
４：白錆発生率１％未満
３：白錆発生率１％以上、５％未満
２：白錆発生率５％以上、２０％未満
１：白錆発生率２０％以上
(Ii) Processed material:
For flat plate test pieces with end and back surfaces sealed, 7mm Erichsen processing was applied to the center, and then the salt spray test (SST) specified in JIS Z 2371 was conducted. The rate was evaluated. Corrosion resistance evaluation criteria are shown below.
5: No white rust generation 4: White rust generation rate of less than 1% 3: White rust generation rate of 1% or more, less than 5% 2: White rust generation rate of 5% or more, less than 20% 1: White rust generation rate of 20% or more
（３）加工性
防錆油としてＺ３（出光興産製）を塗油後に角筒深絞り加工を実施し、試験後の外観を観察し評価した。ブランク径１００ｍｍ、角筒ポンチ幅５０ｍｍ、肩Ｒ５ｍｍ、しわ押さえ圧９．８ｋＮの条件で絞り加工を行った。評価基準を以下に示す。
５：変化無し
４：僅かに皮膜変色
３：皮膜が変色もしくは僅かに加工傷発生
２：加工傷発生もしくは僅かにカス発生
１：加工傷発生大もしくは皮膜剥離大
(3) Workability After applying Z3 (made by Idemitsu Kosan Co., Ltd.) as a rust-preventing oil, square tube deep drawing was performed, and the appearance after the test was observed and evaluated. Drawing was performed under the conditions of a blank diameter of 100 mm, a square tube punch width of 50 mm, a shoulder R of 5 mm, and a wrinkle holding pressure of 9.8 kN. The evaluation criteria are shown below.
5: No change 4: Discoloration of the film slightly 3: Discoloration of the film or slight processing scratches generated 2: Processing scratches generated or slight residue generated 1: Large processing scratches generated or large film peeling
Ｎｏ．３９、４０は、粒状の析出物が無く、塗装二次密着性、加工部耐食性、加工性に劣る。Ｎｏ．４１は、粒状析出物が少ない、もしくは出方が不均一で、大きな析出物が見られ、塗装密着性や耐食性に劣る。
Ｎｏ．３１〜３８の本発明例の皮膜構成を用いることにより、良好な塗装密着性、耐食性、加工性を得ることができる。
No. Nos. 39 and 40 have no granular precipitates and are inferior in coating secondary adhesion, processed part corrosion resistance, and workability. No. No. 41 has a small amount of granular precipitates or is uneven in appearance, shows large precipitates, and is inferior in coating adhesion and corrosion resistance.
No. Good coating adhesion, corrosion resistance, and workability can be obtained by using the film configurations of the present invention examples of 31 to 38.
１ 金属材料
２ 電解槽
３ 電解液
４、５ 電極
６ 電源
７、８ 開閉器
９、１０ トランス
１１、１２ コンダクターロール
１３、１４ シンクロール
DESCRIPTION OF SYMBOLS 1 Metal material 2 Electrolysis tank 3 Electrolyte solution 4, 5 Electrode 6 Power supply 7, 8 Switch 9, 10 Transformer 11, 12 Conductor roll 13, 14 Sink roll
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| KR20150075765A (en) * | 2013-12-26 | 2015-07-06 | 주식회사 포스코 | Surface treated metallic material and surface treatment method for metallic material |
| JP2016084527A (en) * | 2014-10-24 | 2016-05-19 | Ｊｆｅスチール株式会社 | Steel sheet for vessel and manufacturing method thereof |
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