JPH0867834A - Anticorrosive composition for coated or noncoated zinc steel and anticorrosive treatment method - Google Patents
Anticorrosive composition for coated or noncoated zinc steel and anticorrosive treatment methodInfo
- Publication number
- JPH0867834A JPH0867834A JP2616295A JP2616295A JPH0867834A JP H0867834 A JPH0867834 A JP H0867834A JP 2616295 A JP2616295 A JP 2616295A JP 2616295 A JP2616295 A JP 2616295A JP H0867834 A JPH0867834 A JP H0867834A
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- steel
- sulfide
- rust
- uncoated
- 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
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- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
- Chemical Treatment Of Metals (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、亜鉛系被覆鋼及び無被
覆鋼用防錆組成物に関し、更に詳しくは、亜鉛系被覆鋼
及び無被覆鋼の一次防錆処理又は塗装前処理に使用され
る非クロメート系の塗布型防錆組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rust preventive composition for zinc-based coated steel and uncoated steel, and more specifically, it is used for primary rust-prevention treatment or pretreatment for coating of zinc-based coated steel and uncoated steel. The present invention relates to a non-chromate coating type rust preventive composition.
【０００２】[0002]
【従来の技術】鋼表面に亜鉛を含む金属をメッキ又は溶
射により被覆した亜鉛系被覆鋼、及び、上記被覆を施さ
ない無被覆鋼の一次防錆処理又は塗装前処理には、従来
からクロムイオンを含有するクロメート系処理剤が広く
用いられている。上記クロメート系処理剤としては、例
えば、特開平５−２７９８６７号公報には、クロムイオ
ン（Ｃｒ6+、Ｃｒ3+）と水分散性樹脂からなる塗布型ク
ロメート系処理剤が開示されている。しかし、上記クロ
メート系処理剤は、有毒なクロムイオンを含有している
ため、無公害化するための排水処理のコストアップ、作
業環境における人体への悪影響等の問題があり、また、
処理剤により形成されるクロメート被膜を含む製品から
のクロム溶出による環境汚染等のおそれもある。2. Description of the Related Art Zinc-based coated steel whose surface is coated with a metal containing zinc by plating or thermal spraying, and uncoated steel without the above coating have been conventionally treated with chromium ions for primary rust prevention or pretreatment. A chromate-based treating agent containing is widely used. As the chromate-based treatment agent, for example, JP-A-5-279867 discloses a coating type chromate-based treatment agent composed of chromium ions (Cr 6+ , Cr 3+ ) and a water-dispersible resin. However, since the chromate-based treatment agent contains toxic chromium ions, there are problems such as an increase in the cost of wastewater treatment for making pollution-free, and an adverse effect on the human body in the working environment.
There is also a risk of environmental pollution due to elution of chromium from a product containing a chromate film formed by a treating agent.
【０００３】上記欠点を解決する方法として、クロムを
含有しない防錆処理剤又は防錆処理方法の開発が考えら
れる。このようなものとして、特公平５−３７２３４号
公報には、硫化水素ガス又は硫化水素ガスを溶解させた
水溶液と亜鉛メッキ鋼板又は無被覆鋼板とを接触させ、
その後塗装する防錆処理方法が開示されている。特公平
５−３８７９０号公報には、マンガン、鉄、ニッケル、
コバルト等の金属硫化物であって、特定の範囲の溶解度
積を有するものを含有する防錆用被覆組成物が開示され
ている。また、特公平５−７６５５２号公報には、硫化
水素と反応しうる金属表面に塗装膜を形成後、硫化水素
を含有する水溶液又は硫化水素を含有する水蒸気を塗装
金属と接触させて、塗装膜下面に金属硫化物を生成させ
る防錆処理方法が開示されている。As a method for solving the above-mentioned drawbacks, development of an anticorrosive agent or an anticorrosive method which does not contain chromium can be considered. As such, Japanese Patent Publication No. 5-37234 discloses that hydrogen sulfide gas or an aqueous solution in which hydrogen sulfide gas is dissolved is brought into contact with a galvanized steel sheet or an uncoated steel sheet,
A rustproofing method of coating thereafter is disclosed. Japanese Patent Publication No. 5-38790 discloses manganese, iron, nickel,
A rust preventive coating composition containing a metal sulfide such as cobalt having a solubility product in a specific range is disclosed. Further, in Japanese Patent Publication No. 5-76552, after forming a coating film on the surface of a metal capable of reacting with hydrogen sulfide, an aqueous solution containing hydrogen sulfide or steam containing hydrogen sulfide is brought into contact with the coating metal to form a coating film. A rustproofing method for producing metal sulfides on the lower surface is disclosed.
【０００４】[0004]
【発明が解決しようとする課題】しかし、硫化水素ガス
又は硫化水素ガスを溶解させた水溶液を用いて塗装下地
の防錆処理を行う方法は、硫化物層を形成させるに際し
て、直接硫化水素ガスと金属表面とを接触させるので、
有害な硫化水素ガスが環境中に漏れやすく工業的な利用
は困難であった。また、金属硫化物を含有する防錆用被
覆組成物は、金属表面に塗布して使用されるが、塗布後
相当期間が経過して塗膜中に水分が浸入したときか又は
腐食したときに、組成物中に含有される金属硫化物が一
部溶解して金属表面に硫化物層を形成するものであるた
め、塗膜形成時に積極的に硫化物層を形成させる方法に
比べ、防錆力、耐剥離性に劣っていた。更に、硫化水素
を含有する水溶液又は硫化水素を含有する水蒸気を接触
させて塗装金属の防錆処理を行う方法は、作業中に硫化
水素ガスが発生しやすく、作業環境における人体への悪
影響等の問題があった。However, a method of performing rust-preventive treatment for a coating base using hydrogen sulfide gas or an aqueous solution in which hydrogen sulfide gas is dissolved is a method for directly forming hydrogen sulfide gas when forming a sulfide layer. Because it makes contact with the metal surface,
Hazardous hydrogen sulfide gas easily leaks into the environment, making industrial use difficult. Further, the rust preventive coating composition containing a metal sulfide is used by being applied to the metal surface, but when water penetrates into the coating film or corrodes after a considerable period of time has passed after application. Since the metal sulfide contained in the composition is partially dissolved to form a sulfide layer on the metal surface, it is more rust-proof than a method of forming a sulfide layer positively during coating film formation. It was inferior in strength and peeling resistance. Furthermore, the method of performing anticorrosion treatment of the coating metal by contacting an aqueous solution containing hydrogen sulfide or water vapor containing hydrogen sulfide, hydrogen sulfide gas is easily generated during the work, such as adverse effects on the human body in the work environment. There was a problem.
【０００５】本発明は、上記状況に鑑みてなされたもの
であり、クロメート系処理剤と同等以上の優れた防錆力
を有し、耐剥離性に優れた非クロメート系の塗装型防錆
組成物であって、特に亜鉛系被覆鋼及び無被覆鋼に好適
に用い得るものを提供すること、並びに、それを用いた
工業的に容易に利用可能な防錆処理方法を提供すること
を目的とするものである。The present invention has been made in view of the above circumstances and has a non-chromate coating type rust preventive composition having an excellent rust preventive power equal to or higher than that of a chromate treating agent and excellent in peeling resistance. The object of the present invention is to provide a product that can be suitably used for zinc-based coated steel and uncoated steel, and to provide an industrially easily usable rust preventive treatment method using the product. To do.
【０００６】[0006]
【課題を解決するための手段】本発明の要旨は、亜鉛系
被覆鋼及び無被覆鋼用防錆組成物を、水性樹脂１〜８０
重量部及び水９９〜２０重量部からなる溶液に、硫化物
イオンを０．１〜１００００ｐｐｍ含有させ、ｐＨを７
以上とするところにある。以下に本発明を詳述する。DISCLOSURE OF THE INVENTION The gist of the present invention is to provide a rust preventive composition for zinc-based coated steel and uncoated steel as an aqueous resin 1-80.
A solution consisting of 99 parts by weight of water and 99 to 20 parts by weight of water contains 0.1 to 10000 ppm of sulfide ions and has a pH of 7
That's all there is to it. The present invention is described in detail below.
【０００７】本発明においては、水性樹脂及び水からな
る溶液に硫化物イオンを含有させる。水性樹脂は、塗膜
を形成して亜鉛又は鉄の硫化物層の耐久性を高め、防錆
力を向上させるので、本発明の亜鉛系被覆鋼及び無被覆
鋼用防錆組成物の構成要件の１つとなる。上記水性樹脂
としては、ｐＨ７以上で水に溶解又は分散するものであ
れば特に限定されず、例えば、ポリオレフィン樹脂、ポ
リウレタン樹脂、ポリエステル樹脂、アクリル樹脂、エ
ポキシ樹脂、アルキド樹脂等を挙げることができる。こ
れらのうち、ポリオレフィン樹脂が好ましく、なかで
も、防錆性の点で、カルボン酸変性されたポリエチレン
が特に好ましい。In the present invention, a solution consisting of an aqueous resin and water contains sulfide ions. The water-based resin forms a coating film to enhance the durability of the sulfide layer of zinc or iron and to improve the rust preventive power, so that the constituent requirements of the rust preventive composition for zinc-based coated steel and uncoated steel of the present invention It will be one of. The water-based resin is not particularly limited as long as it dissolves or disperses in water at pH 7 or higher, and examples thereof include a polyolefin resin, a polyurethane resin, a polyester resin, an acrylic resin, an epoxy resin, and an alkyd resin. Of these, polyolefin resins are preferable, and carboxylic acid-modified polyethylene is particularly preferable from the viewpoint of rust prevention.
【０００８】上記水性樹脂及び水からなる溶液中の水性
樹脂及び水の配合割合は、水性樹脂１〜８０重量部、水
９９〜２０重量部である。水性樹脂が１重量部未満であ
り、水が９９重量部を超えると、防錆組成物塗膜の膜厚
が充分とならず防錆力が不足し、水性樹脂が８０重量部
を超え、水が２０重量部未満であると、防錆組成物塗膜
の膜厚が大きくなりすぎ、また、含有する硫化物の水へ
の溶解量が少なすぎるので、上記範囲に限定される。好
ましくは水性樹脂１０〜４０重量部、水９０〜６０重量
部である。The mixing ratio of the aqueous resin and water in the solution comprising the above aqueous resin and water is 1 to 80 parts by weight of the aqueous resin and 99 to 20 parts by weight of water. When the amount of the water-based resin is less than 1 part by weight and the amount of water exceeds 99 parts by weight, the film thickness of the rust preventive composition coating film is insufficient and the rust preventive power is insufficient, and the amount of the water-based resin exceeds 80 parts by weight. Is less than 20 parts by weight, the film thickness of the rust-preventive composition coating film becomes too large, and the amount of the contained sulfide dissolved in water is too small, so the content is limited to the above range. Aqueous resin is preferably 10 to 40 parts by weight and water is 90 to 60 parts by weight.
【０００９】上記硫化物イオンは、ＨＳ- 又はＳ2-であ
る。上記硫化物イオンの供給源としては、水性樹脂及び
水からなる溶液中に、０．１ｐｐｍ以上の硫化物イオン
を溶解させ得る水可溶性硫化物であれば特に限定され
ず、例えば、硫化ナトリウム（Ｎａ2 Ｓ）、硫化カリウ
ム（Ｋ2 Ｓ）、硫化アンモニウム（（ＮＨ4 ）2 Ｓ）、
硫化水素アンモニウム（ＮＨ4 ＨＳ）、硫化カルシウム
（ＣａＳ）、硫化ストロンチウム（ＳｒＳ）、硫化アル
ミニウム（Ａｌ2 Ｓ3 ）、硫化バリウム（ＢａＳ）、硫
化ゲルマニウム（ＧｅＳ）、硫化マンガン（ＭｎＳ）、
硫化ランタン（Ｌａ2 Ｓ3 ）等を挙げることができる。
これらのうち、硫化マンガン（ＭｎＳ）、硫化アンモニ
ウム（（ＮＨ4 ）2 Ｓ）、硫化水素アンモニウム（ＮＨ
4 ＨＳ）が好ましい。これらは、単独で使用されてもよ
く、２種以上が併用されてもよい。[0009] The sulfide ions, HS -, or S 2-. The source of the sulfide ion is not particularly limited as long as it is a water-soluble sulfide capable of dissolving 0.1 ppm or more of sulfide ion in a solution composed of an aqueous resin and water, and examples thereof include sodium sulfide (Na 2 S), potassium sulfide (K 2 S), ammonium sulfide ((NH 4 ) 2 S),
Ammonium hydrogen sulfide (NH 4 HS), calcium sulfide (CaS), strontium sulfide (SrS), aluminum sulfide (Al 2 S 3 ), barium sulfide (BaS), germanium sulfide (GeS), manganese sulfide (MnS),
Examples thereof include lanthanum sulfide (La 2 S 3 ).
Of these, manganese sulfide (MnS), ammonium sulfide ((NH 4 ) 2 S), ammonium hydrogen sulfide (NH
4 HS) is preferred. These may be used alone or in combination of two or more.
【００１０】上記硫化物イオンの含有濃度は、水性樹脂
及び水からなる溶液中０．１〜１００００ｐｐｍであ
る。０．１ｐｐｍ未満であると、防錆組成物の塗布乾燥
時に亜鉛系被覆鋼表面又は無被覆鋼表面と防錆組成物塗
膜との界面に、均一な亜鉛又は鉄の硫化物層を形成でき
ず、１００００ｐｐｍを超えると、防錆組成物塗膜中
に、水可溶性物が過剰に残存して透水性が増大しブリス
ター（ふくれ）の発生等による防錆力の低下が生じ、ま
た、硫化物特有の臭気が問題となるので、上記範囲に限
定される。好ましくは１〜１０００ｐｐｍである。The content concentration of the sulfide ion is 0.1 to 10000 ppm in the solution containing the aqueous resin and water. When it is less than 0.1 ppm, a uniform zinc or iron sulfide layer can be formed at the interface between the zinc-based coated steel surface or the uncoated steel surface and the rust-preventive composition coating film when the rust-preventive composition is applied and dried. If the amount exceeds 10,000 ppm, the water-soluble substance excessively remains in the coating film of the rust preventive composition, the water permeability increases, and the rust preventive power decreases due to the occurrence of blisters (blisters). Since the peculiar odor becomes a problem, it is limited to the above range. It is preferably 1 to 1000 ppm.
【００１１】本発明の亜鉛系被覆鋼及び無被覆鋼用防錆
組成物の水素イオン濃度は、ｐＨ７以上である。ｐＨ７
未満であると、含有する硫化物から硫化水素が発生して
悪臭を放ち、また、水に分散した水性樹脂がゲル化する
おそれがあるので、上記範囲に限定される。好ましくは
ｐＨ８〜ｐＨ１２である。ｐＨ調整は、例えば、アンモ
ニア水又はその他のアミン系化合物；水酸化リチウム、
水酸化カリウム、水酸化ナトリウム等の金属水酸化物等
を用いて行うことができる。The hydrogen ion concentration of the rust preventive composition for zinc-based coated steel and uncoated steel of the present invention is pH 7 or more. pH 7
If it is less than the above range, hydrogen sulfide may be generated from the contained sulfide to give off a bad odor, and the aqueous resin dispersed in water may gel. It is preferably pH 8 to pH 12. The pH can be adjusted by, for example, ammonia water or other amine compounds; lithium hydroxide,
It can be carried out using a metal hydroxide such as potassium hydroxide or sodium hydroxide.
【００１２】本発明においては、上記硫化物イオンに加
えて、更に、難溶性硫化物の粒子を水性樹脂及び水から
なる溶液中に分散させるのが好ましい。難溶性硫化物
は、腐食環境下で防錆組成物塗膜中に水分が浸入した場
合、硫化物イオンを徐々に放出し、被塗物と防錆組成物
塗膜との界面の亜鉛又は鉄の硫化物層を補修するので、
本発明の目的達成をより確実にする。上記難溶性硫化物
としては、水溶液中で硫化物イオンを解離するものであ
れば特に限定されず、例えば、硫化マンガン（Ｍｎ
Ｓ2 ）、硫化モリブデン（ＭｏＳ2 、Ｍｏ2 Ｓ5 、Ｍｏ
Ｓ3 、ＭｏＳ4 ）、硫化鉄（ＦｅＳ、ＦｅＳ2 、Ｆｅ2
Ｓ3 ）、硫化バナジウム（ＶＳ4 、Ｖ2 Ｓ5 、Ｖ
2 Ｓ3 ）、硫化ニッケル（ＮｉＳ）、硫化ランタン（Ｌ
ａ2 Ｓ3 ）、硫化アンチモン（Ｓｂ2 Ｓ3 ）、硫化ビス
マス（ＢｉＳ、Ｂｉ2 Ｓ3 ）等を挙げることができる。In the present invention, in addition to the above sulfide ions, it is preferable to disperse the particles of the hardly soluble sulfide in a solution containing an aqueous resin and water. The sparingly soluble sulfide, when water penetrates into the rust preventive composition coating film in a corrosive environment, gradually releases sulfide ions, and zinc or iron at the interface between the object to be coated and the rust preventive composition coating film. Since it repairs the sulfide layer of
The object of the present invention is achieved more reliably. The sparingly soluble sulfide is not particularly limited as long as it dissociates sulfide ions in an aqueous solution, and for example, manganese sulfide (Mn
S 2 ), molybdenum sulfide (MoS 2 , Mo 2 S 5 , Mo
S 3 , MoS 4 ), iron sulfide (FeS, FeS 2 , Fe 2
S 3 ), vanadium sulfide (VS 4 , V 2 S 5 , V
2 S 3 ), nickel sulfide (NiS), lanthanum sulfide (L
a 2 S 3 ), antimony sulfide (Sb 2 S 3 ), bismuth sulfide (BiS, Bi 2 S 3 ) and the like.
【００１３】上記難溶性硫化物の添加量は、水性樹脂１
００重量部に対して２．５〜２００重量部である。２．
５重量部未満であると、硫化物イオンの供給が少なすぎ
て亜鉛又は鉄の硫化物層を充分補修することができず、
２００重量部を超えると、難溶性硫化物の量が過剰とな
り透水性が増大して防錆力が低下するので、上記範囲に
限定される。好ましくは５〜５０重量部である。The addition amount of the above-mentioned sparingly soluble sulfide is based on the water-based resin 1
It is 2.5 to 200 parts by weight with respect to 00 parts by weight. 2.
When it is less than 5 parts by weight, the supply of sulfide ions is too small to sufficiently repair the sulfide layer of zinc or iron,
If it exceeds 200 parts by weight, the amount of the hardly soluble sulfide becomes excessive, the water permeability increases, and the rust preventive power decreases, so the content is limited to the above range. It is preferably 5 to 50 parts by weight.
【００１４】本発明においては、上記水性樹脂及び水か
らなる溶液に硫化物イオンを含有させたもの、又は、上
記水性樹脂及び水からなる溶液に硫化物イオン及び難溶
性硫化物の粒子を含有させたものに、更に、りん酸イオ
ンを含有させることがより好ましい。上記りん酸イオン
の供給源としては特に限定されず、例えば、りん酸（Ｈ
3 ＰＯ4 ）、りん酸ナトリウム（Ｎａ3 ＰＯ4 ）、りん
酸一水素ナトリウム（Ｎａ2 ＨＰＯ4 ）、りん酸二水素
ナトリウム（ＮａＨ2 ＰＯ4 ）、りん酸カリウム（Ｋ3
ＰＯ4 ）、りん酸一水素カリウム（Ｋ2 ＨＰＯ4 ）、り
ん酸二水素カリウム（ＫＨ2 ＰＯ4 ）、りん酸アンモニ
ウム（（ＮＨ4 ）3 ＰＯ4 ）、りん酸一水素アンモニウ
ム（（ＮＨ4 ）2 ＨＰＯ4 ）、りん酸二水素アンモニウ
ム（（ＮＨ4 ）Ｈ2 ＰＯ4 ）等を挙げることができ、更
に、りん酸ヒドラジニウム等のりん酸の低分子アミン
塩、りん酸エチル等の比較的低分子のりん酸エステル等
を挙げることができる。これらのうち、りん酸アンモニ
ウム（（ＮＨ4 ）3 ＰＯ4 ）、りん酸一水素アンモニウ
ム（（ＮＨ4 ）2 ＨＰＯ4 ）、りん酸二水素アンモニウ
ム（（ＮＨ4 ）Ｈ2 ＰＯ4 ）等の揮発性塩基との塩；り
ん酸ヒドラジニウム等のりん酸の低分子アミン塩が好ま
しい。In the present invention, a solution containing the above-mentioned aqueous resin and water containing sulfide ions, or a solution containing the above-mentioned aqueous resin and water containing particles of sulfide ions and sparingly soluble sulfides. It is more preferable to further add phosphate ion to the above. The source of the phosphate ion is not particularly limited, and examples thereof include phosphoric acid (H
3 PO 4 ), sodium phosphate (Na 3 PO 4 ), sodium monohydrogen phosphate (Na 2 HPO 4 ), sodium dihydrogen phosphate (NaH 2 PO 4 ), potassium phosphate (K 3
PO 4 ), potassium monohydrogen phosphate (K 2 HPO 4 ), potassium dihydrogen phosphate (KH 2 PO 4 ), ammonium phosphate ((NH 4 ) 3 PO 4 ), ammonium monohydrogen phosphate ((NH 4 ) 2 HPO 4 ), ammonium dihydrogen phosphate ((NH 4 ) H 2 PO 4 ), and the like, and further, low molecular weight amine salts of phosphoric acid such as hydrazinium phosphate, ethyl phosphate and the like. Examples thereof include low molecular weight phosphoric acid ester. Of these, volatilization of ammonium phosphate ((NH 4 ) 3 PO 4 ), ammonium monohydrogen phosphate ((NH 4 ) 2 HPO 4 ), ammonium dihydrogen phosphate ((NH 4 ) H 2 PO 4 ), etc. Salts with organic bases; low molecular weight amine salts of phosphoric acid such as hydrazinium phosphate are preferred.
【００１５】上記りん酸イオンの含有量は、５００〜５
０００ｐｐｍである。りん酸イオンの含有量が５００ｐ
ｐｍ未満であると、亜鉛系被覆鋼又は無被覆鋼と塗膜と
の界面におけるりん酸亜鉛層又はりん酸鉄層等の形成が
不充分となり、硫化物イオンにより形成される硫化亜鉛
層等の防錆性を補充する効果がなくなる。りん酸イオン
の含有量が５０００ｐｐｍを超えると塗膜中の電解質量
が増大し塗膜の透水性が増すので、塩水噴霧試験性や耐
水性の低下を引き起こす。また、過剰のりん酸イオンの
添加は、防錆組成物中において、経時的に水性樹脂をゲ
ル化させるので、防錆組成物の貯蔵安定性を悪化させ
る。好ましくは１０００〜５０００ｐｐｍである。The content of the above phosphate ion is 500 to 5
It is 000 ppm. The content of phosphate ion is 500p
When it is less than pm, the formation of a zinc phosphate layer or an iron phosphate layer at the interface between the zinc-based coated steel or uncoated steel and the coating film is insufficient, resulting in a zinc sulfide layer formed by sulfide ions. The effect of replenishing anticorrosive properties is lost. When the content of phosphate ion exceeds 5000 ppm, the electrolytic mass in the coating film increases and the water permeability of the coating film increases, which causes deterioration of salt spray testability and water resistance. Also, the addition of an excess of phosphate ions causes the aqueous resin to gel in the rust preventive composition over time, and thus deteriorates the storage stability of the rust preventive composition. It is preferably 1000 to 5000 ppm.
【００１６】本発明の亜鉛系被覆鋼及び無被覆鋼用防錆
組成物には、更に、他の成分が配合されていてもよい。
上記他の成分としては、例えば、シリカ粒子、顔料、界
面活性剤等を挙げることができる。また、本発明におい
ては、水性樹脂と難溶性硫化物粒子又は顔料との親和性
の向上、水性樹脂と亜鉛又は鉄の硫化物層若しくはりん
酸塩層との密着性の向上等のために、シランカップリン
グ剤が配合されていてもよい。The zinc-based coated steel and the uncoated steel rust preventive composition of the present invention may further contain other components.
Examples of the other components include silica particles, pigments, surfactants and the like. Further, in the present invention, for improving the affinity between the aqueous resin and the sparingly soluble sulfide particles or pigment, for improving the adhesion between the aqueous resin and the sulfide layer or phosphate layer of zinc or iron, or the like, A silane coupling agent may be blended.
【００１７】上記シリカ粒子は、防錆力、耐擦傷性、塗
装密着性等の改善剤として用いられる。上記シリカ粒子
としては、ナトリウム等の不純物が少なく、弱アルカリ
系のものであれば特に限定されず、例えば、スノーテッ
クスＮ（日産化学工業社製）、アデライトＡＴ−２０Ｎ
（旭電化工業社製）等の市販のシリカゾル；市販のアエ
ロジル粉末シリカ粒子等を挙げることができる。上記シ
リカ粒子の粒径は、１０〜２０ｍμが好ましい。The above silica particles are used as an agent for improving rust prevention, scratch resistance, coating adhesion and the like. The silica particles are not particularly limited as long as they have few impurities such as sodium and are weakly alkaline, and include, for example, Snowtex N (manufactured by Nissan Chemical Industries, Ltd.) and Adelite AT-20N.
(Asahi Denka Kogyo Co., Ltd.) and other commercially available silica sols; commercially available Aerosil powder silica particles and the like. The particle size of the silica particles is preferably 10 to 20 mμ.
【００１８】上記顔料としては、例えば、酸化チタン
（ＴｉＯ2 ）、酸化亜鉛（ＺｎＯ）、酸化ジルコニウム
（ＺｒＯ）、炭酸カルシウム（ＣａＣＯ3 ）、硫酸バリ
ウム（ＢａＳＯ4 ）、アルミナ（Ａｌ2 Ｏ3 ）、カオリ
ンクレー、カーボンブラック、酸化鉄（Ｆｅ2 Ｏ3 、Ｆ
ｅ3 Ｏ4 ）等の無機顔料；有機顔料等の各種着色顔料等
を挙げることができる。上記シランカップリング剤とし
ては、例えば、γ−アミノプロピルトリメトキシシラ
ン、γ−アミノプロピルトリエトキシシラン、γ−グリ
シドキシプロピルトリメトキシシラン、γ−メタクリロ
キシプロピルトリメトキシシラン、Ｎ−［２−（ビニル
ベンジルアミノ）エチル］−３−アミノプロピルトリメ
トキシシラン等を挙げることができる。Examples of the pigment include titanium oxide (TiO 2 ), zinc oxide (ZnO), zirconium oxide (ZrO), calcium carbonate (CaCO 3 ), barium sulfate (BaSO 4 ), alumina (Al 2 O 3 ). , Kaolin clay, carbon black, iron oxide (Fe 2 O 3 , F
It can include various coloring pigments such as organic pigments; e 3 O 4) inorganic pigments such. Examples of the silane coupling agent include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and N- [2- (Vinylbenzylamino) ethyl] -3-aminopropyltrimethoxysilane and the like can be mentioned.
【００１９】水性樹脂の造膜性を向上させ、より均一で
平滑な塗膜を形成するために、溶剤を用いてもよい。上
記溶剤としては、塗料に一般的に用いられるものであれ
ば特に限定されず、例えば、アルコール系、ケトン系、
エステル系、エーテル系のもの等を挙げることができ
る。A solvent may be used in order to improve the film-forming property of the aqueous resin and form a more uniform and smooth coating film. The solvent is not particularly limited as long as it is one that is commonly used in paints, for example, alcohol-based, ketone-based,
Examples thereof include ester type and ether type.
【００２０】本発明の亜鉛系被覆鋼及び無被覆鋼用防錆
組成物は、亜鉛系被覆鋼、又は、亜鉛系被覆等を施さな
い無被覆鋼の防錆処理に使用することができる。上記防
錆処理は、上記亜鉛系被覆鋼及び無被覆鋼用防錆組成物
を被塗物に塗布し、塗布後に被塗物を熱風で加熱し、乾
燥させる方法であってもよく、予め被塗物を加熱し、そ
の後上記亜鉛系被覆鋼及び無被覆鋼用防錆組成物を熱時
塗布し、乾燥させる方法であってもよい。上記加熱の温
度は、上記いずれの方法であっても、５０〜２５０℃で
ある。５０℃未満であると、防錆力が不足し、２５０℃
を超えると、硫化物が分解して防錆力が不足するので、
上記範囲に限定される。好ましくは７０〜１００℃であ
る。塗布後に被塗物を熱風で加熱し、乾燥させる場合、
乾燥の時間は、１秒〜５分が好ましい。The anticorrosive composition for zinc-based coated steel and uncoated steel according to the present invention can be used for anticorrosion treatment of zinc-based coated steel or uncoated steel not coated with zinc-based coating. The rust-preventing treatment may be a method in which the zinc-based coated steel and the uncoated steel rust-preventive composition are applied to an object to be coated, and after the application, the object to be coated is heated with hot air and dried. A method in which the coating material is heated, and then the above-mentioned zinc-based coated steel and uncoated steel anticorrosion composition is applied while hot and dried may be used. The heating temperature is 50 to 250 ° C. in any of the above methods. If the temperature is less than 50 ° C, the rust preventive power is insufficient, and the temperature is 250 ° C.
If it exceeds, the sulfide will decompose and the rust preventive power will be insufficient, so
It is limited to the above range. It is preferably 70 to 100 ° C. When the coated object is heated with hot air after coating and dried,
The drying time is preferably 1 second to 5 minutes.
【００２１】上記防錆処理において、上記亜鉛系被覆鋼
及び無被覆鋼用防錆組成物の塗布膜厚は、乾燥膜厚が
０．１μｍ以上であることが好ましい。０．１μｍ未満
であると、防錆力が不足する。乾燥膜厚が厚すぎると、
塗装前処理としては不経済であり、塗装にも不都合であ
るので、より好ましくは０．１〜２０μｍである。更に
好ましくは０．１〜〜１０μｍである。上記防錆処理に
おいて、上記亜鉛系被覆鋼及び無被覆鋼用防錆組成物の
塗布方法は特に限定されず、一般に使用されるロールコ
ート、エアスプレー、エアレススプレー、浸漬等の方法
により塗布することができる。In the rust-preventing treatment, the coating thickness of the rust-preventive composition for zinc-based coated steel and uncoated steel is preferably a dry coating thickness of 0.1 μm or more. If it is less than 0.1 μm, the rust preventive power is insufficient. If the dry film thickness is too thick,
Since it is uneconomical as a pretreatment for coating and inconvenient for coating, it is more preferably 0.1 to 20 μm. More preferably, it is 0.1 to 10 μm. In the rust-preventing treatment, the coating method of the rust-preventive composition for the zinc-based coated steel and uncoated steel is not particularly limited, and it may be applied by a commonly used method such as roll coating, air spraying, airless spraying or dipping. You can
【００２２】[0022]
【作用】本発明の亜鉛系被覆鋼及び無被覆鋼用防錆組成
物は、塗布することにより被塗物の表面に硫化物層を形
成する。一般に、鉄や亜鉛等の金属の硫化物は安定性が
大きく、例えば、鉄は天然では黄鉄鉱として存在してお
り、亜鉛は９０％以上が閃亜鉛鉱として産出される等、
長期にわたって変質することがない。また、溶解度積か
らもわかるとおり、極めて水に溶けにくい。更に、実験
によっても、鉄や亜鉛等の金属の硫化物の安定性は確か
められ、例えば、亜鉛メッキ鋼板表面を硫化処理により
硫化亜鉛に変えたものについて、腐食電流密度を測定す
ると、未処理の場合の１０％以下であり、クロメート系
処理剤による腐食抑制効果と同等以上の防錆効果がある
ことが判明した。このため、本発明の亜鉛系被覆鋼及び
無被覆鋼用防錆組成物を亜鉛系被覆鋼又は無被覆鋼に使
用して防錆処理をすると、含有する硫化物イオンの作用
により鉄又は亜鉛の硫化物層が生成し、極めて安定な防
錆層が形成される。また、防錆処理において硫化水素ガ
ス又はその水溶液を使用する必要がなく、安全である。When the anticorrosive composition for zinc-based coated steel and uncoated steel of the present invention is applied, a sulfide layer is formed on the surface of the article to be coated. Generally, sulfides of metals such as iron and zinc are highly stable. For example, iron exists as pyrite in nature, and 90% or more of zinc is produced as sphalerite.
It does not deteriorate over a long period of time. In addition, as can be seen from the solubility product, it is extremely insoluble in water. Furthermore, the stability of sulfides of metals such as iron and zinc was also confirmed by experiments, and, for example, when the corrosion current density was measured for the zinc-plated steel sheet surface changed to zinc sulfide by sulfidation treatment, It was found to be 10% or less of the case, and it has been proved that there is a corrosion inhibition effect equal to or higher than the corrosion inhibition effect by the chromate-based treatment agent. Therefore, when the rust preventive treatment is performed using the zinc-based coated steel and the uncoated steel rust-preventive composition of the present invention on the zinc-based coated steel or the uncoated steel, the sulfide ions contained therein cause the formation of iron or zinc. A sulfide layer is formed and an extremely stable rust preventive layer is formed. In addition, it is safe because it is not necessary to use hydrogen sulfide gas or its aqueous solution in the rust prevention treatment.
【００２３】本発明の亜鉛系被覆鋼及び無被覆鋼用防錆
組成物は、更に、りん酸イオンを含有することができ
る。りん酸イオンも亜鉛系被覆鋼又は無被覆鋼と反応し
て、水に不溶のりん酸亜鉛、りん酸鉄等のりん酸塩を形
成する性質を有するので、硫化物層が未形成である金属
素地の部分を補修して、硫化物イオンによる効果と相乗
的に防錆効果を発揮する。このようなりん酸塩は、中
性、アルカリ性環境下では、硫化物に比べて安定性に劣
るが、酸性環境下では、硫化物よりも安定である。従っ
て、腐食環境下でのアノード部位等の酸性環境下におい
て、被塗物と塗膜との界面に濃化溶出したりん酸イオン
と亜鉛、鉄等の金属とが反応して、安定なりん酸塩層を
形成することによって、防錆効果を更に高めることがで
きる。The rust preventive composition for zinc-based coated steel and uncoated steel according to the present invention may further contain a phosphate ion. Since phosphate ions also have the property of reacting with zinc-based coated steel or uncoated steel to form phosphates such as zinc phosphate, iron phosphate, etc., which are insoluble in water, metals with no sulfide layer formed. It repairs the base part and exerts a rust preventive effect synergistically with the effect of sulfide ions. Such a phosphate is less stable than a sulfide in a neutral or alkaline environment, but is more stable than an sulfide in an acidic environment. Therefore, in an acidic environment such as the anode site in a corrosive environment, the phosphate ions that are concentrated and eluted at the interface between the object to be coated and the coating film react with metals such as zinc and iron to produce stable phosphoric acid. By forming the salt layer, the rust prevention effect can be further enhanced.
【００２４】[0024]
【実施例】以下に実施例を掲げて本発明をさらに詳しく
説明するが、本発明はこれら実施例にのみ限定されるも
のではない。The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
【００２５】実施例１ 水性樹脂としてポリエチレン系樹脂エマルジョン２０重
量％を、水８０重量％と混合した。水可溶性硫化物とし
て硫化ナトリウム（Ｎａ2 Ｓ）を用い、濃度２．４ｐｐ
ｍ（硫化物イオン濃度として１ｐｐｍ）となるように上
記混合溶液に溶解し、ｐＨ９．０となるように調整して
防錆組成物を得た。得られた防錆組成物を、予め板温が
８０℃になるよう加熱した市販の溶融亜鉛メッキ鋼板
（７０×１５０×２．３ｍｍ）に、バーコート（＃５）
で、乾燥膜厚が４〜５μｍとなるように塗布した。Example 1 20% by weight of a polyethylene resin emulsion as an aqueous resin was mixed with 80% by weight of water. Sodium sulfide (Na 2 S) was used as the water-soluble sulfide, and the concentration was 2.4 pp.
m (1 ppm as sulfide ion concentration) was dissolved in the above mixed solution and adjusted to pH 9.0 to obtain a rust preventive composition. The obtained rust-preventive composition was applied to a commercially available hot-dip galvanized steel sheet (70 × 150 × 2.3 mm) which had been preheated to a plate temperature of 80 ° C. by bar coating (# 5).
Then, the coating was applied so that the dry film thickness was 4 to 5 μm.
【００２６】防錆組成物を塗布し、乾燥した溶融亜鉛メ
ッキ鋼板を、下記項目について評価した。結果を表１に
示した。 （１）塩水噴霧試験（ソルトスプレーテスト。以下「Ｓ
ＳＴ」という） ５％食塩水を３５℃で防錆組成物塗布面に噴霧し、２４
時間後の白錆の程度を５点満点で評価した。 （２）耐水試験 室温で水道水に１週間浸漬後、表面の白化の程度を５点
満点で評価した。The hot-dip galvanized steel sheet coated with the rust preventive composition and dried was evaluated for the following items. The results are shown in Table 1. (1) Salt spray test (salt spray test.
"ST") 5% saline solution is sprayed on the surface coated with the rust preventive composition at 35 ° C.
The degree of white rust after the lapse of time was evaluated on a scale of 5 points. (2) Water resistance test After immersion in tap water for 1 week at room temperature, the degree of whitening of the surface was evaluated on a scale of 5 points.
【００２７】実施例２〜１１ 表１に示す水可溶性硫化物を、表１に示す濃度で使用
し、表１に示すｐＨに調整したこと以外は、実施例１と
同様にして防錆組成物を得、塗布、乾燥し、評価した。
結果を表１に示した。Examples 2 to 11 The rust preventive composition was prepared in the same manner as in Example 1 except that the water-soluble sulfides shown in Table 1 were used at the concentrations shown in Table 1 and the pH values shown in Table 1 were adjusted. Was obtained, coated, dried and evaluated.
The results are shown in Table 1.
【００２８】比較例１ 水可溶性硫化物を用いなかったこと以外は、実施例１と
同様にして防錆組成物を得、塗布、乾燥し、評価した。
結果を表１に示した。Comparative Example 1 A rust preventive composition was obtained, coated, dried and evaluated in the same manner as in Example 1 except that the water-soluble sulfide was not used.
The results are shown in Table 1.
【００２９】比較例２〜３ 水可溶性硫化物として硫化ナトリウム（Ｎａ2 Ｓ）を、
表１に示す濃度で使用し、表１に示すｐＨに調整したこ
と以外は、実施例１と同様にして防錆組成物を得、塗
布、乾燥し、評価した。結果を表１に示した。Comparative Examples 2-3 Sodium sulfide (Na 2 S) was used as the water-soluble sulfide,
A rust preventive composition was obtained, coated, dried and evaluated in the same manner as in Example 1 except that the concentration was used as shown in Table 1 and the pH was adjusted as shown in Table 1. The results are shown in Table 1.
【００３０】比較例４ 水可溶性硫化物の代わりに、ストロンチウムクロメート
を樹脂１００重量部に対して５．０重量部使用し、表１
に示すｐＨに調整したこと以外は、実施例１と同様にし
て防錆組成物を得、塗布、乾燥し、評価した。結果を表
１に示した。Comparative Example 4 In place of the water-soluble sulfide, 5.0 parts by weight of strontium chromate was used with respect to 100 parts by weight of the resin.
A rust preventive composition was obtained, coated, dried and evaluated in the same manner as in Example 1 except that the pH was adjusted to that shown in. The results are shown in Table 1.
【００３１】実施例１２〜２０、比較例５〜６ 難溶性硫化物として、表２に示す難溶性硫化物を、表２
に示す添加量で分散させ、表２に示すｐＨに調整したこ
と以外は、実施例１と同様にして防錆組成物を得、塗
布、乾燥し、評価した。結果を表２に示した。Examples 12 to 20 and Comparative Examples 5 to 6 As the sparingly soluble sulfides, the sparingly soluble sulfides shown in Table 2 are shown in Table 2
A rust preventive composition was obtained, coated, dried and evaluated in the same manner as in Example 1 except that the pH was adjusted to the value shown in Table 2 by dispersing with the addition amount shown in. The results are shown in Table 2.
【００３２】実施例２１〜２５、比較例７、８ 表３に示す水可溶性硫化物を、表３に示す濃度で使用
し、難溶性硫化物として、表３に示す難溶性硫化物を、
表３に示す添加量で分散させ、更に、りん酸アンモニウ
ム（（ＮＨ4 ）3 ＰＯ4 ）を、りん酸イオン濃度が表３
に示す濃度になるように添加し、表３に示すｐＨに調整
したこと以外は、実施例１と同様にして防錆組成物を
得、塗布、乾燥し、評価した。結果を表３に示した。た
だし、ＳＳＴは、４８時間後の白錆の程度を５点満点で
評価した。Examples 21 to 25, Comparative Examples 7 and 8 The water-soluble sulfides shown in Table 3 were used at the concentrations shown in Table 3, and the sparingly soluble sulfides shown in Table 3 were used as the sparingly soluble sulfides.
Dispersion was carried out with the addition amount shown in Table 3, and ammonium phosphate ((NH 4 ) 3 PO 4 ) was added at a phosphate ion concentration of Table 3
A rust preventive composition was obtained, coated, dried and evaluated in the same manner as in Example 1 except that the pH was adjusted to the concentration shown in Table 3 and the pH was adjusted to that shown in Table 3. The results are shown in Table 3. However, SST evaluated the degree of white rust after 48 hours on a scale of 5 points.
【００３３】比較例９ 水可溶性硫化物、難溶性硫化物代及びりん酸アンモニウ
ム（（ＮＨ4 ）3 ＰＯ4 ）を使用せず、代わりに、スト
ロンチウムクロメートを樹脂１００重量部に対して５．
０重量部使用し、表３に示すｐＨに調整したこと以外
は、実施例１と同様にして防錆組成物を得、塗布、乾燥
し、評価した。結果を表３に示した。ただし、ＳＳＴ
は、４８時間後の白錆の程度を５点満点で評価した。Comparative Example 9 Water-soluble sulfides, sparingly soluble sulfides and ammonium phosphate ((NH 4 ) 3 PO 4 ) were not used. Instead, strontium chromate was added to 100 parts by weight of resin.
A rust preventive composition was obtained, coated, dried and evaluated in the same manner as in Example 1 except that 0 part by weight was used and the pH was adjusted as shown in Table 3. The results are shown in Table 3. However, SST
The white rust after 48 hours was evaluated on a scale of 5 points.
【００３４】[0034]
【表１】 [Table 1]
【００３５】[0035]
【表２】 [Table 2]
【００３６】[0036]
【表３】 [Table 3]
【００３７】[0037]
【発明の効果】本発明によれば、上述の構成としたの
で、有害なクロムを使用することがなく、しかも、クロ
メート系処理剤と同等以上の優れた防錆力を有し、耐剥
離性に優れた亜鉛系被覆鋼及び無被覆鋼用防錆組成物を
提供することができる。EFFECTS OF THE INVENTION According to the present invention, since it has the above-mentioned constitution, it does not use harmful chromium, and has excellent rust-preventing power equivalent to or more than that of the chromate-type treating agent, and peeling resistance. It is possible to provide a rust preventive composition for zinc-based coated steel and uncoated steel, which is excellent in heat resistance.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０９Ｄ 5/00 ＰＰＴ // Ｃ２３Ｃ 22/60 22/68 (72)発明者 寺岡 美香 大阪府寝屋川市池田中町19番17号 日本ペ イント株式会社内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification number Internal reference number FI Technical indication C09D 5/00 PPT // C23C 22/60 22/68 (72) Inventor Mika Teraoka Neyagawa City, Osaka Prefecture 19-17 Ikedanaka-cho Japan Paint Co., Ltd.
Claims (5)
０重量部からなる溶液に、硫化物イオンを０．１〜１０
０００ｐｐｍ含有させてなるｐＨ７以上であることを特
徴とする亜鉛系被覆鋼及び無被覆鋼用防錆組成物。1. An aqueous resin 1 to 80 parts by weight and water 99 to 2
To a solution consisting of 0 parts by weight, 0.1 to 10 sulfide ions are added.
A rust preventive composition for zinc-based coated steel and uncoated steel, which has a pH of 7 or more and is contained at 000 ppm.
鋼用防錆組成物に、難溶性の硫化物を水性樹脂１００重
量部に対して２．５〜２００重量部分散させてなること
を特徴とする亜鉛系被覆鋼及び無被覆鋼用防錆組成物。2. The zinc-based coated steel and the uncoated steel rust preventive composition according to claim 1, wherein 2.5 to 200 parts by weight of a sparingly soluble sulfide is dispersed in 100 parts by weight of an aqueous resin. A rust preventive composition for zinc-based coated steel and uncoated steel.
鋼用防錆組成物に、りん酸イオンを５００〜５０００ｐ
ｐｍ含有させてなることを特徴とする亜鉛系被覆鋼及び
無被覆鋼用防錆組成物。3. The zinc-based coated steel and the uncoated steel rust-preventive composition according to claim 1, further containing phosphate ions at 500 to 5000 p.
A rust preventive composition for zinc-based coated steel and uncoated steel, which is characterized by containing pm.
鋼用防錆組成物に、りん酸イオンを５００〜５０００ｐ
ｐｍ含有させてなることを特徴とする亜鉛系被覆鋼及び
無被覆鋼用防錆組成物。4. The zinc-based coated steel and uncoated steel rust-preventing composition according to claim 2, and a phosphate ion of 500 to 5000 p.
A rust preventive composition for zinc-based coated steel and uncoated steel, which is characterized by containing pm.
覆鋼及び無被覆鋼用防錆組成物を亜鉛系被覆鋼又は無被
覆鋼に塗布し、その後、前記亜鉛系被覆鋼又は無被覆鋼
を５０〜２５０℃となるように加熱し乾燥するか、又
は、予め亜鉛系被覆鋼又は無被覆鋼を５０〜２５０℃に
加熱し、その後、請求項１、２、３又は４記載の亜鉛系
被覆鋼及び無被覆鋼用防錆組成物を塗布し乾燥すること
を特徴とする亜鉛系被覆鋼及び無被覆鋼の防錆処理方
法。5. The zinc-based coated steel or the uncoated steel rust preventive composition according to claim 1, 2, 3 or 4 is applied to zinc-based coated steel or uncoated steel, and then the zinc-based coated steel or The uncoated steel is heated to 50 to 250 ° C. and dried, or the zinc-based coated steel or the uncoated steel is preheated to 50 to 250 ° C., and then the coated steel or the uncoated steel is then heated. A method for rust-proofing a zinc-based coated steel and an uncoated steel, which comprises applying the rust-preventive composition for a zinc-based coated steel and an uncoated steel and drying the composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7026162A JP2993860B2 (en) | 1994-06-22 | 1995-01-19 | Rust prevention composition for zinc-based coated steel and uncoated steel and rust prevention treatment method |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16473194 | 1994-06-22 | ||
| JP6-164731 | 1994-06-22 | ||
| JP7026162A JP2993860B2 (en) | 1994-06-22 | 1995-01-19 | Rust prevention composition for zinc-based coated steel and uncoated steel and rust prevention treatment method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0867834A true JPH0867834A (en) | 1996-03-12 |
| JP2993860B2 JP2993860B2 (en) | 1999-12-27 |
Family
ID=26363912
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7026162A Expired - Fee Related JP2993860B2 (en) | 1994-06-22 | 1995-01-19 | Rust prevention composition for zinc-based coated steel and uncoated steel and rust prevention treatment method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2993860B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10195345A (en) * | 1997-01-10 | 1998-07-28 | Nippon Paint Co Ltd | Rust-proofing coating agent containing triazinethiol, method for rust-proofing and rust-proofed metallic metal |
| US6607587B1 (en) | 1998-02-18 | 2003-08-19 | Nippon Steel Corporation | Anticorrosive coating material and method of rust prevention |
| WO2004079044A1 (en) * | 2003-02-28 | 2004-09-16 | Columbia Chemical Corporation | A corrosion inhibiting composition for metals |
| JP2007138264A (en) * | 2005-11-21 | 2007-06-07 | Noguchi Koki Kk | Rust inhibitor for steel surface |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508851B (en) * | 2009-03-10 | 2011-10-26 | 广州化工研究设计院 | Novel environment friendly high-efficiency rust-preventive pigment and method for producing the same |
-
1995
- 1995-01-19 JP JP7026162A patent/JP2993860B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10195345A (en) * | 1997-01-10 | 1998-07-28 | Nippon Paint Co Ltd | Rust-proofing coating agent containing triazinethiol, method for rust-proofing and rust-proofed metallic metal |
| US6607587B1 (en) | 1998-02-18 | 2003-08-19 | Nippon Steel Corporation | Anticorrosive coating material and method of rust prevention |
| WO2004079044A1 (en) * | 2003-02-28 | 2004-09-16 | Columbia Chemical Corporation | A corrosion inhibiting composition for metals |
| JP2007138264A (en) * | 2005-11-21 | 2007-06-07 | Noguchi Koki Kk | Rust inhibitor for steel surface |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2993860B2 (en) | 1999-12-27 |
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