JPH0641472A - Corrosion inhibitor for metal - Google Patents
Corrosion inhibitor for metalInfo
- Publication number
- JPH0641472A JPH0641472A JP4090332A JP9033292A JPH0641472A JP H0641472 A JPH0641472 A JP H0641472A JP 4090332 A JP4090332 A JP 4090332A JP 9033292 A JP9033292 A JP 9033292A JP H0641472 A JPH0641472 A JP H0641472A
- Authority
- JP
- Japan
- Prior art keywords
- metal
- water
- agent
- synthetic resin
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は金属防食剤に関するもの
であり、特に鉄、鋼、鋳鉄等の鉄材料の防食剤として有
用なものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal anticorrosive agent, and particularly useful as an anticorrosive agent for iron materials such as iron, steel and cast iron.
【０００２】[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、これらの混合物、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）。2. Description of the Related Art Conventionally, a metal anticorrosive agent comprises a hexavalent chromium supplying substance, a metal powder selected from zinc, manganese, aluminum, magnesium, a mixture thereof, and an alloy thereof, and a surfactant. The composition is provided (Japanese Patent Publication No. 52-1902).
【０００３】[0003]
【発明が解決しようとする課題】しかしながら上記従来
の金属防食剤には有害物質である６価クロム供給物質が
含まれているので、取扱いや廃水処理の点で問題がある
し、上記金属防食剤は金属表面に塗布され乾燥してから
塗膜を硬化させるのに３３０℃前後の高温加熱処理を必
要とし、エネルギーが浪費されかつ被処理金属の熱変性
と言う問題もある。更に熱処理後の塗膜表面硬度が充分
でなく傷付き易い。However, since the above-mentioned conventional metal anticorrosive agent contains a hexavalent chromium supplying substance which is a harmful substance, there is a problem in handling and wastewater treatment. Requires a high temperature heat treatment at about 330 ° C. to cure the coating film after being applied to the metal surface and drying, energy is wasted and there is a problem that the metal to be treated is thermally denatured. Furthermore, the coating film surface hardness after heat treatment is not sufficient and is easily scratched.
【０００４】[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、水溶性合成樹脂バインダ
ーと、被処理金属よりもイオン化傾向の大きい金属の微
粉末と、該金属の酸化防止剤と、通電剤とからなる金属
防食剤を提供するものである。As a means for solving the above-mentioned conventional problems, the present invention provides a water-soluble synthetic resin binder, a fine metal powder having a greater ionization tendency than the metal to be treated, and oxidation of the metal. The present invention provides a metal anticorrosive agent comprising an inhibitor and a current-carrying agent.
【０００５】〔水溶性合成樹脂バインダー〕本発明の水
溶性合成樹脂バインダーには、加熱硬化後においても速
やかに再吸水あるいは再吸湿する水溶性合成樹脂が用い
られる。このような水溶性合成樹脂としては、アクリル
酸、メタクリル酸、イタコン酸、アトロパ酸、シトラコ
ン酸等のα−β不飽和脂肪酸の一種または二種以上の重
合体のカリウム、ナトリウム、リチウム等の金属との塩
類、あるいはアンモニア、アミン等の窒素含有塩基との
塩類、あるいは上記α−β不飽和脂肪酸の一種または二
種以上とアクリルエステル、メタクリルエステル、スチ
レン、酢酸ビニル、塩化ビニル、塩化ビニリデン、アク
リロニトリル、メタクリロニトリル等の他のビニル単量
体の一種または二種以上との共重合体の上記金属あるい
は窒素含有塩基との塩類、酢酸ビニルと上記のようなビ
ニル単量体の共重合体の鹸化物等が例示されるが、上記
α−β不飽和脂肪酸を含む共重合体のアミン塩は本発明
にとって望ましい水溶性合成樹脂である。また本発明の
水溶性合成樹脂としては、塗膜の硬度（鉛筆硬度）とし
てＦ〜Ｈ程度の硬調なものでかつ下記する金属微粉末の
自己犠牲作用を阻害せず、良好な通電性を確保するため
には、速やかな吸水吸湿性がある方が望ましい。しかし
被覆性を確保するためには耐水性の良好なものが望まし
い。上記水溶性合成樹脂バインダーは本発明の金属防食
剤に通常固形分として１〜２０重量％、望ましくは２．
５〜１０重量％添加される。[Water-Soluble Synthetic Resin Binder] As the water-soluble synthetic resin binder of the present invention, a water-soluble synthetic resin that quickly reabsorbs water or reabsorbs moisture even after being heated and cured is used. Examples of such a water-soluble synthetic resin include metals such as potassium, sodium, and lithium of one or more polymers of α-β unsaturated fatty acids such as acrylic acid, methacrylic acid, itaconic acid, atropic acid, and citraconic acid. Or salts with a nitrogen-containing base such as ammonia or amine, or one or more of the above α-β unsaturated fatty acids with acrylic ester, methacrylic ester, styrene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile. A salt of the above-mentioned metal or a nitrogen-containing base with a copolymer of one or more other vinyl monomers such as methacrylonitrile, a copolymer of vinyl acetate and the above-mentioned vinyl monomer. Examples of the saponified product include amine salts of copolymers containing α-β unsaturated fatty acids, which are desirable for the present invention. It is. As the water-soluble synthetic resin of the present invention, the hardness (pencil hardness) of the coating film is as high as F to H, and it does not inhibit the self-sacrificing action of the metal fine powder described below, and secures good electrical conductivity. In order to do so, it is desirable that the water absorption and hygroscopicity be rapid. However, in order to secure the covering property, a material having good water resistance is desirable. The above water-soluble synthetic resin binder is usually contained in the metal anticorrosive agent of the present invention in an amount of 1 to 20% by weight, preferably 2.
5 to 10% by weight is added.
【０００６】〔金属微粉末〕本発明において用いられる
金属微粉末は被処理金属よりもイオン化傾向の大きな金
属の微粉末であり、粉末の形態はフレーク状、粒状のい
ずれでもよい。また該金属微粉末の純度は望ましくは９
９．０重量％以上、更に望ましくは９９．５重量％以上
であり、該金属微粉末の粒径は望ましくは６μ、更に望
ましくは５μ以下である。金属微粉末の純度が９９．０
重量％以上であれば優れた防食効果が得られ、また粒径
が６μ以下であれば緻密でかつ平滑な防食性被膜が得ら
れ、優れた防食効果が得られる。本発明にとって最も望
ましい粒径は３〜５μである。被処理金属が鉄の場合に
は、鉄よりもイオン化傾向の大きい亜鉛、アルミニウ
ム、亜鉛−アルミニウム合金が望ましく、特に望ましい
のは亜鉛とアルミニウムとの併用である。亜鉛とアルミ
ニウムとを併用した場合にはイオン化傾向は亜鉛＜アル
ミニウムであり、塗膜中において亜鉛微粉末が下層にア
ルミニウム微粉末が上層に配置されることが望ましい。
アルミニウム微粉末を上層に配置させるには、ケロシ
ン、ミネラルスピリット、ミネラルターペン等の高沸点
有機溶剤、脂肪酸、脂肪酸エステル、脂肪酸アミド等の
脂肪酸またはその誘導体、ベンゾトリアゾール、メチル
ベンゾトリアゾール等のトリアゾール系化合物等によっ
て該アルミニウム微粉末の表面を処理し、更にソルビタ
ン界面活性剤および／または脂肪酸系界面活性剤で処理
しておく。上記金属微粉末は本発明の金属防食剤中に通
常２〜７５重量％、望ましくは１０〜５０重量％添加さ
れるが、亜鉛微粉末とアルミニウム微粉末とを併用する
場合は、亜鉛微粉末１〜５０重量％、アルミニウム微粉
末１〜２５重量％、望ましくは亜鉛微粉末５〜３５重量
％、アルミニウム微粉末５〜１５重量％である。[Fine metal powder] The fine metal powder used in the present invention is a fine metal powder having a greater ionization tendency than the metal to be treated, and the powder may be in the form of flakes or particles. The purity of the fine metal powder is preferably 9
The content of the fine metal powder is 9.0% by weight or more, more preferably 99.5% by weight or more, and the particle size of the metal fine powder is preferably 6 μ, more preferably 5 μ or less. The purity of the fine metal powder is 99.0.
When it is at least wt%, an excellent anticorrosion effect is obtained, and when the particle size is 6 μm or less, a dense and smooth anticorrosion coating is obtained, and an excellent anticorrosion effect is obtained. The most desirable particle size for the present invention is 3-5 μ. When the metal to be treated is iron, zinc, aluminum, and a zinc-aluminum alloy, which have a greater ionization tendency than iron, are desirable, and a combination of zinc and aluminum is particularly desirable. When zinc and aluminum are used in combination, the ionization tendency is zinc <aluminum, and it is desirable that the zinc fine powder is arranged in the lower layer and the aluminum fine powder is arranged in the upper layer in the coating film.
In order to arrange the fine aluminum powder in the upper layer, kerosene, mineral spirits, high boiling point organic solvents such as mineral terpenes, fatty acids, fatty acid esters, fatty acid amides such as fatty acid amides or derivatives thereof, benzotriazole, triazole compounds such as methylbenzotriazole Etc., the surface of the aluminum fine powder is treated, and further treated with a sorbitan surfactant and / or a fatty acid surfactant. The above metal fine powder is usually added to the metal anticorrosive agent of the present invention in an amount of 2 to 75% by weight, preferably 10 to 50% by weight. When zinc fine powder and aluminum fine powder are used in combination, zinc fine powder 1 .About.50% by weight, aluminum fine powder 1 to 25% by weight, preferably zinc fine powder 5 to 35% by weight, and aluminum fine powder 5 to 15% by weight.
【０００７】〔酸化防止剤〕本発明の金属防食剤は水性
であるから、金属微粉末が水と反応して酸化して水酸化
物となることを防止する必要がある。このために添加さ
れる酸化防止剤としてはヒドロキシ酢酸、グリコール
酸、グリセリン酸、酒石酸、グルコン酸、クエン酸等の
オキシ酸のカリウム、ナトリウム、リチウム等の金属と
の塩類、あるいはアンモニア、アミン等の窒素含有塩基
との塩類、あるいはケロシン、ミネラルスピリット、脂
肪酸またはその誘導体、トリアゾール系化合物等の被膜
形成物質等である。オキシ酸塩類の場合は本発明の金属
防食剤中固形分として通常０．０１〜５重量％、望まし
くは０．０５〜１．５重量％添加され、被膜形成物質の
場合は該物質または該物質を適当な溶剤で適当濃度希釈
した溶液中に該金属微粉末を浸漬処理するかまたはスプ
レー等により塗布する。[Antioxidant] Since the metal anticorrosive agent of the present invention is aqueous, it is necessary to prevent the fine metal powder from reacting with water to oxidize to form a hydroxide. Antioxidants added for this purpose include salts of hydroxyacetic acid, glycolic acid, glyceric acid, tartaric acid, gluconic acid, oxyacids such as citric acid with metals such as potassium, sodium and lithium, or ammonia, amines and the like. Examples thereof include salts with nitrogen-containing bases, kerosene, mineral spirits, fatty acids or derivatives thereof, and film-forming substances such as triazole compounds. In the case of oxyacid salts, it is usually added in an amount of 0.01 to 5% by weight, preferably 0.05 to 1.5% by weight as a solid content in the metal anticorrosive agent of the present invention. In the case of a film-forming substance, the substance or the substance is added. The metal fine powder is dipped in a solution diluted with a suitable solvent to a suitable concentration, or applied by spraying or the like.
【０００８】〔通電剤〕本発明において用いられる通電
剤としては、ドデシルトリメチルアンモニウムクロリ
ド、ドデシルジメチルアンモニウムクロリド等の第４級
アンモニウム塩を含有するカチオン系界面活性剤が例示
される。上記通電剤は本発明の金属防食剤中通常固形分
として通常０．００１〜２重量％、望ましくは０．０１
〜０．９重量％程度添加される。本発明の通電剤は上記
水溶性合成樹脂の通電性を補助するために使用される。[Electrifying Agent] Examples of the conducting agent used in the present invention include cationic surfactants containing quaternary ammonium salts such as dodecyltrimethylammonium chloride and dodecyldimethylammonium chloride. The above current-carrying agent is usually contained in the metal anticorrosive agent of the present invention in an amount of usually 0.001 to 2% by weight, preferably 0.01
~ 0.9 wt% is added. The current-carrying agent of the present invention is used to assist the current-carrying property of the water-soluble synthetic resin.
【０００９】〔溶剤〕本発明の金属防食剤は水溶液とし
て提供されるが、上記金属微粉末の分散性を良好ならし
めるために、望ましくは水溶性の有機溶剤が添加され
る。上記水溶性有機溶剤としてはメタノール、エタノー
ル、１−プロパノール、２−プロパノール、ｔ−ブチル
アルコール、エチレングリコール、プロピレングリコー
ル、１，２−プロパンジオール、１，３−プロパンジオ
ール、グリセリン、アセトン、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、プロピルカルビトール、ブチ
ルカルビトール、ジアセトンアルコール等があげられ
る。望ましい水溶性有機溶剤としてはエチレングリコー
ル、プロピレングリコール、ジアセトンアルコール、エ
チルセロソルブ、エチルカルビトール、ブチルセロソル
ブがあり、該水溶性有機溶剤の添加量は通常本発明の金
属防食剤中３〜３０重量％、望ましくは８〜２０重量％
である。[Solvent] The metal anticorrosive agent of the present invention is provided as an aqueous solution, but a water-soluble organic solvent is preferably added in order to improve the dispersibility of the fine metal powder. Examples of the water-soluble organic solvent include methanol, ethanol, 1-propanol, 2-propanol, t-butyl alcohol, ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, glycerin, acetone, methylcellosolve. , Ethyl cellosolve, butyl cellosolve, methyl carbitol, ethyl carbitol, propyl carbitol, butyl carbitol, diacetone alcohol and the like. Preferred water-soluble organic solvents include ethylene glycol, propylene glycol, diacetone alcohol, ethyl cellosolve, ethyl carbitol and butyl cellosolve, and the amount of the water-soluble organic solvent added is usually 3 to 30% by weight in the metal anticorrosive agent of the present invention. , Preferably 8 to 20% by weight
Is.
【００１０】〔増粘剤〕本発明の金属防食剤の塗布層の
厚みを確保するためには増粘剤の使用が望ましい。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、カチオン澱粉、非イオン澱粉、ペクチン、
グァーガム、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、アクリル重合体
のナトリウム塩等があげられる。望ましい増粘剤として
は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、メチルセルローズがある。該増粘剤の添加量は
本発明の金属防食剤中固形分として０．１〜２重量％、
望ましくは０．２〜０．８重量％である。[Thickener] In order to secure the thickness of the coating layer of the metal anticorrosive agent of the present invention, it is desirable to use a thickener. As the thickener used in the present invention, methyl cellulose, carboxymethyl cellulose, hydroxymethyl cellulose, ethyl cellulose, carboxyethyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol, starch, cationic starch, nonionic starch, pectin,
Examples include guar gum, tamarind gum, roast bean gum, galactomannan, carrageenan, agar, and sodium salt of acrylic polymer. Preferred thickeners include hydroxymethyl cellulose, hydroxyethyl cellulose and methyl cellulose. The amount of the thickener added is 0.1 to 2% by weight as solid content in the metal anticorrosive agent of the present invention,
It is preferably 0.2 to 0.8% by weight.
【００１１】〔消泡剤〕本発明の金属防食剤をピンホー
ル等の欠陥がなく被処理金属表面に塗布するためには消
泡剤の使用が望ましい。本発明に添加される消泡剤とし
てはシリコーン系、フッ素系、オイル系等がある。シリ
コーン系としてはジメチルシリコーン、ジエチルシリコ
ーン、フッ素系ではフッ化メタノール、２フッ化メタノ
ール、フッ化エタノール、２フッ化エタノール、オイル
系では石油系としてケロシン、ミネラルスピリット、ミ
ネラルターペント、ホワイトスピンドル、動物系として
牛脂、豚脂等があり、植物系では硬化ヒマシ油、ヒマシ
油、桐油、硬化大豆油等がある。望ましい消泡剤として
はケロシン、ミネラルスピリット、ホワイトスピンド
ル、桐油、硬化ヒマシ油がある。該消泡剤の添加量は本
発明の金属防食剤中０．０１〜５重量％、望ましくは
０．１〜１重量％である。[Antifoaming Agent] In order to apply the metal anticorrosive agent of the present invention to the metal surface to be treated without defects such as pinholes, it is desirable to use an antifoaming agent. As the defoaming agent added to the present invention, there are silicone type, fluorine type, oil type and the like. Silicone-based dimethyl silicone, diethyl silicone, fluorine-based fluorinated methanol, 2 fluorinated methanol, fluorinated ethanol, 2 fluorinated ethanol, oil-based petroleum-based kerosene, mineral spirits, mineral terpentes, white spindles, animals The system includes beef tallow, lard, etc., and the plant system includes hydrogenated castor oil, castor oil, tung oil, hydrogenated soybean oil and the like. Preferred defoamers include kerosene, mineral spirits, white spindles, tung oil, hydrogenated castor oil. The amount of the defoaming agent added is 0.01 to 5% by weight, preferably 0.1 to 1% by weight in the metal anticorrosive agent of the present invention.
【００１２】〔処理方法〕本発明の金属防食剤のｐＨは
通常６．５〜９．５の範囲に調節されるが、該金属防食
剤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
磨を行ない、更に必要あればトリクロルエチレン、パー
クロルエチレン、ベンゼン、トルエン、キシレン等の有
機溶剤で洗浄し、乾燥後本発明の金属防食剤を浸漬、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。その後室温に放置し、必要あれば空気を送って
乾燥し、２００〜２３０℃前後で少なくとも１５分間の
加熱処理を行なう。このようにして該金属表面には本発
明の金属防食剤に起因する防食性被膜が形成される。該
防食性被膜上には所望なれば更に塗料によって塗装が施
されてもよい。[Treatment Method] The pH of the metal anticorrosive agent of the present invention is usually adjusted in the range of 6.5 to 9.5. To treat the metal surface to be treated with the metal anticorrosive agent, first, The metal surface is polished by shot blasting, sand blasting, etc., and if necessary, washed with an organic solvent such as trichloroethylene, perchlorethylene, benzene, toluene, xylene, etc., and after drying, the metal anticorrosive agent of the present invention is dipped and sprayed. , A roll coater, a curtain flow coater, a rotary brush coater, electrostatic coating, etc. Then, it is left to stand at room temperature, air is blown if necessary to dry it, and heat treatment is carried out at about 200 to 230 ° C. for at least 15 minutes. In this way, an anticorrosive coating derived from the metal anticorrosive agent of the present invention is formed on the metal surface. If desired, the anticorrosive coating may be further coated with a paint.
【００１３】[0013]
【作用】本発明の金属防食剤に起因する防食性被膜にお
いては、該被膜中に含まれる被処理金属よりもイオン化
傾向の大きい金属微粉末が、該被処理金属に先立って腐
食即ち酸化される。このような該金属微粉末の酸素捕捉
作用（自己犠牲作用と云う）によって、被処理金属の酸
化即ち腐食が防止される。In the anticorrosive coating film resulting from the metal anticorrosive agent of the present invention, the fine metal powder having a greater ionization tendency than the metal to be treated contained in the film is corroded or oxidized prior to the metal to be treated. . Oxygen, that is, corrosion, of the metal to be treated is prevented by such an oxygen scavenging action (called a self-sacrifice action) of the metal fine powder.
【００１４】水溶性合成樹脂はこのような自己犠牲作用
を有する金属微粉末のバインダーとして強固な被膜を形
成し、かつ速やかな吸水吸湿性によって上記金属微粉末
の自己犠牲作用を円滑に進める場を提供し、一方該被処
理金属表面が外界に曝露されることを防止するが、該水
溶性合成樹脂の被膜が硬く耐水性を有すると、該金属微
粉末の粒子間の通電即ちイオン移動が困難となり、自己
犠牲作用が阻害されるのでこの場合には通電剤の添加に
より良好な通電性を確保する。The water-soluble synthetic resin forms a strong film as a binder of the fine metal powder having such a self-sacrificing action, and provides a place where the self-sacrificing action of the fine metal powder can be smoothly promoted by its rapid water absorption and hygroscopicity. On the other hand, the surface of the metal to be treated is prevented from being exposed to the outside, but when the coating film of the water-soluble synthetic resin is hard and water resistant, it is difficult to conduct electricity, that is, ion transfer between particles of the fine metal powder. Since the self-sacrificing action is hindered, in this case, good electrical conductivity is ensured by adding an electrically conductive agent.
【００１５】更に本発明の金属防食剤は水性であるか
ら、使用前に金属微粉末が水と反応することを防止する
必要があり、そのために酸化防止剤を添加する。Further, since the metal anticorrosive agent of the present invention is aqueous, it is necessary to prevent the fine metal powder from reacting with water before use, and therefore an antioxidant is added.
【００１６】[0016]
〔実施例１〕エチルアクリレート：アクリル酸＝２：８
重量比の共重合体を１／３カセイソーダ、１／３アンモ
ニア、１／３モノエタノールアミンで中和し、３５重量
％水溶液とする（水溶性合成樹脂Ａ）。上記水溶性合成
樹脂Ａを使用して下記の処方により金属防食剤Ａ（ｐＨ
８）を調製する。 水溶性合成樹脂Ａ ２５ 重量部 アルミニウムペースト＊1 ８ 〃 亜鉛微粉末＊2 ３５ 〃 プロピレングリコール（溶剤） ８ 〃 ヒドロキシメチルセルローズ（増粘剤） ０．８〃 ジメチルシリコーン（消泡剤） ０．２〃 水 ２３．０〃 ＊1 ：粒径５〜６μのアルミニウム微粉末をケロシンで
処理した後、該アルミニウム微粉末７５重量部、エチル
ステアレート１５重量部、ベンゾトリアゾール５重量
部、ソルビタンモノラウレート５重量部を混合してペー
ストとした。 ＊2 ：亜鉛微粉末はアトマイズ法によって製造した粒径
３〜５μのものを用いた。 上記処方においては、亜鉛微粉末、アルミニウムペース
ト、溶剤を均一に混合した後、水溶性合成樹脂Ａ、通電
剤および消泡剤を添加し攪拌しつゝ増粘剤を徐々に添加
混合し、次いで３００メッシュの篩にて濾過し金属防食
剤Ａとする。[Example 1] Ethyl acrylate: acrylic acid = 2: 8
The copolymer in a weight ratio is neutralized with 1/3 caustic soda, 1/3 ammonia and 1/3 monoethanolamine to obtain a 35 wt% aqueous solution (water-soluble synthetic resin A). Using the above water-soluble synthetic resin A, the metal anticorrosive agent A (pH
8) is prepared. Water-soluble synthetic resin A 25 parts by weight Aluminum paste * 1 8 〃 Zinc fine powder * 2 35 〃 Propylene glycol (solvent) 8 〃 Hydroxymethyl cellulose (thickener) 0.8 〃 Dimethyl silicone (antifoaming agent) 0.2 〃 Water 23.0 〃 * 1 : 75 parts by weight of aluminum fine powder, 15 parts by weight of ethyl stearate, 5 parts by weight of benzotriazole, sorbitan monolaurate after treating aluminum fine powder having a particle size of 5 to 6 µ with kerosene 5 parts by weight were mixed to form a paste. * 2 : Zinc fine powder having a particle size of 3 to 5 μm manufactured by the atomization method was used. In the above formulation, zinc fine powder, aluminum paste and solvent are uniformly mixed, then water-soluble synthetic resin A, a current-carrying agent and a defoaming agent are added and stirred, and then a thickener is gradually added and mixed. The metal anticorrosive A is obtained by filtering through a 300 mesh screen.
【００１７】〔実施例２〕ｎ−ブチルアクリレート：メ
タクリル酸＝３：７重量比の共重合体を２／３アンモニ
ア、１／３ジエタノールアミンで中和し、３５重量％水
溶液とする（水溶性合成樹脂Ｂ）。上記水溶性合成樹脂
Ｂおよび実施例１で使用したアルミニウムペーストと亜
鉛微粉末を使用して下記の処方により実施例１と同様に
混合して金属防食剤Ｂ（ｐＨ７．５）を調製する。 水溶性合成樹脂Ｂ １８ 重量部 アルミニウムペースト １０ 〃 亜鉛微粉末 ２２ 〃 プロピレングリコール（溶剤） ７ 〃 エチルセロソルブ（溶剤） ３ 〃 ヒドロキシメチルセルローズ（増粘剤） ０．８〃 ステアリルトリメチルアンモニウムクロリド（通電剤）０．２〃 ２−フッ化メタノール（消泡剤） ０．５〃 水 ３８．５〃Example 2 A copolymer of n-butyl acrylate: methacrylic acid = 3: 7 weight ratio was neutralized with 2/3 ammonia and 1/3 diethanolamine to prepare a 35 weight% aqueous solution (water-soluble synthesis). Resin B). Using the water-soluble synthetic resin B, the aluminum paste used in Example 1 and zinc fine powder, the metal anticorrosive agent B (pH 7.5) is prepared by mixing in the same manner as in Example 1 according to the following formulation. Water-soluble synthetic resin B 18 parts by weight Aluminum paste 10 〃 Fine zinc powder 22 〃 Propylene glycol (solvent) 7 〃 Ethyl cellosolve (solvent) 3 〃 Hydroxymethyl cellulose (thickener) 0.8 〃 Stearyl trimethyl ammonium chloride (current carrying agent) ) 0.2〃 2-fluorinated methanol (antifoaming agent) 0.5〃 water 38.5〃
【００１８】〔実施例３〕エチルアクリレート：アクリ
ル酸＝３：７重量比の共重合体をアンモニアで中和し、
３５重量％水溶液とする（水溶性合成樹脂Ｃ）。上記水
溶性合成樹脂Ｃおよび実施例１で使用したアルミニウム
ペーストと亜鉛微粉末を使用して下記の処方により実施
例１と同様に混合して金属防食剤Ｃ（ｐＨ８．５）を調
製する。 水溶性合成樹脂Ｃ １１ 重量部 アルミニウムペースト １０ 〃 亜鉛微粉末 ２０ 〃 エチレングリコール（溶剤） ７ 〃 ジアセトンアルコール（溶剤） １０ 〃 ヒドロキシエチルセルローズ（増粘剤） ０．３５〃 ラウリルトリメチルアンモニウムクロリド（通電剤） ０．３〃 ホワイトスピンドル（消泡剤） ０．３５〃 水 ４８ 〃Example 3 A copolymer of ethyl acrylate: acrylic acid = 3: 7 weight ratio was neutralized with ammonia,
A 35 wt% aqueous solution is prepared (water-soluble synthetic resin C). Using the water-soluble synthetic resin C, the aluminum paste used in Example 1, and zinc fine powder, the metal anticorrosive agent C (pH 8.5) is prepared by mixing in the same manner as in Example 1 according to the following formulation. Water-soluble synthetic resin C 11 parts by weight Aluminum paste 10 〃 Fine zinc powder 20 〃 Ethylene glycol (solvent) 7 〃 Diacetone alcohol (solvent) 10 〃 Hydroxyethyl cellulose (thickener) 0.35 〃 Lauryl trimethyl ammonium chloride (electric current) Agent) 0.3〃 White spindle (defoamer) 0.35〃 Water 48〃
【００１９】〔試験〕 1. 試料 (1) 鋼板：ＳＳ−４１鋼板（５０×１００×０．５mm）
を使用した。該鋼板は表面をショットブラストし次いで
トリクロルエチレンで洗浄を行ない乾燥した。 (2) ねじ：長さ７５mm、径２mm、頭部８mm、ねじ部５０
mmのプラスねじを使用した。 2. 塗布 (1) 鋼板 上記鋼板に上記金属防食剤Ａ，Ｂ，Ｃを各々厚さ３０μ
に塗布し、１時間風乾する。その後２００〜２３０℃で
２０分間の加熱処理を行なう。 (2) ねじ 上記ねじを上記金属防食剤Ａ，Ｂ，Ｃの各々に浸漬し、
引上げた後脱水機で１分間脱水を行なった後１分間風乾
し、その後２００〜２３０℃で３０分間の加熱処理を行
なう。この操作は２回繰返される。[Test] 1. Sample (1) Steel plate: SS-41 steel plate (50 × 100 × 0.5 mm)
It was used. The surface of the steel sheet was shot blasted, washed with trichlorethylene and dried. (2) Screw: length 75 mm, diameter 2 mm, head 8 mm, screw 50
mm Phillips screws were used. 2. Application (1) Steel plate The above steel plates are each coated with the above metal anticorrosive agents A, B, and C to a thickness of 30 μm.
And air dry for 1 hour. After that, heat treatment is performed at 200 to 230 ° C. for 20 minutes. (2) Screw The above screw is dipped in each of the above metal anticorrosive agents A, B and C,
After pulling up, dehydration is performed for 1 minute with a dehydrator, followed by air drying for 1 minute, and then heat treatment at 200 to 230 ° C. for 30 minutes. This operation is repeated twice.
【００２０】〔試験結果〕 1. 塗膜の密着性および硬度 上記金属防食剤Ａ，Ｂ，Ｃを塗布した鋼板についてゴバ
ン目試験（密着性）および鉛筆硬度を測定した。結果を
表１に示す。[Test Results] 1. Adhesion and Hardness of Coating Film The steel sheet coated with the above-described metal anticorrosives A, B, and C was subjected to a gouge stitch test (adhesion) and a pencil hardness. The results are shown in Table 1.
【表１】 [Table 1]
【００２１】表１によれば金属防食剤Ａ，Ｂ，Ｃはいず
れも鋼板に良好な密着性を示し、かつ硬度も充分である
ことが認められる。It can be seen from Table 1 that each of the metal anticorrosive agents A, B and C exhibits good adhesion to the steel sheet and has sufficient hardness.
【００２２】2. 塩水噴霧試験 上記鋼板およびねじについてＪＩＳ−Ｚ−２３７１に準
じて塩水噴霧試験を行なった。その結果は表２に示され
る。2. Salt Spray Test A salt spray test was conducted on the above steel plates and screws according to JIS-Z-2371. The results are shown in Table 2.
【表２】 評価 ○：変化なし，△：若干発錆，×：全面発錆 *1：Ｂ',Ｃ' はＢ，Ｃから通電剤を除いた比較例であ
る。 *2：ＤはＡ，Ｂ，Ｃで用いたねじに８μの亜鉛メッキを
施した後クロメート処理した試料である。[Table 2] Evaluation ◯: No change, Δ: Slight rusting, ×: Full surface rusting * 1 : B ′, C ′ are comparative examples in which the current-carrying agent was removed from B and C. * 2 : D is a sample used for A, B, and C, which is zinc plated with 8μ and then chromated.
【００２３】表２によれば本発明の金属防食剤Ａ，Ｂ，
Ｃはいずれも優れた防食性を示すが、速やかな吸水吸湿
性を有する水溶性合成樹脂Ａを使用した金属防食剤Ａの
場合は通電剤を添加する必要はないが吸水吸湿性の低い
水溶性合成樹脂Ｂ，Ｃを使用した場合、通電剤が添加さ
れていないＢ',Ｃ' および亜鉛−クロメート処理品Ｄは
いずれも防食性が劣る。According to Table 2, the metal anticorrosive agents A, B, and
C shows excellent anticorrosion properties, but in the case of the metal anticorrosion agent A using the water-soluble synthetic resin A having rapid water absorption and hygroscopicity, it is not necessary to add an energizing agent, but the water absorption is low. When synthetic resins B and C are used, B ′ and C ′ to which a current-carrying agent is not added and the zinc-chromate treated product D are inferior in corrosion resistance.
【００２４】3. 耐水性試験 純水に室温下で鋼板およびねじを２００時間浸漬し、そ
の後の塗膜の変化をみた。その結果を表３に示す。3. Water resistance test Steel plates and screws were immersed in pure water at room temperature for 200 hours, and changes in the coating film were observed. The results are shown in Table 3.
【表３】 評価 ○：変化なし，△：若干発錆，×：全面発錆[Table 3] Evaluation ○: No change, △: Slight rusting, ×: Full-scale rusting
【００２５】表３によれば本発明の金属防食剤Ａ，Ｂ，
Ｃはいずれも優れた防食性を示すが、吸水吸湿性の低い
水溶性合成樹脂Ｂ，Ｃを使用し通電剤が添加されていな
いＢ',Ｃ' はいずれも耐水性に劣り、また亜鉛−クロメ
ート処理品Ｄも耐水性が充分でない。According to Table 3, the metal anticorrosive agents A, B, and
Both C have excellent anticorrosion properties, but water-soluble synthetic resins B and C having low water absorption and hygroscopicity are used, and B'and C'without an energizing agent have poor water resistance, and zinc- The chromate-treated product D also has insufficient water resistance.
【００２６】4. 耐侯性試験 上記鋼板を各々京都府城陽市において南面に角度４５°
で、３０日間放置して耐侯性試験を行なった。その結果
を表４に示す。4. Weather resistance test Each of the above steel sheets was formed at an angle of 45 ° on the south side in Joyo City, Kyoto Prefecture.
Thus, the weather resistance test was conducted by leaving it for 30 days. The results are shown in Table 4.
【表４】 評価 ○：変化なし，△：若干発錆，×：全面発錆[Table 4] Evaluation ○: No change, △: Slight rusting, ×: Full-scale rusting
【００２７】表４によれば、本発明の金属防食剤Ａ，
Ｂ，Ｃはいずれも優れた耐侯性を示すが、吸水吸湿性の
低い水溶性合成樹脂Ｂ，Ｃを使用し通電剤が添加されて
いないＢ',Ｃ' はいずれも耐侯性が劣る。According to Table 4, the metal anticorrosive agent A of the present invention,
Both B and C show excellent weather resistance, but B'and C'which are water-soluble synthetic resins B and C having low water absorption and hygroscopicity and to which no current-carrying agent is added have poor weather resistance.
【００２８】[0028]
【発明の効果】したがって本発明においては６価クロム
等の有害物質を含有しない、優れた耐食性を金属に与え
る金属防食剤が提供される。Therefore, the present invention provides a metal anticorrosive agent which does not contain harmful substances such as hexavalent chromium and gives excellent corrosion resistance to metals.
Claims (5)
よりもイオン化傾向の大きい金属の微粉末と、該金属の
酸化防止剤とからなることを特徴とする金属防食剤1. A metal anticorrosive comprising a water-soluble synthetic resin binder, a fine powder of a metal having a greater ionization tendency than the metal to be treated, and an antioxidant for the metal.
よりもイオン化傾向の大きい金属の微粉末と、該金属の
酸化防止剤と、通電剤とからなる請求項１に記載の金属
防食剤2. A metal anticorrosive agent according to claim 1, which comprises a water-soluble synthetic resin binder, a fine powder of a metal having an ionization tendency higher than that of the metal to be treated, an antioxidant for the metal, and a current-carrying agent.
属よりもイオン化傾向の大きい金属は、亜鉛、アルミニ
ウム、亜鉛−アルミニウム合金からなる群から選ばれた
一種または二種以上の金属である請求項１に記載の金属
防食剤3. The metal to be treated is iron, and the metal having a greater ionization tendency than the metal to be treated is one or more metals selected from the group consisting of zinc, aluminum and zinc-aluminum alloy. The metal anticorrosive agent according to claim 1.
項１に記載の金属防食剤4. The metal anticorrosive agent according to claim 1, wherein the antioxidant is an oxyacid salt.
する界面活性剤である請求項１に記載の金属防食剤5. The metal anticorrosive agent according to claim 1, wherein the current-carrying agent is a surfactant containing a quaternary ammonium salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09033292A JP3259976B2 (en) | 1992-03-13 | 1992-03-13 | Metal anticorrosive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09033292A JP3259976B2 (en) | 1992-03-13 | 1992-03-13 | Metal anticorrosive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0641472A true JPH0641472A (en) | 1994-02-15 |
| JP3259976B2 JP3259976B2 (en) | 2002-02-25 |
Family
ID=13995567
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP09033292A Expired - Fee Related JP3259976B2 (en) | 1992-03-13 | 1992-03-13 | Metal anticorrosive |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3259976B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0444931A2 (en) * | 1990-02-28 | 1991-09-04 | Sanwa Kagaku Kenkyusho Co., Ltd. | Use of 3-oxygermylpropionic acid to treat and prevent diabetes due to autoimmune diseases |
| US6960247B2 (en) | 2003-07-22 | 2005-11-01 | Hoden Seimitsu Kako Kenkyusho Co., Ltd. | Chromium-free water reducible rust inhibitive paint for metals |
| JP2006348147A (en) * | 2005-06-15 | 2006-12-28 | Kunihiko Hirose | Method for producing zinc flake containing metal of different kind and method for producing self-sacrifice type rust-preventive anti-corrosive agent using the same |
| KR20120022708A (en) | 2009-04-21 | 2012-03-12 | 엔오에프 메탈 코팅스 아시아 퍼시픽 가부시키가이샤 | Zinc-based black rust inhibitor, rust inhibiting coating film, and rust inhibiting metal member |
| KR102059640B1 (en) * | 2019-06-19 | 2019-12-27 | (주)방수하는사람들 | Aqueous acryl waterproof material and method for constructing waterproof structure using the same |
| KR102075591B1 (en) * | 2019-06-19 | 2020-02-11 | (주)방수하는사람들 | Method for constructing waterproof structure with heat insulation for metallic substrate |
| KR102075592B1 (en) * | 2019-06-19 | 2020-02-11 | (주)방수하는사람들 | Aqueous coating composition for concrete structure |
-
1992
- 1992-03-13 JP JP09033292A patent/JP3259976B2/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0444931A2 (en) * | 1990-02-28 | 1991-09-04 | Sanwa Kagaku Kenkyusho Co., Ltd. | Use of 3-oxygermylpropionic acid to treat and prevent diabetes due to autoimmune diseases |
| EP0444931B1 (en) * | 1990-02-28 | 1994-08-10 | Sanwa Kagaku Kenkyusho Co., Ltd. | Use of 3-oxygermylpropionic acid to treat and prevent diabetes due to autoimmune diseases |
| US6960247B2 (en) | 2003-07-22 | 2005-11-01 | Hoden Seimitsu Kako Kenkyusho Co., Ltd. | Chromium-free water reducible rust inhibitive paint for metals |
| JP2006348147A (en) * | 2005-06-15 | 2006-12-28 | Kunihiko Hirose | Method for producing zinc flake containing metal of different kind and method for producing self-sacrifice type rust-preventive anti-corrosive agent using the same |
| JP4509873B2 (en) * | 2005-06-15 | 2010-07-21 | 邦彦 廣瀬 | Method for producing zinc flakes containing different metals and method for producing self-sacrificial anticorrosive agent using the same |
| KR20120022708A (en) | 2009-04-21 | 2012-03-12 | 엔오에프 메탈 코팅스 아시아 퍼시픽 가부시키가이샤 | Zinc-based black rust inhibitor, rust inhibiting coating film, and rust inhibiting metal member |
| JP5631868B2 (en) * | 2009-04-21 | 2014-11-26 | Ｎｏｆメタルコーティングス株式会社 | Zinc-based black rust preventive agent, rust preventive film and rust preventive metal member |
| KR102059640B1 (en) * | 2019-06-19 | 2019-12-27 | (주)방수하는사람들 | Aqueous acryl waterproof material and method for constructing waterproof structure using the same |
| KR102075591B1 (en) * | 2019-06-19 | 2020-02-11 | (주)방수하는사람들 | Method for constructing waterproof structure with heat insulation for metallic substrate |
| KR102075592B1 (en) * | 2019-06-19 | 2020-02-11 | (주)방수하는사람들 | Aqueous coating composition for concrete structure |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3259976B2 (en) | 2002-02-25 |
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