JP2004010930A - Self-sacrificial corrosion inhibitor for metal, and method for preventing corrosion of metal - Google Patents
Self-sacrificial corrosion inhibitor for metal, and method for preventing corrosion of metal Download PDFInfo
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- JP2004010930A JP2004010930A JP2002163728A JP2002163728A JP2004010930A JP 2004010930 A JP2004010930 A JP 2004010930A JP 2002163728 A JP2002163728 A JP 2002163728A JP 2002163728 A JP2002163728 A JP 2002163728A JP 2004010930 A JP2004010930 A JP 2004010930A
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- metal
- water
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- thermoplastic resin
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は特に鋼鉄、鋳鉄等の鉄系金属表面を防食処理するための自己犠牲型金属防食剤、および該金属防食剤を使用した金属防食方法に関するものであり、本発明によって得られる金属防食被膜は通電性を有する。
【０００２】
【従来の技術】
従来、金属防食剤としては６価クロム供給物質と、亜鉛、マンガン、アルミニウム、マグネシウム、これら混合物、およびこれらの合金から選ばれた金属粉末と、界面活性剤とからなる組成が提供されている（特公昭５２−１９０２号公報）。
また、水溶性合成樹脂と、亜鉛、アルミニウム、亜鉛アルミニウム合金粉末と、酸化防止剤と、通電剤とからなる組成が提供されている（特開平６−４１４７２号公報）。
更に水不溶性熱可塑性樹脂粉末と、亜鉛、アルミニウム、亜鉛アルミニウム合金粉末と、水溶性防錆剤、界面活性剤と増粘剤とからなる組成が提供されている（特願２０００−０３９１７１号公報）。
【０００３】
【発明が解決しようとする課題】
上記６価クロムを含む組成にあっては、有害物質である６価クロムによる環境汚染が問題となり、また水溶性合成樹脂を含む組成にあっては、得られる金属防食被膜の耐水性が充分でないと云う問題点があり、水不溶性熱可塑性樹脂粉末を含む組成にあっては、得られる金属防食被膜の耐水性は良好であるが、金属粉末相互の結着性が悪くなり、電気抵抗値が電気亜鉛メッキ被膜や溶融亜鉛メッキ被膜よりも高くなってしまうと云う問題点がある。
【０００４】
【課題を解決するための手段】
本発明は上記従来の課題を解決するための手段として、被処理金属よりもイオン化傾向の大きな金属粉末の一種または二種以上と、水不溶性熱可塑性樹脂の水性エマルジョンと、水溶性防錆剤と、界面活性剤と、増粘剤とからなる自己犠牲型金属防食剤を提供するものであり、該被処理金属は鉄系金属であり、該金属粉末は亜鉛粉末および／またはアルミニウム粉末および／または亜鉛−アルミニウム合金粉末であることが望ましい。
更に本発明では、水不溶性熱可塑性樹脂の水性エマルジョンに水溶性防錆剤と、界面活性剤と、増粘剤とを混合し更に被処理金属よりもイオン化傾向の大きな金属粉末の一種または二種以上を分散せしめて処理液とし、該処理液を被処理金属表面に付着させて加熱処理することにより該水性エマルジョン中に分散している水不溶性熱可塑性樹脂粒子を溶融させると共に被処理金属表面に付着せしめ、該熱可塑性樹脂付着層を接着剤として該金属粉末を該被処理金属表面に接着固定して金属防食被膜を形成する金属防食方法を提供するものである。
該被処理金属は鉄系金属であり、該金属粉末は亜鉛粉末および／またはアルミニウム粉末および／または亜鉛−アルミニウム合金粉末であることが望ましい。
【０００５】
【作用】
本発明の処理液には、水不溶性の熱可塑性樹脂の水性エマルジョンに、水溶性防錆剤と、界面活性剤と、増粘剤とを添加混合した水性混合液に上記金属粉末が安定に分散されている。
上記処理液を被処理金属表面に付着させて加熱処理すると、該水性エマルジョン中に分散している水不溶性の熱可塑性樹脂粒子が軟化して該被処理金属表面に付着して金属防食被膜が形成される。該熱可塑性樹脂粒子は粒径が通常２μｍ 以下であり極く小径であるから、金属粉末相互が緻密に結着することが出来、該金属防食被膜の電気抵抗値が低くなる。該金属防食被膜において、該熱可塑性樹脂は水に不溶のため、該金属防食被膜の耐水性は高くなる。
上記処理液は上記のように毒性のない成分のみから構成され、６価クロム源等の有毒成分は全く含まない。
【０００６】
【発明の実施の形態】
本発明を以下に詳細に説明する。
〔水不溶性熱可塑性樹脂の水性エマルジョン〕
本発明においては金属粉末相互を接着するために水不溶性熱可塑性樹脂の水性エマルジョンが使用される。上記水不溶性熱可塑性樹脂としては、アクリル樹脂、スチレン樹脂、酢酸ビニル樹脂、塩化ビニル樹脂、ポリプロピレン、ポリエチレン、エチレン・酢酸ビニル樹脂、弗化ビニル樹脂、弗化ビニリデン樹脂、熱可塑性エポキシ樹脂、熱可塑性ウレタン樹脂、ポリエステル樹脂、エポキシ化ポリエステル樹脂、スチレン系エラストマー、オレフィン系エラストマー、ウレタン系エラストマー等が例示される。
【０００７】
上記水不溶性熱可塑性樹脂は水あるいは水と水溶性有機溶剤との混合溶剤中に分散した水性エマルジョンとして提供される。該水性エマルジョンとしては、ノニオン系界面活性剤を使用したノニオン性エマルジョンが望ましいが、ノニオン系界面活性剤とアニオン系界面活性剤とを併用したノニオン−アニオン性エマルジョン、ノニオン系界面活性剤とカチオン系界面活性剤とを併用したノニオン−カチオン性エマルジョン、また用途によってはアニオン性エマルジョンやカチオン性エマルジョンも使用出来る。
上記水性エマルジョンに分散している水不溶性熱可塑性樹脂粒子の平均粒子径は通常２μｍ 以下であるが、本発明においては１μｍ 以下のものが望ましい。
【０００８】
また本発明の金属防食方法にあっては、通常２５０℃程度の加熱処理が行われるので、該熱可塑性樹脂もそれに対応して、２５０℃以下望ましくは１９０〜２４０℃、更に望ましくは２００〜２３０℃の範囲の融点を有するものであることが望ましい。
【０００９】
上記水性エマルジョンの使用量は、該水性エマルジョン中の熱可塑性樹脂として通常１〜７０質量％、望ましくは５〜４０質量％である。
【００１０】
〔金属粉末〕
本発明において使用される金属粉末としては、被処理金属よりもイオン化傾向の大きな金属の粉末であって、被処理金属が例えば鉄系金属の場合には、亜鉛、アルミニウム、亜鉛−アルミニウム合金等の粉末が例示される。該金属粉末は望ましくは純度９９．０質量％以上、更に望ましくは９９．５質量％以上である。また粉末形状はフレーク状であることが望ましい。そして亜鉛の場合には、該フレークの厚みは５μｍ 以下、直径１５μｍ 以下、更に望ましくは厚みは３μｍ 以下、直径は１０μｍ 以下であり、アルミニウムの場合には、該フレークの厚みは２μｍ 以下、直径は８μｍ 以下、更に望ましくは厚みは１μｍ 以下、直径は５μｍ 以下、亜鉛−アルミニウム合金の場合は厚み５μｍ 以下、直径は１５μｍ 以下、更に望ましくは厚み３μｍ 以下、直径は１０μｍ 以下で、いずれの金属粉末の場合も、厚みが薄ければ薄い方が望ましい。
更に上記金属または合金の一部もしくは全部を銀、金、ニッケル、チタン、銅等の粉末またはフレークを使用してもよい。
【００１１】
該金属粉末の表面を高級脂肪酸、高級脂肪族アルコール、高融点ワックス、高融点パラフィン、酸化防止剤等の処理剤で処理してもよい。該金属粉末表面をこれら処理剤で処理するには、これら処理剤をケロシン、ミネラルスピリット、ミネラルターペント等の溶剤に溶解させ、該溶液中に該金属粉末を浸漬したり、該溶液を該金属粉末に噴霧混合する。
【００１２】
金属粉末として亜鉛粉末、アルミニウム粉末が単独で使用されるより、亜鉛粉末とアルミニウム粉末とを併用する場合の方が自己犠牲型防食性が良く、亜鉛粉末とアルミニウム粉末とを併用する表面処理によって、イオン化傾向がアルミニウムより小さくかつ比重の重い亜鉛粉末が下層に配され、アルミニウム粉末が上層に配され易くなって望ましい自己犠牲型防食性が付与される。
【００１３】
上記金属粉末は本発明の金属防食剤によって形成される被膜に低電気抵抗値を与え、被処理金属表面を導電性に保つものであって、該金属防食剤中に通常１〜７５質量％、望ましくは５〜４０質量％添加される。自己犠牲型防食性が重要な場合は、上記したように亜鉛粉末とアルミニウム粉末とを併用し、この場合には亜鉛粉末がアルミニウム粉末より倍以上添加される。亜鉛粉末とアルミニウム粉末とを併用する場合は、亜鉛粉末の添加量は１〜３０質量％、望ましくは５〜２５質量％、アルミニウム粉末の添加量は１〜２５質量％、望ましくは２〜１５質量％の範囲に設定される。
更に金属粉末材料として、銀、金、ニッケル、チタン、銅を用いると、得られる被膜の電気抵抗値が更に低くなり、得られる被膜の導電性が更に大きくなるので、このような処理剤は金属防食処理の他に電磁波シールド処理、光触媒等多方面の用途に使用出来る。
【００１４】
〔水溶性防錆剤〕
本発明で使用される水溶性防錆剤は自動車ラジエーター・内燃機関等の冷却水用の水溶性防錆剤で、鉄鋼、鋳鉄、銅、銅合金、ハンダ、亜鉛、アルミニウムに対し腐食防止効果を発揮する水溶性防錆剤で、防錆力試験（金属腐食性試験）ＪＡＯＳ−７０１４に合格した防錆剤であれば良く、その組成はヒプリックアシッドのジエタノールアミド、ヒプリックアシッドのジエチルアミド、サクシニックアシッドのジエタノールアミド等の低級有機酸のアミドと、ジシクロヘキシルアミンの亜硝酸塩、シクロヘキシルアミンの亜硝酸塩、ジエタノールアミンの亜硝酸塩等のアミンの亜硝酸塩等を配合したものがある。該水溶性防錆剤の添加量は通常０．１〜１０質量％、望ましくは０．５〜５質量％である。
【００１５】
〔界面活性剤〕 本発明の金属防食剤においては、水に金属粉末および水不溶性熱可塑性樹脂の水性エマルジョンを良好に分散させるために界面活性剤が添加される。上記界面活性剤としては、例えばポリオキシエチレンノニルフェニル・エーテル、ポリオキシエチレンオクチルフェニル・エーテル等のアルキルアリル・エーテル型非イオン活性剤、ポリオキシエチレンブチル・エーテル、ポリオキシエチレンオクチル・エーテル、ポリオキシエチレンラウリル・エーテル、ポリオキシエチレンオレイル・エーテル、ポリオキシエチレンステアリル・エーテル等のアルキル・エーテル型非イオン活性剤、ポリオキシエチレンラウレート、ポリオキシエチレンオレエート、ポリオキシエチレンステアレート等のアルキルエステル型非イオン活性剤、ポリプロピレングリコール・ポリエチレングリコールエーテルのようなエチレンオキサイド・プロピレンオキサイド・ブロック共重合型非イオン活性剤等を挙げることができる。
分子中に環境ホルモン汚染のおそれのある芳香族が入っていない界面活性剤が望ましく、またＨ．Ｌ．Ｂ．（Ｈｙｄｏｐｈｉｌｅ−Ｌｉｐｏｐｈｉｌｅ Ｂａｌａｎｃｅ）が７以上で１８以下の非イオン活性剤は、本発明に使用する界面活性剤として好ましいものである。更に好ましい界面活性剤のＨ．Ｌ．Ｂ．は１１〜１４の範囲である。該界面活性剤の添加量は通常０．０５〜８質量％、望ましくは０．１〜５質量％である。
【００１６】
〔増粘剤〕
本発明の金属防食剤においては、処理液の被処理金属表面に対する塗布層の厚みを確保するために、増粘剤を添加しなければならない。本発明において用いられる増粘剤としてはメチルセルローズ、カルボキシメチルセルローズ、ヒドロキシメチルセルローズ、エチルセルローズ、カルボキシエチルセルローズ、ヒドロキシエチルセルローズ、ポリビニルアルコール、澱粉、非イオン澱粉、ペクチン、グアーガム、タマリンドガム、ローストビーンガム、ガラクトマンナン、カラギーナン、寒天等の水溶性増粘剤が挙げられる。更に好ましい増粘剤としては、カルボキシメチルセルローズ、ヒドロキシメチルセルローズ、ヒドロキシエチルセルローズである。上記増粘剤の添加量は通常０．０５〜５質量％、望ましくは０．１〜２質量％である。
【００１７】
〔調整水〕
本発明の金属防食剤の処理液を調製するには、蒸留水や脱イオン交換水を使用するが煮沸処理した水道水でも良い。
【００１８】
〔殺菌剤〕
本発明の金属防食剤において、該処理液は略中性近くであるため、該処理液を長期間安定に保存するためには細菌、黴、酵母、藻類等の広範囲の種類の微生物に対して抑制作用のある殺菌剤を添加することが望ましい。該殺菌剤は本発明の処理液に使用される各成分と相溶性の良いものを選択して添加する。
本発明において使用される該殺菌剤としてはイソチアゾリン系化合物、有機窒素硫黄化合物、有機窒素化合物、有機窒素ハロゲン化合物、クロルヘキシジン塩、有機窒素化合物と有機硫黄ハロゲン化合物の複合剤、有機窒素化合物と有機窒素硫黄化合物との複合剤等を挙げることが出来る。望ましい殺菌剤はイソチアゾリン系化合物、クロルヘキシジン塩である。該殺菌剤の添加量は通常０．０１〜５質量％、望ましくは０．０１〜２質量％である。
【００１９】
〔水性溶剤〕
本発明の金属防食剤の処理液において、上記防錆剤、界面活性剤と相乗して処理液中の金属粉末の分散を良好ならしめるため、更に溶剤として水溶性の有機溶剤が添加されることが望ましい。該水溶性有機溶剤としては、例えば１−プロパノール、２−プロパノール、一級ブタノール、二級ブタノール、三級ブタノール、エチレングリコール、ジエチレングリコール、プロピレングリコール、ジプロピレングリコール、グリセリン、メチルセロソルブ、エチルセロソルブ、ブチルセロソルブ、メチルカルビトール、エチルカルビトール、ブチルカルビトール、ブチレングリコール、２−エチル−１，３−ヘキサンジオール、ネオペンチルグリコール、１，５−ペンタンジオール、２，３−ジメチル−２，２−ブタンジオール、エチレングリコール−モノ−ｔ−ブチルエーテル、ジアセトンアルコール等が挙げられる。更に好ましい水溶性有機溶剤としては、グリセリン、エチレングリコール、ジエチレングリコール、プロピレングリコール、ブチレングリコール、ジプロピレングリコール、２−エチル−１，３−ヘキサンジオール、１，５−ペンタンジオールがあり、該水溶性有機溶剤の添加量は、通常３〜４５質量％、望ましくは８〜３８質量％である。
【００２０】
〔オーバーコート剤〕
本発明において上記処理液において処理した後、更に耐蝕性を付与するためにクロム酸処理の代替としてオーバーコート剤を塗布することが望ましい。このオーバーコート剤としては、油溶性および水溶性の樹脂を使用する。油溶性および水溶性樹脂は例えば、フェノール樹脂、ケトン樹脂、塩素化ポリプロピレン、塩素化ポリエチレン、塩素化ポリ塩化ビニル、イソブチレン無水マレイン酸共重合体、アクリロニトリル−アクリルゴム−スチレン共重合体、アクリロニトリル−エチレン・プロピレン・ジエンゴム−スチレン共重合体、アクリロニトリル−スチレン共重合体、メチルメタアクリレート−ブタジエン−スチレン共重合体、エチレン−酢酸ビニル共重合体、ポリテトラフルオロエチレン、フッ化エチレン−プロピレン共重合体、ポリパーフルオロアルコキシアルカン、エチレン−テトラフルオロエチレン共重合体、ポリ三フッ化塩化エチレン、ポリフッ化ビニリデン樹脂、三フッ化塩化エチレン−エチレン共重合体、ポリアセタール、ポリアミド、ポリエーテルエーテルケトン、ポリエチレン、ポリエチレンオキサイド、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリ塩化ビニリデン樹脂、ポリ塩化ビニル、ポリ酢酸ビニル、ポリスチレン、ポリスルフォン、ポリエーテルスルフォン、ポリパラビニルフェノール、ポリビニルブチラール、ポリビニルホルマール、ポリブタジエン、ポリブチレンテレフタレート、ポリプロピレン、メタクリル樹脂、エポキシ樹脂、変性エポキシ樹脂、キシレン樹脂、シアルリフタレート樹脂、ジアリルイソフタレート樹脂、アルキルレゾルシノール系樹脂、ビニルエステル樹脂、不飽和ポリエステル樹脂、ポリイミド、ポリウレタン、マレイン酸樹脂、メラミン樹脂、尿素樹脂、ガラス繊維強化プラスチック、ガラス繊維強化熱可塑性プラスチック、シリコーン樹脂、シリコーンと樹脂とを特殊結合したもの、変性シリコーン樹脂等が挙げられ、これらの樹脂を１種ないし２種以上混合した樹脂を使用塗布する。その割合は、樹脂分として１０〜１００質量％、更に好ましくは２０〜８０質量％である。
【００２１】
〔処理方法〕
本発明の金属防食剤においては、使用に際して金属粉末、界面活性剤、水不溶性熱可塑性樹脂の水性エマルジョン、増粘剤、水、所望なれば水溶性有機溶剤、防錆剤、殺菌剤を配合し、よく混合攪拌して金属粉末を分散させて処理液を調整するが、該処理液の粘度は通常岩田式フォードカップ♯４で４０±５秒の範囲に調整される。該処理液を用いて被処理金属表面を処理するには、まず該金属表面をショットブラスト、サンドブラスト等によって研磨し、更に所望なればｎ−ヘキサン、キシレン、メチルエチルケトン、アセトン等の有機溶剤で洗浄し乾燥後上記処理液を浸漬、スプレー、ロールコーター、カーテンフローコーター、回転ブラシコーター、静電塗装等によって該金属表面に塗布する。処理液塗布後は室温に放置し、必要あれば空気を送って乾燥し、そして１５０〜１６０℃で少なくとも１０分間予備加熱乾燥し、続いて２３０℃〜２４０℃で少なくとも１０分加熱処理を行なう。
上記加熱処理によって、該金属表面には本発明の金属防食剤の自己犠牲型金属防食被膜が形成される。防食性の向上や被膜の摩擦による剥がれを防止するため、この金属防食被膜上には所望なれば更に上記オーバーコート剤による被覆が施されてもよい。また本発明の金属防食剤の調製時に金属粉末の代わりに無機顔料を添加することにより水系塗料を調製することが出来るのでこれをオーバーコート剤として使用することも出来る。
【００２２】
〔実施例１〕
下記の材料を充分攪拌混合する。
〔調製方法〕
アルミニウムペーストと、亜鉛粉末と、熱可塑性ポリウレタンエマルジョン樹脂と、ポリオキシエチレンオクチルアルコールエーテルと、ジエチレングリコールと、エチレングリコールと殺菌剤と、防錆剤とを添加溶解したイオン交換水を攪拌混合し、その中にヒドロキシエチルセルローズを加えて２４時間攪拌・脱泡する。この液を２００メッシュの篩で濾過し処理液Ａとする。
処理液Ａの粘度は岩田式フォードカップ＃４で４３秒であった。
【００２４】
〔実施例２〕
下記の処方を実施例１と同様に攪拌混合する。
〔実施例３〕
下記の処方を実施例１と同様に攪拌混合する。
【００２６】
〔オーバーコート剤の調製〕
下記組成の混合物によりオーバーコート剤である処理液を調製した。
〔試験〕
１．試料
（１）鋼板：ＳＳ−４１鋼板（１５０×７０×２．３ｍｍ）を使用した。該鋼板はｎ−ヘキサンで洗浄し、乾燥後ショットブラストによって表面を研磨し
、次いでｎ−ヘキサン→エーテルで洗浄し、乾燥した。
（２）ねじ：長さ７５ｍｍ、径２ｍｍ、頭部８ｍｍ、ねじ部５０ｍｍのプラスねじを使用した。該ねじはｎ−ヘキサンで洗浄し、乾燥後ショットブラストによっ
て表面を研磨し、次いでｎ−ヘキサンで洗浄し、乾燥した。
【００２８】
２．塗布および熱処理
（１）鋼板
上記鋼板に上記処理液Ａ，Ｂ，Ｃを加熱処理後に１２〜１５μｍ になるように塗布し、１分間風乾後１５０〜１６０℃の乾燥機に入れ１０分間予備乾燥し、その後２５０℃で１０分加熱処理を行った。その後そのまゝのものと該オーバーコート剤の処理液１，２，３をそれぞれ膜厚３〜６μｍ になるよ
うに塗布し乾燥機に入れ１８０℃で１０分間加熱処理した。
（２）ねじ
上記ねじを上記処理液Ａ，Ｂ，Ｃの各々に浸漬し、引き上げた後、脱水機（カゴの径２００ｍｍ、深さ２００ｍｍ、回転速度４００回／分）にて、正回転５秒、逆回転５秒で脱水処理を行い、１分間風乾後１５０℃で１０分間予備加熱乾燥し、その後２５０℃で１０分間加熱処理を行った。その後そのまゝのものと該オーバーコート剤の処理液１，２，３をそれぞれ浸漬し、引き上げた後脱水機（カゴの径２００ｍｍ、深さ２００ｍｍ、回転速度２５０回／分）にて正回転５秒で脱水処理を行い乾燥機で１８０℃、１０分間加熱処理を行
った。
この処理は、処理液Ａ，Ｂ，Ｃは２回塗布し、該オーバーコート剤の処理
は１回のみ塗布した。
【００２９】
〔試験結果〕
１．鋼板の塗膜の外観
塗膜の外観を目視観察した結果は以下の通りであった。
（１）処理液Ａによる処理試料：鼠色のなめらかな表面であるがあまり綺麗ではな
い塗膜である。
（２）処理液Ｂによる処理試料：銀白色の美しいなめらかな表面の塗膜である。
（３）処理液Ｃによる処理試料：銀白色の美しいなめらかな表面の塗膜である。
（４）処理液Ａに処理液１を処理した試料：鼠色のなめらかな表面であるがあまり
綺麗ではない塗膜である。
（５）処理液Ａに処理液２を処理した試料：鼠色のなめらかな表面であるがあまり
綺麗ではない塗膜である。
（６）処理液Ａに処理液３を処理した試料：鼠色のなめらかな表面であるがあまり
綺麗ではない塗膜である。
（７）処理液Ｂに処理液１を処理した試料：銀白色の美しいなめらかな表面の塗膜
であり、かつ艶がある。
（８）処理液Ｂに処理液２を処理した試料：銀白色の美しいなめらかな表面の塗膜
であり、かつ艶がある。
（９）処理液Ｂに処理液３を処理した試料：銀白色の美しいなめらかな表面の塗膜
であり、かつ艶がある。
（１０） 処理液Ｃに処理液１を処理した試料：銀白色の美しいなめらかな表面の塗
膜であり、かつ艶がある。
（１１） 処理液Ｃに処理液２を処理した試料：銀白色の美しいなめらかな表面の塗膜であり、かつ艶がある。
（１２） 処理液Ｃに処理液３を処理した試料：銀白色の美しいなめらかな表面の塗
膜であり、かつ艶がある。
【００３０】
２．塗膜の密着性
（１）試験方法
鋼板：処理液Ａ，Ｂ，Ｃで処理した鋼板と処理液Ａ，Ｂ，Ｃで処理した鋼板の上に処理液１，２，３をオーバーコート処理した鋼板について、ゴバ
ン目試験を行った。
ねじ：処理液Ａ，Ｂ，Ｃで処理したねじを処理液Ａ，Ｂ，Ｃで処理した鋼板の上に該ねじの頭部を手で強く３回摩擦し、塗膜の剥離による付着物の有
無を調べた。
【００３１】
（２）試験結果
上記試験結果を表１に示す。
【表１】
表１によれば、上記処理液Ａ，Ｂ，Ｃは処理液Ａの場合、テープテストにて若干剥離するがオーバーコート処理することにより優れた密着性能を有することがわかる。
【００３３】
３．塩水噴霧試験
（１）鋼板
上記防錆処理した鋼板にクロス目を入れて、ＪＩＳ−Ｚ−２３７１７に準
じ塩水噴霧試験を行った。その結果を表２に示す。
【００３４】
【表２】
トル処理品である。
評価
○：変化なし
×１）：塗膜面のクロス切れ目に錆発生
×２）：塗膜面のクロス切れ目に錆は無いが、表面に２〜３箇所小さい錆
発生
×３）：塗膜面のクロス切れ目に錆は無いが、表面に２／３以上錆発生
【００３５】
（２）ねじ
上記防錆処理したねじを５本１組として、ＪＩＳ−Ｚ−２３７１７に準じ
塩水噴霧を行った。その結果を表３に示す。
【表３】
ロメートル処理品である。
評価
○：変化なし
×１）：５本中１本に錆発生
×２）：５本中３本に錆発生
【００３６】
表２および表３によれば、本発明の金属防食剤による処理液Ａ，Ｂ，Ｃを塗布後処理液１，２，３によってオーバーコート処理された試料は実用性のある防食性を示し、特に処理液Ｃによる処理後処理液３によってオーバーコート処理した試料は優れた自己犠牲防食性を示し、従来の亜鉛メッキ物と比較しても充分優れた自己犠牲防食性を発揮していることが示された。
【００３７】
〔電気抵抗測定〕
本発明の金属防食剤の処理液Ａ，Ｂ，Ｃで鋼板上に１５〜２０μｍの塗膜を形成させ、その電気抵抗値をＨＩＯＫＩ製テスターＫＩＴＨＩＴｅｓｔｅｒ３０２１ にてテスター針３００ｇ 圧で測定した。
【００３８】
〔測定結果〕
処理液Ａによる塗膜：１０Ω／ｃｍ
処理液Ｂによる塗膜：６Ω／ｃｍ
処理液Ｃによる塗膜：２Ω／ｃｍ
【００３９】
〔電気抵抗測定２〕
本発明の金属防食剤の処理液Ａ，Ｂ，Ｃで鋼板上に１５〜２０μｍ の塗膜を形成させ、その上に処理液１，２，３で３〜５μｍ のオーバーコート膜を形成させ、該鋼板の電気抵抗値をＨＩＯＫＩ製テスターＫＩＴＨＩＴｅｓｔｅｒ３０２１ にてテスター針３００ｇ 圧で測定した。
【００４０】
〔測定結果〕
上記測定結果より本発明の金属防食剤は導電性が改善され、またオーバーコート剤を塗布するとやゝ導電性は低下するが良好な導電性を示している。
【００４２】
【発明の効果】
本発明の金属防食剤および該金属防食剤の処理液による処理後の塗膜中のいずれにも有害な物質は一切含まれず、更に廃棄処理後にも有害成分あるいは有害成分を生成するような成分は含まれておらず、本発明の金属防食剤を使用する金属防食処理方法は地球環境に優しい省資源、省エネルギーの処理方法であり、かつ電気亜鉛メッキ、溶融亜鉛メッキ、衝撃亜鉛メッキ等に比べても優れた自己犠牲型防食性と導電性とを有する金属防食剤である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention particularly relates to a self-sacrifice type metal anticorrosion agent for anticorrosion treatment of iron-based metal surfaces such as steel and cast iron, and a metal anticorrosion method using the metal anticorrosion agent, and a metal anticorrosion coating obtained by the present invention. Has conductivity.
[0002]
[Prior art]
Conventionally, as a metal anticorrosive, a composition comprising a hexavalent chromium supply material, a metal powder selected from zinc, manganese, aluminum, magnesium, a mixture thereof, and an alloy thereof, and a surfactant has been provided ( Japanese Patent Publication No. 52-1902).
Further, there is provided a composition comprising a water-soluble synthetic resin, zinc, aluminum, zinc-aluminum alloy powder, an antioxidant, and a current-carrying agent (JP-A-6-41472).
Further, there is provided a composition comprising a water-insoluble thermoplastic resin powder, zinc, aluminum, zinc-aluminum alloy powder, a water-soluble rust inhibitor, a surfactant and a thickener (Japanese Patent Application No. 2000-039171). .
[0003]
[Problems to be solved by the invention]
In the composition containing hexavalent chromium, environmental pollution by harmful hexavalent chromium becomes a problem, and in the composition containing a water-soluble synthetic resin, the obtained metal anticorrosive film has insufficient water resistance. In a composition containing a water-insoluble thermoplastic resin powder, the resulting metal anticorrosive coating has good water resistance, but the binding property between the metal powders is poor, and the electric resistance value is low. There is a problem that it becomes higher than the electrogalvanized film or the hot-dip galvanized film.
[0004]
[Means for Solving the Problems]
The present invention, as means for solving the above-mentioned conventional problems, as one or two or more kinds of metal powder having a large ionization tendency than the metal to be treated, an aqueous emulsion of a water-insoluble thermoplastic resin, and a water-soluble rust inhibitor. A self-sacrifice type metal corrosion inhibitor comprising a surfactant and a thickener, wherein the metal to be treated is an iron-based metal, and the metal powder is a zinc powder and / or an aluminum powder and / or Desirably, it is a zinc-aluminum alloy powder.
Further, in the present invention, a water-soluble rust inhibitor, a surfactant, and a thickener are mixed with an aqueous emulsion of a water-insoluble thermoplastic resin, and one or two kinds of metal powders having a greater ionization tendency than the metal to be treated. By dispersing the above into a treatment liquid, the treatment liquid is adhered to the surface of the metal to be treated, and the water-insoluble thermoplastic resin particles dispersed in the aqueous emulsion are melted by heat treatment. An object of the present invention is to provide a metal anticorrosion method of forming a metal anticorrosive coating by adhering and fixing the metal powder to the surface of the metal to be treated by using the thermoplastic resin adhesion layer as an adhesive.
The metal to be treated is an iron-based metal, and the metal powder is desirably zinc powder and / or aluminum powder and / or zinc-aluminum alloy powder.
[0005]
[Action]
In the treatment liquid of the present invention, the metal powder is stably dispersed in an aqueous mixture obtained by adding a water-soluble rust inhibitor, a surfactant, and a thickener to an aqueous emulsion of a water-insoluble thermoplastic resin. Have been.
When the treatment liquid is adhered to the surface of the metal to be treated and heated, the water-insoluble thermoplastic resin particles dispersed in the aqueous emulsion are softened and adhere to the surface of the metal to be treated to form a metal anticorrosive film. Is done. Since the thermoplastic resin particles have a particle size of usually 2 μm or less and a very small diameter, the metal powders can be tightly bound to each other, and the electric resistance value of the metal anticorrosive coating is reduced. In the metal anticorrosion coating, the thermoplastic resin is insoluble in water, so that the metal anticorrosion coating has high water resistance.
The treatment liquid is composed of only non-toxic components as described above, and does not include any toxic components such as a hexavalent chromium source.
[0006]
BEST MODE FOR CARRYING OUT THE INVENTION
The present invention will be described in detail below.
(Aqueous emulsion of water-insoluble thermoplastic resin)
In the present invention, an aqueous emulsion of a water-insoluble thermoplastic resin is used for bonding metal powders to each other. Examples of the water-insoluble thermoplastic resin include acrylic resin, styrene resin, vinyl acetate resin, vinyl chloride resin, polypropylene, polyethylene, ethylene / vinyl acetate resin, vinyl fluoride resin, vinylidene fluoride resin, thermoplastic epoxy resin, and thermoplastic resin. Examples include urethane resins, polyester resins, epoxidized polyester resins, styrene-based elastomers, olefin-based elastomers, urethane-based elastomers, and the like.
[0007]
The water-insoluble thermoplastic resin is provided as an aqueous emulsion dispersed in water or a mixed solvent of water and a water-soluble organic solvent. As the aqueous emulsion, a nonionic emulsion using a nonionic surfactant is desirable, but a nonionic-anionic emulsion using a nonionic surfactant and an anionic surfactant in combination, a nonionic surfactant and a cationic A nonionic-cationic emulsion in combination with a surfactant, or an anionic emulsion or a cationic emulsion can be used depending on the application.
The average particle size of the water-insoluble thermoplastic resin particles dispersed in the aqueous emulsion is usually 2 μm or less, but is preferably 1 μm or less in the present invention.
[0008]
In addition, in the metal corrosion protection method of the present invention, since the heat treatment is usually performed at about 250 ° C., the thermoplastic resin is also correspondingly corresponding to 250 ° C. or less, preferably 190 ° C. to 240 ° C., and more preferably 200 ° C. to 230 ° C. Desirably, it has a melting point in the range of ° C.
[0009]
The use amount of the above-mentioned aqueous emulsion is usually 1 to 70% by mass, preferably 5 to 40% by mass as the thermoplastic resin in the aqueous emulsion.
[0010]
(Metal powder)
The metal powder used in the present invention is a powder of a metal having a higher ionization tendency than the metal to be treated, and when the metal to be treated is, for example, an iron-based metal, zinc, aluminum, a zinc-aluminum alloy, or the like. A powder is exemplified. The metal powder preferably has a purity of 99.0% by mass or more, more preferably 99.5% by mass or more. The powder is desirably in the form of flakes. In the case of zinc, the thickness of the flake is 5 μm or less, the diameter is 15 μm or less, more preferably the thickness is 3 μm or less, and the diameter is 10 μm or less. In the case of aluminum, the thickness of the flake is 2 μm or less and the diameter is 8 μm or less, more preferably, the thickness is 1 μm or less, the diameter is 5 μm or less, and in the case of a zinc-aluminum alloy, the thickness is 5 μm or less, the diameter is 15 μm or less, more preferably the thickness is 3 μm or less, and the diameter is 10 μm or less. Also in this case, it is desirable that the thickness is thinner.
Further, a powder or flake of silver, gold, nickel, titanium, copper or the like may be used for a part or all of the metal or alloy.
[0011]
The surface of the metal powder may be treated with a treating agent such as a higher fatty acid, a higher aliphatic alcohol, a high melting point wax, a high melting point paraffin, or an antioxidant. To treat the surface of the metal powder with these treating agents, these treating agents are dissolved in a solvent such as kerosene, mineral spirit, or mineral turpentine, and the metal powder is immersed in the solution or the solution is treated with the metal. Spray mix into powder.
[0012]
Zinc powder as the metal powder, aluminum powder is used alone, the use of zinc powder and aluminum powder together has better self-sacrifice corrosion protection, and the surface treatment using zinc powder and aluminum powder together, Zinc powder having a lower ionization tendency and a higher specific gravity than aluminum is disposed in the lower layer, and the aluminum powder is easily disposed in the upper layer, thereby providing a desirable self-sacrifice type corrosion protection.
[0013]
The metal powder gives the coating formed by the metal anticorrosive of the present invention a low electric resistance value and keeps the surface of the metal to be treated conductive, and usually 1 to 75% by mass in the metal anticorrosive, Desirably, 5 to 40% by mass is added. When self-sacrifice corrosion protection is important, zinc powder and aluminum powder are used in combination as described above. In this case, zinc powder is added at least twice as much as aluminum powder. When zinc powder and aluminum powder are used in combination, the addition amount of zinc powder is 1 to 30% by mass, preferably 5 to 25% by mass, and the addition amount of aluminum powder is 1 to 25% by mass, preferably 2 to 15% by mass. % Range.
Further, when silver, gold, nickel, titanium, or copper is used as the metal powder material, the obtained film has a further lower electric resistance and the obtained film has higher conductivity. In addition to anticorrosion treatment, it can be used for various applications such as electromagnetic wave shielding treatment and photocatalyst.
[0014]
(Water-soluble rust inhibitor)
The water-soluble rust inhibitor used in the present invention is a water-soluble rust inhibitor for cooling water of automobile radiators, internal combustion engines, etc., and has a corrosion inhibitory effect on steel, cast iron, copper, copper alloy, solder, zinc, and aluminum. Any water-soluble rust inhibitor that can be used as long as it has passed the rust prevention test (metal corrosion test) JAOS-7014. The composition is diethanolamide of hypric acid, diethylamide of hyprick acid, and succin. There is a blend of an amide of a lower organic acid such as diethanolamide of Nick Acid, and a nitrite of an amine such as nitrite of dicyclohexylamine, nitrite of cyclohexylamine, and nitrite of diethanolamine. The amount of the water-soluble rust inhibitor is usually 0.1 to 10% by mass, preferably 0.5 to 5% by mass.
[0015]
[Surfactant] In the metal anticorrosive of the present invention, a surfactant is added in order to favorably disperse the aqueous emulsion of the metal powder and the water-insoluble thermoplastic resin in water. Examples of the surfactant include, for example, an alkylallyl ether type nonionic surfactant such as polyoxyethylene nonylphenyl ether and polyoxyethylene octylphenyl ether, polyoxyethylene butyl ether, polyoxyethylene octyl ether, and polyoxyethylene octyl ether. Alkyl ether type nonionic surfactants such as oxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, and alkyls such as polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate Ester type nonionic activators, ethylene oxide / propylene oxide / block copolymer type nonionic activators such as polypropylene glycol / polyethylene glycol ether, etc. Door can be.
Surfactants that do not contain aromatics that may contaminate environmental hormones in their molecules are desirable. L. B. A nonionic surfactant having a (Hydophile-Lipophile Balance) of 7 or more and 18 or less is preferable as a surfactant used in the present invention. More preferred surfactants include H.I. L. B. Is in the range of 11-14. The amount of the surfactant is usually 0.05 to 8% by mass, preferably 0.1 to 5% by mass.
[0016]
(Thickener)
In the metal anticorrosive of the present invention, a thickener must be added in order to secure the thickness of the coating layer of the treatment liquid on the surface of the metal to be treated. Examples of the thickener used in the present invention include methylcellulose, carboxymethylcellulose, hydroxymethylcellulose, ethylcellulose, carboxyethylcellulose, hydroxyethylcellulose, polyvinyl alcohol, starch, nonionic starch, pectin, guar gum, tamarind gum, roast bean. Water-soluble thickeners such as gum, galactomannan, carrageenan, agar and the like. More preferred thickeners are carboxymethyl cellulose, hydroxymethyl cellulose and hydroxyethyl cellulose. The amount of the thickener added is usually 0.05 to 5% by mass, preferably 0.1 to 2% by mass.
[0017]
(Conditioning water)
In order to prepare the treatment liquid of the metal anticorrosive of the present invention, distilled water or deionized water is used, but tap water which has been subjected to boiling treatment may be used.
[0018]
〔Fungicide〕
In the metal anticorrosive of the present invention, since the treatment liquid is almost neutral, bacteria, molds, yeasts, algae and a wide variety of microorganisms are required to stably store the treatment liquid for a long period of time. It is desirable to add a bactericide having an inhibitory action. The bactericide is selected from those having good compatibility with each component used in the treatment liquid of the present invention.
Examples of the disinfectant used in the present invention include isothiazoline compounds, organic nitrogen sulfur compounds, organic nitrogen compounds, organic nitrogen halogen compounds, chlorhexidine salts, complexing agents of organic nitrogen compounds and organic sulfur halogen compounds, organic nitrogen compounds and organic nitrogen. Examples thereof include a complexing agent with a sulfur compound. Desirable fungicides are isothiazoline-based compounds, chlorhexidine salts. The amount of the fungicide to be added is generally 0.01 to 5% by mass, preferably 0.01 to 2% by mass.
[0019]
(Aqueous solvent)
In the treatment solution of the metal anticorrosive agent of the present invention, a water-soluble organic solvent is further added as a solvent in order to improve the dispersion of the metal powder in the treatment solution in synergy with the rust inhibitor and the surfactant. Is desirable. Examples of the water-soluble organic solvent include 1-propanol, 2-propanol, primary butanol, secondary butanol, tertiary butanol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, methyl cellosolve, ethyl cellosolve, butyl cellosolve, Methyl carbitol, ethyl carbitol, butyl carbitol, butylene glycol, 2-ethyl-1,3-hexanediol, neopentyl glycol, 1,5-pentanediol, 2,3-dimethyl-2,2-butanediol, Examples include ethylene glycol-mono-t-butyl ether and diacetone alcohol. More preferred water-soluble organic solvents include glycerin, ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, dipropylene glycol, 2-ethyl-1,3-hexanediol, and 1,5-pentanediol. The addition amount of the solvent is usually 3 to 45% by mass, preferably 8 to 38% by mass.
[0020]
(Overcoat agent)
In the present invention, it is desirable to apply an overcoat agent instead of the chromic acid treatment in order to further impart corrosion resistance after the treatment with the treatment solution. As this overcoat agent, an oil-soluble and water-soluble resin is used. Oil-soluble and water-soluble resins include, for example, phenolic resins, ketone resins, chlorinated polypropylene, chlorinated polyethylene, chlorinated polyvinyl chloride, isobutylene maleic anhydride copolymer, acrylonitrile-acrylic rubber-styrene copolymer, acrylonitrile-ethylene -Propylene-diene rubber-styrene copolymer, acrylonitrile-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer, ethylene-vinyl acetate copolymer, polytetrafluoroethylene, fluorinated ethylene-propylene copolymer, Polyperfluoroalkoxy alkane, ethylene-tetrafluoroethylene copolymer, poly (ethylene trifluoride) chloride, polyvinylidene fluoride resin, ethylene trifluoride-ethylene copolymer, polyacetal, polyamide, poly -Ether ether ketone, polyethylene, polyethylene oxide, polyethylene terephthalate, polyethylene naphthalate, polyvinylidene chloride resin, polyvinyl chloride, polyvinyl acetate, polystyrene, polysulfone, polyethersulfone, polyparavinylphenol, polyvinylbutyral, polyvinylformal, Polybutadiene, polybutylene terephthalate, polypropylene, methacrylic resin, epoxy resin, modified epoxy resin, xylene resin, sialyl phthalate resin, diallyl isophthalate resin, alkyl resorcinol resin, vinyl ester resin, unsaturated polyester resin, polyimide, polyurethane, maleic Acid resin, melamine resin, urea resin, glass fiber reinforced plastic, glass fiber reinforced thermoplastic plus Click, that silicone resin, a silicone resin and a special coupling, modified silicone resins and the like, to one without these resins using coated two or more mixed resins. The proportion is 10 to 100% by mass, more preferably 20 to 80% by mass as a resin component.
[0021]
〔Processing method〕
In the metal anticorrosive of the present invention, a metal powder, a surfactant, an aqueous emulsion of a water-insoluble thermoplastic resin, a thickener, water, a water-soluble organic solvent if desired, a rust inhibitor, and a bactericide are blended when used. The processing solution is prepared by mixing and stirring well to disperse the metal powder, and the viscosity of the processing solution is usually adjusted within a range of 40 ± 5 seconds using an Iwata-type Ford cup # 4. In order to treat the metal surface to be treated with the treatment liquid, the metal surface is first polished by shot blasting, sand blasting or the like, and further washed with an organic solvent such as n-hexane, xylene, methyl ethyl ketone or acetone if desired. After drying, the treatment liquid is applied to the metal surface by dipping, spraying, roll coater, curtain flow coater, rotating brush coater, electrostatic coating or the like. After the treatment liquid is applied, it is left at room temperature, dried by blowing air if necessary, and preheat-dried at 150 to 160 ° C. for at least 10 minutes, and then heat-treated at 230 to 240 ° C. for at least 10 minutes.
By the heat treatment, a self-sacrifice-type metal anticorrosive film of the metal anticorrosive of the present invention is formed on the metal surface. In order to improve the anticorrosion property and to prevent the coating from being peeled off by friction, the metal anticorrosion coating may be further coated with the above-mentioned overcoating agent if desired. In addition, an aqueous paint can be prepared by adding an inorganic pigment instead of a metal powder at the time of preparing the metal anticorrosive of the present invention, so that it can be used as an overcoat agent.
[0022]
[Example 1]
The following materials are thoroughly mixed.
(Preparation method)
Aluminum paste, zinc powder, thermoplastic polyurethane emulsion resin, polyoxyethylene octyl alcohol ether, diethylene glycol, ethylene glycol, a bactericide, and a rust inhibitor were added and dissolved by stirring and mixing ion-exchanged water. Hydroxyethyl cellulose is added thereto, and the mixture is stirred and defoamed for 24 hours. This solution was filtered through a 200-mesh sieve to obtain treatment liquid A.
The viscosity of the treatment liquid A was 43 seconds with an Iwata-type Ford cup # 4.
[0024]
[Example 2]
The following formulation is stirred and mixed as in Example 1.
[Example 3]
The following formulation is stirred and mixed as in Example 1.
[0026]
(Preparation of overcoat agent)
A treatment liquid as an overcoat agent was prepared from a mixture having the following composition.
〔test〕
1. Sample (1) Steel plate: SS-41 steel plate (150 × 70 × 2.3 mm) was used. The steel plate was washed with n-hexane, dried, polished by shot blasting, and then washed with n-hexane → ether and dried.
(2) Screw: A Phillips screw having a length of 75 mm, a diameter of 2 mm, a head of 8 mm, and a screw portion of 50 mm was used. The screw was washed with n-hexane, and after drying, the surface was polished by shot blasting, then washed with n-hexane and dried.
[0028]
2. Coating and heat treatment (1) Steel plate The above-mentioned treatment liquids A, B, and C are applied to the steel plate after the heat treatment so as to have a thickness of 12 to 15 µm, air-dried for 1 minute, put in a dryer at 150 to 160 ° C, and pre-dried for 10 minutes. Then, a heat treatment was performed at 250 ° C. for 10 minutes. Thereafter, the as-treated solution and the treating solutions 1, 2, and 3 of the overcoat agent were applied so as to have a film thickness of 3 to 6 μm, respectively, placed in a drier, and heated at 180 ° C. for 10 minutes.
(2) Screw The screw was immersed in each of the treatment liquids A, B, and C, pulled up, and then rotated forward 5 times by a dehydrator (cage diameter 200 mm, depth 200 mm, rotation speed 400 times / minute). A dehydration treatment was performed for 5 seconds with a reverse rotation of 5 seconds, air-dried for 1 minute, preliminarily heated and dried at 150 ° C. for 10 minutes, and then heated at 250 ° C. for 10 minutes. After that, the as-treated solution and the treatment liquids 1, 2, and 3 of the overcoat agent are immersed, respectively, and lifted up. Then, a forward rotation is performed by a dehydrator (cage diameter 200 mm, depth 200 mm, rotation speed 250 times / minute). Dehydration treatment was performed in 5 seconds, and heat treatment was performed at 180 ° C. for 10 minutes using a dryer.
In this treatment, the treatment liquids A, B, and C were applied twice, and the treatment of the overcoat agent was applied only once.
[0029]
〔Test results〕
1. The appearance of the coating film of the steel sheet was visually observed and the results were as follows.
(1) Sample treated with treatment solution A: a coating film having a smooth, grayish surface but not very clean.
(2) Sample treated with the treatment liquid B: a silver-white coating film with a smooth surface.
(3) Sample treated with treatment solution C: a silver-white coating film with a smooth surface.
(4) Sample obtained by treating the treatment liquid 1 with the treatment liquid A: a coating film having a smooth, grayish surface but not very clean.
(5) A sample obtained by treating the treatment liquid A with the treatment liquid A: a coating film having a rattan smooth surface but not very clean.
(6) A sample obtained by treating the treatment liquid 3 with the treatment liquid A: a coating film having a rattan smooth surface but not very clean.
(7) Sample obtained by treating the treatment liquid 1 with the treatment liquid B: a silver-white coating film having a beautiful smooth surface and gloss.
(8) Sample obtained by treating the treatment liquid 2 with the treatment liquid B: a silver-white coating film having a beautiful smooth surface and gloss.
(9) A sample obtained by treating the treatment liquid 3 with the treatment liquid B: a silver-white coating film having a beautiful smooth surface and gloss.
(10) Sample obtained by treating the treatment liquid 1 with the treatment liquid C: a silver-white coating film having a beautiful smooth surface and gloss.
(11) Sample obtained by treating the treatment liquid 2 with the treatment liquid C: a silver-white coating film having a beautiful smooth surface and gloss.
(12) Sample obtained by treating the treatment liquid 3 with the treatment liquid C: a silver-white coating film having a beautiful smooth surface and gloss.
[0030]
2. Adhesion of coating film (1) Test method Steel sheet: Treatment liquids 1, 2, and 3 were overcoated on a steel sheet treated with treatment liquids A, B, and C and a steel sheet treated with treatment liquids A, B, and C. The steel plate was subjected to a Gobang test.
Screw: A screw treated with the treatment liquids A, B, and C is rubbed by hand three times on a steel plate treated with the treatment liquids A, B, and C by hand. The presence or absence was checked.
[0031]
(2) Test results The test results are shown in Table 1.
[Table 1]
According to Table 1, it can be seen that the treatment liquids A, B, and C slightly peel off in the tape test in the case of the treatment liquid A, but have excellent adhesion performance by being overcoated.
[0033]
3. Salt Spray Test (1) Steel Sheet A salt water spray test was performed according to JIS-Z-23717 by inserting a cross into the rust-proofed steel sheet. Table 2 shows the results.
[0034]
[Table 2]
Evaluation ：: No change × 1): Rust generated at cross cut on coating surface × 2): No rust at cross cut on coating surface, but rust generated at few places on surface × 3): Coated surface There is no rust at the cross cut, but more than 2/3 of the surface is rusted.
(2) Screws A set of five rust-proof screws was sprayed with salt water according to JIS-Z-23717. Table 3 shows the results.
[Table 3]
Evaluation ：: No change × 1): Rust occurred in one out of five × 2): Rust occurred in three out of five
According to Tables 2 and 3, the samples overcoated with the treatment solutions 1, 2, and 3 after the treatment solutions A, B, and C with the metal anticorrosive of the present invention exhibit practical anticorrosion properties, In particular, the sample overcoated with the treatment liquid 3 after the treatment with the treatment liquid C exhibits excellent self-sacrifice corrosion resistance, and exhibits sufficiently excellent self-sacrifice corrosion resistance as compared with conventional galvanized products. Indicated.
[0037]
(Electrical resistance measurement)
A coating film of 15 to 20 μm was formed on a steel plate with the treatment liquids A, B, and C of the metal anticorrosive agent of the present invention, and the electric resistance was measured with a tester KITHITester 3021 manufactured by HIOKI at a pressure of a tester needle of 300 g.
[0038]
〔Measurement result〕
Coating with treatment liquid A: 10Ω / cm
Coating with treatment liquid B: 6Ω / cm
Coating with treatment liquid C: 2Ω / cm
[0039]
[Electrical resistance measurement 2]
A coating of 15 to 20 μm is formed on a steel plate with the treatment liquids A, B, and C of the metal anticorrosive of the present invention, and an overcoat film of 3 to 5 μm is formed thereon with the treatment liquids 1, 2, and 3. The electric resistance of the steel sheet was measured with a tester KITHISTER 3021 manufactured by HIOKI at a pressure of 300 g of a tester needle.
[0040]
〔Measurement result〕
From the above measurement results, the conductivity of the metal anticorrosive of the present invention is improved, and when the overcoat agent is applied, the conductivity is slightly lowered, but shows good conductivity.
[0042]
【The invention's effect】
The metal anticorrosive of the present invention and any of the coatings after the treatment with the metal anticorrosive treating solution do not contain any harmful substances, and further, components that generate harmful components or harmful components even after disposal. Not included, the metal anticorrosion treatment method using the metal anticorrosive agent of the present invention is an environmentally friendly resource saving and energy saving treatment method, and compared with electrogalvanizing, hot-dip galvanizing, impact galvanizing, etc. Is also a metal anticorrosive having excellent self-sacrifice type anticorrosion properties and conductivity.
Claims (4)
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| JP2002163728A JP2004010930A (en) | 2002-06-05 | 2002-06-05 | Self-sacrificial corrosion inhibitor for metal, and method for preventing corrosion of metal |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005238001A (en) * | 2004-02-24 | 2005-09-08 | Hoden Seimitsu Kako Kenkyusho Ltd | Metal product applied with rustpreventive coating |
| JP2006219512A (en) * | 2005-02-08 | 2006-08-24 | Daicel Chem Ind Ltd | Water-dispersible resin treating agent for metal surface and surface-treated metal plate |
| KR102059640B1 (en) * | 2019-06-19 | 2019-12-27 | (주)방수하는사람들 | Aqueous acryl waterproof material and method for constructing waterproof structure using the same |
-
2002
- 2002-06-05 JP JP2002163728A patent/JP2004010930A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005238001A (en) * | 2004-02-24 | 2005-09-08 | Hoden Seimitsu Kako Kenkyusho Ltd | Metal product applied with rustpreventive coating |
| JP4490133B2 (en) * | 2004-02-24 | 2010-06-23 | 株式会社放電精密加工研究所 | Anti-rust coated metal products |
| JP2006219512A (en) * | 2005-02-08 | 2006-08-24 | Daicel Chem Ind Ltd | Water-dispersible resin treating agent for metal surface and surface-treated metal plate |
| KR102059640B1 (en) * | 2019-06-19 | 2019-12-27 | (주)방수하는사람들 | Aqueous acryl waterproof material and method for constructing waterproof structure using the same |
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