JPH11269676A - Pickling liquid for stainless steel - Google Patents
Pickling liquid for stainless steelInfo
- Publication number
- JPH11269676A JPH11269676A JP7737098A JP7737098A JPH11269676A JP H11269676 A JPH11269676 A JP H11269676A JP 7737098 A JP7737098 A JP 7737098A JP 7737098 A JP7737098 A JP 7737098A JP H11269676 A JPH11269676 A JP H11269676A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen peroxide
- stainless steel
- acid
- weight
- pickling
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Anti-Oxidant Or Stabilizer Compositions (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ステンレス鋼の酸
洗処理液に関する。詳しくは、公害面などで問題となっ
ている硝酸を使用しないステンレス鋼の酸洗処理液に関
する。The present invention relates to a pickling treatment solution for stainless steel. More specifically, the present invention relates to a pickling treatment solution for stainless steel that does not use nitric acid, which is a problem in terms of pollution.
【０００２】[0002]
【従来の技術】従来からステンレス鋼の酸洗は、一般に
弗酸及び硝酸の混酸を使用することで行われてきた。し
かし、硝酸を用いることは、環境面、公害面で大きな問
題が生じている。すなわち、酸洗時のＮＯX ガスの発
生、高濃度の硝酸イオンを含む処理廃液による海域の汚
染等が深刻な問題となっている。このような問題に対応
するため、廃液からの硝酸イオンの除去が必要になって
おり、その技術もさることながら設備費用やランニング
コストの面で実施が極めて困難な状況にある。2. Description of the Related Art Conventionally, pickling of stainless steel has been generally performed by using a mixed acid of hydrofluoric acid and nitric acid. However, the use of nitric acid poses major environmental and pollution problems. That is, serious problems such as generation of NOx gas at the time of pickling and pollution of the sea area due to a processing waste liquid containing a high concentration of nitrate ion are caused. In order to cope with such a problem, it is necessary to remove nitrate ions from the waste liquid, and it is extremely difficult to implement the technology in terms of equipment costs and running costs, in addition to the technology.
【０００３】かかる状況下、硝酸を使用しない酸洗浴が
強く求められている。例えば特開昭６０−２４３２８９
号公報には弗酸−塩酸−過酸化水素からなるチタン、ス
テンレス鋼等の酸洗方法が開示されている。本発明者ら
の知見によると、この方法は硝酸を使用しない有効な処
方であり、特に弗酸−塩酸−過酸化水素浴はステンレス
鋼表面が均一に処理でき、硝酸−弗酸浴より酸洗速度が
速い利点を有する。Under such circumstances, there is a strong demand for a pickling bath that does not use nitric acid. For example, JP-A-60-243289
Japanese Patent Application Laid-Open Publication No. Hei 11 (1995) discloses a method for pickling titanium, stainless steel or the like made of hydrofluoric acid-hydrochloric acid-hydrogen peroxide. According to the findings of the present inventors, this method is an effective formulation without using nitric acid, and in particular, a hydrofluoric acid-hydrochloric acid-hydrogen peroxide bath can uniformly treat the surface of stainless steel, and is more pickling than a nitric acid-hydrofluoric acid bath. It has the advantage of high speed.
【０００４】しかしこの浴の致命的な欠点は、処理時浴
中での過酸化水素の分解が甚だしい点である。特にステ
ンレス鋼の溶解時の鉄、クロム、ニッケル等の金属濃度
が１０ｇ／ｌ以上では、過酸化水素の自己分解が激しく
なり、大過剰の補給が必要となり不経済となるばかりで
なく安定した浴の維持が困難となる。[0004] The fatal disadvantage of this bath, however, is that the decomposition of hydrogen peroxide in the bath during processing is severe. In particular, when the concentration of metals such as iron, chromium, and nickel at the time of melting stainless steel is 10 g / l or more, self-decomposition of hydrogen peroxide becomes severe, and a large excess of replenishment is required. Maintenance becomes difficult.
【０００５】過酸化水素を安定化する試みとして、本発
明とは基本組成を異にするが、特開昭５３−１５２２７
号公報に過酸化水素−ハロゲンイオンにを含む無機酸
（塩酸・弗酸など）−無機酸（硫酸・燐酸）浴に第４級
アンモニュウム塩を加えることが、特開平６−２１２４
６３号公報には硫酸−Ｆｅ3+−弗酸−過酸化水素（公知
の安定剤が添加されたもの）系が開示され、後者では公
知の安定剤として８−ヒドロキシキノリン、スズ酸ナト
リウム、燐酸、フェナセチンなどが例示されている。As an attempt to stabilize hydrogen peroxide, the basic composition is different from that of the present invention.
Japanese Patent Application Laid-Open No. 6-2124 discloses that a quaternary ammonium salt is added to an inorganic acid (sulfuric acid / phosphoric acid) bath containing hydrogen peroxide-halogen ions and an inorganic acid (sulfuric acid / phosphoric acid).
No. 63 discloses a sulfuric acid-Fe 3+ -hydrofluoric acid-hydrogen peroxide system (to which a known stabilizer has been added). In the latter, 8-hydroxyquinoline, sodium stannate, phosphoric acid , Phenacetin and the like.
【０００６】[0006]
【発明が解決しようとする課題】安定剤の機能として
は、単に過酸化水素を安定化させることに留まらず以下
の点が要求される。 １）酸洗能力を極端に低下させないこと。（溶解速度や
表面仕上がりへの影響が少ないこと） ２）少量の添加で有効なこと。 ３）長時間有効であること。 これらの機能を満たす安定剤は、上述した公知の安定剤
はもとより、未だ見いだされていないのが実状である。
本発明は、従来技術における上記のような課題を解決
し、硝酸を含有しない新規なステンレス鋼の酸洗液を提
供することにある。The function of the stabilizer is not limited to merely stabilizing hydrogen peroxide, but the following points are required. 1) The pickling ability should not be extremely reduced. (Must have little effect on dissolution rate and surface finish) 2) Be effective with a small amount of addition. 3) To be effective for a long time. In fact, stabilizers satisfying these functions have not yet been found, in addition to the known stabilizers described above.
An object of the present invention is to solve the above-mentioned problems in the prior art and to provide a novel stainless steel pickling solution containing no nitric acid.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、弗酸−塩
酸−過酸化水素系に着目し鋭意検討を重ねた結果、第四
成分として式（１）に示すエチレングリコールモノフェ
ニルエーテル又はポリエチレングリコールモノフェニル
エーテルを使用することで上記課題を解決できることを
見いだした。Means for Solving the Problems The present inventors have conducted intensive studies focusing on a hydrofluoric acid-hydrochloric acid-hydrogen peroxide system. As a result, ethylene glycol monophenyl ether represented by the formula (1) or It has been found that the above problem can be solved by using polyethylene glycol monophenyl ether.
【０００８】[0008]
【化２】 Embedded image
【０００９】すなわち、本発明は弗酸、塩酸、過酸化水
素及び式（１）に示すエチレングリコールモノフェニル
エーテル又はポリエチレングリコールモノフェニルエー
テル（以下「エチレングリコールモノフェニルエーテル
類」という）を含有することを特徴とするステンレス鋼
の酸洗処理液に関する。That is, the present invention comprises hydrofluoric acid, hydrochloric acid, hydrogen peroxide and ethylene glycol monophenyl ether or polyethylene glycol monophenyl ether represented by the formula (1) (hereinafter referred to as "ethylene glycol monophenyl ethers"). A pickling treatment solution for stainless steel characterized by the following characteristics:
【００１０】[0010]
【発明の実施の形態】本発明に使用する弗酸、塩酸、過
酸化水素は任意の濃度の水溶液が使用できるが、通常、
弗酸は４６重量％程度、塩酸及び過酸化水素は３５重量
％程度のものが工業薬品として入手可能な点から好まし
い。弗酸、塩酸及び過酸化水素の処理液中への初期添加
量及び保持濃度は、弗酸１〜１０重量％、塩酸０．１〜
１０重量％及び過酸化水素０．１〜５重量％となる量及
び濃度である。好ましくは、弗酸２〜４重量％、塩酸
０．５〜２重量％、過酸化水素０．５〜３重量％であ
る。弗酸、塩酸及び過酸化水素の濃度がこれらの範囲よ
り小さいと実用上必要な酸洗速度が保てなくなり、大き
いと必要以上に酸洗速度が速くなったり不経済となる。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hydrofluoric acid, hydrochloric acid and hydrogen peroxide used in the present invention can be used in any concentration.
About 46% by weight of hydrofluoric acid and about 35% by weight of hydrochloric acid and hydrogen peroxide are preferable because they can be obtained as industrial chemicals. The initial addition amount and retention concentration of hydrofluoric acid, hydrochloric acid and hydrogen peroxide to the processing solution are 1 to 10% by weight of hydrofluoric acid and 0.1 to 0.1% of hydrochloric acid.
The amount and concentration are 10% by weight and 0.1 to 5% by weight of hydrogen peroxide. Preferably, it is 2 to 4% by weight of hydrofluoric acid, 0.5 to 2% by weight of hydrochloric acid and 0.5 to 3% by weight of hydrogen peroxide. If the concentrations of hydrofluoric acid, hydrochloric acid and hydrogen peroxide are lower than these ranges, the pickling rate practically required cannot be maintained, and if it is higher, the pickling rate becomes unnecessarily high or uneconomical.
【００１１】エチレングリコールモノフェニルエーテル
類の処理液中への初期添加量及び保持濃度は、０．００
５〜１重量％、好ましくは、０．０１〜０．１重量％と
なる量及び濃度である。０．００５重量％以下では安定
剤としての機能が不十分となる。添加量が増加するに従
って良好な機能が発揮されるようになるが、過度の添加
は不経済となるばかりか、酸洗液中への溶解性の面で好
ましくない。[0011] The initial addition amount and retained concentration of ethylene glycol monophenyl ethers in the processing solution are 0.00
The amount and concentration are 5 to 1% by weight, preferably 0.01 to 0.1% by weight. When the content is less than 0.005% by weight, the function as a stabilizer becomes insufficient. As the amount of addition increases, a good function is exhibited. However, excessive addition is not only uneconomical but also unfavorable in terms of solubility in the pickling solution.
【００１２】弗酸、塩酸、過酸化水素及びエチレングリ
コールモノフェニルエーテル類は、それぞれ個別に使用
して浴を調整しても、予め混合した後調整しても良い。
予め混合する場合は過酸化水素にエチレングリコールモ
ノフェニルエーテル類を溶解、混合させて使用すると好
都合である。酸洗処理はスプレーノズル等を用いた噴射
法や、エアレーションやポンプ循環を併用した浸漬法な
ど所望の方法を適宜選択すれば良い。Hydrofluoric acid, hydrochloric acid, hydrogen peroxide and ethylene glycol monophenyl ether may be used individually to adjust the bath, or may be adjusted after mixing them in advance.
When mixing in advance, it is convenient to use ethylene glycol monophenyl ethers dissolved and mixed in hydrogen peroxide. For the pickling treatment, a desired method such as an injection method using a spray nozzle or the like or an immersion method using aeration and pump circulation may be appropriately selected.
【００１３】処理温度は室温から６０℃程度の範囲で実
施できるが、ステンレス鋼の酸洗速度と過酸化水素の安
定性の兼ね合い考慮して４０〜５０℃で処理するのが好
ましい。処理は、予め所定濃度の処理液を調整した後、
薬品の補充を行わないか、適宜補充し限界まで処理する
バッチ処理でも良いし、浴組成を一定に保つように薬品
連続的供給と排出を行う連続処理でも良い。エチレング
リコールモノフェニルエーテル類使用によって、過酸化
水素が安定化され金属濃度を高く保持できる点から連続
処理を行うのが効果的である。The treatment temperature can be in the range of room temperature to about 60 ° C., but it is preferable to perform the treatment at 40 to 50 ° C. in consideration of the pickling speed of stainless steel and the stability of hydrogen peroxide. After adjusting the processing solution at a predetermined concentration in advance,
A batch process in which the chemical is not replenished, or a chemical is replenished and processed to the limit, or a continuous process in which the chemical is continuously supplied and discharged so as to keep the bath composition constant may be used. By using ethylene glycol monophenyl ethers, it is effective to carry out continuous treatment in that hydrogen peroxide is stabilized and the metal concentration can be kept high.
【００１４】[0014]
【発明の効果】弗酸−塩酸−過酸化水素のステンレス鋼
酸洗浴に、第四成分としてエチレングリコールモノフェ
ニルエーテル類を加えることにより、環境や公害面で問
題のある硝酸を使用することなく、基本浴の性能を低下
させることなく過酸化水素の安定化を達成することがで
きる。EFFECT OF THE INVENTION By adding ethylene glycol monophenyl ethers as a fourth component to a stainless steel pickling bath of hydrofluoric acid-hydrochloric acid-hydrogen peroxide, nitric acid, which is problematic in terms of environment and pollution, can be used. Hydrogen peroxide stabilization can be achieved without degrading the performance of the basic bath.
【００１５】[0015]
【実施例】以下に本発明を実施例によって詳細に説明す
るが、本発明は実施例によって制限されるものではな
い。EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to the examples.
【００１６】実施例１ ステンレス鋼ＳＵＳ３０４を予め弗酸、塩酸、過酸化水
素を用いて溶解し、その液を用いて弗酸４重量％、塩酸
２重量％、過酸化水素３重量％、トータル金属濃度約３
５ｇ／Ｌとなるように調整し、それぞれに所定量のエチ
レングリコールモノフェニルエーテル類を添加して、４
５℃、２時間静置後の過酸化水素濃度を分析し、添加無
しの場合と比較した。エチレングリコールモノフェニル
エーテル類の添加により、金属濃度約３５ｇ／Ｌで、過
酸化水素が安定化されることがわかった。結果を第１表
に示す。Example 1 Stainless steel SUS304 was previously dissolved using hydrofluoric acid, hydrochloric acid and hydrogen peroxide, and the resulting solution was used to obtain 4% by weight of hydrofluoric acid, 2% by weight of hydrochloric acid, 3% by weight of hydrogen peroxide and total metal. Concentration about 3
It was adjusted to 5 g / L, and a predetermined amount of ethylene glycol monophenyl ether was added to each,
The hydrogen peroxide concentration after standing at 5 ° C. for 2 hours was analyzed and compared with the case without addition. It was found that the addition of ethylene glycol monophenyl ether stabilizes hydrogen peroxide at a metal concentration of about 35 g / L. The results are shown in Table 1.
【００１７】実施例２ 弗酸４重量％、塩酸２重量％あるいは１重量％、過酸化
水素１重量％あるいは３重量％となる液を調整し、ステ
ンレス鋼ＳＵＳ３０４の溶解速度を測定した。安定剤と
して、エチレングリコールモノフェニルエーテル類を添
加しても、未添加と比べて、溶解速度は、殆ど変化しな
かった。結果を第２表に示す。Example 2 A solution containing 4% by weight of hydrofluoric acid, 2% by weight or 1% by weight of hydrochloric acid, and 1% by weight or 3% by weight of hydrogen peroxide was prepared, and the dissolution rate of stainless steel SUS304 was measured. Even when ethylene glycol monophenyl ethers were added as a stabilizer, the dissolution rate hardly changed as compared with when no ethylene glycol monophenyl ether was added. The results are shown in Table 2.
【００１８】[0018]
【表１】 [Table 1]
【００１９】[0019]
【表２】 [Table 2]
───────────────────────────────────────────────────── フロントページの続き (72)発明者 下村 正 東京都葛飾区新宿６丁目１番１号 三菱瓦 斯化学株式会社東京研究所内 ──────────────────────────────────────────────────続 き Continued on front page (72) Inventor Tadashi Shimomura 6-1-1 Shinjuku, Katsushika-ku, Tokyo Mitsubishi Gas Chemical Co., Ltd. Tokyo Research Laboratory
Claims (2)
表されるエチレングリコールモノフェニルエーテル又は
ポリエチレングリコールモノフェニルエーテルを含有す
ることを特徴とするステンレス鋼の酸洗処理液。 【化１】 1. A pickling treatment solution for stainless steel comprising hydrofluoric acid, hydrochloric acid, hydrogen peroxide and ethylene glycol monophenyl ether or polyethylene glycol monophenyl ether represented by the formula (1). Embedded image
０重量％、過酸化水素が０．１〜３重量％及び式（１）
で表されるエチレングリコールモノフェニルエーテル又
はポリエチレングリコールモノフェニルエーテルが０．
０１〜０．１重量％である請求項１記載のステンレス鋼
の酸洗処理液。2. Hydrofluoric acid is 1 to 4% by weight, hydrochloric acid is 0.1 to 1% by weight.
0% by weight, 0.1 to 3% by weight of hydrogen peroxide and the formula (1)
Of ethylene glycol monophenyl ether or polyethylene glycol monophenyl ether represented by
The pickling treatment solution for stainless steel according to claim 1, wherein the amount is from 0.1 to 0.1% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7737098A JPH11269676A (en) | 1998-03-25 | 1998-03-25 | Pickling liquid for stainless steel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7737098A JPH11269676A (en) | 1998-03-25 | 1998-03-25 | Pickling liquid for stainless steel |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11269676A true JPH11269676A (en) | 1999-10-05 |
Family
ID=13632022
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7737098A Pending JPH11269676A (en) | 1998-03-25 | 1998-03-25 | Pickling liquid for stainless steel |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11269676A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005036288A (en) * | 2003-07-16 | 2005-02-10 | Asahi Denka Kogyo Kk | Pickling bath composition for metal surface |
| US20090017636A1 (en) * | 2007-07-13 | 2009-01-15 | Tokyo Ohka Kogyo Co., Ltd. | Titanium nitride-stripping liquid, and method for stripping titanium nitride coating film |
-
1998
- 1998-03-25 JP JP7737098A patent/JPH11269676A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005036288A (en) * | 2003-07-16 | 2005-02-10 | Asahi Denka Kogyo Kk | Pickling bath composition for metal surface |
| US20090017636A1 (en) * | 2007-07-13 | 2009-01-15 | Tokyo Ohka Kogyo Co., Ltd. | Titanium nitride-stripping liquid, and method for stripping titanium nitride coating film |
| US8623236B2 (en) * | 2007-07-13 | 2014-01-07 | Tokyo Ohka Kogyo Co., Ltd. | Titanium nitride-stripping liquid, and method for stripping titanium nitride coating film |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4172662B2 (en) | Metal surface treatment method | |
| JP2700061B2 (en) | Method of forming phosphate film | |
| US3140203A (en) | Method of and composition for treating aluminum and aluminum alloys | |
| CN110592604A (en) | Environment-friendly bright pickling agent and preparation method thereof | |
| CN112111740A (en) | Removing liquid for nickel-phosphorus coating, preparation method and removing method for nickel-phosphorus coating | |
| JPH11269676A (en) | Pickling liquid for stainless steel | |
| JPH09217184A (en) | Pickling treatment liquid | |
| US4678541A (en) | Baths and process for chemical polishing of stainless steel surfaces | |
| US4636368A (en) | Stabilized acidic aqueous solutions containing hydrogen peroxide and metallic ions and processes | |
| JP3160051B2 (en) | Pickling accelerator, pickling liquid composition containing pickling accelerator, and method for promoting pickling of metal using the same | |
| JPH09228082A (en) | Pickling solution for stainless steel | |
| KR100666527B1 (en) | Pickling stainless steel in the absence of nitric acid | |
| US3094489A (en) | Method and composition for brightening aluminum | |
| JP3378033B2 (en) | Chemical polishing liquid for brass | |
| EP2809831B1 (en) | Use of nitrogen compounds in the pickling of stainless steel | |
| JPH09241872A (en) | Pickling solution for stainless steel | |
| JP3361680B2 (en) | Surface treatment solution for copper or copper alloy | |
| JP3907245B2 (en) | Stabilization method of acidic hydrogen peroxide solution containing iron | |
| JPS58110682A (en) | Pickling method for stainless steel with suppressed generation of nox | |
| KR900003471B1 (en) | Aqueous solution of alkali metal compositions and adding method | |
| EP0599903A1 (en) | Hydrofluoric acid compositions. | |
| JPH01215993A (en) | Additive for pickling acid solution | |
| WO1999032690A1 (en) | Pickling process with at least two steps | |
| JP3042912B2 (en) | Pickling accelerator, pickling liquid composition containing pickling accelerator, and method for accelerating metal pickling using the same | |
| WO2021090582A1 (en) | Method for suppressing decrease in concentration of oxidizing agent in sulfuric acid solution containing persulfuric acid component |