JP2004084002A - Surface treatment film superior in corrosion-preventive property and lubricity, solution for forming it, and metallic material coated with surface treatment film - Google Patents
Surface treatment film superior in corrosion-preventive property and lubricity, solution for forming it, and metallic material coated with surface treatment film Download PDFInfo
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【０００１】
【発明の属する技術分野】
本発明は、クロムや鉛成分を含有することなく防食性、潤滑性に優れた表面処理膜とそれを形成するための溶液、および表面処理膜を塗装した金属材料に関するものである。
【０００２】
【従来の技術】
従来から、金属材料や金属部品等における耐腐食性の向上を目的として種々の表面処理剤が開発され実用に供されている。一般的に、腐食の要因は金属表面における酸化反応であり、これを防止するのに空気遮断を目的として金属表面に塗装や塗油を施して表面処理膜を形成することが行われている。
【０００３】
しかしながら、従来の表面処理膜では機械的強度が弱く、また金属との結合力も弱いため膜厚を十分に厚くする必要があり、高い寸法精度を要求される金属部品等においては寸法が変わってしまい適用することができないという問題点や、薄膜にするとクラックを生じて耐久性・防水性等が低下するという問題点があった。また、小物部品に塗装した場合、部品どうしが接着してしまい後で分離工程を必要とし、更にこの分離工程で塗膜が剥離して不良品を発生させる場合があるという問題点や、膜の焼付け時に母材の熱膨張の影響でクラックを発生させるもという問題点あった。
【０００４】
【発明が解決しようとする課題】
本発明は上記のような従来の問題点を解決して、膜厚を薄くしても十分な機械的強度や金属との結合力を得ることができ、また伸縮性があってクラックの発生を最小に抑えることができて優れた耐食性を発揮し、しかも塗装時における部品どうしの接着も防止して生産効率を高めることができ、更には母材の熱膨張の影響も受けにくくクラックの発生を有効に防止することができる防食性、潤滑性に優れた表面処理膜とそれを形成するための溶液、および表面処理膜を塗装した金属材料を提供することを目的として完成されたものである。
【０００５】
【課題を解決するための手段】
上記の課題を解決するためになされた本発明は、アスペクト比が３０〜１７０００のフィラーと金属微粒子と樹脂を主成分とし、前記フィラーが積層された状態となっていることを特徴とする防食性、潤滑性に優れた表面処理膜と、前記各主成分を有機溶媒に分散させて、常温常圧における粘度を１０ｐａ・Ｓ以下とした防食性、潤滑性に優れた表面処理膜を形成するための溶液と、前記防食性、潤滑性に優れた表面処理膜を形成した金属材料である。
【０００６】
【発明の実施の形態】
以下に、本発明の好ましい実施の形態を示す。
本発明の表面処理膜は、アスペクト比が３０〜１７０００のフィラーと金属微粒子と樹脂を主成分とし、前記フィラーが積層された状態となっている点に特徴を有する。
ここでアスペクト比とは、フィラーの長さ／厚みの比をいい、このようなアスペクト比が３０以上の大きいフィラーを層状に含有させることにより、処理膜自体のバリアー性と伸縮性を同時に兼ね備えたものとし、高い耐腐食性を発揮させることができる。ただし、アスペクト比が１７０００より大きいと、分散性が損なわれ、スプレー塗装時に塗料ミストが安定せず塗装ムラを起こしやすいとともに、ノズルの詰まり現象を起こしやすいので１７０００以下とする。なお、ここでいうフィラーとは、無機物であり扁平な板形状のものである。
【０００７】
前記フィラーは０．１〜５０重量％、好ましくは１．０〜３０重量％、金属微粒子は１．０〜９５重量％、好ましくは５．０〜８０重量％、樹脂は０．１〜８０重量％、好ましくは１．０〜６０重量％含んでいる。なお、後述するように、金属酸化物を０．１〜８０重量％の範囲で適宜加えることもできる。
フィラーが０．１重量％未満では後述するように塩水浸漬テストに顕著な効果が認められず、５０重量％より多いと処理剤の寿命が著しく低下することが確認されている。
前記金属微粒子は、母材に対して犠牲電極性を有し、金属表面における電極電位の差を小さくして電池反応を抑制するので、腐食の進行を阻止し耐腐食性を高めることができる。なお、金属微粒子としては、例えば、亜鉛、アルミニウム、錫、マグネシウム、鉄、ニッケル、チタン、けい素、ジルコニウム等を用いることができる。
金属微粒子が１．０重量％未満では塩水浸漬テストに顕著な効果が認められず、９５重量％より多いと処理剤の沈降現象が大きく使用上好ましくない。
樹脂が０．１重量％未満では塗膜の柔軟性が低下し、焼付け時のクラックの促進を招き、防食性が低下する。一方、８０重量％より多いと粘度が高くまた、ゲル化が早いため、処理剤の寿命を著しく低下させるだけでなく、フィラーの分散性も低下する。
【０００８】
また、前記主成分として、更に金属酸化物を含有させることもできる。
金属酸化物は隠ぺい力の向上を目的とするもので、０．１重量％未満では塗膜表面に存在する微細な空孔を目止めする効果が低く、防食性が低下する。一方、８０重量％より多いと表面処理剤の寿命を低下させ、また沈降現象を促進し再分散化を阻害する。
このような金属酸化物としては、例えば、酸化亜鉛、アルミナ、酸化錫、酸化鉄、酸化ニッケル、酸化チタン、酸化ケイ素、酸化ジルコニウム等を用いることができる。
【０００９】
前記フィラー成分としては、雲母を用いることができる。雲母は、白雲母、ソーダ雲母、金雲母、燐雲母等の天然雲母、あるいはフッ素金雲母、フッ素四珪素雲母等の人工雲母が使用できる。
【００１０】
更に、雲母の表面が酸化チタンで被覆してあるものとすることもできる。この場合は、溶液での分散が容易となる利点がある。酸化チタンはアナターゼまたはルチル結晶であり、その被覆率は１０〜７０％の範囲が好ましい。
また、雲母の表面が酸化チタンで被覆後、更に酸化鉄で被覆してあるものとすることもでき、酸化鉄の被覆率は２０〜６０％の範囲が好ましい。
【００１１】
なお、雲母の平均粒径は１〜５００μｍの範囲が好ましく、また雲母の厚みは３００Å以上が好ましい。
【００１２】
また本発明では、前述したようなフィラー、金属微粒子、樹脂、更に金属酸化物の各主成分を有機溶媒に分散させて、常温常圧における粘度を１０ｐａ・Ｓ以下（１ｐａ・Ｓ＝１０ポイズ）とした溶液を用いて、防食性、潤滑性に優れた表面処理膜を形成する。
ここで、常温常圧における粘度を１０ｐａ・Ｓ以下としたのは、これより大きいと処理溶液の取り扱いが難しくなるとともに、薄くて均一な塗膜の成形が難しくなるからである。
【００１３】
また、前記有機溶媒として直鎖のアルコール系で、塗膜中成分の金属酸化物の出発原料として有機金属化合物を混合したものを用いることもできる。
有機金属化合物は、Ｒ１ｎ（Ｍ）ｍＯＲ２の化学式で表記される。
Ｍは金属系成分で、例えばＳｉ、Ｔｉ、Ｚｒ、Ｍｇ、Ａｌ、Ｓｎ、Ｚｎ、Ｆｅ、Ｎｉ等である。
Ｒ１、Ｒ２はアルコキシド構成成分で、例えばメチル基、エチル基、プロピル基、ブチル基、アルキル基、ビニル基、アリル基、エポキシ基、フェニル基、トリル基、アクリル基、メタクリロキシル基等である。また、ｎ＝０〜３、ｍ＝１〜４である。
【００１４】
以上にような溶液を用いて、各種金属材料や金属部品の表面に防食性、潤滑性に優れた表面処理膜を形成する。この場合、塗布方法としてはスプレー法や刷毛塗り法やディッピング法等、任意の手段を適用することができる。また、防食性、潤滑性に優れた表面処理膜を二層コートとして塗装することもでき、更に、三層以上にコートすることも勿論可能である。
【００１５】
このように、本発明の表面処理膜は、アスペクト比が３０〜１７０００のフィラーと金属微粒子と樹脂を主成分とし、前記フィラーが積層された状態となった構造であり、以下のような種々の効果を発揮することとなる。
（１）無機有機複合塗膜であり、またフィラーの積層構造であるために、塗膜焼付け時の母材熱膨張係数に左右されにくく、伸縮性があり、クラックの発
生を最小に抑えることができる。
（２）アスペクト比の高い無機フィラーを含有するので、処理膜のバリアー性が高く、また伸縮性も同時に兼ね備えており、高い耐腐食性を得ることがで
きる。
（３）金属微粒子を含有することにより、母材に対して犠牲電極性を有する。
（４）扁平無機フィラーを含有するために、特に小物部品に塗装する際の製品ど
うしの接着を防止しながら塗装を行う事ができる。
（５）特に、薄膜で耐食性を向上させたい部分へ適応でき、金属部品等の塗装に
より製品寸法形状を損なうことなく処理することが可能となる。
（６）使用する雲母の酸化チタン及び酸化鉄による着色効果が得られ、意匠性も
向上させることができる。
（７）表面処理工程において、溶液乾燥時の付着性が雲母の剥離性により改善さ
れ、容易に分離できることとなる。
（８）十分な潤滑性を付与することができる。
（９）従来のようにクロム、鉛成分を含有しておらず安全性に優れており、しか
も高い防食性が得られる。
【００１６】
＜実施例１＞
塗装溶液の調整として、工業用エタノール、工業用イソプロパノール、工業用ブタノールにポリビニルブチラールを溶解させ、金属微粉末、板状無機粉末を混合して攪拌分散して塗装溶液を調整した。各成分の重量比は以下の通りである。
工業用エタノール ５００部
工業用イソプロパノール ３００部
工業用ブタノール ８０部
テトラエチルオルソシリケート １０部
ポリビニルブチラール ３０部
亜鉛微粉末 ５０部
メルク社製イリオジン（１００）２０部
上記塗装溶液をテトラエチルオルソシリケート加水分解終了後に、各成分を混合し、ディスパーで攪拌し調整した。得られた塗装溶液をスプレーガンにて母材に噴霧し塗膜を作成した後、１７５℃の乾燥機中で３０分焼付けを行い塗膜とした。なお、噴霧圧はエアー量が２０Ｌ／ｍｉｎで、塗料送りスピードは８〜９ｃｃ／ｍｉｎとした。得られた塗膜を各温度で焼成後、蛍光Ｘ線にて各成分比率を測定した結果は、表１に示すとおりであった。
【００１７】
【表１】
＜実施例２＞
回転式のバレルスプレーにより小物部品に塗膜を作成し、耐湿性テスト（８０℃９５％ＲＨ保持）、耐塩水性テスト（５重量％ＮａＣｌａｑ浸漬）、３５℃塩水噴霧テスト（ＪＩＳ Ｚ２３７１準拠）を行い、塗膜の耐食性能を調査した。なお、塗膜作成スピードは１〜１．５μｍ／ｍｉｎで行った。
使用サンプルは、７ｍｍ×５．５ｍｍφ円筒形部品を用い、各耐食テストは以下の内容で行った。
耐湿テスト；８０℃９５％ＲＨ恒温恒湿槽内で２００Ｈ保持後のサンプルの状態を観察した。
塩水浸漬テスト；５重量％ＮａＣｌａｑ中に室温で浸漬。２４時間後のサンプルの状態を観察した。
塩水噴霧テスト；ＪＩＳ Ｚ２３７１に準拠した塩水噴霧テストを行った。
テスト結果は、表２に示すとおりであった。
【表２】
【表３】
＜実施例３＞
希土類磁石（Ｎｄ−Ｆｅ−Ｂボンド磁石）の表面に塗装したサンプルを恒温恒湿槽８０℃（９５％ＲＨ）に保持し、経時変化を調査した。なお、サンプルの塗装条件（塗装時間、塗料送り、焼付け温度、焼付け時間）は、前記実施例２と同じである。
テスト結果は、表５に示すとおりであった。
Ｎ＝１０で実施し、Ｘ／１０でＸ値は実体顕微鏡３０倍で点錆を確認できた数である。また、各サンプル５〜１０は以下のとおりであり、各サンプルのコート組成は表４に示すとおりである。
サンプル５；ＮＯ ＣＯＡＴ
サンプル６；エポキシ樹脂コート
サンプル７；金属粉末を樹脂に混練した塗装膜コート
サンプル８；金属粉末＋金属酸化物粉末を樹脂に混練した塗装膜コート
サンプル９、サンプル１０；金属粉末＋扁平金属酸化物粉末を樹脂に混練した塗装膜コート
【表４】
また、塩水浸漬テストとして、５重量％塩化ナトリウム水溶液にサンプルを浸漬し室温（２３℃）で保持各時間後にサンプルを実体顕微鏡観察した。サンプル塗装条件は同条件（塗装時間、塗料送り、焼付け温度、焼付け時間）である。得られた結果を表６に示す。
【表６】
なお、図２に塗膜表面のＳＥＭ写真を示すが、扁平雲母が重なるようにして皮膜を形成していることが判る。
【００２１】
＜実施例４＞
雲母サイズの表面処理時の剥離効果試験として、バレルスプレー塗装条件を、表面処理材送りスピード８ｃｃ／ｍｉｎ、エアー圧０．１〜０．３Ｍｐａ、エアー量１０Ｌ／ｍｉｎ、治具回転スピード１５回転／ｍｉｎ、塗装時間１５分で行った。サンプル処理剤を３種類調整し、所定の時間バレルスプレーコートを磁石部品に施して下記のようなサンプル１１〜サンプル１４とし、製品同士の接着度合いを目視で確認して評価した。
サンプル１１：雲母粉体を混合していない塗装
サンプル１２：粒径の大きな雲母Ａ（平均＝７０μｍ）を３重量％添加した処理剤で塗装
サンプル１３：粒径の小さな雲母Ｂ（１５μｍアンダー）を３重量％添加した処理剤でのコート
サンプル１４：雲母ＡとＢを１：１で混合した粉末を３重量％添加した処理剤のコート。
評価は目視で行い、投入磁石部品の数量に対して１０％以上の接着があったものに関しては×、１％以上１０％未満の接着があったものに関しては△、１％以下の接着は○と評価した。得られた結果を表７に示す。
なお、使用した磁石のサイズは、７ｍｍ×５．５ｍｍφ円筒形部品である。
この表７からも明らかなように、添加した扁平無機物の雲母が層間剥離現象を起こすため、接触する塗装面のすべり性を向上させるとともに、さらに塗膜の剥れ現象を防止することが確認できた。
【表７】
＜実施例５＞
表８に示すように、扁平無機物（メルク社製イリオジン）として種々の色のものを添加した結果、塗装膜自体の外観色を変化させることが可能であることが確認できた。
【表８】
【発明の効果】
以上の説明からも明らかなように、本発明は膜厚を薄くしても十分な機械的強度や金属との結合力を得ることができ、また伸縮性があってクラックの発生を最小に抑えることができて優れた耐食性を発揮し、しかも塗装時における部品どうしの接着も防止して生産効率を高めることができ、更には母材の熱膨張の影響も受けにくくクラックの発生を有効に防止することができるものである。
よって本発明は従来の問題点を一掃した防食性、潤滑性に優れた表面処理膜とそれを形成するための溶液、および表面処理膜を塗装した金属材料として、産業の発展に寄与するところは極めて大である。
【図面の簡単な説明】
【図１】膜厚と塗装時間の関係を示すグラフである。
【図２】塗膜表面のＳＥＭ写真である。[0001]
TECHNICAL FIELD OF THE INVENTION
TECHNICAL FIELD The present invention relates to a surface treatment film having excellent corrosion protection and lubricity without containing chromium and lead components, a solution for forming the same, and a metal material coated with the surface treatment film.
[0002]
[Prior art]
BACKGROUND ART Conventionally, various surface treatment agents have been developed and put to practical use for the purpose of improving the corrosion resistance of metal materials and metal parts. Generally, the cause of corrosion is an oxidation reaction on a metal surface, and in order to prevent this, a coating or oiling is applied to the metal surface to form a surface treatment film for the purpose of blocking air.
[0003]
However, the mechanical strength of the conventional surface treatment film is weak, and the bonding force with the metal is also weak. Therefore, the film thickness needs to be sufficiently large, and the dimensions of metal parts and the like that require high dimensional accuracy are changed. There is a problem that it cannot be applied, and there is a problem that when it is made into a thin film, cracks are generated, and durability and waterproofness are reduced. Also, when applied to small parts, the parts adhere to each other and require a separation step later, and furthermore, in this separation step, the coating film may be peeled off and defective products may be generated. There is a problem that cracks are generated due to the thermal expansion of the base material during baking.
[0004]
[Problems to be solved by the invention]
The present invention solves the conventional problems as described above, and can obtain sufficient mechanical strength and bonding force with metal even when the film thickness is reduced. It can be suppressed to a minimum and exhibits excellent corrosion resistance, and also prevents adhesion of parts during painting, increasing production efficiency, and is less susceptible to thermal expansion of the base material, and reduces the occurrence of cracks It has been completed for the purpose of providing a surface treatment film excellent in corrosion resistance and lubricity that can be effectively prevented, a solution for forming the same, and a metal material coated with the surface treatment film.
[0005]
[Means for Solving the Problems]
The present invention made in order to solve the above-mentioned problem has an anticorrosion property characterized in that a filler having an aspect ratio of 30 to 17000, metal fine particles, and a resin are main components, and the filler is laminated. In order to form a surface-treated film having excellent lubricity and a surface-treated film having excellent anti-corrosion properties and lubricity having a viscosity at room temperature and normal pressure of 10 pa · S or less by dispersing the above main components in an organic solvent. And a metal material formed with the above solution and a surface treatment film having excellent corrosion resistance and lubricity.
[0006]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, preferred embodiments of the present invention will be described.
The surface treatment film of the present invention is characterized in that a filler having an aspect ratio of 30 to 17000, metal fine particles and a resin are the main components, and the filler is laminated.
Here, the aspect ratio refers to the ratio of the length / thickness of the filler. By including such a large filler having an aspect ratio of 30 or more in a layer, the treated film itself has both the barrier property and the elasticity at the same time. It can exhibit high corrosion resistance. However, if the aspect ratio is larger than 17000, the dispersibility is impaired, and the paint mist is not stable during spray coating, which tends to cause coating unevenness and nozzle clogging. The filler referred to here is an inorganic substance having a flat plate shape.
[0007]
The filler is 0.1 to 50% by weight, preferably 1.0 to 30% by weight, the metal fine particles are 1.0 to 95% by weight, preferably 5.0 to 80% by weight, and the resin is 0.1 to 80% by weight. %, Preferably 1.0 to 60% by weight. In addition, as described later, a metal oxide can be appropriately added in a range of 0.1 to 80% by weight.
When the amount of the filler is less than 0.1% by weight, no remarkable effect is observed in the salt water immersion test as described later, and when the amount is more than 50% by weight, it is confirmed that the life of the treating agent is significantly reduced.
The metal fine particles have a sacrificial electrode property with respect to the base material, and reduce the difference in electrode potential on the metal surface to suppress the battery reaction, so that the progress of corrosion can be prevented and the corrosion resistance can be increased. In addition, as the metal fine particles, for example, zinc, aluminum, tin, magnesium, iron, nickel, titanium, silicon, zirconium and the like can be used.
When the amount of the metal fine particles is less than 1.0% by weight, a remarkable effect in the salt water immersion test is not recognized, and when the amount is more than 95% by weight, the treatment agent sedimentation phenomenon is large, which is not preferable in use.
If the amount of the resin is less than 0.1% by weight, the flexibility of the coating film is reduced, which promotes cracks during baking and lowers the corrosion resistance. On the other hand, when the content is more than 80% by weight, the viscosity is high and the gelation is fast, so that not only the life of the treating agent is significantly reduced, but also the dispersibility of the filler is reduced.
[0008]
Further, a metal oxide can be further contained as the main component.
The purpose of the metal oxide is to improve the hiding power. When the content is less than 0.1% by weight, the effect of blocking fine pores existing on the coating film surface is low, and the anticorrosion property is reduced. On the other hand, when the content is more than 80% by weight, the life of the surface treating agent is shortened, the sedimentation phenomenon is promoted, and redispersion is inhibited.
As such a metal oxide, for example, zinc oxide, alumina, tin oxide, iron oxide, nickel oxide, titanium oxide, silicon oxide, zirconium oxide, or the like can be used.
[0009]
As the filler component, mica can be used. As the mica, natural mica such as muscovite, soda mica, phlogopite and phosphorous mica, or artificial mica such as fluorophlogopite and tetrasilicon mica can be used.
[0010]
Further, the surface of the mica may be coated with titanium oxide. In this case, there is an advantage that dispersion in a solution becomes easy. Titanium oxide is an anatase or rutile crystal, and its coverage is preferably in the range of 10 to 70%.
Further, the surface of the mica may be coated with titanium oxide and then further coated with iron oxide, and the coating ratio of iron oxide is preferably in the range of 20 to 60%.
[0011]
The average particle size of the mica is preferably in the range of 1 to 500 μm, and the thickness of the mica is preferably 300 ° or more.
[0012]
Further, in the present invention, the above-mentioned main components of the filler, metal fine particles, resin, and metal oxide are dispersed in an organic solvent, and the viscosity at room temperature and normal pressure is 10 pa · S or less (1 pa · S = 10 poise). A surface treatment film having excellent anticorrosion properties and lubricity is formed by using the above solution.
Here, the reason why the viscosity at normal temperature and normal pressure is 10 pa · S or less is that if the viscosity is higher than this, it becomes difficult to handle the processing solution and it is difficult to form a thin and uniform coating film.
[0013]
Alternatively, a mixture of an organic metal compound as a starting material of a metal oxide as a component in a coating film, which is a linear alcohol-based organic solvent, may be used.
The organometallic compound is represented by a chemical formula of R1n (M) mOR2.
M is a metal component, for example, Si, Ti, Zr, Mg, Al, Sn, Zn, Fe, Ni, or the like.
R1 and R2 are alkoxide constituents such as a methyl group, an ethyl group, a propyl group, a butyl group, an alkyl group, a vinyl group, an allyl group, an epoxy group, a phenyl group, a tolyl group, an acryl group, and a methacryloxyl group. . Further, n = 0 to 3 and m = 1 to 4.
[0014]
By using the above-mentioned solution, a surface treatment film having excellent corrosion resistance and lubricity is formed on the surface of various metal materials and metal parts. In this case, as a coating method, any means such as a spray method, a brush coating method, and a dipping method can be applied. In addition, a surface treatment film having excellent anticorrosion properties and lubricity can be applied as a two-layer coating, and it is of course possible to coat three or more layers.
[0015]
As described above, the surface treatment film of the present invention has a structure in which an aspect ratio is mainly composed of a filler having a particle size of 30 to 17000, metal fine particles, and a resin, and the filler is laminated. It will be effective.
(1) Since it is an inorganic-organic composite coating film and has a laminated structure of filler, it is hardly influenced by the thermal expansion coefficient of the base material when the coating film is baked, has elasticity, and minimizes the occurrence of cracks. it can.
(2) Since the treated film contains an inorganic filler having a high aspect ratio, the treated film has high barrier properties and also has elasticity, so that high corrosion resistance can be obtained.
(3) By containing metal fine particles, the base material has sacrificial electrode properties.
(4) Since the flat inorganic filler is contained, coating can be performed while preventing adhesion between products particularly when coating small parts.
(5) In particular, the thin film can be applied to a portion where corrosion resistance is desired to be improved, and it is possible to apply a metal part or the like to a product without impairing the product dimensions and shape.
(6) The coloring effect of the mica used by titanium oxide and iron oxide can be obtained, and the design can be improved.
(7) In the surface treatment step, the adhesiveness at the time of drying the solution is improved by the peelability of the mica, so that the mica can be easily separated.
(8) Sufficient lubricity can be provided.
(9) It does not contain chromium and lead components as in the prior art, is excellent in safety, and has high corrosion resistance.
[0016]
<Example 1>
As a preparation of the coating solution, polyvinyl butyral was dissolved in industrial ethanol, industrial isopropanol, and industrial butanol, and a metal fine powder and a plate-like inorganic powder were mixed and dispersed by stirring to prepare a coating solution. The weight ratio of each component is as follows.
Industrial ethanol 500 parts Industrial isopropanol 300 parts Industrial butanol 80
[0017]
[Table 1]
<Example 2>
A coating film is formed on small parts by rotary barrel spraying, and a moisture resistance test (80 ° C., 95% RH retention), a salt water resistance test (5% by weight NaClaq immersion), and a 35 ° C. salt water spray test (JIS Z2371 compliant) are performed. The corrosion resistance of the coating film was investigated. In addition, the coating film formation speed was 1 to 1.5 μm / min.
The sample used was a 7 mm × 5.5 mm φ cylindrical part, and each corrosion resistance test was performed as follows.
Moisture resistance test: The state of the sample after holding for 200 hours in an 80 ° C., 95% RH constant temperature and humidity chamber was observed.
Salt water immersion test; immersion in 5% by weight NaClaq at room temperature. The state of the sample after 24 hours was observed.
Salt spray test: A salt spray test based on JIS Z2371 was performed.
The test results were as shown in Table 2.
[Table 2]
[Table 3]
<Example 3>
The sample coated on the surface of the rare earth magnet (Nd-Fe-B bonded magnet) was kept in a constant temperature and humidity chamber at 80 ° C (95% RH), and the change with time was examined. The coating conditions of the sample (coating time, paint feed, baking temperature, baking time) are the same as those in Example 2.
The test results were as shown in Table 5.
The test was carried out at N = 10, and the X value at X / 10 is the number at which spot rust was confirmed with a stereoscopic microscope at 30 ×. The samples 5 to 10 are as follows, and the coating composition of each sample is as shown in Table 4.
Sample 5: NO COAT
Sample 6; Epoxy resin coated sample 7; Paint film coated with metal powder kneaded in resin Sample 8; Painted film coated with metal powder + metal oxide powder kneaded in resin Sample 9, Sample 10: Metal powder + flat metal oxide Painted film coat made by kneading powder with resin [Table 4]
As a salt water immersion test, the sample was immersed in a 5% by weight aqueous solution of sodium chloride and kept at room temperature (23 ° C.). The sample coating conditions were the same (coating time, paint feed, baking temperature, baking time). Table 6 shows the obtained results.
[Table 6]
In addition, FIG. 2 shows an SEM photograph of the coating film surface, and it can be seen that the film is formed such that the flat mica overlaps.
[0021]
<Example 4>
As a peeling effect test at the time of surface treatment of mica size, barrel spray coating conditions were as follows: surface treatment material feeding speed 8 cc / min, air pressure 0.1 to 0.3 Mpa, air amount 10 L / min, jig rotation speed 15 rotation / min, a coating time of 15 minutes. Three kinds of sample treating agents were adjusted, and barrel spray coating was applied to the magnet parts for a predetermined time to obtain Samples 11 to 14 as described below, and the degree of adhesion between the products was visually confirmed and evaluated.
Sample 11: Painted sample not mixed with mica powder Sample 12: Painted with a treating agent to which 3% by weight of mica A having a large particle size (average = 70 μm) was added Sample 13: Mica B having a small particle size (under 15 μm) Coating with treatment agent added at 3% by weight Sample 14: Coat of treatment agent added at 3% by weight of a powder obtained by mixing mica A and B at a ratio of 1: 1.
The evaluation was carried out by visual inspection. For those having an adhesion of 10% or more with respect to the number of input magnet parts, x: For those having an adhesion of 1% or more and less than 10%, Δ: for adhesion of 1% or less Was evaluated. Table 7 shows the obtained results.
The size of the magnet used is a cylindrical part of 7 mm × 5.5 mmφ.
As is clear from Table 7, since the added mica of the flat inorganic substance causes the delamination phenomenon, it can be confirmed that the slip property of the painted surface in contact with the mica is improved and the peeling phenomenon of the coating film is further prevented. Was.
[Table 7]
<Example 5>
As shown in Table 8, as a result of adding various colors as flat inorganic substances (Iriodin manufactured by Merck), it was confirmed that the appearance color of the coating film itself could be changed.
[Table 8]
【The invention's effect】
As is clear from the above description, the present invention can obtain sufficient mechanical strength and bonding force with metal even when the film thickness is reduced, and has elasticity to minimize the occurrence of cracks. It has excellent corrosion resistance and prevents parts from sticking together during painting to increase production efficiency, and is less affected by the thermal expansion of the base material, effectively preventing cracks. Is what you can do.
Therefore, the present invention eliminates the problems of the conventional anti-corrosion, surface treatment film with excellent lubricity and a solution for forming the same, and as a metal material coated with the surface treatment film, where it contributes to industrial development Very large.
[Brief description of the drawings]
FIG. 1 is a graph showing a relationship between a film thickness and a coating time.
FIG. 2 is an SEM photograph of a coating film surface.
Claims (15)
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| JP2002247010A JP2004084002A (en) | 2002-08-27 | 2002-08-27 | Surface treatment film superior in corrosion-preventive property and lubricity, solution for forming it, and metallic material coated with surface treatment film |
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| JP2002247010A JP2004084002A (en) | 2002-08-27 | 2002-08-27 | Surface treatment film superior in corrosion-preventive property and lubricity, solution for forming it, and metallic material coated with surface treatment film |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100508961B1 (en) * | 2002-12-13 | 2005-08-17 | 한국지질자원연구원 | a composition powder with surface treatment and manufacturing method thereof |
| WO2009129380A2 (en) * | 2008-04-16 | 2009-10-22 | C-3 Int'l, Llc | Methods for enhancing lubricity of surfaces |
| JP2012071490A (en) * | 2010-09-29 | 2012-04-12 | Jfe Steel Corp | Cold-rolled steel sheet |
| JP2021512983A (en) * | 2018-02-06 | 2021-05-20 | サーモロン コリア カンパニー リミテッド | Non-adhesive ceramic coating containing diamond and colored mica |
-
2002
- 2002-08-27 JP JP2002247010A patent/JP2004084002A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100508961B1 (en) * | 2002-12-13 | 2005-08-17 | 한국지질자원연구원 | a composition powder with surface treatment and manufacturing method thereof |
| WO2009129380A2 (en) * | 2008-04-16 | 2009-10-22 | C-3 Int'l, Llc | Methods for enhancing lubricity of surfaces |
| WO2009129380A3 (en) * | 2008-04-16 | 2010-01-14 | C-3 Int'l, Llc | Methods for enhancing lubricity of surfaces |
| JP2012071490A (en) * | 2010-09-29 | 2012-04-12 | Jfe Steel Corp | Cold-rolled steel sheet |
| JP2021512983A (en) * | 2018-02-06 | 2021-05-20 | サーモロン コリア カンパニー リミテッド | Non-adhesive ceramic coating containing diamond and colored mica |
| JP7182636B2 (en) | 2018-02-06 | 2022-12-02 | サーモロン コリア カンパニー リミテッド | Non-stick ceramic coating containing diamond and colored mica |
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