JP2010215973A - Surface-treated galvanized metal material and surface treatment solution - Google Patents
Surface-treated galvanized metal material and surface treatment solution Download PDFInfo
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本発明は、クロム化合物や有機樹脂を含まないにもかかわらず、優れた深絞り加工性と耐食性とを示す、亜鉛系めっき金属材料、特に亜鉛系めっき鋼板と、その表面処理用の表面処理液に関する。 The present invention relates to a zinc-based plated metal material, particularly a zinc-based plated steel sheet, and a surface treatment liquid for the surface treatment, which exhibits excellent deep drawing workability and corrosion resistance despite the absence of a chromium compound or an organic resin. About.
本発明に従って表面処理された亜鉛系めっき金属材料は、特に速乾油を用いた深絞り加工に適しており、家電、建材、自動車部品等の分野に適用することができる。中でも、本発明は、家電用精密機器の分野で使用する小型モーターケース用途に特に適している。 The zinc-based plated metal material surface-treated in accordance with the present invention is particularly suitable for deep drawing using quick-drying oil, and can be applied to fields such as home appliances, building materials, and automobile parts. Among these, the present invention is particularly suitable for small motor case applications used in the field of home appliance precision equipment.
亜鉛系めっき鋼板の耐食性を向上させるために、クロメート処理を施して鋼板表面のめっき層上にクロメート皮膜を形成することは周知であり、従来から一般に行われてきた。しかし、環境問題に対する意識の高まりから、使用する処理液が人体に有害な６価クロムを含有するクロメート処理の代りに、クロム化合物を用いない表面処理が望まれるようになってきた。 In order to improve the corrosion resistance of the zinc-based plated steel sheet, it is well known and generally performed to form a chromate film on the plated layer on the steel sheet surface by performing chromate treatment. However, due to increased awareness of environmental problems, surface treatment that does not use a chromium compound has been desired instead of chromate treatment in which the treatment liquid used contains hexavalent chromium that is harmful to the human body.
特許文献１（特開平４−２９３７８９号公報）には、鋼板表面に、第１段階として金属シリケートのアルカリ性水性溶液で洗浄してシリケート皮膜を形成し、続く段階でその鋼板をシラン含有水溶液で洗浄するという技術が開示されている。この技術については、後述の特許文献２において、耐食性が不十分であったり、塗装性が悪かったり、耐疵付き性に劣るなどの問題があるとされている。 In Patent Document 1 (Japanese Patent Application Laid-Open No. 4-293789), a silicate film is formed on a steel sheet surface by washing with an alkaline aqueous solution of metal silicate as a first stage, and the steel sheet is washed with a silane-containing aqueous solution at a subsequent stage. The technique of doing is disclosed. Regarding this technique, in Patent Document 2 described later, it is said that there are problems such as insufficient corrosion resistance, poor paintability, and poor scratch resistance.
特許文献２（特開２０００−４５０７８号公報）には、Ｓｉ／Ｌｉモル比が３３〜６６のリチウムシリケートからなる無機成分と有機樹脂とで構成されるいわゆる有機・無機複合皮膜が形成された、耐食性、潤滑性、耐傷つき性、耐指紋性、塗装性を表面処理鋼板が開示されている。しかし、この従来技術では、皮膜中の樹脂成分が８％以上とかなりの割合を占めており、前述した近年の深絞り工程では、成形時に皮膜の一部が剥離して成形品を汚す現象（以下、この現象を「黒ずみ」と称する）が生じやすいと思われる。 In Patent Document 2 (Japanese Patent Laid-Open No. 2000-45078), a so-called organic / inorganic composite film composed of an inorganic component composed of lithium silicate having a Si / Li molar ratio of 33 to 66 and an organic resin is formed. A surface-treated steel sheet is disclosed with respect to corrosion resistance, lubricity, scratch resistance, fingerprint resistance, and paintability. However, in this prior art, the resin component in the film accounts for a significant proportion of 8% or more, and in the above-mentioned recent deep drawing process, a part of the film peels off at the time of molding, and the molded product is soiled ( Hereinafter, this phenomenon is referred to as “darkening”).
特許文献３（特開２０００−２１９９７６号公報）には、ケイ酸塩化合物とチオカルボニル基含有化合物およびバナジウム酸化合物のうちの少なくとも１種とを含む皮膜層を形成した、耐食性を有する耐熱処理鋼板が開示されている。 Patent Document 3 (Japanese Patent Laid-Open No. 2000-219976) discloses a heat-resistant steel sheet having corrosion resistance, in which a film layer containing a silicate compound, at least one of a thiocarbonyl group-containing compound and a vanadate compound is formed. Is disclosed.
特許文献４（特開２００２−３０７６１３号公報）には、Ｌｉ／Ｓｉ原子比＝０.４〜０.７のリチウムシリケートを皮膜成分とし、かつ潤滑剤を含有する皮膜を備える潤滑処理鋼板が開示されている。この潤滑処理は、主として、熱延鋼板または冷延鋼板（特に高強度鋼板）を対象とし、鋼板表面に上記皮膜を設けることにより、プレス加工時の皮膜剥離によるプレスかすの発生を抑制することを目的とする。 Patent Document 4 (Japanese Patent Application Laid-Open No. 2002-307613) discloses a lubricated steel sheet including a film containing lithium silicate having a Li / Si atomic ratio of 0.4 to 0.7 as a film component and containing a lubricant. Has been. This lubrication treatment is mainly intended for hot-rolled steel sheets or cold-rolled steel sheets (especially high-strength steel sheets). By providing the above-mentioned film on the steel sheet surface, it is possible to suppress the occurrence of press debris due to film peeling during press working. Objective.
特許文献５（特開２００７−１３８２２５号公報）には、Ｓi／Ｌiモル比が１〜４のリチウムシリケートに対して、シランカップリング剤、バナジウム化合物を含有し、樹脂、ワックス、クロムを含有しない表面処理液およびそれにより表面処理された亜鉛めっき鋼板が開示されている。この表面処理法は、主として黒ずみの発生を防止でき、耐食性も改善できる。 Patent Document 5 (Japanese Patent Laid-Open No. 2007-138225) contains a silane coupling agent and a vanadium compound with respect to lithium silicate having a Si / Li molar ratio of 1 to 4, and does not contain a resin, wax, or chromium. A surface treatment liquid and a galvanized steel sheet surface-treated thereby are disclosed. This surface treatment method can mainly prevent darkening and improve corrosion resistance.
特許文献５に開示された技術によれば、速乾油を用いて亜鉛系めっき鋼板を厳しい条件下で深絞り加工した場合にも黒ずみ発生が著しく抑制されることで示される優れた深絞り加工性を示し、従って加工後に無洗浄、無塗装で使用できる、６価クロムを含まない耐食性に優れた表面処理皮膜を有する表面処理金属材料とその製造方法、ならびにそれに用いる表面処理液が提供される。 According to the technique disclosed in Patent Document 5, excellent deep drawing is shown by the fact that the occurrence of darkening is remarkably suppressed even when a zinc-based plated steel sheet is deep drawn under severe conditions using fast drying oil. Provided is a surface-treated metal material having a surface-treated film that does not contain hexavalent chromium and has excellent corrosion resistance, and can be used without being washed or painted after processing, and a surface treatment liquid used therefor .
しかし、この技術を精密家電用の亜鉛めっき鋼板製モーターケースに適用した場合、加工性、耐食性などは良好であるが、油が鋼板表面に拡がりやすいという問題があって、駆動部の潤滑油が鋼板を伝って漏れ出すという問題を生ずることが明らかとなった。これは表面処理皮膜が潤滑油を弾かないためであると推測される。本発明の課題は、亜鉛系めっき鋼板の表面処理において、特許文献５により達成されるような深絞り加工性と耐食性は維持したまま、油弾き性を改良することにある。 However, when this technology is applied to a galvanized steel plate motor case for precision home appliances, workability and corrosion resistance are good, but there is a problem that the oil tends to spread on the surface of the steel plate. It became clear that the problem of leaking along the steel plate occurred. This is presumed to be because the surface treatment film does not repel lubricating oil. An object of the present invention is to improve oil repellency while maintaining the deep drawing workability and corrosion resistance as achieved by Patent Document 5 in the surface treatment of a zinc-based plated steel sheet.
亜鉛系めっき鋼板表面に形成した無機成分を主体とする表面処理皮膜について、油弾き性の観点から検討した結果、リチウムシリケート（ケイ酸リチウム）に、ケイ酸ナトリウム（ケイ酸ソーダ又はナトリウムシリケート）、バナジウム化合物およびシランカップリング剤を併用した非クロム系の皮膜とすることにより、油弾き性が促進されると共に優れた加工性、耐食性が得られることが判明した。 As a result of examining the surface treatment film mainly composed of inorganic components formed on the surface of the zinc-based plated steel sheet from the viewpoint of oil repellent properties, lithium silicate (lithium silicate), sodium silicate (sodium silicate or sodium silicate), It has been found that by using a non-chromium film in which a vanadium compound and a silane coupling agent are used in combination, oil repelling properties are promoted and excellent workability and corrosion resistance are obtained.
本発明は、水性媒質中に、Ｓｉ／Ｌｉモル比が１〜４の範囲内のリチウムシリケートと、該リチウムシリケート１００質量部に対して５〜４００質量部の量の、Ｓｉ／Ｎａモル比が１〜４の範囲内のケイ酸ナトリウムとを主成分とし、この主成分１００質量部に対して、５〜５０質量部のシランカップリング剤と、０.２〜１０質量部（バナジウム金属として）の量のバナジウム化合物と、を含有することを特徴とする、亜鉛系めっき金属材料用表面処理液である。 In the aqueous medium, the Si / Li molar ratio is 5 to 400 parts by mass with respect to 100 parts by mass of lithium silicate having a Si / Li molar ratio of 1 to 4 and 100 parts by mass of the lithium silicate. The main component is sodium silicate within a range of 1 to 4, and 5 to 50 parts by mass of a silane coupling agent and 0.2 to 10 parts by mass (as vanadium metal) with respect to 100 parts by mass of the main component. A surface treatment solution for a zinc-based plated metal material, characterized by containing a vanadium compound in an amount of.
別の側面からは、本発明は、亜鉛系めっき層の上に乾燥表面処理皮膜を備える亜鉛系めっき金属材料であって、該皮膜は、Ｓｉ／Ｌｉモル比が１〜４の範囲内のリチウムシリケートと、該リチウムシリケート１００質量部に対して５〜４００質量部の量の、Ｓｉ／Ｎａモル比が１〜４の範囲内のケイ酸ナトリウムとを主成分とし、この主成分１００質量部に対して、５〜５０質量部のシランカップリング剤と、０.２〜１０質量部（バナジウム金属として）のバナジウム化合物とを含有する皮膜であることを特徴とする亜鉛系めっき金属材料である。 From another aspect, the present invention provides a zinc-based plated metal material comprising a dry surface-treated film on a zinc-based plated layer, the film comprising a lithium having a Si / Li molar ratio in the range of 1 to 4. The main component is silicate and sodium silicate having a Si / Na molar ratio of 1 to 4 in an amount of 5 to 400 parts by mass with respect to 100 parts by mass of the lithium silicate. On the other hand, it is a zinc-based plated metal material characterized by being a film containing 5 to 50 parts by mass of a silane coupling agent and 0.2 to 10 parts by mass (as vanadium metal) of a vanadium compound.
本発明の好適態様を列挙すると、次の通りである。
・前記シランカップリング剤がエポキシ基含有シランカップリング剤である；
・前記表面処理液又は前記乾燥表面処理皮膜が、前記主成分１００質量部に対して０.０１〜１０質量部のワックスをさらに含有する；
・前記表面処理液又は前記乾燥表面処理皮膜が、前記主成分１００質量部に対して０.２〜１０質量部のオキシカルボン酸をさらに含有する；
・前記オキシカルボン酸がリンゴ酸である；
・前記表面処理液又は前記乾燥表面処理皮膜が、前記主成分１００質量部に対して０.２〜１０質量部のアルコキシシランをさらに含有する；
前記アルコキシシランがテトラメトキシシランおよび／またはテトラエトキシシランである；
前記皮膜の付着量が０.０５〜１０ｇ／ｍ2の範囲内である。
The preferred embodiments of the present invention are listed as follows.
-The silane coupling agent is an epoxy group-containing silane coupling agent;
The surface treatment liquid or the dried surface treatment film further contains 0.01 to 10 parts by mass of wax with respect to 100 parts by mass of the main component;
-The said surface treatment liquid or the said dry surface treatment film | membrane further contains 0.2-10 mass parts oxycarboxylic acid with respect to 100 mass parts of said main components;
The oxycarboxylic acid is malic acid;
-The said surface treatment liquid or the said dry surface treatment film | membrane further contains 0.2-10 mass parts alkoxysilane with respect to 100 mass parts of the said main components;
The alkoxysilane is tetramethoxysilane and / or tetraethoxysilane;
The coating amount of the film is in the range of 0.05 to 10 g / m 2 .
本発明はまた、亜鉛系めっき鋼板の少なくとも片面のめっき層の上に前記表面処理液を塗布した後、加熱して乾燥皮膜を形成することを特徴とする、表面処理された亜鉛系めっき鋼板の製造方法も提供する。この方法において、前記加熱は、亜鉛系めっき鋼板の最高到達温度が５０℃以上、２００℃以下の温度となるように行うことが好ましい。 The present invention also provides a surface-treated zinc-based plated steel sheet, wherein the surface-treated liquid is applied on at least one surface of a zinc-plated steel sheet and then heated to form a dry film. A manufacturing method is also provided. In this method, the heating is preferably performed so that the maximum temperature reached by the galvanized steel sheet is 50 ° C. or higher and 200 ° C. or lower.
本発明によれば、使用する表面処理液または形成された表面処理皮膜が、有害な６価クロムを含めてクロム化合物を実質的に含有していないので、環境面で有利である。この皮膜は、特に亜鉛系めっき鋼板を深絞り加工した際に起こり易い、深絞り加工時の黒ずみ発生を防止でき、しかも皮膜の耐食性に著しく優れている。また、本発明に係る表面処理皮膜を有する亜鉛系めっき鋼板を精密家電用モーターケースに適用した場合でも、深絞り加工性、耐食性は維持したまま、油弾き性を改良することができ、製品価値を著しく高めることができる。 According to the present invention, since the surface treatment liquid to be used or the formed surface treatment film does not substantially contain chromium compounds including harmful hexavalent chromium, it is advantageous in terms of environment. This film can prevent the occurrence of darkening at the time of deep drawing, which is likely to occur particularly when a zinc-based plated steel sheet is deep drawn, and is extremely excellent in the corrosion resistance of the film. Moreover, even when the zinc-based plated steel sheet having the surface-treated film according to the present invention is applied to a motor case for precision home appliances, the oil repellent property can be improved while maintaining the deep drawability and corrosion resistance, and the product value Can be significantly increased.
本発明に係る亜鉛系めっき金属材料用表面処理液は、水性媒質中にリチウムシリケートと、ケイ酸ナトリウムと、バナジウム化合物と、シランカップリング剤とを含有する。水性媒質は、水のみからなるものでも、水と水混和性有機溶媒（例、アルコール、ケトンなど）との混合溶媒でもよい。好ましい水性媒質は水単独である。 The surface treatment liquid for zinc-based plated metal material according to the present invention contains lithium silicate, sodium silicate, a vanadium compound, and a silane coupling agent in an aqueous medium. The aqueous medium may be composed only of water or a mixed solvent of water and a water-miscible organic solvent (eg, alcohol, ketone, etc.). A preferred aqueous medium is water alone.
リチウムシリケート（別名：ケイ酸リチウム）は、皮膜を形成するベース成分である。リチウムシリケートのＳｉ／Ｌｉモル比は１〜４の範囲であり、好ましくは２〜３の範囲である。リチウムシリケートのＳｉ／Ｌｉモル比をこの範囲にすることで、深絞り加工において黒ずみの生じない皮膜を得ることができる。リチウムシリケートのＳｉ／Ｌｉモル比が１未満では、皮膜が吸水し易く、べとつきが生じ、Ｓｉ／Ｌｉモル比が４を超えると、深絞り加工での黒ずみが生じやすくなる。 Lithium silicate (also known as lithium silicate) is a base component that forms a film. The Si / Li molar ratio of lithium silicate is in the range of 1-4, preferably in the range of 2-3. By setting the Si / Li molar ratio of lithium silicate within this range, it is possible to obtain a film without darkening in deep drawing. When the Si / Li molar ratio of the lithium silicate is less than 1, the film easily absorbs water and stickiness occurs. When the Si / Li molar ratio exceeds 4, the darkening in deep drawing tends to occur.
表面処理液中のリチウムシリケートの濃度は１〜２０質量％の範囲が好ましい。１質量％未満では、濃度が薄すぎて、皮膜を形成させるときに、多量の水分を乾燥させなければならず、実用的ではない。２０質量％を超えると、リチウムシリケートが沈殿して、表面処理液の安定性に問題を生じることがある。 The concentration of lithium silicate in the surface treatment liquid is preferably in the range of 1 to 20% by mass. If it is less than 1% by mass, the concentration is too thin and a large amount of moisture must be dried when forming a film, which is not practical. If it exceeds 20% by mass, lithium silicate may precipitate, causing a problem in the stability of the surface treatment solution.
リチウムシリケートは、市販のものでよく、たとえば、日本化学工業社製「ケイ酸リチウム３５」、「ケイ酸リチウム４５」、日産化学社製「リチウムシリケート３５」等を用いることができる。リチウムシリケートのＳｉ／Ｌｉモル比の調整は、リチウムシリケートの水溶液に対して、モル比を上げるときはコロイダルシリカ、下げるときは水酸化リチウムを溶解させて行うことができる。 The lithium silicate may be a commercially available product, and for example, “Lithium silicate 35”, “Lithium silicate 45” manufactured by Nippon Chemical Industry Co., Ltd., “Lithium silicate 35” manufactured by Nissan Chemical Co., Ltd. can be used. Adjustment of the Si / Li molar ratio of lithium silicate can be carried out by dissolving colloidal silica when increasing the molar ratio and dissolving lithium hydroxide when decreasing the molar ratio with respect to the aqueous solution of lithium silicate.
ケイ酸ナトリウム（ケイ酸ソーダ、ナトリウムシリケート、または水ガラスとも呼ばれる）は、皮膜を形成するベース成分であると同時に、潤滑油に対する油弾き性を付与する成分でもある。ケイ酸ナトリウムのＳｉ／Ｎａモル比は１〜４の範囲であり、好ましくは２〜３の範囲である。ケイ酸ナトリウムも、市販品（例、トクヤマ製３号水ガラス等）を利用することができ、Ｓｉ／Ｎａモル比の調整も上と同様に、ケイ酸ナトリウムの水溶液にコロイダルシリカまたは水酸化ナトリウムを添加して溶解させることにより行うことができる。 Sodium silicate (also referred to as sodium silicate, sodium silicate, or water glass) is a base component that forms a film, and at the same time, a component that imparts oil resilience to the lubricating oil. The Si / Na molar ratio of sodium silicate is in the range of 1-4, preferably in the range of 2-3. As for sodium silicate, a commercially available product (eg, No. 3 water glass manufactured by Tokuyama) can be used, and the adjustment of the Si / Na molar ratio is similar to the above in the case of colloidal silica or sodium hydroxide in an aqueous solution of sodium silicate. Can be added and dissolved.
表面処理液（従って、表面処理皮膜）中のケイ酸ナトリウムの量は、リチウムシリケート１００質量部に対し５〜４００質量部となるようにする。ケイ酸ナトリウムの量がこの範囲より少ないと十分な油弾き性が確保できず、この範囲より多いと深絞り加工性が低下する場合がある。この量は、好ましくは５０〜３００質量部、さらに好ましくは１００〜２００質量部である。 The amount of sodium silicate in the surface treatment liquid (and therefore the surface treatment film) is set to 5 to 400 parts by mass with respect to 100 parts by mass of lithium silicate. If the amount of sodium silicate is less than this range, sufficient oil repellency cannot be ensured, and if it exceeds this range, deep drawability may be reduced. This amount is preferably 50 to 300 parts by mass, more preferably 100 to 200 parts by mass.
上記２種類のケイ酸塩（即ち、リチウムシリケートとケイ酸ナトリウム）が、本発明に係る表面処理液および表面処理皮膜の皮膜形成ベース成分、即ち、主成分である。いずれのケイ酸塩についても２種以上の混合物を使用することができ、その場合の各ケイ酸塩の前記モル比は混合割合を加味した平均値とする。 The two types of silicates (namely, lithium silicate and sodium silicate) are the film-forming base components of the surface treatment liquid and the surface treatment film according to the present invention, that is, the main components. As for any silicate, two or more kinds of mixtures can be used, and the molar ratio of each silicate in that case is an average value considering the mixing ratio.
本発明で使用するバナジウム化合物としては、バナジン酸アンモニウム、バナジン酸ナトリウム、バナジン酸カリウム、バナジン酸ストロンチウム、バナジン酸水素ナトリウムなどのバナジン酸塩化合物、硫酸バナジル、硝酸バナジル、塩化バナジルなどのバナジル化合物、五酸化バナジウム、三酸価バナジウム、二酸化バナジウムなどの酸化バナジウム化合物などが挙げられる。 Examples of vanadium compounds used in the present invention include vanadate compounds such as ammonium vanadate, sodium vanadate, potassium vanadate, strontium vanadate, sodium hydrogen vanadate, vanadyl compounds such as vanadyl sulfate, vanadyl nitrate, and vanadyl chloride, Examples thereof include vanadium oxide compounds such as vanadium pentoxide, vanadium triacid, and vanadium dioxide.
表面処理液中のバナジウム化合物の量は、バナジウム金属換算で、前記主成分１００質量部に対して０.２〜１０質量部となるようにする。バナジウム化合物の量がこの範囲より少ないと十分な耐食性が確保できず、この範囲より多いとバナジウム化合物が沈殿して、表面処理液の安定性に問題を生じる。この量は、好ましくは０.５〜７質量部、さらに好ましくは１〜５質量部である。 The amount of the vanadium compound in the surface treatment liquid is set to 0.2 to 10 parts by mass with respect to 100 parts by mass of the main component in terms of vanadium metal. When the amount of the vanadium compound is less than this range, sufficient corrosion resistance cannot be ensured. When the amount is more than this range, the vanadium compound is precipitated, causing a problem in the stability of the surface treatment liquid. This amount is preferably 0.5 to 7 parts by mass, more preferably 1 to 5 parts by mass.
本発明で用いるシランカップリング剤は、水溶液中への溶解性と耐食性向上効果の観点から、エポキシ基を含有するシランカップリング剤を用いることが好ましい。そのようなシランカップリング剤の例としては、３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルメチルジメトキシシラン、β−(３,４−エポキシシクロヘキシル)エチルトリメトキシシランなどが挙げられる。これに加えて、または代えて、例えば、３−メルカプトプロピルトリメトキシシラン、３−メタクリロキシプロピルトリメトキシシラン、３−アミノプロピルトリエトキシシランなどの他のシランカップリング剤を使用することもできる。シランカップリング剤は１種または２種以上用いることができる。 The silane coupling agent used in the present invention is preferably a silane coupling agent containing an epoxy group from the viewpoints of solubility in an aqueous solution and an effect of improving corrosion resistance. Examples of such silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. . In addition or alternatively, other silane coupling agents such as 3-mercaptopropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and the like can be used. One or more silane coupling agents can be used.
表面処理液中のシランカップリング剤の量は、前記主成分１００質量部に対して５〜５０質量部、好ましくは１０〜４０質量部の割合とする。シランカップリング剤の配合量がこの範囲より少ないと、十分な耐食性が確保できず、この範囲より多くしても、耐食性の向上効果が飽和し、経済的ではない。 The amount of the silane coupling agent in the surface treatment liquid is 5 to 50 parts by mass, preferably 10 to 40 parts by mass with respect to 100 parts by mass of the main component. If the amount of the silane coupling agent is less than this range, sufficient corrosion resistance cannot be ensured, and if it exceeds this range, the effect of improving the corrosion resistance is saturated and it is not economical.
本発明に係る表面処理液は、黒ずみ抑制効果を高めるためにワックスを含有することができる。本発明で使用するのに適したワックスとしては、ポリオレフィンワックス、パラフィンワックス、マイクロクリスタリンワックス、各種天然ワックスなどを挙げることができるが、特に好ましいのはポリオレフィンワックスである。ワックスの平均粒径は０.０１〜０.５μｍの範囲内が好ましい。 The surface treatment liquid according to the present invention can contain a wax in order to enhance the darkening suppressing effect. Suitable waxes for use in the present invention include polyolefin waxes, paraffin waxes, microcrystalline waxes, various natural waxes and the like, with polyolefin waxes being particularly preferred. The average particle size of the wax is preferably in the range of 0.01 to 0.5 μm.
表面処理液中のワックスの量は、前記主成分１００質量部に対して０.０１〜１０質量部、好ましくは０.０１〜２.０質量部の割合とする。ワックスの配合量がこの範囲より少ないと黒ずみの抑制効果が発揮されず、この範囲より多くなっても黒ずみの発生に対して逆効果となるため好ましくない。 The amount of the wax in the surface treatment liquid is 0.01 to 10 parts by mass, preferably 0.01 to 2.0 parts by mass with respect to 100 parts by mass of the main component. If the blending amount of the wax is less than this range, the effect of suppressing darkening is not exhibited, and if it exceeds this range, the effect against darkening is adversely affected.
ワックス量が多くなりすぎると黒ずみが発生し易くなるのは、厳しい加工条件下では金型が１００℃以上の高温となり、融点の低いワックスは溶融して金型に凝着し、量が多いとかえって黒ずみの原因となるためである。上記所定量の範囲内であればこのような現象は生じず、黒ずみに対してはプラスの効果となる。 When the amount of the wax is too large, darkening is likely to occur. Under severe processing conditions, the mold becomes a high temperature of 100 ° C. or higher, and the wax having a low melting point melts and adheres to the mold. On the contrary, it causes darkening. Such a phenomenon does not occur if the amount is within the predetermined range, and a positive effect is obtained against darkening.
また、本発明の表面処理液には、上記処理液中のワックスに代えて、オキシカルポン酸およびアルコキシシランから選ばれた少なくとも１種の化合物を加えるか、またはこの化合物をワックスと一緒に加えることができる。それにより、深絞り加工での黒ずみの発生が抑制され、且つ耐食性のさらなる改善が得られる。 Further, in the surface treatment liquid of the present invention, at least one compound selected from oxycarponic acid and alkoxysilane may be added instead of the wax in the treatment liquid, or this compound may be added together with the wax. it can. Thereby, the occurrence of darkening in deep drawing is suppressed, and further improvement in corrosion resistance is obtained.
使用できるオキシカルボン酸としては、酒石酸、リンゴ酸、およびクエン酸を挙げることができる。この中で特に好ましいのはリンゴ酸である。アルコキシシランは、テトラアルコキシシランを意味する。好ましいのはテトラメトキシシラン（メチルシリケート）およびテトラエトキシシラン（エチルシリケート）である。オキシカルボン酸とアルコキシシランは、いずれか一方の１種または２種以上を使用してもよく、あるいはそれぞれの１種または２種以上を併用してもよい.
好ましくは、少なくとも１種のオキシカルボン酸と少なくとも１種のアルコキシシランとを併用する。その場合の両者の割合は特に制限されないが、一般的にはオキシカルボン酸：アルコキシシランの質量比が１:１０〜１０：１の範囲内であると、上記効果がより顕著となるので好ましい。
Examples of oxycarboxylic acids that can be used include tartaric acid, malic acid, and citric acid. Of these, malic acid is particularly preferred. Alkoxysilane means tetraalkoxysilane. Preference is given to tetramethoxysilane (methyl silicate) and tetraethoxysilane (ethyl silicate). One or more of oxycarboxylic acid and alkoxysilane may be used, or one or more of each may be used in combination.
Preferably, at least one oxycarboxylic acid and at least one alkoxysilane are used in combination. In this case, the ratio of the two is not particularly limited, but in general, it is preferable that the mass ratio of oxycarboxylic acid: alkoxysilane is in the range of 1:10 to 10: 1 because the above effect becomes more remarkable.
オキシカルボン酸およびアルコキシシランの量（２種以上の化合物を使用する場合はそれらの合計量）は、主成分１００質量部に対してそれぞれ０.２〜１０質量部、好ましくは０.２〜５質量部の割合とする。これらの化合物の配合量が少なすぎると黒ずみの抑制効果が小さくなり、多すぎると処理液の安定性が低下する。 The amount of oxycarboxylic acid and alkoxysilane (the total amount when two or more compounds are used) is 0.2 to 10 parts by mass, preferably 0.2 to 5 parts per 100 parts by mass of the main component. The ratio is part by mass. When the compounding amount of these compounds is too small, the effect of suppressing darkening becomes small, and when it is too large, the stability of the treatment liquid decreases.
これらの化合物を添加することにより黒ずみ発生が抑制されるメカニズムは完全には解明されていないが、これらの化合物はシリケートの分子同士を結合する作用があり、このため皮膜がより強固なものとなり、皮膜が金型による摺動を受けても剥離がおきにくくなるためではないかと推定される。 The mechanism by which the darkening is suppressed by adding these compounds has not been completely elucidated, but these compounds have the effect of binding silicate molecules together, which makes the film stronger, It is presumed that it is difficult for the film to peel off even when the film is slid by the mold.
本発明の表面処理液には、上述した成分以外に、黒ずみ発生、耐食性、油弾き性に害を及ぼさない程度に、防錆剤、消泡剤、界面活性剤等の他の添加剤を配合してもよい。
本発明の表面処理液は、各種の金属材料、特に亜鉛系めっき金属材料の表面処理に適用することができるが、その効果をより有効に発揮させる意味で好ましい金属材料は、亜鉛系めっき鋼板である。特に、この亜鉛系めっき鋼板を使用したモーターケースに適用する場合に、好ましい結果が得られる。
In addition to the components described above, the surface treatment liquid of the present invention is blended with other additives such as rust preventives, antifoaming agents, surfactants, etc. to the extent that they do not adversely affect blackening, corrosion resistance, and oil repellent properties May be.
The surface treatment liquid of the present invention can be applied to the surface treatment of various metal materials, in particular, zinc-based plated metal materials, but a preferable metal material in the sense of exerting its effect more effectively is a zinc-based plated steel plate. is there. In particular, when applied to a motor case using this galvanized steel sheet, preferable results are obtained.
前述したように、亜鉛系めっき鋼板は、めっきが軟らかいため、厳しいプレス加工時に黒ずみが発生し易いが、本発明に従って表面処理を施すことにより、厳しい深絞り加工を施す場合にも黒ずみ発生を防止でき、さらに耐食性の向上を図ることができる。さらに、このめっき鋼板をモーターケースに適用した場合に駆動部の潤滑油が鋼板を伝わって漏れ出すという不都合を回避することができる。以下では、基材が亜鉛系めっき鋼板である場合を例にとって説明する。 As mentioned above, galvanized steel sheets tend to be darkened during severe press working due to the soft plating, but surface treatment according to the present invention prevents blackening even when severe deep drawing is performed. In addition, the corrosion resistance can be improved. Furthermore, when this plated steel plate is applied to a motor case, it is possible to avoid the inconvenience that the lubricating oil in the drive section leaks through the steel plate. Below, it demonstrates taking the case where a base material is a zinc-plated steel plate as an example.
好ましい基材である亜鉛系めっき鋼板の種類は特に限定されず、電気亜鉛めっき鋼板、電気亜鉛−ニッケル合金めっき鋼板、溶融亜鉛めっき鋼板、溶融亜鉛−アルミ合金めっき鋼板、溶融亜鉛−鉄めっき合金鋼板（合金化溶融亜鉛めっき鋼板を含む）などを含む各種の亜鉛系めっき鋼板に対して本発明を適用できる。中でも、めっき層がより柔らかく、プレス加工時の黒ずみが発生し易い、純亜鉛めっき鋼板、特に電気亜鉛めっき鋼板に適用した場合に、本発明の効果はより顕著となる。亜鉛系めっきのめっき付着量も特に制限されず、従来公知の通常の付着量でよい。 There are no particular limitations on the type of galvanized steel sheet that is a preferred base material. Electrogalvanized steel sheet, electrogalvanized nickel-plated steel sheet, hot-dip galvanized steel sheet, hot-dip zinc-aluminum alloy plated steel sheet, hot-dip zinc-iron plated alloy steel sheet The present invention can be applied to various zinc-based plated steel sheets including (including alloyed hot-dip galvanized steel sheets). Among them, the effect of the present invention becomes more remarkable when applied to a pure galvanized steel sheet, particularly an electrogalvanized steel sheet, in which the plating layer is softer and darkening is likely to occur during press working. The amount of zinc-based plating is not particularly limited, and may be a conventionally known normal amount.
表面処理は、本発明に係る表面処理液を亜鉛系めっき鋼板の少なくとも片面のめっき層の上に塗布した後、加熱して、めっき層の上に乾燥表面処理皮膜を形成することにより実施できる。こうして亜鉛系めっき層の上に形成された表面処理皮膜は、Ｓｉ／Ｌｉモル比が１〜４の範囲内のリチウムシリケートと、リチウムシリケート１００質量部に対して５〜４００質量部の量のＳｉ／Ｎａモル比が１〜４の範囲内のケイ酸ナトリウムとを主成分とし、これら主成分１００質量部に対して５〜５０質量部のシランカップリング剤および０.２〜１０質量部（バナジウム金属として）のバナジウム化合物を含有する。 The surface treatment can be carried out by applying the surface treatment liquid according to the present invention on the plated layer on at least one side of the galvanized steel sheet and then heating to form a dry surface-treated film on the plated layer. The surface treatment film thus formed on the zinc-based plating layer is composed of lithium silicate having a Si / Li molar ratio in the range of 1 to 4 and Si in an amount of 5 to 400 parts by mass with respect to 100 parts by mass of lithium silicate. The main component is sodium silicate having a / Na molar ratio in the range of 1 to 4, and 5 to 50 parts by mass of a silane coupling agent and 0.2 to 10 parts by mass (vanadium with respect to 100 parts by mass of these main components. As a metal).
この表面処理皮膜は、必要に応じて、前記主成分１００質量部に対して、０.０１〜１０質量部のワックス、０.２〜１０質量部のオキシカルボン酸および／または０.２〜１０質量部のアルコキシシランをさらに含有しうる。 This surface-treated film may be added in an amount of 0.01 to 10 parts by weight of wax, 0.2 to 10 parts by weight of oxycarboxylic acid and / or 0.2 to 10 parts per 100 parts by weight of the main component. A part by mass of alkoxysilane may further be contained.
この乾燥表面処理皮膜の付着量（両面の場合は片面当たり）は０.０５〜１０ｇ／ｍ2の範囲内とすることが好ましい。付着量が０.０５ｇ／ｍ2未満であると、十分な耐食性が得られない。付着量が１０ｇ／ｍ2を超えると、耐食性の向上が飽和する上、皮膜の密着性が低下することがある。表面処理は基材鋼板の両面に施すことが好ましいが、片面処理も可能である。片面処理の場合、他の面は未処理でもよく、或いは他の表面処理を施してよい。 The adhesion amount of the dry surface-treated film (per one surface in the case of both surfaces) is preferably in the range of 0.05 to 10 g / m 2 . If the adhesion amount is less than 0.05 g / m 2 , sufficient corrosion resistance cannot be obtained. When the adhesion amount exceeds 10 g / m 2 , the improvement in corrosion resistance is saturated and the adhesion of the film may be lowered. The surface treatment is preferably performed on both sides of the base steel plate, but single-sided treatment is also possible. In the case of single-sided treatment, the other surface may be untreated, or other surface treatment may be performed.
表面処理液の塗布方法は、特に限定されず、工業的に一般に用いられるロールコーター法、スプレー塗装などの種々の方法が適用できる。
塗布後の加熱（皮膜の焼付け）も、通常実施される熱風式、赤外式、誘導加熱式等の方法によって実施すればよい。加熱は、基材である亜鉛系めっき鋼板の最高到達温度が５０〜２００℃の範囲となるように行うことが好ましい。この加熱温度が５０℃未満では、焼付けが皮膜形成には不十分で、十分な耐食性が得ることができず、２００℃を超えると、皮膜の耐食性の向上が得られなくなることがある。
The coating method of the surface treatment liquid is not particularly limited, and various methods such as a roll coater method and spray coating that are generally used industrially can be applied.
What is necessary is just to implement the heating after application | coating (baking of a film | membrane) by methods, such as a hot air type, infrared type, induction heating type, etc. which are normally implemented. It is preferable to perform the heating so that the highest achieved temperature of the zinc-based plated steel sheet as the base material is in the range of 50 to 200 ° C. If the heating temperature is less than 50 ° C., baking is insufficient for film formation and sufficient corrosion resistance cannot be obtained, and if it exceeds 200 ° C., improvement in corrosion resistance of the film may not be obtained.
こうして表面処理された亜鉛系めっき鋼板は、プレス加工性に優れているので、速乾油を塗布しただけで深絞り加工に供することができ、その際の黒ずみ発生が著しく抑制される。深絞り加工が加工深さの大きい高速での連続加工という厳しい加工条件であっても、黒ずみ発生の抑制が達成される。加工後は、そのまま、すなわち無洗浄および無塗装で、製品として使用できる。加工後も表面処理皮膜は実質的に健全であり、基材に対して防食皮膜として機能し、亜鉛系めっきの耐食性を著しく向上させる。プレス加工後にアルカリまたは溶剤による脱脂を行い、さらに塗装を施す場合に比べて、コスト面で著しく優位であるのみならず、環境の面でも非常に好ましい製品となる。またモーターケースに適用した場合に油弾き性が良好で、油が鋼板を伝わって漏れ出すという不都合を回避することができる。 Since the surface-treated zinc-based plated steel sheet is excellent in press workability, it can be used for deep drawing just by applying quick-drying oil, and the occurrence of darkening at that time is remarkably suppressed. Suppression of blackening can be achieved even under severe processing conditions in which deep drawing is performed continuously at a high speed with a large processing depth. After processing, the product can be used as it is, that is, without washing and without painting. Even after processing, the surface treatment film is substantially healthy, functions as an anticorrosion film on the substrate, and remarkably improves the corrosion resistance of the zinc-based plating. Compared to the case of degreasing with alkali or solvent after press working and further coating, it is not only a significant advantage in terms of cost but also a very favorable product in terms of the environment. Further, when applied to a motor case, the oil repellent property is good, and the inconvenience that the oil leaks through the steel plate can be avoided.
以下、実施例により本発明を具体的に説明するが、これによって本発明が限定されるものではない。なお、以下の実施例および比較例中、％は全て質量％を表す。また、焼付け温度は、塗布後の加熱時の鋼板の最高到達温度を意味する。 EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited by this. In the following examples and comparative examples,% represents mass%. The baking temperature means the highest temperature reached by the steel sheet during heating after application.
（実施例１）
電気亜鉛めっき鋼板（板厚０.８ｍｍ、片面あたりのめっき目付け量２０ｇ／ｍ2）の片面のめっき層の上に、Ｓｉ／Ｌｉモル比１のリチウムシリケートを４％（質量％、以下同じ）、Ｓｉ／Ｎａモル比３のケイ酸ナトリウムを６％、バナジン酸アンモニウムをバナジウム換算で０.２％、およびシランカップリング剤として３−グリシドキシプロピルトリメトキシシランを３％の量でそれぞれ含有する水溶液をスピンコーターで塗布し、２００℃で焼付けて、付着量が１ｇ／ｍ2の表面処理皮膜を形成し、表面処理亜鉛系めっき鋼板の試験片を作製した。
Example 1
4% (mass%, the same shall apply hereinafter) of lithium silicate with a Si / Li molar ratio of 1 on the plating layer on one side of an electrogalvanized steel sheet (plate thickness: 0.8 mm, plating weight per side: 20 g / m 2 ) Si / Na molar ratio 3 sodium silicate 6%, ammonium vanadate 0.2% in terms of vanadium, and 3% glycidoxypropyltrimethoxysilane as silane coupling agent An aqueous solution to be coated was applied with a spin coater and baked at 200 ° C. to form a surface-treated film with an adhesion amount of 1 g / m 2 , thereby preparing a test piece of a surface-treated galvanized steel sheet.
（実施例２〜１０および比較例１〜８）
表面処理液の組成、その塗布後の焼付け温度および付着量を表１に示すように変更した以外は、実施例１と同様な方法で、表面処理亜鉛系めっき鋼板の試験片を作製した。これらの試験片について、下記に示す要領で耐食性、深絞り加工性および油弾き性を調査した。試験結果も表１に併せて示す。
(Examples 2 to 10 and Comparative Examples 1 to 8)
A test piece of a surface-treated galvanized steel sheet was prepared in the same manner as in Example 1 except that the composition of the surface treatment liquid, the baking temperature after application, and the amount of adhesion were changed as shown in Table 1. About these test pieces, the corrosion resistance, deep drawing workability, and oil repellency were investigated as follows. The test results are also shown in Table 1.
（耐食性試験）
実施例および比較例で得られた各試験片を塩水噴霧試験に供し、耐食性の評価を行った。試験は、ＪＩＳＺ−２３７１規格に準拠した塩水噴霧装置を用いて、塩水濃度５％、槽内温度３５℃、噴霧圧力２００ＰＳＩの条件で行い、４８時間後の表面に発生した白錆の面積率を測定した。評価は次の５段階にて行った。○以上であれば、合格であると判断できる。
(Corrosion resistance test)
Each test piece obtained in the examples and comparative examples was subjected to a salt spray test to evaluate the corrosion resistance. The test is performed using a salt spray device conforming to the JISZ-2371 standard under the conditions of a salt water concentration of 5%, a bath temperature of 35 ° C., and a spray pressure of 200 PSI, and the area ratio of white rust generated on the surface after 48 hours is measured. It was measured. Evaluation was performed in the following five stages. ○ If it is above, it can be judged to be acceptable.
◎：白錆面積率０％、
○：白錆面積率５％未満、
△：白錆面積率５％以上、１０％未満、
×：白錆面積率１０％以上、５０％未満、
××：白錆面積率５０％以上。
A: White rust area ratio 0%,
○: White rust area ratio less than 5%,
Δ: White rust area ratio 5% or more, less than 10%,
×: White rust area ratio 10% or more, less than 50%,
XX: White rust area ratio 50% or more.
（深絞り加工性試験）
実施例および比較例で得られた各試験片に対して、次の条件で金型の手入れ無しに連続５個の円筒加工を実施した。この加工条件は、加工深さが大きく、高速の連続加工である小型モーターケースの加工を模したものであり、厳しい加工条件であると言える。
(Deep drawing workability test)
For each test piece obtained in the examples and comparative examples, five consecutive cylinders were processed under the following conditions without maintenance of the mold. This processing condition simulates the processing of a small motor case having a large processing depth and high-speed continuous processing, and can be said to be a severe processing condition.
試験片：９０ｍｍφ（板厚：５ｍｍ）、
ポンチ径：５０ｍｍφ、ダイス径：５２ｍｍφ、
ＢＨ荷重：１０ｋＮ、
絞り速度：８００ｍｍ／ｍｉｎ、
温度：２５℃、
塗油：日本工作油製Ｇ６２３１Ｆ（速乾油）。
Test piece: 90 mmφ (plate thickness: 5 mm),
Punch diameter: 50 mmφ, die diameter: 52 mmφ,
BH load: 10 kN,
Aperture speed: 800 mm / min,
Temperature: 25 ° C
Oiling: G6231F (quick drying oil) manufactured by Nippon Kosaku Oil.
５個目に加工した円筒加工品の加工部（金型の摺動を受けた部分）をろ紙でふき取り、ろ紙の変色程度を観察した。また、目視で加工部の疵の程度を観察した。評価基準は次の通りである。やはり、○以上であれば商品として合格である。 The processed part (the part subjected to sliding of the mold) of the fifth cylindrical processed product was wiped with filter paper, and the degree of discoloration of the filter paper was observed. Further, the degree of wrinkles in the processed part was visually observed. The evaluation criteria are as follows. After all, if it is more than ○, it is accepted as a product.
◎：ろ紙の変色なし、加工品にも疵が付かない、
○：ろ紙の変色若干あり、加工品には疵が付かない、
△：ろ紙の変色大、加工品には疵が付かない、
×：ろ紙の変色大、加工品に若干疵が付着する、
××：ろ紙の変色大、加工品への疵の付着大。
◎: No discoloration of filter paper, no wrinkles on processed products,
○: There is a slight discoloration of the filter paper, and the processed product is not wrinkled.
△: Large discoloration of filter paper, no wrinkles on processed products,
×: Large discoloration of the filter paper, slight wrinkles on the processed product,
XX: Large discoloration of filter paper, large adhesion of soot to processed products.
（油弾き性試験）
試験片に速乾油を塗布し自然乾燥させた後、潤滑油を１０μＬ滴下し、５時間後に潤滑油の拡散面積を測定した。やはり、○以上であれば商品として合格である。
(Oil repellency test)
After applying quick-drying oil to the test piece and allowing it to dry naturally, 10 μL of lubricating oil was dropped, and the diffusion area of the lubricating oil was measured after 5 hours. After all, if it is more than ○, it is accepted as a product.
◎：拡散面積６０ｍｍ2未満、
○：拡散面積６０mm2以上、１００ｍｍ2未満、
△：拡散面積１００mm2以上、２００ｍｍ2未満、
×：拡散面積２００mm2以上、３００ｍｍ2未満、
××：拡散面積３００mm2以上。
A: Diffusion area less than 60 mm 2
○: Diffusion area 60 mm 2 or more, less than 100 mm 2
Δ: Diffusion area 100 mm 2 or more, less than 200 mm 2
×: Diffusion area 200 mm 2 or more, less than 300 mm 2
XX: Diffusion area 300 mm 2 or more.
表１からわかるように、本発明に従った組成の表面処理液を用いて亜鉛系めっき鋼板を表面処理すると、耐食性、深絞り加工性（黒ずみ）および油弾き性のいずれも良好であった。 As can be seen from Table 1, when the galvanized steel sheet was surface-treated using the surface treatment liquid having the composition according to the present invention, all of the corrosion resistance, deep drawing workability (darkening) and oil repelling property were good.
これに対し、皮膜形成の主成分である２種類のケイ酸塩のうち、ケイ酸ナトリウムの割合が少なすぎた比較例１では油弾き性が不芳となり、これが多すぎた比較例２では深絞り加工性が不芳となった。 In contrast, of the two types of silicates that are the main components of film formation, Comparative Example 1 in which the proportion of sodium silicate was too low resulted in poor oil repellency, and in Comparative Example 2 in which this was too much, it was deep. Drawing workability was unsatisfactory.
残りの比較例についても、リチウムシリケートのＳｉ／Ｌｉモル比、ケイ酸ナトリウムのＳｉ／Ｎａモル比、バナジウム化合物若しくはシランカップリング剤の含有量が本発明の範囲外となることで、少なくとも一つの特性が悪くなった。 For the remaining comparative examples, the Si / Li molar ratio of lithium silicate, the Si / Na molar ratio of sodium silicate, the vanadium compound or the content of the silane coupling agent falls outside the scope of the present invention, so that at least one The characteristics deteriorated.
Claims (17)
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| KR20150113171A (en) | 2013-02-08 | 2015-10-07 | 제이에프이 스틸 가부시키가이샤 | Surface-treatment solution for zinc or zinc alloy coated steel sheet, zinc or zinc alloy coated steel sheet with surface-treatment film and method of producing same |
| KR20160085306A (en) | 2013-11-29 | 2016-07-15 | 제이에프이 스틸 가부시키가이샤 | Zinc or zinc alloy coated steel sheet with surface treatment film, and method of producing same |
| JP2020143360A (en) * | 2019-02-28 | 2020-09-10 | 奥野製薬工業株式会社 | Zinc-based composite plating liquid, method for forming zinc-based composite plating film, and method for forming composite oxide film |
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| KR101896011B1 (en) * | 2017-06-16 | 2018-09-06 | (주)넥스트에어로스 | Anti-corrision varnish composition and forming method for anti-corrision coating layer using the same |
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| JP2003151808A (en) * | 2001-11-09 | 2003-05-23 | Sumitomo Special Metals Co Ltd | Rare-earth-based permanent magnet having corrosion- resistant coating film, its manufacturing method, and treating liquid for forming corrosion-resistant coating film |
| JP2008019492A (en) * | 2006-07-14 | 2008-01-31 | Sumitomo Metal Ind Ltd | Surface treatment liquid suitable for galvanized steel sheet |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20150113171A (en) | 2013-02-08 | 2015-10-07 | 제이에프이 스틸 가부시키가이샤 | Surface-treatment solution for zinc or zinc alloy coated steel sheet, zinc or zinc alloy coated steel sheet with surface-treatment film and method of producing same |
| KR20160085306A (en) | 2013-11-29 | 2016-07-15 | 제이에프이 스틸 가부시키가이샤 | Zinc or zinc alloy coated steel sheet with surface treatment film, and method of producing same |
| JP2020143360A (en) * | 2019-02-28 | 2020-09-10 | 奥野製薬工業株式会社 | Zinc-based composite plating liquid, method for forming zinc-based composite plating film, and method for forming composite oxide film |
| JP7417888B2 (en) | 2019-02-28 | 2024-01-19 | 奥野製薬工業株式会社 | Zinc-based composite plating solution, method for forming zinc-based composite plating film, and method for forming composite oxide film |
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