JPH07166384A - Gelation inhibitor and method for cleaning metal with the same - Google Patents
Gelation inhibitor and method for cleaning metal with the sameInfo
- Publication number
- JPH07166384A JPH07166384A JP31353693A JP31353693A JPH07166384A JP H07166384 A JPH07166384 A JP H07166384A JP 31353693 A JP31353693 A JP 31353693A JP 31353693 A JP31353693 A JP 31353693A JP H07166384 A JPH07166384 A JP H07166384A
- Authority
- JP
- Japan
- Prior art keywords
- cleaning
- gelation
- cleaning liquid
- metal
- inhibitor
- 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.)
- Granted
Links
Landscapes
- Detergent Compositions (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は金属洗浄液用ゲル化抑制
剤及びそれを用いる金属洗浄方法に関し、さらに詳しく
は洗浄液のゲル化を顕著に抑制し、長時間にわたる洗浄
装置の安定稼動を可能にするゲル化抑制剤及び金属洗浄
方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gelation inhibitor for a metal cleaning liquid and a metal cleaning method using the same, and more specifically, it significantly suppresses gelation of the cleaning liquid and enables stable operation of the cleaning device for a long time. To a gelation inhibitor and a metal cleaning method.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】金属お
もに鋼板を洗浄する方法としては、従来、例えば冷間圧
延後の鋼板の洗浄では、浸漬、スプレー、ブラッシン
グ、電解洗浄等の工程を組み合わせて行う方法が使用さ
れており、これにより鋼板表面に付着した圧延油、鉄粉
またはこれらの反応生成物等が除去される。2. Description of the Related Art Conventionally, as a method for cleaning a steel sheet, mainly a metal sheet, for example, in the case of washing a steel sheet after cold rolling, a combination of steps such as dipping, spraying, brushing and electrolytic cleaning is used. The method of carrying out is used, whereby rolling oil, iron powder or reaction products thereof, etc. adhering to the surface of the steel sheet are removed.
【０００３】このような洗浄方法においては、現在、図
１に示すような装置を用いて洗浄液を循環使用する方法
が一般的に用いられている。この装置では、洗浄槽１と
循環槽２の間で洗浄液３を循環させながら、鋼板４を洗
浄槽１内の洗浄液３中を通過させ（浸漬洗浄）、あるい
は洗浄槽１内を通過する鋼板４に接近させて電極を設け
る（電解洗浄）等して鋼板の洗浄を行う。しかしなが
ら、この方法によると洗浄液の循環流動中に空気の巻き
込み等により洗浄液が発泡し、気泡が系外に流出するこ
とにより、洗浄液原単位、排水処理性、さらに作業環境
性等が悪化するなど、種々の問題が生じる。また電解洗
浄工程を有する場合、発生した気泡により電解電流密度
の低下が生じる場合もある。In such a cleaning method, at present, a method in which a cleaning liquid is circulated and used by using an apparatus as shown in FIG. 1 is generally used. In this apparatus, while circulating the cleaning liquid 3 between the cleaning tank 1 and the circulation tank 2, the steel plate 4 is passed through the cleaning liquid 3 in the cleaning tank 1 (immersion cleaning), or the steel plate 4 is passed through the cleaning tank 1. The steel plate is cleaned by providing an electrode (electrolytic cleaning) in close proximity to. However, according to this method, the cleaning liquid is foamed due to the entrainment of air during the circulation flow of the cleaning liquid, and the bubbles flow out of the system, thereby deteriorating the basic unit of the cleaning liquid, the wastewater treatment property, and the work environment property. Various problems arise. In addition, when an electrolytic cleaning step is included, the generated bubbles may cause a decrease in electrolytic current density.
【０００４】このような発泡の原因は、主に洗浄液中に
含まれる界面活性剤、洗浄後蓄積する圧延油等が分解さ
れてできる脂肪酸石鹸によるものであるが、中でも、脂
肪酸石鹸による発泡が非常に大きく寄与している。これ
らの問題の対策として、洗浄槽もしくは循環槽の洗浄液
に継続的または定期的に、あるいはスポット的に一定量
の高級アルコール等の消泡剤を直接添加する方法が提案
されている（特公昭６０−５６４３９号公報）。The cause of such foaming is mainly a surfactant contained in the cleaning liquid, a fatty acid soap formed by decomposing rolling oil accumulated after cleaning, etc. Among them, the foaming by the fatty acid soap is very serious. Greatly contributes to As a measure against these problems, a method has been proposed in which a fixed amount of a defoaming agent such as higher alcohol is directly added to a cleaning liquid in a cleaning tank or a circulating tank continuously or periodically or spotwise (Japanese Patent Publication No. Sho 60). -56439 gazette).
【０００５】しかし、洗浄液中に上記油中の不鹸化分、
未鹸化分、脂肪酸石鹸のような鹸化分、さらには消泡剤
として従来用いられてきた高級アルコール等が存在する
と、消泡性は良好であるものの、しばしば洗浄液がゲル
化してしまう。このゲル化は、上記不鹸化分の脂肪酸石
鹸によるミセルが高級アルコールの存在により膨大化す
ることに起因する。However, the unsaponifiable matter in the above-mentioned oil is contained in the cleaning liquid,
In the presence of unsaponifiable matter, saponified matter such as fatty acid soap, and higher alcohols conventionally used as a defoaming agent, the defoaming property is good, but the cleaning solution often gels. This gelation is due to the fact that the micelles of the above-mentioned unsaponifiable fatty acid soap become huge due to the presence of higher alcohols.
【０００６】こうして洗浄液がゲル化すると、ゲルが金
属上に付着したり、電解電流密度が低下したりすること
により洗浄性が低下し、さらには洗浄液の増粘、固化等
により装置内での洗浄液循環が不能となり操業停止に陥
いることとなる。When the cleaning liquid gels in this way, the gel adheres to the metal and the electrolytic current density decreases, which deteriorates the cleaning property. Further, the cleaning liquid thickens and solidifies, so that the cleaning liquid in the apparatus is cleaned. The circulation becomes impossible and the operation is suspended.
【０００７】そこで、金属洗浄液のゲル化を抑制し、洗
浄性を低下させることなく、装置を長時間にわたり安定
して稼動させ得る方法の開発が望まれていた。Therefore, it has been desired to develop a method of suppressing the gelation of the metal cleaning liquid and allowing the apparatus to operate stably for a long time without deteriorating the cleaning property.
【０００８】[0008]
【課題を解決するための手段】本発明者らは、かかる実
情に鑑み鋭意検討した結果、金属洗浄液中に後述する特
定の水溶性高分子を含有させれば、洗浄液のゲル化を抑
制し、装置の安定稼動を可能にすることを見出し、本発
明を完成するに至った。Means for Solving the Problems The inventors of the present invention have made extensive studies in view of such circumstances, and as a result, if a specific water-soluble polymer described later is contained in the metal cleaning liquid, gelation of the cleaning liquid is suppressed, The inventors have found that stable operation of the apparatus is possible, and have completed the present invention.
【０００９】すなわち、本発明は、分子中にエチレンオ
キシドを含むアルキレンオキシド繰返し単位を有する数
平均分子量が２０００以上の水溶性高分子を含有するこ
とを特徴とする金属洗浄液用ゲル化抑制剤を提供するも
のである。That is, the present invention provides a gelation inhibitor for a metal cleaning liquid, which comprises a water-soluble polymer having an alkylene oxide repeating unit containing ethylene oxide in the molecule and having a number average molecular weight of 2000 or more. It is a thing.
【００１０】本発明は、さらに、洗浄液中に金属を浸漬
する工程を有する金属洗浄方法において、該工程中に洗
浄液に上記ゲル化抑制剤を添加することを特徴とする金
属洗浄方法を提供するものである。The present invention further provides a metal cleaning method comprising a step of immersing a metal in a cleaning solution, wherein the gelation inhibitor is added to the cleaning solution during the step. Is.
【００１１】本発明のゲル化抑制剤に使用されるエチレ
ンオキシドを含むアルキレンオキシド繰返し単位を有す
る水溶性高分子の数平均分子量は２０００以上、とくに
４０００以上が好ましい。分子量の上限はとくに限定さ
れないが、それ自体がゲル化しない範囲で選択すること
が好ましい。上記水溶性高分子は、下記一般式（１）The number average molecular weight of the water-soluble polymer having an alkylene oxide repeating unit containing ethylene oxide used in the gelation inhibitor of the present invention is preferably 2,000 or more, more preferably 4,000 or more. The upper limit of the molecular weight is not particularly limited, but it is preferable to select it within the range where it does not gel itself. The water-soluble polymer is represented by the following general formula (1)
【００１２】[0012]
【化１】 [Chemical 1]
【００１３】（式中、Ｒ1 及びＲ2 は、同一または異な
って、水素原子、水酸基を有してもよいアルキル基、ア
ラルキル基またはアルケニル基を示し、Ａ．Ｏはエチレ
ンオキシド又はエチレンオキシド−プロピレンオキシド
を示し、ｎはＡ．Ｏの付加モル数を示す）で表わされる
化合物であることが好ましい。上記Ｒ1 及びＲ2 はとも
に水素原子であることがとくに好ましい。(In the formula, R 1 and R 2 are the same or different and each represents a hydrogen atom, an alkyl group which may have a hydroxyl group, an aralkyl group or an alkenyl group, and A.O is ethylene oxide or ethylene oxide-propylene oxide. And n is the number of moles of A.O added). It is particularly preferable that both R 1 and R 2 are hydrogen atoms.
【００１４】本発明のゲル化抑制剤は、上記水溶性高分
子のみからなるものであってもよいが、水溶液として
も、公知のアルカリ性金属洗浄液に含有させても、ま
た、高級アルコール等の消泡剤に含有させたものでもよ
い。The gelation inhibitor of the present invention may be composed of only the above water-soluble polymer, but it may be contained as an aqueous solution or in a known alkaline metal cleaning solution, or may be used to remove higher alcohols and the like. It may be contained in a foaming agent.
【００１５】本発明のゲル化抑制剤の洗浄液中への添加
量は、上記水溶性高分子が、後述する高級アルコール等
の消泡剤に対し１重量％（以下、単に「％」という）以
上３０％以下、好ましくは１０％以上、とくに好ましく
は２０％以上添加されるよう設定することが好ましい。
３０％を超えると洗浄液の粘度が上昇し好ましくない。The amount of the gelation inhibitor of the present invention added to the cleaning liquid is at least 1% by weight (hereinafter, simply referred to as "%") of the water-soluble polymer with respect to the defoaming agent such as higher alcohol described below. 30% or less, preferably 10% or more, and particularly preferably 20% or more is preferably added.
If it exceeds 30%, the viscosity of the cleaning liquid increases, which is not preferable.
【００１６】本発明において洗浄に与かる金属は、図１
に示すような洗浄装置において搬送可能な金属板、とく
に鋼板であることが好ましい。The metal used for cleaning in the present invention is shown in FIG.
It is preferable to use a metal plate, particularly a steel plate, that can be transported in the cleaning device as shown in FIG.
【００１７】本発明に使用される洗浄液としては、アル
カリ剤または、アルカリ剤とキレート剤、界面活性剤と
の混合液が挙げられる。アルカリ剤としては、例えば水
酸化ナトリウム、水酸化カリウムまたはケイ酸ナトリウ
ム、リン酸ナトリウム、炭酸ナトリウム等のナトリウム
塩等が一般的に用いられる。また、キレート剤として
は、例えばオキシカルボン酸、アルカノールアミン、ア
ミノカルボン酸等が用いられ、界面活性剤としては、ア
ニオン型及びノニオン型界面活性剤が一般的に用いられ
る。使用されるアルカリ水溶液のアルカリ濃度は、洗浄
液中通常０．５〜１０％である。Examples of the cleaning liquid used in the present invention include an alkaline agent or a mixed solution of an alkaline agent with a chelating agent and a surfactant. As the alkaline agent, for example, sodium hydroxide, potassium hydroxide or sodium salts such as sodium silicate, sodium phosphate and sodium carbonate are generally used. As the chelating agent, for example, oxycarboxylic acid, alkanolamine, aminocarboxylic acid, etc. are used, and as the surfactant, anionic and nonionic surfactants are generally used. The alkaline concentration of the aqueous alkaline solution used is usually 0.5 to 10% in the cleaning liquid.
【００１８】上記洗浄液には、通常、消泡剤が添加され
る。消泡剤としては、高級アルコール、とくに炭素数８
〜２４のアルコールが好ましい。該消泡剤は洗浄液中に
０．０５％以上、好ましくは０．１％以上１０％以下添
加される。An antifoaming agent is usually added to the cleaning liquid. As a defoaming agent, higher alcohols, especially 8 carbon atoms
-24 alcohols are preferred. The antifoaming agent is added to the cleaning liquid in an amount of 0.05% or more, preferably 0.1% or more and 10% or less.
【００１９】本発明の金属洗浄方法においては、例えば
図１に示すような洗浄液の循環使用が可能な装置を用
い、洗浄液３中に金属４を浸漬する工程に際し、洗浄液
３中に本発明のゲル化抑制剤を添加する。該ゲル化抑制
剤は、洗浄槽１中の洗浄液及び／又は循環槽２中の洗浄
液に添加することができる。なお、ゲル化抑制剤は、前
記水溶性高分子そのものをフレーク状物として添加して
もよいが、水溶液として添加することが洗浄液の均一性
を保つうえで好ましい。In the metal cleaning method of the present invention, for example, an apparatus capable of circulating the cleaning liquid as shown in FIG. 1 is used, and the gel of the present invention is immersed in the cleaning liquid 3 during the step of immersing the metal 4 in the cleaning liquid 3. Add an anti-oxidant. The gelation inhibitor can be added to the cleaning liquid in the cleaning tank 1 and / or the cleaning liquid in the circulation tank 2. The water-soluble polymer itself may be added as a flake-like substance to the gelation inhibitor, but it is preferable to add it as an aqueous solution in order to maintain the uniformity of the cleaning liquid.
【００２０】[0020]
【発明の効果】本発明のゲル化抑制剤及びそれを用いる
金属洗浄方法により、洗浄液のゲル化が顕著に抑制さ
れ、洗浄性を低下させることなく、長時間にわたり安定
して装置を稼動させることができる。EFFECTS OF THE INVENTION The gelation inhibitor of the present invention and the metal cleaning method using the same suppresses gelation of the cleaning liquid remarkably, and enables stable operation of the apparatus for a long time without deteriorating the cleaning property. You can
【００２１】[0021]
【実施例】以下に本発明を実施例により具体的に説明す
るが、本発明はこれらに限定されるものではない。 実施例１ 図１に示す装置を用い、表１に記載の被験物の水溶液を
洗浄液中に添加した。試験条件を下記に示す。EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. Example 1 Using the apparatus shown in FIG. 1, the aqueous solution of the test substance shown in Table 1 was added to the washing solution. The test conditions are shown below.
【００２２】（試験条件） 攪拌機：ＴＫホモミキサー、８０００rpm 、 温度：８０℃、 洗浄液量：４００cm3 、 ＮａＯＨ濃度：２．０％、 防錆油濃度：１．０％、 石鹸濃度：１．０％、（＋量論グリセリン） 消泡剤濃度：１．０％、 抑制剤濃度：０．２％(Test conditions) Stirrer: TK homomixer, 8000 rpm, temperature: 80 ° C., washing liquid amount: 400 cm 3 , NaOH concentration: 2.0%, rust preventive oil concentration: 1.0%, soap concentration: 1.0 %, (+ Stoichiometric glycerin) Defoamer concentration: 1.0%, Inhibitor concentration: 0.2%
【００２３】それぞれの被験物の添加後、ゲル化が発現
するまでの時間を測定した。結果を併せて表１に示す。After the addition of each test substance, the time until gelation was developed was measured. The results are also shown in Table 1.
【００２４】[0024]
【表１】 [Table 1]
【００２５】＊１ 旭電化（株）製、ポリオキシエチレ
ン−ポリオキシプロピレン共重合体〔ＥＯ／ＰＯ＝５
（モル比）〕 ＊２ 旭電化（株）製、ポリオキシエチレン−ポリオキ
シプロピレン共重合体〔ＥＯ／ＰＯ＝５（モル比）〕 ＊３ 旭電化（株）製、ポリオキシエチレン−ポリオキ
シプロピレン共重合体〔ＥＯ／ＰＯ＝５（モノ比）〕* 1 Polyoxyethylene-polyoxypropylene copolymer manufactured by Asahi Denka Co., Ltd. [EO / PO = 5
(Molar ratio)] * 2 Asahi Denka Co., Ltd. polyoxyethylene-polyoxypropylene copolymer [EO / PO = 5 (molar ratio)] * 3 Asahi Denka Co., Ltd. polyoxyethylene-polyoxy Propylene copolymer [EO / PO = 5 (mono ratio)]
【００２６】表１に示す結果より明らかなように、本発
明品を洗浄液中に添加した場合には、ゲル化までの時間
が著しく長くなることがわかる。また、分子量の大きい
もの（４０００以上）のものは、少量の添加でもゲル化
が顕著に抑制された。As is clear from the results shown in Table 1, when the product of the present invention is added to the cleaning liquid, the time until gelation becomes extremely long. Further, those having a large molecular weight (4000 or more) were remarkably suppressed in gelation even when added in a small amount.
【００２７】なお、本発明品を洗浄液中に添加後、鋼板
を浸漬し、洗浄操作を行ったところ、長時間にわたりゲ
ル化が抑制され、洗浄性の低下をきたすことなく安定し
て装置を稼動させることができた。After the product of the present invention was added to the cleaning liquid, the steel sheet was immersed and the cleaning operation was performed. As a result, gelation was suppressed for a long time, and the apparatus was operated stably without lowering the cleaning property. I was able to do it.
【図１】洗浄液を循環使用する一般的な洗浄方法に用い
られる装置の概略を示す断面図である。FIG. 1 is a sectional view schematically showing an apparatus used in a general cleaning method in which a cleaning liquid is circulated and used.
１ 洗浄槽 ２ 循環槽 ３ 洗浄液 ４ 鋼板 ５ 送り配管 ６ 戻り配管 ７ 循環パイプ ８ 仕切板 1 Cleaning Tank 2 Circulation Tank 3 Cleaning Liquid 4 Steel Plate 5 Feed Pipe 6 Return Pipe 7 Circulation Pipe 8 Partition Plate
───────────────────────────────────────────────────── フロントページの続き (72)発明者 三津橋 浩行 和歌山県和歌山市湊1334 花王株式会社和 歌山研究所内 (72)発明者 古市 繁樹 東京都千代田区丸の内１丁目１番２号 日 本鋼管株式会社内 (72)発明者 奈良 正 東京都千代田区丸の内１丁目１番２号 日 本鋼管株式会社内 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Hiroyuki Mitsuhashi 1334 Minato Wakayama, Wakayama Prefecture Kao Corporation Wakayama Laboratory (72) Inventor Shigeki Furuichi 1-2-1, Marunouchi, Chiyoda-ku, Tokyo Co., Ltd. (72) Inventor Tadashi Nara 1-2-1, Marunouchi, Chiyoda-ku, Tokyo Nikko Steel Tube Co., Ltd.
Claims (2)
レンオキシド繰返し単位を有する数平均分子量が２００
０以上の水溶性高分子を含有することを特徴とする金属
洗浄液用ゲル化抑制剤。1. A number average molecular weight of 200 having an alkylene oxide repeating unit containing ethylene oxide in the molecule.
A gelation inhibitor for a metal cleaning liquid, which contains 0 or more water-soluble polymer.
金属洗浄方法において、該工程中に洗浄液に請求項１記
載のゲル化抑制剤を添加することを特徴とする金属洗浄
方法。2. A metal cleaning method comprising a step of immersing a metal in a cleaning solution, wherein the gelation inhibitor according to claim 1 is added to the cleaning solution during the step.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5313536A JP2973072B2 (en) | 1993-12-14 | 1993-12-14 | Gelling inhibitor and gelation suppressing method using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5313536A JP2973072B2 (en) | 1993-12-14 | 1993-12-14 | Gelling inhibitor and gelation suppressing method using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07166384A true JPH07166384A (en) | 1995-06-27 |
| JP2973072B2 JP2973072B2 (en) | 1999-11-08 |
Family
ID=18042506
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5313536A Expired - Fee Related JP2973072B2 (en) | 1993-12-14 | 1993-12-14 | Gelling inhibitor and gelation suppressing method using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2973072B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10102100A (en) * | 1996-09-30 | 1998-04-21 | Toyota Motor Corp | Water-soluble detergent |
-
1993
- 1993-12-14 JP JP5313536A patent/JP2973072B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10102100A (en) * | 1996-09-30 | 1998-04-21 | Toyota Motor Corp | Water-soluble detergent |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2973072B2 (en) | 1999-11-08 |
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