JPS6315351B2 - - Google Patents
Info
- Publication number
- JPS6315351B2 JPS6315351B2 JP54132552A JP13255279A JPS6315351B2 JP S6315351 B2 JPS6315351 B2 JP S6315351B2 JP 54132552 A JP54132552 A JP 54132552A JP 13255279 A JP13255279 A JP 13255279A JP S6315351 B2 JPS6315351 B2 JP S6315351B2
- Authority
- JP
- Japan
- Prior art keywords
- benzotriazole
- copper
- weight
- group
- anionic surfactant
- 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
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
- C23F11/14—Nitrogen-containing compounds
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
本発明は防錆剤組成物に関する。更に詳しくは
ベンゾトリアゾール、ベンゾチアゾール又はこれ
らの誘導体と特定の構造を有する陰イオン性界面
活性剤を併用してなる鉄及び非鉄金属特に銅に対
して有効な防錆剤組成物に関する。
銅は地金の美しい赤銅色が商品の色調に生かさ
れて用いられる事が多く、銅製品についてはその
赤銅色が商品価値として重要視されている。その
ため銅の加工、仕上げ工程において変色防止の為
性能のよい防錆剤が要求されている。銅の変色防
止用防錆剤としては従来より、ベンゾトリアゾー
ル、ベンゾチアゾール又はこれらの誘導体がよく
知られている。しかし、鉄、真鋳等銅以外の金属
が共存する機械類においては共存する金属すべて
に防錆効果を発現することが望ましく、種々検討
がなされている。米国特許第3891568号や英国特
許第1402880号明細書にはベンゾトリアゾールの
アルカリ金属塩が有効である旨、特開昭51−
138548号公報にはベンゾトリアゾールがチオカー
バメートの共存下で耐海水性が大きく、非鉄金属
にも有効である旨、特公昭50−13225号、特開昭
51−59041号、特開昭51−29338号各公報にはベン
ゾトリアゾールがアミン類と共に鉄、非鉄金属用
として用いうる旨、特開昭51−13338号公報、米
国特許第3969237号、米国特許第4014894号明細書
にはベンゾトリアゾールがカルボン酸との併用に
おいて鉄、非鉄用として有効である旨、独国公開
特許第2429512号、特公昭50−13751号、特公昭50
−13752号、特公昭50−13753号、特公昭50−
13750号各公報にはベンゾトリアゾールが、カル
ボン酸のアミン塩との共存下で有効である旨の記
載が認められる。
しかし、これらの防錆剤は必ずしも未だ防錆効
果は充分でなく、特に、水溶液として用いた場合
には銅面への吸着は充分ではない。カルボン酸の
アミン塩は、分子の中央に塩構造があり、全体的
に親水性が大きいばかりでなく、水溶液中では解
離し、又、PHの影響を受け易く、特にPHが８以上
になるとフリーのアミンが生成し、皮膚カブレを
起し易い組成物となつて、その作業性は極めて悪
くなる。
そこで本発明者らはこれらの欠点を解決する為
金属面との吸着性の極めて大きな防錆剤を得べく
鋭意研究した結果、ベンゾトリアゾール、ベンゾ
チアゾール又はこれらの誘導体と特定の構造を有
する陰イオン性界面活性剤を含有する組成物が
鉄、非鉄金属特に銅に対して優れた防錆効果を有
することを見い出し本発明を完成した。
即ち本発明は
(a) ベンゾトリアゾール、ベンゾチアゾール、メ
チルベンゾトリアゾール、エチルベンゾトリア
ゾール及び２―メルカプトベンゾチアゾールか
らなる群より選ばれる１種又は２種以上の化合
物と、
(b) 下記の式(1)〜(3)で表わされる化合物からなる
群より選ばれる陰イオン性界面活性剤
（式(1)〜(3)において、R1はＨ又はCH3、R2は
炭素数７〜17のアルキル基又はアルケニル基、
ｎは１、２又は３、Ｍはアルカリ金属である）
とを(b)100重量部に対して(a)１〜50重量部の割
合で含有することを特徴とする防錆剤組成物を
提供するものである。
本発明による組成物が、いかにして優れた防錆
効果を有するかの機作は明らかではないが、用い
られている陰イオン性界面活性剤の特徴的構造
が、ベンゾトリアゾール等と共働して金属表面と
キレート化合物に似た皮膜を素早く形成し金属と
腐食環境の間の物理的障壁となるためと考えられ
るが詳細については未解明である。
本発明において使用されるベンゾトリアゾー
ル、ベンゾチアゾール、メチルベンゾトリアゾー
ル、エチルベンゾトリアゾール及び２―メルカプ
トベンゾチアゾールは１種又は２種以上の混合物
として用いられるが、ベンゾトリアゾールとメチ
ルベンゾトリアゾールを１：１の重量比で配合し
たものを一方成分として用いた組成物が優れた防
錆効果を有する。
本発明の使用にあたつては、ベンゾトリアゾー
ル、ベンゾチアゾール、メチルベンゾトリアゾー
ル、エチルベンゾトリアゾール及び２―メルカプ
トベンゾチアゾールからなる群より選ばれる１種
又は２種以上の化合物は、上記式(1)〜(3)で表わさ
れる陰イオン性界面活性剤100重量部に対し１〜
50重量部、好ましくは５〜30重量部配合し、0.01
〜1.0重量％の水溶液、好ましくは0.05〜0.3重量
％水溶液として用いられる。尚、水溶液のPHを５
〜10として用いると一層優れた効果を示す。
かくして、本発明の防錆剤組成物を用いること
により、鉄、非鉄金属特に銅に対して著しい変色
防止効果即ち防錆効果を付与し得る。
次に実施例をあげ本発明を具体的に説明するが
本発明はこれらの実施例に限定されるものではな
い。
実施例 １
陰イオン性界面活性剤とベンゾトリアゾールを
４：１の重量比で配合した0.2％水溶液を調製し、
該水溶液中に銅板を温度80℃で１分間浸漬し風乾
した後、SO2ガスを含む湿潤箱中に55〜60℃で５
日間放置し、銅板表面の変色割合を肉眼にて観察
を行い表１の結果を得た。尚、ベンゾトリアゾー
ル又は陰イオン性界面活性剤単品での結果も合わ
せ掲載する。
The present invention relates to rust inhibitor compositions. More specifically, the present invention relates to a rust preventive composition that is effective against iron and non-ferrous metals, particularly copper, which is formed by using benzotriazole, benzothiazole, or a derivative thereof in combination with an anionic surfactant having a specific structure. Copper is often used because the beautiful red copper color of the base metal is used to create the color tone of products, and the red copper color of copper products is considered important as a commercial value. Therefore, there is a need for a highly efficient rust inhibitor to prevent discoloration during copper processing and finishing processes. Conventionally, benzotriazole, benzothiazole, or derivatives thereof are well known as rust inhibitors for preventing discoloration of copper. However, in machinery in which metals other than copper, such as iron and brass, coexist, it is desirable that all of the coexisting metals exhibit a rust-preventing effect, and various studies are being carried out. U.S. Patent No. 3,891,568 and British Patent No. 1,402,880 state that alkali metal salts of benzotriazole are effective.
Japanese Patent Publication No. 138548 states that benzotriazole has high seawater resistance in the coexistence of thiocarbamates and is effective against non-ferrous metals.
51-59041 and JP 51-29338 disclose that benzotriazole can be used together with amines for iron and nonferrous metals, JP 51-13338, U.S. Patent No. 3969237, and U.S. Patent No. The specification of No. 4014894 states that benzotriazole is effective for ferrous and non-ferrous materials when used in combination with carboxylic acids, and describes that benzotriazole is effective for ferrous and non-ferrous metals when used in combination with carboxylic acids, and is disclosed in German Published Patent No. 2429512, Japanese Patent Publication No. 13751-1975, and Japanese Patent Publication No. 1972-13751.
-13752, Special Publication No. 13753, Special Publication No. 13753, Special Publication No. 13752-
No. 13750 discloses that benzotriazole is effective in coexistence with an amine salt of a carboxylic acid. However, these anticorrosive agents do not necessarily have a sufficient anticorrosive effect, and in particular, when used as an aqueous solution, adsorption to copper surfaces is not sufficient. Amine salts of carboxylic acids have a salt structure in the center of the molecule, and are not only highly hydrophilic as a whole, but also dissociate in aqueous solutions and are easily affected by pH, especially when the pH is 8 or higher. amines are produced, resulting in a composition that tends to cause skin irritation, and its workability becomes extremely poor. Therefore, in order to solve these drawbacks, the present inventors conducted intensive research to obtain a rust preventive agent with extremely high adsorption to metal surfaces.As a result, we found that benzotriazole, benzothiazole, or their derivatives and anions with a specific structure were developed. The inventors have discovered that a composition containing a surfactant has an excellent antirust effect on iron and nonferrous metals, especially copper, and have completed the present invention. That is, the present invention provides (a) one or more compounds selected from the group consisting of benzotriazole, benzothiazole, methylbenzotriazole, ethylbenzotriazole, and 2-mercaptobenzothiazole, and (b) the following formula (1) Anionic surfactant selected from the group consisting of compounds represented by ) to (3) (In formulas (1) to (3), R 1 is H or CH 3 , R 2 is an alkyl group or alkenyl group having 7 to 17 carbon atoms,
n is 1, 2 or 3, M is an alkali metal)
The present invention provides a rust preventive composition containing 1 to 50 parts by weight of (a) to 100 parts by weight of (b). The mechanism of how the composition according to the present invention has an excellent antirust effect is not clear, but the characteristic structure of the anionic surfactant used works together with benzotriazole and the like. It is thought that this is because a film similar to a chelate compound is quickly formed on the metal surface and acts as a physical barrier between the metal and the corrosive environment, but the details are unknown. Benzotriazole, benzothiazole, methylbenzotriazole, ethylbenzotriazole, and 2-mercaptobenzothiazole used in the present invention can be used alone or as a mixture of two or more, but benzotriazole and methylbenzotriazole are mixed in a ratio of 1:1. A composition using one of the components in the weight ratio has an excellent antirust effect. In the use of the present invention, one or more compounds selected from the group consisting of benzotriazole, benzothiazole, methylbenzotriazole, ethylbenzotriazole and 2-mercaptobenzothiazole are represented by the above formula (1). 1 to 100 parts by weight of the anionic surfactant represented by (3)
50 parts by weight, preferably 5 to 30 parts by weight, 0.01
It is used as a ~1.0% by weight aqueous solution, preferably a 0.05-0.3% by weight aqueous solution. In addition, the pH of the aqueous solution is 5
-10 shows even better effects. Thus, by using the rust preventive composition of the present invention, a remarkable discoloration prevention effect, that is, a rust prevention effect can be imparted to iron and nonferrous metals, especially copper. Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples. Example 1 A 0.2% aqueous solution containing an anionic surfactant and benzotriazole in a weight ratio of 4:1 was prepared,
The copper plate was immersed in the aqueous solution at a temperature of 80°C for 1 minute, air-dried, and then placed in a humid box containing SO 2 gas at 55-60°C for 5 minutes.
The copper plate was left to stand for several days, and the rate of discoloration on the surface of the copper plate was observed with the naked eye, and the results shown in Table 1 were obtained. The results for benzotriazole or anionic surfactant alone are also shown.
【表】
＊＊ 陰イオン性界面活性剤ではないが従来
品として使用されている。
実施例 ２
ベンゾトリアゾール（BTA）、ベンゾチアゾー
ル（BTH）、メチルベンゾトリアゾール
（MBTA）、エチルベンゾトリアゾール（EBTA）
及び２―メルカプトベンゾチアゾール（MBTH）
について、銅板を真鋳板に代え実施例１と同様の
実験を行い表２の結果を得た。[Table] ** Although not an anionic surfactant, it is used as a conventional product.
Example 2 Benzotriazole (BTA), benzothiazole (BTH), methylbenzotriazole (MBTA), ethylbenzotriazole (EBTA)
and 2-mercaptobenzothiazole (MBTH)
Regarding this, an experiment similar to that of Example 1 was conducted by replacing the copper plate with a brass plate, and the results shown in Table 2 were obtained.
【表】
実施例 ３
陰イオン性界面活性剤としてラウロイル―Ｎ―
メチルアラネート（Na塩：C11H23CON（CH3）
CH2CH2COONa）を用い、ベンゾトリアゾール
（BTA）とメチルベンゾトリアゾール（MBTA）
の混合物の比率を変え、実施例１と同様の実験を
行い表３の結果を得た。[Table] Example 3 Lauroyl-N- as anionic surfactant
Methyl alanate (Na salt: C 11 H 23 CON (CH 3 )
CH 2 CH 2 COONa), benzotriazole (BTA) and methylbenzotriazole (MBTA)
An experiment similar to that in Example 1 was conducted by changing the ratio of the mixture, and the results shown in Table 3 were obtained.
【表】【table】
Claims (1)
ル、メチルベンゾトリアゾール、エチルベンゾ
トリアゾール及び２―メルカプトベンゾチアゾ
ールからなる群より選ばれる１種又は２種以上
の化合物と、 (b) 下記の式(1)〜(3)で表わされる化合物からなる
群より選ばれる陰イオン性界面活性剤 （式(1)〜(3)において、R1はＨ又はCH3、R2は
炭素数７〜17のアルキル基又はアルケニル基、
ｎは１、２又は３、Ｍはアルカリ金属である）
とを(b)100重量部に対して(a)１〜50重量部の割
合で含有することを特徴とする防錆剤組成物。 ２ 式(1)〜(3)においてＭがナトリウムである特許
請求の範囲第１項記載の防錆剤組成物。[Scope of Claims] 1 (a) one or more compounds selected from the group consisting of benzotriazole, benzothiazole, methylbenzotriazole, ethylbenzotriazole and 2-mercaptobenzothiazole; (b) the following: Anionic surfactant selected from the group consisting of compounds represented by formulas (1) to (3) (In formulas (1) to (3), R 1 is H or CH 3 , R 2 is an alkyl group or alkenyl group having 7 to 17 carbon atoms,
n is 1, 2 or 3, M is an alkali metal)
A rust preventive composition comprising 1 to 50 parts by weight of (a) to 100 parts by weight of (b). 2. The rust preventive composition according to claim 1, wherein M in formulas (1) to (3) is sodium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13255279A JPS5658977A (en) | 1979-10-15 | 1979-10-15 | Rust preventive composite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13255279A JPS5658977A (en) | 1979-10-15 | 1979-10-15 | Rust preventive composite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5658977A JPS5658977A (en) | 1981-05-22 |
| JPS6315351B2 true JPS6315351B2 (en) | 1988-04-04 |
Family
ID=15083950
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13255279A Granted JPS5658977A (en) | 1979-10-15 | 1979-10-15 | Rust preventive composite |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5658977A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002503260A (en) * | 1995-07-20 | 2002-01-29 | モンサント・カンパニー | Improved water-soluble metal working fluid |
| US6238621B1 (en) * | 1998-05-27 | 2001-05-29 | Solutia Inc. | Corrosion inhibiting compositions |
| AU5005799A (en) * | 1998-07-23 | 2000-02-14 | Solutia Inc. | Method of inhibiting darkening, blackening or tarnishing of magnesium and magnesium alloys and compositions therefor |
| WO2000005433A1 (en) * | 1998-07-23 | 2000-02-03 | Solutia Inc. | Method of inhibiting darkening, blackening or tarnishing of aluminium and aluminium alloys and compositions therefore |
| GB9924358D0 (en) * | 1999-10-14 | 1999-12-15 | Brad Chem Technology Ltd | Corrosion inhibiting compositions |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5815543B2 (en) * | 1975-12-26 | 1983-03-26 | 栗田工業株式会社 | Kinzokufushiyokuboushizai |
-
1979
- 1979-10-15 JP JP13255279A patent/JPS5658977A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5658977A (en) | 1981-05-22 |
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