JPS5925034B2 - Corrosion inhibitor for copper - Google Patents
Corrosion inhibitor for copperInfo
- Publication number
- JPS5925034B2 JPS5925034B2 JP5050081A JP5050081A JPS5925034B2 JP S5925034 B2 JPS5925034 B2 JP S5925034B2 JP 5050081 A JP5050081 A JP 5050081A JP 5050081 A JP5050081 A JP 5050081A JP S5925034 B2 JPS5925034 B2 JP S5925034B2
- Authority
- JP
- Japan
- Prior art keywords
- copper
- corrosion
- present
- systems
- 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
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
- C23F11/16—Sulfur-containing compounds
- C23F11/165—Heterocyclic compounds containing sulfur as hetero atom
Description
【発明の詳細な説明】
本発明は、銅及び銅合金材料等の腐食を防止する為の防
食剤に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an anticorrosive agent for preventing corrosion of copper and copper alloy materials.
本発明は、特に、その毒性が問題。される、食品製造業
、ソーラシステムに用いられる熱媒体、冷媒体循環系な
どに有用な銅相防食剤に関する。一般工業用密閉又は開
放式（循環）冷却水系などの銅及び銅合金の腐食を防止
する為に、従来ではベンゾトリアゾール、ベンゾイミダ
ゾール、トリルトリアゾール、イミダゾリン及びこれら
のアルキル誘導体などを主剤とする防食剤が用いられて
いた。The present invention is particularly problematic in its toxicity. The present invention relates to a copper phase anticorrosive agent useful in the food manufacturing industry, heating medium used in solar systems, cooling medium circulation systems, etc. In order to prevent corrosion of copper and copper alloys in general industrial sealed or open (circulating) cooling water systems, anticorrosive agents based on benzotriazole, benzimidazole, tolyltriazole, imidazoline, and their alkyl derivatives have conventionally been used. was used.
ところがこれらの防食剤は、何れも人体に摂取されると
少なからぬ毒性を発現するものであり、従つて例えば食
品製造業、ソーラシステムに用いられるエチレングリコ
ール、プロピレングリコールを含む冷却水系等冷媒系な
どの、間接的に人体に摂取される可能性のあるところで
は使用することができないのであつた。However, all of these anticorrosive agents exhibit considerable toxicity when ingested by the human body, and are therefore used in refrigerant systems such as cooling water systems containing ethylene glycol and propylene glycol used in the food manufacturing industry and solar systems. However, it could not be used where there is a possibility that it could be indirectly ingested by the human body.
従つて、従来かかる冷媒系などは銅及び銅合金の腐食に
対する配慮がなされないまま運転されており、例えば熱
交換器の銅製チューブが使用中に腐食されて寿命が短か
くなるなどした。Therefore, conventional refrigerant systems have been operated without consideration given to the corrosion of copper and copper alloys, and for example, the copper tubes of the heat exchanger corrode during use, resulting in a shortened service life.
本発明者等は、これらの食品製造業、ソーラシステムの
冷媒系などに使用可能な、無毒の銅相防食剤を開発すべ
く鋭意研究した結果、従来殺藻剤、防カビ剤、柑橘類用
腐敗防止剤、或は家畜用駆虫剤などとして用いられ、且
つ食品衛生法に基づく食品添加物成分の指定を受けてい
る２−（４−テアゾリル）＝ベンゾイミダゾールが銅及
び銅合金の防食に有効であることを見出し、本発明を完
成するに至つた。The present inventors have conducted extensive research to develop a non-toxic copper-phase corrosion inhibitor that can be used in the food manufacturing industry and in the refrigerant systems of solar systems. 2-(4-teazolyl)benzimidazole, which is used as a preventive agent or a deworming agent for livestock, and is designated as a food additive ingredient under the Food Sanitation Act, is effective in preventing corrosion of copper and copper alloys. This discovery led to the completion of the present invention.
本発明の目的は、水中に於ける銅及び銅合金材料等の腐
食を防止し、特にその毒性が問題とされる食品製造業、
ソーラシステムの熱媒体、冷媒循環系などに有用な銅相
防食剤を提供することにある。The purpose of the present invention is to prevent corrosion of copper and copper alloy materials in water, and particularly for the food manufacturing industry where toxicity is a problem.
The purpose of the present invention is to provide a copper phase anticorrosive agent useful for heat transfer medium, refrigerant circulation systems, etc. of solar systems.
即ち、本発明の銅相防食剤は、２−（４−テアゾリル）
−ベンゾイミダゾールを主成分とすることを特徴とする
ものである。本発明に係る２−（４−チアゾリル）−ベ
ンゾイミダゾール（以下、チアベンダゾールと記す）は
塩として用いてもよい。That is, the copper phase corrosion inhibitor of the present invention is 2-(4-teazolyl)
- It is characterized by containing benzimidazole as the main component. 2-(4-thiazolyl)-benzimidazole (hereinafter referred to as thiabendazole) according to the present invention may be used as a salt.
かかる塩としては、例えばアミン塩が挙げられる。本発
明の防食剤の添加濃度（被防食処理水系に於ける濃度）
は、テアベンダゾールの量として、通常は０．５ｐμｍ
以上で効果が現われる。Examples of such salts include amine salts. Addition concentration of the anticorrosive agent of the present invention (concentration in the water system to be treated for corrosion protection)
is usually 0.5 pμm as the amount of theabendazole
The above effects will appear.
５０ｐμｍを超えると、効果はほゞ一定する。Above 50 pμm, the effect remains almost constant.
５０ｐμｍを超えて添加することは不経済となる。Adding more than 50 pμm becomes uneconomical.
また、本発明の銅相防食剤は冷媒体や熱媒体と共に用い
られることも可能であるが、その場合の添加量は、例え
ばプロピレングリコールなどの冷媒共存系では１ｐμｍ
以上であることが好ましい。Further, the copper phase anticorrosive agent of the present invention can be used together with a cooling medium or a heating medium, but in that case, the amount added is, for example, 1 pμm in a system coexisting with a refrigerant such as propylene glycol.
It is preferable that it is above.
テアベンダゾールの水に対する溶解度は、室温下で約３
０ｐμｍであり、この濃度程度までなら直接被処理水系
に溶解することができるが、それ以上の場合には、従来
法通り適宜の溶媒に先づ溶かしてから使用する。また、
例えばエチレングリコールを含む冷媒系では約０．８％
まで溶解度が改善されるので、この濃度までならば、か
かる冷媒系に直接溶解することが可能である。また本発
明の防食剤は、必要に応じて例えば重クロム酸塩、重合
リン酸塩、ホスホン酸塩、多価金属塩、モリブデン酸塩
、亜硝酸塩、オキシカルボン酸塩などの添加剤、及び／
又は、例えば一般の工業用密閉もしくは開放循環冷却水
系などに用いられる場合には、既存の防食剤、例えばベ
ンゾトリアゾール、トリルトリアゾール、イミダゾール
、イミダゾリン及びこれらの誘導体などと併用しても良
い。The solubility of theabendazole in water is approximately 3 at room temperature.
The concentration is 0 pμm, and it can be directly dissolved in the water system to be treated up to this concentration, but if the concentration is higher than that, it is used after dissolving it in an appropriate solvent as in the conventional method. Also,
For example, in a refrigerant system containing ethylene glycol, it is approximately 0.8%.
Since the solubility is improved up to this concentration, it is possible to directly dissolve it in such a refrigerant system up to this concentration. Furthermore, the anticorrosive agent of the present invention may contain additives such as dichromate, polymerized phosphate, phosphonate, polyvalent metal salt, molybdate, nitrite, oxycarboxylate, etc., as necessary.
Alternatively, when used in general industrial closed or open circulation cooling water systems, for example, it may be used in combination with existing anticorrosive agents such as benzotriazole, tolyltriazole, imidazole, imidazoline, and derivatives thereof.
当然ながら、本発明の防食剤の水溶液は無色透明であり
、且つ食品添加物成分の指定を受けているところからも
明らかな様に、無毒であり、取扱い上の危険も全くない
。Naturally, the aqueous solution of the anticorrosive agent of the present invention is colorless and transparent, and as is clear from the fact that it is designated as a food additive component, it is non-toxic and poses no danger in handling.
本発明の銅用防食剤は、防食剤の毒性が問題となる、ビ
ール醸造等各種飲料水もしくは各種乳製品などの製造業
、製氷業、冷凍倉庫、冷凍庫、漁船、コンテナ船或は、
アイススケート場などの間接冷媒循環系、寒冷地のセン
トラルヒーテインーグ用、冷凍装置の融氷液もしくは霜
取用、太陽熱利用の給湯、冷暖房システムなどの熱媒も
しくは不凍液の循環系、化学工場、機械工場の間接冷・
熱媒体の循環系、一般工業用密閉もしくは開放式循環冷
却水系などの銅用防食剤として有用である。The anticorrosive agent for copper of the present invention is suitable for use in manufacturing industries such as beer brewing and other manufacturing industries such as various drinking water or various dairy products, where the toxicity of anticorrosive agents is a problem, ice making industry, frozen warehouses, freezers, fishing boats, container ships, or
Indirect refrigerant circulation systems such as ice skating rinks, central heating in cold regions, ice melting fluid or defrost in refrigeration equipment, hot water supply using solar heat, heating medium or antifreeze circulation systems such as air conditioning systems, chemical factories, Indirect cooling in machine shops
It is useful as a corrosion inhibitor for copper in heat medium circulation systems, general industrial closed or open circulation cooling water systems, etc.
実施例 １Ｃ１−、ＳＯ４２−を含有する水中に本発明
の銅用防食剤を加えて回転円板腐食試験を行なつた。Example 1 A rotating disk corrosion test was conducted by adding the copper corrosion inhibitor of the present invention to water containing C1- and SO42-.
水道水（横浜市水）に塩化ナトリウム及び硫酸ナトリウ
ムを所定量添加し、得られたＣｌ−、ＳＯ４２−を含有
する水中にチアベンダゾールを加え、６０℃に保つた。
この水中で銅円板（径５０ｍｍ）を、１６０ｒｐｍで１
６０時間回転させ、試験片の腐食減量を測定し、腐食速
度（Ｍｄｄ、ミリグラムで表わした１平方デシメートル
当りの１日間の腐食量、〜／Ｄｍｌ／Ｄａｙ）を算出し
た。塩化ナトリウム、硫酸ナトリウム、及び防食剤とし
てチアベンダゾールの添加量、及び測定結果から得られ
た腐食速度を第１表に示した。第１表に示した結果から
も明らかな通り、本発明の銅用防食剤は、例えばＣ１−
、ＳＯ４２−などの銅腐食性イオンを高濃度に含有する
水系においても、略０．５ｐｐｍ以上の濃度で配合する
ことにより、良好な防食能を発現する。Predetermined amounts of sodium chloride and sodium sulfate were added to tap water (Yokohama City Water), and thiabendazole was added to the resulting water containing Cl- and SO42-, which was kept at 60°C.
In this water, a copper disk (diameter 50 mm) was heated at 160 rpm.
The test piece was rotated for 60 hours, and the corrosion weight loss of the test piece was measured, and the corrosion rate (Mdd, amount of corrosion per day per square decimeter expressed in milligrams, ~/Dml/Day) was calculated. Table 1 shows the amounts of sodium chloride, sodium sulfate, and thiabendazole as an anticorrosive agent, as well as the corrosion rates obtained from the measurement results. As is clear from the results shown in Table 1, the copper corrosion inhibitor of the present invention, for example, C1-
Even in an aqueous system containing a high concentration of copper corrosive ions such as , SO42-, etc., good anti-corrosion performance can be achieved by blending at a concentration of about 0.5 ppm or more.
実施例 ２
横浜市水にプロピレングリコールを２５重量％含有すべ
く混合し、この混合溶液にチアベンダゾールを加え、４
０℃に保つた。Example 2 Yokohama city water was mixed with propylene glycol to contain 25% by weight, thiabendazole was added to this mixed solution, and 4
It was kept at 0°C.
得られた溶液に実施例１で用いたのと同＝形状の銅円板
を浸漬し、１６０ｒｐｍ、１９１時間回転させた。チア
ベンダゾールの添加量、及び銅の腐食速度を第２表に示
した。第２表に示した結果からも明らかなとおり、本発
明の防食剤は、例えばソーラシステムの冷媒系として用
いられるプロピレングリコールを含有する水系に、略１
ｐｐｍ以上添加することにより優れた防食能を発現する
。A copper disk having the same shape as that used in Example 1 was immersed in the resulting solution and rotated at 160 rpm for 191 hours. Table 2 shows the amount of thiabendazole added and the corrosion rate of copper. As is clear from the results shown in Table 2, the anticorrosive agent of the present invention can be applied to an aqueous system containing propylene glycol used as a refrigerant system in a solar system, for example, by approx.
Excellent anticorrosion ability is exhibited by adding more than ppm.
Claims (1)
成分とする銅相防食剤。1 A copper phase anticorrosive agent containing 2-(4-thiazolyl)-benzimidazole as a main component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5050081A JPS5925034B2 (en) | 1981-04-06 | 1981-04-06 | Corrosion inhibitor for copper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5050081A JPS5925034B2 (en) | 1981-04-06 | 1981-04-06 | Corrosion inhibitor for copper |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57164987A JPS57164987A (en) | 1982-10-09 |
| JPS5925034B2 true JPS5925034B2 (en) | 1984-06-13 |
Family
ID=12860659
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5050081A Expired JPS5925034B2 (en) | 1981-04-06 | 1981-04-06 | Corrosion inhibitor for copper |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5925034B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015141250A1 (en) * | 2014-03-18 | 2015-09-24 | 栗田工業株式会社 | Nitrifying bacterium inhibitor, and nitrifying bacterium inhibition method |
| JP2015193876A (en) * | 2014-03-31 | 2015-11-05 | 栗田工業株式会社 | Method for inhibiting corrosion of copper-based member and corrosion inhibitor |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4039271A1 (en) * | 1990-12-08 | 1992-06-11 | Basf Ag | METHOD FOR PROTECTING COPPER AND COOL ALLOY SURFACES FROM CORROSION |
-
1981
- 1981-04-06 JP JP5050081A patent/JPS5925034B2/en not_active Expired
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015141250A1 (en) * | 2014-03-18 | 2015-09-24 | 栗田工業株式会社 | Nitrifying bacterium inhibitor, and nitrifying bacterium inhibition method |
| JP2015174862A (en) * | 2014-03-18 | 2015-10-05 | 栗田工業株式会社 | Nitrifying bacterium inhibitor and nitrifying bacterium inhibition method |
| JP2015193876A (en) * | 2014-03-31 | 2015-11-05 | 栗田工業株式会社 | Method for inhibiting corrosion of copper-based member and corrosion inhibitor |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57164987A (en) | 1982-10-09 |
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