JP4648565B2 - Rust preventive agent for metal and steel - Google Patents
Rust preventive agent for metal and steel Download PDFInfo
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- JP4648565B2 JP4648565B2 JP2001124463A JP2001124463A JP4648565B2 JP 4648565 B2 JP4648565 B2 JP 4648565B2 JP 2001124463 A JP2001124463 A JP 2001124463A JP 2001124463 A JP2001124463 A JP 2001124463A JP 4648565 B2 JP4648565 B2 JP 4648565B2
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Description
【０００１】
【発明の属する技術分野】
本発明は、家電用、建材用、自動車用等に用いられる亜鉛系、アルミ系合金めっき鋼材に関し、特に、クロムを含有しない、耐食性に優れたクロメートフリー型の亜鉛系、アルミ系合金めっき鋼材に関するものである。
【０００２】
【従来の技術】
亜鉛めっき鋼材、亜鉛合金めっき鋼材、あるいはアルミ系合金めっき鋼材は、海水等の塩分を含む環境や高温多湿環境下において、表面に白錆が発生し外観を著しく損ねたり、電子機器に使用されている場合は、導電性やアース性を損なう等の問題を有していた。そのため、これらのめっき鋼材を使用する際には、クロメート処理と称する化成処理を施して白錆の発生を抑制させることが一般的である。このクロメート処理は種々の処理液の構成があるが、例えば、クロム酸とシリカコロイドからなる処理液を塗布し乾燥させるものがあり、Ｃｒの付着量が５０ｍｇ／ｍ2程度と微量であるにもかかわらず、極めて優れた耐白錆性を有する。また、めっき鋼材は塗装して使用される場合も多いが、その場合においても、塗膜との密着性を向上させるためにクロメート処理される場合がある。
【０００３】
このように、クロメート処理は、形成する皮膜が性能的にも優れている上に、安価かつ簡便に鋼材に処理することが出来ることから、一般的に用いられている処理法である。しかし、クロメート処理は、毒性を有するクロム酸を用いているため、処理工程での排液処理や作業者への安全性、更には、クロメート処理鋼材を使用した製品の廃棄時の６価クロムの溶出による地球環境への影響が懸念されるようになってきている。
【０００４】
そこで、クロムを全く含まない処理方法の開発が試みられてきた。例えば、特開平８−２３９７７６号公報では硫化物を用いた処理剤が開示されている。しかし、硫化物は特有な臭気を放つものがあり、これらの処理剤の取り扱い性を悪くしていた。また、特開昭５３−３１７３７号公報には、ジチオール−Ｓ−トリアジン誘導体を添加した水溶性防錆塗料が開示されている。しかし、この防錆塗料は、軟鋼、銅、真ちゅう等の金属の防食を目的に開発されたものである。従って、亜鉛系やアルミ系のめっき鋼材の場合、トリアジン誘導体の作用が充分には発揮されず、耐食性や密着性の向上作用が不十分である。これは水溶性防錆塗料に添加したトリアジンチオールのような防錆剤が金属表面に吸着することでインヒビター作用を発現するためであり、金属種によって吸着性が異なることが原因と考えられる。
【０００５】
【発明が解決しようとする課題】
このように、亜鉛系、アルミ系めっき鋼材の耐食性や塗装密着性を向上させるには、これらの金属表面に有効に作用する防錆剤を含有する水溶性塗料を見いだすことがひとつの方策である。しかし、防錆剤として充分な効果を有するものが現在のところ見いだされていないのが実状であった。
本発明はこのような実状に鑑み、クロムを含有せずに良好な耐食性と塗装密着性を発現する防錆剤、防錆塗料、防錆処理鋼材を提供することを目的としたものである。
【０００６】
【課題を解決するための手段】
本発明は、水と固形分として水性樹脂および水性樹脂１００質量部に対して水酸化Ｍｇと微粒シリカとからなる複合コロイドを０．１〜５０質量部、微粒シリカを０．１〜１００質量部含有する金属用防錆剤であり、さらには、亜鉛めっき、亜鉛合金めっき、アルミ系合金めっきを施した鋼材の表面に該金属用防錆剤から形成した付着量０．１ｇ／ｍ2から１００ｇ／ｍ2の皮膜を有する防錆処理鋼材である。
【０００７】
【発明の実施の形態】
一般に、代替クロメート処理皮膜として有効であるためには、（１）腐食液や酸素等の腐食反応物質の浸透を防止すること、（２）防錆膜の金属素地との密着性を有すること、（３）防錆膜の傷つきや欠陥が生じた際に、露出した金属の腐食の抑制作用を有すること、（４）防錆膜の上塗り塗料との密着性が良好なこと等を満たす必要がある。このうち、（１）、（２）、（４）は水溶性樹脂の特性に大きく依存しており、樹脂構造の最適化で達成することが可能である。ただし、（１）に関しては、樹脂構造のみならず、シリカコロイド等の添加が有効であることが既に知られている。一方、（３）に関しては、樹脂に期待することは困難である。樹脂被覆層は、一旦傷つき等でダメージを受けるとそれを自己修復する機能を有さないからである。一方、クロメート皮膜の場合には、自己修復作用で皮膜欠陥部を修復し不動態化させることで耐食性を保持している。これは、６価のクロム酸が疵部に溶出し、露出金属部で金属と反応して３価の不動態性金属水酸化物を形成するためと考えられている。
【０００８】
したがって、クロメート処理以外で耐食性を向上させようとした場合には、水溶性樹脂による耐食性の発現を基本としつつ、皮膜の欠陥部での自己修復性もしくは耐食性を発現するための添加剤を付与する必要がある。この添加剤は、水溶性樹脂溶液に可溶であり、成膜した後には樹脂皮膜中で安定に存在し、皮膜の欠陥等で腐食環境に曝された時に初めて耐食性を発現するものでなければならない。本発明者らは、鋭意検討した結果、そのような作用を有する物質として水酸化Ｍｇとシリカコロイドからなる複合コロイドが最適であることを見出し、本発明となしたものである。
【０００９】
ここで、水酸化Ｍｇとは塗料中では微粒子もしくはコロイド状に分散して存在することが可能な物質である。さらに、複合コロイドとしては、この水酸化Ｍｇとシリカコロイドが吸着した状態で存在しているものをいう。このような複合コロイドは水素結合による吸着が主と推定されるが、一部はＭｇとＳｉが置換した状態で結合しているものも考えられる。この複合コロイドの作製方法は特に限定されるものではないが、例えば、純水中にシリカコロイドを分散させた後にケイ化Ｍｇの粉末を添加する方法がある。ケイ化Ｍｇはシリカコロイド水溶液に添加されると溶解し、Ｍｇ水酸化物とＳｉＯ2になるが、その際、既に溶液中に存在するシリカコロイドとも反応して複合コロイドを生成する。この複合コロイド中のＭｇは、塗膜中では、酸化Ｍｇ、水酸化Ｍｇ、あるいはＭｇイオンに変化したり、シリカコロイドと一体化した状態で塗膜中に分散している。
【００１０】
この複合コロイドの防錆剤としての作用機構は完全には解明されていないが、以下のように考えている。すなわち、複合コロイドは、塗料中で分散しているが、塗膜に疵部や欠陥部が生じて濡れ環境になると、溶出し金属露出部に吸着する。ここで、吸着層は腐食抑制のバリア層になることが期待できる。さらに、Ｍｇは亜鉛の腐食生成物を耐食性の良好な塩基性塩化亜鉛の状態で安定化する作用があり、腐食が初期の状態で停止する。
【００１１】
本発明の金属用防錆剤は、水と、固形分としての水性樹脂、水酸化Ｍｇと微粒シリカとからなる複合コロイド、及び微粒シリカからなるが、水性樹脂１００質量部に対して複合コロイドが０．１質量部未満では耐食性の発現効果が十分ではなく、５０質量部を超えると耐食性向上作用が飽和するだけでなく、塗料としての安定性が低下しゲル化しやすくなる。また、微粒シリカも０．１質量部未満では耐食性の発現効果が十分ではなく、１００質量部を超えると耐食性向上作用が飽和するだけでなく、塗料としての安定性が低下しゲル化しやすくなる。一般に、本発明の金属用防錆剤中の固形分含有量は、１〜７５％程度でよい。
【００１２】
次に本発明の金属用防錆剤は、各種の鋼材の表面に塗布することで耐食性の向上作用が得られるが、鋼材としては、例えば溶融亜鉛めっき鋼材、溶融Ｚｎ−Ａｌめっき鋼材、溶融Ｚｎ−Ａｌ−Ｍｇめっき鋼材、溶融Ｚｎ−Ａｌ−Ｍｇ−Ｓｉめっき鋼材、溶融Ｚｎ−Ａｌ−Ｓｉめっき鋼材、溶融Ａｌ−Ｓｉめっき鋼材、溶融Ａｌ−Ｓｉ−Ｍｇめっき鋼材、溶融Ａｌ−Ｓｉめっき鋼材、溶融Ｓｎ−Ｚｎめっき鋼材、溶融Ｚｎ−Ｆｅめっき鋼材、電気Ｚｎめっき鋼材、電気Ｚｎ−Ｆｅめっき鋼材、電気Ｚｎ−Ｎｉめっき鋼材、電気Ｚｎ−Ｃｏめっき鋼材、電気Ｚｎ−Ｃｒめっき鋼材、電気Ｚｎ−Ｍｇめっき鋼材がある。鋼材の形状は特に特定されないが、冷延鋼板、熱延鋼板、線材、棒鋼、鋼管等が挙げられる。
【００１３】
本発明で用いる水性樹脂としては、例えばポリオレフィン樹脂、ポリウレタン樹脂、アクリル樹脂、ポリカーボネート樹脂、エポキシ樹脂、ポリエステル樹脂、アルキド樹脂、フェノール樹脂、その他の加熱硬化型樹脂などがある。特に好ましい樹脂としては、ポリオレフィン樹脂、ポリウレタン樹脂がある。
【００１４】
本発明の微粒シリカは、微細な粒径を持つために水中に分散させたときに安定な分散状態を維持できる特性を有するものを総称して云うものである。例えば「スノーテックス−Ｏ」や「アデライトＡＴ−２０Ａ」やシリカゲル、アエロジルなどがある。
【００１５】
本発明の防錆剤は、上記の成分以外の成分を含有することもできる。例えば、顔料、界面活性剤、シランカップリング剤等がある。このような顔料としては、酸化チタン、酸化亜鉛、酸化ジルコニウム、炭化カルシウム、硫酸バリウム、アルミナ、カーボンブラック、酸化鉄などの無機顔料や有機顔料などがある。また、シランカップリング剤としては、例えば、γ−グリシドキシプロピルメトキシシラン、γ−グリシドキシプロピルエトキシシラン、γ−アミノプロピルトリメトキシシランなどがある。
【００１６】
本発明の防錆剤は、各種の被覆方法で被覆することが可能であり、例えば、ロールコーティング法、スプレイ法、ディップ法等がある。塗布後は乾燥、焼き付け処理をすることが望ましい。焼付け温度は水性樹脂により異なり、一義的には決まらないが、１００℃から２００℃程度の場合が多い。皮膜の付着量は、０．１ｇ／ｍ2未満では耐食性の向上作用が不足し、耐食性のみを考えれば５ｇ／ｍ2以上が望ましい。１００ｇ／ｍ2を超えると、耐食性向上作用が飽和するのみならず経済的でなく、皮膜の応力が大きくなり密着性が低下し、剥離による耐食性の低下が認められる。また、溶接性を確保する必要がある場合には、被覆後もある程度の通電性が必要であることから、３ｇ／ｍ2以下程度にすると良い。
【００１７】
【実施例】
次に実施例により本発明を更に詳しく述べる。
【００１８】
評価試料は、１５０ｍｍ×７０ｍｍ、厚さ１ｍｍの冷延鋼板に表１に示した各種のめっきを施したものを原板とし、防錆剤をバーコーターで塗布し、４００℃の熱風乾燥炉で板温が１５０℃となるように焼き付け、表１に示した付着量（ｇ／ｍ2)の塗膜を形成して作製した。防錆剤は、水性樹脂１００質量部に対し複合コロイドと微粒シリカを表１に示した量（質量部数）で配合して作製した。水性樹脂として東邦化学社製オレフィン樹脂、微粒シリカとして日産化学社製スノーテックス−Ｃ、ケイ化マグネシウムとして微粉末試薬を用いた。
【００１９】
耐食性の評価は、ＪＩＳ Ｚ ２３７１の塩水噴霧試験を２４０時間行い、白錆の発生面積率を５点満点で分類して評価した。
評価基準は、白錆発生面積に応じて、
５点：白錆発生無し
４点：白錆２０％以下
３点：白錆４０％以下
２点：白錆６０％以下
１点：白錆６１％以上
とした。評価は、平板部と７ｍｍ高さのエリクセン加工部（１０ｍｍφ）の二箇所についてそれぞれ行った。評点４以上を合格とした。
【００２０】
【表１】
実施例１から２７はいずれも白錆発生量が２０％以下の評点４以上であるのに対して、本発明の範囲外の比較例１から３は白錆発生量が４０％以上と耐食性が劣る結果となっている。
【００２２】
【発明の効果】
本発明の金属用防錆剤を用いることにより、鋼材の耐食性を向上させることができる。このことにより、亜鉛めっき層の付着量を低減させたり、更には、鋼材の寿命を高めることが可能となり、省資源、省エネルギーに貢献することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to zinc-based and aluminum-based alloy-plated steel materials used for home appliances, building materials, automobiles, and the like, and particularly relates to chromate-free zinc-based and aluminum-based alloy-plated steel materials that do not contain chromium and have excellent corrosion resistance. Is.
[0002]
[Prior art]
Zinc-plated steel, zinc-alloy-plated steel, or aluminum-based alloy-plated steel is used in electronic equipment that has white rust on the surface and is significantly damaged in environments containing salt such as seawater and high-temperature and high-humidity environments. If it is, there are problems such as loss of conductivity and grounding. Therefore, when using these plated steel materials, it is common to perform the chemical conversion treatment called chromate treatment to suppress the generation of white rust. This chromate treatment has a variety of treatment liquid configurations. For example, there is one in which a treatment liquid composed of chromic acid and silica colloid is applied and dried, and the amount of Cr deposited is as small as about 50 mg / m 2. Regardless, it has excellent white rust resistance. Also, the plated steel material is often used after being coated, but even in that case, the chromate treatment may be performed in order to improve the adhesion to the coating film.
[0003]
As described above, the chromate treatment is a treatment method that is generally used because the film to be formed is excellent in performance and can be easily and inexpensively treated into a steel material. However, since chromate treatment uses toxic chromic acid, drainage treatment in the treatment process and safety for workers, and further, hexavalent chromium at the time of disposal of products using chromate-treated steel There is a growing concern about the impact of elution on the global environment.
[0004]
Accordingly, attempts have been made to develop treatment methods that do not contain chromium at all. For example, JP-A-8-239776 discloses a treatment agent using sulfide. However, some sulfides emit a peculiar odor, which makes handling of these treatment agents worse. Japanese Patent Application Laid-Open No. 53-31737 discloses a water-soluble rust preventive paint to which a dithiol-S-triazine derivative is added. However, this rust preventive paint has been developed for the purpose of corrosion protection of metals such as mild steel, copper, and brass. Therefore, in the case of zinc-based and aluminum-based plated steel materials, the action of the triazine derivative is not sufficiently exhibited, and the action of improving corrosion resistance and adhesion is insufficient. This is because a rust preventive agent such as triazine thiol added to the water-soluble rust preventive paint exhibits an inhibitory action when adsorbed on the metal surface, and it is considered that the adsorptivity varies depending on the metal species.
[0005]
[Problems to be solved by the invention]
Thus, in order to improve the corrosion resistance and paint adhesion of zinc-based and aluminum-based plated steel materials, one measure is to find water-soluble paints containing rust inhibitors that effectively act on these metal surfaces. . However, the actual situation is that no effective anticorrosive agent has been found at present.
The present invention has been made in view of such a situation, and an object of the present invention is to provide a rust preventive agent, a rust preventive paint, and a rust preventive treated steel material that do not contain chromium and exhibit good corrosion resistance and paint adhesion.
[0006]
[Means for Solving the Problems]
In the present invention, 0.1-50 parts by mass of a composite colloid composed of Mg hydroxide and fine silica and 0.1-100 parts by mass of fine silica with respect to 100 parts by mass of an aqueous resin and an aqueous resin as water and solid content a metal anti-corrosion agent containing, furthermore, galvanized, zinc alloy plating, 100g from deposition amount 0.1 g / m 2 on the surface of the steel material which has been subjected to an aluminum-based alloy plating has been formed from the metal for rust agents It is a rust-proofing steel material having a / m 2 film.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
In general, in order to be effective as an alternative chromate treatment film, (1) to prevent the penetration of corrosion reaction materials such as corrosive liquid and oxygen, (2) to have adhesion to the metal substrate of the rust preventive film, (3) When the rust preventive film is damaged or defective, it must have the effect of inhibiting the corrosion of the exposed metal, and (4) It must satisfy the good adhesion with the top coat of the rust preventive film. is there. Among these, (1), (2), and (4) depend greatly on the characteristics of the water-soluble resin, and can be achieved by optimizing the resin structure. However, regarding (1), it is already known that addition of not only the resin structure but also silica colloid or the like is effective. On the other hand, regarding (3), it is difficult to expect the resin. This is because the resin coating layer does not have a function of self-healing once it is damaged due to scratches or the like. On the other hand, in the case of a chromate film, the corrosion resistance is maintained by repairing and passivating the film defect by a self-repairing action. This is thought to be because hexavalent chromic acid elutes in the collar and reacts with the metal at the exposed metal to form a trivalent passive metal hydroxide.
[0008]
Therefore, when trying to improve the corrosion resistance other than the chromate treatment, an additive for expressing self-repairability or corrosion resistance at the defective part of the film is given while the basic expression is corrosion resistance by the water-soluble resin. There is a need. This additive must be soluble in a water-soluble resin solution, stably present in the resin film after film formation, and not exhibit corrosion resistance for the first time when exposed to a corrosive environment due to film defects, etc. Don't be. As a result of intensive studies, the present inventors have found that a composite colloid composed of Mg hydroxide and silica colloid is optimal as a substance having such an action, and the present invention has been achieved.
[0009]
Here, Mg hydroxide is a substance that can be dispersed in the form of fine particles or colloid in the paint. Further, the composite colloid refers to a composite colloid existing in a state where Mg hydroxide and silica colloid are adsorbed. Such a composite colloid is presumed to be mainly adsorbed by hydrogen bonds, but some may be bonded in a state where Mg and Si are substituted. The method for producing this composite colloid is not particularly limited. For example, there is a method in which a silica colloid is dispersed in pure water and then Mg silicide powder is added. Mg silicide dissolves when added to an aqueous silica colloid solution to become Mg hydroxide and SiO 2 , but at this time, it reacts with the silica colloid already present in the solution to form a composite colloid. Mg in the composite colloid is dispersed in the coating film in the state of being changed to Mg oxide, Mg hydroxide, or Mg ion, or being integrated with the silica colloid.
[0010]
The mechanism of action of this composite colloid as a rust inhibitor has not been fully elucidated, but is considered as follows. That is, the composite colloid is dispersed in the coating material, but when a ridge or a defect occurs in the coating film and becomes a wet environment, it elutes and adsorbs on the exposed metal part. Here, the adsorption layer can be expected to become a barrier layer for inhibiting corrosion. Furthermore, Mg has the effect | action which stabilizes the corrosion product of zinc in the state of basic zinc chloride with favorable corrosion resistance, and corrosion stops in an initial state.
[0011]
The metal anticorrosive agent of the present invention is composed of water, an aqueous resin as a solid content, a composite colloid composed of Mg hydroxide and fine silica, and fine silica, but the composite colloid is contained in 100 parts by mass of the aqueous resin. If the amount is less than 0.1 parts by mass, the effect of developing the corrosion resistance is not sufficient. If the amount exceeds 50 parts by mass, not only the corrosion resistance improving action is saturated, but also the stability as a paint is lowered and gelation tends to occur. Also, if the fine silica is less than 0.1 parts by mass, the effect of developing the corrosion resistance is not sufficient, and if it exceeds 100 parts by mass, not only the corrosion resistance improving action is saturated, but also the stability as a paint is lowered and the gelation tends to occur. Generally, the solid content in the metal rust preventive of the present invention may be about 1 to 75%.
[0012]
Next, the anticorrosive agent for metals of the present invention can improve the corrosion resistance by applying to the surface of various steel materials. Examples of the steel materials include hot dip galvanized steel, hot dip Zn-Al galvanized steel, hot dip Zn. -Al-Mg plated steel material, molten Zn-Al-Mg-Si plated steel material, molten Zn-Al-Si plated steel material, molten Al-Si plated steel material, molten Al-Si-Mg plated steel material, molten Al-Si plated steel material, Hot Sn-Zn plated steel, Hot Zn-Fe plated steel, Electrical Zn plated steel, Electrical Zn-Fe plated steel, Electrical Zn-Ni plated steel, Electrical Zn-Co plated steel, Electrical Zn-Cr plated steel, Electrical Zn- There is Mg plated steel. The shape of the steel material is not particularly specified, and examples thereof include a cold-rolled steel plate, a hot-rolled steel plate, a wire rod, a bar steel, and a steel pipe.
[0013]
Examples of the aqueous resin used in the present invention include polyolefin resins, polyurethane resins, acrylic resins, polycarbonate resins, epoxy resins, polyester resins, alkyd resins, phenol resins, and other thermosetting resins. Particularly preferred resins include polyolefin resins and polyurethane resins.
[0014]
The fine silica of the present invention is a generic term for a fine silica having a characteristic that can maintain a stable dispersion state when dispersed in water. For example, there are “Snowtex-O”, “Adelite AT-20A”, silica gel, Aerosil and the like.
[0015]
The rust preventive agent of the present invention can also contain components other than the above components. For example, there are pigments, surfactants, silane coupling agents and the like. Examples of such pigments include inorganic pigments and organic pigments such as titanium oxide, zinc oxide, zirconium oxide, calcium carbide, barium sulfate, alumina, carbon black, and iron oxide. Examples of the silane coupling agent include γ-glycidoxypropylmethoxysilane, γ-glycidoxypropylethoxysilane, and γ-aminopropyltrimethoxysilane.
[0016]
The rust preventive agent of the present invention can be coated by various coating methods such as a roll coating method, a spray method, a dip method, and the like. It is desirable to dry and bake after coating. The baking temperature differs depending on the aqueous resin and is not uniquely determined, but is often about 100 ° C. to 200 ° C. If the coating amount is less than 0.1 g / m 2 , the effect of improving the corrosion resistance is insufficient, and if considering only the corrosion resistance, 5 g / m 2 or more is desirable. When it exceeds 100 g / m 2 , the corrosion resistance improving action is saturated and it is not economical, and the stress of the film increases, the adhesion decreases, and a decrease in corrosion resistance due to peeling is observed. In addition, when it is necessary to ensure weldability, a certain degree of electrical conductivity is required even after coating, and therefore it is preferable to set it to about 3 g / m 2 or less.
[0017]
【Example】
Next, the present invention will be described in more detail by way of examples.
[0018]
The evaluation sample is a cold-rolled steel sheet of 150 mm x 70 mm, 1 mm thick, with various platings shown in Table 1 as the original plate, coated with a rust preventive agent with a bar coater, and plated in a hot air drying oven at 400 ° C. The film was baked to a temperature of 150 ° C., and a coating film having an adhesion amount (g / m 2 ) shown in Table 1 was formed. The rust preventive was prepared by blending the composite colloid and fine silica in the amount (parts by mass) shown in Table 1 with 100 parts by mass of the aqueous resin. An olefin resin manufactured by Toho Chemical Co., Ltd. was used as an aqueous resin, Snowtex-C manufactured by Nissan Chemical Co., Ltd. as fine silica, and a fine powder reagent as magnesium silicide.
[0019]
Corrosion resistance was evaluated by conducting a salt spray test of JIS Z 2371 for 240 hours and classifying the area ratio of white rust on a 5-point scale.
The evaluation criteria are as follows:
5 points: no white rust generation 4 points: white rust 20% or less 3 points: white rust 40% or less 2 points: white rust 60% or less 1 point: white rust 61% or more The evaluation was performed for two portions of the flat plate portion and the 7 mm high Erichsen processed portion (10 mmφ). A score of 4 or higher was accepted.
[0020]
[Table 1]
In each of Examples 1 to 27, white rust generation amount is 20% or less with a rating of 4 or more, while Comparative Examples 1 to 3 outside the scope of the present invention have white rust generation amount of 40% or more and corrosion resistance. The result is inferior.
[0022]
【The invention's effect】
By using the metal anticorrosive agent of the present invention, the corrosion resistance of the steel material can be improved. This makes it possible to reduce the adhesion amount of the galvanized layer and further to increase the life of the steel material, thereby contributing to resource saving and energy saving.
Claims (2)
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| Application Number | Priority Date | Filing Date | Title |
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| JP2001124463A JP4648565B2 (en) | 2001-04-23 | 2001-04-23 | Rust preventive agent for metal and steel |
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| JP2001124463A JP4648565B2 (en) | 2001-04-23 | 2001-04-23 | Rust preventive agent for metal and steel |
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| JP4648565B2 true JP4648565B2 (en) | 2011-03-09 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2003082271A (en) * | 2001-09-11 | 2003-03-19 | Tohcello Co Ltd | Coating composition and laminated body |
| WO2019188461A1 (en) * | 2018-03-29 | 2019-10-03 | 株式会社神戸製鋼所 | Coated galvanized steel sheet |
| JP7235556B2 (en) * | 2018-03-29 | 2023-03-08 | 株式会社神戸製鋼所 | Painted galvanized steel sheet |
| JP7166955B2 (en) * | 2018-03-29 | 2022-11-08 | 株式会社神戸製鋼所 | Painted galvanized steel sheet |
| JP7112349B2 (en) | 2018-03-29 | 2022-08-03 | 株式会社神戸製鋼所 | Painted galvanized steel sheet |
| WO2019188460A1 (en) * | 2018-03-29 | 2019-10-03 | 株式会社神戸製鋼所 | Coated galvanized steel sheet |
| JP7112350B2 (en) | 2018-03-29 | 2022-08-03 | 株式会社神戸製鋼所 | Painted galvanized steel sheet |
| WO2019188237A1 (en) * | 2018-03-29 | 2019-10-03 | 株式会社神戸製鋼所 | Coated galvanized steel sheet |
| KR102636130B1 (en) * | 2022-03-04 | 2024-02-15 | 고려제강 주식회사 | Steel wire and Spring with excellent antibacterial and corrosion resistance and Manufacturing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2001049455A (en) * | 1999-08-17 | 2001-02-20 | Nippon Steel Corp | Chromium-free high corrosion resistance surface treated metallic material |
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| JP2001049455A (en) * | 1999-08-17 | 2001-02-20 | Nippon Steel Corp | Chromium-free high corrosion resistance surface treated metallic material |
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