Solution composition for steel sheet surface treatment, steel sheet surface-treated with the same and method for producing the same
A composition of trivalent chromium and other additives applied to hot-dip plated steel materials forms a stable coating that addresses corrosion and blackening resistance issues, enhancing the materials' durability and appearance in humid environments.
Patent Information
- Application Number
- JP2024537521
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2021-12-20
- Filing Date
- 2022-12-20
- Publication Date
- 2024-12-20
- Estimated Expiration
- 2042-12-20
AI Technical Summary
Existing methods for improving the corrosion resistance and blackening resistance of highly corrosion-resistant hot-dip plated steel materials, particularly those with Zn, Mg, and Al coatings, face issues such as surface defects, appearance deterioration, and foreign material defects, especially in humid environments, and the use of hexavalent chromium is regulated due to environmental concerns.
A solution composition comprising 0.1 to 10% trivalent chromium compound, 0.1 to 10% acidity regulator, 1 to 20% adhesion improver, 1 to 15% corrosion resistance improver, 0.1 to 25% film forming agent, 0.01 to 2% lubricant, and 0.5 to 10% co-solvent, applied to the steel surface and heat-treated at 50 to 250°C, forming a coating layer with a thickness of 0.2 to 3.0 μm.
The solution provides a stable coating that enhances corrosion resistance and blackening resistance, reduces foreign matter defects, and extends product life, while maintaining solution stability and preventing surface defects.
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Figure 2024546377000001_ABST
Abstract
Description
[Technical field]
[0001] The present invention relates to a solution composition capable of improving the corrosion resistance and blackening resistance of a steel sheet, a steel sheet surface-treated using the same, and a method for producing the steel sheet. [Background technology]
[0002] Highly corrosion-resistant hot-dip plated steel materials having a plating layer containing zinc (Zn), magnesium (Mg), and aluminum (Al) are known as steel materials with excellent red rust corrosion resistance.
[0003] However, such highly corrosion-resistant hot-dip plated steel products have a problem that, since the exposed surface thereof is mostly made of zinc or zinc alloy, when exposed to a general environment, particularly a humid atmosphere, the surface is prone to develop dot-like corrosion defects, which deteriorate the appearance. Recently, in contract processing, foreign matter defects have also been occurring in which the coating layer of the hot-dip plated steel product adheres to the rolls when passing through the rolls.
[0004] To solve these problems, in the past, hexavalent chromium or chromate treatment was applied to plated steel sheets to ensure corrosion resistance and blackening resistance. However, hexavalent chromium has been designated as a harmful environmental substance, and regulations on the use of hexavalent chromium are currently being strengthened. Furthermore, when hexavalent chromium is used as a surface treatment agent for plated steel sheets, there is a defect that the surface of the steel sheet turns black or black spots are generated.
[0005] Therefore, currently, a method has been developed in which a surface treatment solution composition containing trivalent chromium is coated on a plated steel sheet to ensure the corrosion resistance and blackening resistance of the plated steel sheet.
[0006] For example, Patent Document 1 applies a chemical conversion treatment method in which a steel sheet is immersed in a composition containing trivalent chromium. This method requires a long immersion time to be applicable to the continuous process of steel companies, and the chemical conversion treatment method has problems such as impairing the fingerprint resistance of the steel sheet.
[0007] On the other hand, Patent Documents 2 and 3 disclose that a composition containing trivalent chromium can be applied to a continuous line of a steel company by coating a plated steel sheet by a spray or roll coater method, and fingerprint resistance can be ensured. However, these compositions contain porous silica components, and are therefore not suitable for Mg and Al alloys, which tend to discolor rapidly in a humid atmosphere. In addition, porous silica has a strong hygroscopic property, which causes a problem of inducing rapid discoloration in Zn-Mg-Al alloy steel sheets. [Prior art documents] [Patent documents]
[0008] [Patent Document 1] Korean Patent Publication No. 10-2009-0024450 [Patent Document 2] Korean Patent Publication No. 10-2004-0046347 [Patent Document 3] Japanese Patent Publication No. 2002-069660 Summary of the Invention [Problem to be solved by the invention]
[0009] One embodiment of the present invention provides a solution composition having excellent solution stability for improving the appearance corrosion resistance and blackening resistance of a steel sheet by controlling the composition of a coating solution applied to the surface of a highly corrosion-resistant plated steel sheet, and provides a steel sheet surface-treated using the same and a manufacturing method thereof.
[0010] The object of the present invention is not limited to the above. The object of the present invention can be understood from the entire content of this specification, and a person having ordinary skill in the art to which the present invention pertains will have no difficulty in understanding the additional object of the present invention. [Means for solving the problem]
[0011] One embodiment of the present invention provides a solution composition for treating a steel sheet surface, comprising: (a) 0.1 to 10% by weight of a trivalent chromium compound, (b) 0.1 to 10% by weight of an acidity regulator, (c) 1 to 20% by weight of an adhesion improver, (d) 1 to 15% by weight of a corrosion resistance improver, (e) 0.1 to 25% by weight of a film-forming agent, (f) 0.01 to 2% by weight of a lubricant, (g) 0.5 to 10% by weight of a co-solvent, and (h) the balance solvent.
[0012] Another embodiment of the present invention provides a surface-treated steel sheet, comprising a steel sheet and a coating layer formed from the solution composition on at least one surface of the steel sheet.
[0013] Another embodiment of the present invention provides a method for producing a surface-treated steel sheet, the method including the steps of providing a steel sheet, applying the solution composition to at least one surface of the steel sheet, and heat-treating the steel sheet to which the solution composition has been applied at 50 to 250°C. Effect of the Invention
[0014] According to the present invention, a solution composition having excellent solution stability can be provided, and by coating the solution composition on a steel sheet, a steel sheet having excellent corrosion resistance and blackening resistance can be provided.
[0015] Furthermore, it has the effect of improving the lifespan of the product by improving the defects caused by foreign matter during the coating process. [Brief description of the drawings]
[0016] [Figure 1] In one embodiment of the present invention, (a) a plated steel sheet on which surface (edge) corrosion has occurred and (b) a plated steel sheet on which surface corrosion has not occurred are shown. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0017] The inventors of the present invention have conducted extensive research in order to obtain a solution composition that is advantageous for improving not only the corrosion resistance but also the blackening resistance of a coated steel sheet, for example, a highly corrosion-resistant hot-dip plated steel sheet, when the steel sheet is subjected to a coating treatment.
[0018] As a result, it is possible to provide a solution composition in which an acidity regulator, an adhesion improver, a corrosion resistance improver, a film-forming agent, a lubricant, and a co-solvent are mixed in appropriate amounts together with a trivalent chromium compound, and this solution composition has high solution stability. It has been confirmed that when such a solution composition is used for surface treatment of a steel sheet, the intended effect can be obtained, and the present invention has been completed.
[0019] The present invention will be described in detail below.
[0020] First, a solution composition for surface treatment of a steel sheet according to one embodiment of the present invention will be specifically described.
[0021] The solution composition according to the present invention can contain (a) 0.1 to 10% by weight of a trivalent chromium compound, (b) 0.1 to 10% by weight of an acidity regulator, (c) 1 to 20% by weight of an adhesion improver, (d) 1 to 15% by weight of a corrosion resistance improver, (e) 0.1 to 25% by weight of a film-forming agent, (f) 0.01 to 2% by weight of a lubricant, (g) 0.5 to 10% by weight of a co-solvent, and (h) the remaining solvent.
[0022] The content of the solution composition of the present invention is based on 100% by weight.
[0023] As will be described in detail later, the solution composition can form a coating layer on at least one surface of a substrate to which the composition can be applied. In the present invention, the substrate can be the above-mentioned steel sheet, for example, a highly corrosion-resistant hot-dip plated steel material, and a non-limiting example thereof can be a Zn-Mg-Al alloy plated steel sheet.
[0024] Each component constituting the solution composition will be described in detail below.
[0025] (a) Trivalent chromium compound 0.1 to 10% by weight
[0026] In the solution composition of the present invention, the trivalent chromium compound mainly forms an insoluble coating on the surface of the steel sheet, thereby improving the corrosion resistance due to a barrier effect.
[0027] In the solution composition of the present invention, if the content of the trivalent chromium compound is less than 0.1%, a strong insoluble coating cannot be formed sufficiently, and therefore the moisture penetrating into the surface of the steel sheet cannot be effectively blocked, resulting in failure to ensure corrosion resistance. On the other hand, if the content exceeds 10%, there is a risk of foreign matter defects occurring due to the excessive chromium content.
[0028] In the present invention, the type of the trivalent chromium compound is not particularly limited, but it is preferably one or more compounds selected from the group consisting of chromium sulfate, chromium nitrate, chromium phosphate, chromium fluoride, chromium chloride, and mixtures thereof.
[0029] (b) Acidity regulator 0.1 to 10% by weight
[0030] In the solution composition of the present invention, the acidity regulator functions to adjust the pH of the solution so that the components in the composition are stable in the solution and can react appropriately under coating conditions to stably form a coating.
[0031] If the content of such an acidity regulator is less than 0.1%, the pH of the solution may become high, resulting in a risk of reduced solution stability. On the other hand, if the content exceeds 10%, there is a possibility that corrosion resistance, etc. may not be ensured due to residual acid after drying.
[0032] In the present invention, the type of the acidity regulator is not particularly limited, but is preferably phosphoric acid, nitric acid, sulfuric acid, hydrofluoric acid, hydrochloric acid, (NH 4 )H 2 PO 4 , (NH 4 ) 2 HPO 4 , NaH2 PO 4 , Na 2 HPO 4 The acid may be one or more selected from the group consisting of phytic acid, glycolic acid, lactic acid, acetic acid, oxalic acid, and mixtures thereof.
[0033] (c) Adhesion improver 1 to 20% by weight
[0034] In the solution composition of the present invention, the adhesion improver combines with the above-mentioned trivalent chromium compound and film-forming agent, and also with the steel sheet, thereby playing a role in improving the adhesion and corrosion resistance of the coating layer.
[0035] If the content of such adhesion improver is less than 1%, the adhesion to the steel sheet may not be sufficiently secured, which may result in the occurrence of foreign matter defects, whereas if the content exceeds 20%, an excessive amount of the adhesion improver remains after the coating film is formed, which may result in the corrosion resistance and the like not being secured.
[0036] In the present invention, the type of the adhesion improver is not particularly limited, but is preferably vinyl methoxysilane, vinyl trimethoxysilane (VTMS), vinyl epoxy silane, vinyl triepoxy silane, 3-aminopropyl triepoxy silane, 3-glycidoxypropyl trimethoxysilane, 3-methaglyoxypropyl trimethoxysilane, γ-glycidoxypropyl triethoxysilane, γ-glycidoxytrimethyl dimethoxysilane, N-(3-(trimethoxysilyl)propyl)ethylenediamine (AEAPTMS), 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 3-(2,3-epoxypropoxy)propyltriethoxysilane, 3-(2,3-epoxypropoxy)propylmethyldiethox The methylaminopropylsilane may be one or more selected from the group consisting of ethylaminopropylsilane, 3-(2,3-epoxypropoxy)propylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl-3-aminopropyl)methyldimethoxysilane, N-(2-aminoethyl-3-aminopropyl)trimethoxysilane, Diethylenetriaminopropyltrimethoxysilane, 3-Ureidopropyltrimethoxysilane, N-Phenylaminopropyltrimethoxysilane, (3-Glycidyloxypropyl)trimethoxysilane (GPTMS), Methyltrimethoxysilane (MTMS), and mixtures thereof.
[0037] (d) Corrosion resistance improver 1 to 15% by weight
[0038] In the solution composition of the present invention, the corrosion resistance improver fills any gaps that may exist between the trivalent chromium compound and the film-forming agent while forming a passivation film, thereby playing a role in suppressing the generation of corrosion.
[0039] If the content of such a corrosion resistance improver is less than 1%, it is difficult to ensure corrosion resistance because a sufficient passive film cannot be formed, while if the content exceeds 15%, the solution stability may decrease due to an excessively high solid content.
[0040] In the present invention, the type of the corrosion resistance improver is not particularly limited, but may be preferably one or more selected from the group consisting of vanadyl acetylacetonate, ammonium metavanadate, potassium metavanadate, sodium metavanadate, vanadium trioxide, vanadium acetylacetate, ammonium metavanadate, silicon oxide, and mixtures thereof.
[0041] (e) 0.1 to 25% by weight of a film-forming agent
[0042] In the solution composition of the present invention, the film-forming agent is a component added to form a strong film layer on the steel sheet surface together with the trivalent chromium compound, adhesion improver, and crosslinking agent. That is, it is advantageous for improving the film-forming effect, which is insufficient with inorganic components alone, and for improving the alkali resistance and corrosion resistance of the steel sheet to pipe-making oil.
[0043] If the content of the film-forming agent is less than 0.1%, the film formation is insufficient, making it difficult to ensure resistance to pipe-making oil and alkali resistance, whereas if the content exceeds 25%, there is a risk of foreign matter defects occurring.
[0044] In the present invention, the type of the film-forming agent is not particularly limited, but is preferably one or more selected from the group consisting of polyurethane resin (cationic or non-ionic), acrylic emulsion (cationic or non-ionic), and mixtures thereof.
[0045] (f) Lubricant: 0.01 to 2% by weight
[0046] In the solution composition of the present invention, the lubricant plays a role in improving the slipperiness of the steel sheet surface, improving the workability, and suppressing the occurrence of foreign matter defects.
[0047] If the lubricant content is less than 0.01%, the slip properties of the steel sheet surface may be insufficient, which may result in the generation of foreign matter defects, whereas if the lubricant content exceeds 2%, the solution stability may decrease.
[0048] In the present invention, the type of the lubricant is not particularly limited, but it may be one or more selected from the group consisting of Polytetrafluoroethylene (PTFE), Polyethylene (PE), Carnauba wax, and mixtures thereof.
[0049] (g) Co-solvent 0.5 to 10% by weight
[0050] In the solution composition of the present invention, the co-solvent serves to adjust the evaporation rate of the solvent during the drying process during the coating operation and to suppress defects on the coating surface after drying.
[0051] If the content of the co-solvent is less than 0.5%, the effect of controlling the volatilization rate during drying is insufficient, so that the evaporation rate of the main solvent is abrupt at the boiling point, causing a surface defect called popping, which leads to problems such as a decrease in corrosion resistance, etc. On the other hand, if the content exceeds 10%, the solution stability may decrease due to abrupt changes in the viscosity and density of the solution.
[0052] In the present invention, the type of the co-solvent is not particularly limited, but is preferably one or more selected from the group consisting of ethanol, isopropyl alcohol, methanol, tallow alcohol, 2-butoxyethanol, diethylene glycol monobutyl ether, and mixtures thereof.
[0053] (h) Solvent
[0054] The solution composition of the present invention may contain a solvent as the remaining component, and in the present invention, water (distilled water, deionized water) may be used as the solvent.
[0055] Hereinafter, a surface-treated steel sheet having a coating layer formed by surface-treating the steel sheet with the above-mentioned solution composition according to another embodiment of the present invention will be described in detail.
[0056] In the present invention, the steel sheet that can be surface-treated with the solution composition is not particularly limited, but can be, for example, a plated steel sheet.
[0057] It should be noted that the plated steel sheet targeted by the present invention can be applied to all types of plated steel sheets, such as electroplated steel sheets, electro-alloy-plated steel sheets, alloyed hot-dip galvanized steel sheets, hot-dip aluminum-plated steel sheets, and aluminum-plated steel sheets.
[0058] However, it will be apparent that, as a non-limiting example, the steel sheet may be a hot-dip galvanized steel sheet or a ternary (Zn-Mg-Al) hot-dip galvanized steel sheet.
[0059] A coating layer can be formed on at least one surface of the above-mentioned plated steel sheet by coating the solution composition of the present invention. In this case, the coating layer can be formed to a thickness of 0.2 to 3.0 μm on the plating layer of the plated steel sheet.
[0060] If the thickness of the coating layer is less than 0.2 μm, the effects of the coating layer, such as corrosion resistance and blackening resistance, will not be fully obtained. On the other hand, if the thickness exceeds 3.0 μm, friction with the rolls that come into contact with the material during the successive steps for forming the coating layer will occur, and the coating layer may fall off, resulting in foreign matter defects.
[0061] Here, the above thickness means the thickness after drying.
[0062] Further, in the present invention, a method for producing a surface-treated steel sheet using the above solution composition will be described.
[0063] Specifically, the method may include the steps of providing a steel sheet, applying the solution composition of the present invention to at least one surface of the steel sheet, and heat treating the steel sheet to which the composition has been applied.
[0064] The steel sheet may be the above-mentioned plated steel sheet, and non-limiting examples thereof may include a hot-dip galvanized steel sheet or a ternary (Zn-Mg-Al) hot-dip galvanized steel sheet.
[0065] The solution composition of the present invention can be applied to the steel sheet by any commonly used coating method, and is not particularly limited.
[0066] For example, one method may be selected from bar coating, roll coating, spray coating, dipping coating, and the like.
[0067] On the other hand, by heat treating a steel sheet to which a composition has been applied by the above-mentioned coating method, a coating layer can be formed with a constant thickness.
[0068] At this time, the heat treatment is preferably carried out in the temperature range of 50 to 250° C., but if the heat treatment temperature is less than 50° C., a proper solid coating layer is not formed and a liquid solution remains, which may result in failure to ensure the desired corrosion resistance. On the other hand, if the temperature exceeds 250° C., there is a problem that the coating layer deteriorates and discolors due to the excessively high temperature, which may result in poor corrosion resistance and blackening resistance.
[0069] In the present invention, the heat treatment process may include a drying process so that the applied composition has a solid form, and the steel sheet after the heat treatment may have a coating layer having a thickness of 0.2 to 3.0 μm after drying. In this case, the drying method is not particularly limited, but it is clear that equipment such as a hot air drying furnace or an induction heating furnace (induction oven) can be used, and the drying conditions may be according to conventional methods.
[0070] Hereinafter, the present invention will be described in more detail through examples. However, the description of the examples is for illustrating the implementation of the present invention, and the present invention is not limited by the description of the examples. The scope of the present invention is determined by the matters described in the claims and matters that can be reasonably inferred therefrom. EXAMPLES
[0071] [Production of solution composition for steel sheet surface treatment] In order to measure the physical properties of the solution composition for surface treatment of steel sheet according to the present invention, the solution composition was prepared using the following materials.
[0072] First, phosphoric acid was added to distilled water (solvent) as an acidity regulator, and then chromium nitrate, a trivalent chromium compound, was added at about 40°C and stirred for about 30 minutes. Using the same method, 3-glycidoxypropyltrimethoxysilane, an adhesion promoter, silicon oxide, a corrosion resistance improver, urethane resin, a film former, PE wax, a lubricant, and ethanol, a co-solvent, were added every 30 minutes while stirring.
[0073] At this time, the content of each component is shown in Table 1 below.
[0074] [Table 1]
[0075] solution stability In order to confirm whether the prepared solution composition maintains its stability under certain conditions, the following experiment was carried out.
[0076] After measuring the initial viscosity (Vi) of each solution composition of the above Invention Examples 1 to 15 and Comparative Examples 1 to 14, the composition was stored in an oven at 50°C for 120 hours, cooled to 25°C, and the viscosity (VI) at 25°C was measured. Each measured viscosity value was substituted into the following mathematical formula 1, and the solution stability was evaluated based on the measured value (ΔV). The results are shown in Table 3 below.
[0077] [Mathematical formula 1] △V = (Vl-Vi) / Vi × 100(%)
[0078] <Evaluation criteria for solution stability> ○: ΔV value is less than 20(%) or no gelation is observed when visually observed ×: ΔV value is 20(%) or more, or gelation is observed when visually observed.
[0079] [Manufacturing of surface-treated steel sheets] Next, the solution composition prepared above was applied to the surface of a steel sheet by bar coating, and then heat-treated while passing through an induction oven to obtain each surface-treated steel sheet. The coating amount during the bar coating was about 25 mg / m2 based on Cr. 2 The experiment was carried out so that
[0080] In this case, a Zn-Al-Mg alloy hot-dip galvanized steel sheet (Al: 13.0%, Mg: 5.0%) was used as the steel sheet for applying the solution composition, and a test piece was prepared by cutting into a size of 7 cm × 15 cm (horizontal × vertical) and subjecting to a degreasing treatment.
[0081] The heat treatment temperature during the above surface treatment and the thickness of the formed coating layer are shown in Table 2 below.
[0082] [Table 2]
[0083] In order to measure the physical properties of the surface-treated steel sheets manufactured as described above, the flat plate corrosion resistance, processed part corrosion resistance, pipe-making oil corrosion resistance, alkali resistance, pitting corrosion resistance, foreign object defects, etc. were measured according to the following methods and standards. The results are shown in Table 3 below.
[0084] Plate corrosion resistance Based on the method specified in ASTM B117, each steel plate (test piece) was treated with the solution composition, and then the rate of white rust formation on the steel plate over time was measured.
[0085] <Evaluation criteria for plate corrosion resistance> ○: White rust has occurred for 144 hours or more △: White rust occurred for 96 hours or more but less than 144 hours ×: White rust occurrence time is less than 96 hours
[0086] Corrosion resistance of processed parts The surface-treated steel sheet (test piece) was pushed up to a height of 6 mm using an Erichsen tester, and the degree of white rust generation after 24 hours was measured.
[0087] <Evaluation criteria for corrosion resistance of processed parts> ○: White rust does not occur, or if it does occur, it is very fine △: White rust has formed on the circle and some of it has washed away, but it has not washed away to the outside. ×: White rust occurs and flows outside the circle
[0088] Piping oil invasiveness The steel sheet (test piece) surface-treated as described above was immersed in pipe-making oil at room temperature for 24 hours, and the color difference before and after immersion was measured. The pipe-making oil used was BW WELL MP-411 from Buhmwoo Co., Ltd., Korea, diluted with 10% water.
[0089] <Evaluation criteria for pipe-making oil abrasion> ○: ΔE≦2 △:2<ΔE≦3 ×:3<ΔE
[0090] Alkali resistance The steel sheet (test piece) surface-treated as described above was immersed in a degreasing solution at 60°C for 2 minutes, then washed with water and air-blowing was performed, and the color difference before and after was measured. The alkaline degreasing solution used was Parkerizing's Finecleaner L 4460 A: 20g / 2.4L + L 4460 B: 12g / 2.4L (pH=12).
[0091] <Evaluation criteria for alkali resistance> ○: ΔE≦2 △:2<ΔE≦4 ×:4<ΔE
[0092] Spot corrosion resistance Dew was applied to the surface of the steel plate (test piece) that had been surface-treated as described above using a sprayer, and the two spray-treated steel plates were then butted together, packaged, and placed in a thermohygrostat for 8 cycles, with 6 hours at high temperature and humidity (42°C, 95%) and 6 hours at low humidity (15°C, 60%), and the number of point defects on the surface was then measured. The scan area of the steel plate was 150 x 50 mm. 2 This was then enlarged 100 times to reveal that the area of the corrosive point defect was 29,500 μm 2 Only the above items were counted.
[0093] <Evaluation criteria for pitting corrosion resistance> ○: Number of dots ≦20 △: 20<Number of dots≦40 ×:40<Number of dots
[0094] Foreign body defects In order to evaluate foreign matter defects on the steel plate (test piece) that had been surface treated as described above, a test piece with a surface area of approximately 4 cm 2 After covering the probe with white gauze, a weight of 10 kg was placed on the probe, and the probe was rubbed back and forth on the steel plate surface 100 times. The whiteness value of the gauze before and after rubbing (ΔL = L before -L after In order to simulate high humidity conditions, the steel plate and the probe were placed in a humidity chamber, and the humidity in the chamber was maintained at 95% or more using a humidifier, after which the friction evaluation was performed.
[0095] <Evaluation criteria for foreign matter defects> ○: ΔL≦2.5 △:2.5<ΔL≦5.0 ×:5.0<ΔL
[0096] [Table 3]
[0097] As shown in Table 3 above, the solution compositions of Examples 1 to 15 were excellent in solution stability, and the steel sheets surface-treated with such solution compositions also showed extremely excellent results in all evaluations.
[0098] In contrast, in Comparative Example 1, in which no trivalent chromium compound was added, the corrosion resistance due to the barrier effect was insufficient, and the flat plate corrosion resistance, processed part corrosion resistance, and pitting corrosion resistance were poor.
[0099] It can be seen that in Comparative Example 2, the content of trivalent chromium compounds was excessively high, and foreign matter defects occurred.
[0100] Comparative Example 3 was a case where no acidity regulator was added, and the solution stability was poor. The flat plate corrosion resistance and processed part corrosion resistance of the steel plate surface-treated with such a solution composition were poor.
[0101] In Comparative Example 4, the content of the acidity regulator was excessive, resulting in a large amount of acid remaining in the solution, and the flat plate corrosion resistance, processed part corrosion resistance, and pitting corrosion resistance of the surface-treated steel plate were poor.
[0102] In Comparative Example 5, the content of the adhesion improver was insufficient, and a foreign matter defect occurred.
[0103] In Comparative Example 6, the content of adhesion promoter was too high, and the remaining unreacted silane caused the surface-treated steel plate to have poor flat plate corrosion resistance, processed area corrosion resistance, and pitting corrosion resistance.
[0104] In Comparative Example 7, the content of the corrosion resistance improver was insufficient, and the corrosion resistance was insufficient, with the flat plate corrosion resistance, processed portion corrosion resistance, and pitting corrosion resistance being poor.
[0105] In Comparative Example 8, the content of the corrosion resistance improver was excessive, and the excessively high solid content resulted in poor solution stability, poor alkali resistance of the surface-treated steel sheet, and the occurrence of foreign matter defects.
[0106] In Comparative Example 9, in which no film-forming agent was added, the surface-treated steel sheet was inferior in corrosion resistance to pipe-making oil and alkali resistance.
[0107] In Comparative Example 10, the content of the film-forming agent was excessive, and foreign matter defects occurred.
[0108] Comparative Example 11 was a case where no lubricant was added, and foreign matter defects occurred.
[0109] In Comparative Example 12, the content of the lubricant was excessive, and the solution stability was insufficient, and the corrosion resistance of the processed part of the surface-treated steel sheet was poor.
[0110] In Comparative Example 13, no cosolvent was added, and not only did the surface-treated steel sheet have surface defects, but also had extremely poor corrosion resistance properties such as flat plate corrosion resistance, processed part corrosion resistance, and pitting corrosion resistance.
[0111] In Comparative Example 14, the content of the co-solvent was excessive, and the solution stability was poor, and the corrosion resistance of the processed part of the surface-treated steel sheet was poor.
[0112] FIG. 1 shows the surface shape of a steel sheet (Example 1) that was surface-treated with the solution composition of the present invention and the surface shape of a steel sheet that was surface-treated with a conventional composition.
[0113] As shown in FIG. 1, it can be seen that the steel sheet (a) surface-treated with the conventional solution composition has defects at the edges, whereas the steel sheet (b) surface-treated with the solution composition of the present invention has a smooth surface all the way to the edges without any defects.
Claims
1. (a) 0.1 to 10% by weight of a trivalent chromium compound; (b) 0.1 to 10% by weight of an acidity regulator; (c) 1 to 20% by weight of an adhesion improver; (d) 1 to 15 wt. % of a corrosion resistance improver; (e) 0.1 to 25% by weight of a film-forming agent; (f) 0.01 to 2% by weight of a lubricant; (g) 0.5 to 10% by weight of a co-solvent, and (h) A solution composition for the surface treatment of steel sheet, the balance of which comprises a solvent.
2. 2. The solution composition for treating a steel sheet surface according to claim 1, wherein the trivalent chromium compound is one or more selected from the group consisting of chromium sulfate, chromium nitrate, chromium phosphate, chromium fluoride, chromium chloride, and mixtures thereof.
3. The acidity regulator may be phosphoric acid, nitric acid, sulfuric acid, hydrofluoric acid, hydrochloric acid, (NH 4 ) H 2 P.O. 4 , (NH 4 ) 2 H.P.O. 4 , NaH 2 P.O. 4 , Na 2 H.P.O. 4 2. The solution composition for steel sheet surface treatment according to claim 1, wherein the active ingredient is one or more selected from the group consisting of phytic acid, glycolic acid, lactic acid, acetic acid, oxalic acid, and mixtures thereof.
4. The adhesion improver is preferably vinyl methoxy silane, vinyl trimethoxy silane (VTMS), vinyl epoxy silane, vinyl triepoxy silane, 3-aminopropyl triepoxy silane, 3-glycidoxypropyl trimethoxy silane, 3-methaglyoxypropyl trimethoxy silane, γ-glycidoxypropyl triethoxy silane, γ-glycidoxytrimethyl dimethoxy silane, N-(3-(trimethoxysilyl)propyl)ethylenediamine (AEAPTMS), 2-(3 , 4-Epoxycyclohexyl) ethyltrimethoxysilane, 2-(3,4-Epoxycyclohexyl) ethyltriethoxysilane, 3-(2,3-Epoxypropoxy) propyltrim ethoxysilane, 3-(2,3-Epoxypropoxy)propyltriethoxysilane, 3-( 2,3-Epoxypropoxy) propylmethyldiethoxysilane, 3-(2,3-Epoxypr opoxy)propylmethyldimethoxysilane, 3-Aminopropyltriethoxysilane, 3-Aminopropyltrimethoxysilane, 3-Aminopropylmethyldie thoxysilane, N-(2-Aminoethyl-3-aminopropyl)methyldimethoxysilane, N-(2-Aminoethyl-3-aminopropyl)trimethoxysilane, Diet The solution composition for steel sheet surface treatment according to claim 1, which is one or more selected from the group consisting of hylenetriaminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, (3-glycidyloxypropyl)trimethoxysilane (GPTMS), methyltrimethoxysilane (MTMS), and mixtures thereof.
5. 2. The solution composition for surface treatment of steel sheet according to claim 1, wherein the corrosion resistance improver is one or more selected from the group consisting of vanadyl acetylacetonate, ammonium metavanadate, potassium metavanadate, sodium metavanadate, vanadium trioxide, vanadium acetylacetate, ammonium metavanadate, silicon oxide, and mixtures thereof.
6. 2. The solution composition for treating a steel sheet according to claim 1, wherein the film-forming agent is one or more selected from the group consisting of polyurethane resin (cationic or non-ionic), acrylic emulsion (cationic or non-ionic), and a mixture thereof.
7. 2. The solution composition for treating a steel sheet surface according to claim 1, wherein the lubricant is one or more selected from the group consisting of polytetrafluoroethylene (PTFE), polyethylene (PE), Carnauba wax, and mixtures thereof.
8. 2. The solution composition for treating a steel sheet surface according to claim 1, wherein the co-solvent is at least one selected from the group consisting of ethanol, isopropyl alcohol, methanol, tallow alcohol, 2-butoxyethanol, diethylene glycol monobutyl ether, and mixtures thereof.
9. The solution composition for treating a steel sheet surface according to claim 1 , wherein the solvent is water.
10. A steel plate, A surface-treated steel sheet comprising: a coating layer formed on at least one surface of the steel sheet from the composition according to any one of claims 1 to 9.
11. The surface-treated steel sheet according to claim 10, wherein the coating layer has a thickness of 0.2 to 3.0 μm.
12. providing a steel plate; applying a composition according to any one of claims 1 to 9 to at least one surface of the steel sheet; and heat treating the steel sheet coated with the composition at 50 to 250°C.
13. The method for producing a surface-treated steel sheet according to claim 12, wherein the steel sheet is a Zn-Al-Mg system hot-dip galvanized steel sheet.
14. The step of applying the composition comprises: The method for producing a surface-treated steel sheet according to claim 12, wherein the coating is carried out by one or more methods selected from the group consisting of bar coating, roll coating, spray coating, and dipping coating.
Citation Information
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