JP2601788B2 - anti-rust - Google Patents
anti-rustInfo
- Publication number
- JP2601788B2 JP2601788B2 JP948884A JP948884A JP2601788B2 JP 2601788 B2 JP2601788 B2 JP 2601788B2 JP 948884 A JP948884 A JP 948884A JP 948884 A JP948884 A JP 948884A JP 2601788 B2 JP2601788 B2 JP 2601788B2
- Authority
- JP
- Japan
- Prior art keywords
- rust
- acid
- copper
- weight ratio
- water
- 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.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Description
【発明の詳細な説明】 本発明は銅および銅合金用防錆剤の改良に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to improvements in rust inhibitors for copper and copper alloys.
従来より、銅および銅合金製の素材，半製品，完成品
を屋内暴露あるいは屋内雰囲気で１カ月から６カ月程度
の一時防錆を行なう際は、鉄鋼と同様に、一般に、防錆
油が使用されている。Conventionally, rust-preventive oils are generally used for copper and copper alloy materials, semi-finished products, and finished products for temporary rust prevention for one to six months in indoor exposure or indoor atmosphere for about one to six months. Have been.
しかし、被防錆体の使用目的によつては、アルカリ脱
脂又は溶剤脱脂等によつてこの防錆油を除去する必要が
あり、このため工程の短縮、コスト低減、あるいは安全
衛生面の点で大きな障害となつていた。However, depending on the purpose of use of the rust-prevented body, it is necessary to remove the rust-preventive oil by means of alkali degreasing or solvent degreasing, etc., which leads to shortening of the process, cost reduction, or safety and sanitation. It was a major obstacle.
この防錆油の欠点を改善するために、本発明者らは、
先に防錆油と同等の防錆力を有し、並びに油状で不乾性
の特質を保ちながら、しかも防錆期間後は水あるいは蒸
気のフラツシング、又は水に浸漬することにより容易に
除去できる防錆剤を、特願昭53−80932号（特開昭55−8
460号）として提案し、脱脂工程の省略を図つた。In order to improve the disadvantages of this rust-preventive oil, the present inventors
It has the same rust-preventing power as rust-preventing oil, and it can be easily removed by water or steam flushing or immersion in water after the rust-preventing period, while maintaining the oily and non-drying characteristics. The rust agent is disclosed in Japanese Patent Application No. 53-80932 (JP-A-55-8809).
No. 460) to eliminate the degreasing step.
この防錆剤は、発電プラント、化学プラント等の水・
蒸気系統の機器、配管の内外面防錆をはじめ、機械加工
品の工程間防錆に多くの実績を挙げている。This rust preventive is used in water and power plants, chemical plants, etc.
It has many achievements in rust prevention between processes of machined products, including rust prevention on steam system equipment and piping inside and outside.
しかしながら、上記先願の防錆剤は、用途として鉄鋼
製品に限られ、銅および銅合金には効果がなく、又、次
に挙げる現場からの多様な要求から、更に粘度の低下と
微小隙間等への浸透性向上の必要に迫られた。However, the rust inhibitor of the prior application is limited to steel products as an application and has no effect on copper and copper alloys. Further, due to the following various requirements from the site, the viscosity is further reduced and fine gaps are reduced. The need to improve penetration into
（１） 粘度を下げることによつて鋼管等への流し塗り
の際の残留量を少なくし、かつ作業時間を更に短縮す
る。(1) By reducing the viscosity, the amount of residue at the time of flow coating on a steel pipe or the like is reduced, and the working time is further shortened.
（２） 組立後微小隙間等に塗布する機器があるが、上
記防錆剤が浸透していかず、発錆する場合がある。(2) Although there are devices that apply to minute gaps and the like after assembly, the rust preventive does not penetrate and rust may occur.
本発明者等は、これらの点について改善を図るべく研
究を重ねた結果、炭素数16〜20の脂肪族飽和分岐二塩基
酸のトリエタノールアミン塩の10〜50重量比の水溶液
に、水溶性防錆薬剤0.1〜５重量比および炭素数１〜３
のアルコールの10〜50重量比を配合することによつて下
記の点を満足する本発明防錆剤を完成するに至つた。The present inventors have conducted studies to improve on these points, and as a result, a 10 to 50 weight ratio aqueous solution of a triethanolamine salt of an aliphatic saturated branched dibasic acid having 16 to 20 carbon atoms is soluble in water. Rust preventive agent 0.1-5 weight ratio and carbon number 1-3
By mixing 10 to 50 weight ratios of the above alcohols, the rust preventive of the present invention satisfying the following points was completed.
（１） 銅および銅合金に対し防錆油と同等の防錆力が
ある。(1) It has the same rust-preventing power as rust-preventive oil against copper and copper alloys.
（２） 油状で不乾性の特質を保持している。(2) It has an oily and non-drying characteristic.
（３） 水あるいは蒸気のフラツシング、又は水への浸
漬により、容易に溶解、除去可能である。(3) It can be easily dissolved and removed by flushing with water or steam or immersion in water.
（４） 低粘度化が可能となつた。(4) The viscosity can be reduced.
（５） 微小隙間への浸透性が向上した。(5) The permeability into the minute gap is improved.
本発明において、炭素数16〜20の脂肪族飽和分岐二塩
基酸は、例えば次の構造式のものが使用される。In the present invention, as the aliphatic saturated branched dibasic acid having 16 to 20 carbon atoms, for example, one having the following structural formula is used.
（上記，配合のものは岡村製油株式会社製:OSK−DA
SB−20として市販されている。） 上記SB−20は環状ケトンのシクロヘキサノンをオレフ
イン（ブタジエン）の存在下に、フエントン試薬により
開環二量化したものであるが、ケトン及びオレフインを
種々変更することにより需要に応じた品を製造すること
ができる。例えば、環状ケトンはシクロヘキサノンの他
にシクロペンタノン、シクロヘプタノン、シクロドデカ
ノン等、又、オレフインとしてはブタジエンの他にスチ
レン、マレイン酸、イソプレン、ジビニルベンゼン、シ
クロペンタジエン等があげられる。 (The above compound is manufactured by Okamura Oil Co., Ltd .: OSK-DA
Commercially available as SB-20. The above SB-20 is obtained by ring-opening dimerization of cyclohexanone, a cyclic ketone, with a phenton reagent in the presence of olefin (butadiene). By changing the ketone and olefin, various products can be produced according to demand. be able to. For example, cyclic ketones include cyclopentanone, cycloheptanone, cyclododecanone and the like in addition to cyclohexanone, and olefins include styrene, maleic acid, isoprene, divinylbenzene, cyclopentadiene and the like in addition to butadiene.
なお、上記合成法により製造される長鎖二塩基酸の
内、下記の特長を満足する本発明防錆剤の原料として使
用する場合、理論的にSB−20が最適である。In addition, among the long-chain dibasic acids produced by the above synthesis method, when used as a raw material of the rust preventive agent of the present invention satisfying the following features, SB-20 is theoretically optimal.
防錆期間中、防錆皮膜は硬化することなく何時迄も
水溶性を保ち経日変化のない事、（このため飽和脂肪酸
が必要となる。） 防錆剤の塗布後、溶剤のアルコール、水は蒸発する
が溶剤の蒸発後も、粉体化（固型化）することなく常に
油状を保つ事（他の直鎖二塩基酸等は粉体であるが、SB
−20はエチル基の分岐があるために液体 である。） 吸湿性が少ない事、（C16〜C20が適当である。） すなわち、上記SB−20は、分岐二塩基酸のため、融点
は６〜15℃と低く、常温で液体（油状）であること、及
び飽和酸のため、防錆期間中に硬化されることもなく、
何時迄も経日変化がないことが特長である。During the rust prevention period, the rust prevention film does not cure and remains water-soluble for as long as possible and does not change over time. (Therefore, saturated fatty acids are required.) Evaporates, but keeps oily without powdering (solidification) even after evaporation of the solvent. (Other linear dibasic acids are powder, but SB
-20 is liquid due to ethyl group branching It is. That is, it has low hygroscopicity (C 16 to C 20 is suitable.) That is, since the above SB-20 is a branched dibasic acid, its melting point is as low as 6 to 15 ° C., and it is a liquid (oil) at room temperature. Due to the presence of a saturated acid, without being cured during the rust prevention period,
The feature is that there is no change over time until any time.
上記二塩基酸を中和するアルカリ剤としてはトリエタ
ノールアミンが適切である。トリエタノールアミン以外
のアルカリ剤、例えば他のアルカノールアミン（ジエタ
ノールアミン、モノエタノールアミン等）、アンモニ
ア、及び他の有機アミン類の塩は銅および銅合金に対し
て銅ガード剤を配合しても、緑青を発生させるなど悪影
響を与え、しかもアンモニア臭、アミン臭の悪臭があ
り、又水溶性が悪くなる等使用に耐えなかつた。また、
アミン以外のアルカリ剤、例えば水酸化ナトリウム、水
酸化カリウム等のアルカリ金属類の塩（無機塩）は、本
発明防錆剤組成物の乾燥後、適切な油状を保つことがで
きず、粉体化傾向にあり好ましくない。Triethanolamine is suitable as the alkaline agent for neutralizing the dibasic acid. Alkaline agents other than triethanolamine, such as salts of other alkanolamines (diethanolamine, monoethanolamine, etc.), ammonia, and other organic amines, can be used with copper and copper alloys even with a copper guard agent. In addition, there was an adverse effect such as generation of odors, and there was a bad smell of ammonia odor and amine odor. Also,
Alkali agents other than amines, for example, salts (inorganic salts) of alkali metals such as sodium hydroxide and potassium hydroxide cannot maintain an appropriate oil after drying of the rust preventive composition of the present invention. It is not preferable because of the tendency to change.
また、上記二塩基酸以外の有機酸例えば炭素数６〜20
の直鎖二塩基酸（アジピン酸、ピメリン酸、スベリン
酸、アゼライン酸、セバシン酸、ドデカン−２酸等）、
芳香族カルボン酸（安息香酸、フタール酸、パラ・ター
シヤリー・ブチル安息香酸等）、及びオキシカルボン酸
（グルコン酸、クエン酸等）等のトリエタノールアミン
塩は、粉体化傾向にあり、適切な油状を保つことができ
ない、又は吸湿性が強く、高湿度の条件下では垂れ落ち
てしまう等、適切ではなかつた。Organic acids other than the above dibasic acids, for example, those having 6 to 20 carbon atoms.
Linear dibasic acids (adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecane-2 acid, etc.),
Triethanolamine salts such as aromatic carboxylic acids (benzoic acid, phthalic acid, para-tertiary butyl benzoic acid, etc.) and oxycarboxylic acids (gluconic acid, citric acid, etc.) tend to be powdered, It was not appropriate because it could not keep oily or had strong hygroscopicity and dropped under high humidity conditions.
上記の二塩基酸トリエタノールアミン塩だけでは銅お
よび銅合金に対して特に有効ではないので、水溶性防錆
薬剤として公知の銅ガード剤（ベンゾトリアゾール、メ
チルベンゾトリアゾール、メルカプトベンゾチアゾール
等）を配合すると、金属表面に分子吸着されるか、不働
態化するので、長期間にわたつて優れた防錆力を発揮で
きる。Since the above dibasic acid triethanolamine salt alone is not particularly effective for copper and copper alloys, a known copper guard agent (benzotriazole, methylbenzotriazole, mercaptobenzothiazole, etc.) is blended as a water-soluble rust preventive agent. Then, the molecules are adsorbed on the metal surface or passivated, so that excellent rust prevention can be exhibited over a long period of time.
銅ガード剤の配合量は、上記中和塩溶液に対して0.1
〜0.5重量比の範囲が好ましい。その配合量が0.1重量比
以下では殆んど効果がなく、５重量％以上配合してもそ
れに比例するだけの効果の増大はみられず不経済だから
である。The compounding amount of the copper guard agent is 0.1 to the above neutralized salt solution.
A range of .about.0.5 weight ratio is preferred. If the amount is less than 0.1% by weight, there is almost no effect, and if the amount is more than 5% by weight, the effect is not increased in proportion to it, and it is uneconomical.
又、炭素数１〜３のアルコールとしてメチルアルコー
ル、エチルアルコール、イソプロピルアルコール等を配
合するものであり、ブチルアルコール等炭素数４以上の
アルコールは悪臭、又は水溶性減少の点で使用できな
い。従つて、衛生面と性能面からエチルアルコールが最
も好ましい。Further, methyl alcohol, ethyl alcohol, isopropyl alcohol and the like are blended as alcohols having 1 to 3 carbon atoms, and alcohols having 4 or more carbon atoms such as butyl alcohol cannot be used due to bad smell or reduced water solubility. Therefore, ethyl alcohol is most preferable in terms of hygiene and performance.
アルコールの添加量は10〜50重量比が適切である。こ
れを配合することによつて粘度は10〜20センチポイズ低
下し、25℃で約10センチポイズになり、浸透性も著しく
向上する。10重量比以下では上記の性状は得られない
し、50重量比以上になると、スプレイ等で塗布した時レ
ベリング性がむしろ悪化する。An appropriate amount of alcohol to be added is 10 to 50 weight ratio. By incorporating this, the viscosity is reduced by 10 to 20 centipoise, to about 10 centipoise at 25 ° C., and the permeability is significantly improved. If the ratio is less than 10% by weight, the above properties cannot be obtained. If the ratio is more than 50% by weight, the leveling property is rather deteriorated when applied by spraying or the like.
以下、本発明の実施例を挙げて説明する。 Hereinafter, an example of the present invention will be described.
実施例 表−１の配合割合に基づいて、本発明防錆剤を調製
し、それぞれに圧延銅板TCuP（50×100×1mm）、および
復水器用黄銅継目無管BsTF−２（φ19×70mm）を浸漬塗
布し、引き上げ後、１昼夜自然乾燥した。このものを試
験片として、屋外格納防錆試験器内に吊り下げ、60日間
の防錆試験を行なつた。なお、この試験器は屋外の大気
に開放されているが、試験片に雨がかからない構造にな
つている。Examples The rust preventives of the present invention were prepared based on the blending ratios in Table 1, and each of them was rolled copper plate TCuP (50 × 100 × 1 mm) and brass seamless tube for condenser BsTF-2 (φ19 × 70 mm). Was applied by dip coating, pulled up, and then naturally dried for one day. Using this as a test piece, it was hung in a rust prevention tester stored outdoors and a rust prevention test was performed for 60 days. This tester is open to the outside atmosphere, but has a structure in which the test piece does not rain.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特公 昭31−514（ＪＰ，Ｂ１) ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-B-31-514 (JP, B1)
Claims (1)
トリエタノールアミン塩の10〜50重量比の水溶液に、水
溶性防錆薬剤0.1〜５重量比および炭素数１〜３のアル
コールの10〜50重量比を配合してなる防錆剤。An aqueous solution of a triethanolamine salt of an aliphatic saturated branched dibasic acid having 16 to 20 carbon atoms in a weight ratio of 10 to 50, a water-soluble rust preventive agent having a 0.1 to 5 weight ratio and a A rust inhibitor containing 10 to 50 weight ratio of alcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP948884A JP2601788B2 (en) | 1984-01-24 | 1984-01-24 | anti-rust |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP948884A JP2601788B2 (en) | 1984-01-24 | 1984-01-24 | anti-rust |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60155689A JPS60155689A (en) | 1985-08-15 |
| JP2601788B2 true JP2601788B2 (en) | 1997-04-16 |
Family
ID=11721614
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP948884A Expired - Lifetime JP2601788B2 (en) | 1984-01-24 | 1984-01-24 | anti-rust |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2601788B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100985269B1 (en) * | 2007-11-19 | 2010-10-04 | 주식회사 포스코 | Coating Composition and Method for Reducing Precipitation Material on Surface of Steel Plate in Continuous Annealing |
| JP5363893B2 (en) * | 2009-07-06 | 2013-12-11 | 中部電力株式会社 | Method for treating ferrous metal surface exposed to superheated steam |
| CA2866125C (en) * | 2012-03-08 | 2020-07-21 | The Lubrizol Corporation | Waterborne coatings, compositions, and methods thereof that provide improved corrosion protection |
-
1984
- 1984-01-24 JP JP948884A patent/JP2601788B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60155689A (en) | 1985-08-15 |
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