CN112771208A - Stain removing agent, method for producing same, and method for removing stains using same - Google Patents
Stain removing agent, method for producing same, and method for removing stains using same Download PDFInfo
- Publication number
- CN112771208A CN112771208A CN201980003766.6A CN201980003766A CN112771208A CN 112771208 A CN112771208 A CN 112771208A CN 201980003766 A CN201980003766 A CN 201980003766A CN 112771208 A CN112771208 A CN 112771208A
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- China
- Prior art keywords
- alkali
- stain
- polyhydric phenol
- acid
- present
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Classifications
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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
-
- 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
- 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
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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)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
The invention aims to provide a stain remover which strongly removes stains generated by pickled steel and has small environmental load. The present invention is a stain removing agent characterized by comprising a polyhydric phenol and an alkali, having a pH value of more than 10 and an oxidation-reduction potential of-250 mV or less, a method for producing the same, and a method for removing stains using the stain removing agent.
Description
Technical Field
The present invention relates to a desmutting agent for removing stains generated on the surface of a steel material after pickling the steel material, a method for producing the same, and a desmutting method using the same.
Background
Descaling treatment, so-called "pickling", of the hot-rolled steel strip is performed by immersing the steel strip in an acid solution such as hydrochloric acid or sulfuric acid. In the pickling, the scale itself is dissolved in the acid solution, or the acid solution reaches the steel surface through a crack in the scale to cause dissolution of metal and hydrogen generation, and the scale is separated from the steel surface.
After the pickling, the acid solution is washed with warm water and dried, but a black insoluble residue called smut may be attached to the steel surface.
The dirt is a generic name of black or brown substances that are strongly adhered to the steel surface when the scale and the strip steel matrix are dissolved by pickling, and is considered to be formed of carbon contained in the steel in a fine powder form or iron ions in pickling that re-precipitate on the surface of the steel sheet as iron oxide or iron hydroxide during washing and drying.
The adhesion of the stains darkens the color tone of the steel sheet and also causes color unevenness, and if the stains remain on the surface, they adversely affect the lubrication treatment and various surface treatments in the subsequent steps, and the value of the steel material is significantly reduced, so that it is necessary to remove the stains.
As a method for removing the contamination, it is known that a steel material is sulfuric acid-washed and then immersed in a solution containing 400g/L or more of HNO3A method of removing stains in a nitric acid aqueous solution at 25 to 80 ℃ (patent document 1), a method of combining an alkaline agent such as sodium hydroxide with an oxidizing agent such as perchloric acid or permanganate (non-patent documents 1 and 2), and a method of treating with a 0.5 to 10% aqueous solution of a phosphonate salt adjusted to a pH of 4 to 9 (patent document 3). Further, a rust cleaning agent for iron, copper, or the like, which is not a method for removing stains, and which is obtained by combining a polyhydric phenol such as gallic acid or tannic acid with an alkaline agent such as sodium hydroxide to adjust the pH to 8 to 10, is also known (patent document 4).
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 61-69989
Patent document 2: japanese laid-open patent publication No. 6-330359
Patent document 3: japanese patent No. 3207636
Patent document 4: japanese patent laid-open publication No. 2003-342762
Non-patent document
Non-patent document 1: "surface of practice technology", volume 33 (1986), No. 8, pages 311 to 317.
Disclosure of Invention
Technical problem to be solved by the invention
The method of patent document 1 involves the generation of NO derived from nitric acidXThe problem of environmental pollution is not preferable because not only the dirt but also the steel surface are dissolved.
The method of non-patent document 1 has a problem of large environmental load, and the method of patent document 2 is characterized in that the decontaminated solution is regenerated by electrolytic oxidation and recycled, but manganese is a heavy metal and has a problem of environmental load. Further, treatment of the treatment liquid such as recycling and treatment of the washing water after the sewage treatment are required, which requires a lot of labor and cost. Further, the use of such heavy metals is likely to be prohibited in the future.
The method of patent document 3 has a problem that a sufficient decontamination capability cannot be obtained although the environmental load is small. In addition, the method of patent document 4 has a problem that the effect of removing the firmly adhered dirt cannot be obtained regardless of the slight rust.
The present inventors have conducted extensive studies on a stain remover having a small environmental load and an excellent stain removing effect, and as a result, have found that a solution having an oxidation-reduction potential of-250 mV or less in a solution of a polyhydric phenol and an alkali has an excellent stain removing effect, and have completed the present invention.
Means for solving the problems
The stain remover is characterized by comprising polyhydric phenol and alkali, wherein the pH value exceeds 10 and the oxidation-reduction potential is below-250 mV.
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 base is at least one selected from the group consisting of an alkali metal hydroxide, an alkali metal salt, ammonia, and an organic amine.
The present invention is characterized by further containing a divalent iron ion.
The present invention is a method for producing a stain removing agent, characterized by mixing a polyhydric phenol and an alkali to produce a stain removing agent having a pH value of more than 10 and an oxidation-reduction potential of-250 mV or less.
The present invention is a method for removing stains from a steel material, characterized by bringing a stain remover, which is obtained by mixing a polyhydric phenol and an alkali and has a pH value of more than 10 and an oxidation-reduction potential of-250 mV or less, into contact with the pickled steel material to remove stains adhering to the steel material.
ADVANTAGEOUS EFFECTS OF INVENTION
The stain remover is characterized by comprising a polyhydric phenol and an alkali, and having a pH value of more than 10 and an oxidation-reduction potential of-250 mV or less, so that stains firmly adhered to steel materials can be strongly removed by the oxidation-reduction potential.
Further, according to the present invention, since nitric acid, which has a problem of environmental pollution, and perchlorate or permanganate, which has a large environmental load, are not used, there is an advantage that the environmental load is small.
Detailed Description
The invention contains polyhydric phenol and alkali, has a pH value of more than 10 and an oxidation-reduction potential of less than-250 mV, and can be used for pickling metals such as carbon steel, alloy steel and the like.
In the present invention, the polyhydric phenol includes a compound having 2 or more phenolic hydroxyl groups on an aromatic ring.
Examples of the compound having 2 or more phenolic hydroxyl groups on the aromatic ring include compounds having 2 or more hydroxyl groups on the benzene ring, and specific examples thereof include dihydric phenols such as hydroquinone, catechol, and resorcinol, and trihydric phenols such as pyrogallol and phloroglucinol.
The polyphenol of the present invention may be a polyphenol carboxylic acid having 2 or more hydroxyl groups on the benzene ring and further having a carboxyl group, and examples of the polyphenol carboxylic acid include diphenol carboxylic acids such as dihydroxybenzoic acid, caffeic acid, hydroxy salicylic acid, protocatechuic acid, gentisic acid, and orchic acid, and triphenolic carboxylic acids such as gallic acid.
The polyphenol of the present invention may be a condensate of the above polyphenol or polyphenol carboxylic acid, and examples of the condensate include ellagic acid, tannic acid, epigallocatechin gallate, quercetin, gallocatechin (gallocatechin), epicatechin gallate, and the like.
In the present invention, in order to obtain a more significant decontamination effect, hydroquinone, pyrogallol, gallic acid, and tannic acid are preferable, and pyrogallol, gallic acid, and tannic acid are particularly preferable. These polyhydric phenols may be used alone or in combination of two or more.
In the present invention, the alkali constituting the stain remover together with the polyhydric phenol is not particularly limited as long as it can make the pH of the stain remover to be a pH exceeding 10, and an alkali generally used in the art can be preferably used. Specific examples thereof include alkali metal hydroxides, alkali metal salts, ammonia, and organic amines. These bases may be used alone or in combination of two or more.
Examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, and lithium hydroxide; examples of the alkali metal salt include sodium carbonate and potassium carbonate. As ammonia, an aqueous ammonia solution; as the organic amine, alkanolamine and alkylamine can be cited.
Examples of the alkanolamine include alkanolamines having 1 to 9 carbon atoms such as monomethanolamine, dimethanolamine, trimethanolamine, monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, monoisopropanolamine, methylethanolamine, dimethylethanolamine, methyldiethanolamine, ethylethanolamine, diethylethanolamine, ethyldiethanolamine, N-methylpropanolamine, N-dimethylethanolamine, 2-amino-2-methyl-1-propanol, trishydroxyaminomethane, and triisopropanolamine.
Examples of the alkylamine include primary, secondary and tertiary amines having 1 to 6 carbon atoms such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine and cyclohexylamine, and a quaternary ammonium salt such as an aqueous tetramethylammonium hydroxide solution can be preferably used.
In the present invention, sodium hydroxide, sodium carbonate, and monoethanolamine are preferred among the above from the viewpoint of excellent detergency. These bases may be used alone or in combination of two or more.
In the present invention, the content of the polyhydric phenol is 0.5 to 40% by mass, preferably 1.0 to 40% by mass, and particularly preferably 2.0 to 40% by mass, based on the entire detergent.
The content of the alkali may be an amount that brings the pH of the detergent to a pH exceeding 10, preferably an amount that brings the pH to 11 or more, particularly preferably an amount that brings the pH to 14, and the desired pH can be achieved by appropriately selecting and blending the alkali.
The oxidation-reduction potential of the stain remover of the present invention is-250 mV or less, preferably-300 mV or less, particularly preferably-400 mV or less, from the viewpoint of stain removal.
In the present invention, the soil release agent having a pH value of more than 10 and an oxidation-reduction potential of-250 mV or less can be produced by mixing the polyhydric phenol and the alkali so as to achieve the concentration range and the pH value.
As described above, in the present invention, since an excellent stain removing effect can be obtained by including the polyhydric phenol and the alkali and making the pH and the oxidation-reduction potential within the numerical ranges as described above, the stain removing agent of the present invention can be obtained by appropriately mixing the desired polyhydric phenol and the alkali to prepare a solution or a mixed solution and adjusting the pH and the oxidation-reduction potential of the liquid, and the present invention can be easily carried out without any particular examples and can also be confirmed for its stain removing effect.
The stain remover of the present invention can remove oil adhering to steel materials, and therefore, can be used as a degreasing agent (cleaning agent) for steel materials, and can remove oil and stains at the same time, and therefore, is suitable for the treatment of steel materials to which oil and stains adhere.
Further, as described above, the stain remover of the present invention can be produced by mixing the polyhydric phenol and the alkali so as to achieve a predetermined concentration range and pH, and therefore, the stain remover can be produced by using the alkali solution before mixing for degreasing of steel material and then adding the polyhydric phenol to the alkali solution to remove the stains.
In the present invention, it is preferable that the iron-containing composition further contains divalent iron ions. Ferrous iron is suitable for decontamination because it lowers the oxidation-reduction potential when added to the decontamination agent of the present invention. When the divalent iron is contained, the content is not particularly limited, and the content of the divalent iron in the stain remover before the contact with the steel material is 1 to 100000ppm, preferably 1 to 50000ppm, particularly preferably 1 to 10000ppm, based on the whole stain remover.
In the decontamination process of the present invention, ferrous iron is eluted from the steel material to be treated and is present in the decontamination agent. Therefore, the meaning of "making the detergent of the present invention contain divalent iron" includes: adding ferrous iron to the stain removing agent before contacting with the steel material to make it contain ferrous iron; and, when the stain removing agent of the present invention (including both a stain removing agent containing divalent iron or a stain removing agent containing no divalent iron) is brought into contact with a steel material, the stain removing agent is made to contain divalent iron eluted from the steel material.
The detergent of the present invention may contain a chelating agent, a surfactant, a water-soluble organic solvent, and the like in addition to the polyhydric phenol and the alkali. As the chelating agent, aminocarboxylic acid, hydroxycarboxylic acid, nitrilotriacetic acid, etc.; as the surfactant, a nonionic surfactant, an anionic surfactant, or the like can be used. As the water-soluble organic solvent, a glycol solvent, an alcohol solvent, or the like can be used.
These chelating agents, surfactants, water-soluble organic solvents and the like are preferable because they exert effects not only in the decontamination but also in the degreasing of steel materials.
The stain remover of the present invention can be produced by mixing the polyhydric phenol and the alkali in a solvent, and the mixing may be carried out immediately before the contact with the steel material, or a solution obtained by mixing the polyhydric phenol and the alkali may be prepared in advance. The solvent is preferably water, and may contain, in addition to water, a water-soluble organic solvent such as a glycol solvent or an alcohol solvent.
In addition, as described above, when the stain removing agent of the present invention contains divalent iron, and further contains a chelating agent, a surfactant, a water-soluble organic solvent, or the like, when the polyhydric phenol is mixed with the alkali, the divalent iron, the chelating agent, the surfactant, the water-soluble organic solvent, or the like may be added and mixed at the same time or sequentially.
In addition, the polyphenol and the alkali can be added into different solvents for dissolution, and the dissolved solutions are mixed; or, either one of the polyhydric phenol and the alkali may be dissolved in the solvent, and then the other component may be added for dissolution; alternatively, the polyhydric phenol and the base may be added to the solvent at the same time for mixing. The mixing can be carried out at room temperature or at elevated temperature.
The method of removing a stain according to the present invention can be carried out by bringing the stain remover into contact with the pickled steel material. The contact method is not particularly limited as long as the stain on the surface of the steel material can be sufficiently contacted with the stain remover. For example, the pickled steel material may be immersed in the stain remover, or the stain remover may be sprayed or applied to the pickled steel material.
The contact between the pickled steel and the stain remover may be carried out at normal temperature or under heating (for example, 20 to 90 ℃), and the contact time may vary depending on the contact method, the amount of the stain fixed, or the state of the stain fixed, and when the dipping method is employed, the contact may be carried out at 70 ℃ for about 5 to 30 minutes.
The present invention will be described in more detail below with reference to examples, but the present invention can be implemented in various other forms without departing from the spirit or essential characteristics thereof. Therefore, the foregoing embodiments are merely exemplary in all respects, and the scope of the present invention is shown in the claims and is not limited by the present disclosure. Further, variations and modifications falling within the scope of the claims are within the scope of the present invention.
< measurement of pH value and Oxidation-reduction potential >
The pH of the solution in which the polyhydric phenol and the alkali were dissolved was measured using a pH measuring instrument (Portable pH meter < D-74 >, manufactured by horiba, Ltd.).
The measurement was performed at 25 ℃ and was performed with the electrode fixed in a state without stirring.
The oxidation-reduction potential was measured using the same apparatus and ORP electrode under the same conditions.
< evaluation method >
First, carbon steel (30mm square, thickness 2mm) having scale attached thereto was immersed in 10 mass% sulfuric acid at 70 ℃ for 30 minutes to remove scale and generate dirt. Then, the acid attached to the carbon steel was washed away with tap water. After washing, the surface of the carbon steel was dried by a dryer to prepare a carbon steel having contaminants adhered thereto.
The carbon steel with the contaminants attached, prepared in the above-described steps, was immersed in 150mL of each reagent shown in table 1 in a 200mL beaker. The dipping temperature was set to 70 ℃ and the dipping time was set to 10 minutes. Then, the carbon steel was taken out, washed with tap water, and the surface condition of the carbon steel dried by a dryer was evaluated for its L value at an irradiation angle of 45 degrees by a spectrocolorimeter (CM-512 m3A, manufactured by Konika Mingta K.K.). The L value before decontamination was 40.
The evaluation methods were classified as "excellent", "good", and "x" in order from good to bad according to the following criteria;
very good: l value of 60 or more
O: l value of 50 or more and less than 60
X: the value of L is less than 50.
Examples 1 to 10
The soil release agents of examples 1 to 10 were produced by dissolving the polyhydric phenol shown in table 1 and the alkali in water so that the concentrations thereof were as shown in table 1. The obtained soil release agent had an oxidation-reduction potential and a pH value as shown in Table 1. The obtained soil release agents of examples 1 to 10 were evaluated by the above-described evaluation methods, and the soil release effect was confirmed.
Comparative examples 1 to 8
The soil release agents of comparative examples 1 to 8 were produced by dissolving the components shown in table 1 in water so that the concentrations thereof were as shown in table 1. The resulting composition had an oxidation-reduction potential and a pH as shown in table 1.
The compositions of comparative examples 1 to 8 were evaluated in the same manner as in examples, and the decontamination effect was confirmed.
[ Table 1]
Claims (6)
1. A stain remover characterized by comprising a polyhydric phenol and an alkali, having a pH of more than 10 and an oxidation-reduction potential of-250 mV or less.
2. The stain remover according to claim 1, wherein the polyhydric phenol is at least one member selected from the group consisting of hydroquinone, pyrogallol, gallic acid, and tannic acid.
3. The stain remover according to claim 1, wherein the base is at least one or more selected from the group consisting of an alkali metal hydroxide, an alkali metal salt, ammonia, and an organic amine.
4. The soil remover according to any one of claims 1 to 3, further comprising divalent iron ions.
5. A process for producing a stain remover, characterized by mixing a polyhydric phenol with an alkali to produce a stain remover having a pH of more than 10 and an oxidation-reduction potential of-250 mV or less.
6. A method for removing stains from a steel material, characterized by bringing a stain remover, which is obtained by mixing a polyhydric phenol and an alkali and has a pH value of more than 10 and an oxidation-reduction potential of-250 mV or less, into contact with the acid-washed steel material to remove stains adhering to the steel material.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2019/035096 WO2021044605A1 (en) | 2019-09-05 | 2019-09-05 | Smut remover, method for producing same, and smut removal method using same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112771208A true CN112771208A (en) | 2021-05-07 |
Family
ID=74130481
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201980003766.6A Pending CN112771208A (en) | 2019-09-05 | 2019-09-05 | Stain removing agent, method for producing same, and method for removing stains using same |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPWO2021044605A1 (en) |
| KR (1) | KR102201059B1 (en) |
| CN (1) | CN112771208A (en) |
| WO (1) | WO2021044605A1 (en) |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4094701A (en) * | 1976-03-18 | 1978-06-13 | Oxy Metal Industries Corporation | Method for cleaning tin surfaces |
| JPS6169989A (en) | 1984-09-14 | 1986-04-10 | Nippon Steel Corp | Pickling method of hot-rolled ferritic stainless steel plate |
| JPH06330359A (en) | 1993-05-18 | 1994-11-29 | Daido Steel Co Ltd | Desmutting treatment of steel material |
| JP2831564B2 (en) * | 1994-03-18 | 1998-12-02 | 日本ペイント株式会社 | Alkaline cleaning solution |
| JP2003342762A (en) | 2002-05-21 | 2003-12-03 | Hiroshi Takimoto | Cleaning agent for metallic product and cleaning method |
| JP4481760B2 (en) * | 2004-08-03 | 2010-06-16 | 伊藤製油株式会社 | Pickling corrosion inhibitor and corrosion-resistant pickling solution using the same |
| JP5903682B2 (en) * | 2011-12-01 | 2016-04-13 | 中部キレスト株式会社 | Corrosion inhibitor for alkaline cleaning liquid, alkaline cleaning liquid, and metal cleaning method using the alkaline cleaning liquid |
| JP6494362B2 (en) * | 2015-03-25 | 2019-04-03 | 三菱重工業株式会社 | Dissolution removal composition |
| CN104988519B (en) * | 2015-07-30 | 2018-05-01 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of restrainer and the method that pickling is carried out with the restrainer |
| JP3207636U (en) | 2016-08-31 | 2016-11-24 | 雪枝 菊地 | Cover for holding mobile device |
| 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 |
-
2019
- 2019-09-05 WO PCT/JP2019/035096 patent/WO2021044605A1/en active Application Filing
- 2019-09-05 CN CN201980003766.6A patent/CN112771208A/en active Pending
- 2019-09-05 KR KR1020207002973A patent/KR102201059B1/en active IP Right Grant
- 2019-09-05 JP JP2019571093A patent/JPWO2021044605A1/ja not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2021044605A1 (en) | 2021-03-11 |
| WO2021044605A1 (en) | 2021-03-11 |
| KR102201059B1 (en) | 2021-01-08 |
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