JP2006169595A - Corrosion inhibitor composition for cleaning by chelating agent-organic acid - Google Patents
Corrosion inhibitor composition for cleaning by chelating agent-organic acid Download PDFInfo
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本発明は、金属表面の錆やスケールなどの酸化物皮膜を除去するためのキレート剤・有機酸洗液に添加する腐食抑制剤に関し、洗浄液中の金属素地の腐食、孔食を抑制するための添加剤に関する。 The present invention relates to a corrosion inhibitor to be added to a chelating agent / organic pickling solution for removing oxide films such as rust and scale on a metal surface, and to suppress corrosion and pitting corrosion of a metal substrate in the cleaning solution. It relates to additives.
金属表面に付着している錆やスケール等の酸化皮膜を除去するために、塩酸、硫酸等の無機酸や、シュウ酸、リンゴ酸、グルコン酸、クエン酸等の有機酸や、ニトリロ３酢酸、エチレンジアミン４酢酸、ヒドロキシエチルエチレンジアミン３酢酸、ジエチレントリアミン５酢酸等のポリアミノカルボン酸や、そのアルカリ金属塩、アンモニウム塩、アミン塩や、アミノトリ（メチレンホスホン酸）、１-ヒドロキシエチリデン-１，１-ホスホン酸、エチレンジアミンテトラ（メチレンホスホン酸）、 ヘキサメチレンジアミンテトラ（メチレンホスホン酸）、ジエチレンテトラミンペンタ（メチレンホスホン酸）、２-ホスホノブタン-１，２，４-トリカルボン酸等のホスホン酸や、そのアルカリ金属塩、アンモニウム塩、アミン塩が金属の溶解性分として使用されてきた。 In order to remove oxide films such as rust and scale attached to the metal surface, inorganic acids such as hydrochloric acid and sulfuric acid, organic acids such as oxalic acid, malic acid, gluconic acid and citric acid, nitrilotriacetic acid, Polyaminocarboxylic acids such as ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, alkali metal salts, ammonium salts, amine salts thereof, aminotri (methylenephosphonic acid), 1-hydroxyethylidene-1,1-phosphonic acid , Phosphonic acids such as ethylenediaminetetra (methylenephosphonic acid), hexamethylenediaminetetra (methylenephosphonic acid), diethylenetetraminepenta (methylenephosphonic acid), 2-phosphonobutane-1,2,4-tricarboxylic acid, and alkali metal salts thereof , Ammonium salts, amine salts dissolve metals It has been used as a minute.
しかし、溶解性分のみの使用では、酸化物皮膜を除去する以外に金属素地の腐食、水素脆性、孔食生成などの弊害をもたらす。これらを抑制ないし防止する目的で、各種の腐食抑制剤が使用されてきており、ポリエチレンイミン、ポリアリルアミン、４級のアンモニウム塩等の有機アミン類、ヘキサメチレンテトラミン等のホルマリン関連物質、チオ尿素、メルカプトベンゾチアゾール等の硫黄化合物、２-プロピン-１-オール、１-ヘキシン-３-オール、ブチンジオール等のアセチレンアルコール類が腐食抑制剤として公知である。 However, the use of only the soluble component causes adverse effects such as corrosion of the metal substrate, hydrogen embrittlement, and pitting corrosion in addition to removing the oxide film. For the purpose of suppressing or preventing these, various corrosion inhibitors have been used, such as polyethyleneimine, polyallylamine, organic amines such as quaternary ammonium salts, formalin related substances such as hexamethylenetetramine, thiourea, Sulfur compounds such as mercaptobenzothiazole, acetylene alcohols such as 2-propyne-1-ol, 1-hexyn-3-ol, and butynediol are known as corrosion inhibitors.
腐食抑制剤としてイミダゾリンの四級カチオン化合物が開示され（特許文献１）、有機酸洗浄用腐食抑制剤組成物も開示されている。（特許文献２）しかし、近年の環境問題で、効果のあったヘキサメチレンテトラミン等のホルマリン関連物質や、チオ尿素が、変異原性物質に位置づけられ、アセチレンアルコール系の２-プロピン-１-オール（別名プロパギルアルコール）も毒性が強く、使用困難となってきた。又、上記の腐食抑制剤単独では効果が充分でない。
本発明は上記のような事情に着目してなされたものであって、その目的は、変異原性物質であるヘキサメチレンテトラミンや、チオ尿素を使用しないで、キレート剤や有機酸洗浄に於いて腐食抑制効果のある製剤を提供することにある。 The present invention has been made paying attention to the above-mentioned circumstances, and its purpose is not to use a mutagenic substance such as hexamethylenetetramine or thiourea, but in chelating agents and organic acid washing. The object is to provide a preparation having a corrosion-inhibiting effect.
上記課題を解決することのできた本発明の腐食抑制剤の製剤とは、化１で示される両性の界面活性剤である２-アルキル-Ｎ-カルボキシアルキル-Ｎ-ヒドキシアルキルイミダゾリニウムベタインおよび／または化２で示される両性の界面活性剤であるβ-アルキルアミノカルボン酸のアルカリ金属塩の１種以上からなることを特徴とするキレート剤・有機酸洗浄用腐食抑制剤組成物である。
（化１）
Ｒ１は炭素数が１〜２０の分枝が有って良いアルキル基、アルケニル基、アルキニル基、炭素数が６〜２０のアリール基、ベンジル基、複素環基を示す。
Ｒ２，Ｒ３は炭素数が１〜３のアルキレン基を示す
（化２）
Ｒ１は炭素数が１〜２０の分枝が有って良いアルキル基、アルケニル基、アルキニル基、炭素数が６〜２０のアリール基、ベンジル基、複素環基を示す。
Ｒ２は炭素数が１〜２のアルキレン基を示す
Ｍはナトリウム、カリウム、リチウム等のアルカリ金属を示す。
The preparation of the corrosion inhibitor of the present invention that has solved the above-mentioned problems includes 2-alkyl-N-carboxyalkyl-N-hydroxyalkylimidazolinium betaine, which is an amphoteric surfactant represented by Chemical Formula 1: A corrosion inhibitor composition for cleaning a chelating agent / organic acid, characterized by comprising at least one alkali metal salt of β-alkylaminocarboxylic acid, which is an amphoteric surfactant represented by Chemical Formula 2.
(Chemical formula 1)
R1 represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group having 6 to 20 carbon atoms, a benzyl group, or a heterocyclic group, which may have a branch having 1 to 20 carbon atoms.
R2 and R3 each represent an alkylene group having 1 to 3 carbon atoms (Chemical Formula 2)
R1 represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group having 6 to 20 carbon atoms, a benzyl group, or a heterocyclic group, which may have a branch having 1 to 20 carbon atoms.
R2 represents an alkylene group having 1 to 2 carbon atoms, and M represents an alkali metal such as sodium, potassium, or lithium.
また前記で示される両性の界面活性剤である２-アルキル-Ｎ-カルボキシアルキル-Ｎ-ヒドロキシアルキルイミダゾリニウムベタイン（化１）が、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および／または２-アルキル-Ｎ-カルボキシエチル-Ｎ-ヒドロキシエチルイミダゾリニウムベタイン で有る物や、および／またはβ-アルキルアミノカルボン酸のアルカリ金属塩（化２）から選ばれる少なくとも１種は、目や皮膚に対する刺激が少なく、ベビーシャンプーや、ボディーシャンプーの基材に使用されるもので安全性が高いものである。腐食抑制機能はまだ充分に解明されていないが、両性の界面活性剤は水溶性が良く、金属表面に対する吸着が良くなることで腐食抑制の効果が出る物と考えられる。 In addition, 2-alkyl-N-carboxyalkyl-N-hydroxyalkylimidazolinium betaine (Chemical Formula 1), which is the amphoteric surfactant shown above, is converted to 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazole. At least one selected from the group consisting of nitrobetaine and / or 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine and / or an alkali metal salt of β-alkylaminocarboxylic acid (Chemical Formula 2) Has little irritation to eyes and skin, and is used as a base material for baby shampoos and body shampoos and has high safety. Although the corrosion inhibitory function has not yet been fully elucidated, amphoteric surfactants are considered to be water-soluble and have an effect of inhibiting corrosion due to better adsorption to the metal surface.
また本発明は前記で示される両性の界面活性剤である２-アルキル-Ｎ-カルボキシアルキル-Ｎ-ヒドロキシアルキルイミダゾリニウムベタイン（化１）および／またはβ-アルキルアミノカルボン酸のアルカリ金属塩（化２）の１種以上と、メルカプタン基（ＨＳ−）、チオシアン酸基（−ＳＣＮ）、もしくはメルカプタン基のアルカリ金属塩（ＮａＳ−、ＫＳ−，ＬｉＳ−）を有する有機化合物から選ばれる少なくとも１種の混合物とからなることを特徴とするキレート剤・有機酸洗浄用腐食抑制剤組成物である。
両者を混合使用することで、相乗効果が発生し腐食抑制効果が良くなる。
In addition, the present invention provides an alkali metal salt of 2-alkyl-N-carboxyalkyl-N-hydroxyalkylimidazolinium betaine (Chemical Formula 1) and / or β-alkylaminocarboxylic acid, which is the amphoteric surfactant shown above. And at least one selected from organic compounds having a mercaptan group (HS-), a thiocyanic acid group (-SCN), or an alkali metal salt of a mercaptan group (NaS-, KS-, LiS-). It is a corrosion inhibitor composition for cleaning a chelating agent / organic acid, characterized by comprising a mixture of seeds.
By using both in combination, a synergistic effect is generated and the corrosion inhibition effect is improved.
前記のメルカプタン基（ＨＳ−）、チオシアン酸基（−ＳＣＮ）、もしくはメルカプタン基のアルカリ金属塩（ＮａＳ−、ＫＳ−，ＬｉＳ−）を有する有機化合物の代表例としてが、メルカプトベンゾチアゾール、メルカプトベンゾイミダゾール、２，４，６-トリメルカプト-Ｓ-トリアジン、２-ジブチルアミノ-４，６-ジメルカプト-Ｓ-トリアジン、２-アニリノ-４，６-ジメルカプト-Ｓ-トリアジン、３-メルカプト-１-プロパンスルホン酸、１-チオグリセロール、２-アミノチオフェノール、４-アミノチオフェノール、チオ安息香酸、グリセロール-モノチオグリコレート、β-メルカプトプロピオン酸、β-メルカプト酢酸、β-メルカプトマレイン酸、β-メルカプトリンゴ酸、Ｐ-ヒドロキシチオフェノール、チオサリチル酸、チオテレフタル酸、２-メルカプトエタノール、メルカプトフェノール、チオ酢酸、α-メルカプトトルエン、チオシアン酸ナトリウム、チオシアン酸カリウム、チオシアン酸リチウム、チオシアン酸アンモニウム、ジメチルジチオカルバミン酸ナトリウム、ジエチルジチオカルバミン酸ナトリウム等が選ばれる。 Representative examples of the organic compound having the mercaptan group (HS-), thiocyanate group (-SCN), or alkali metal salt of the mercaptan group (NaS-, KS-, LiS-) include mercaptobenzothiazole, mercaptobenzo Imidazole, 2,4,6-trimercapto-S-triazine, 2-dibutylamino-4,6-dimercapto-S-triazine, 2-anilino-4,6-dimercapto-S-triazine, 3-mercapto-1- Propanesulfonic acid, 1-thioglycerol, 2-aminothiophenol, 4-aminothiophenol, thiobenzoic acid, glycerol-monothioglycolate, β-mercaptopropionic acid, β-mercaptoacetic acid, β-mercaptomaleic acid, β -Mercaptomalic acid, P-hydroxythiophenol, thiosalicylic acid, thioterephthalic acid, - mercaptoethanol, mercapto phenol, thioacetic acid, alpha-dimercaptotoluene, sodium thiocyanate, potassium thiocyanate, lithium thiocyanate, ammonium thiocyanate, sodium dimethyl dithiocarbamate, sodium diethyl dithiocarbamate or the like is selected.
各々の腐食抑制剤はキレート剤・有機酸洗浄液に、０．００００１〜１０ｗｔ％添加することで効果的な腐食抑制を示す。両性の界面活性剤である２-アルキル-Ｎ-カルボキシアルキル-Ｎ-ヒドロキシアルキルイミダゾリニウムベタインおよび／またはβ-アルキルアミノカルボン酸のアルカリ金属塩は、０．００１ｗｔ％以下では腐食抑制を示さず、より効果的には０．００５ｗｔ％以上であり、１０ｗｔ％以上では腐食抑制効果が飽和となり価格も高くつきより効果的には１ｗｔ％以下である。メルカプタン基（ＨＳ−）、チオシアン酸基（−ＳＣＮ）、もしくはメルカプタン基のアルカリ金属塩（ＮａＳ−、ＫＳ−，ＬｉＳ−）を有する有機化合物は、０．００００１ｗｔ％以下では腐食抑制を示さず、より効果的には０．０００１ｗｔ％以上であり、１ｗｔ％以上では腐食抑制効果が飽和となり価格も高くつきより効果的には０．１ｗｔ％以下である。 Each corrosion inhibitor exhibits effective corrosion inhibition by adding 0.00001 to 10 wt% to the chelating agent / organic acid cleaning solution. The amphoteric surfactants 2-alkyl-N-carboxyalkyl-N-hydroxyalkylimidazolinium betaine and / or alkali metal salt of β-alkylaminocarboxylic acid show no corrosion inhibition at 0.001 wt% or less. More effectively, it is 0.005 wt% or more, and if it is 10 wt% or more, the corrosion inhibiting effect is saturated and the price is high, and more effectively it is 1 wt% or less. An organic compound having a mercaptan group (HS-), a thiocyanic acid group (-SCN), or an alkali metal salt of a mercaptan group (NaS-, KS-, LiS-) does not exhibit corrosion inhibition at 0.00001 wt% or less, More effectively, it is 0.0001 wt% or more, and if it is 1 wt% or more, the corrosion inhibiting effect becomes saturated and the price is high, and more effectively it is 0.1 wt% or less.
対象となるキレート剤としては、ニトリロ３酢酸、エチレンジアミン４酢酸、ヒドロキシエチルエチレンジアミン３酢酸、ジエチレントリアミン５酢酸等のポリアミノカルボン酸や、そのアルカリ金属塩、アンモニウム塩、アミン塩であり、アミノトリ（メチレンホスホン酸）、１-ヒドロキシエチリデン-１，１-ホスホン酸、エチレンジアミンテトラ（メチレンホスホン酸）、ヘキサメチレンジアミンテトラ（メチレンホスホン酸）、ジエチレンテトラミンペンタ（メチレンホスホン酸）、２-ホスホノブタン-１，２，４-トリカルボン酸等のホスホン酸や、そのアルカリ金属塩、アンモニウム塩、アミン塩であり、有機酸としては、ギ酸、酢酸、シュウ酸、クエン酸、酒石酸、リンゴ酸、ヒドロキシ酢酸、グルコン酸、チオグリコール酸、チオリンゴ酸等の有機酸や、そのアルカリ金属塩、アンモニウム塩、アミン塩などが挙げられる。 The target chelating agents include polyaminocarboxylic acids such as nitrilotriacetic acid, ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, alkali metal salts, ammonium salts, and amine salts thereof, and aminotri (methylenephosphonic acid). ) 1-hydroxyethylidene-1,1-phosphonic acid, ethylenediaminetetra (methylenephosphonic acid), hexamethylenediaminetetra (methylenephosphonic acid), diethylenetetraminepenta (methylenephosphonic acid), 2-phosphonobutane-1,2,4 -Phosphonic acid such as tricarboxylic acid and its alkali metal salts, ammonium salts, amine salts, organic acids include formic acid, acetic acid, oxalic acid, citric acid, tartaric acid, malic acid, hydroxyacetic acid, gluconic acid, thioglycol Acid, thi And organic acids such as malic acid, its alkali metal salts, ammonium salts, and amine salts.
また本発明の腐食抑制剤は、使用する洗浄剤に添加しても良く、また濃厚な洗浄剤原液に添加しておき、使用時に水で希釈使用しても良い。また洗浄剤との混合を良くするために、溶剤や界面活性剤を併用しても良い。 Further, the corrosion inhibitor of the present invention may be added to the cleaning agent to be used, or may be added to a concentrated cleaning agent stock solution and diluted with water at the time of use. In order to improve mixing with the cleaning agent, a solvent or a surfactant may be used in combination.
またサビ金属との親和性を良くし、洗浄剤の浸透性を向上させる界面活性剤を併用しても良い。 Further, a surfactant that improves the affinity with the rust metal and improves the permeability of the cleaning agent may be used in combination.
また本発明の腐食抑制剤は、他の腐食抑制剤と併用しても良い。併用する他の腐食抑制剤としては、繊維の柔軟仕上げ剤や、シャンプーリンス剤として使用され人体の安全性が比較的良好な４級カチオン製剤や、アルキルアミン、ポリアミン、ポリエチレンイミン、ポリアリルアミン、エチレンジアミンＥＯ／ＰＯ付加物（旭電化、プルロニックＴＲシリーズ）、ケイ皮アルデヒド、ヒダントイン、５，５-ジメチルヒダントイン、アラントイン、グリオキシル酸や、亜リン酸、次亜リン酸、ジエチルヒドロキシアミン、Ｌ-ソルビン酸、Ｌ-アスコルビン酸等の還元剤などが挙げられる。 The corrosion inhibitor of the present invention may be used in combination with other corrosion inhibitors. Other corrosion inhibitors that can be used in combination include fiber softeners, quaternary cationic preparations that are used as champulence agents and have relatively good human safety, alkylamines, polyamines, polyethyleneimines, polyallylamines, and ethylenediamines. EO / PO adducts (Asahi Denka, Pluronic TR series), cinnamaldehyde, hydantoin, 5,5-dimethylhydantoin, allantoin, glyoxylic acid, phosphorous acid, hypophosphorous acid, diethylhydroxyamine, L-sorbic acid And a reducing agent such as L-ascorbic acid.
また本発明の腐食抑制剤は、これを添加したキレート剤・有機酸洗浄液を金属表面に吹き付けるか金属表面をキレート剤・有機酸洗浄液に浸漬することのいずれの洗浄方法を用いても良い。 The corrosion inhibitor of the present invention may use any cleaning method of spraying a chelating agent / organic acid cleaning solution to which the corrosion inhibitor is added to the metal surface or immersing the metal surface in the chelating agent / organic acid cleaning solution.
また本発明の腐食抑制剤は、塩酸、硫酸、リン酸、スルファミン酸、フッ酸、硝酸等の無機酸や、無機酸と有機酸の混合酸による酸洗浄においても使用可能であり、効果を示す。 The corrosion inhibitor of the present invention can also be used in acid cleaning with inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, sulfamic acid, hydrofluoric acid, and nitric acid, and mixed acids of inorganic acids and organic acids. .
以下、実施例を挙げて本発明を具体的に説明するが、本発明はもとより下記実施例によって制限を受けるものではなく、前・後記の趣旨に適合し得る範囲で適当に変更を加えて実施することも勿論可能であり、それらはいずれも本発明の技術的範囲に包含される。
実施例１
EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited by the following examples, but may be implemented with appropriate modifications within a range that can meet the purpose described above and below. Of course, any of these is also included in the technical scope of the present invention.
Example 1
酸性の標準キレート剤・有機酸洗浄液〔ヒドロオキシエチレンジアミン３酢酸の３ナトリウム塩の４０％水溶液（キレストＨ、キレスト社製）を５ｗｔ％と、クエン酸１水塩を３ｗｔ％加えたｐＨ３．７の水溶液〕に、２-椰子アルキル-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ソフタゾリンＣＬ（川研ファインケミカル社製、含量３６％）を、０．１ｗｔ％添加した洗浄液２００ｇに、試験片として２４０番研磨の冷延鋼板（６０×４０×２ｍｍ、５０ｃｍ２）を浸漬し、８０℃に６時間放置して、前後の重量変化から腐食量と防食率を測定した。結果を表１に示す。
実施例２
Acidic standard chelating agent / organic acid cleaning solution [Hydroxyethylenediamine triacetic acid trisodium salt 40% aqueous solution (Cyrest H, manufactured by Chillest Co., Ltd.) 5 wt% and citric acid monohydrate 3 wt% pH 3.7 Aqueous solution] was tested by adding 200 wt.% Of a sootazoline CL (manufactured by Kawaken Fine Chemical Co., Ltd., content: 36%), 2-sodium alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine As a piece, a cold-rolled steel plate (No. 240) (60 × 40 × 2 mm, 50 cm 2 ) was immersed and allowed to stand at 80 ° C. for 6 hours. The results are shown in Table 1.
Example 2
酸性の標準キレート剤・有機酸洗浄液に、２-椰子アルキル-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ソフタゾリンＣＬの０．１％と、メルカプトベンゾチアゾールのナトリウム塩（サンビットＮ-Ｇ、三新化学工業社製）を０．０１ｗｔ％添加した洗浄液２００ｇに、実施例１と同様に試験をした結果を表１に示す。
実施例３
In acid standard chelating agent / organic acid cleaning solution, 2-sodium alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine 0.1% of softazolin CL and mercaptobenzothiazole sodium salt (Sanbit N Table 1 shows the results of testing in the same manner as in Example 1 on 200 g of a cleaning solution to which 0.01 wt% of -G, manufactured by Sanshin Chemical Industry Co., Ltd. was added.
Example 3
酸性の標準キレート剤・有機酸洗浄液に、２-椰子アルキル-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ソフタゾリンＣＬの０．１％と、メルカプトベンズイミダゾール（サンダントＭＢ、三新化学工業社製）を０．０１ｗｔ％添加した洗浄液２００ｇに、実施例１と同様に試験をした結果を表１に示す。
実施例４
In acid standard chelating agent and organic acid cleaning solution, 2-sodium alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, 0.1% of softazolin CL, and mercaptobenzimidazole (Sandant MB, Sanshin Chemical Co., Ltd.) Table 1 shows the results of testing in the same manner as in Example 1 on 200 g of a cleaning solution to which 0.01 wt% of Kogyo Co., Ltd. was added.
Example 4
酸性の標準キレート剤・有機酸洗浄液に、２-椰子アルキル-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ソフタゾリンＣＬの０．１％と、ジメチルジチオカルバミン酸のナトリウム塩（４０％水溶液、サンセラーＳ−４０、三新化学工業社製）を０．０５ｗｔ％添加した洗浄液２００ｇに、実施例１と同様に試験をした結果を表１に示す。
実施例５
To acidic standard chelating agent / organic acid cleaning solution, 2-sodium alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, 0.1% of softazolin CL, and sodium salt of dimethyldithiocarbamic acid (40% aqueous solution) Table 1 shows the results of testing in the same manner as in Example 1 on 200 g of a cleaning solution to which 0.05 wt% of Sunceller S-40, manufactured by Sanshin Chemical Industry Co., Ltd.) was added.
Example 5
酸性の標準キレート剤・有機酸洗浄液に、２-椰子アルキル-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ソフタゾリンＣＬの０．１％と、メルカプトベンゾチアゾールのナトリウム塩の０．０１ｗｔ％と、５，５-ジメチルヒダントイン（ＭＲＣユニテック社製）を０．１ｗｔ％添加した洗浄液２００ｇに、実施例１と同様に試験をした結果を表１に示す。
実施例６
In acid standard chelating agent / organic acid cleaning solution, 2-sodium alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, 0.1% of softazolin CL, and sodium salt of mercaptobenzothiazole, 0.01 wt. Table 1 shows the results of testing in the same manner as in Example 1 on 200 g of a cleaning solution to which 0.1 wt% and 5,5-dimethylhydantoin (manufactured by MRC Unitech) were added.
Example 6
酸性の標準キレート剤・有機酸洗浄液に、β-椰子アルキルアミノプロピオン酸ナトリウム化合物であるリポミンＬＡ（ライオン社製、含量２０％）を０．１ｗｔ％添加した洗浄液２００ｇに、実施例１と同様に試験をした結果を表１に示す。
実施例７
In the same manner as in Example 1, 200 g of a cleaning solution obtained by adding 0.1 wt% of lipomin LA (produced by Lion Corporation, content 20%), which is a sodium β-coconut alkylaminopropionate compound, to an acidic standard chelating agent / organic acid cleaning solution The test results are shown in Table 1.
Example 7
酸性の標準キレート剤・有機酸洗浄液に、β-椰子アルキルアミノプロピオン酸ナトリウム化合物であるリポミンＬＡ（ライオン社製、含量２０％）の０．１ｗｔ％と、メルカプトベンゾチアゾールのナトリウム塩（サンビットＮ-Ｇ、三新化学工業社製）を０．０１ｗｔ％添加した洗浄液２００ｇに、実施例１と同様に試験をした結果を表１に示す。
比較例１
In an acidic standard chelating agent / organic acid cleaning solution, 0.1 wt% of lipomin LA (Lion Corporation, content 20%), a sodium β-coconut alkylaminopropionate compound, and a sodium salt of mercaptobenzothiazole (Sunbit N Table 1 shows the results of testing in the same manner as in Example 1 on 200 g of a cleaning solution to which 0.01 wt% of -G, manufactured by Sanshin Chemical Industry Co., Ltd. was added.
Comparative Example 1
酸性の標準キレート剤・有機酸洗浄液２００ｇに、無添加で実施例１と同様に試験をした結果を表１に示す。（ブランク例）
比較例２
Table 1 shows the results of tests conducted in the same manner as in Example 1 with no addition to 200 g of an acidic standard chelating agent / organic acid cleaning solution. (Blank example)
Comparative Example 2
酸性の標準キレート剤・有機酸洗浄液に、メルカプトベンゾチアゾールのナトリウム塩の０．０１ｗｔ％を０．１ｗｔ％添加した洗浄液２００ｇに、実施例１と同様に試験をした結果を表１に示す。
比較例３
Table 1 shows the results of testing in the same manner as in Example 1 on 200 g of a cleaning solution obtained by adding 0.01 wt% of a sodium salt of mercaptobenzothiazole to an acidic standard chelating agent / organic acid cleaning solution.
Comparative Example 3
酸性の標準キレート剤・有機酸洗浄液に、メルカプトベンズイミダゾールの０．０１ｗｔ％を添加した洗浄液２００ｇに、実施例１と同様に試験をした結果を表１に示す。
比較例４
Table 1 shows the results of testing in the same manner as in Example 1 on 200 g of a cleaning solution obtained by adding 0.01 wt% of mercaptobenzimidazole to an acidic standard chelating agent / organic acid cleaning solution.
Comparative Example 4
酸性の標準キレート剤・有機酸洗浄液に、ジメチルジチオカルバミン酸のナトリウム塩（４０％）０．０５ｗｔ％を添加した洗浄液２００ｇに、実施例１と同様に試験をした結果を表１に示す。
比較例５
Table 1 shows the results of testing in the same manner as in Example 1 on 200 g of a cleaning solution obtained by adding 0.05 wt% of sodium salt (40%) of dimethyldithiocarbamic acid to an acidic standard chelating agent / organic acid cleaning solution.
Comparative Example 5
酸性の標準キレート剤・有機酸洗浄液に、５，５-ジメチルヒダントイン０．１ｗｔ％を添加した洗浄液２００ｇに、実施例１と同様に試験をした結果を表１に示す。
比較例６
Table 1 shows the results of testing in the same manner as in Example 1 on 200 g of a cleaning solution obtained by adding 0.1 wt% of 5,5-dimethylhydantoin to an acidic standard chelating agent / organic acid cleaning solution.
Comparative Example 6
酸性の標準キレート剤・有機酸洗浄液に、２-椰子アルキル-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ソフタゾリンＣＬの０．１％と、変異原性物質であるチオ尿素の０．０１ｗｔ％を添加した洗浄液２００ｇに、実施例１と同様に試験をした結果を表１に示す。
比較例７
In acid standard chelating agent / organic acid cleaning solution, 0.1% of 2-azoalkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, softazolin CL, and 0 of mutagenic substance, thiourea Table 1 shows the results of testing in the same manner as in Example 1 on 200 g of cleaning liquid added with 0.01 wt%.
Comparative Example 7
酸性の標準キレート剤・有機酸洗浄液に、有機酸洗浄用腐食抑制剤組成物として、特公３３６４００６に開示されている２-プロピン-１-オールの０．１ｗｔ％と、ココナットアミン（ファーミンＣ、花王社製）の０．１ｗｔ％を添加した洗浄液２００ｇに、実施例１と同様に試験をした結果を表１に示す。
実施例８
In an acidic standard chelating agent / organic acid cleaning solution, 0.1 wt% of 2-propin-1-ol disclosed in Japanese Patent No. 3364006 as a corrosion inhibitor composition for organic acid cleaning, coconut amine (Farmin C) Table 1 shows the results of tests conducted in the same manner as in Example 1 on 200 g of a cleaning solution to which 0.1 wt% of Kao Corporation was added.
Example 8
アルカリ性の標準キレート剤・有機酸洗浄液〔エチレンジアミン４酢酸の３ナトリウム塩（キレストＣ、キレスト社製）を５ｗｔ％に、水酸化ナトリウムを添加してｐＨ９．１に調整した水溶液〕に、２-椰子アルキル-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ソフタゾリンＣＬ（川研ファインケミカル社製）の０．１ｗｔ％と、メルカプトベンゾチアゾールのナトリウム塩の０．０１ｗｔ％と、５，５-ジメチルヒダントインの０．１ｗｔ％を添加した洗浄液２００ｇに、試験片として２４０番研磨の冷延鋼板（６０×４０×２ｍｍ、５０ｃｍ２）を浸漬し、８０℃に６時間放置して、前後の重量変化から腐食量と防食率を測定した。結果を表２に示す。
比較例８
2-alkoxide to an alkaline standard chelating agent / organic acid cleaning solution (an aqueous solution adjusted to pH 9.1 by adding sodium hydroxide to 5 wt% of ethylenediaminetetraacetic acid trisodium salt (Cyrest C, manufactured by Crest Co.)) 0.1 wt% of alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, softazolin CL (manufactured by Kawaken Fine Chemical Co., Ltd.), 0.01 wt% of sodium salt of mercaptobenzothiazole, 5,5- A No. 240 polished cold-rolled steel plate (60 × 40 × 2 mm, 50 cm 2 ) was immersed as a test piece in 200 g of a cleaning solution to which 0.1 wt% of dimethylhydantoin was added, and left at 80 ° C. for 6 hours, before and after the weight. The amount of corrosion and the corrosion protection rate were measured from the change. The results are shown in Table 2.
Comparative Example 8
アルカリ性の標準キレート剤・有機酸洗浄液２００ｇに、無添加で実施例８と同様に試験をした結果を表２に示す。（ブランク例）
比較例９
Table 2 shows the results of tests conducted in the same manner as in Example 8 with no addition to 200 g of an alkaline standard chelating agent / organic acid cleaning solution. (Blank example)
Comparative Example 9
アルカリ性の標準キレート剤・有機酸洗浄液に、メルカプトベンゾチアゾールのナトリウム塩の０．０１ｗｔ％を添加した洗浄液２００ｇに、実施例８と同様に試験をした結果を表２に示す。
比較例１０
Table 2 shows the results of testing in the same manner as in Example 8 on 200 g of a cleaning solution obtained by adding 0.01 wt% of a sodium salt of mercaptobenzothiazole to an alkaline standard chelating agent / organic acid cleaning solution.
Comparative Example 10
アルカリ性の標準キレート剤・有機酸洗浄液に、５，５-ジメチルヒダントインの０．１ｗｔ％を添加した洗浄液２００ｇに、実施例８と同様に試験をした結果を表２に示す。 Table 2 shows the results of testing in the same manner as in Example 8 on 200 g of a cleaning solution obtained by adding 0.1 wt% of 5,5-dimethylhydantoin to an alkaline standard chelating agent / organic acid cleaning solution.
酸性の標準キレート剤・有機酸洗浄液に、２-椰子アルキル-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単独使用の実施例１は、防食率８２．１％を示し、２-椰子アルキル-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と、メルカプタン基（ＨＳ−）、もしくはメルカプタン基のアルカリ金属塩（ＮａＳ−、ＫＳ−，ＬｉＳ−）を有する有機化合物の併用である実施例２，３，４はそれぞれ相乗効果を示し、実施例２に５，５-ジメチルヒダントインを添加した実施例５では、より相乗効果を示した。 Example 1 in which 2-octylalkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine alone was used in an acidic standard chelating agent / organic acid cleaning solution showed an anticorrosion rate of 82.1%. -N-Carboxymethyl-N-hydroxyethylimidazolinium betaine and a combination of an organic compound having a mercaptan group (HS-) or an alkali metal salt of a mercaptan group (NaS-, KS-, LiS-) 2, 3 and 4 each showed a synergistic effect, and Example 5 in which 5,5-dimethylhydantoin was added to Example 2 showed a more synergistic effect.
β-椰子アルキルアミノプロピオン酸ナトリウム化合物単独使用の実施例６は、防食率８３．４％を示し、β-椰子アルキルアミノプロピオン酸ナトリウム化合物と、メルカプトベンゾチアゾールのナトリウム塩の併用である実施例７は、相乗効果を示した。 Example 6 using the β-coconut alkylaminopropionate sodium compound alone shows an anticorrosion rate of 83.4% and is a combination of β-coconut alkylaminopropionate sodium compound and a sodium salt of mercaptobenzothiazole. Showed a synergistic effect.
２-椰子アルキル-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が入っていない比較例２，３，４，５は、防食率が３０％以下で効果が無く、変異原性物質であるチオ尿素と、２-椰子アルキル-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との併用は防食率９４．５％と効果を示した。有機酸洗浄用腐食抑制剤組成物として、特公３３６４００６に開示されている２-プロピン-１-オールと、ココナットアミンを添加した比較例７は、防食率５３．８％で余りよい効果を示さなかった。 Comparative Examples 2, 3, 4, and 5 that do not contain 2-coconut alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine are mutagenic substances that have an anticorrosion rate of 30% or less and are ineffective. The combined use of thiourea and 2-coconut alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine was effective at an anticorrosion rate of 94.5%. Comparative Example 7 to which 2-propyne-1-ol and coconutamine disclosed in Japanese Patent No. 3364006 are added as a corrosion inhibitor composition for organic acid cleaning has a corrosion prevention rate of 53.8% and a very good effect. Not shown.
アルカリ性の標準キレート剤・有機酸洗浄液に、２-椰子アルキル-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と、メルカプタン基（ＨＳ−）、もしくはメルカプタン基のアルカリ金属塩（ＮａＳ−、ＫＳ−，ＬｉＳ−）を有する有機化合物と、５，５-ジメチルヒダントインを添加した実施例６は、防食率９７．８％で効果を示し、２-椰子アルキル-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が添加されていない比較例９，１０は、効果が悪い。
Alkaline standard chelating agent / organic acid cleaning solution with 2-coconut alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine and mercaptan group (HS-) or alkali metal salt of mercaptan group (NaS-, KS) Example 6, to which an organic compound having-, LiS-) and 5,5-dimethylhydantoin were added, showed an effect at an anticorrosion rate of 97.8% and showed 2-coconut alkyl-N-carboxymethyl-N-hydroxyethyl. The comparative examples 9 and 10 to which imidazolinium betaine is not added are ineffective.
Claims (6)
（化１）
Ｒ１は炭素数が１〜２０の分枝が有って良いアルキル基、アルケニル基、アルキニル基、炭素数が６〜２０のアリール基、ベンジル基、複素環基を示す。
Ｒ２，Ｒ３は炭素数が１〜３のアルキレン基を示す。
（化２）
Ｒ１は炭素数が１〜２０の分枝が有って良いアルキル基、アルケニル基、アルキニル基、炭素数が６〜２０のアリール基、ベンジル基、複素環基を示す。
Ｒ２は炭素数が１〜３のアルキレン基を示す。
Ｍはナトリウム、カリウム、リチウム等のアルカリ金属を示す。 From one or more of the amphoteric surfactants 2-alkyl-N-carboxyalkyl-N-hydroxyalkylimidazolinium betaine (Chemical Formula 1) and / or alkali metal salt of β-alkylaminocarboxylic acid (Chemical Formula 2) A chelating agent / corrosion inhibitor composition for cleaning an organic acid.
(Chemical formula 1)
R1 represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group having 6 to 20 carbon atoms, a benzyl group, or a heterocyclic group, which may have a branch having 1 to 20 carbon atoms.
R2 and R3 each represent an alkylene group having 1 to 3 carbon atoms.
(Chemical formula 2)
R1 represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group having 6 to 20 carbon atoms, a benzyl group, or a heterocyclic group, which may have a branch having 1 to 20 carbon atoms.
R2 represents an alkylene group having 1 to 3 carbon atoms.
M represents an alkali metal such as sodium, potassium or lithium.
A metal surface is cleaned by spraying a chelating agent / organic acid cleaning solution to which the corrosion inhibitor composition according to claim 5 is added or immersing the metal surface in the chelating agent / organic acid cleaning solution. How to wash metal.
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