JP2012201966A - Method for inhibiting corrosion of copper member, and corrosion inhibitor - Google Patents
Method for inhibiting corrosion of copper member, and corrosion inhibitor Download PDFInfo
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本発明は、水に接した銅系部材の腐食抑制技術に関する。詳しくは、冷却水系などの水系に接する銅管等の銅系部材に対し、薬剤を用いて腐食を抑制する技術に関する。 The present invention relates to a technique for inhibiting corrosion of a copper-based member in contact with water. More specifically, the present invention relates to a technique for suppressing corrosion of a copper-based member such as a copper pipe in contact with an aqueous system such as a cooling water system using a chemical.
銅は熱伝導性に優れる特性を有し、空調機器や熱交換器などの伝熱管などに広く使用されているが、これらの水系に接する銅系部材には腐食の問題がある。特に、最近の機器は高効率化が進んでおり、熱交換器に用いられる銅管の肉厚が非常に薄くなっていることから、腐食の発生は銅管の貫通漏洩につながる危険性が高い。よって、銅系部材に腐食を発生させないこと、発生した腐食を進行させないことが、機器の安定稼動、長寿命化に不可欠である。 Copper has a characteristic of excellent thermal conductivity, and is widely used for heat transfer tubes such as air conditioners and heat exchangers. However, these copper-based members in contact with water systems have a problem of corrosion. In particular, the efficiency of recent equipment is increasing, and the thickness of copper pipes used in heat exchangers is extremely thin. Therefore, the occurrence of corrosion has a high risk of lead-through leakage of copper pipes. . Therefore, it is indispensable for stable operation and long life of the equipment that the copper-based member does not corrode and does not proceed with the generated corrosion.
一般に、腐食反応は金属の溶出反応（アノード反応）と酸化剤の還元反応（カソード反応）が対になって進行する。例えば、冷却水のようなｐＨ中性から弱アルカリ性の環境では、水中の溶存酸素が酸化剤としてカソード反応の担い手になる。 In general, the corrosion reaction proceeds by a pair of metal elution reaction (anode reaction) and oxidant reduction reaction (cathode reaction). For example, in a pH neutral to weakly alkaline environment such as cooling water, dissolved oxygen in the water becomes a catalyst for the cathode reaction as an oxidizing agent.
従来、水系に接する銅系部材の腐食を抑制するために、ベンゾトリアゾール、トリルトリアゾール、メルカプトベンゾチアゾールといったアゾール系の銅用防食剤を水系に添加する水処理が行われている（例えば、特許文献１，２）。冷却水系などの水系に、これらのアゾール系銅用防食剤を添加することにより、水系に接する銅系部材に対して優れた腐食抑制効果を発揮することが知られており、広く適用されている。
即ち、アゾール系の銅用防食剤は、腐食反応における金属の溶出反応（アノード反応）を抑制する効果に優れており、良好な腐食抑制効果を示す。
Conventionally, in order to suppress corrosion of a copper-based member in contact with an aqueous system, water treatment in which an azole-based anticorrosive agent for copper such as benzotriazole, tolyltriazole, or mercaptobenzothiazole is added to the aqueous system has been performed (for example, Patent Documents). 1, 2). It is known that by adding these azole copper anticorrosives to an aqueous system such as a cooling water system, it exhibits an excellent corrosion-inhibiting effect on copper-based members in contact with the aqueous system, and is widely applied. .
That is, the azole-type anticorrosive agent for copper is excellent in the effect of suppressing the metal elution reaction (anode reaction) in the corrosion reaction, and exhibits a good corrosion-inhibiting effect.
しかしながら、アゾール系銅用防食剤を添加した場合においても、腐食の発生及び進行を十分に抑制できない場合もある。例えば、酸化剤の過剰添加など、何らかの原因によりアゾール系銅用防食剤よりなる防食皮膜が局部的に破壊され、皮膜の破壊された部分からの銅の溶出をアゾール系銅用防食剤が抑えきれない結果、皮膜破壊部が局部的なアノードとなり、腐食が進行する場合がある。 However, even when an azole copper anticorrosive is added, the occurrence and progression of corrosion may not be sufficiently suppressed. For example, an anti-corrosion film made of an azole copper anti-corrosion agent is locally destroyed for some reason, such as excessive addition of an oxidizing agent, and the elution of copper from the destroyed part of the film can be suppressed by the azole copper anti-corrosion agent. As a result, the film destruction part becomes a local anode, and corrosion may proceed.
本発明は、上記従来の問題を解決し、冷却水系などの水系に接する銅管等の銅系部材に対して、少量の薬剤を用いて、腐食の発生を効果的に抑制する腐食抑制方法及び腐食抑制剤を提供することを課題とする。 The present invention solves the above-mentioned conventional problems, and uses a small amount of chemicals for a copper-based member such as a copper pipe in contact with an aqueous system such as a cooling water system, and effectively suppresses the occurrence of corrosion and It is an object to provide a corrosion inhibitor.
本発明者は上記課題を解決すべく鋭意検討を重ねた結果、特定の疎水基置換含窒素不飽和複素環化合物が、水系に接した銅系部材のカソード反応抑制効果に優れること、この疎水基置換含窒素不飽和複素環化合物と、アノード反応抑制効果に優れるアゾール系銅用防食剤との併用により、少量の薬剤添加で、銅系部材の腐食を効果的に抑制することができることを見出した。 As a result of intensive studies to solve the above problems, the present inventors have found that the specific hydrophobic group-substituted nitrogen-containing unsaturated heterocyclic compound is excellent in the cathode reaction suppression effect of the copper-based member in contact with the aqueous system. It has been found that by using a substituted nitrogen-containing unsaturated heterocyclic compound and an azole copper anticorrosive having an excellent anode reaction inhibitory effect, corrosion of a copper-based member can be effectively suppressed with a small amount of chemical addition. .
本発明はこのような知見に基いて達成されたものであり、以下を要旨とする。 The present invention has been achieved on the basis of such findings, and the gist thereof is as follows.
［１］ 銅系部材と接する水系に対し、下記式（１）で表される化合物（以下、「疎水基置換含窒素不飽和複素環化合物」と称す。）と、アゾール系銅用防食剤とを添加することを特徴とする銅系部材の腐食抑制方法。 [1] For an aqueous system in contact with a copper-based member, a compound represented by the following formula (1) (hereinafter referred to as “hydrophobic group-substituted nitrogen-containing unsaturated heterocyclic compound”), an azole-based anticorrosive for copper, A method for inhibiting corrosion of a copper-based member, comprising adding
（上記（１）式中、環Ａは１位と３位が窒素原子で、２位、４位及び５位が炭素原子で構成された含窒素不飽和５員環であり、Ｒ１は疎水基を表す。ただし、含窒素不飽和５員環Ａの窒素原子及び炭素原子は、Ｒ１以外の任意の置換基を有していてもよい。） (In the above formula (1), ring A is a nitrogen-containing unsaturated 5-membered ring in which the 1st and 3rd positions are nitrogen atoms and the 2nd, 4th and 5th positions are carbon atoms, and R 1 is hydrophobic. (However, the nitrogen atom and carbon atom of the nitrogen-containing unsaturated 5-membered ring A may have an optional substituent other than R 1 ).
［２］ 前記疎水基置換含窒素不飽和複素環化合物が、イミダゾール系化合物、イミダゾリン系化合物、イミダゾリニウム塩系化合物及びイミダゾリウム塩系化合物よりなる群から選ばれる１種又は２種以上であることを特徴とする［１］に記載の銅系部材の腐食抑制方法。 [2] The hydrophobic group-substituted nitrogen-containing unsaturated heterocyclic compound is one or more selected from the group consisting of imidazole compounds, imidazoline compounds, imidazolinium salt compounds, and imidazolium salt compounds. The method for inhibiting corrosion of a copper-based member according to [1].
［３］ 前記置換基Ｒ１が、炭素数６〜１８のアルキル基であることを特徴とする［１］又は［２］に記載の銅系部材の腐食抑制方法。 [3] The method for inhibiting corrosion of a copper-based member according to [1] or [2], wherein the substituent R 1 is an alkyl group having 6 to 18 carbon atoms.
［４］ 前記疎水基置換含窒素不飽和複素環化合物が、アルキル基の炭素数が６〜１８である、２−アルキル−Ｎ−カルボキシメチル−Ｎ−ヒドロキシエチルイミダゾリニウムベタインであることを特徴とする［３］に記載の銅系部材の腐食抑制方法。 [4] The hydrophobic group-substituted nitrogen-containing unsaturated heterocyclic compound is 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, wherein the alkyl group has 6 to 18 carbon atoms. The method for inhibiting corrosion of a copper-based member according to [3].
［５］ 前記アゾール系銅用防食剤が、ベンゾトリアゾールであることを特徴とする［１］ないし［４］のいずれかに記載の銅系部材の腐食抑制方法。 [5] The method for inhibiting corrosion of a copper-based member according to any one of [1] to [4], wherein the azole-based copper anticorrosive is benzotriazole.
［６］ 前記水系が、酸化性スライムコントロール剤が添加されている水系であることを特徴とする［１］ないし［５］のいずれかに記載の銅系部材の腐食抑制方法。 [6] The method for inhibiting corrosion of a copper-based member according to any one of [1] to [5], wherein the aqueous system is an aqueous system to which an oxidizing slime control agent is added.
［７］ 水系に接する銅系部材の腐食を抑制する腐食抑制剤であって、下記（１）で表される化合物（以下「疎水基置換含窒素不飽和複素環化合物」と称す。）と、アゾール系銅用防食剤とを含むことを特徴とする銅系部材の腐食抑制剤。 [7] A corrosion inhibitor that suppresses corrosion of a copper-based member in contact with an aqueous system, the compound represented by the following (1) (hereinafter referred to as “hydrophobic group-substituted nitrogen-containing unsaturated heterocyclic compound”), A corrosion inhibitor for copper-based members, comprising an azole-based copper anticorrosive.
（上記（１）式中、環Ａは１位と３位が窒素原子で、２位、４位及び５位が炭素原子で構成された含窒素不飽和５員環であり、Ｒ１は疎水基を表す。ただし、含窒素不飽和５員環Ａの窒素原子及び炭素原子は、Ｒ１以外の任意の置換基を有していてもよい。） (In the above formula (1), ring A is a nitrogen-containing unsaturated 5-membered ring in which the 1st and 3rd positions are nitrogen atoms and the 2nd, 4th and 5th positions are carbon atoms, and R 1 is hydrophobic. (However, the nitrogen atom and carbon atom of the nitrogen-containing unsaturated 5-membered ring A may have an optional substituent other than R 1 ).
［８］ 前記疎水基置換含窒素不飽和複素環化合物が、イミダゾール系化合物、イミダゾリン系化合物、イミダゾリニウム塩系化合物及びイミダゾリウム塩系化合物よりなる群から選ばれる１種又は２種以上であることを特徴とする［７］に記載の銅系部材の腐食抑制剤。 [8] The hydrophobic group-substituted nitrogen-containing unsaturated heterocyclic compound is one or more selected from the group consisting of imidazole compounds, imidazoline compounds, imidazolinium salt compounds, and imidazolium salt compounds. The corrosion inhibitor for copper-based members according to [7].
［９］ 前記置換基Ｒ１が、炭素数６〜１８のアルキル基であることを特徴とする［７］又は［８］に記載の銅系部材の腐食抑制剤。 [9] The corrosion inhibitor for copper-based members according to [7] or [8], wherein the substituent R 1 is an alkyl group having 6 to 18 carbon atoms.
［１０］ 前記疎水基置換含窒素不飽和複素環化合物が、アルキル基の炭素数が６〜１８である、２−アルキル−Ｎ−カルボキシメチル−Ｎ−ヒドロキシエチルイミダゾリニウムベタインであることを特徴とする［９］に記載の銅系部材の腐食抑制剤。 [10] The hydrophobic group-substituted nitrogen-containing unsaturated heterocyclic compound is 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, wherein the alkyl group has 6 to 18 carbon atoms. The corrosion inhibitor for copper-based members according to [9].
［１１］ 前記アゾール系銅用防食剤が、ベンゾトリアゾールであることを特徴とする［７］ないし［１０］のいずれかに記載の銅系部材の腐食抑制剤。 [11] The corrosion inhibitor for copper-based members according to any one of [7] to [10], wherein the azole-based anticorrosive for copper is benzotriazole.
一般に、腐食反応は金属の溶出反応（アノード反応）と酸化剤の還元反応（カソード反応）が対になって進行する。
従って、銅管等の銅系部材が接する水系に対し、アノード反応抑制効果に優れる薬剤とカソード反応抑制効果に優れる薬剤を添加することにより、銅系部材表面に耐食性、耐久性に優れる皮膜が形成され、腐食の発生及び進行を有効に抑制することが可能となる。
In general, the corrosion reaction proceeds by a pair of metal elution reaction (anode reaction) and oxidant reduction reaction (cathode reaction).
Therefore, a coating with excellent corrosion resistance and durability is formed on the surface of a copper-based member by adding a chemical having an excellent anodic reaction suppressing effect and a chemical having an excellent cathodic reaction-suppressing effect to an aqueous system in contact with a copper-based member such as a copper tube. Thus, the occurrence and progression of corrosion can be effectively suppressed.
本発明で用いる疎水基置換含窒素不飽和複素環化合物は、銅系部材のカソード反応抑制効果に優れ、一方、アゾール系銅用防食剤はアノード反応抑制効果に優れることから、本発明によれば、水系に対し疎水基置換含窒素不飽和複素環化合物とアゾール系銅用防食剤とを添加することにより、優れた防食効果を得ることが可能となる。 According to the present invention, the hydrophobic group-substituted nitrogen-containing unsaturated heterocyclic compound used in the present invention is excellent in the cathode reaction suppression effect of the copper-based member, while the azole copper anticorrosive is excellent in the anode reaction suppression effect. By adding the hydrophobic group-substituted nitrogen-containing unsaturated heterocyclic compound and the azole copper anticorrosive to the aqueous system, an excellent anticorrosive effect can be obtained.
従って、本発明によれば、水系に接した銅系部材の腐食を効果的に抑制して、水系の機器を長期に亘り安定に稼動させると共に、その寿命を大幅に延長させることが可能となる。 Therefore, according to the present invention, it is possible to effectively suppress the corrosion of the copper-based member in contact with the aqueous system, to stably operate the water-based equipment for a long period of time, and to greatly extend its life. .
以下に本発明の銅系部材の腐食抑制方法及び腐食抑制剤の実施の形態を詳細に説明する。 DESCRIPTION OF EMBODIMENTS Embodiments of a method for inhibiting corrosion of a copper-based member and a corrosion inhibitor according to the present invention will be described in detail below.
本発明においては、以下の疎水基置換含窒素不飽和複素環化合物とアゾール系銅用防食剤とを銅系部材に接する水系に添加する。 In the present invention, the following hydrophobic group-substituted nitrogen-containing unsaturated heterocyclic compound and azole-based anticorrosive agent for copper are added to an aqueous system in contact with a copper-based member.
＜疎水基置換含窒素不飽和複素環化合物＞
本発明に係る疎水基置換含窒素不飽和複素環化合物は、下記式（１）で表される化合物である。
<Hydrophobic group-substituted nitrogen-containing unsaturated heterocyclic compound>
The hydrophobic group-substituted nitrogen-containing unsaturated heterocyclic compound according to the present invention is a compound represented by the following formula (1).
（上記（１）式中、環Ａは１位と３位が窒素原子で、２位、４位及び５位が炭素原子で構成された含窒素不飽和５員環であり、Ｒ１は疎水基を表す。ただし、含窒素不飽和５員環Ａの窒素原子及び炭素原子は、Ｒ１以外の任意の置換基を有していてもよい。） (In the above formula (1), ring A is a nitrogen-containing unsaturated 5-membered ring in which the 1st and 3rd positions are nitrogen atoms and the 2nd, 4th and 5th positions are carbon atoms, and R 1 is hydrophobic. (However, the nitrogen atom and carbon atom of the nitrogen-containing unsaturated 5-membered ring A may have an optional substituent other than R 1 ).
疎水基置換含窒素不飽和複素環化合物としては、イミダゾール系化合物、イミダゾリン系化合物、イミダゾリニウム塩系化合物及びイミダゾリウム塩系化合物が挙げられ、特に、上記式（１）中のＲ１が、疎水性に優れた炭素数６〜１８のアルキル基であるものが好ましい。 Examples of the hydrophobic group-substituted nitrogen-containing unsaturated heterocyclic compound include imidazole compounds, imidazoline compounds, imidazolinium salt compounds, and imidazolium salt compounds. In particular, R 1 in the above formula (1) is: What is a C6-C18 alkyl group excellent in hydrophobicity is preferable.
このような化合物としては、含窒素不飽和５員環Ａに各種官能基が導入されたものを用いることも可能であり、例えば含窒素不飽和５員環Ａの置換基Ｒ１が結合した炭素原子に隣接する窒素原子に、アルキル基、ヒドロキシアルキル基、カルボキシルアルキル基などから選択される１種以上が導入された化合物を好適に用いることができる。 As such a compound, a compound in which various functional groups are introduced into a nitrogen-containing unsaturated 5-membered ring A can be used, for example, a carbon to which a substituent R 1 of the nitrogen-containing unsaturated 5-membered ring A is bonded. A compound in which one or more selected from an alkyl group, a hydroxyalkyl group, a carboxylalkyl group, and the like are introduced into a nitrogen atom adjacent to the atom can be suitably used.
このような化合物として、例えば２−ヘキシルイミダゾール、２−ヘプチルイミダゾール、２−オクチルイミダゾール、２−ノニルイミダゾール、２−デシルイミダゾール、２−ウンデシルイミダゾール、２−ドデシルイミダゾール、２−トリデシルイミダゾール、２−テトラデシルイミダゾール、２−ペンタデシルイミダゾール、２−ヘキサデシルイミダゾール、２−ヘプタデシルイミダゾール、２−オクタデシルイミダゾール、２−アルキル−Ｎ−カルボキシメチル−Ｎ−ヒドロキシエチルイミダゾリニウムベタイン（アルキル基の炭素数は６〜１８）、２−アルキル−Ｎ−ヒドロキシエチル−Ｎ−カルボキシラートメチルイミダゾリニウム塩（アルキル基の炭素数は６〜１８）、２−アルキル−Ｎ，Ｎ−ビスヒドロキシエチルイミダゾリニウム塩（アルキル基の炭素数は６〜１８）、１−メチル−１−ヒドロキシエチル−２−牛脂アルキル−イミダゾリニウム塩などが例示され、２−アルキル−Ｎ−カルボキシメチル−Ｎ−ヒドロキシエチルイミダゾリニウムベタイン（アルキル基の炭素数は６〜１８）が好適である。 Examples of such compounds include 2-hexylimidazole, 2-heptylimidazole, 2-octylimidazole, 2-nonylimidazole, 2-decylimidazole, 2-undecylimidazole, 2-dodecylimidazole, 2-tridecylimidazole, 2 -Tetradecylimidazole, 2-pentadecylimidazole, 2-hexadecylimidazole, 2-heptadecylimidazole, 2-octadecylimidazole, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine (carbon of alkyl group) The number is 6 to 18), 2-alkyl-N-hydroxyethyl-N-carboxylatemethylimidazolinium salt (the alkyl group has 6 to 18 carbon atoms), 2-alkyl-N, N-bishydroxyethylimidazo Examples thereof include nium salts (the alkyl group has 6 to 18 carbon atoms), 1-methyl-1-hydroxyethyl-2-tallow alkyl-imidazolinium salt, and the like, and 2-alkyl-N-carboxymethyl-N-hydroxyethyl An imidazolinium betaine (the alkyl group has 6 to 18 carbon atoms) is preferred.
これらの疎水基置換含窒素不飽和複素環化合物は、１種を単独で用いてもよく、２種以上を併用してもよい。 These hydrophobic group-substituted nitrogen-containing unsaturated heterocyclic compounds may be used alone or in combination of two or more.
＜アゾール系銅用防食剤＞
アゾール系銅用防食剤としては、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及びそれぞれの誘導体などが例示され、ベンゾトリアゾールが特に好適である。
<Azole copper anticorrosive>
Examples of the azole copper anticorrosive include tolyltriazole, benzotriazole, mercaptobenzothiazole and their derivatives, and benzotriazole is particularly preferred.
これらのアゾール系銅用防食剤は、１種を単独で用いてもよく、２種以上を併用してもよい。 These azole copper anticorrosives may be used alone or in combination of two or more.
＜水系への添加量＞
本発明に用いる疎水基置換含窒素不飽和複素環化合物及びアゾール系銅用防食剤の水系への添加に際しては、処理対象水系の水質、銅系部材の表面積などにより最適な効果を得られる濃度に調整して用いることができる。
<Amount added to water system>
When adding the hydrophobic group-substituted nitrogen-containing unsaturated heterocyclic compound and the azole-based anticorrosive agent for copper used in the present invention to the aqueous system, the concentration is such that the optimal effect can be obtained depending on the water quality of the water system to be treated, the surface area of the copper-based member, etc. It can be used after adjusting.
疎水基置換含窒素不飽和複素環化合物の水系への添加濃度は、通常０．２〜２０ｍｇ／Ｌの範囲であり、好ましくは０．５〜１０ｍｇ／Ｌである。 The concentration of the hydrophobic group-substituted nitrogen-containing unsaturated heterocyclic compound added to the aqueous system is usually in the range of 0.2 to 20 mg / L, preferably 0.5 to 10 mg / L.
アゾール系銅用防食剤の水系への添加濃度は、通常０．２〜２０ｍｇ／Ｌの範囲であり、好ましくは０．５〜１０ｍｇ／Ｌである。 The concentration of the azole copper anticorrosive added to the aqueous system is usually in the range of 0.2 to 20 mg / L, preferably 0.5 to 10 mg / L.
疎水基置換含窒素不飽和複素環化合物とアゾール系銅用防食剤との添加濃度の相関については特に制限はないが、アゾール系銅用防食剤の添加濃度に対して疎水基置換含窒素不飽和複素環化合物の添加濃度が０．１〜１０重量倍程度となるように用いることが好ましい。 There is no particular limitation on the correlation between the addition concentration of the hydrophobic group-substituted nitrogen-containing unsaturated heterocyclic compound and the azole copper anticorrosive, but the hydrophobic group-substituted nitrogen-containing unsaturated relative to the addition concentration of the azole copper anticorrosive It is preferable to use it so that the addition concentration of the heterocyclic compound is about 0.1 to 10 times by weight.
＜処理対象水系の条件＞
本発明による処理時（即ち、疎水基置換含窒素不飽和複素環化合物とアゾール系銅用防食剤の添加時）の水系の温度（水温）としては、本発明の効果を得ることができる条件であれば特に制限はないが、５〜６０℃の範囲が好ましい。また、処理時の水系のｐＨとしては、通常４〜１１の範囲で処理が行われる。
<Conditions of target water system>
The aqueous temperature (water temperature) at the time of treatment according to the present invention (that is, at the time of addition of a hydrophobic group-substituted nitrogen-containing unsaturated heterocyclic compound and an azole copper anticorrosive) is a condition that can obtain the effect of the present invention. Although there will be no restriction | limiting in particular if it exists, the range of 5-60 degreeC is preferable. Moreover, as a pH of the aqueous system at the time of a process, a process is normally performed in the range of 4-11.
本発明による処理時の水系の流速についても、本発明の効果を得ることができる条件であれば特に制限はないが、通常０．１〜２ｍ／ｓｅｃの範囲で処理を行う。静止条件においても処理を行うことが可能であるが、この場合には、添加した薬剤の銅系部材表面への拡散が律速となるため、添加濃度を高めるなどの措置が必要となる。 The flow rate of the aqueous system during the treatment according to the present invention is not particularly limited as long as the effect of the present invention can be obtained, but the treatment is usually performed in the range of 0.1 to 2 m / sec. Although it is possible to perform the treatment even in a stationary condition, in this case, since the diffusion of the added drug to the surface of the copper-based member becomes rate-limiting, measures such as increasing the concentration of addition are required.
疎水基置換含窒素不飽和複素環化合物とアゾール系銅用防食剤の水系への添加方法には特に制限はなく、各成分を別々に添加することも可能であり、あらかじめ疎水基置換含窒素不飽和複素環化合物とアゾール系銅用防食剤とを一剤に配合した水処理剤として水系へ添加することも可能である。 There are no particular restrictions on the method of adding the hydrophobic group-substituted nitrogen-containing unsaturated heterocyclic compound and the azole copper anticorrosive to the aqueous system, and each component can be added separately. It is also possible to add to a water system as a water treatment agent which mix | blended the saturated heterocyclic compound and the azole type | system | group anticorrosive for copper.
本発明においては、本発明の効果を阻害しない範囲で、疎水基置換含窒素不飽和複素環化合物及びアゾール系銅用防食剤以外の他の水処理剤、例えば防食剤、スケール防止剤、分散剤、スライムコントロール剤、剥離剤、消泡剤、界面活性剤、キレート剤などを併用することが可能である。 In the present invention, water treatment agents other than hydrophobic group-substituted nitrogen-containing unsaturated heterocyclic compounds and azole copper anticorrosives, such as anticorrosives, scale inhibitors, and dispersants, as long as the effects of the present invention are not impaired. , Slime control agents, release agents, antifoaming agents, surfactants, chelating agents and the like can be used in combination.
特に、本発明の銅系部材の腐食抑制方法は、適用水系に酸化性スライムコントロール剤が添加されている水系においても、良好な腐食抑制効果を発揮することができるという特長を有し、本発明の適用水系には、酸化性スライムコントロール剤が添加されていてもよい。このような酸化性スライムコントロール剤としては、次亜塩素酸及びその塩、次亜臭素酸及びその塩、塩素化イソシアヌル酸及びその塩、例えば塩素化スルファミン酸及びその塩や臭素化スルファミン酸及びその塩のようなクロラミン化合物やブロマミン化合物、過酸化水素などが挙げられる。 In particular, the method for inhibiting corrosion of a copper-based member of the present invention has a feature that it can exhibit a good corrosion-inhibiting effect even in an aqueous system in which an oxidizing slime control agent is added to the applied aqueous system. An oxidizing slime control agent may be added to the applied water system. Such oxidizing slime control agents include hypochlorous acid and salts thereof, hypobromite and salts thereof, chlorinated isocyanuric acid and salts thereof, such as chlorinated sulfamic acid and salts thereof, brominated sulfamic acid and salts thereof. Examples include chloramine compounds such as salts, bromamine compounds, and hydrogen peroxide.
また、スケール防止剤として低分子量ポリマーを併用添加しても良い。 Further, a low molecular weight polymer may be added in combination as a scale inhibitor.
低分子量ポリマーとしては特に制限はなく、冷却水系のスケール防止剤として用いられているものをいずれも好適に用いることができる。例えば、アクリル酸、メタアクリル酸、ＨＡＰＳ（２−ヒドロキシ−３−アリルオキシ−１−プロパンスルホン酸）、マレイン酸、ＡＭＰＳ（２−アクリルアミド−２−メチルプロパンスルホン酸）、ＨＥＭＡ（２−ヒドロキシエチルメタアクリレート）、アクリル酸メチル、スチレンスルホン酸、イソブチレンよりなる群から選ばれる１種又は２種以上のモノマーが重合又は共重合した、ホモポリマー又はコポリマー、好ましくはアクリル酸、メタアクリル酸、ＨＡＰＳ、マレイン酸、ＡＭＰＳ、イソブチレンよりなる群から選ばれる１種又は２種以上のモノマーが重合又は共重合した、ホモポリマー又はコポリマーであって、平均分子量が５，０００〜５０，０００の低分子量水溶性ポリマーが挙げられる。
これらの低分子ポリマーは１種を単独で用いても良く、２種以上を併用しても良い。
There is no restriction | limiting in particular as a low molecular weight polymer, All can be used suitably as what is used as a scale inhibitor of a cooling water system. For example, acrylic acid, methacrylic acid, HAPS (2-hydroxy-3-allyloxy-1-propanesulfonic acid), maleic acid, AMPS (2-acrylamido-2-methylpropanesulfonic acid), HEMA (2-hydroxyethylmeta) Acrylate), methyl acrylate, styrene sulfonic acid, isobutylene, one or two or more monomers polymerized or copolymerized, homopolymer or copolymer, preferably acrylic acid, methacrylic acid, HAPS, male A low molecular weight water-soluble polymer having an average molecular weight of 5,000 to 50,000, which is a homopolymer or copolymer obtained by polymerizing or copolymerizing one or more monomers selected from the group consisting of acid, AMPS, and isobutylene Is mentioned.
These low molecular weight polymers may be used alone or in combination of two or more.
低分子量ポリマーの添加量としては、冷却水系の循環水中の固形分濃度として５〜５０ｍｇ／Ｌとすることが好ましい。 The addition amount of the low molecular weight polymer is preferably 5 to 50 mg / L as the solid content concentration in the circulating water of the cooling water system.
＜銅系部材の腐食抑制剤＞
本発明の銅系部材の腐食抑制剤は、前述の疎水基置換含窒素不飽和複素環化合物とアゾール系銅用防食剤とを含有するものであり、これらが一剤化されたものであってもよく、各成分が別々に提供されるものであってもよい。
<Corrosion inhibitor for copper-based materials>
The corrosion inhibitor for a copper-based member of the present invention contains the above-described hydrophobic group-substituted nitrogen-containing unsaturated heterocyclic compound and an azole-based anticorrosive for copper, and these are combined into one agent. Alternatively, each component may be provided separately.
本発明の銅系部材の腐食抑制剤中の各成分の含有割合には特に制限はなく、また、本発明の銅系部材の腐食抑制剤は、疎水基置換含窒素不飽和複素環化合物及びアゾール系銅用防食剤以外の防食剤、スケール防止剤、分散剤、スライムコントロール剤、剥離剤、消泡剤、界面活性剤、キレート剤等の他の薬剤を含むものであってもよいが、疎水基置換含窒素不飽和複素環化合物とアゾール系銅用防食剤との併用による優れた効果を十分に得るために、本発明の銅系部材の腐食抑制剤は、疎水基置換含窒素不飽和複素環化合物に対して、アゾール系銅用防食剤の割合が１０〜１０００重量％、特に５０〜５００重量％程度となるようにこれらを含有することが好ましい。 The content ratio of each component in the corrosion inhibitor of the copper-based member of the present invention is not particularly limited, and the corrosion inhibitor of the copper-based member of the present invention includes a hydrophobic group-substituted nitrogen-containing unsaturated heterocyclic compound and an azole. It may contain other agents such as anticorrosives other than copper anticorrosives, scale inhibitors, dispersants, slime control agents, release agents, antifoaming agents, surfactants, chelating agents, etc. In order to sufficiently obtain the excellent effect of the combined use of the group-substituted nitrogen-containing unsaturated heterocyclic compound and the azole copper anticorrosive, the corrosion inhibitor for the copper-based member of the present invention is a hydrophobic group-substituted nitrogen-containing unsaturated complex. It is preferable to contain these so that the ratio of the azole copper anticorrosive agent is 10 to 1000% by weight, particularly about 50 to 500% by weight with respect to the ring compound.
以下に実施例を挙げて本発明をより具体的に説明する。 Hereinafter, the present invention will be described more specifically with reference to examples.
［実施例１，２、比較例１〜１０］
ＪＩＳ Ｋ０１００「工業用水腐食試験方法」に記載された「回転法」に準拠した評価を行った。ビーカー内の１Ｌの試験水に、試験片１枚を取り付けた支持棒を浸漬し、試験片表面の線流速が０．５ｍ／ｓｅｃとなるよう支持棒を回転させた。試験前後の試験片の重量変化より銅の腐食速度を測定する方法で評価を行った。
[Examples 1 and 2 and Comparative Examples 1 to 10]
Evaluation based on "Rotation method" described in JIS K0100 "Industrial water corrosion test method" was performed. A support rod attached with one test piece was immersed in 1 L of test water in a beaker, and the support rod was rotated so that the linear flow velocity on the surface of the test piece was 0.5 m / sec. Evaluation was performed by measuring the corrosion rate of copper from the change in weight of the test piece before and after the test.
試験水、用いた薬剤、試験片、試験条件は以下の通りである。 Test water, chemicals used, test pieces, and test conditions are as follows.
＜試験水＞
水道水（栃木県野木町）、あるいは模擬冷却水に、マレイン酸イソブチレン共重合体（マレイン酸：イソブチレン＝５０：５０（モノマーモル比），分子量２０，０００）を固形分濃度として５ｍｇ／Ｌ、モノクロロスルファミン酸塩（ナトリウム塩を主体とする）をＤＰＤ法による全残留塩素測定値として１０ｍｇ／Ｌとなるよう添加したものを試験水とした。
模擬冷却水は、純水に塩化カルシウム、硫酸マグネシウム、炭酸水素ナトリウム、ケイ酸ナトリウム３号を所定量添加し、水酸化ナトリウムあるいは硫酸によりｐＨを所定の値に調整したものを用いた。
試験に用いた水道水の平均的な水質を表１に、模擬冷却水の水質を表２に示す。
<Test water>
In tap water (Nogi-machi, Tochigi Prefecture) or simulated cooling water, isobutylene maleate copolymer (maleic acid: isobutylene = 50: 50 (monomer molar ratio), molecular weight 20,000) as a solid content concentration of 5 mg / L, monochloro Test water was prepared by adding sulfamate (mainly sodium salt) so that the total residual chlorine measured by the DPD method was 10 mg / L.
As the simulated cooling water, a predetermined amount of calcium chloride, magnesium sulfate, sodium bicarbonate, sodium silicate No. 3 was added to pure water, and the pH was adjusted to a predetermined value with sodium hydroxide or sulfuric acid.
Table 1 shows the average quality of tap water used in the test, and Table 2 shows the quality of simulated cooling water.
＜薬剤＞
疎水基置換含窒素不飽和複素環化合物：２−アルキル−Ｎ−カルボキシメチル−Ｎ−ヒドロキシエチルイミダゾリニウムベタイン（アルキル基が炭素数６〜１８のアルキル基である化合物の混合物）
アゾール系銅用防食剤：ベンゾトリアゾール
<Drug>
Hydrophobic group-substituted nitrogen-containing unsaturated heterocyclic compound: 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine (mixture of compounds in which the alkyl group is an alkyl group having 6 to 18 carbon atoms)
Azole copper anticorrosive: benzotriazole
＜試験片＞
長辺５０ｍｍ、短辺３０ｍｍ、厚さ１ｍｍの銅（Ｃ１２２０）製試験片（ねじ止め用のφ４ｍｍ穴あき）
<Specimen>
Copper (C1220) test piece with a long side of 50 mm, a short side of 30 mm, and a thickness of 1 mm (φ4 mm hole for screwing)
＜試験条件＞
試験温度：４０℃
試験期間：７日間（試験開始３日目に試験水を全量交換）
<Test conditions>
Test temperature: 40 ° C
Test period: 7 days (change all test water on the 3rd day of the test)
表３に示す試験水に、表３に示す薬剤を表３に示す添加濃度で添加して（ただし、比較例１，６では薬剤添加せず）、銅製試験片の腐食速度（ｍｄｄ）を求め、結果を表３に示した。 The chemicals shown in Table 3 were added to the test water shown in Table 3 at the addition concentrations shown in Table 3 (however, no chemicals were added in Comparative Examples 1 and 6), and the corrosion rate (mdd) of the copper test piece was obtained. The results are shown in Table 3.
＜考察＞
表３より、試験水水質によらず疎水基置換含窒素不飽和複素環化合物として用いた２−アルキル−Ｎ−カルボキシメチル−Ｎ−ヒドロキシエチルイミダゾリニウムベタイン（炭素数６〜１８のアルキル基）及びアゾール系銅用防食剤として用いたベンゾトリアゾールを併用することにより、それぞれ単独添加条件に比べて腐食速度が大きく抑制されていることが明らかであり、両成分を併用することによる相乗効果が確認された。
<Discussion>
From Table 3, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine (alkyl group having 6 to 18 carbon atoms) used as a hydrophobic group-substituted nitrogen-containing unsaturated heterocyclic compound regardless of the test water quality And benzotriazole used as an anti-corrosive agent for azole-based copper, it is clear that the corrosion rate is greatly suppressed compared to the single addition condition, and the synergistic effect by using both components is confirmed It was done.
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