JP2002060963A - Method for producing corrosion protective-converted steel - Google Patents
Method for producing corrosion protective-converted steelInfo
- Publication number
- JP2002060963A JP2002060963A JP2000247508A JP2000247508A JP2002060963A JP 2002060963 A JP2002060963 A JP 2002060963A JP 2000247508 A JP2000247508 A JP 2000247508A JP 2000247508 A JP2000247508 A JP 2000247508A JP 2002060963 A JP2002060963 A JP 2002060963A
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- Prior art keywords
- coating
- treatment
- steel material
- anticorrosion
- aqueous solution
- Prior art date
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、厳しい腐食環境下
で使用されるラインパイプ、海洋構造物等に好適な防食
被覆を有する防食被覆鋼材に係り、とくに防食被覆の接
着耐久性の向上に関する。本発明でいう鋼材は、鋼管、
鋼板、形鋼、棒鋼、線材を含むものとする。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an anticorrosion-coated steel material having an anticorrosion coating suitable for line pipes, marine structures and the like used in severe corrosive environments, and more particularly to an improvement in the adhesion durability of the anticorrosion coating. The steel material in the present invention is a steel pipe,
It shall include steel plates, steel bars, steel bars, and wire rods.
【０００２】[0002]
【従来の技術】ガス、水道、電気配線等の配管、光ケー
ブル保護管、ラインパイプなどの地中埋設管や、港湾、
河川などの土木工事において使用される鋼管杭、鋼管矢
板、鋼矢板の土木建材や、建築屋根材、壁材などには、
鋼材の防食用に有機樹脂の塗装等による防食被覆処理が
施される。防食被覆処理としては、耐久性などの要求仕
様に応じて様々な種類や膜厚の塗装が施されている。2. Description of the Related Art Underground pipes such as gas, water, electric wiring, optical cable protection pipes, line pipes, etc.
For steel pipe piles, steel pipe sheet piles, steel sheet piles used in civil engineering works such as rivers, construction roofing materials, wall materials, etc.
An anti-corrosion coating treatment such as coating of an organic resin is performed for anti-corrosion of the steel material. As the anticorrosion coating treatment, various types and thicknesses of coating are applied according to required specifications such as durability.
【０００３】最近では、ライフサイクルコストの観点か
ら、防食被覆処理が施された鋼材には、ますます長い防
食寿命を有することが期待されるようになってきた。と
くに、地中埋設管や土木建材などは社会的インフラとい
うこともあり、数十年以上の防食寿命が望まれている。
従来から、鋼材への防食被覆処理を施すに際しては、予
め、酸洗、ブラスト処理などの鋼板表面の酸化被膜除去
処理を行ったのちに、防食被覆処理のための下地処理が
施されている。[0003] In recent years, from the viewpoint of life cycle costs, it has been expected that steel materials subjected to anticorrosion coating treatment have an even longer anticorrosion life. In particular, underground pipes and civil engineering materials are social infrastructures, and anticorrosion life of several decades or more is desired.
2. Description of the Related Art Conventionally, when a steel material is subjected to an anticorrosion coating process, an oxide film removal process such as pickling and blasting is performed on a steel sheet surface, and then a base treatment for the anticorrosion coating process is performed.
【０００４】鋼材表面に施される防食被覆の寿命は、
被膜（塗膜）と下地との密着性、被覆（塗装）材料自
体の劣化、の２点から決定されるといわれている。被膜
（塗膜）と下地との密着性が良好であっても、被覆（塗
装）材料自体が、例えば、屋外であれば太陽光に起因す
る紫外線による耐候劣化や、地中埋設管などであれば耐
熱劣化などにより、劣化し、被覆の防食性が低下する場
合がある。また、被覆（塗装）材料自体の劣化がなく健
全であっても、被膜（塗膜）と下地との密着性が低下し
て鋼材への保護性を失う（防食性の低下）という場合も
ある。[0004] The life of the anticorrosion coating applied to the steel surface is as follows:
It is said to be determined from two points: adhesion between the coating film (coating film) and the base, and deterioration of the coating (painting) material itself. Even if the adhesion between the coating (coating) and the substrate is good, if the coating (coating) material itself is outdoors, for example, it may be weather-resistant deterioration due to ultraviolet rays caused by sunlight, or may be an underground pipe. For example, the coating may be deteriorated due to heat resistance deterioration or the like, and the corrosion resistance of the coating may be reduced. Further, even if the coating (painting) material itself is healthy without deterioration, the adhesion between the coating film (coating film) and the base material may be reduced and the protection property to the steel material may be lost (decrease in corrosion resistance). .
【０００５】しかしながら、近年、被覆（塗装）材料自
体の改良が著しくすすみ、防食被覆の寿命は、被膜（塗
膜）と下地との密着性により決定されることが多くなっ
ている。有機樹脂の塗装による防食被覆では、塗膜と下
地との密着性不良により、例えば、端面からの塗膜の剥
離、あるいは、全体的な接着強度の低下、ふくれなどの
不具合が生じる。このような不具合が発生すると、塗装
の補修あるいは塗り直しといった作業が必要になる。こ
れらの作業には莫大な費用を要し、特に社会的インフラ
の場合には社会的コスト負担も大きくなる。したがっ
て、塗膜と下地との密着性、塗膜と下地との接着耐久性
を向上し、防食被覆の寿命を長寿命化して、補修や塗り
替えを極力回避することが必要である。However, in recent years, the coating (coating) material itself has been remarkably improved, and the life of the anticorrosion coating is often determined by the adhesion between the coating (coating) and the base. In the anticorrosion coating by coating of an organic resin, poor adhesion between the coating film and the base causes problems such as peeling of the coating film from the end face, reduction in overall adhesive strength, and blistering. When such a problem occurs, work such as repairing or repainting the paint is required. These operations require enormous costs, especially in the case of social infrastructure, and increase the social cost burden. Therefore, it is necessary to improve the adhesion between the coating film and the base and the adhesion durability between the coating film and the base, prolong the life of the anticorrosion coating, and avoid repair and repainting as much as possible.
【０００６】鋼材の防食被覆処理のための下地処理とし
ては、従来から例えば、リン酸塩処理、クロメート処
理、各種カップリング剤処理、陽極酸化処理、などが知
られている。クロメート処理以外の下地処理では、被膜
（塗膜）が剥離しやすく防食性が不十分であった。一
方、クロメート処理は、十分な防食性を保持するために
は塗布量を多くしなければならず、また比較的高い加熱
温度を必要とし、生産性が低下するなどの問題があっ
た。[0006] As a base treatment for anticorrosion coating of steel materials, for example, phosphate treatment, chromate treatment, various coupling agent treatments, anodization treatment, and the like are conventionally known. In the base treatment other than the chromate treatment, the coating film (coating film) was easily peeled, and the corrosion resistance was insufficient. On the other hand, the chromate treatment has problems that the coating amount must be increased in order to maintain sufficient anticorrosion properties, a relatively high heating temperature is required, and productivity is reduced.
【０００７】このような問題に対し、例えば、特開平9-
268374号公報には、ブラスト処理した鋼管の外面に、２
〜８重量％のモリブデン酸アンモニウム、0.5 〜２重量
％のリン酸、0.1 〜0.5 重量％のエチレンジアミン四酢
酸と0.5 〜５重量％のポリビニルアルコールを含む混合
水溶液を、被膜乾燥重量が30〜100mg/m2になるように塗
布したのち、120 〜180 ℃で加熱焼き付けし、ついで有
機樹脂の防食被覆を施す塗覆装鋼管の製造方法が提案さ
れている。特開平9-268374号公報に記載された技術によ
れば、耐陰極剥離性と経済性を兼ね備えた防食被覆鋼管
が得られるとしている。To solve such a problem, see, for example,
No. 268374 discloses that the outer surface of a blasted steel pipe has
A mixed aqueous solution containing ８8% by weight of ammonium molybdate, 0.5 to 2% by weight of phosphoric acid, 0.1 to 0.5% by weight of ethylenediaminetetraacetic acid and 0.5 to 5% by weight of polyvinyl alcohol is used. After m 2, and the coating was heated and baked at 120 to 180 ° C., and then the production method of the coating-covering steel pipe subjected to corrosion coating of the organic resin has been proposed. According to the technique described in Japanese Patent Application Laid-Open No. 9-268374, it is stated that an anticorrosion-coated steel pipe having both cathode peeling resistance and economy can be obtained.
【０００８】しかしながら、これらの下地処理では、処
理に長時間を要するうえ、厳しい腐食環境下では、依然
として被膜（塗膜）と下地との密着性が不足し、防食被
覆の防食性が不十分であるという問題があった。[0008] However, these substrate treatments require a long time for the treatment, and in a severe corrosive environment, the adhesion between the film (coating film) and the substrate is still insufficient, and the anticorrosion of the anticorrosive coating is insufficient. There was a problem.
【０００９】[0009]
【発明が解決しようとする課題】これら塗膜と下地との
密着性不良現象には、塗膜の環境遮断性も関係するが、
とくに塗膜と下地との接着界面における接着特性および
電気化学的な特性が大きく関係している。このようなこ
とから、塗膜と下地との密着性を向上し、防食被覆の寿
命（耐久性）を向上させるためには、適切な下地処理を
施すことが肝要となる。The phenomenon of poor adhesion between the coating film and the substrate involves the environmental barrier properties of the coating film.
In particular, the adhesion characteristics and the electrochemical characteristics at the adhesion interface between the coating film and the base are significantly related. For this reason, in order to improve the adhesion between the coating film and the base and to improve the life (durability) of the anticorrosion coating, it is important to perform an appropriate base treatment.
【００１０】本発明は、上記した従来技術の問題を解決
し、被膜と下地との密着性、接着耐久性を向上し、耐久
性に優れた防食被覆を有する、防食被覆鋼材の製造方法
を提供することを目的とする。The present invention solves the above-mentioned problems of the prior art, and provides a method for producing an anticorrosion-coated steel material having an anticorrosion coating having improved durability and adhesion between a film and a base and having excellent durability. The purpose is to do.
【００１１】[0011]
【課題を解決するための手段】本発明者らは、上記した
課題を達成するために、防食被覆処理の下地処理方法に
ついて鋭意検討した。その結果、鋼材表面にモリブデン
酸ナトリウム（Na2MoO 4 ・2H2O）とモリブデン酸アンモ
ニウム((NH4)6Mo7O24 ・4H2O）の混合水溶液を接触させ
ることにより、下地処理時間を短縮できるとともに、被
膜と下地との密着性、接着耐久性が向上し、防食被覆の
耐久性が格段に向上することを知見した。Means for Solving the Problems The present inventors have made the above-mentioned description.
In order to achieve the task, the base treatment method of anticorrosion coating
I studied hard about it. As a result, molybdenum
Sodium acid (NaTwoMoO Four・ 2HTwoO) and ammo molybdate
((NHFour)6Mo7Otwenty four・ 4HTwoO)
By doing so, it is possible to reduce the time required for
The adhesion between the film and the base and the adhesion durability are improved,
It was found that the durability was significantly improved.
【００１２】本発明は、上記した知見に基づいて、さら
に検討を加え完成されたものである。すなわち、本発明
は、鋼材表面に下地処理を施したのち、好ましくは乾燥
処理を施し、ついで防食被覆処理を施す防食被覆鋼材の
製造方法において、前記下地処理が、前記鋼材表面に、
0.001M〜1.0Mのモリブデン酸ナトリウムと0.001M〜1.0M
のモリブデン酸アンモニウムとを含む混合水溶液を接触
させる処理であることを特徴とする防食被覆鋼材の製造
方法であり、また、本発明では、前記混合水溶液が、さ
らに0.001M〜1.0Mのリン酸を含むことが好ましく、ま
た、本発明では、前記混合水溶液を接触させる処理が、
鋼材表面に厚さ：２〜100nm のモリブデンを含む反応層
を形成する処理であることが好ましい。The present invention has been completed based on the above findings and further studies. That is, the present invention provides a method for manufacturing a corrosion-resistant coated steel material, which is preferably subjected to a drying treatment after a steel material surface is subjected to a base treatment, and then subjected to a corrosion protection coating treatment, wherein the base treatment is performed on the steel material surface.
0.001M ~ 1.0M sodium molybdate and 0.001M ~ 1.0M
It is a method for producing an anticorrosion-coated steel material, characterized in that it is a process of contacting a mixed aqueous solution containing ammonium molybdate.In the present invention, the mixed aqueous solution further contains 0.001 M to 1.0 M phosphoric acid. Preferably, in the present invention, the treatment of contacting the mixed aqueous solution,
Preferably, the treatment is to form a reaction layer containing molybdenum with a thickness of 2 to 100 nm on the surface of the steel material.
【００１３】[0013]
【発明の実施の形態】本発明は、鋼材表面に防食被覆を
施し、鋼材の防食性を向上させた防食被覆鋼材の製造方
法である。本発明では、防食被覆処理を施す前に、鋼材
表面に下地処理を施す。なお、本発明では、鋼材表面に
めっき層が存在しても何ら問題ない。本発明における下
地処理は、鋼材表面に、0.001M〜1.0Mのモリブデン酸ナ
トリウム（Na2MoO4 ・2H2O）と0.001M〜1.0Mのモリブデ
ン酸アンモニウム((NH4)6Mo7O24 ・4H2O）とを含む混合
水溶液を接触させる処理である。本発明では、モリブデ
ン酸ナトリウムとモリブデン酸アンモニウムとを混合し
た水溶液を用いて下地処理を行うことに特徴がある。モ
リブデン酸ナトリウム単独、あるいはモリブデン酸アン
モニウム単独では、被膜と下地との接着耐久性が低く、
また、所定の接着強度あるいは接着耐久性を得るために
は反応時間が長すぎて生産性が低下する。BEST MODE FOR CARRYING OUT THE INVENTION The present invention is a method for producing an anticorrosion-coated steel material in which the surface of the steel material is provided with an anticorrosion coating to improve the corrosion resistance of the steel material. In the present invention, before the anticorrosion coating treatment is applied, the steel material surface is subjected to a base treatment. In the present invention, there is no problem even if a plating layer exists on the surface of the steel material. In the undercoating treatment in the present invention, 0.001 M to 1.0 M sodium molybdate (Na 2 MoO 4 .2H 2 O) and 0.001 M to 1.0 M ammonium molybdate ((NH 4 ) 6 Mo 7 O 24・ This is a treatment in which a mixed aqueous solution containing 4H 2 O) is brought into contact. The present invention is characterized in that the base treatment is performed using an aqueous solution in which sodium molybdate and ammonium molybdate are mixed. Sodium molybdate alone or ammonium molybdate alone has low adhesion durability between the coating and the base,
In addition, the reaction time is too long to obtain a predetermined adhesive strength or adhesive durability, and the productivity is reduced.
【００１４】モリブデン酸ナトリウムは、暖房用温水配
管のインヒビターとして知られており、鋼材表面を不動
態化する。これは、モリブデン酸の鋼材表面への吸着に
より達成されると考えられているが、メカニズムは現在
のところ不明である。混合水溶液中のモリブデン酸ナト
リウム、モリブデン酸アンモニウムの濃度はいずれも0.
001M〜1.0Mの範囲に限定した。モリブデン酸ナトリウ
ム、モリブデン酸アンモニウムの濃度がそれぞれ0.001M
未満では、鋼板板面全体に十分な被膜の生成がなく、被
膜と下地との接着耐久性向上効果が少なく、一方、モリ
ブデン酸ナトリウム、モリブデン酸アンモニウムの濃度
が1.0Mを超えると、反応層が厚くなりすぎ脆くなる、
被膜と下地との接着耐久性向上効果が飽和し、含有量
に見合う効果が期待でなくなり、経済的に不利となる。
このため、混合水溶液中のモリブデン酸ナトリウムの濃
度は0.001M〜1.0M、モリブデン酸アンモニウムの濃度は
0.001M〜1.0Mに限定した。なお、モリブデン酸ナトリウ
ムの濃度はより好ましくは0.01M 〜0.2Mであり、モリブ
デン酸アンモニウムの濃度はより好ましくは0.01M 〜0.
2Mである。[0014] Sodium molybdate is known as an inhibitor of hot water piping for heating and passivates the surface of steel. It is believed that this is achieved by the adsorption of molybdic acid on the steel surface, but the mechanism is currently unknown. The concentrations of sodium molybdate and ammonium molybdate in the mixed aqueous solution are both 0.
Limited to the range of 001M to 1.0M. The concentration of sodium molybdate and ammonium molybdate is 0.001M each
If the concentration is less than 1.0%, the effect of improving the adhesion durability between the coating and the base is small, and if the concentration of sodium molybdate or ammonium molybdate exceeds 1.0M, the reaction layer will not be formed. Too thick and brittle,
The effect of improving the adhesion durability between the film and the substrate is saturated, and the effect corresponding to the content is not expected, which is economically disadvantageous.
For this reason, the concentration of sodium molybdate in the mixed aqueous solution is 0.001 M to 1.0 M, and the concentration of ammonium molybdate is
Limited to 0.001M to 1.0M. The concentration of sodium molybdate is more preferably 0.01M to 0.2M, and the concentration of ammonium molybdate is more preferably 0.01M to 0.2M.
2M.
【００１５】また、本発明では、混合水溶液に、0.001M
〜1.0Mのモリブデン酸ナトリウムと0.001M〜1.0Mのモリ
ブデン酸アンモニウムに加えて、0.001M〜1.0Mのリン酸
（H3PO4 ）を含むことが好ましい。混合水溶液中に、モ
リブデン酸ナトリウム、モリブデン酸アンモニウムに加
えて、リン酸を含むことにより、鋼材との反応性、塗膜
と下地との接着耐久性が顕著に向上し、防食被覆鋼材の
防食性が向上する。リン酸の濃度が0.001M未満では、上
記した効果が少なく、一方、1.0Mを超えると、リン酸に
よるエッチング効果が強くなり反応層が形成しないた
め、塗膜と下地との接着耐久性が低下する。なお、リン
酸の濃度はより好ましくは0.01M 〜0.1Mである。[0015] In the present invention, 0.001 M
It is preferable to contain 0.001 M to 1.0 M phosphoric acid (H 3 PO 4 ) in addition to 1.01.0 M sodium molybdate and 0.001 M to 1.0 M ammonium molybdate. By containing phosphoric acid in addition to sodium molybdate and ammonium molybdate in the mixed aqueous solution, the reactivity with the steel material and the durability of the adhesion between the coating film and the base material are remarkably improved. Is improved. If the concentration of phosphoric acid is less than 0.001M, the above effect is small, while if it exceeds 1.0M, the etching effect by phosphoric acid becomes strong and a reaction layer is not formed, so that the adhesion durability between the coating film and the base decreases. I do. The concentration of phosphoric acid is more preferably 0.01M to 0.1M.
【００１６】上記した混合水溶液を鋼材表面に接触させ
る方法としては、とくに限定されないが、鋼材表面に混
合水溶液を塗布するか、あるいは鋼材を混合水溶液中に
浸漬するのが好ましい。混合水溶液と鋼材表面との反応
により、鋼材表面にモリブデン（Mo）を含む反応層が形
成される。反応層の厚さは、２〜100nm とするのが好ま
しい。この厚さの反応層を形成するためには、数十秒〜
数十分程度の処理時間を必要とする。The method of bringing the mixed aqueous solution into contact with the surface of the steel material is not particularly limited, but it is preferable to apply the mixed aqueous solution to the surface of the steel material or to immerse the steel material in the mixed aqueous solution. The reaction between the mixed aqueous solution and the steel material surface forms a reaction layer containing molybdenum (Mo) on the steel material surface. The thickness of the reaction layer is preferably 2 to 100 nm. It takes several tens of seconds to form a reaction layer of this thickness.
It requires several tens of minutes of processing time.
【００１７】この反応層の厚さは、オージェ電子分光装
置の深さ方向分析によって測定されるMo付着量で評価す
ることができる。本発明では、下地処理に使用する上記
した濃度の混合水溶液の温度はとくに限定されないが、
反応を促進する意味から、溶液あるいは鋼材の温度を室
温以上、好ましくは20〜40℃に調整して使用してもよ
い。溶液または鋼材の温度が高すぎると、反応が進行し
すぎて反応層が脆弱となる。The thickness of the reaction layer can be evaluated based on the amount of Mo adhering measured by a depth direction analysis using an Auger electron spectrometer. In the present invention, the temperature of the mixed aqueous solution having the above-mentioned concentration used for the base treatment is not particularly limited,
From the viewpoint of accelerating the reaction, the temperature of the solution or the steel material may be adjusted to room temperature or higher, preferably 20 to 40 ° C. before use. If the temperature of the solution or the steel material is too high, the reaction proceeds too much and the reaction layer becomes brittle.
【００１８】なお、下地処理を施す前に、表面の汚れ、
汚染物質、スケールなどをできる限り除去しておくこと
が好ましく、ブラスト処理や酸洗などを行うのが好まし
い。また、上記した下地処理を施したのちに、カップリ
ング剤処理などの他の下地処理を施しても何ら問題はな
い。下地処理を施された鋼材は、ついで水洗してもよ
い。また、適度な反応時間の後、水分を飛ばす意味で、
乾燥処理を行うのが好ましい。乾燥処理の方法は、下地
処理後の鋼材を、室温で放置してもよく、また、処理時
間を短縮するために、ブローア等により、常温空気吹付
け、あるいは温風吹付け、あるいは鋼材を80〜120 ℃に
加熱する処理としてもよく、とくに限定されない。Before applying the base treatment, the surface should be stained,
It is preferable to remove contaminants, scale, and the like as much as possible, and it is preferable to perform blast treatment, pickling, and the like. In addition, there is no problem even if another base treatment such as a coupling agent treatment is performed after the above-described base treatment is performed. The steel material subjected to the base treatment may then be washed with water. In addition, after an appropriate reaction time, in the sense that water is blown off,
It is preferable to perform a drying treatment. The method of the drying treatment may be as follows: the steel material after the base treatment may be left at room temperature, and in order to shorten the treatment time, blow the room temperature air with a blower or the like, or blow the steel material with 80 to 80 ° C. The treatment may be performed by heating to 120 ° C., but is not particularly limited.
【００１９】下地処理を施され、好ましくは乾燥処理を
施された鋼材は、ついで表面に防食被覆処理を施され
る。防食被覆処理としては、通常の有機樹脂の防食被覆
とするのが好ましい。有機樹脂の防食被覆は、例えば、
ポリオレフィン樹脂、エポキシ樹脂、アクリル樹脂また
はポリエステル樹脂、ウレタン樹脂を含む塗料を、鋼材
表面にスプレー塗装、刷毛塗り、ロールコーター等によ
り所定の膜厚を被覆するのが好ましい。The steel material which has been subjected to the base treatment and preferably subjected to the drying treatment is then subjected to anticorrosion coating treatment on the surface. As the anticorrosion coating treatment, it is preferable to use a normal organic resin anticorrosion coating. Anticorrosion coating of organic resin, for example,
It is preferable that a paint containing a polyolefin resin, an epoxy resin, an acrylic resin or a polyester resin, or a urethane resin is coated on the steel material to a predetermined thickness by spray coating, brush coating, a roll coater, or the like.
【００２０】また、防食被覆は、有機樹脂のライニング
としてもよい。有機樹脂のライニングは、接着剤を被覆
し、その上層としてポリエチレン樹脂、ポリプロピレン
樹脂、ポリブテン樹脂等をホットプレス、加熱圧着ロー
ル等により圧着して、所定の厚さに調整して被覆するの
が好ましい。The anticorrosion coating may be an organic resin lining. The lining of the organic resin is preferably coated with an adhesive, and as an upper layer thereof, a polyethylene resin, a polypropylene resin, a polybutene resin, or the like is pressed by a hot press, a hot press roll, or the like, and is adjusted to a predetermined thickness and coated. .
【００２１】[0021]
【実施例】以下、本発明を実施例にて詳細に説明する。
鋼材として、軟鋼板を用意した。まず、軟鋼板に、表面
汚染物質ならびに酸化層を除去するため、ブラスト処理
を施した。その後、表１に示す条件で下地処理を施し
た。下地処理に用いた混合水溶液は、純水に、工業用試
薬である、モリブデン酸ナトリウム(Na2MoO4・2H2O) と
モリブデン酸アンモニウム((NH4)6Mo7O24・4H2O) ある
いはさらにおよびリン酸(H3PO3) を表１に示す濃度にな
るように、それぞれ所定量溶解し、調整した溶液を用い
た。なお、溶液の温度は、表１に示す温度とし、ヒータ
で加熱保持した。The present invention will be described below in detail with reference to examples.
A mild steel plate was prepared as a steel material. First, a mild steel plate was subjected to a blast treatment to remove surface contaminants and an oxide layer. Thereafter, a base treatment was performed under the conditions shown in Table 1. The mixed aqueous solution used for the base treatment is pure water, industrial reagents, sodium molybdate (Na 2 MoO 4・ 2H 2 O) and ammonium molybdate ((NH 4 ) 6 Mo 7 O 24・ 4H 2 O) Alternatively, a solution prepared by dissolving predetermined amounts of phosphoric acid (H 3 PO 3 ) and the phosphoric acid (H 3 PO 3 ) in the respective concentrations shown in Table 1 was used. The temperature of the solution was as shown in Table 1, and the solution was heated and held by a heater.
【００２２】また、下地処理は、上記した混合水溶液を
鋼材表面に接触させることにより行い、接触方法として
は、混合水溶液をナイロン製刷毛で軟鋼板に塗布する
方法（刷毛）、軟鋼板を混合水溶液中に浸漬する方法
（浸漬）を用いた。なお、の方法では、混合水溶液を
塗布し３min 後純水で純水で軟鋼板表面を洗い流した。
また、の方法では、浸漬時間を２min とした。なお、
いずれの場合でも、軟鋼板は40℃に予熱した。The base treatment is carried out by bringing the mixed aqueous solution into contact with the surface of the steel material. As a contact method, a method of applying the mixed aqueous solution to a mild steel plate with a nylon brush (brush), The method of immersion in (immersion) was used. In the above method, the mixed aqueous solution was applied, and after 3 minutes, the surface of the mild steel sheet was washed away with pure water with pure water.
In the method (1), the immersion time was set to 2 minutes. In addition,
In each case, the mild steel plate was preheated to 40 ° C.
【００２３】下地処理後、軟鋼板を純水で水洗した。水
洗後、200 ℃雰囲気（炉内）中で、約３min保持する乾
燥処理を実施した。下地処理（乾燥処理）後、軟鋼板に
防食被覆処理を行い、防食被覆鋼材とした。防食被覆処
理は、有機樹脂の塗装、または有機樹脂のライニングと
した。有機樹脂の塗装は、塗料としてエポキシ系樹脂塗
料とし、スプレー塗装により所定の膜厚（100 μm ）の
塗装を行った。また、有機樹脂のライニングは、エポキ
シ系接着剤を塗装したのち、ポリエチレン樹脂をホット
プレスにて圧着し、接着層を介し1.5mm の低密度ポリエ
チレン層を形成した。After the base treatment, the mild steel sheet was washed with pure water. After washing with water, a drying treatment was performed in a 200 ° C. atmosphere (in a furnace) for about 3 minutes. After the base treatment (drying treatment), the mild steel plate was subjected to an anticorrosion coating treatment to obtain an anticorrosion coated steel material. The anticorrosion coating treatment was an organic resin coating or an organic resin lining. The coating of the organic resin was made of an epoxy resin paint, and a predetermined thickness (100 μm) was applied by spray coating. The lining of the organic resin was coated with an epoxy adhesive, and then pressed with a polyethylene resin by hot pressing to form a 1.5 mm low-density polyethylene layer via the adhesive layer.
【００２４】得られた防食被覆鋼材から、試験片（大き
さ：100 ×100mm ）を採取し、塩水噴霧試験、温塩水浸
漬試験を実施した。なお、防食被覆として有機樹脂のラ
イニングを施した防食被覆鋼材についてはさらに、陰極
剥離試験を実施した。試験方法はつぎの通りとした。 （１）塩水噴霧試験 各試験片の中央部に、50×50mmの大きさのクロスカット
（幅 1mm）を導入し、JIS Z 2371の規定に準拠して塩水
噴霧試験を90日間実施した。試験後、クロスカットから
の防食被覆の剥離幅を測定した。 （２）温塩水浸漬試験 各試験片の端部を2mm 程度研削し端部を揃えたのち、濃
度：３質量％NaClの温塩水（液温度：60℃）に、1000時
間浸漬した。浸漬後、端部からの防食被覆の剥離距離を
測定した。また、ポリエチレン樹脂ライニング材につい
ては被覆を、10mm幅で鋼材表面に対し直角方向に約60mm
引張り、防食被覆が剥離するときの単位長さ当たりの平
均剥離荷重を求め、接着強度（Ｎ／mm）と定義し、試験
前の接着強度に対する比を求め、接着強度保持率（％）
としてを評価した。エポキシ系樹脂塗装材については、
断面積が100 mm2 の断面形状が円形の鋼製治具を、接着
剤を介して塗装表面に接着し、その後、治具まわりの塗
装を強制的に剥離し、治具をつかんで引張試験を実施
し、接着部分が破断する最大荷重を求め、接着強度(MP
a) と定義し、試験前の接着強度に対する比を求め、接
着強度保持率（％）として評価した。 （３）陰極剥離試験 陰極剥離試験は、ASTM G8 の規定に準拠して実施した。
各試験片の中央部に、５mmφの人工欠陥を設け、70mmφ
の円筒を立て中に３質量％NaCl溶液を満たした。また、
対極を白金電極として、鋼材面を参照電極(SCE) に対し
て−1.5Vに保持した。これを60℃の電気炉中に30日間暴
露した。試験後、欠陥部から広がった剥離距離を測定し
た。Test specimens (size: 100 × 100 mm) were collected from the obtained anticorrosion-coated steel material and subjected to a salt spray test and a hot salt water immersion test. In addition, the cathodic peeling test was further performed on the anticorrosion-coated steel material coated with an organic resin as the anticorrosion coating. The test method was as follows. (1) Salt Spray Test A 50 × 50 mm cross cut (1 mm width) was introduced into the center of each test piece, and a salt spray test was performed for 90 days in accordance with the provisions of JIS Z 2371. After the test, the peel width of the anticorrosion coating from the cross cut was measured. (2) Hot salt water immersion test The end of each test piece was ground by about 2 mm, and the ends were aligned. Then, the test piece was immersed in warm salt water (concentration: 3% by mass NaCl, liquid temperature: 60 ° C) for 1000 hours. After immersion, the peel distance of the anticorrosion coating from the end was measured. In addition, for polyethylene resin lining material, the coating is 10 mm wide and about 60 mm in the direction perpendicular to the steel surface.
The average peeling load per unit length when the anti-corrosion coating is peeled off is determined, and defined as the adhesive strength (N / mm), the ratio to the adhesive strength before the test is determined, and the adhesive strength retention rate (%)
Was evaluated. For epoxy resin coating materials,
The cross-sectional area is the cross-sectional shape of 100 mm 2 circular steel jig via the adhesive adhered to the painted surface, then forcibly peeled off paint around the jig, tensile grabbed jig test The maximum load at which the bonded part breaks is determined, and the bonding strength (MP
a), the ratio to the adhesive strength before the test was determined, and evaluated as the adhesive strength retention (%). (3) Cathodic peel test The cathodic peel test was performed in accordance with the provisions of ASTM G8.
An artificial defect of 5 mmφ was provided at the center of each test piece, and 70 mmφ
Was filled with a 3% by mass NaCl solution while standing. Also,
The counter electrode was a platinum electrode, and the steel surface was kept at -1.5 V with respect to the reference electrode (SCE). This was exposed in an electric furnace at 60 ° C. for 30 days. After the test, the peel distance extending from the defect was measured.
【００２５】これらの結果を表１に示す。Table 1 shows the results.
【００２６】[0026]
【表１】 [Table 1]
【００２７】本発明例は、いずれも剥離距離は少なく、
接着強度保持率も高く、耐塩水噴霧性、耐温塩水浸漬性
に優れ、また、有機樹脂のライニングの防食被覆では耐
陰極剥離性に優れている。これに対し、本発明の範囲を
外れる比較例では、耐塩水噴霧性、耐温塩水浸漬性、耐
陰極剥離性が低下していた。In each of the examples of the present invention, the peel distance is small,
It also has a high adhesive strength retention rate, and is excellent in salt spray resistance and hot salt water immersion resistance, and is excellent in cathodic peeling resistance in an anticorrosion coating of an organic resin lining. On the other hand, in the comparative examples outside the range of the present invention, the salt spray resistance, the hot salt water immersion resistance, and the cathode peeling resistance were reduced.
【００２８】[0028]
【発明の効果】以上、説明したように、本発明によれ
ば、被膜と下地との接着耐久性が向上し、防食被覆鋼材
の防食寿命を長寿命化することができる。また、本発明
によれば、長期間にわたり、防食被覆の補修、再被覆等
を行う必要がなくなり、経費の節減ができ、産業上格段
の効果を奏する。また、厳しい腐食環境においても、長
期間の防食が可能になり、腐食および塗装劣化による社
会的損失を回避することができるという効果もある。As described above, according to the present invention, the durability of adhesion between the coating and the base is improved, and the anticorrosion life of the anticorrosion-coated steel material can be extended. Further, according to the present invention, there is no need to repair or recoat the anticorrosion coating over a long period of time, so that costs can be reduced and industrially remarkable effects can be obtained. Further, even in a severe corrosive environment, it is possible to prevent corrosion for a long period of time and to avoid social loss due to corrosion and deterioration of paint.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 望月 一雄 千葉県千葉市中央区川崎町１番地 川崎製 鉄株式会社技術研究所内 (72)発明者 白鳥 晋一 千葉県千葉市中央区川崎町１番地 川崎製 鉄株式会社技術研究所内 Ｆターム(参考） 4F100 AA02B AA33B AB03A AK01C AK04C AK53D BA03 BA04 BA07 BA10A BA10C DD07A EJ65D EJ68B GB90 JB01 JB02 JK06 JL00 YY00B 4K026 AA02 BA08 BA12 BB08 BB10 CA16 CA26 CA29 DA15 DA16 EA04 EB08 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Kazuo Mochizuki, 1st Kawasaki-cho, Chuo-ku, Chiba City, Chiba Prefecture Inside the Technical Research Institute of Kawasaki Steel Co., Ltd. (72) Shinichi Shiratori 1, Kawasaki-cho, Chuo-ku, Chiba City, Chiba Prefecture 4F100 AA02B AA33B AB03A AK01C AK04C AK53D BA03 BA04 BA07 BA10A BA10C DD07A EJ65D EJ68B GB90 JB01 JB02 JK06 JL00 YY00B 4K026 AA02 BA08 BA12 BB08 DA08
Claims (3)
被覆処理を施す防食被覆鋼材の製造方法において、前記
下地処理が、前記鋼材表面に、0.001M〜1.0Mのモリブデ
ン酸ナトリウムと0.001M〜1.0Mのモリブデン酸アンモニ
ウムとを含む混合水溶液を接触させる処理であることを
特徴とする防食被覆鋼材の製造方法。1. A method for producing an anticorrosion-coated steel material in which a steel material surface is subjected to an undercoating treatment and then subjected to an anticorrosion coating treatment, wherein the undercoating treatment comprises adding 0.001M to 1.0M sodium molybdate and 0.001M to the steel material surface. A method for producing an anticorrosion-coated steel material, which is a process of contacting a mixed aqueous solution containing up to 1.0 M ammonium molybdate.
のリン酸を含むことを特徴とする請求項１に記載の防食
被覆鋼材の製造方法。2. The mixed aqueous solution further comprises 0.001M to 1.0M.
The method for producing an anticorrosion-coated steel material according to claim 1, comprising phosphoric acid.
材表面に厚さ：２〜100nm のモリブデンを含む反応層を
形成する処理であることを特徴とする請求項１または２
に記載の防食被覆鋼材の製造方法。3. The method of claim 1, wherein the treatment of bringing the mixed aqueous solution into contact is a treatment of forming a reaction layer containing molybdenum with a thickness of 2 to 100 nm on the surface of the steel material.
3. The method for producing a corrosion-resistant coated steel material according to item 1.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009209394A (en) * | 2008-03-03 | 2009-09-17 | Jfe Steel Corp | Manufacturing method of resin-coated steel |
| JP2009209393A (en) * | 2008-03-03 | 2009-09-17 | Jfe Steel Corp | Method for producing resin-coated steel |
| JP2009209391A (en) * | 2008-03-03 | 2009-09-17 | Jfe Steel Corp | Manufacturing method of resin-coated steel |
| JP2009209392A (en) * | 2008-03-03 | 2009-09-17 | Jfe Steel Corp | Method for producing resin-covered steel member |
| CN105369236A (en) * | 2015-12-17 | 2016-03-02 | 山东建筑大学 | Non-chrome passivating agent for brown zinc coating |
| CN105369237A (en) * | 2015-12-17 | 2016-03-02 | 山东建筑大学 | Brown passivant |
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2000
- 2000-08-17 JP JP2000247508A patent/JP3546271B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009209394A (en) * | 2008-03-03 | 2009-09-17 | Jfe Steel Corp | Manufacturing method of resin-coated steel |
| JP2009209393A (en) * | 2008-03-03 | 2009-09-17 | Jfe Steel Corp | Method for producing resin-coated steel |
| JP2009209391A (en) * | 2008-03-03 | 2009-09-17 | Jfe Steel Corp | Manufacturing method of resin-coated steel |
| JP2009209392A (en) * | 2008-03-03 | 2009-09-17 | Jfe Steel Corp | Method for producing resin-covered steel member |
| CN105369236A (en) * | 2015-12-17 | 2016-03-02 | 山东建筑大学 | Non-chrome passivating agent for brown zinc coating |
| CN105369237A (en) * | 2015-12-17 | 2016-03-02 | 山东建筑大学 | Brown passivant |
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