JP2004175871A - Detergent for metal surface and method for deterging metal surface by using the same - Google Patents
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、キレート剤系洗浄剤でアルミニウム等の金属を使用した装置、機器等を洗浄する際に金属表面の腐食を抑制し、スケール洗浄に十分な時間をかけることができ、優れた洗浄効果を発揮する金属表面の洗浄剤及びそれを用いた金属表面の洗浄方法に関する。
【０００２】
【従来の技術】
水系、ガス系において、スケールの付着による効率回復、または定期的な母材の点検を目的にスケール洗浄を行う。スケール種は、水系では炭酸カルシウム、硫酸カルシウム、ケイ酸カルシウム、ガス系では硫酸カルシウムなどのカルシウム系スケールである。
これらのスケールを除去するため、一般には塩酸、硝酸、硫酸、リン酸などの無機酸やクエン酸、蓚酸、リンゴ酸、グルコン酸などの有機酸、エチレンジアミン四酢酸（ＥＤＴＡ），ニトリロ三酢酸（ＮＴＡ），ジエチレントリアミン五酢酸（ＤＴＰＡ），ヒドロキシエチレンジアミン三酢酸（ＨＥＤＴＡ），ヒドロキシエチレンジホスホン酸（ＨＥＤＰ）などのキレート剤などの洗浄剤を含む洗浄液が用いられる。
洗浄対象とする金属製の装置や機器（以下、被洗浄物という）の構造は複雑化、小型化され、かつ被洗浄物を構成する材料は鋼材、銅、アルミニウム、種々の合金などの複数の材料を用いた複雑な構成が多くなってきている。特に、構成材料にアルミニウム材が含まれる被洗浄物を洗浄する場合、無機酸、有機酸およびキレート剤には有効な防食剤がないため、洗浄剤として適用するケースはほとんどなかった。ただし、キレート剤系はアルミニウム材に対する腐食速度が無機酸、有機酸ほど速くないので、洗浄時間を短くして（スケールの洗浄効果は不十分であるが）適用しているケースがまれにある。
【０００３】
従来、洗浄剤に関して次の提案がなされている。
（１）アルカリ（ＮａＯＨ，ＫＯＨ，Ｎａ２ＣＯ３）と防食剤としてケイ酸塩とを含む、ｐＨ１０〜１４のアルミニウム金属表面の洗浄剤（例えば、特許文献１参照。）。
（２）アルミニウム合金部材の陰極電解処理に先だって、ケイ酸ソーダ、ホウ酸ソーダ及び炭酸ソーダから選ばれる少なくとも１種と、必要に応じて８ｇ／Ｌ以下のリン酸ソーダからなるアルカリビルダーの水溶液にてアルミニウム合金部材を洗浄する電解前処理方法（例えば、特許文献２参照。）。
（３）（Ａ）アミノ酸型キレート剤、（Ｂ）グルコン酸塩、（Ｃ）アルカリビルダー及び（Ｄ）陰イオン性界面活性剤および／または非イオン性界面活性剤を含む鋼板の表面清浄剤組成物（例えば、特許文献３参照。）。
（４）ナトリウムイオン、カリウムイオンおよびルビジウムイオンからなる陽イオン群から選ばれる陽イオンと、水酸イオン、炭酸イオンおよびシュウ酸イオンからなる陰イオン群から選ばれる陰イオンとが組み合わされた塩を主成分とする洗浄剤（例えば、特許文献４参照。）。
（５）スルファミン酸１０〜８０質量％、炭酸ナトリウム５〜５０質量％、結合剤０．１〜２０質量％、酸性溶液に可溶な滑沢剤０．０１〜１０質量％を主成分として含有すると共に、スルファミン酸と炭酸ナトリウムとの質量比を１：１〜１０：１の間に設定した錠剤型スケール洗浄剤（例えば、特許文献５参照。）。
（６）脂肪分解酵素と非イオン系界面活性剤とを含有する金属材料用の水溶性洗浄剤であり、必要に応じて炭酸塩等のｐＨを６．５〜１０に調整できる緩衝剤およびキレート剤が添加される洗浄剤（例えば、特許文献６参照。）。
【０００４】
【特許文献１】
特公昭６３−２１７５４号公報
【特許文献２】
特開平８−２６９７５７号公報
【特許文献３】
特開平１１−１５８４９２号公報
【特許文献４】
特開平１１−９２７８９号公報
【特許文献５】
特開平５−５００９５号公報
【特許文献６】
特開平８−１８８８９３号公報
【０００５】
【発明が解決しようとする課題】
アルミニウムまたはアルミニウム合金は、酸やアルカリには本質的に耐食性のない材料であり、その表面を洗浄する場合には、前述した従来技術（１）及び（２）のように、アルカリ性洗浄液にケイ酸塩などの防食剤を添加した洗浄液が用いられている。一方、アルミニウム材の表面に付着したカルシウム系スケールは、このようなアルカリ系洗浄剤では除去することはできず、酸系またはキレート剤系を適用するのが一般的である。
しかしながら、アルミニウム材洗浄用の酸系またはキレート剤を含む洗浄剤に添加する最適な防食剤がないため、アルミニウム材の表面に付着したカルシウム系スケールの洗浄は困難であった。キレート剤系洗浄剤を使用する場合スケールの溶解に時間を要するので、アルミニウムに対する腐食性をできるだけ小さくすることが課題である。キレート剤系洗浄剤は一般にアルカリ性であるが、前述した従来技術（１）及び（２）において防食剤として用いられているケイ酸塩（オルトケイ酸、メタケイ酸、二ケイ酸、四ケイ酸のナトリウム、カリウム塩）は、キレート剤系洗浄剤に溶解しない。つまり、前記ケイ酸塩は水には溶けるが、キレート剤系洗浄剤と混合するとケイ酸塩が析出、白濁し、沈殿してしまう。したがって、ケイ酸塩はアルミニウムの防食剤として有効かもしれないが、キレート剤系洗浄剤を使用する場合の防食剤としては実用性がない。
このように従来は、アルミニウム材の腐食を抑えながら、表面のカルシウム系スケール等を効果的に洗浄するための洗浄液は提供されておらず、洗浄剤を使用する場合、アルミニウム材を傷めない程度の短い洗浄時間で実施するか、または物理的方法（たとえばブラスト洗浄、高圧水洗浄など）で洗浄しているのが現状である。従って、残存スケールがあったり、死角部分はそのままスケールが残っていたりして本来の性能復帰まで至らないまま装置あるいは機器を再使用している場合が多い。
【０００６】
本発明は前記事情に鑑みてなされたもので、アルミニウム等の金属表面を効果的に洗浄できるとともに腐食を減少できる金属表面の洗浄剤及びそれを用いた金属表面の洗浄方法の提供を目的としている。
【０００７】
【課題を解決するための手段】
前記目的を達成するために、本発明は、キレート剤１質量部と、防食剤として炭酸塩０．５〜２０質量部とを含むことを特徴とする金属表面の洗浄剤を提供する。
本発明の洗浄剤において、溶液のｐＨが６．０以上であることが好ましい。
また、洗浄する金属表面はアルミニウムまたはアルミニウム合金を含むものであってもよい。
さらに、キレート剤は、エチレンジアミン四酢酸、ニトリロ三酢酸、ジエチレントリアミン五酢酸、ヒドロキシエチレンジアミン三酢酸、ヒドロキシエチレンジホスホン酸、グルタミン酸二酢酸、メチルグリシン二酢酸、アスパラギン酸二酢酸、またはそれらの塩からなる群から選択される１種または２種以上であるこのとが好ましい。
本発明の洗浄剤において、さらにノニオン性界面活性剤、アニオン性界面活性剤からなる群から選択される１種又は２種以上の界面活性剤を含有させてもよい。
また本発明は、前記洗浄剤で金属表面を洗浄することを特徴とする金属表面の洗浄方法を提供する。
【０００８】
【発明の実施の形態】
本発明の金属表面の洗浄剤は、キレート剤１質量部と、防食剤として炭酸塩０．５〜２０質量部とを含むことを特徴としている。
この洗浄剤の剤形は限定されず、使用者が使用時に水に溶かして所定濃度の洗浄液を調製するための粉末状、顆粒状、成形錠剤などの固体状としてもよいし、予め水に溶かしてそのまま或いは希釈して用いることができる液状としてもよい。以下の説明において、洗浄剤は固体（粉末状、顆粒状、錠剤状等）および水に溶かした液状の何れの剤形をも含むものとし、洗浄液と記する場合もある。
【０００９】
本発明の洗浄剤に用いるキレート剤は、キレート剤（あるいは金属封鎖剤とも称される）として従来公知の各種化合物が使用でき、例えばエチレンジアミン四酢酸（ＥＤＴＡ）、ニトリロ三酢酸（ＮＴＡ）、ジエチレントリアミン五酢酸（ＤＴＰＡ）、ヒドロキシエチレンジアミン三酢酸（ＨＥＤＴＡ）、ヒドロキシエチレンジホスホン酸（ＨＥＤＰ）等のエチレン系キレート剤、グルタミン酸二酢酸（ＧＤＡ）、メチルグリシン二酢酸（ＭＧＤＡ）、アスパラギン酸二酢酸（ＡＤＡ）等のアミノ酸系キレート剤、またはそれらの塩からなる群から選択される１種または２種以上が好ましい。
【００１０】
本発明の洗浄剤において防食剤として用いる炭酸塩は、炭酸または重炭酸のアルカリ金属塩が好ましく、特に炭酸または重炭酸のナトリウム塩またはカリウム塩、例えば炭酸ナトリウム、重炭酸ナトリウム、重炭酸カリウムからなる群から選択される１種または２種以上が好ましい。これらの炭酸塩は水に対する溶解性が良く、従来は洗浄剤成分として配合される場合はあったが、これらの炭酸塩をキレート剤系洗浄剤に配合することで、洗浄剤のアルミニウム材に対する腐食を減少させる作用があることは知られておらず、本発明により見出された。
【００１１】
本発明の洗浄剤において、キレート剤に対する炭酸塩の配合比率は、キレート剤１質量部に対して炭酸塩０．５〜２０質量部、好ましくは炭酸塩１〜１０質量部、特に好ましくは４〜１０質量部程度とする。炭酸塩の配合比率が前記範囲未満であると、該洗浄剤を用いてアルミニウム材の表面を洗浄する際に、アルミニウム材表面の腐食抑制効果が十分に得られなくなる。一方、炭酸塩の配合比率が前記範囲を越えると、アルミニウム材に対する腐食は減少するものの、洗浄液中の炭酸塩濃度が高まってｐＨ調整が困難となる、洗浄後の濯ぎに手間がかかるなどの問題が生じる。
【００１２】
本発明の洗浄剤において、溶液（洗浄液）のｐＨは６．０以上であることが好ましい。洗浄液のｐＨが６．０未満であると、金属表面のカルシウム系スケールなどの汚染物質に対する洗浄能力が低下する。一方、ｐＨが極端に高いと、それによってアルミニウム材が腐食されるおそれがあるため、ｐＨの上限は１２以下とするのが好ましい。洗浄液のｐＨを調整するために、適当な無機酸や水酸化アルカリを添加することが望ましい。またクエン酸塩、リン酸塩、ホウ酸塩などの緩衝剤を添加してもよい。
【００１３】
本発明の洗浄剤によって洗浄する被洗浄物は特に限定されることなく、鋼材、銅、アルミニウムなどの各種金属からなる表面を有する装置、機器等が挙げられるが、特に本発明の洗浄剤はアルミニウム材の腐食を抑制しつつ、カルシウム系スケール等の汚染物質の洗浄効果が得られるために、アルミニウムまたはアルミニウム合金を含む金属表面の洗浄用に好適に用いられる。
【００１４】
本発明の洗浄剤には、前記キレート剤と炭酸塩の他に、ｐＨ調整剤（酸、アルカリ剤）、緩衝剤（クエン酸塩、リン酸塩、ホウ酸塩等）、界面活性剤などを添加することができる。
ｐＨ調整剤としては塩酸、硫酸、ホウ酸、リン酸などの無機酸、クエン酸、酢酸、リンゴ酸などの有機酸、水酸化ナトリウム、水酸化カリウムなどの水酸化アルカリが好適に用いられる。
緩衝剤としては、溶液のｐＨを６．０以上に維持できればよく、例えば水溶液のｐＨが６．０以上のクエン酸、リン酸またはホウ酸のナトリウム塩、カリウム塩、アンモニウム塩などが挙げられる。
界面活性剤としては、ノニオン性界面活性剤、アニオン性界面活性剤からなる群から選択される１種又は２種以上の界面活性剤を用いることが好ましい。界面活性剤の添加により、カルシウム系スケールの除去能力がさらに向上する。好適なノニオン性界面活性剤としては、例えばポリオキシアルキレンアルキルエーテル、グリセリン脂肪酸エステル、ソルビタン脂肪酸エステル、ポリエチレングリコール脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、脂肪酸アルカノールアミドなどを挙げることができる。好適なアニオン性界面活性剤としては脂肪酸モノカルボン酸塩、アルキルベンゼンスルホン酸塩、硫酸アルキル塩、スルホコハク酸ジアルキルエステルなどを挙げることができる。界面活性剤の添加量は、キレート剤１質量部に対し、０〜５質量部、好ましくは０〜１質量部程度とするのが好ましい。
【００１５】
また本発明の金属表面の洗浄方法は、キレート剤１質量部と、防食剤として炭酸塩０．５〜２０質量部とを含む本発明に係る洗浄剤（洗浄液）で金属表面を洗浄することを特徴とする。
本発明の方法で用いる洗浄液は通常、水溶液の形態で用いられるが、必要に応じてアルコール、アセトンなどの有機溶媒を混入した溶液とすることもできる。洗浄液が水溶液である場合、洗浄液中のキレート剤の濃度は１〜３０質量％程度、好ましくは１〜２０質量％程度とされる。
【００１６】
この洗浄液を用いた被洗浄物の洗浄工程は、例えば被洗浄物の槽内を洗浄する場合、槽内に洗浄液を満たし、必要に応じて撹拌したり、超音波を照射しながら一定時間放置したり、あるいは流路内を洗浄する場合には、洗浄液を流路内に一定時間循環させながら、流路内壁の洗浄を行う方法が採用される。
この洗浄工程の処理時間は、通常１〜１００時間程度、好ましくは１〜２４時間程度とするのが好ましい。
また、この洗浄工程の洗浄液温は１０〜７０℃、好ましくは２０〜６０℃程度とするのが好ましい。
【００１７】
この洗浄工程は、通常１回で行われるが、洗浄液を交換しながら短時間の処理を複数回繰り返し行っても良い。
洗浄工程の終了後、被洗浄物から剥落したスケール等の汚染物質を含む洗浄液を抜き出し、廃棄する。その後、高圧水洗浄などを行って被洗浄物を水洗して濯ぎ、スケール等の汚染物質を水流で排出すると共に、被洗浄物内の洗浄液を流し去る。濯ぎ終了後、被洗浄物は必要に応じて乾燥される。
【００１８】
本発明の洗浄剤は、キレート剤に防食剤として炭酸塩を添加したことによって、カルシウム系スケール等の汚染物質に対して十分な洗浄効果を有すると同時に金属表面、特にアルミニウム材の表面に対する腐食を減少させることができる。したがって、本発明によれば、アルミニウム等の金属表面の腐食が少なくなり、洗浄に十分な時間をかけることができ、スケール等の汚染物質に対して優れた洗浄効果を発揮する金属表面の洗浄剤及びそれを用いた金属表面の洗浄方法を提供することができる。
以下、実施例によって本発明の効果を明確にする。
【００１９】
【実施例】
（実施例１：アルミニウムの腐食試験）
腐食試験に供した洗浄液Ｎｏ．１〜１８の組成を表１に示す。
洗浄液Ｎｏ．１０〜１４、１６〜１８は、キレート剤と炭酸塩とを１：０．５以上の質量比で含む本発明に係る実施例である。洗浄液Ｎｏ．１は精製水のみの比較例であり、洗浄液Ｎｏ．２〜８および１５は、キレート剤を含むが炭酸塩を含まない比較例である。また洗浄剤Ｎｏ．９は、キレート剤と炭酸塩とを１：０．２の質量比で含む比較例である。なお、表１中、ＥＤＴＡ４−Ｎａはエチレンジアミン四酢酸４ナトリウム、ＮＴＡ−３Ｎａはニトリロ三酢酸３ナトリウム、ＨＥＤＴＡ−３Ｎａはヒドロキシエチレンジアミン三酢酸３ナトリウム、ＧＤＡ−Ｎａはグルタミン酸二酢酸ナトリウム、ＭＧＤＡ−３Ｎａはメチルグリシン二酢酸３ナトリウム、ＡＤＡ−４Ｎａはアスパラギン酸二酢酸４ナトリウム、ＨＥＤＰ−Ｋはヒドロキシエチレンジホスホン酸カリウム、炭酸Ｎａは炭酸ナトリウム、重炭酸Ｎａは炭酸水素ナトリウム、炭酸Ｋは炭酸カリウム、重炭酸Ｋは炭酸水素カリウムを表す。
洗浄液Ｎｏ．２〜１８のｐＨは、１Ｎ硫酸と１Ｎ水酸化ナトリウムを用いて、すべてｐＨ１０になるように調整した。洗浄液Ｎｏ．１はｐＨ調整していない。アルミニウム板（Ａｌ：９９．８５％以上）のテストピースを用い、以下の方法で腐食試験を行った。
６０℃の恒温水中に冷却管付きフラスコに各洗浄液５００ｍＬを入れ、テストピース（表面積：３１．０ｃｍ２）を１枚吊るし、３０ｒｐｍでスターラー撹拌しながら、５時間処理した。処理前後のテストピースの重量差から、各洗浄液のアルミニウム腐食量を求めた。その結果を表２にまとめて記す。
【００２０】
【表１】
【表２】
表２の結果から、キレート剤と炭酸塩とを含む本発明に係る実施例（Ｎｏ．１０〜１４，１６〜１８）の洗浄液は、キレート剤のみを添加した比較例（Ｎｏ．２〜８および１５）に比べて、アルミニウム腐食量が低かった。またキレート剤１質量部に対して炭酸塩を０．５質量部未満配合したＮｏ．９と、同じく０．５質量部添加したＮｏ．１０とを比べた結果、炭酸塩はキレート剤１質量部に対し０．５質量部以上添加するのが好ましいことがわかる。キレート剤１質量部に対して炭酸塩を４質量部以上添加したＮｏ．１３，１４，１６〜１８の各洗浄液は、顕著に低いアルミニウム腐食性を示した。
【００２３】
（実施例２：硫酸カルシウムの溶解試験）
表１に記したものと同じ洗浄液のうち表３に記した各洗浄液を用い、硫酸カルシウムの溶解能力を比較した。なお、Ｎｏ．１３の洗浄液については、１Ｎ硫酸と１Ｎ水酸化ナトリウムを用いて、同一の組成でｐＨの異なる（ｐＨ５，６および１１）洗浄液（それぞれ表３において１３＊で表す）を作製し、試験に供した。
洗浄液１００ｍＬを１００ｍＬビーカーに採り、硫酸カルシウム（試薬特級）５．０ｇを入れ、マグネチックスターラーで撹拌した（室温）。５時間後、洗浄液を濾過し、濾液中のカルシウム濃度を原子吸光硬度計により測定した。結果を表３にまとめて記す。
【００２４】
【表３】
表３の結果から、キレート剤の配合量を増加するに従って硫酸カルシウム溶解量が増加した。またＮｏ．１３の洗浄液について、同一の洗浄液組成でｐＨを変えた洗浄液での比較の結果、ｐＨ６以上とすることで、それ以下のｐＨ（ｐＨ５）の場合と比べて硫酸カルシウム溶解量が急増すること、すなわち洗浄能力が増加することが確認された。
【００２６】
【発明の効果】
本発明の洗浄剤は、キレート剤に防食剤として炭酸塩を添加したことによって、カルシウム系スケール等の汚染物質に対して十分な洗浄効果を有すると同時に金属表面、特にアルミニウム材の表面に対する腐食を減少させることができる。したがって、本発明によれば、アルミニウム等の金属表面の腐食が少なくなり、洗浄に十分な時間をかけることができ、スケール等の汚染物質に対して優れた洗浄効果を発揮する金属表面の洗浄剤及びそれを用いた金属表面の洗浄方法を提供することができる。[0001]
TECHNICAL FIELD OF THE INVENTION
INDUSTRIAL APPLICABILITY The present invention suppresses corrosion of a metal surface when cleaning an apparatus or an apparatus using a metal such as aluminum with a chelating agent-based cleaning agent, and can take a sufficient time for scale cleaning, and has an excellent cleaning effect. The present invention relates to a cleaning agent for a metal surface exhibiting the following, and a method for cleaning a metal surface using the same.
[0002]
[Prior art]
In water and gas systems, scale cleaning is performed for the purpose of recovery of efficiency due to scale adhesion or regular inspection of base materials. The scale type is a calcium-based scale such as calcium carbonate, calcium sulfate, and calcium silicate in an aqueous system, and calcium sulfate in a gas system.
In order to remove these scales, generally, inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid, organic acids such as citric acid, oxalic acid, malic acid and gluconic acid, ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA) ), A cleaning solution containing a cleaning agent such as a chelating agent such as diethylenetriaminepentaacetic acid (DTPA), hydroxyethylenediaminetriacetic acid (HEDTA), or hydroxyethylenediphosphonic acid (HEDP) is used.
The structure of a metal device or equipment to be cleaned (hereinafter, referred to as an object to be cleaned) is complicated and miniaturized, and a material constituting the object to be cleaned is a plurality of materials such as steel, copper, aluminum, and various alloys. Complex configurations using materials are increasing. In particular, when cleaning an object to be cleaned containing an aluminum material as a constituent material, inorganic acids, organic acids and chelating agents have no effective anticorrosive agent, and therefore, there have been almost no cases where they are applied as a cleaning agent. However, since the chelating agent system does not corrode aluminum materials as quickly as inorganic acids and organic acids, there are rare cases where the cleaning time is shortened (although the cleaning effect of the scale is insufficient).
[0003]
Conventionally, the following proposals have been made regarding cleaning agents.
(1) A detergent for an aluminum metal surface having a pH of 10 to 14 and containing an alkali (NaOH, KOH, Na 2 CO 3 ) and a silicate as an anticorrosive (see, for example, Patent Document 1).
(2) Prior to the cathodic electrolytic treatment of the aluminum alloy member, an aqueous solution of an alkali builder comprising at least one selected from sodium silicate, sodium borate and sodium carbonate and, if necessary, 8 g / L or less of sodium phosphate. (See, for example, Patent Document 2).
(3) A composition for cleaning a surface of a steel sheet containing (A) an amino acid type chelating agent, (B) a gluconate, (C) an alkali builder, and (D) an anionic surfactant and / or a nonionic surfactant. (For example, see Patent Document 3).
(4) A salt obtained by combining a cation selected from the group of cations consisting of sodium ion, potassium ion and rubidium ion with an anion selected from the group of anions consisting of hydroxide ion, carbonate ion and oxalate ion A cleaning agent as a main component (for example, see Patent Document 4).
(5) Sulfamic acid 10 to 80% by mass, sodium carbonate 5 to 50% by mass, binder 0.1 to 20% by mass, lubricant containing 0.01 to 10% by mass soluble in acidic solution And a tablet-type scale detergent in which the mass ratio of sulfamic acid to sodium carbonate is set between 1: 1 and 10: 1 (for example, see Patent Document 5).
(6) A water-soluble detergent for a metal material containing a lipolytic enzyme and a nonionic surfactant, a buffer and a chelate capable of adjusting the pH of a carbonate or the like to 6.5 to 10 as necessary. A cleaning agent to which an agent is added (for example, see Patent Document 6).
[0004]
[Patent Document 1]
JP-B-63-21754 [Patent Document 2]
Japanese Patent Application Laid-Open No. 8-269775 [Patent Document 3]
JP-A-11-158492 [Patent Document 4]
JP-A-11-92789 [Patent Document 5]
JP-A-5-50095 [Patent Document 6]
Japanese Patent Application Laid-Open No. 8-188893
[Problems to be solved by the invention]
Aluminum or an aluminum alloy is essentially a material that does not have corrosion resistance to acids and alkalis. When the surface is cleaned, as described in the prior arts (1) and (2), silicate is added to the alkaline cleaning liquid. A cleaning solution to which an anticorrosive such as salt is added is used. On the other hand, the calcium-based scale attached to the surface of the aluminum material cannot be removed by such an alkali-based cleaning agent, and an acid-based or chelating agent-based system is generally used.
However, there is no optimal anticorrosive agent to be added to a cleaning agent containing an acid or a chelating agent for cleaning an aluminum material, so that it is difficult to clean a calcium-based scale attached to the surface of an aluminum material. When a chelating agent-based cleaning agent is used, it takes time to dissolve the scale. Therefore, it is a problem to minimize the corrosiveness to aluminum as much as possible. Chelating agent-based detergents are generally alkaline, but silicates (orthosilicate, metasilicate, disilicate, sodium tetrasilicate) used as anticorrosives in the above-mentioned prior arts (1) and (2). , Potassium salt) does not dissolve in the chelating agent-based detergent. That is, the silicate is soluble in water, but when mixed with a chelating agent-based detergent, the silicate precipitates, becomes cloudy, and precipitates. Thus, while silicates may be effective as aluminum anticorrosives, they are not practical as anticorrosives when using chelating detergents.
As described above, conventionally, there has not been provided a cleaning liquid for effectively cleaning calcium-based scales and the like on the surface while suppressing corrosion of the aluminum material. At present, the cleaning is performed in a short cleaning time or by a physical method (for example, blast cleaning, high-pressure water cleaning, etc.). Therefore, in many cases, the apparatus or apparatus is reused without reaching the original performance because there is a residual scale or the scale remains in the blind spot portion.
[0006]
The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a metal surface cleaning agent capable of effectively cleaning a metal surface such as aluminum and reducing corrosion, and a method of cleaning a metal surface using the same. .
[0007]
[Means for Solving the Problems]
In order to achieve the above object, the present invention provides a metal surface cleaner comprising 1 part by mass of a chelating agent and 0.5 to 20 parts by mass of a carbonate as an anticorrosive.
In the cleaning agent of the present invention, the pH of the solution is preferably 6.0 or more.
The metal surface to be cleaned may include aluminum or an aluminum alloy.
Further, the chelating agent is a group consisting of ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylenediaminetriacetic acid, hydroxyethylenediphosphonic acid, glutamic acid diacetate, methylglycine diacetate, aspartate diacetate, or salts thereof. This is preferably one or two or more selected from
The cleaning agent of the present invention may further contain one or more surfactants selected from the group consisting of nonionic surfactants and anionic surfactants.
Further, the present invention provides a method for cleaning a metal surface, comprising cleaning the metal surface with the cleaning agent.
[0008]
BEST MODE FOR CARRYING OUT THE INVENTION
The metal surface cleaning agent of the present invention is characterized by containing 1 part by mass of a chelating agent and 0.5 to 20 parts by mass of a carbonate as an anticorrosive.
The form of the detergent is not limited, and may be in the form of a powder, granules, or a solid such as a molded tablet, for dissolving in water at the time of use by a user to prepare a washing solution having a predetermined concentration, or dissolving in water in advance. It may be a liquid that can be used as it is or diluted. In the following description, the detergent includes both solid (powder, granule, tablet, etc.) and liquid forms dissolved in water, and may be referred to as a washing liquid.
[0009]
As the chelating agent used in the cleaning agent of the present invention, various compounds conventionally known as chelating agents (also referred to as sequestering agents) can be used. For example, ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), diethylenetriaminepentane Ethylene chelating agents such as acetic acid (DTPA), hydroxyethylenediaminetriacetic acid (HEDTA), hydroxyethylenediphosphonic acid (HEDP), glutamate diacetate (GDA), methylglycine diacetate (MGDA), aspartate diacetate (ADA) And the like, or one or more selected from the group consisting of amino acid-based chelating agents or salts thereof.
[0010]
The carbonate used as an anticorrosive in the detergent of the present invention is preferably an alkali metal carbonate or bicarbonate, particularly a sodium or potassium carbonate or bicarbonate such as sodium carbonate, sodium bicarbonate or potassium bicarbonate. One or more selected from the group is preferred. These carbonates have good solubility in water, and were conventionally blended as a detergent component. However, by blending these carbonates with a chelating detergent, the corrosion of the detergent on aluminum materials can be improved. It is not known to have the effect of reducing, and was found by the present invention.
[0011]
In the detergent of the present invention, the mixing ratio of the carbonate to the chelating agent is 0.5 to 20 parts by mass of the carbonate, preferably 1 to 10 parts by mass of the carbonate, and particularly preferably 4 to 10 parts by mass with respect to 1 part by mass of the chelating agent. It is about 10 parts by mass. When the compounding ratio of the carbonate is less than the above range, when the surface of the aluminum material is cleaned using the cleaning agent, the effect of suppressing corrosion of the aluminum material surface cannot be sufficiently obtained. On the other hand, if the compounding ratio of the carbonate exceeds the above range, the corrosion to the aluminum material is reduced, but the carbonate concentration in the cleaning liquid is increased, so that the pH adjustment becomes difficult, and the rinsing after the cleaning is troublesome. Occurs.
[0012]
In the cleaning agent of the present invention, the pH of the solution (washing liquid) is preferably 6.0 or more. When the pH of the cleaning liquid is less than 6.0, the cleaning ability of the metal surface against contaminants such as calcium-based scale is reduced. On the other hand, when the pH is extremely high, the aluminum material may be corroded by the extremely high pH. Therefore, the upper limit of the pH is preferably 12 or less. In order to adjust the pH of the cleaning solution, it is desirable to add an appropriate inorganic acid or alkali hydroxide. Further, a buffer such as citrate, phosphate, and borate may be added.
[0013]
The object to be cleaned by the cleaning agent of the present invention is not particularly limited, and examples thereof include devices and devices having surfaces made of various metals such as steel, copper, and aluminum. Since the effect of cleaning contaminants such as calcium-based scale can be obtained while suppressing corrosion of the material, it is suitably used for cleaning a metal surface containing aluminum or an aluminum alloy.
[0014]
In the cleaning agent of the present invention, in addition to the chelating agent and the carbonate, a pH adjuster (acid, alkali agent), a buffer (citrate, phosphate, borate, etc.), a surfactant and the like are used. Can be added.
As the pH adjuster, inorganic acids such as hydrochloric acid, sulfuric acid, boric acid and phosphoric acid, organic acids such as citric acid, acetic acid and malic acid, and alkali hydroxides such as sodium hydroxide and potassium hydroxide are preferably used.
The buffering agent only needs to maintain the pH of the solution at 6.0 or higher, and examples thereof include sodium, potassium, and ammonium salts of citric acid, phosphoric acid, or boric acid having an aqueous solution of 6.0 or higher.
As the surfactant, it is preferable to use one or more surfactants selected from the group consisting of nonionic surfactants and anionic surfactants. The addition of the surfactant further improves the ability to remove calcium-based scale. Suitable nonionic surfactants include, for example, polyoxyalkylene alkyl ethers, glycerin fatty acid esters, sorbitan fatty acid esters, polyethylene glycol fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and fatty acid alkanolamides. Suitable anionic surfactants include fatty acid monocarboxylate, alkylbenzene sulfonate, alkyl sulfate, dialkyl sulfosuccinate and the like. The amount of the surfactant to be added is preferably 0 to 5 parts by mass, more preferably about 0 to 1 part by mass, per 1 part by mass of the chelating agent.
[0015]
The method for cleaning a metal surface according to the present invention includes cleaning the metal surface with the cleaning agent (cleaning liquid) according to the present invention containing 1 part by mass of a chelating agent and 0.5 to 20 parts by mass of a carbonate as an anticorrosive. Features.
The washing solution used in the method of the present invention is usually used in the form of an aqueous solution, but may be a solution mixed with an organic solvent such as alcohol or acetone, if necessary. When the washing liquid is an aqueous solution, the concentration of the chelating agent in the washing liquid is about 1 to 30% by mass, preferably about 1 to 20% by mass.
[0016]
In the step of cleaning the object to be cleaned using this cleaning liquid, for example, when cleaning the inside of the tank of the object to be cleaned, the tank is filled with the cleaning liquid and, if necessary, stirred or left for a predetermined time while irradiating ultrasonic waves. In the case of washing the inside of the flow path or washing the inside of the flow path, a method of cleaning the inner wall of the flow path while circulating the cleaning liquid in the flow path for a certain time is adopted.
The processing time of this washing step is usually about 1 to 100 hours, preferably about 1 to 24 hours.
Further, the temperature of the cleaning liquid in this cleaning step is preferably 10 to 70 ° C, more preferably about 20 to 60 ° C.
[0017]
This cleaning step is usually performed once, but a short-time process may be repeated a plurality of times while changing the cleaning liquid.
After the completion of the cleaning process, a cleaning liquid containing contaminants such as scales that has fallen off from the object to be cleaned is extracted and discarded. Thereafter, the object to be cleaned is washed with water and rinsed by performing high-pressure water cleaning, and contaminants such as scales are discharged by a water flow, and the cleaning liquid in the object to be cleaned is washed away. After the rinsing, the object to be cleaned is dried if necessary.
[0018]
The cleaning agent of the present invention has a sufficient cleaning effect against contaminants such as calcium-based scale by adding a carbonate as a corrosion inhibitor to the chelating agent, and at the same time, corrodes the metal surface, particularly the surface of the aluminum material. Can be reduced. Therefore, according to the present invention, corrosion of a metal surface such as aluminum is reduced, sufficient time can be taken for cleaning, and a cleaning agent for a metal surface exhibiting an excellent cleaning effect on contaminants such as scale. And a method for cleaning a metal surface using the same.
Hereinafter, the effects of the present invention will be clarified by examples.
[0019]
【Example】
(Example 1: Corrosion test of aluminum)
Cleaning liquid No. subjected to the corrosion test. Table 1 shows the compositions of Nos. 1 to 18.
Cleaning solution No. Examples 10 to 14 and 16 to 18 are examples according to the present invention containing a chelating agent and a carbonate in a mass ratio of 1: 0.5 or more. Cleaning solution No. No. 1 is a comparative example using purified water only. 2-8 and 15 are comparative examples containing a chelating agent but no carbonate. The cleaning agent No. 9 is a comparative example containing a chelating agent and a carbonate at a mass ratio of 1: 0.2. In Table 1, EDTA4-Na is tetrasodium ethylenediaminetetraacetate, NTA-3Na is trisodium nitrilotriacetate, HEDTA-3Na is trisodium hydroxyethylenediaminetriacetate, GDA-Na is sodium glutamate diacetate, and MGDA-3Na is Methylglycine diacetate trisodium, ADA-4Na is aspartate diacetate tetrasodium, HEDP-K is potassium hydroxyethylene diphosphonate, Na carbonate is sodium carbonate, Na bicarbonate is sodium hydrogen carbonate, K carbonate is potassium carbonate, and K carbonate represents potassium hydrogen carbonate.
Cleaning solution No. The pH of 2 to 18 was adjusted to pH 10 using 1N sulfuric acid and 1N sodium hydroxide. Cleaning solution No. No. 1 was not pH adjusted. Using a test piece of an aluminum plate (Al: 99.85% or more), a corrosion test was performed by the following method.
500 mL of each washing solution was placed in a flask equipped with a cooling tube in constant temperature water at 60 ° C., and one test piece (surface area: 31.0 cm 2 ) was hung and treated with a stirrer at 30 rpm for 5 hours. From the weight difference between the test pieces before and after the treatment, the amount of aluminum corrosion of each cleaning solution was determined. The results are summarized in Table 2.
[0020]
[Table 1]
[Table 2]
From the results in Table 2, the cleaning liquids of Examples (Nos. 10 to 14, 16 to 18) according to the present invention containing a chelating agent and a carbonate contained Comparative Examples (Nos. Compared with 15), the amount of aluminum corrosion was low. In addition, No. 1 containing less than 0.5 part by mass of a carbonate with respect to 1 part by mass of a chelating agent. No. 9 and 0.5% by mass of No. 9 As a result of comparison with 10, it is found that it is preferable to add 0.5 parts by mass or more of the carbonate to 1 part by mass of the chelating agent. No. 4 in which 4 parts by mass or more of a carbonate was added to 1 part by mass of a chelating agent. Each of the cleaning liquids 13, 14, 16 to 18 showed remarkably low aluminum corrosion.
[0023]
(Example 2: Dissolution test of calcium sulfate)
The dissolving ability of calcium sulfate was compared using each of the cleaning solutions shown in Table 3 among the same cleaning solutions shown in Table 1. In addition, No. With respect to the 13 cleaning liquids, 1N sulfuric acid and 1N sodium hydroxide were used to prepare cleaning liquids having the same composition (pH 5, 6, and 11) (each represented by 13 * in Table 3) and subjected to the test. .
100 mL of the washing solution was placed in a 100 mL beaker, 5.0 g of calcium sulfate (special grade reagent) was added, and the mixture was stirred with a magnetic stirrer (room temperature). After 5 hours, the washing solution was filtered, and the calcium concentration in the filtrate was measured by an atomic absorption hardness meter. The results are summarized in Table 3.
[0024]
[Table 3]
From the results in Table 3, the amount of dissolved calcium sulfate increased as the amount of the chelating agent increased. No. As a result of comparison of the 13 cleaning liquids with the same cleaning liquid composition and a different pH value, it was found that when the pH value was 6 or higher, the amount of dissolved calcium sulfate was sharply increased as compared with the case of a lower pH value (pH 5). It was confirmed that the cleaning ability increased.
[0026]
【The invention's effect】
The cleaning agent of the present invention has a sufficient cleaning effect against contaminants such as calcium-based scale by adding a carbonate as a corrosion inhibitor to the chelating agent, and at the same time, corrodes the metal surface, particularly the surface of the aluminum material. Can be reduced. Therefore, according to the present invention, the corrosion of a metal surface such as aluminum can be reduced, sufficient time can be taken for cleaning, and a cleaning agent for a metal surface exhibiting an excellent cleaning effect on contaminants such as scale. And a method for cleaning a metal surface using the same.
Claims (6)
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