WO2021044605A1 - Smut remover, method for producing same, and smut removal method using same - Google Patents

Smut remover, method for producing same, and smut removal method using same Download PDF

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Publication number
WO2021044605A1
WO2021044605A1 PCT/JP2019/035096 JP2019035096W WO2021044605A1 WO 2021044605 A1 WO2021044605 A1 WO 2021044605A1 JP 2019035096 W JP2019035096 W JP 2019035096W WO 2021044605 A1 WO2021044605 A1 WO 2021044605A1
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Prior art keywords
smut
remover
alkali
polyhydric phenol
steel material
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PCT/JP2019/035096
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French (fr)
Japanese (ja)
Inventor
敏史 上恐
勇介 藤井
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朝日化学工業株式会社
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Application filed by 朝日化学工業株式会社 filed Critical 朝日化学工業株式会社
Priority to PCT/JP2019/035096 priority Critical patent/WO2021044605A1/en
Priority to JP2019571093A priority patent/JPWO2021044605A1/ja
Priority to KR1020207002973A priority patent/KR102201059B1/en
Priority to CN201980003766.6A priority patent/CN112771208A/en
Publication of WO2021044605A1 publication Critical patent/WO2021044605A1/en

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C23G1/19—Iron or steel
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
    • C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
    • C23G5/032—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing oxygen-containing compounds

Definitions

  • the present invention relates to a smut remover for removing smut generated on the surface of a steel material after pickling the steel material, a method for producing the same, and a method for removing smut using the same.
  • the descale treatment of the hot-rolled steel strip is performed by immersing the steel strip in an acid solution such as hydrochloric acid or sulfuric acid.
  • an acid solution such as hydrochloric acid or sulfuric acid.
  • the scale itself dissolves in the acid solution, or the acid solution reaches the surface of the steel material through cracks in the scale, causing metal dissolution and hydrogen generation, and the scale is desorbed from the surface of the steel material.
  • the acid solution is rinsed with warm water and dried, but at this time, a black insoluble residue called smut may adhere to the surface of the steel material.
  • This smut is a general term for black and brown substances that firmly adhere to the steel surface when the scale and steel strip base are melted by pickling, and the carbon contained in the steel is in the form of fine powder. It is also considered that iron ions during pickling are reprecipitated on the surface of the steel sheet as iron oxide or iron hydroxide during washing and drying with water.
  • Adhesion of smut darkens the color tone of the steel sheet and causes color unevenness, and if smut remains on the surface, it adversely affects the lubrication treatment and various surface treatments in the subsequent process, and significantly reduces the value of the steel material. It becomes necessary to remove the smut.
  • Patent Document 1 a method of removing smut by immersing a steel material in a nitric acid aqueous solution containing 400 g / L or more of HNO 3 at 25 to 80 ° C. after washing with sulfuric acid
  • Patent Document 2 A method in which the alkaline agent of No. 1 and an oxidizing agent such as perchloric acid or permanganate are combined (Non-Patent Document 1 and Patent Document 2), the pH value is adjusted to 4 to 9, 0.5 to 10%.
  • Patent Document 3 A method of treating with an aqueous solution of phosphonate
  • Patent Document 4 a rust cleaning agent such as iron or copper whose pH is adjusted to 8 to 10 by combining a polyhydric phenol such as gallic acid or tannic acid with an alkaline agent such as sodium hydroxide.
  • Patent Document 1 The method of Patent Document 1 is not preferable because it has a problem of environmental pollution due to the generation of NO X due to nitric acid and also dissolves not only the smut but also the surface of the steel material.
  • Non-Patent Document 1 has a problem that it has a large environmental load
  • Patent Document 2 is characterized in that the solution after removing the smut is regenerated by electrolytic oxidation and recycled and reused, but manganese is used. It is a heavy metal, and the problem of environmental load remains. In addition, it takes time and effort to treat the treatment liquid such as reusing and reusing and washing water after the smut treatment, which requires a great deal of cost. Moreover, there is a high possibility that the use of such heavy metals will be prohibited in the future.
  • Patent Document 3 has a relatively small environmental load, but has a problem that sufficient smut removal ability cannot be obtained.
  • the method of Patent Document 4 has a problem that, apart from slight iron rust, the effect of removing the strongly adhered smut cannot be obtained.
  • the present inventors have surprisingly found that the redox potential is -250 mV in a solution of polyhydric phenol and alkali.
  • the following inventions have been found to have an excellent smut removing effect, and the present invention has been completed.
  • the present invention is a smut remover containing polyhydric phenol and alkali, having a pH of more than 10 and a redox potential of ⁇ 250 mV or less.
  • the present invention is characterized in that the polyhydric phenol is at least one selected from hydroquinone, pyrogallol, gallic acid and tannic acid.
  • the present invention is characterized in that the alkali is at least one selected from alkali metal hydroxide, alkali metal salt, ammonia and organic amine.
  • the present invention is characterized by further containing divalent iron ions.
  • the present invention is a method for producing a smut remover, which comprises mixing a polyhydric phenol and an alkali to produce a smut remover having a pH of more than 10 and an oxidation-reduction potential of ⁇ 250 mV or less. ..
  • a smut remover having a pH of more than 10 and an oxidation-reduction potential of ⁇ 250 mV or less, which is produced by mixing polyhydric phenol and alkali, is brought into contact with a steel material after pickling.
  • a method for removing a smut of a steel material which comprises removing the smut adhering to the steel material.
  • the present invention is a smut remover containing polyhydric phenol and alkali, having a pH of more than 10 and a redox potential of ⁇ 250 mV or less. Therefore, the redox potential firmly adheres to the steel material. It is possible to strongly remove the smut that has been removed.
  • the present invention is a smut remover containing polyhydric phenol and alkali, having a pH of more than 10 and an oxidation-reduction potential of -250 mV or less, and can be used for acid cleaning of metals such as carbon steel and alloy steel.
  • examples of the polyvalent phenol include compounds having two or more phenolic hydroxyl groups in the aromatic ring.
  • Examples of the compound having two or more phenolic hydroxyl groups in the aromatic ring include compounds having two or more hydroxyl groups in the benzene ring, and specific examples thereof include divalent phenols such as hydroquinone, catechol, and resorcinol. Examples thereof include trivalent phenols such as pyrogallol and fluororesorcinol.
  • the polyhydric phenol of the present invention may be a polyhydric phenolcarboxylic acid having two or more hydroxyl groups on the benzene ring and further having a carboxyl group, and examples of the polyhydric phenolcarboxylic acid include dihydroxybenzoic acid.
  • examples thereof include dihydric phenolcarboxylic acids such as dihydroxyphenylacetic acid, caffeic acid, hydroxysalicylic acid, protocatechuic acid, gentidic acid and orseric acid, and trivalent phenolcarboxylic acids such as gallic acid.
  • the polyhydric phenol of the present invention may be a condensate of the polyhydric phenol or the polyhydric phenol carboxylic acid, and such condensate includes elladic acid, tannic acid, epigallocatechin gallate, quercetin, galocatechol, Epigallocatechin gallate and the like can be mentioned.
  • hydroquinone, pyrogallol, gallic acid, and tannic acid are preferable, and pyrogallol, gallic acid, and tannic acid are particularly preferable, in order to obtain a more remarkable smut removing effect.
  • One type of these polyhydric phenols may be used alone, or two or more types may be used in combination.
  • the alkali constituting the smut remover together with the polyhydric phenol is not particularly limited as long as the pH of the smut remover can be a pH exceeding 10, and is commonly used in this technical field. Can be preferably used. Specific examples thereof include alkali metal hydroxides, alkali metal salts, ammonia and organic amines. One type of these alkalis may be used alone, or two or more types may be used in combination.
  • alkali metal hydroxide examples include sodium hydroxide, potassium hydroxide, lithium hydroxide and the like
  • alkali metal salt examples include sodium carbonate and potassium carbonate.
  • ammonia examples include aqueous ammonia solutions
  • examples of organic amines include alkanolamines and alkylamines.
  • alkanolamines include monomethanolamine, dimethanolamine, trimethanolamine, monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, monoisopropanolamine, methylethanolamine, dimethylethanolamine, methyldiethanolamine, ethylethanolamine, etc.
  • Those with 1 to 9 carbon atoms such as diethylethanolamine, ethyldiethanolamine, N-methylpropanolamine, N-dimethylethanolamine, 2-amino-2-methyl-1-propanol, trishydroxyaminomethane, triisopanolamine, etc. can give.
  • alkylamine examples include primary amines having 1 to 6 carbon atoms, secondary amines, tertiary amines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine and cyclohexylamine, and further.
  • a quaternary ammonium salt such as an aqueous solution of tetramethylammonium hydroxide can also be preferably used.
  • sodium hydroxide, sodium carbonate, and monoethanolamine are preferable because they are excellent in smut removal property.
  • One type of these alkalis may be used alone, or two or more types may be used in combination.
  • the polyhydric phenol is contained in an amount of 0.5% by mass to 40% by mass, preferably 1.0% by mass to 40% by mass, particularly 2.0% by mass or more, based on the total amount of the smut remover. It is preferably contained in an amount of 40% by mass.
  • the alkali may contain an amount such that the pH of the smut remover exceeds 10 and preferably contains an amount having a pH of 11 or more, particularly a pH of 14, and the above-mentioned alkali.
  • the desired pH can be obtained by appropriately selecting and blending from the above.
  • the redox potential of the smut remover of the present invention is ⁇ 250 mV or less, preferably ⁇ 300 mV or less, and particularly preferably ⁇ 400 mV or less, from the viewpoint of smut removal.
  • a smut remover having a pH of more than 10 and a redox potential of ⁇ 250 mV or less can be obtained.
  • an excellent smut removing effect can be obtained by containing a polyhydric phenol and an alkali and setting the pH and the oxidation-reduction potential in the numerical ranges as described above.
  • the smut remover may be prepared by appropriately mixing a desired polyhydric phenol and an alkali to prepare a solution or a mixed solution, and the pH of the solution and the oxidation-reduction potential may be adjusted, even if there is no specific example.
  • the present invention can be easily carried out, and its smut removing effect can be confirmed.
  • the smut remover of the present invention can remove the oil adhering to the steel material, it can also be used as a degreasing agent (cleaning agent) for the steel material, and both the oil and the smut can be removed. It is convenient for treating steel materials with smut.
  • the smut remover of the present invention can be produced by mixing polyhydric phenol and alkali so as to have a predetermined concentration range and pH, so that the alkaline solution before mixing is used for degreasing steel materials. After that, the polyhydric phenol can be added to the alkaline solution to remove the smut as a smut remover.
  • divalent iron ions When divalent iron is added to the smut remover of the present invention, it lowers its redox potential, which is convenient for removing smut.
  • divalent iron When divalent iron is contained, the content thereof is not particularly limited, but the smut remover before contact with the steel material contains 1 to 100,000 ppm, preferably 1 to 50,000 ppm, based on the entire smut remover. In particular, it is preferably contained in an amount of 1 to 10000 ppm.
  • the divalent iron is eluted from the steel material to be treated in the process of removing the smut of the present invention and is present in the smut removing agent. Therefore, in the smut remover of the present invention, the inclusion of divalent iron means that the smut remover before contact with the steel material is contained by adding divalent iron, and the smut remover of the present invention is contained. It also includes containing divalent iron eluted from the steel material when the steel material is brought into contact with the steel material (including both those containing divalent iron and those not containing divalent iron).
  • the smut remover of the present invention can further contain a chelating agent, a surfactant, a water-soluble organic solvent, etc. in addition to the polyhydric phenol and the alkali.
  • a chelating agent aminocarboxylic acid, oxycarboxylic acid, nitrilotriacetic acid and the like can be used, and as the surfactant, a nonionic surfactant, anionic activator and the like can be used.
  • the water-soluble organic solvent a glycol-based solvent, an alcohol-based solvent, or the like can be used.
  • chelating agents are preferable because they are effective not only in removing smut but also in degreasing steel materials.
  • the smut remover of the present invention can be produced by mixing a polyhydric phenol and an alkali in a solvent, and the mixture may be mixed immediately before contact with a steel material, or may be mixed in advance.
  • a solution in which valent phenol and alkali are mixed may be prepared.
  • the solvent is preferably water, and other than water, a water-soluble organic solvent such as a glycol solvent or an alcohol solvent may be contained.
  • the smut remover of the present invention contains divalent iron
  • a chelating agent, a surfactant, a water-soluble organic solvent, etc. a polyhydric phenol and an alkali
  • divalent iron, a chelating agent, a surfactant, a water-soluble organic solvent and the like may be added simultaneously or sequentially and mixed.
  • the polyvalent phenol and the alkali may be dissolved by adding them to separate solvents, and the dissolved solutions may be mixed, or one of the polyvalent phenol and the alkali may be dissolved in the solvent and then the other. Ingredients may be added and dissolved, or polyhydric phenol and alkali may be added to the solvent at the same time and mixed. Mixing can be carried out at room temperature or at warm temperature.
  • the smut removing method of the present invention can be carried out by bringing the smut removing agent into contact with the steel material after pickling.
  • the contact method is not particularly limited as long as the smut on the surface of the steel material can sufficiently contact the smut remover.
  • the pickled steel material may be immersed in a smut remover, or the pickled steel material may be sprayed or coated with a smut remover.
  • the contact between the steel material and the smut remover after pickling can be carried out at room temperature or warming, for example, 20 to 90 ° C., and the contact time varies depending on the contact method, the amount of smut fixed and the state of sticking.
  • the dipping method it can be carried out at 70 ° C. for about 5 to 30 minutes.
  • ⁇ Evaluation method> First, a carbon steel (30 mm square, 2 mm thick) to which scale was attached was immersed in 10% by mass sulfuric acid at 70 ° C. for 30 minutes to remove the scale and generate a smut. Then, the acid adhering to the carbon steel was washed with tap water. After washing with water, the surface of the carbon steel was dried with a dryer to prepare the carbon steel to which the smut was attached.
  • the carbon steel to which the smut was attached prepared in the above step was immersed in 150 mL of each agent shown in Table 1 in a 200 mL beaker.
  • the immersion temperature was 70 ° C. and the immersion time was 10 minutes.
  • the carbon steel is taken out, washed with tap water, and the state of the carbon steel surface after drying with a dryer is measured by the spectrophotometer (manufactured by Konica Minolta Co., Ltd., CM-512m3A) at an irradiation angle of 45 degrees. Evaluated at.
  • the L value before removing the smut was 40.
  • the judgment method was set to ⁇ , ⁇ , and ⁇ in order from the one with the best evaluation according to the following criteria.
  • ⁇ L value 60 or more
  • ⁇ L value 50 or more and less than 60
  • ⁇ L value less than 50
  • Examples 1-10 The smut remover of Examples 1 to 10 was produced by dissolving the polyhydric phenol and the alkali shown in Table 1 in water so as to have the concentrations shown in Table 1.
  • the obtained smut remover had an oxidation-reduction potential and pH as shown in Table 1.
  • evaluation was performed according to the above evaluation method, and the smut removal effect was confirmed.
  • Comparative Examples 1 to 8 The smut removers of Comparative Examples 1 to 8 were produced by dissolving each component shown in Table 1 in water so as to have the concentration shown in Table 1. The obtained composition had an oxidation-reduction potential and pH as shown in Table 1. Using the obtained compositions of Comparative Examples 1 to 8, evaluation was performed according to the same evaluation method as in Examples, and the smut removing effect was confirmed.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
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  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

Abstract

The purpose of the present invention is to provide a smut remover which can strongly remove smuts generated on a steel material after acid pickling and has small environmental load. A smut remover characterized by comprising a polyhydric phenol and an alkali, having a pH value of more than 10, and also having an oxidation-reduction potential of -250 mV or less; a method for producing the smut remover; and a smut removal method using the smut remover.

Description

スマット除去剤、その製造方法およびそれを用いるスマット除去方法Smut remover, its manufacturing method and smut removal method using it
　本発明は、鋼材の酸洗後、鋼材表面に生ずるスマットを除去するスマット除去剤、その製造方法およびそれを用いるスマット除去方法に関する。 The present invention relates to a smut remover for removing smut generated on the surface of a steel material after pickling the steel material, a method for producing the same, and a method for removing smut using the same.
　熱延鋼帯の脱スケール処理、いわゆる「酸洗」は、塩酸、硫酸などの酸液に鋼帯を浸漬して行う。酸洗時には、スケール自体が酸液へ溶解し、あるいはスケール中の亀裂を通って酸液が鋼材表面に到達し金属の溶解と水素発生が起こり、スケールが鋼材表面から脱離する。 The descale treatment of the hot-rolled steel strip, so-called "pickling", is performed by immersing the steel strip in an acid solution such as hydrochloric acid or sulfuric acid. During pickling, the scale itself dissolves in the acid solution, or the acid solution reaches the surface of the steel material through cracks in the scale, causing metal dissolution and hydrogen generation, and the scale is desorbed from the surface of the steel material.
　酸洗後は、酸液を温水で洗い流し乾燥させるが、このとき鋼材表面にスマットといわれる黒色の不溶解性残渣が付着することがある。 After pickling, the acid solution is rinsed with warm water and dried, but at this time, a black insoluble residue called smut may adhere to the surface of the steel material.
　このスマットは、酸洗によりスケール、鋼帯素地が溶解した際に、鋼表面に強固に付着する黒色や茶褐色の物質の総称であり、鉄鋼に含まれていた炭素が微粉末状になったものや、酸洗中の鉄イオンが水洗乾燥時に酸化鉄や水酸化鉄として鋼板表面に再析出したものからなると考えられている。 This smut is a general term for black and brown substances that firmly adhere to the steel surface when the scale and steel strip base are melted by pickling, and the carbon contained in the steel is in the form of fine powder. It is also considered that iron ions during pickling are reprecipitated on the surface of the steel sheet as iron oxide or iron hydroxide during washing and drying with water.
　スマットの付着は鋼板の色調を暗くするとともに、色むらを生じさせるほか、スマットが表面に残留していると、後工程の潤滑処理や各種表面処理に悪影響を与え、鋼材価値を著しく下げるため、スマットを除去する必要が生ずる。 Adhesion of smut darkens the color tone of the steel sheet and causes color unevenness, and if smut remains on the surface, it adversely affects the lubrication treatment and various surface treatments in the subsequent process, and significantly reduces the value of the steel material. It becomes necessary to remove the smut.
　スマット除去方法としては、鋼材を硫酸酸洗後、４００ｇ／Ｌ以上のＨＮＯ３を含有する２５～８０℃の硝酸水溶液中に浸漬してスマット除去を行う方法（特許文献１）、水酸化ナトリウムなどのアルカリ剤と、過塩素酸や過マンガン酸塩などの酸化剤と、を組み合わせた方法（非特許文献１、特許文献２）、ｐＨ値を４～９に調整した、０．５～１０％のホスホン酸塩水溶液で処理をする方法（特許文献３）が知られている。また、スマット除去方法ではないが、没食子酸やタンニン酸などの多価フェノールと、水酸化ナトリウムなどのアルカリ剤と、を組み合わせ、ｐＨを８～１０に調整した鉄や銅などの錆び洗浄剤（特許文献４）が知られている。 As a method for removing smut, a method of removing smut by immersing a steel material in a nitric acid aqueous solution containing 400 g / L or more of HNO 3 at 25 to 80 ° C. after washing with sulfuric acid (Patent Document 1), sodium hydroxide, etc. A method in which the alkaline agent of No. 1 and an oxidizing agent such as perchloric acid or permanganate are combined (Non-Patent Document 1 and Patent Document 2), the pH value is adjusted to 4 to 9, 0.5 to 10%. A method of treating with an aqueous solution of phosphonate (Patent Document 3) is known. In addition, although it is not a method for removing smut, a rust cleaning agent such as iron or copper whose pH is adjusted to 8 to 10 by combining a polyhydric phenol such as gallic acid or tannic acid with an alkaline agent such as sodium hydroxide ( Patent Document 4) is known.
特開昭６１－６９９８９号公報Japanese Unexamined Patent Publication No. 61-69089 特開平６－３３０３５９号公報Japanese Unexamined Patent Publication No. 6-330359 特許第３２０７６３６号公報Japanese Patent No. 3207636 特開２００３－３４２７６２号公報Japanese Unexamined Patent Publication No. 2003-342762
　特許文献１の方法は、硝酸に起因するＮＯＸの発生による環境汚染の問題があり、また、スマットだけではなく鋼材表面も溶解するため、好ましくない。 The method of Patent Document 1 is not preferable because it has a problem of environmental pollution due to the generation of NO X due to nitric acid and also dissolves not only the smut but also the surface of the steel material.
　非特許文献１の方法は、環境負荷が大きいという問題があり、特許文献２の方法は、スマット除去後の溶液を電解酸化で再生して、循環再使用することを特徴としているものの、マンガンは重金属であり、環境負荷の問題が残る。加えて再生再使用など処理液やスマット処理後の水洗水の処理、手間を要し多大な経費を要する。しかも、将来的にはこのような重金属の使用が禁止されるおそれが多分にある。 The method of Non-Patent Document 1 has a problem that it has a large environmental load, and the method of Patent Document 2 is characterized in that the solution after removing the smut is regenerated by electrolytic oxidation and recycled and reused, but manganese is used. It is a heavy metal, and the problem of environmental load remains. In addition, it takes time and effort to treat the treatment liquid such as reusing and reusing and washing water after the smut treatment, which requires a great deal of cost. Moreover, there is a high possibility that the use of such heavy metals will be prohibited in the future.
　特許文献３の方法は、環境負荷は比較的小さいが、十分なスマット除去能力が得られないという問題がある。加えて、特許文献４の方法では、軽微な鉄錆びはともかく、強固に付着したスマットを除去するという効果が得られないという問題がある。 The method of Patent Document 3 has a relatively small environmental load, but has a problem that sufficient smut removal ability cannot be obtained. In addition, the method of Patent Document 4 has a problem that, apart from slight iron rust, the effect of removing the strongly adhered smut cannot be obtained.
　本発明者らは、環境負荷が小さく、スマット除去効果に優れたスマット除去剤について、鋭意研究を重ねた結果、全く意外にも、多価フェノールとアルカリとの溶液において、酸化還元電位が－２５０ｍＶ以下のものが優れたスマット除去効果を有することを見出し、本発明を完成した。 As a result of intensive research on a smut remover having a small environmental load and an excellent smut removing effect, the present inventors have surprisingly found that the redox potential is -250 mV in a solution of polyhydric phenol and alkali. The following inventions have been found to have an excellent smut removing effect, and the present invention has been completed.
　本発明は、多価フェノールとアルカリとを含み、ｐＨが１０を超えかつ酸化還元電位が－２５０ｍＶ以下であることを特徴とするスマット除去剤である。 The present invention is a smut remover containing polyhydric phenol and alkali, having a pH of more than 10 and a redox potential of −250 mV or less.
　また、本発明は、多価フェノールが、ヒドロキノン、ピロガロール、没食子酸およびタンニン酸から選ばれる少なくとも１種以上であることを特徴とする。 Further, the present invention is characterized in that the polyhydric phenol is at least one selected from hydroquinone, pyrogallol, gallic acid and tannic acid.
　また、本発明は、アルカリが、水酸化アルカリ金属、アルカリ金属塩、アンモニア、有機アミンから選ばれる少なくとも１種以上であることを特徴とする。 Further, the present invention is characterized in that the alkali is at least one selected from alkali metal hydroxide, alkali metal salt, ammonia and organic amine.
　また、本発明は、さらに２価の鉄イオンを含有することを特徴とする。 Further, the present invention is characterized by further containing divalent iron ions.
　また、本発明は、多価フェノールとアルカリとを混合して、ｐＨが１０を超えかつ酸化還元電位が－２５０ｍＶ以下のスマット除去剤を製造することを特徴とするスマット除去剤の製造方法である。 Further, the present invention is a method for producing a smut remover, which comprises mixing a polyhydric phenol and an alkali to produce a smut remover having a pH of more than 10 and an oxidation-reduction potential of −250 mV or less. ..
　また、本発明は、多価フェノールとアルカリとを混合して製造された、ｐＨが１０を超えかつ酸化還元電位が－２５０ｍＶ以下のスマット除去剤と、酸洗処理後の鋼材とを接触させて、該鋼材に付着したスマットを除去することを特徴とする鋼材のスマット除去方法である。 Further, in the present invention, a smut remover having a pH of more than 10 and an oxidation-reduction potential of −250 mV or less, which is produced by mixing polyhydric phenol and alkali, is brought into contact with a steel material after pickling. , A method for removing a smut of a steel material, which comprises removing the smut adhering to the steel material.
　本発明は、多価フェノールとアルカリとを含み、ｐＨが１０を超えかつ酸化還元電位が－２５０ｍＶ以下であることを特徴とするスマット除去剤であるので、その酸化還元電位により鋼材に強固に固着したスマットを強力に除去することができる。 The present invention is a smut remover containing polyhydric phenol and alkali, having a pH of more than 10 and a redox potential of −250 mV or less. Therefore, the redox potential firmly adheres to the steel material. It is possible to strongly remove the smut that has been removed.
　また、本発明によれば、環境汚染の問題がある硝酸や環境負荷の大きい過塩素酸塩や過マンガン酸塩を用いないので、環境負荷が小さいという利点がある。 Further, according to the present invention, since nitric acid, which has a problem of environmental pollution, and perchlorate and permanganate, which have a large environmental load, are not used, there is an advantage that the environmental load is small.
　本発明は、多価フェノールとアルカリとを含み、ｐＨ１０を超えかつ酸化還元電位が－２５０ｍＶ以下のスマット除去剤であり、炭素鋼、合金鋼等の金属の酸洗浄に用いることができる。 The present invention is a smut remover containing polyhydric phenol and alkali, having a pH of more than 10 and an oxidation-reduction potential of -250 mV or less, and can be used for acid cleaning of metals such as carbon steel and alloy steel.
　本発明において、多価フェノールとしては、芳香環に２個以上のフェノール性水酸基を有する化合物があげられる。 In the present invention, examples of the polyvalent phenol include compounds having two or more phenolic hydroxyl groups in the aromatic ring.
　前記芳香環に２個以上のフェノール性水酸基を有する化合物としては、たとえばベンゼン環に２個以上の水酸基を有する化合物があげられ、具体的には、たとえばヒドロキノン、カテコール、レゾルシノールなどの二価フェノール、ピロガロール、フロログルシノールなどの三価フェノールなどがあげられる。 Examples of the compound having two or more phenolic hydroxyl groups in the aromatic ring include compounds having two or more hydroxyl groups in the benzene ring, and specific examples thereof include divalent phenols such as hydroquinone, catechol, and resorcinol. Examples thereof include trivalent phenols such as pyrogallol and fluororesorcinol.
　本発明の多価フェノールは、ベンゼン環に２個以上の水酸基を有しさらにカルボキシル基を有する多価フェノールカルボン酸であってもよく、かかる多価フェノールカルボン酸としては、たとえば、ジヒドロキシ安息香酸、ジヒドロキシフェニル酢酸、カフェイン酸、ヒドロキシサリチル酸、プロトカテク酸、ゲンチジン酸、オルセリン酸などの二価フェノールカルボン酸、没食子酸などの三価フェノールカルボン酸があげられる。 The polyhydric phenol of the present invention may be a polyhydric phenolcarboxylic acid having two or more hydroxyl groups on the benzene ring and further having a carboxyl group, and examples of the polyhydric phenolcarboxylic acid include dihydroxybenzoic acid. Examples thereof include dihydric phenolcarboxylic acids such as dihydroxyphenylacetic acid, caffeic acid, hydroxysalicylic acid, protocatechuic acid, gentidic acid and orseric acid, and trivalent phenolcarboxylic acids such as gallic acid.
　本発明の多価フェノールは、前記多価フェノールまたは多価フェノールカルボン酸の縮合物であってもよく、かかる縮合物としては、エラジン酸、タンニン酸、没食子酸エピガロカテキン、クエルセチン、ガロカテコール、エピカテキンガラートなどがあげられる。 The polyhydric phenol of the present invention may be a condensate of the polyhydric phenol or the polyhydric phenol carboxylic acid, and such condensate includes elladic acid, tannic acid, epigallocatechin gallate, quercetin, galocatechol, Epigallocatechin gallate and the like can be mentioned.
　本発明においては、より顕著なスマット除去効果を得るために、ヒドロキノン、ピロガロール、没食子酸、タンニン酸が好ましく、とりわけ、ピロガロール、没食子酸、タンニン酸が好ましい。これらの多価フェノールは、１種類を単独で用いてもよく、また２種類以上を併用してもよい。 In the present invention, hydroquinone, pyrogallol, gallic acid, and tannic acid are preferable, and pyrogallol, gallic acid, and tannic acid are particularly preferable, in order to obtain a more remarkable smut removing effect. One type of these polyhydric phenols may be used alone, or two or more types may be used in combination.
　本発明において、多価フェノールとともにスマット除去剤を構成するアルカリとしては、スマット除去剤のｐＨを、１０を超えたｐＨとすることができるものであれば、特に限定されず、この技術分野において常用されるものを好適に使用することができる。具体的には、たとえば水酸化アルカリ金属、アルカリ金属塩、アンモニアまたは有機アミンがあげられる。これらのアルカリは、１種類を単独で用いてもよく、また２種類以上を併用してもよい。 In the present invention, the alkali constituting the smut remover together with the polyhydric phenol is not particularly limited as long as the pH of the smut remover can be a pH exceeding 10, and is commonly used in this technical field. Can be preferably used. Specific examples thereof include alkali metal hydroxides, alkali metal salts, ammonia and organic amines. One type of these alkalis may be used alone, or two or more types may be used in combination.
　水酸化アルカリ金属としては、水酸化ナトリウム、水酸化カリウム、水酸化リチウムなどがあげられ、アルカリ金属塩としては、炭酸ナトリウム、炭酸カリウムがあげられる。アンモニアとしては、アンモニア水溶液があげられ、有機アミンとしては、アルカノールアミン、アルキルアミンがあげられる。 Examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, lithium hydroxide and the like, and examples of the alkali metal salt include sodium carbonate and potassium carbonate. Examples of ammonia include aqueous ammonia solutions, and examples of organic amines include alkanolamines and alkylamines.
　アルカノールアミンとしては、モノメタノールアミン、ジメタノールアミン、トリメタノールアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、モノプロパノールアミン、モノイソプロパノールアミン、メチルエタノールアミン、ジメチルエタノールアミン、メチルジエタノールアミン、エチルエタノールアミン、ジエチルエタノールアミン、エチルジエタノールアミン、Ｎ－メチルプロパノールアミン、Ｎ－ジメチルエタノールアミン、２－アミノ－２－メチル－１－プロパノール、トリスヒドロキシアミノメタン、トリイソパノールアミンなどの炭素数１～９のものがあげられる。 Examples of alkanolamines include monomethanolamine, dimethanolamine, trimethanolamine, monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, monoisopropanolamine, methylethanolamine, dimethylethanolamine, methyldiethanolamine, ethylethanolamine, etc. Those with 1 to 9 carbon atoms such as diethylethanolamine, ethyldiethanolamine, N-methylpropanolamine, N-dimethylethanolamine, 2-amino-2-methyl-1-propanol, trishydroxyaminomethane, triisopanolamine, etc. can give.
　アルキルアミンとしては、たとえばメチルアミン、ジメチルアミン、トリメチルアミン、エチルアミン、ジエチルアミン、トリエチルアミン、シクロヘキシルアミンなどの炭素数１～６の第１級アミン、第２級アミン、第３級アミンがあげられ、さらには水酸化テトラメチルアンモニウム水溶液などの第４級アンモニウム塩も好適に使用することができる。 Examples of the alkylamine include primary amines having 1 to 6 carbon atoms, secondary amines, tertiary amines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine and cyclohexylamine, and further. A quaternary ammonium salt such as an aqueous solution of tetramethylammonium hydroxide can also be preferably used.
　本発明においては、上記のうち、スマット除去性に優れることから、水酸化ナトリウム、炭酸ナトリウム、モノエタノールアミが好ましい。これらのアルカリは、１種類を単独で用いることもでき、２種類以上を併用することもできる。 In the present invention, among the above, sodium hydroxide, sodium carbonate, and monoethanolamine are preferable because they are excellent in smut removal property. One type of these alkalis may be used alone, or two or more types may be used in combination.
　本発明において、多価フェノールは、スマット除去剤全体に対して、０．５質量％～４０質量％、好ましくは１．０質量％～４０質量％含まれており、とりわけ２．０質量％～４０質量％含まれているのが好ましい。 In the present invention, the polyhydric phenol is contained in an amount of 0.5% by mass to 40% by mass, preferably 1.0% by mass to 40% by mass, particularly 2.0% by mass or more, based on the total amount of the smut remover. It is preferably contained in an amount of 40% by mass.
　また、アルカリは、スマット除去剤のｐＨが１０を超えるｐＨとなる量を含有していればよく、好ましくはｐＨが１１以上、とりわけｐＨ１４となる量を含有していることが好ましく、上記のアルカリから適宜選択して配合することにより、所望のｐＨとすることができる。 Further, the alkali may contain an amount such that the pH of the smut remover exceeds 10 and preferably contains an amount having a pH of 11 or more, particularly a pH of 14, and the above-mentioned alkali. The desired pH can be obtained by appropriately selecting and blending from the above.
　また、本発明のスマット除去剤の酸化還元電位は－２５０ｍＶ以下であり、スマット除去の観点から、好ましくは－３００ｍＶ以下であり、とりわけ好ましくは－４００ｍＶ以下である。 Further, the redox potential of the smut remover of the present invention is −250 mV or less, preferably −300 mV or less, and particularly preferably −400 mV or less, from the viewpoint of smut removal.
　本発明においては、多価フェノールとアルカリとを、前記の濃度範囲およびｐＨとなるよう混合することにより、ｐＨが１０を超えかつ酸化還元電位が―２５０ｍＶ以下のスマット除去剤とすることができる。 In the present invention, by mixing polyhydric phenol and alkali so as to have the above concentration range and pH, a smut remover having a pH of more than 10 and a redox potential of −250 mV or less can be obtained.
　上記のとおり、本発明においては、多価フェノールとアルカリとを含み、ｐＨと酸化還元電位とを、前記のような数値範囲とすることにより、優れたスマット除去効果が得られるので、本発明のスマット除去剤は、所望の多価フェノールと、アルカリとを、適宜混合して、溶液ないし混合液とし、液のｐＨと酸化還元電位とを調整すればよく、格別具体的な実施例がなくとも、容易に本発明を実施することができ、かつそのスマット除去効果も確認することができる。 As described above, in the present invention, an excellent smut removing effect can be obtained by containing a polyhydric phenol and an alkali and setting the pH and the oxidation-reduction potential in the numerical ranges as described above. The smut remover may be prepared by appropriately mixing a desired polyhydric phenol and an alkali to prepare a solution or a mixed solution, and the pH of the solution and the oxidation-reduction potential may be adjusted, even if there is no specific example. The present invention can be easily carried out, and its smut removing effect can be confirmed.
　また、本発明のスマット除去剤は、鋼材に付着した油分を除去できるので、鋼材の脱脂剤（洗浄剤）としても使用することができ、油分とスマットとを共に除去することもできるので油分とスマットとが付着した鋼材の処理には好都合である。 Further, since the smut remover of the present invention can remove the oil adhering to the steel material, it can also be used as a degreasing agent (cleaning agent) for the steel material, and both the oil and the smut can be removed. It is convenient for treating steel materials with smut.
　また、前記のとおり、本発明のスマット除去剤は、多価フェノールとアルカリとを、所定の濃度範囲およびｐＨとなるよう混合することにより製造できるので、混合前のアルカリ液を鋼材の脱脂に使用したのちに、該アルカリ液に前記多価フェノールを加えて、スマット除去剤として、スマットを除去することができる。 Further, as described above, the smut remover of the present invention can be produced by mixing polyhydric phenol and alkali so as to have a predetermined concentration range and pH, so that the alkaline solution before mixing is used for degreasing steel materials. After that, the polyhydric phenol can be added to the alkaline solution to remove the smut as a smut remover.
　本発明においては、さらに２価の鉄イオンを含有することが好ましい。２価の鉄は、本発明のスマット除去剤に添加した場合には、その酸化還元電位を低下させるので、スマット除去に好都合である。２価の鉄を含有させる場合、その含有量は、特に限定されないが、鋼材と接触させる前のスマット除去剤においては、スマット除去剤全体に対して、１～１０００００ｐｐｍ、好ましくは１～５００００ｐｐｍ含まれ、とりわけ１～１００００ｐｐｍ含まれているのが好ましい。 In the present invention, it is preferable to further contain divalent iron ions. When divalent iron is added to the smut remover of the present invention, it lowers its redox potential, which is convenient for removing smut. When divalent iron is contained, the content thereof is not particularly limited, but the smut remover before contact with the steel material contains 1 to 100,000 ppm, preferably 1 to 50,000 ppm, based on the entire smut remover. In particular, it is preferably contained in an amount of 1 to 10000 ppm.
　また、２価の鉄は、本発明のスマット除去の過程において、処理対象の鋼材から溶出して、スマット除去剤中に存在する。よって、本発明のスマット除去剤において、２価の鉄を含有させるということは、鋼材に接触させる前のスマット除去剤に２価の鉄を加えて含有させることのほか、本発明のスマット除去剤（２価の鉄を含有するもの、または２価の鉄を含有しないものの双方を含む）と鋼材とを接触させた際に、鋼材から溶出される２価の鉄を含有させることをも含む。 Further, the divalent iron is eluted from the steel material to be treated in the process of removing the smut of the present invention and is present in the smut removing agent. Therefore, in the smut remover of the present invention, the inclusion of divalent iron means that the smut remover before contact with the steel material is contained by adding divalent iron, and the smut remover of the present invention is contained. It also includes containing divalent iron eluted from the steel material when the steel material is brought into contact with the steel material (including both those containing divalent iron and those not containing divalent iron).
　本発明のスマット除去剤は、多価フェノールとアルカリ以外に、さらにキレート剤、界面活性剤、水溶性有機溶剤などを含有させることができる。キレート剤としては、アミノカルボン酸、オキシカルボン酸、ニトリロトリ酢酸等を用いることができ、界面活性剤としては、非イオン性界面活性剤、アニオン活性剤等を用いることができる。また、水溶性有機溶剤としては、グリコール系溶剤、アルコール系溶剤等を用いることができる。 The smut remover of the present invention can further contain a chelating agent, a surfactant, a water-soluble organic solvent, etc. in addition to the polyhydric phenol and the alkali. As the chelating agent, aminocarboxylic acid, oxycarboxylic acid, nitrilotriacetic acid and the like can be used, and as the surfactant, a nonionic surfactant, anionic activator and the like can be used. Further, as the water-soluble organic solvent, a glycol-based solvent, an alcohol-based solvent, or the like can be used.
　これらのキレート剤、界面活性剤、水溶性有機溶剤などは、スマット除去だけでなく、鋼材の脱脂においても効果を奏するものであり、好ましい。 These chelating agents, surfactants, water-soluble organic solvents, etc. are preferable because they are effective not only in removing smut but also in degreasing steel materials.
　本発明のスマット除去剤は、多価フェノールと、アルカリとを、溶媒中で混合することにより、製造することができ、前記混合は、鋼材と接触させる直前に混合させてもよく、あるいは予め多価フェノールと、アルカリとを、混合した溶液などとしておいてもよい。溶媒としては、水が好ましく、水以外にはグリコール系溶剤、アルコール系溶剤などの水溶性有機溶媒が含有されていてもよい。 The smut remover of the present invention can be produced by mixing a polyhydric phenol and an alkali in a solvent, and the mixture may be mixed immediately before contact with a steel material, or may be mixed in advance. A solution in which valent phenol and alkali are mixed may be prepared. The solvent is preferably water, and other than water, a water-soluble organic solvent such as a glycol solvent or an alcohol solvent may be contained.
　また、前記のとおり、本発明のスマット除去剤に２価の鉄を含有させる場合、さらにキレート剤、界面活性剤、水溶性有機溶剤などを含有させる場合には、多価フェノールと、アルカリとを混合する際に、２価の鉄、キレート剤、界面活性剤、水溶性有機溶剤などを同時に、または逐次的に加えて混合すればよい。 Further, as described above, when the smut remover of the present invention contains divalent iron, and when further containing a chelating agent, a surfactant, a water-soluble organic solvent, etc., a polyhydric phenol and an alkali are used. At the time of mixing, divalent iron, a chelating agent, a surfactant, a water-soluble organic solvent and the like may be added simultaneously or sequentially and mixed.
　また、多価フェノールと、アルカリとを、別々の溶媒に加えて溶解し、溶解した溶液を混合してもよく、あるいは溶媒に多価フェノールとアルカリとのいずれか一方を溶解したのち、他方の成分を加えて溶解してもよく、または溶媒に多価フェノールとアルカリとを同時に加えて混合してもよい。混合は、室温ないし加温下に、実施することができる。 Further, the polyvalent phenol and the alkali may be dissolved by adding them to separate solvents, and the dissolved solutions may be mixed, or one of the polyvalent phenol and the alkali may be dissolved in the solvent and then the other. Ingredients may be added and dissolved, or polyhydric phenol and alkali may be added to the solvent at the same time and mixed. Mixing can be carried out at room temperature or at warm temperature.
　本発明のスマット除去方法は、前記のスマット除去剤と、酸洗後の鋼材とを接触させることにより実施することができる。接触方法は、鋼材表面のスマットとスマット除去剤とが十分に接触できる方法であればよく、特に限定されない。たとえば、酸洗後の鋼材をスマット除去剤に浸漬してもよく、酸洗後の鋼材にスマット除去剤を噴霧や塗布してもよい。 The smut removing method of the present invention can be carried out by bringing the smut removing agent into contact with the steel material after pickling. The contact method is not particularly limited as long as the smut on the surface of the steel material can sufficiently contact the smut remover. For example, the pickled steel material may be immersed in a smut remover, or the pickled steel material may be sprayed or coated with a smut remover.
　酸洗後の鋼材とスマット除去剤との接触は、常温ないし加温下、たとえば２０～９０℃、で実施することができ、接触時間は、接触方法、スマットの固着量や固着状態によって異なるが、浸漬法によるときは、７０℃で、５～３０分間程度行うことができる。 The contact between the steel material and the smut remover after pickling can be carried out at room temperature or warming, for example, 20 to 90 ° C., and the contact time varies depending on the contact method, the amount of smut fixed and the state of sticking. When the dipping method is used, it can be carried out at 70 ° C. for about 5 to 30 minutes.
　以下、実施例により、本発明をさらに詳細に説明するが、本発明は、その精神または主要な特徴から逸脱することなく、他のいろいろな形態で実施できる。したがって、前述の実施形態はあらゆる点で単なる例示に過ぎず、本発明の範囲は特許請求の範囲に示すものであって、明細書本文には何ら拘束されない。さらに、特許請求の範囲に属する変形や変更は全て本発明の範囲内のものである。 Hereinafter, the present invention will be described in more detail by way of examples, but the present invention can be carried out in various other forms without departing from its spirit or main features. Therefore, the above-described embodiment is merely an example in all respects, and the scope of the present invention is shown in the claims and is not bound by the text of the specification. Furthermore, all modifications and modifications that fall within the scope of the claims are within the scope of the present invention.
＜ｐＨ，酸化還元電位の測定＞
　多価フェノールとアルカリとを溶解した溶液のｐＨを、ｐＨ測定装置（ポータブルｐＨメータ＜Ｄ－７４＞、株式会社堀場製作所製）を用いて測定した。
　測定は２５℃で行い、攪拌なしの状態で、電極をホールドして測定した。
　酸化還元電位は、前記と同じ装置を用い、同条件でＯＲＰ電極を用いて測定した。 <Measurement of pH and redox potential>
The pH of the solution in which polyhydric phenol and alkali were dissolved was measured using a pH measuring device (portable pH meter <D-74>, manufactured by Horiba Seisakusho Co., Ltd.).
The measurement was performed at 25 ° C., and the measurement was performed by holding the electrode without stirring.
The redox potential was measured using the same apparatus as described above and using an ORP electrode under the same conditions.
＜評価方法＞
　まず、スケールの付着した炭素鋼（３０ｍｍ角、２ｍｍ厚）を７０℃の１０質量％硫酸に３０分間浸漬してスケールを除去してスマットを発生させた。その後、水道水にて炭素鋼に付着した酸を水洗した。水洗後、ドライヤーにより炭素鋼表面を乾燥させて、スマットの付着した炭素鋼を準備した。 <Evaluation method>
First, a carbon steel (30 mm square, 2 mm thick) to which scale was attached was immersed in 10% by mass sulfuric acid at 70 ° C. for 30 minutes to remove the scale and generate a smut. Then, the acid adhering to the carbon steel was washed with tap water. After washing with water, the surface of the carbon steel was dried with a dryer to prepare the carbon steel to which the smut was attached.
　上記工程にて準備したスマットの付着した炭素鋼を２００ｍＬのビーカーに表１に示す各剤１５０ｍＬに浸漬した。浸漬温度は７０℃、浸漬時間は１０分間とした。その後、炭素鋼を取り出し、水道水にて水洗して、ドライヤーにて乾燥後の炭素鋼表面の状態を分光測色計（コニカミノルタ株式会社製、ＣＭ－５１２ｍ３Ａ）の照射角４５度におけるＬ値にて評価した。なお、スマット除去前のＬ値は４０であった。 The carbon steel to which the smut was attached prepared in the above step was immersed in 150 mL of each agent shown in Table 1 in a 200 mL beaker. The immersion temperature was 70 ° C. and the immersion time was 10 minutes. After that, the carbon steel is taken out, washed with tap water, and the state of the carbon steel surface after drying with a dryer is measured by the spectrophotometer (manufactured by Konica Minolta Co., Ltd., CM-512m3A) at an irradiation angle of 45 degrees. Evaluated at. The L value before removing the smut was 40.
　判定方法は、下記の基準にしたがって、評価が良い方から順に◎、○、×とした。
　◎：Ｌ値６０以上
　○：Ｌ値５０以上６０未満
　×：Ｌ値５０未満 The judgment method was set to ◎, ○, and × in order from the one with the best evaluation according to the following criteria.
⊚: L value 60 or more ○: L value 50 or more and less than 60 ×: L value less than 50
実施例１～１０
　表１に示す多価フェノールとアルカリとを、表1に示す濃度となるように水に溶解することにより、実施例１～１０のスマット除去剤を製造した。得られたスマット除去剤は、表１に示すとおりの酸化還元電位とｐＨを有するものであった。得られた実施例１～１０のスマット除去剤を用いて、上記の評価方法にしたがって評価し、スマット除去効果を確認した。 Examples 1-10
The smut remover of Examples 1 to 10 was produced by dissolving the polyhydric phenol and the alkali shown in Table 1 in water so as to have the concentrations shown in Table 1. The obtained smut remover had an oxidation-reduction potential and pH as shown in Table 1. Using the obtained smut removers of Examples 1 to 10, evaluation was performed according to the above evaluation method, and the smut removal effect was confirmed.
比較例１～８
　表１に示す各成分を、表１に示す濃度となるように水に溶解することにより、比較例１～８のスマット除去剤を製造した。得られた組成物は、表１に示すとおりの酸化還元電位とｐＨを有するものであった。
　得られた比較例１～８の組成物を用いて、実施例と同じ評価方法にしたがって評価し、スマット除去効果を確認した。 Comparative Examples 1 to 8
The smut removers of Comparative Examples 1 to 8 were produced by dissolving each component shown in Table 1 in water so as to have the concentration shown in Table 1. The obtained composition had an oxidation-reduction potential and pH as shown in Table 1.
Using the obtained compositions of Comparative Examples 1 to 8, evaluation was performed according to the same evaluation method as in Examples, and the smut removing effect was confirmed.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001

Claims (6)

  1. 　多価フェノールとアルカリとを含み、ｐＨが１０を超えかつ酸化還元電位が－２５０ｍＶ以下であることを特徴とするスマット除去剤。 A smut remover containing polyhydric phenol and alkali, having a pH of more than 10 and a redox potential of -250 mV or less.
  2. 　多価フェノールが、ヒドロキノン、ピロガロール、没食子酸およびタンニン酸から選ばれる少なくとも１種以上であることを特徴とする請求項１に記載のスマット除去剤。 The smut remover according to claim 1, wherein the polyhydric phenol is at least one selected from hydroquinone, pyrogallol, gallic acid and tannic acid.
  3. 　アルカリが、水酸化アルカリ金属、アルカリ金属塩、アンモニアおよび有機アミンから選ばれる少なくとも１種以上であることを特徴とする請求項１に記載のスマット除去剤。 The smut remover according to claim 1, wherein the alkali is at least one selected from alkali metal hydroxides, alkali metal salts, ammonia and organic amines.
  4. 　さらに２価の鉄イオンを含有することを特徴とする請求項１～３のいずれか１項に記載のスマット除去剤。 The smut remover according to any one of claims 1 to 3, further containing divalent iron ions.
  5. 　多価フェノールとアルカリとを混合して、ｐＨが１０を超えかつ酸化還元電位が－２５０ｍＶ以下のスマット除去剤を製造することを特徴とするスマット除去剤の製造方法。 A method for producing a smut remover, which comprises mixing a polyhydric phenol and an alkali to produce a smut remover having a pH of more than 10 and an oxidation-reduction potential of -250 mV or less.
  6. 　多価フェノールとアルカリとを混合して製造された、ｐＨが１０を超えかつ酸化還元電位が－２５０ｍＶ以下のスマット除去剤と、酸洗処理後の鋼材とを接触させて、該鋼材に付着したスマットを除去することを特徴とする鋼材のスマット除去方法。 A smut remover having a pH of more than 10 and an oxidation-reduction potential of -250 mV or less, which was produced by mixing polyhydric phenol and alkali, was brought into contact with the pickled steel material and adhered to the steel material. A method for removing smut from a steel material, which comprises removing smut.
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JPH07258690A (en) * 1994-03-18 1995-10-09 Nippon Paint Co Ltd Alkali de-fatting cleaning solution
JP2013136826A (en) * 2011-12-01 2013-07-11 Chubu Kiresuto Kk Corrosion inhibitor for alkali cleaning liquid, alkali cleaning liquid, and method for cleaning metal by using the alkali cleaning liquid
JP2018127661A (en) * 2017-02-07 2018-08-16 日本パーカライジング株式会社 Process liquid and iron oxide removal method

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