JP4703813B2 - Acid cleaning liquid and corrosion inhibitor added thereto - Google Patents
Acid cleaning liquid and corrosion inhibitor added thereto Download PDFInfo
- Publication number
- JP4703813B2 JP4703813B2 JP2000132740A JP2000132740A JP4703813B2 JP 4703813 B2 JP4703813 B2 JP 4703813B2 JP 2000132740 A JP2000132740 A JP 2000132740A JP 2000132740 A JP2000132740 A JP 2000132740A JP 4703813 B2 JP4703813 B2 JP 4703813B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- corrosion
- corrosion inhibitor
- acid cleaning
- sulfur compound
- 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.)
- Expired - Lifetime
Links
Landscapes
- Detergent Compositions (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、金属表面に付着している錆、熱延スケールなどの酸化物被膜およびボイラ、熱交換器などの金属表面に堆積した硬度成分を除去するための金属の酸洗浄液およびこれに添加する腐食抑制剤に関する。
【０００２】
【従来の技術】
従来から前記金属表面の酸化物被膜および硬度成分を除去するために、塩酸、硫酸、スルファミン酸などの無機酸や、リンゴ酸、クエン酸などの有機酸の水溶液が使用されている。しかしこれらの酸洗浄液は、酸化物被膜や硬度成分を除去するとき金属素地も腐食する。特に金属が孔食されるので、金属の品質を低下させ、ボイラや熱交換器に多大な損傷を与える。金属素地の腐食を防止する目的で腐食抑制剤が使用される。従来技術の腐食抑制剤は、第１級〜第３級アミンを単独でまたはそれらを組合せたものである。また特開昭６１−３７９８８には第４級アンモニウム塩、特公昭４３−２２１６８、特公昭４４−２６５３５、特公昭４９−１５１４４、特開昭５０−５１９３９、特公昭５２−４２５２８、特公昭５２−４２５２９にはイミダゾリン化合物がそれぞれ開示されている。
【０００３】
【発明が解決しようとする課題】
最近、排水規制が厳しくなり、酸洗浄廃液をカチオン交換樹脂を用いて処理をし、溶存した金属を吸着除去し、酸を回収する方法が採用されている。前記アミン類、イミダゾリン化合物を腐食抑制剤として酸洗浄液に添加すると、アミン類、イミダゾリン化合物中の窒素原子がプロトネーションされて陽電荷を帯びたカチオンになる。また第４級アンモニウム塩は、それ自身カチオンである。これらのカチオンを含んだ酸洗浄廃液をカチオン交換樹脂で処理すると、金属とともにこれらのカチオンがイオン交換樹脂に吸着され、イオン交換樹脂の金属吸着能力を低下させるという問題がある。さらに腐食抑制剤が再生されず、回収した酸洗浄液に新たに腐食抑制剤を添加しなければならない。
【０００４】
本発明の目的は、金属素地の腐食を抑制して金属表面に付着している酸化物被膜や硬度成分を除去し、かつカチオン交換樹脂に悪影響を及ぼさずに再生できる金属の酸洗浄液およびそれに添加される腐食抑制剤を提供することである。
【０００５】
【課題を解決するための手段】
本発明は、硫酸、塩酸、スルファミン酸およびクエン酸から選択される少なくとも１種の酸液中に、腐食抑制剤として界面活性剤と有機硫黄化合物を添加してなる鋼材（ステンレス鋼材を除く）の酸洗浄液であって、前記界面活性剤が化４に示すアニオン系界面活性剤の少なくとも１種であり、前記硫黄化合物がチオ尿素化合物、チアゾール化合物、メルカプト化合物、スルフィド化合物およびチオカルバミン酸塩から選択される少なくとも１種であることを特徴とする腐食抑制および孔食抑制に優れた鋼材の酸洗浄液である。
【０００６】
【化４】
（式中Ｒは水素または炭素数１〜１８の直鎖または分岐してもよいアルキル基を表し、Ｘはカリウムまたはナトリウムを表す。）
【０００８】
本発明に従う酸洗浄液は、腐食抑制剤として、化４に示すアニオン系界面活性剤と有機硫黄化合物とを含み、プロトネーションされる窒素原子を含まないので、本腐食抑制剤を添加した酸洗浄廃液をカチオン交換樹脂で再生する際に、金属吸着能力が低下せず、かつ酸洗浄液とともに再生される。また有機硫黄化合物を含むので腐食抑制効果が優れている。
【００１０】
有機硫黄化合物として、チオ尿素化合物、チアゾール化合物、メルカプト化合物、スルフィド化合物およびチオカルバミン酸塩の腐食抑制効果が優れていることは、本発明者らが実験によって確認したものである。
【００１１】
また本発明は、有機硫黄化合物が、チオ尿素、ジエチルチオ尿素および２−メルカプトベンゾチアゾールから選ばれる１種以上であることを特徴とする。
【００１２】
本発明に従えば、有機硫黄化合物としては、前記の各物質が入手し易く、特に好ましい。
【００１３】
また本発明は、前記酸液１Ｌ中に、化５に示すアニオン系界面活性剤１〜１００００ｍｇと、前記有機硫黄化合物１〜１００００ｍｇとを含むことを特徴とする。
【化５】
本発明に従えば、酸洗浄液１Ｌに化５に示すアニオン系界面活性剤１〜１００００ｍｇと、有機硫黄化合物とを１〜１００００ｍｇ、好ましくは５〜２０００ｍｇ添加して酸洗浄液組成物が構成される。
添加量が１ｍｇ未満では腐食抑制効果がなく、逆に１００００ｍｇを超えて添加しても腐食抑制効果は向上しない。本発明の酸洗浄液組成物は、１０〜１００℃の範囲で安定して金属の酸洗に使用できるが、特に５０℃以上で使用するときは酸洗浄液１Ｌに対して、前記腐食抑制剤組成物を５ｍｇ以上添加することが好ましく、５ｍｇ未満では孔食が発生することがある。
また本発明は、前述の腐食抑制剤が、化６に示すアニオン系界面活性剤および前記有機硫黄化合物の合計１００重量部に対し、粉末状の水溶性無機塩１０〜２０００重量部を混合した混合粉末であることを特徴とする粉末状腐食抑制剤である。
【化６】
【００１４】
本発明に従えば、前記腐食抑制剤１００重量部に対し、粉末状の水溶性無機塩１０〜２０００重量部、好ましくは、５０〜２０００重量部を混合する。粉末状の水溶性無機塩類は、前記腐食抑制剤が吸湿によって固化するのを防止する。粉末状の水溶性無機塩類の混合割合が、１０重量部未満では、粉末状腐食抑制剤の吸着による固化が充分に防げず、また２０００重量部を超えると腐食抑制能力が低下する。
【００１５】
また本発明は、粉末状の水溶性無機塩が無水硫酸ナトリウムであることを特徴とする。
【００１６】
本発明に従えば、前記粉末状の腐食抑制剤組成物としては、充分な乾燥作用を有し、酸洗浄液に容易に溶解し、かつ安価で入手し易い点から無水硫酸ナトリウムが好ましく用いられる。
【００２１】
酸洗浄液としては、特に限定されるものではないが、硫酸、塩酸、スルファミン酸などの無機酸、リンゴ酸、クエン酸などの有機酸の少なくとも１種以上を水で希釈して用いられる。
【００２２】
腐食抑制剤を構成するアニオン系界面活性剤と、有機硫黄化合物とは、使用に際して酸洗浄液に別々に添加するか予め混合しておいて添加してもよい。また濃厚な酸液に予め腐食抑制剤を添加しておき、使用に際し水で希釈してもよい。
【００２３】
本発明の酸洗浄液組成物を用いて金属表面を洗浄する方法は、特に限定されないが、金属表面に酸洗浄液組成物を噴霧するか、酸洗浄液組成物中に浸漬することが好ましい。
【００２５】
また、酸洗浄液１Ｌに前記粉末状腐食抑制剤を１０〜２００００ｍｇ、好ましくは５０〜１００００ｍｇ添加する。添加量が１０ｍｇ未満では腐食抑制剤効果がなく、２００００ｍｇを超えて添加しても腐食抑制効果は向上しない。本発明の酸洗浄液組成物は、１０〜１００℃の広範囲の温度で金属の酸洗に使用できるが、特に５０℃以上で使用するときは酸洗浄液１Ｌに対して、前記粉末状腐食抑制剤を５０ｍｇ以上添加することが好ましく、５０ｍｇ以下では孔食が発生することがある。
【００２６】
【発明の実施の形態】
以下、実施例および比較例によって、本発明にかかる酸洗浄液組成物をより具体的に説明するが、本発明はこれら実施例に限定されるものではない。
【００２７】
実施例１
硫酸１００ｇと第１鉄イオン５０ｇとを水によって１Ｌとした酸洗浄液に、本発明のアニオン系界面活性剤として、アルキル（Ｃ12）ベンゼンスルフォン酸ナトリウムを１００ｍｇ添加し、さらに有機硫黄化合物としてチオ尿素を７５ｍｇと、２−メルカプトベンゾチアゾールを７５ｍｇとを添加した。この液を７０℃まで加温した後、予め硫酸に浸漬して黒皮を除去した高炭素鋼（０．７５％Ｃ）を３０分間浸漬した。その後、腐食量を測定し、併せて孔食の有無を観察した。その結果を表１に示す。
【００２８】
実施例２
塩酸１００ｇと第１鉄イオン５０ｇとを水によって１Ｌとした酸洗浄液に、本発明のアニオン系界面活性剤として、アルキル（Ｃ12）ベンゼンスルフォン酸ナトリウムを１００ｍｇ添加し、さらに有機硫黄化合物としてチオ尿素を７５ｍｇと、２−メルカプトベンゾチアゾールとを７５ｍｇとを添加した。この液を５０℃まで加温した後、予め塩酸に浸漬して黒皮を除去した高炭素鋼（０．７５％Ｃ）を３０分間浸漬した。その後、腐食量を測定し、併せて孔食の有無を観察した。その結果を表１に示す。
【００２９】
実施例３
スルファミン酸１００ｇを溶解し、水によって１Ｌとした酸洗浄液に、本発明のアニオン系界面活性剤として、アルキル（Ｃ12）ベンゼンスルフォン酸ナトリウムを５００ｍｇ添加し、さらに有機硫黄化合物としてチオ尿素１０００ｍｇと、ジエチルチオ尿素５００ｍｇとを添加した。この液を６０℃まで加温した後、予めサンドペーパ４００番で研磨した軟鋼板（０．０８％Ｃ）を４時間浸漬した。その後、腐食量を測定し、併せて孔食の有無を観察した。その結果を表１に示す。
【００３０】
実施例４
クエン酸１００ｇを溶解し、水によって１Ｌとした酸洗浄液に、本発明のアニオン系界面活性剤として、アルキル（Ｃ12）ベンゼンスルフォン酸ナトリウムを５００ｍｇ添加し、さらに有機硫黄化合物としてチオ尿素１０００ｍｇと、ジエチルチオ尿素５００ｍｇとを添加した。この液を８０℃まで加温した後、予めサンドペーパ４００番で研磨した軟鋼板（０．０８％Ｃ）を４時間浸漬した。その後、腐食量を測定し、併せて孔食の有無を観察した。その結果を表１に示す。
【００３１】
比較例１
実施例１と同じ条件で実験を行った。ただし、本発明のアニオン系界面活性剤と有機硫黄化合物は用いていない。その結果を表１に示す。
【００３２】
比較例２
実施例２と同じ条件で実験を行った。ただし、本発明のアニオン系界面活性剤と有機硫黄化合物は用いていない。その結果を表１に示す。
【００３３】
比較例３
実施例３と同じ条件で実験を行った。ただし、本発明のアニオン系界面活性剤と有機硫黄化合物は用いていない。その結果を表１に示す。
【００３４】
比較例４
実施例４と同じ条件で実験を行った。ただし、本発明のアニオン系界面活性剤と有機硫黄化合物は用いていない。その結果を表１に示す。
【００３５】
【表１】
【発明の効果】
以上のように本発明によれば、プロトネーションされる窒素原子を含まず、かつ効果的に腐食を抑制し、孔食も生じない。
【００３７】
また本発明によれば、腐食抑制剤の吸湿、固化を防止し、かつ酸洗浄液に添加したときに容易に溶解する。
【００３８】
また本発明による酸洗浄液は前記腐食抑制剤が添加されているので、カチオン交換樹脂を用いた酸洗浄廃液の処理に際して、カチオン交換樹脂の吸着能力を低下させず、腐食抑制剤も酸洗浄液とともに再生でき、かつ充分に腐食を抑制でき、金属の酸洗コストを低減できる。[0001]
BACKGROUND OF THE INVENTION
The present invention is added, rust adhering to the metal surface, oxide coating and boilers, such as hot-rolling scale, metal acid cleaning solution to remove the hardness components deposited on the metal surfaces such as heat exchanger Contact and thereto It relates to corrosion inhibitors for.
[0002]
[Prior art]
Conventionally, aqueous solutions of inorganic acids such as hydrochloric acid, sulfuric acid and sulfamic acid and organic acids such as malic acid and citric acid have been used to remove the oxide film and hardness component on the metal surface. However, these acid cleaning solutions also corrode metal substrates when removing oxide coatings and hardness components. In particular, since the metal is pitting, the quality of the metal is deteriorated and the boiler and the heat exchanger are seriously damaged. Corrosion inhibitors are used to prevent corrosion of the metal substrate. Prior art corrosion inhibitors are primary to tertiary amines alone or in combination. JP-A-61-37988 discloses quaternary ammonium salts, JP-B 43-22168, JP-B 44-26535, JP-B 49-15144, JP-A 50-51939, JP-B 52-42528, JP-B 52- No. 42529 discloses imidazoline compounds, respectively.
[0003]
[Problems to be solved by the invention]
Recently, regulations on drainage have become stricter, and a method has been adopted in which acid cleaning waste liquid is treated with a cation exchange resin, and dissolved metals are adsorbed and removed to recover acid. When the amines and imidazoline compounds are added to the acid washing solution as a corrosion inhibitor, the nitrogen atoms in the amines and imidazoline compounds are protonated to become positively charged cations. The quaternary ammonium salt is itself a cation. When the acid cleaning waste liquid containing these cations is treated with a cation exchange resin, there is a problem that these cations are adsorbed on the ion exchange resin together with the metal, and the metal adsorption capacity of the ion exchange resin is lowered. Furthermore, since the corrosion inhibitor is not regenerated, a new corrosion inhibitor must be added to the recovered acid cleaning solution.
[0004]
An object of the present invention is to inhibit corrosion of the metal matrix to remove oxide coating and the hardness components adhered to the metal surface, and called acid washing solution up for metal that can be played without adversely affecting the cation exchange resin It is to provide a corrosion inhibitor added to it.
[0005]
[Means for Solving the Problems]
The present invention relates to a steel material (excluding stainless steel material) obtained by adding a surfactant and an organic sulfur compound as a corrosion inhibitor to at least one acid solution selected from sulfuric acid, hydrochloric acid, sulfamic acid and citric acid. An acid cleaning solution, wherein the surfactant is at least one of the anionic surfactants shown in Chemical Formula 4 , and the sulfur compound is selected from a thiourea compound, a thiazole compound, a mercapto compound, a sulfide compound, and a thiocarbamate. It is an acid cleaning solution for steel material excellent in corrosion inhibition and pitting corrosion suppression, characterized in that it is at least one kind .
[0006]
[Formula 4]
(In the formula, R represents hydrogen or a linear or branched alkyl group having 1 to 18 carbon atoms, and X represents potassium or sodium.)
[0008]
The acid cleaning liquid according to the present invention contains an anionic surfactant shown in Chemical formula 4 and an organic sulfur compound as a corrosion inhibitor, and does not contain a protonated nitrogen atom. Is regenerated with the acid cleaning solution without reducing the metal adsorption ability. Moreover, since an organic sulfur compound is contained, the corrosion inhibitory effect is excellent.
[0010]
As the organic sulfur compounds, thiourea compounds, thiazole compounds, mercapto compounds, the sulfide compound and the corrosion inhibiting effect of thiocarbamate it is excellent are those present inventors have confirmed by experiment.
[0011]
The present invention is an organic sulfur compound, characterized in that at least one selected from Chionyo arsenide, diethyl thiourea and 2-mercaptobenzothiazole.
[0012]
According to the present invention, as the organic sulfur compound, the above-mentioned substances are easily available and particularly preferable.
[0013]
Further, the present invention is characterized in that 1 L of the anionic surfactant shown in Chemical formula 5 and 1 to 10,000 mg of the organic sulfur compound are contained in 1 L of the acid solution.
[Chemical formula 5]
According to the present invention, 1 to 10000 mg of an anionic surfactant shown in Chemical Formula 5 and 1 to 10,000 mg, preferably 5 to 2000 mg of an organic sulfur compound are added to 1 L of the acid cleaning solution to constitute an acid cleaning solution composition.
If the addition amount is less than 1 mg, there is no corrosion-inhibiting effect. Conversely, even if it is added in excess of 10,000 mg, the corrosion-inhibiting effect is not improved. The pickling solution composition of the present invention can be stably used for pickling metals in the range of 10 to 100 ° C. Especially when used at 50 ° C. or higher, the corrosion inhibitor composition is used with respect to 1 L of the pickling solution. Is preferably added in an amount of 5 mg or more, and if it is less than 5 mg, pitting corrosion may occur.
The present invention is mixed corrosion inhibitor described above is that the total 100 parts by weight of the anionic surfactant and the organic sulfur compound shown in Formula 6 were mixed powdery water-soluble inorganic salts 10 to 2,000 parts by weight a powdered corrosion inhibitor, which is a powder.
[Chemical 6]
[0014]
According to the present invention, with respect to the corrosion inhibitor 1 00 parts by weight, 10 to 2000 parts by weight powdery water-soluble inorganic salt, preferably, mixing 50 to 2000 parts by weight. Powdery water-soluble inorganic salts, the corrosion inhibitor is prevented from solidifying by moisture absorption. When the mixing ratio of the powdered water-soluble inorganic salt is less than 10 parts by weight, solidification due to adsorption of the powdery corrosion inhibitor can not be sufficiently prevented, and when it exceeds 2000 parts by weight, the corrosion inhibiting ability is lowered.
[0015]
In the present invention, the powdered water-soluble inorganic salt is anhydrous sodium sulfate.
[0016]
According to the present invention, anhydrous sodium sulfate is preferably used as the powdery corrosion inhibitor composition because it has a sufficient drying action, is easily dissolved in an acid cleaning solution, and is inexpensive and easily available.
[0021]
The acid cleaning solution is not particularly limited, but is used by diluting at least one of inorganic acids such as sulfuric acid, hydrochloric acid and sulfamic acid, and organic acids such as malic acid and citric acid with water.
[0022]
The anionic surfactant that constitutes the corrosion inhibitor and the organic sulfur compound may be added separately to the acid cleaning liquid when used, or may be added in advance after mixing. Further, a corrosion inhibitor may be added in advance to a concentrated acid solution and diluted with water when used.
[0023]
The method for cleaning the metal surface using the acid cleaning liquid composition of the present invention is not particularly limited, but it is preferable to spray the acid cleaning liquid composition on the metal surface or immerse it in the acid cleaning liquid composition.
[0025]
Also, the acid cleaning solution 1L powdered corrosion inhibitor 10～20000Mg, preferably added 50～10000Mg. If the addition amount is less than 10 mg, there is no corrosion inhibitor effect, and even if it exceeds 20000 mg, the corrosion inhibition effect is not improved. The pickling solution composition of the present invention can be used for pickling metals at a wide range of temperatures from 10 to 100 ° C. Especially when used at 50 ° C. or higher, the powdered corrosion inhibitor is added to 1 L of the pickling solution. It is preferable to add 50 mg or more, and if it is 50 mg or less, pitting corrosion may occur.
[0026]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, although an acid cleaning liquid composition concerning the present invention is explained more concretely with an example and a comparative example, the present invention is not limited to these examples.
[0027]
Example 1
100 mg of sodium alkyl (C 12 ) benzenesulfonate as an anionic surfactant of the present invention is added to an acid cleaning solution in which 100 g of sulfuric acid and 50 g of ferrous ions are made 1 L with water, and thiourea is further added as an organic sulfur compound. And 75 mg of 2-mercaptobenzothiazole were added. After this solution was heated to 70 ° C., high carbon steel (0.75% C), which had been previously immersed in sulfuric acid to remove the black skin, was immersed for 30 minutes. Thereafter, the amount of corrosion was measured, and the presence or absence of pitting corrosion was also observed. The results are shown in Table 1.
[0028]
Example 2
100 mg of sodium alkyl (C 12 ) benzenesulfonate as an anionic surfactant of the present invention is added to an acid washing solution in which 100 g of hydrochloric acid and 50 g of ferrous ions are made up to 1 L with water, and thiourea is further added as an organic sulfur compound. And 75 mg of 2-mercaptobenzothiazole were added. After this solution was heated to 50 ° C., high carbon steel (0.75% C), which had been previously immersed in hydrochloric acid to remove the black skin, was immersed for 30 minutes. Thereafter, the amount of corrosion was measured, and the presence or absence of pitting corrosion was also observed. The results are shown in Table 1.
[0029]
Example 3
As an anionic surfactant of the present invention, 500 mg of sodium alkyl (C 12 ) benzenesulfonate is added to an acid washing solution in which 100 g of sulfamic acid is dissolved and made up to 1 L with water, and 1000 mg of thiourea as an organic sulfur compound, Diethylthiourea 500 mg was added. After this liquid was heated to 60 ° C., a mild steel plate (0.08% C) previously polished with sandpaper No. 400 was immersed for 4 hours. Thereafter, the amount of corrosion was measured, and the presence or absence of pitting corrosion was also observed. The results are shown in Table 1.
[0030]
Example 4
To an acid washing solution in which 100 g of citric acid is dissolved and made up to 1 L with water, 500 mg of alkyl (C 12 ) sodium benzenesulfonate is added as an anionic surfactant of the present invention, and 1000 mg of thiourea as an organic sulfur compound, Diethylthiourea 500 mg was added. After this liquid was heated to 80 ° C., a mild steel plate (0.08% C) previously polished with sandpaper No. 400 was immersed for 4 hours. Thereafter, the amount of corrosion was measured, and the presence or absence of pitting corrosion was also observed. The results are shown in Table 1.
[0031]
Comparative Example 1
The experiment was performed under the same conditions as in Example 1. However, the anionic surfactant and organic sulfur compound of the present invention are not used. The results are shown in Table 1.
[0032]
Comparative Example 2
The experiment was performed under the same conditions as in Example 2. However, the anionic surfactant and organic sulfur compound of the present invention are not used. The results are shown in Table 1.
[0033]
Comparative Example 3
The experiment was performed under the same conditions as in Example 3. However, the anionic surfactant and organic sulfur compound of the present invention are not used. The results are shown in Table 1.
[0034]
Comparative Example 4
The experiment was performed under the same conditions as in Example 4. However, the anionic surfactant and organic sulfur compound of the present invention are not used. The results are shown in Table 1.
[0035]
[Table 1]
【The invention's effect】
As described above, according to the present invention, the nitrogen atom to be protonated is not contained, corrosion is effectively suppressed, and pitting corrosion does not occur.
[0037]
According to or present invention, moisture corrosion inhibitors, that prevent caking and readily dissolves when added to the acid cleaning solution.
[0038]
Since Also acid wash solution according to the invention the corrosion inhibitor is added, during processing of acid washing waste liquid with a cation exchange resin, without reducing the suction capacity of the cation exchange resin, also acid washing liquid corrosion inhibitor In addition, it can be regenerated and corrosion can be sufficiently suppressed, and the metal pickling cost can be reduced.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000132740A JP4703813B2 (en) | 2000-05-01 | 2000-05-01 | Acid cleaning liquid and corrosion inhibitor added thereto |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000132740A JP4703813B2 (en) | 2000-05-01 | 2000-05-01 | Acid cleaning liquid and corrosion inhibitor added thereto |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001316858A JP2001316858A (en) | 2001-11-16 |
| JP4703813B2 true JP4703813B2 (en) | 2011-06-15 |
Family
ID=18641376
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000132740A Expired - Lifetime JP4703813B2 (en) | 2000-05-01 | 2000-05-01 | Acid cleaning liquid and corrosion inhibitor added thereto |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4703813B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2482223C2 (en) * | 2011-08-19 | 2013-05-20 | Государственное образовательное учреждение высшего профессионального образования "Томский государственный университет" (ТГУ) | Agent for removing rust, scum and other mineral deposits based on glyoxal and derivatives thereof |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100593668B1 (en) | 2004-01-20 | 2006-06-28 | 삼성전자주식회사 | Cleaning liquid composition and cleaning method of semiconductor device using same |
| JP4835214B2 (en) * | 2006-03-17 | 2011-12-14 | Ｊｆｅスチール株式会社 | Pickling method and manufacturing method of stainless steel |
| JP5232381B2 (en) * | 2006-11-28 | 2013-07-10 | 株式会社ネオス | Non-rinsing water-soluble cleaning composition |
| KR101561454B1 (en) * | 2013-11-14 | 2015-10-20 | (주)문성공업 | An acidic compound for cleaning metal material and acompound for adding in the same |
| CN109852977B (en) * | 2019-03-11 | 2024-02-02 | 上海新阳半导体材料股份有限公司 | Tin ball production process, cleaning agent and preparation method thereof |
| CN114622205A (en) * | 2022-03-22 | 2022-06-14 | 河北永创化工科技有限公司 | Neutralization corrosion inhibitor for refinery and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5521582A (en) * | 1978-07-31 | 1980-02-15 | Chemed Corp | Corrosion preventive composition and method thereof |
| JPS57114673A (en) * | 1980-12-29 | 1982-07-16 | Asahi Kagaku Kogyo Kk | Surface cleaning agent of cold rolled steel plate |
| JPS62260081A (en) * | 1986-05-06 | 1987-11-12 | Mitsubishi Heavy Ind Ltd | Method for chemically cleaning surface of stainless steel |
-
2000
- 2000-05-01 JP JP2000132740A patent/JP4703813B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5521582A (en) * | 1978-07-31 | 1980-02-15 | Chemed Corp | Corrosion preventive composition and method thereof |
| JPS57114673A (en) * | 1980-12-29 | 1982-07-16 | Asahi Kagaku Kogyo Kk | Surface cleaning agent of cold rolled steel plate |
| JPS62260081A (en) * | 1986-05-06 | 1987-11-12 | Mitsubishi Heavy Ind Ltd | Method for chemically cleaning surface of stainless steel |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2482223C2 (en) * | 2011-08-19 | 2013-05-20 | Государственное образовательное учреждение высшего профессионального образования "Томский государственный университет" (ТГУ) | Agent for removing rust, scum and other mineral deposits based on glyoxal and derivatives thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2001316858A (en) | 2001-11-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2839146B2 (en) | Rust removal method and composition | |
| EP0086245B1 (en) | Aqueous acid metal cleaning composition and method of use | |
| JP5691039B2 (en) | Corrosion inhibitor composition for acid cleaning | |
| JPS6039119B2 (en) | How to clean metal by spraying method | |
| US4180469A (en) | Dithiocarbamate sulfonium salt inhibitor composition | |
| JP4824925B2 (en) | Chelating agent / corrosion inhibitor composition for organic acid cleaning | |
| AU2015249410B2 (en) | Method and formulations for removing rust and scale from steel and for regenerating pickling liquor in hot-dip galvanization process | |
| JP4703813B2 (en) | Acid cleaning liquid and corrosion inhibitor added thereto | |
| US3730901A (en) | Composition and method for removing copper containing iron oxide scales from ferrous metals | |
| ES2301049T3 (en) | PROCEDURE TO ELIMINATE LASER ESCORIA. | |
| JP3207183B2 (en) | Corrosion inhibitor for acid cleaning of metal, cleaning liquid composition containing the same, and method of cleaning metal using the same | |
| JP2014114505A (en) | Derusting rust-preventive agent and derusting rust prevention method | |
| RU2627377C1 (en) | Composition for dissoluting corrosive deposits | |
| US3506576A (en) | Metal cleaning solution of chelating agent and water-soluble sulfide | |
| US3854996A (en) | Method for removing magnetite scale | |
| JPH06306652A (en) | Corrosion inhibitor for metal and corrosion inhibiting method for metal | |
| EP0858102A3 (en) | Surface treatment composition and method for treating surface of substrate by using the same | |
| CA1219119A (en) | Composition for protecting metal surfaces against corrosion | |
| MXPA06004033A (en) | Formulation for corrosion and scale inhibition. | |
| JP3199824B2 (en) | Cleaning solution for tinplate and cleaning method | |
| JP6013132B2 (en) | Corrosion inhibitor for organic acid cleaning and metal cleaning method using the corrosion inhibitor | |
| US5591270A (en) | Lead oxide removal method | |
| JP3253815B2 (en) | Cleaning method for stainless steel equipment and cleaning agent | |
| JP3398724B2 (en) | Corrosion inhibitor for metallic materials such as steel | |
| US3585142A (en) | Method of removing copper-containing incrustations from ferrous metal surfaces using an aqueous acid solution of aminoalkyl thiourea |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20070426 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20100524 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100601 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100802 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20110222 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20110309 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4703813 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |