JPH0688262A - Corrosion inhibitor for copper - Google Patents
Corrosion inhibitor for copperInfo
- Publication number
- JPH0688262A JPH0688262A JP24049092A JP24049092A JPH0688262A JP H0688262 A JPH0688262 A JP H0688262A JP 24049092 A JP24049092 A JP 24049092A JP 24049092 A JP24049092 A JP 24049092A JP H0688262 A JPH0688262 A JP H0688262A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- corrosion
- corrosion inhibitor
- present
- polyethylene polyamine
- 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.)
- Pending
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)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は銅用腐食防止剤に係り、
特に、銅管等の銅材質部材の孔食発生の前段階としての
電位上昇を抑制し、孔食の発生を有効に防止する銅用腐
食防止剤に関する。The present invention relates to a corrosion inhibitor for copper,
In particular, the present invention relates to a corrosion inhibitor for copper that suppresses an increase in potential as a pre-stage of occurrence of pitting corrosion of a copper material such as a copper pipe and effectively prevents the occurrence of pitting corrosion.
【０００２】[0002]
【従来の技術】冷却水系等の各種水系に使用される銅又
は銅合金よりなる配管、その他の部材では、銅（又は銅
合金）の腐食ないしは腐食による孔食が大きな問題とな
っている。2. Description of the Related Art Corrosion of copper (or copper alloy) or pitting due to corrosion is a serious problem in pipes and other members made of copper or copper alloys used in various water systems such as cooling water systems.
【０００３】従来、銅材質の腐食防止のために、水系に
防止剤を添加する方法が多く採用されており、防食剤と
してはトリルトリアゾール、ベンゾトリアゾール、メル
カプトベンゾチアゾールが主に用いられている。Conventionally, in order to prevent corrosion of copper materials, a method of adding an inhibitor to an aqueous system has been widely adopted, and tolyltriazole, benzotriazole and mercaptobenzothiazole are mainly used as the anticorrosive agent.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、従来の
トリルトリアゾール、ベンゾトリアゾール、メルカプト
ベンゾチアゾールよりなる防食剤では、腐食を十分に防
止し得ない場合があった。特に、地下水を補給水とする
蓄熱冷温水系では、これらの防食剤を用いても、銅材質
の腐食ないし孔食が発生し易い。However, the conventional anticorrosive agent comprising tolyltriazole, benzotriazole and mercaptobenzothiazole may not be able to sufficiently prevent corrosion. In particular, in a heat storage cold / hot water system in which groundwater is used as makeup water, even if these anticorrosive agents are used, corrosion or pitting corrosion of the copper material is likely to occur.
【０００５】本発明は上記従来の問題点を解決し、銅材
質の腐食を、少ない薬剤使用量にて長期にわたり確実に
防止することができる銅用腐食防止剤を提供することを
目的とする。An object of the present invention is to solve the above-mentioned conventional problems and to provide a copper corrosion inhibitor capable of reliably preventing corrosion of a copper material for a long period of time with a small amount of chemicals used.
【０００６】[0006]
【課題を解決するための手段】本発明の銅用腐食防止剤
は、ポリエチレンポリアミンと１，２−ベンゾイソチア
ゾリン−３−オンとを含むことを特徴とする。The corrosion inhibitor for copper of the present invention is characterized by containing polyethylene polyamine and 1,2-benzisothiazolin-3-one.
【０００７】以下に本発明を詳細に説明する。The present invention will be described in detail below.
【０００８】本発明の銅用腐食防止剤において、ポリエ
チレンポリアミンとしては、ペンタエチレンヘキサミ
ン、ヘプタエチレンペンタミン、オクタエチレンヘプタ
ミン、ヘキサエチレンテトラミンなどを用いることがで
きる。In the copper corrosion inhibitor of the present invention, pentaethylenehexamine, heptaethylenepentamine, octaethyleneheptamine, hexaethylenetetramine and the like can be used as the polyethylene polyamine.
【０００９】このようなポリエチレンポリアミンと１，
２−ベンゾイソチアゾリン−３−オンとの使用割合には
特に制限はないが、併用による優れた防食効果を得るた
めには、ポリエチレンポリアミン１００重量部に対し
て、１，２−ベンゾイソチアゾリン−３−オンを５０〜
２００重量部とするのが好ましい。Such polyethylene polyamine and 1,
The ratio of 2-benzisothiazolin-3-one to be used is not particularly limited, but in order to obtain an excellent anticorrosion effect by the combined use, 1,2-benzisothiazolin-3-one is added to 100 parts by weight of polyethylene polyamine. 50 on
It is preferably 200 parts by weight.
【００１０】このような本発明の銅用腐食防止剤は、ポ
リエチレンポリアミンと１，２−ベンゾイソチアゾリン
−３−オンを予め混合した一液型のものであっても良
く、各々別々に提供されたポリエチレンポリアミンと
１，２−ベンゾイソチアゾリン−３−オンを現場にて混
合使用ないし併用するものであっても良い。The copper corrosion inhibitor of the present invention may be a one-pack type in which polyethylene polyamine and 1,2-benzisothiazolin-3-one are mixed in advance, and they are provided separately. Polyethylene polyamine and 1,2-benzisothiazolin-3-one may be mixed and used together in the field.
【００１１】また、本発明の銅用腐食防止剤の使用方法
にも特に制限はなく、例えば、冷温水槽に予め一液に混
合したものを投入添加しても良く、ポリエチレンポリア
ミンと１，２−ベンゾイソチアゾリン−３−オンとを各
々別々に投入添加しても良い。The method of using the corrosion inhibitor for copper according to the present invention is not particularly limited. For example, a mixture of one component previously mixed in a cold / hot water tank may be added and added, and polyethylene polyamine and 1,2- Benzisothiazolin-3-one may be added separately and added.
【００１２】この場合、投入回数は被処理対象系によっ
ても異なるが、本発明の銅用腐食防止剤は長期効果持続
性に優れることから、３〜６カ月に１回の投入添加で十
分な効果が得られる。また、銅材質部材の自然電位を測
定し、その自然電位に基いて投入を制御することもでき
る。具体的には銅管の自然電位が１５０ｍＶを超えた場
合には、本発明の銅用腐食防止剤を投入添加するように
すれば良い。なお、本発明の銅用腐食防止剤の添加量に
ついても、被処理対象水系や投入回数、投入方法によっ
ても異なるが、通常の場合、被処理対象水系の水量１０
００ｍｌに対して５〜５００ｍｇとするのが適当であ
る。In this case, although the number of times of charging differs depending on the system to be treated, since the corrosion inhibitor for copper of the present invention is excellent in long-term effect sustainability, it is sufficient to add it once every 3 to 6 months. Is obtained. It is also possible to measure the natural potential of the copper material member and control the charging based on the natural potential. Specifically, when the natural potential of the copper tube exceeds 150 mV, the corrosion inhibitor for copper of the present invention may be added by addition. The addition amount of the corrosion inhibitor for copper of the present invention also varies depending on the target water system to be treated, the number of times of charging, and the charging method.
It is suitable to set it to 5 to 500 mg per 00 ml.
【００１３】[0013]
【作用】ポリエチレンポリアミンと１，２−ベンゾイソ
チアゾリン−３−オンとの併用による著しく優れた相乗
効果で、従来の防食剤では効果が得られなかった水系に
対しても、極めて良好な電位上昇抑制効果、即ち、腐食
防止効果が得られ、少量の薬剤使用量にて、長期にわた
り銅材質の腐食を確実に防止することができる。The synergistic effect of using polyethylene polyamine and 1,2-benzisothiazolin-3-one in combination is extremely excellent, and is extremely good in suppressing potential rise even in water systems where conventional anticorrosive agents were not effective. The effect, that is, the effect of preventing corrosion can be obtained, and the corrosion of the copper material can be reliably prevented for a long period of time with a small amount of chemicals used.
【００１４】[0014]
【実施例】以下に実施例及び比較例を挙げて、本発明を
より具体的に説明するが、本発明はその要旨を超えない
限り、以下の実施例に限定されるものではない。EXAMPLES The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples unless it exceeds the gist.
【００１５】比較例１ 表１に示す水質の地下水を、図１に示す試験装置で通水
し、自然電位及び腐食の進行を調べた。Comparative Example 1 Ground water having the water quality shown in Table 1 was passed through the test apparatus shown in FIG. 1 to examine the spontaneous potential and the progress of corrosion.
【００１６】なお、図１において、１は水槽、２は流量
計、３はりん脱酸銅管（直径１６ｍｍ、長さ５００ｍ
ｍ、肉厚０．５ｍｍ）、４は電位差計、５はＡｇ／Ａｇ
Ｃｌ比較電極、Ｐはポンプ、Ｖ1 ，Ｖ2 はバルブ、６は
配管であり、水槽１内の水はポンプＰにより、配管６、
流量計２、配管７、りん脱酸銅管３及び配管８を経て室
温にて０．１ｍ／ｓの流速で循環させた。In FIG. 1, 1 is a water tank, 2 is a flow meter, and 3 is a phosphorous deoxidized copper pipe (diameter 16 mm, length 500 m).
m, wall thickness 0.5 mm), 4 is a potentiometer, 5 is Ag / Ag
Cl reference electrode, P is a pump, V 1 and V 2 are valves, 6 is a pipe, and water in the water tank 1 is pumped by a pump P to a pipe 6,
It was circulated at a flow rate of 0.1 m / s at room temperature through the flow meter 2, the pipe 7, the phosphorous deoxidized copper pipe 3 and the pipe 8.
【００１７】[0017]
【表１】 [Table 1]
【００１８】その結果、表２に示す如く、試験開始後経
時的に銅管の自然電位が上昇し、２０日後には自然電位
は銅管の孔食発生電位と言われている１９０ｍＶ（飽和
Ａｇ／ＡｇＣｌ電極）以上に達した。また１２０日後に
銅管を半割りにしたところ、表３に示す如く、緑色の腐
食生成物（Ｘ線回折の結果、塩基性炭酸銅が存在してお
り、化学分析の結果、珪酸銅も存在していることが判
明）が存在し、腐食生成物の下部には無数の孔色が生じ
ており、その最大孔食深さは０．３１ｍｍであることが
判明した。As a result, as shown in Table 2, the spontaneous potential of the copper tube increased with time after the start of the test, and after 20 days, the spontaneous potential was 190 mV (saturated Ag) which is said to be the pitting corrosion potential of the copper tube. / AgCl electrode) or more. After 120 days, the copper tube was halved, and as shown in Table 3, a green corrosion product (as a result of X-ray diffraction, basic copper carbonate was present, and as a result of chemical analysis, copper silicate was also present). It was found that there are innumerable pit colors at the bottom of the corrosion product, and the maximum pit depth is 0.31 mm.
【００１９】実施例１、比較例２〜４ 水槽内に表１に示す薬剤を表１に示す割合で添加したこ
と以外は比較例１と同様に通水試験を行なって、自然電
位の経日変化を調べ、結果を表２に示した。Example 1, Comparative Examples 2 to 4 A water flow test was conducted in the same manner as in Comparative Example 1 except that the chemicals shown in Table 1 were added to the water tank in the proportions shown in Table 1, and the spontaneous potential was changed with time. The changes were examined and the results are shown in Table 2.
【００２０】また、１２０日後のチューブ表面状態と最
大孔食深さを調べ、結果を表３に示した。Further, the tube surface condition and the maximum pitting depth after 120 days were examined, and the results are shown in Table 3.
【００２１】表２，３より、本発明の銅用腐食防止剤に
よれば自然電位の上昇は抑制され、孔食は確実に防止さ
れることが明らかである。It is clear from Tables 2 and 3 that the corrosion inhibitor for copper of the present invention suppresses the increase in spontaneous potential and reliably prevents pitting corrosion.
【００２２】これに対して、従来の防食剤であるトリル
トリアゾールを用いた比較例４では、防食剤を用いない
比較例１の結果と殆ど変わらず、効果が全くない。On the other hand, Comparative Example 4 using the conventional anticorrosive agent tolyltriazole is almost the same as the result of Comparative Example 1 using no anticorrosive agent and has no effect.
【００２３】また、１，２−ベンゾイソチアゾリン−３
−オンとポリエチレンポリアミンとを各々単独で用いた
比較例２，３と実施例１とを比較することにより、ポリ
エチレンポリアミンと１，２−ベンゾイソチアゾリン−
３−オンとの併用により著しく優れた相乗効果が得られ
ていることが明らかである。Further, 1,2-benzisothiazoline-3
-One and polyethylene polyamine were used alone to compare Comparative Examples 2 and 3 with Example 1, to obtain polyethylene polyamine and 1,2-benzisothiazoline-
It is clear that when used in combination with 3-one, a remarkably excellent synergistic effect is obtained.
【００２４】[0024]
【表２】 [Table 2]
【００２５】[0025]
【表３】 [Table 3]
【００２６】[0026]
【発明の効果】以上詳述した通り、本発明の銅用腐食防
止剤によれば、少ない薬剤使用量にて、長期間、腐食な
いし孔食に到る銅材質の電位上昇を抑制し、銅材質の腐
食ないし孔食を有効に防止することができる。このた
め、銅管等の孔食による貫通、漏水事故を確実に防止す
ることが可能とされる。As described above in detail, according to the corrosion inhibitor for copper of the present invention, it is possible to suppress an increase in the potential of the copper material which causes corrosion or pitting corrosion for a long period of time with a small amount of the chemical used. It is possible to effectively prevent material corrosion or pitting corrosion. Therefore, it is possible to reliably prevent penetration and water leakage due to pitting corrosion of copper pipes and the like.
【図面の簡単な説明】[Brief description of drawings]
【図１】実施例及び比較例で用いた通水試験装置を示す
系統図である。FIG. 1 is a system diagram showing a water flow test device used in Examples and Comparative Examples.
１ 水槽 ２ 流量計 ３ りん脱酸銅管 ４ 電位差計 ５ Ａｇ／ＡｇＣｌ比較電極 1 Water tank 2 Flowmeter 3 Phosphorus deoxidizing copper tube 4 Potentiometer 5 Ag / AgCl reference electrode
Claims (1)
ゾイソチアゾリン−３−オンとを含む銅用腐食防止剤。1. A corrosion inhibitor for copper containing polyethylene polyamine and 1,2-benzisothiazolin-3-one.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24049092A JPH0688262A (en) | 1992-09-09 | 1992-09-09 | Corrosion inhibitor for copper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24049092A JPH0688262A (en) | 1992-09-09 | 1992-09-09 | Corrosion inhibitor for copper |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0688262A true JPH0688262A (en) | 1994-03-29 |
Family
ID=17060292
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24049092A Pending JPH0688262A (en) | 1992-09-09 | 1992-09-09 | Corrosion inhibitor for copper |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0688262A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2005038853A1 (en) * | 2003-10-17 | 2007-11-22 | 株式会社東芝 | X-ray equipment |
-
1992
- 1992-09-09 JP JP24049092A patent/JPH0688262A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2005038853A1 (en) * | 2003-10-17 | 2007-11-22 | 株式会社東芝 | X-ray equipment |
| JP4828941B2 (en) * | 2003-10-17 | 2011-11-30 | 株式会社東芝 | X-ray equipment |
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