WO2023121175A1 - Solution composition for steel sheet surface treatment, steel sheet surface-treated using same, and manufacturing method therefor - Google Patents

Solution composition for steel sheet surface treatment, steel sheet surface-treated using same, and manufacturing method therefor Download PDF

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WO2023121175A1
WO2023121175A1 PCT/KR2022/020708 KR2022020708W WO2023121175A1 WO 2023121175 A1 WO2023121175 A1 WO 2023121175A1 KR 2022020708 W KR2022020708 W KR 2022020708W WO 2023121175 A1 WO2023121175 A1 WO 2023121175A1
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steel sheet
solution composition
corrosion resistance
surface treatment
weight
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French (fr)
Korean (ko)
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최창훈
조수현
김태철
김성주
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주식회사 포스코
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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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/50—Treatment of iron or alloys based thereon
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06—Zinc or cadmium or alloys based thereon
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/14—Removing excess of molten coatings; Controlling or regulating the coating thickness
    • C23C2/16—Removing excess of molten coatings; Controlling or regulating the coating thickness using fluids under pressure, e.g. air knives
    • C23C2/18—Removing excess of molten coatings from elongated material
    • C23C2/20—Strips; Plates
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—After-treatment
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—After-treatment
    • C23C2/28—Thermal after-treatment, e.g. treatment in oil bath
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
    • C23C2/36—Elongated material
    • C23C2/40—Plates; Strips
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium

Definitions

  • the present invention relates to a solution composition capable of improving petechial corrosion resistance and blackening resistance of a steel sheet, a steel sheet surface-treated using the same, and a method for manufacturing the steel sheet.
  • a high corrosion-resistant hot-dip galvanized steel material having a plating layer containing zinc (Zn), magnesium (Mg), and aluminum (Al) is known as a steel material having excellent red rust corrosion resistance.
  • Patent Document 1 a method of chemical conversion treatment by immersing a steel sheet in a composition containing trivalent chromium is applied.
  • This method has problems such as a long deposition time to be applied to the continuous process of steel makers, and the chemical treatment method impairs the anti-fingerprint property of the steel sheet.
  • Patent Documents 2 and 3 disclose that by coating a composition containing trivalent chromium on a plated steel sheet in a spray or roll coater method, it can be applied to continuous lines of steel yarn and anti-fingerprint properties can be secured.
  • these compositions contain porous silica components, they are not suitable for Mg and Al-based alloys that cause severe discoloration in a humid atmosphere.
  • porous silica has a strong hygroscopic property, causing rapid discoloration in the Zn-Mg-Al-based alloy steel sheet.
  • 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 Application Publication No. 2002-069660
  • One aspect of the present invention is to improve the point 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, to provide a solution composition having excellent solution stability, and using the same It is intended to provide a surface-treated steel sheet and a manufacturing method thereof.
  • a trivalent chromium compound 20 to 60% 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 20% by weight of a corrosion resistance improver weight%, (e) 0.01 to 3.0% by weight of a petechial corrosion improver, (f) 1 to 20% by weight of a co-solvent, and (g) a solution composition for surface treatment of steel sheet containing the remainder of the solvent.
  • a steel plate a Zn-Mg-Al-based plating layer formed on at least one surface of the steel sheet; and a surface treatment coating layer formed on the plating layer, wherein the surface treatment coating layer is a coating layer formed of the above-described solution composition.
  • Another aspect of the present invention comprises the steps of forming a Zn-Mg-Al-based plating layer by hot-dip galvanizing treatment on at least one surface of a steel sheet; coating the above-described solution composition on the plating layer; And it provides a method for manufacturing a surface-treated coated steel sheet comprising the step of drying the coated steel sheet.
  • the present invention it is possible to provide a solution composition having excellent solution stability without occurrence of precipitation or aggregation even when used after long-term storage, and a steel sheet having excellent point corrosion resistance and blackening resistance by coating the solution composition on the steel sheet. can provide.
  • FIG. 1 illustrates a coated steel sheet (a) with point corrosion (edge portion) and a coated steel sheet (b) without surface corrosion, according to an embodiment of the present invention.
  • the inventors of the present invention have studied in depth to obtain a solution composition that is advantageous for improving not only point corrosion corrosion resistance but also blackening resistance of the coated steel sheet in coating a steel sheet, for example, a high corrosion resistance hot-dip galvanized steel material.
  • the solution composition according to the present invention contains (a) 20 to 60% 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 20% by weight of a corrosion resistance improver. % by weight, (e) 0.01 to 3.0% by weight of a petechial corrosion improver, (f) 1 to 20% by weight of a co-solvent, and (g) the remainder of the solvent.
  • the content of the solution composition of the present invention is based on 100% by weight of the total.
  • the solution composition may form a coating layer on at least one surface of a substrate on which the composition can be applied.
  • the substrate may be the above-mentioned steel sheet, for example, a high corrosion resistance hot-dip galvanized steel sheet, and may be a Zn-Mg-Al-based alloy-coated steel sheet as a non-limiting example.
  • the trivalent chromium compound mainly forms an insoluble film on the surface of the steel sheet to improve corrosion resistance by a barrier effect.
  • the content of the trivalent chromium compound is less than 20% in the solution composition of the present invention, a strong insoluble film cannot be sufficiently formed to effectively block moisture penetrating into the surface of the steel sheet, and as a result, corrosion resistance cannot be secured.
  • the content exceeds 60%, foreign matter defects may occur due to excessive chromium components.
  • the type of the trivalent chromium compound is not particularly limited, but may preferably be at least one selected from the group consisting of chromium sulfate, chromium nitrate, chromium phosphate, chromium fluoride, chromium chloride, and mixtures thereof.
  • the acidity regulator controls the pH of the solution so that the components in the composition stably exist in the solution and reacts appropriately under coating conditions to stably form a film.
  • the content of the acidity regulator is less than 0.1%, the pH of the solution increases and the stability of the solution may deteriorate. On the other hand, if the content exceeds 10%, corrosion resistance may not be secured due to residual acid after drying.
  • the type of acidity regulator is not particularly limited, but preferably phosphoric acid, nitric acid, sulfuric acid, hydrofluoric acid, hydrochloric acid, (NH 4 )H 2 PO 4 , (NH 4 ) 2 HPO 4 , NaH 2 PO 4 , Na 2 HPO 4 , phytic acid, glycolic acid, lactic acid, acetic acid, oxalic acid, and may be at least one selected from the group consisting of mixtures thereof.
  • the adhesion improver binds to the trivalent chromium compound and the like, and also binds to the steel sheet to improve adhesion and corrosion resistance of the coating layer.
  • the content of the adhesion improver is less than 1%, adhesion to the steel sheet may not be sufficiently secured, and foreign matter defects may occur. On the other hand, if the content exceeds 20%, the amount remaining after forming the coating film may be excessive and corrosion resistance may not be secured.
  • the type of the adhesion improver is not particularly limited, but preferably vinylmethoxysilane, vinyltrimethoxysilane (VTMS), vinylepoxysilane, vinyltriepoxysilane, 3-aminopropyltriepoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-metaglycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxytrimethyldimethoxysilane, 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)prop
  • the corrosion resistance improver serves to suppress corrosion by forming a passive film while filling a gap that may exist between the trivalent chromium compound and the adhesion improver.
  • the content of the corrosion resistance improver is less than 1%, a passivation film cannot be sufficiently formed, making it difficult to secure corrosion resistance. On the other hand, if the content exceeds 20%, solution stability may be deteriorated due to excessively high solid content.
  • the type of the corrosion resistance improver is not particularly limited, but preferably, vanadyl acetylacetonate, ammonium metavanadate, potassium metavanadate, meta It may be at least one selected from the group consisting of sodium metavanadate, vanadium trioxide, vanadium acetylacetate, ammonium metavanadate, silicon oxide, and mixtures thereof.
  • the petechial corrosion improver serves to minimize petechial corrosion occurring in the form of petechiae by preventing local penetration of corrosion factors together with the corrosion resistance improver.
  • the content of the petechiae corrosion improver in the solution composition of the present invention is less than 0.01%, local penetration of corrosion factors cannot be blocked, resulting in petechial corrosion.
  • the content exceeds 3.0% the pH of the solution is excessively increased and there is a risk that the stability of the solution is lowered.
  • the type of the point corrosion improver is not particularly limited, but preferably ethylenediamine, hexamethylenediamine, trimethylamine, methylamine, diphenylamine, ethyleneamine, aniline, toluidine, piperidine, It may be at least one selected from the group consisting of aziridine, pyridine, alanine, propylamine, diisopropylamine, monoisopropylamine, dibutylamine, dipropylamine, and mixtures thereof.
  • the co-solvent controls the volatilization rate of the solvent during the drying process during the coating operation to suppress defects on the surface of the film after drying.
  • the type of the co-solvent is not particularly limited, but preferably ethanol, isopropyl alcohol, methanol, tallow alcohol, 2-butoxyethanol, diethylene glycol mono It may be at least one selected from the group consisting of butyl ether (diethylene glycol monobutyl ether) and mixtures thereof.
  • the solution composition of the present invention may contain a solvent as a remaining component, and water (distilled water, deionized water) may be used as the solvent in the present invention.
  • the composition may be surface-treated on a coated steel sheet, preferably a ternary (Zn-Mg-Al-based) hot-dip galvanized steel sheet.
  • the surface-treated steel sheet of the present invention is a steel sheet; a Zn-Mg-Al-based plating layer formed on at least one surface of the steel sheet; and a surface treatment coating layer formed on the plating layer.
  • the steel sheet is a base steel sheet from which a coated steel sheet can be obtained, and in particular, any steel sheet from which a ternary (Zn-Mg-Al-based) hot-dip galvanized steel sheet can be obtained.
  • the composition of the Zn-Mg-Al-based plating layer may include magnesium (Mg): 4.0 to 7.0%, aluminum (Al): 11.0 to 19.5%, the balance Zn and other unavoidable impurities, by weight%.
  • Magnesium (Mg) in the plating layer is an element that serves to improve the corrosion resistance of the plated steel sheet, and the content thereof is preferably 4.0% or more to ensure excellent corrosion resistance, which is the purpose of the present invention. However, if the Mg content is excessive, dross may be generated in the plating bath and an intermetallic compound having high hardness may be excessively formed in the plating layer to deteriorate the bendability of the steel sheet. It can be capped at 7.0%.
  • the aluminum (Al) at 11.0% or more in consideration of this.
  • the Al content is excessive, the melting point of the plating bath increases and the operating temperature becomes excessively high, causing problems due to high-temperature work such as erosion of the plating bath structure and deterioration of the steel sheet. Therefore, it is preferable to limit the Al content to 19.5% or less.
  • the remaining composition is zinc (Zn), and unavoidable impurities may be unintentionally mixed in the process of manufacturing a coated steel sheet having a Zn-Mg-Al-based plating layer. At this time, it is revealed that the meaning of the unavoidable impurities will be easily understood by those skilled in the art.
  • the structure of the above-described Zn-Mg-Al-based plating layer satisfies the following [Relational Expression 1].
  • I(110) represents the X-ray diffraction integrated intensity of the (110) plane crystal peak for the MgZn 2 phase
  • I(103) represents the X-ray diffraction of the (103) plane crystal for the MgZn 2 phase represents the integral strength.
  • the I (110) may have an integrated intensity value in the range of 120 to 200, and the I (103) may have an integrated intensity value in the range of 240 to 300. In this way, it is preferable to satisfy the value of [Relationship 1] within each range.
  • a coating layer formed by coating the composition of the present invention in a solution state may be included on top of the above-described Zn-Mg-Al-based plating layer, and in this case, the coating layer preferably has a thickness of 0.1 to 2.0 ⁇ m.
  • the thickness of the coating layer is less than 0.1 ⁇ m, the surface treatment solution composition is thinly applied to the roughness of the acid portion present on the surface of the coated steel sheet, resulting in a decrease in corrosion resistance.
  • the thickness exceeds 2.0 ⁇ m, the coating layer (coating layer) ) is formed thickly, which deteriorates workability and increases the cost of solution treatment, which is economically unfavorable.
  • the thickness means the thickness after drying.
  • the present invention describes a method for manufacturing a surface-treated steel sheet using the composition.
  • forming a Zn-Mg-Al-based plating layer by hot-dip galvanizing treatment on at least one surface of the steel sheet Coating the coating layer by applying the composition of the present invention in a solution state on the plating layer; and drying the coated steel sheet.
  • a generally used coating method may be applied, and thus, it is not particularly limited.
  • the coating process may be performed by selecting one method from among methods such as bar coating, roll coating, spraying, dipping, spray squeezing, and dip squeezing.
  • the process of drying the steel sheet coated with the composition is preferably performed in a temperature range of 40 to 280° C. based on the final temperature (PMT) of the material steel sheet (steel sheet).
  • the temperature is lower than 40° C. based on the final temperature of the material steel sheet, the formation of a sturdy film structure may be insufficient, resulting in inferior corrosion resistance and blackening resistance.
  • the temperature exceeds 280 ° C., the hardness of the film excessively increases, resulting in poor corrosion resistance of the processed part and poor surface quality such as yellowing due to excessive heat.
  • the steel sheet upon completion of the drying treatment may have a coating layer having a thickness of 0.1 to 2.0 ⁇ m after drying.
  • the means for performing the drying treatment is not particularly limited, but it is noted that facilities such as an induction oven or a hot air drying furnace may be used, and the conditions of these facilities may be in accordance with conventional conditions.
  • a solution composition was prepared using the following materials.
  • ⁇ : ⁇ V value is less than 20 (%) or no gelation phenomenon is observed with the naked eye
  • ⁇ ⁇ V value of 20 (%) or more, or a gelation phenomenon is observed upon visual observation
  • the prepared solution composition was applied to the surface of the steel sheet by a bar coating method, and then dried in an induction oven to obtain each surface-treated steel sheet.
  • the bar coating was carried out so that the adhesion amount of the composition was about 35 mg/m 2 based on Cr.
  • the steel sheet for applying the solution composition is a Zn-Mg-Al alloy hot-dip galvanized steel sheet (plating layer: Mg 5.4% by weight, Al 12.6% by weight, balance Zn and unavoidable impurities, value of [Relationship 1]: 0.40) was used, and it was cut into 7cm ⁇ 15cm (width ⁇ length) and manufactured as a degreased specimen.
  • the drying treatment temperature and the thickness of the coating layer formed during the surface treatment are shown in Table 2 below.
  • White rust generation time is 96 hours or more and less than 144 hours
  • the surface-treated steel sheet (specimen) according to the above was immersed in pipe-forming oil at room temperature and maintained for 24 hours, and then the color difference before/after immersion was measured. At this time, crude oil was used by diluting domestic Beomwoo BW WELL MP-411 in 10% water.
  • Dew is formed on the surface of the steel sheet (specimen) treated as described above using a sprayer, and then the two spray-treated steel sheets are packed facing each other and put in a thermo-hygrostat at high temperature and humidity (42°C, 95%). 6 hours at low temperature and humidity (15° C., 60%) for 6 hours as one cycle for a total of 8 cycles, and then the number of point defects on the surface was measured. At this time, the scan area of the steel sheet was set to 150 ⁇ 50 mm 2 , and only the number of corrosive point defects having an area of 29500 ⁇ m 2 or more was counted by magnifying it 100 times.
  • the steel plate and the probe were placed in a humidity chamber, and a humidity of 95% or more was maintained in the chamber using a humidifier, and then friction evaluation was performed.
  • the solution compositions of Examples 1 to 12 were excellent in solution stability, and the steel sheets surface-treated with these solution compositions also showed excellent results in all evaluation results.
  • Comparative Example 1 when the content of the trivalent chromium compound was insufficient, the corrosion resistance due to the barrier effect was not sufficient, and thus the corrosion resistance of the plate, the corrosion resistance of the processed part, and the corrosion resistance of the point corrosion were inferior.
  • Comparative Example 4 when the content of the acidity regulator was excessive, the acid remaining in the solution increased, resulting in inferior plate corrosion resistance, processed section corrosion resistance, and point corrosion resistance of the surface-treated steel sheet.
  • Comparative Example 7 was a case where the content of the corrosion resistance improver was insufficient, and the corrosion resistance was not sufficient, resulting in inferior plate corrosion resistance, processing corrosion resistance, and point corrosion resistance.
  • Comparative Example 9 is a case where the content of the petechiae corrosion improver was insufficient, and the petechiae corrosion resistance of the surface-treated steel sheet was inferior.
  • FIG. 1 shows the surface shape of a steel sheet surface-treated using a solution composition according to the present invention (Inventive Example 1) and the surface shape of a steel sheet surface-treated with a conventional composition.
  • the surface-treated steel sheet (a) with the conventional solution composition has point corrosion defects at the edge, whereas the surface-treated steel sheet with the solution composition of the present invention has a smooth surface up to the edge without defects. Able to know.

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Abstract

The present invention relates to a solution composition capable of improving pitting corrosion resistance and blackening resistance of a steel sheet, a steel sheet surface-treated using same, and a method for manufacturing the steel sheet.

Description

강판 표면처리용 용액 조성물, 이를 이용하여 표면처리된 강판 및 그 제조방법Solution composition for surface treatment of steel sheet, steel sheet surface-treated using the same and manufacturing method thereof
본 발명은 강판의 점상 부식 내식성 및 내흑변성을 향상시킬 수 있는 용액 조성물, 이를 이용하여 표면처리된 강판 및 상기 강판을 제조하는 방법에 관한 것이다.The present invention relates to a solution composition capable of improving petechial corrosion resistance and blackening resistance of a steel sheet, a steel sheet surface-treated using the same, and a method for manufacturing the steel sheet.
아연(Zn), 마그네슘(Mg) 및 알루미늄(Al)을 함유하는 도금층이 형성된 고내식 용융도금강재는 적청(red rust) 내식성이 우수한 강재로 알려져 있다. A high corrosion-resistant hot-dip galvanized steel material having a plating layer containing zinc (Zn), magnesium (Mg), and aluminum (Al) is known as a steel material having excellent red rust corrosion resistance.
그런데, 이러한 고내식 용융도금강재는 노출면이 대부분 아연 또는 아연 합금으로 이루어져 있어, 일반 환경 특히, 습윤 분위기에 노출되었을 때 표면에 점상의 부식성 결함이 쉽게 발생하여 외관이 나빠지는 문제가 있다. 또한, 최근에는 임가공 공정에서 롤을 통과하면서, 용융도금강재의 코팅층이 롤에 묻어나는 이물성 결함도 발생되고 있다.However, since most of the exposed surfaces of these highly corrosion-resistant hot-dip galvanized steel materials are made of zinc or zinc alloy, dotted corrosive defects easily occur on the surface when exposed to a general environment, particularly a humid atmosphere, resulting in a poor appearance. In addition, in recent years, while passing through the rolls in the toll processing process, foreign matter defects in which the coating layer of the hot-dip galvanized steel material is buried in the rolls have also occurred.
이러한 문제점을 해결하기 위하여, 종래에는 도금처리된 강판에 6가 크롬 또는 크로메이트 처리를 행함으로써 내식성 및 내흑변성을 확보하여 왔다. 그러나, 6가 크롬이 유해 환경물질로 지정되면서 현재에는 6가 크롬 사용에 대한 규제가 강화되고 있는 실정이다. 더욱이, 6가 크롬을 도금강판의 표면처리제로 사용시 강판 표면이 흑색으로 변하거나 흑점이 발생하는 결함의 문제가 있다.In order to solve this problem, conventionally, corrosion resistance and blackening resistance have been secured by performing hexavalent chromium or chromate treatment on the plated steel sheet. However, as hexavalent chromium is designated as a harmful environmental substance, regulations on the use of hexavalent chromium are currently being strengthened. Furthermore, when hexavalent chromium is used as a surface treatment agent for coated steel sheets, there is a problem in that the surface of the steel sheet turns black or black spots occur.
이에, 현재에는 3가 크롬을 함유하는 표면처리 용액 조성물을 도금강판 상에 코팅하여 도금강판의 내식성과 내흑변성을 확보하는 방법이 개발되고 있다.Accordingly, currently, a method for securing corrosion resistance and blackening resistance of a coated steel sheet by coating a surface treatment solution composition containing trivalent chromium on the coated steel sheet is being developed.
예컨대, 특허문헌 1에서는 3가 크롬을 함유한 조성물에 강판을 침적시켜 화성처리하는 방식을 적용하고 있다. 이 방식은 철강사의 연속공정에 적용하기에는 침적시간이 길고, 화성처리 방법은 강판의 내지문성을 저해하는 등의 문제가 있다.For example, in Patent Document 1, a method of chemical conversion treatment by immersing a steel sheet in a composition containing trivalent chromium is applied. This method has problems such as a long deposition time to be applied to the continuous process of steel makers, and the chemical treatment method impairs the anti-fingerprint property of the steel sheet.
한편, 특허문헌 2 및 3에서는 3가 크롬을 함유한 조성물을 도금강판 상에 스프레이 또는 롤코터 방식으로 코팅함으로써, 철강사의 연속라인에 적용이 가능하고 내지문성을 확보할 수 있다고 개시하고 있다. 하지만, 이들 조성물에는 다공질의 실리카 성분이 함유됨에 따라 습윤한 분위기에서 변색 발생이 심한 Mg, Al계 합금에는 적합하지 않다. 뿐만 아니라, 다공질의 실리카는 흡습 성질이 강하여 Zn-Mg-Al계 합금 강판에서는 급격한 변색 발생을 유발시키는 문제가 있다.On the other hand, Patent Documents 2 and 3 disclose that by coating a composition containing trivalent chromium on a plated steel sheet in a spray or roll coater method, it can be applied to continuous lines of steel yarn and anti-fingerprint properties can be secured. However, since these compositions contain porous silica components, they are not suitable for Mg and Al-based alloys that cause severe discoloration in a humid atmosphere. In addition, porous silica has a strong hygroscopic property, causing rapid discoloration in the Zn-Mg-Al-based alloy steel sheet.
[선행기술문헌][Prior art literature]
(특허문헌 1) 한국 특허공개공보 제10-2009-0024450호(Patent Document 1) Korean Patent Publication No. 10-2009-0024450
(특허문헌 2) 한국 특허공개공보 제10-2004-0046347호(Patent Document 2) Korean Patent Publication No. 10-2004-0046347
(특허문헌 3) 일본 특개공보 제2002-069660호(Patent Document 3) Japanese Patent Application Publication No. 2002-069660
본 발명의 일 측면은, 고내식 도금강판의 표면에 적용되는 코팅 용액의 조성을 제어하여 강판의 점상 부식 내식성과 내흑변성을 향상시키고자 하는 것으로서, 용액 안정성이 우수한 용액 조성물을 제공하고, 이를 이용하여 표면처리된 강판 및 이의 제조방법을 제공하고자 하는 것이다.One aspect of the present invention is to improve the point 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, to provide a solution composition having excellent solution stability, and using the same It is intended to provide a surface-treated steel sheet and a manufacturing method thereof.
본 발명의 과제는 상술한 내용에 한정하지 않는다. 본 발명의 과제는 본 명세서의 내용 전반으로부터 이해될 수 있을 것이며, 본 발명이 속하는 기술분야에서 통상의 지식을 가지는 자라면 본 발명의 부가적인 과제를 이해하는데 아무런 어려움이 없을 것이다.The object of the present invention is not limited to the above. The subject of the present invention will be understood from the entire contents of this specification, and those skilled in the art will have no difficulty in understanding the additional subject of the present invention.
본 발명의 일 측면은, (a) 3가 크롬 화합물 20~60중량%, (b) 산도 조절제 0.1~10중량%, (c) 밀착성 향상제 1~20중량%, (d) 내식성 개선제 1~20중량%, (e) 점상 부식 개선제 0.01~3.0중량%, (f) 조용제 1~20중량% 및 (g) 잔부 용제를 포함하는 강판 표면처리용 용액 조성물을 제공한다.In one aspect of the present invention, (a) 20 to 60% 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 20% by weight of a corrosion resistance improver weight%, (e) 0.01 to 3.0% by weight of a petechial corrosion improver, (f) 1 to 20% by weight of a co-solvent, and (g) a solution composition for surface treatment of steel sheet containing the remainder of the solvent.
본 발명의 다른 일 측면은, 강판; 상기 강판의 적어도 일면에 형성된 Zn-Mg-Al계 도금층; 및 상기 도금층 상에 형성된 표면처리 코팅층을 포함하며, 상기 표면처리 코팅층은 상술한 용액 조성물로 형성된 코팅층인 표면처리된 도금강판을 제공한다.Another aspect of the present invention, a steel plate; a Zn-Mg-Al-based plating layer formed on at least one surface of the steel sheet; and a surface treatment coating layer formed on the plating layer, wherein the surface treatment coating layer is a coating layer formed of the above-described solution composition.
본 발명의 또 다른 일 측면은, 강판의 적어도 일면에 용융아연도금처리하여 Zn-Mg-Al계 도금층을 형성하는 단계; 상기 도금층 상에 상술한 용액 조성물을 코팅처리하는 단계; 및 상기 코팅처리된 강판을 건조처리하는 단계를 포함하는 표면처리된 도금강판의 제조방법을 제공한다.Another aspect of the present invention comprises the steps of forming a Zn-Mg-Al-based plating layer by hot-dip galvanizing treatment on at least one surface of a steel sheet; coating the above-described solution composition on the plating layer; And it provides a method for manufacturing a surface-treated coated steel sheet comprising the step of drying the coated steel sheet.
본 발명에 의하면, 장시간 보관 후 사용시에도 침전, 응집 등이 발생하지 않고 우수한 용액 안정성을 가지는 용액 조성물을 제공할 수 있으며, 상기 용액 조성물을 강판 상에 코팅시킴으로써 우수한 점상 부식 내식성과 내흑변성을 가지는 강판을 제공할 수 있다.According to the present invention, it is possible to provide a solution composition having excellent solution stability without occurrence of precipitation or aggregation even when used after long-term storage, and a steel sheet having excellent point corrosion resistance and blackening resistance by coating the solution composition on the steel sheet. can provide.
나아가, 코팅 과정에서 이물 결함을 개선함으로써 제품의 수명을 향상시키는 효과가 있다.Furthermore, there is an effect of improving the lifespan of the product by improving foreign matter defects in the coating process.
도 1은 본 발명의 일 실시예에 있어서, 점상 부식(에지부)이 발생한 도금강판(a) 및 표면 부식이 발생하지 않은 도금강판(b)을 나타낸 것이다.1 illustrates a coated steel sheet (a) with point corrosion (edge portion) and a coated steel sheet (b) without surface corrosion, according to an embodiment of the present invention.
본 발명의 발명자들은 강판, 예컨대 고내식 용융도금강재를 코팅처리함에 있어서, 코팅처리된 강판의 점상 부식 내식성뿐만 아니라 내흑변성을 향상시키는 데에 유리한 용액 조성물을 얻기 위하여 깊이 연구하였다.The inventors of the present invention have studied in depth to obtain a solution composition that is advantageous for improving not only point corrosion corrosion resistance but also blackening resistance of the coated steel sheet in coating a steel sheet, for example, a high corrosion resistance hot-dip galvanized steel material.
그 결과, 3가 크롬 화합물과 함께 산도 조절제, 밀착성 향상제, 내식성 개선제, 점상 부식 개선제 및 조용제를 적정량으로 혼합한 용액 조성물을 제공할 수 있으며, 이 용액 조성물은 용액 안정성이 높다. 이러한 용액 조성물을 강판에 표면처리하는 경우 의도하는 효과를 얻을 수 있음을 확인하고, 본 발명을 완성하기에 이르렀다.As a result, it is possible to provide a solution composition in which a trivalent chromium compound is mixed with an acidity regulator, an adhesion improver, a corrosion resistance improver, a point corrosion improver, and a co-solvent in appropriate amounts, and this solution composition has high solution stability. It was confirmed that the intended effect could be obtained when the surface treatment of such a solution composition was performed on a steel sheet, and the present invention was completed.
이하, 본 발명에 대하여 상세히 설명한다.Hereinafter, the present invention will be described in detail.
먼저, 본 발명의 일 측면에 따른 강판 표면처리용 용액 조성물에 대하여 구체적으로 설명한다.First, a solution composition for surface treatment of steel sheet according to an aspect of the present invention will be described in detail.
본 발명에 따른 용액 조성물은 (a) 3가 크롬 화합물 20~60중량%, (b) 산도 조절제 0.1~10중량%, (c) 밀착성 향상제 1~20중량%, (d) 내식성 개선제 1~20중량%, (e) 점상 부식 개선제 0.01~3.0중량%, (f) 조용제 1~20중량% 및 (g) 잔부 용제를 포함할 수 있다.The solution composition according to the present invention contains (a) 20 to 60% 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 20% by weight of a corrosion resistance improver. % by weight, (e) 0.01 to 3.0% by weight of a petechial corrosion improver, (f) 1 to 20% by weight of a co-solvent, and (g) the remainder of the solvent.
본 발명의 용액 조성물의 함량은 전체 100중량%를 기준으로 한다.The content of the solution composition of the present invention is based on 100% by weight of the total.
후술하여 구체적으로 설명하겠지만, 상기 용액 조성물은 조성물을 도포할 수 있는 기재(substrate)의 적어도 일면에 코팅층을 형성할 수 있다. 본 발명에서 상기 기재는 앞서 언급한 강판, 예컨대 고내식 용융도금강재일 수 있으며, 비 제한적인 일 예로서 Zn-Mg-Al계 합금 도금강판일 수 있다.As will be described in detail later, the solution composition may form a coating layer on at least one surface of a substrate on which the composition can be applied. In the present invention, the substrate may be the above-mentioned steel sheet, for example, a high corrosion resistance hot-dip galvanized steel sheet, and may be a Zn-Mg-Al-based alloy-coated steel sheet as a non-limiting example.
하기에서는, 상기 용액 조성물을 구성하는 각 성분에 대하여 상세히 설명한다.In the following, each component constituting the solution composition will be described in detail.
(a) 3가 크롬 화합물 20~60중량%(a) 20 to 60% by weight of a trivalent chromium compound
본 발명의 용액 조성물에서 3가 크롬 화합물은 강판의 표면에서 주로 불용성 피막을 형성하여, 베리어 효과(Barrier effect)에 의한 내식성 향상을 도모한다.In the solution composition of the present invention, the trivalent chromium compound mainly forms an insoluble film on the surface of the steel sheet to improve corrosion resistance by a barrier effect.
본 발명의 용액 조성물에서 상기 3가 크롬 화합물의 함량이 20% 미만이면 견고한 불용성 피막을 충분히 형성하지 못하여 강판의 표면으로 침투하는 수분을 효과적으로 차단하지 못하며, 그 결과 내식성을 확보할 수 없게 된다. 반면, 그 함량이 60%를 초과하게 되면 과도한 크롬 성분으로 인하여 이물 결함이 발생할 우려가 있다.If the content of the trivalent chromium compound is less than 20% in the solution composition of the present invention, a strong insoluble film cannot be sufficiently formed to effectively block moisture penetrating into the surface of the steel sheet, and as a result, corrosion resistance cannot be secured. On the other hand, when the content exceeds 60%, foreign matter defects may occur due to excessive chromium components.
본 발명에서 상기 3가 크롬 화합물의 종류에 대해 특별히 제한하지는 아니하나, 바람직하게는 황산크롬, 질산크롬, 인산크롬, 불화크롬, 염화크롬 및 이들의 혼합물로 이루어진 군에서 선택된 하나 이상의 것일 수 있다.In the present invention, the type of the trivalent chromium compound is not particularly limited, but may preferably be at least one selected from the group consisting of chromium sulfate, chromium nitrate, chromium phosphate, chromium fluoride, chromium chloride, and mixtures thereof.
(b) 산도 조절제 0.1~10중량%(b) 0.1 to 10% by weight of an acidity regulator
본 발명의 용액 조성물에서 산도 조절제는 용액의 pH를 조절하여 조성물 내 성분들이 용액 내에서 안정하게 존재하고, 코팅 조건하에서 적절하게 반응하여 피막을 안정적으로 형성할 수 있도록 하는 역할을 한다.In the solution composition of the present invention, the acidity regulator controls the pH of the solution so that the components in the composition stably exist in the solution and reacts appropriately under coating conditions to stably form a film.
이러한 산도 조절제의 함량이 0.1% 미만이면 용액의 pH가 높아져 용액 안정성이 저하될 우려가 있고, 반면 그 함량이 10%를 초과하게 되면 건조 후 잔류산으로 인해 내식성 등을 확보하지 못하게 될 수 있다.If the content of the acidity regulator is less than 0.1%, the pH of the solution increases and the stability of the solution may deteriorate. On the other hand, if the content exceeds 10%, corrosion resistance may not be secured due to residual acid after drying.
본 발명에서 상기 산도 조절제의 종류에 대해 특별히 제한하지는 아니하나, 바람직하게는 인산, 질산, 황산, 불산, 염산, (NH4)H2PO4, (NH4)2HPO4, NaH2PO4, Na2HPO4, 피트산(Phytic acid), 글리콜릭산, 젖산, 초산, 옥살릭산 및 이들의 혼합물로 이루어진 군에서 선택된 하나 이상의 것일 수 있다.In the present invention, the type of acidity regulator is not particularly limited, but preferably phosphoric acid, nitric acid, sulfuric acid, hydrofluoric acid, hydrochloric acid, (NH 4 )H 2 PO 4 , (NH 4 ) 2 HPO 4 , NaH 2 PO 4 , Na 2 HPO 4 , phytic acid, glycolic acid, lactic acid, acetic acid, oxalic acid, and may be at least one selected from the group consisting of mixtures thereof.
(c) 밀착성 향상제 1~20중량%(c) 1 to 20% by weight of an adhesion improver
본 발명의 용액 조성물에서 밀착성 향상제는 상기 3가 크롬 화합물 등과 결합하고, 강판과도 결합하여 코팅층의 밀착성 및 내식성 등을 향상시키는 역할을 한다.In the solution composition of the present invention, the adhesion improver binds to the trivalent chromium compound and the like, and also binds to the steel sheet to improve adhesion and corrosion resistance of the coating layer.
이러한 밀착성 향상제의 함량이 1% 미만이면 강판과의 밀착성을 충분히 확보하지 못하여 이물 결함이 발생할 수 있다. 반면, 그 함량이 20%를 초과하게 되면 도막 형성 후 잔존하는 양이 과도하여 내식성 등을 확보하지 못할 수 있다.If the content of the adhesion improver is less than 1%, adhesion to the steel sheet may not be sufficiently secured, and foreign matter defects may occur. On the other hand, if the content exceeds 20%, the amount remaining after forming the coating film may be excessive and corrosion resistance may not be secured.
본 발명에서 상기 밀착성 향상제의 종류에 대해 특별히 제한하지는 아니하나, 바람직하게는 비닐메톡시 실란, 비닐트리메톡시 실란(VTMS), 비닐에폭시 실란, 비닐트리에폭시 실란, 3-아미노프로필트리에폭시 실란, 3-글리시독시프로필트리메톡시 실란, 3-메타글리옥시프로필트리메톡시 실란, γ-글리시독시프로필트리에톡시실란, γ-글리시독시트리메틸디메톡시실란, 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)propylmethyldiethoxysilane, 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) 및 이들의 혼합물로 이루어진 군에서 선택된 하나 이상의 것일 수 있다.In the present invention, the type of the adhesion improver is not particularly limited, but preferably vinylmethoxysilane, vinyltrimethoxysilane (VTMS), vinylepoxysilane, vinyltriepoxysilane, 3-aminopropyltriepoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-metaglycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxytrimethyldimethoxysilane, 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)propylmethyldiethoxysilane, 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. .
(d) 내식성 개선제 1~20중량%(d) 1 to 20% by weight of corrosion resistance improver
본 발명의 용액 조성물에서 내식성 개선제는 상기 3가 크롬 화합물과 밀착성 향상제 등과의 사이에 존재할 수 있는 간극을 채우면서 부동태 피막을 형성하여 부식 생성을 억제하는 역할을 한다.In the solution composition of the present invention, the corrosion resistance improver serves to suppress corrosion by forming a passive film while filling a gap that may exist between the trivalent chromium compound and the adhesion improver.
이러한 내식성 개선제의 함량이 1% 미만이면 부동태 피막을 충분히 형성하지 못하여 내식성 확보에 어려움이 있으며, 반면 그 함량이 20%를 초과하게 되면 지나치게 높은 고형분으로 인해 용액 안정성이 저하될 수 있다.If the content of the corrosion resistance improver is less than 1%, a passivation film cannot be sufficiently formed, making it difficult to secure corrosion resistance. On the other hand, if the content exceeds 20%, solution stability may be deteriorated due to excessively high solid content.
본 발명에서 상기 내식성 개선제의 종류에 대해 특별히 제한하지는 아니하나, 바람직하게는 바나딜 아세틸아세토네이트(Vanadyl acetylacetonate), 메타바나딘산암모늄(Ammonium metavanadate), 메타바나딘산칼륨(Potassium metavanadate), 메타바나딘산나트륨(Sodium metavanadate), 바나듐 삼산화물(Vanadium trioxide), 바나듐 아세틸아세테이트, 암모늄 메타바나데이트, 산화규소 및 이들의 혼합물로 이루어진 군에서 선택된 하나 이상의 것일 수 있다.In the present invention, the type of the corrosion resistance improver is not particularly limited, but preferably, vanadyl acetylacetonate, ammonium metavanadate, potassium metavanadate, meta It may be at least one selected from the group consisting of sodium metavanadate, vanadium trioxide, vanadium acetylacetate, ammonium metavanadate, silicon oxide, and mixtures thereof.
(e) 점상 부식 개선제 0.01~3.0중량%(e) 0.01 to 3.0% by weight of petechial corrosion improver
본 발명의 용액 조성물에서 점상 부식 개선제는 상기 내식성 개선제와 함께 부식 인자의 국부적 침투를 방지하여 점상 형태로 발생하는 점상 부식을 최소화하는 역할을 한다.In the solution composition of the present invention, the petechial corrosion improver serves to minimize petechial corrosion occurring in the form of petechiae by preventing local penetration of corrosion factors together with the corrosion resistance improver.
본 발명의 용액 조성물에서 상기 점상 부식 개선제의 함량이 0.01% 미만이면 부식 인자의 국부적 침투를 차단하지 못하여 점상 부식이 발생하는 문제가 있다. 반면, 그 함량이 3.0%를 초과하게 되면 용액의 pH가 지나치게 상승하여 용액 안정성이 저하될 우려가 있다.If the content of the petechiae corrosion improver in the solution composition of the present invention is less than 0.01%, local penetration of corrosion factors cannot be blocked, resulting in petechial corrosion. On the other hand, when the content exceeds 3.0%, the pH of the solution is excessively increased and there is a risk that the stability of the solution is lowered.
본 발명에서 상기 점상 부식 개선제의 종류에 대하여 특별히 제한하지는 아니하나, 바람직하게는 에틸렌다이아민, 헥사메틸렌다이아민, 트리메틸아민, 메틸아민, 디페닐아민, 에틸렌아민, 아닐린, 톨루이딘, 피페리딘, 아지리딘, 피리딘, 알라닌, 프로필아민, 디이소프로필아민, 모노이소프로필아민, 디부틸아민, 디프로필아민 및 이들의 혼합물로 이루어진 군에서 선택된 하나 이상의 것일 수 있다.In the present invention, the type of the point corrosion improver is not particularly limited, but preferably ethylenediamine, hexamethylenediamine, trimethylamine, methylamine, diphenylamine, ethyleneamine, aniline, toluidine, piperidine, It may be at least one selected from the group consisting of aziridine, pyridine, alanine, propylamine, diisopropylamine, monoisopropylamine, dibutylamine, dipropylamine, and mixtures thereof.
(f) 조용제 1~20중량%(f) 1 to 20% by weight of a co-solvent
본 발명의 용액 조성물에서 조용제는 코팅 작업 중 건조 과정에서 용제의 휘발 속도를 조절하여 건조 후 피막 표면의 결함을 억제하는 역할을 한다.In the solution composition of the present invention, the co-solvent controls the volatilization rate of the solvent during the drying process during the coating operation to suppress defects on the surface of the film after drying.
이러한 조용제의 함량이 1% 미만이면 건조 중 휘발 속도를 조절하는 효과가 미비하여, 주 용제의 증발속도가 비점에서 급격히 끓어올라 소위 포핑(popping) 이라고 하는 표면 결함이 발생하고, 이로 인해 내식성 저하 등의 문제가 있다. 반면, 그 함량이 20%를 초과하게 되면 용액의 점도 및 밀도 등의 급격한 변화로 용액 안정성이 저하될 수 있다.If the content of these co-solvents is less than 1%, the effect of controlling the volatilization rate during drying is insufficient, and the evaporation rate of the main solvent boils rapidly from the boiling point, resulting in surface defects called popping, which causes corrosion resistance degradation, etc. there is a problem with On the other hand, if the content exceeds 20%, stability of the solution may deteriorate due to rapid changes in the viscosity and density of the solution.
본 발명에서 상기 조용제의 종류에 대해 특별히 제한하지는 아니하나, 바람직하게는 에탈올, 이소프로필알코올, 메탄올, 탈로우 알코올(Tallow alcohol), 2-부톡시에탄올(2-butoxyethanol), 디에틸렌 글리콜 모노부틸 에테르(Diethylene glycol monobutyl ether) 및 이들의 혼합물로 이루어진 군에서 선택된 하나 이상의 것일 수 있다.In the present invention, the type of the co-solvent is not particularly limited, but preferably ethanol, isopropyl alcohol, methanol, tallow alcohol, 2-butoxyethanol, diethylene glycol mono It may be at least one selected from the group consisting of butyl ether (diethylene glycol monobutyl ether) and mixtures thereof.
(g) 용제(g) Solvent
본 발명의 용액 조성물은 잔부 성분으로서 용제를 포함할 수 있으며, 본 발명에서 상기 용제로서 물(증류수, 탈이온수)를 사용할 수 있다.The solution composition of the present invention may contain a solvent as a remaining component, and water (distilled water, deionized water) may be used as the solvent in the present invention.
이하, 본 발명의 다른 일 측면에 따른 상술한 용액 조성물을 표면처리하여 일정의 코팅층을 포함하는 표면처리된 강판에 대하여 상세히 설명한다.Hereinafter, a surface-treated steel sheet including a predetermined coating layer by surface-treating the above-described solution composition according to another aspect of the present invention will be described in detail.
본 발명에서 상기 조성물은 도금강판에 표면처리할 수 있으며, 바람직하게는 삼원계(Zn-Mg-Al계) 용융아연도금강판에 표면처리할 수 있다.In the present invention, the composition may be surface-treated on a coated steel sheet, preferably a ternary (Zn-Mg-Al-based) hot-dip galvanized steel sheet.
즉, 본 발명의 표면처리된 강판은 강판; 상기 강판의 적어도 일면에 형성된 Zn-Mg-Al계 도금층; 및 상기 도금층 상에 형성된 표면처리 코팅층을 포함할 수 있다.That is, the surface-treated steel sheet of the present invention is a steel sheet; a Zn-Mg-Al-based plating layer formed on at least one surface of the steel sheet; and a surface treatment coating layer formed on the plating layer.
여기서, 상기 강판은 도금강판을 얻을 수 있는 소지강판(base steel sheet)인 것으로서, 특히 삼원계(Zn-Mg-Al계) 용융아연도금강판을 얻을 수 강판이라면 어떠한 것도 무방하다.Here, the steel sheet is a base steel sheet from which a coated steel sheet can be obtained, and in particular, any steel sheet from which a ternary (Zn-Mg-Al-based) hot-dip galvanized steel sheet can be obtained.
상기 Zn-Mg-Al계 도금층은 그 조성이 중량%로, 마그네슘(Mg): 4.0~7.0%, 알루미늄(Al): 11.0~19.5%, 잔부 Zn 및 기타 불가피한 불순물을 포함할 수 있다.The composition of the Zn-Mg-Al-based plating layer may include magnesium (Mg): 4.0 to 7.0%, aluminum (Al): 11.0 to 19.5%, the balance Zn and other unavoidable impurities, by weight%.
상기 도금층 내의 마그네슘(Mg)은 도금강판의 내식성을 향상시키는 역할을 하는 원소로서, 본 발명에서 목적하는 우수한 내식성의 확보를 위해 그 함량이 4.0% 이상인 것이 바람직하다. 다만, 상기 Mg의 함량이 과도한 경우 도금욕 내에서 드로스를 발생시킬 우려가 있고, 도금층 내에서 경도가 높은 금속간 화합물을 과다하게 형성하여 강판의 굽힘성을 악화시킬 우려가 있으므로, 그 함량을 7.0%로 제한할 수 있다.Magnesium (Mg) in the plating layer is an element that serves to improve the corrosion resistance of the plated steel sheet, and the content thereof is preferably 4.0% or more to ensure excellent corrosion resistance, which is the purpose of the present invention. However, if the Mg content is excessive, dross may be generated in the plating bath and an intermetallic compound having high hardness may be excessively formed in the plating layer to deteriorate the bendability of the steel sheet. It can be capped at 7.0%.
한편, 상기 Mg의 함량을 4.0% 이상으로 첨가함에 의해 도금욕 내에서 Mg 산화에 의한 드로스 발생 위험성이 존재하므로, 이를 고려하여 상기 알루미늄(Al)을 11.0% 이상으로 포함하는 것이 바람직하다. 다만, 상기 Al의 함량이 과도할 경우 도금욕의 융점이 높아지고 그에 따른 조업 온도가 과도하게 높아져 도금욕 구조물의 침식 및 강판의 변성이 초래되는 등의 고온 작업에 따른 문제가 초래될 수 있다. 따라서, 상기 Al은 19.5% 이하로 그 함량을 제한하는 것이 바람직하다.On the other hand, since there is a risk of dross generation due to Mg oxidation in the plating bath by adding the Mg content to 4.0% or more, it is preferable to include the aluminum (Al) at 11.0% or more in consideration of this. However, if the Al content is excessive, the melting point of the plating bath increases and the operating temperature becomes excessively high, causing problems due to high-temperature work such as erosion of the plating bath structure and deterioration of the steel sheet. Therefore, it is preferable to limit the Al content to 19.5% or less.
상기 Mg과 Al을 제외한 잔부 조성은 아연(Zn)이며, Zn-Mg-Al계 도금층을 갖는 도금강판을 제조하는 과정에서 불가피한 불순물이 의도하지 않게 혼입될 수 있다. 이때 불가피한 불순물은 당해 기술분야의 기술자라면 그 의미를 쉽게 이해할 수 있을 것임을 밝혀둔다.Except for Mg and Al, the remaining composition is zinc (Zn), and unavoidable impurities may be unintentionally mixed in the process of manufacturing a coated steel sheet having a Zn-Mg-Al-based plating layer. At this time, it is revealed that the meaning of the unavoidable impurities will be easily understood by those skilled in the art.
상술한 Zn-Mg-Al계 도금층의 조직이 하기 [관계식 1]을 만족하는 것이 바람직하다.It is preferable that the structure of the above-described Zn-Mg-Al-based plating layer satisfies the following [Relational Expression 1].
[관계식 1][Relationship 1]
0.26 ≤ I(110)/I(103) ≤ 0.650.26 ≤ I(110)/I(103) ≤ 0.65
(관계식 1에서, I(110)은 MgZn2상에 대한 (110)면 결정 피크의 X선 회절 적분 강도를 나타내고, 상기 I(103)은 MgZn2상에 대한 (103)면 결정의 X선 회절 적분 강도를 나타낸다.)(In relational expression 1, I(110) represents the X-ray diffraction integrated intensity of the (110) plane crystal peak for the MgZn 2 phase, and I(103) represents the X-ray diffraction of the (103) plane crystal for the MgZn 2 phase represents the integral strength.)
본 발명에서는 상기 Zn-Mg-Al계 도금층의 MgZn2상에 대해 상기 [관계식 1]로 제어함으로써 도금강판의 굽힘성, 백색도 등을 확보할 수 있다.In the present invention, by controlling the MgZn 2 phase of the Zn-Mg-Al-based plating layer according to [Relational Expression 1], it is possible to secure the bendability and whiteness of the plated steel sheet.
상기 [관계식 1]로 정의되는 값이 0.26 미만이면 MgZn2상에 대한 (110)면 결정 대비 MgZn2상에 대한 (103)면 결정의 존재 비율이 과다하여, 굽힘성이나 백색도가 불충분해질 수 있다. 반면, 상기 값이 0.65를 초과하게 되면 MgZn2상에 대한 (103)면 결정 대비 MgZn2상에 대한 (110)면 결정의 존재 비율이 너무 과다하여, 난반사의 증대를 유도하지 못해 백색도가 불충분해지는 문제가 생길 수 있다.If the value defined by [Relationship 1] is less than 0.26, the ratio of (103) plane crystals to MgZn 2 phase to (110) plane crystals to MgZn 2 phase is excessive, resulting in insufficient bendability or whiteness. . On the other hand, if the value exceeds 0.65, the ratio of (110) plane crystals to the MgZn 2 phase compared to (103) plane crystals to the MgZn 2 phase is too excessive, so that the increase in diffuse reflection cannot be induced, resulting in insufficient whiteness. Problems can arise.
이때, 상기 I(110)은 적분 강도의 값이 120~200의 범위를 가질 수 있으며, 상기 I(103)은 적분 강도의 값이 240~300의 범위일 수 있다. 이와 같이, 각 범위 내에서 상기 [관계식 1]의 값을 만족하는 것이 바람직하다.In this case, the I (110) may have an integrated intensity value in the range of 120 to 200, and the I (103) may have an integrated intensity value in the range of 240 to 300. In this way, it is preferable to satisfy the value of [Relationship 1] within each range.
상술한 Zn-Mg-Al계 도금층의 상부에는 본 발명의 조성물을 용액 상태로 코팅처리함으로써 형성된 코팅층을 포함할 수 있으며, 이때 코팅층은 0.1~2.0㎛의 두께를 가지는 것이 바람직하다.A coating layer formed by coating the composition of the present invention in a solution state may be included on top of the above-described Zn-Mg-Al-based plating layer, and in this case, the coating layer preferably has a thickness of 0.1 to 2.0 μm.
상기 코팅층의 두께가 0.1㎛ 미만이면 도금강판 표면에 존재하는 조도의 산 부위에 표면처리 용액 조성물이 얇게 도포되어 내식성이 저하되는 문제가 있으며, 반면, 그 두께가 2.0㎛를 초과하게 되면 피막층(코팅층)이 두껍게 형성됨으로 인해 가공성이 열화되고 용액처리 비용이 상승하여 경제적으로 불리하게 된다.If the thickness of the coating layer is less than 0.1 μm, the surface treatment solution composition is thinly applied to the roughness of the acid portion present on the surface of the coated steel sheet, resulting in a decrease in corrosion resistance. On the other hand, if the thickness exceeds 2.0 μm, the coating layer (coating layer) ) is formed thickly, which deteriorates workability and increases the cost of solution treatment, which is economically unfavorable.
여기서, 상기 두께는 건조 후의 두께를 의미한다.Here, the thickness means the thickness after drying.
나아가, 본 발명은 상기 조성물을 이용하여 표면처리된 강판을 제조하는 방법에 대하여 설명한다.Furthermore, the present invention describes a method for manufacturing a surface-treated steel sheet using the composition.
보다 상세하게는, 강판의 적어도 일면에 용융아연도금처리하여 Zn-Mg-Al계 도금층을 형성하는 단계; 상기 도금층 상에 본 발명의 조성물을 용액 상태로 도포하여 코팅처리하는 단계; 및 상기 코팅처리된 강판을 건조처리하는 단계를 포함할 수 있다.More specifically, forming a Zn-Mg-Al-based plating layer by hot-dip galvanizing treatment on at least one surface of the steel sheet; Coating the coating layer by applying the composition of the present invention in a solution state on the plating layer; and drying the coated steel sheet.
본 발명의 조성물을 용액 상태로 상기 강판에 도포함에 있어서, 일반적으로 사용되는 코팅법을 적용할 수 있으므로, 특별히 한정하지는 아니한다.In applying the composition of the present invention to the steel sheet in a solution state, a generally used coating method may be applied, and thus, it is not particularly limited.
예를 들면, 바코팅, 롤코팅, 스프레이, 침적, 스프레이 스퀴징, 침적 스퀴징 등의 방법 중에서 하나의 방법을 선택하여 코팅 공정을 수행할 수 있다.For example, the coating process may be performed by selecting one method from among methods such as bar coating, roll coating, spraying, dipping, spray squeezing, and dip squeezing.
상기 조성물로 코팅처리된 강판을 건조처리하는 공정은 소재강판(강판)의 최종도달온도(PMT) 기준으로 40~280℃의 온도 범위에서 행해지는 것이 바람직하다.The process of drying the steel sheet coated with the composition is preferably performed in a temperature range of 40 to 280° C. based on the final temperature (PMT) of the material steel sheet (steel sheet).
상기 소재강판의 최종도달온도 기준으로 40℃ 미만이면 견고한 피막구조 형성이 미흡하여 내식성 및 내흑변성이 열위해질 우려가 있다. 반면, 그 온도가 280℃를 초과하게 되면 피막의 경도가 과도하게 증가하여 가공부 내식성이 열위해지고, 과도한 열로 인한 황변 현상 등 표면 품질이 열위해질 수 있다.If the temperature is lower than 40° C. based on the final temperature of the material steel sheet, the formation of a sturdy film structure may be insufficient, resulting in inferior corrosion resistance and blackening resistance. On the other hand, when the temperature exceeds 280 ° C., the hardness of the film excessively increases, resulting in poor corrosion resistance of the processed part and poor surface quality such as yellowing due to excessive heat.
상기 건조처리가 완료된 강판은 건조 후 두께로 0.1~2.0㎛의 코팅층을 가질 수 있다.The steel sheet upon completion of the drying treatment may have a coating layer having a thickness of 0.1 to 2.0 μm after drying.
본 발명에서 상기 건조처리를 행하기 위한 수단으로는 특별히 한정하지는 아니하나, 인덕션 오븐 또는 열풍건조로 등의 설비를 이용할 수 있음을 밝혀두며, 이들 설비의 조건은 통상의 조건에 의할 수 있다.In the present invention, the means for performing the drying treatment is not particularly limited, but it is noted that facilities such as an induction oven or a hot air drying furnace may be used, and the conditions of these facilities may be in accordance with conventional conditions.
이하, 본 발명을 실시예를 통하여 보다 상세하게 설명한다. 그러나, 이러한 실시예의 기재는 본 발명의 실시를 예시하기 위한 것일 뿐 이러한 실시예의 기재에 의하여 본 발명이 제한되는 것은 아니다. 본 발명의 권리범위는 특허청구범위에 기재된 사항과 이로부터 합리적으로 유추되는 사항에 의하여 결정되는 것이기 때문이다.Hereinafter, the present invention will be described in more detail through examples. However, the description of these examples is only for exemplifying the practice of the present invention, and the present invention is not limited by the description of these examples. This is because the scope of the present invention is determined by the matters described in the claims and the matters reasonably inferred therefrom.
[강판 표면처리용 용액 조성물의 제조][Preparation of solution composition for surface treatment of steel sheet]
본 발명의 강판 표면처리용 용액 조성물의 물성을 측정하기 위해 다음과 같은 물질을 사용하여 용액 조성물을 제조하였다. In order to measure the physical properties of the solution composition for surface treatment of steel sheet according to the present invention, a solution composition was prepared using the following materials.
먼저, 증류수(용제)에 산도 조절제로서 인산을 첨가한 후 약 40℃에서 3가 크롬 화합물인 질산크롬을 첨가한 다음, 약 30분간 교반시켰다. 같은 방식으로, 밀착성 향상제인 (3-Glycidyloxypropyl)trimethoxysilane (GPTMS), 내식성 개선제인 산화규소, 점상 부식 개선제인 에틸렌다이아민, 조용제로서 에탄올을 30분 간격으로 각각 첨가하면서 교반시켰다.First, after adding phosphoric acid as an acidity regulator to distilled water (solvent), chromium nitrate, a trivalent chromium compound, was added at about 40° C., followed by stirring for about 30 minutes. In the same manner, (3-Glycidyloxypropyl)trimethoxysilane (GPTMS) as an adhesion improver, silicon oxide as a corrosion resistance improver, ethylenediamine as a point corrosion improver, and ethanol as a co-solvent were added at intervals of 30 minutes while stirring.
이때, 각 성분의 함량은 하기 표 1에 나타내었다.At this time, the content of each component is shown in Table 1 below.
구분division 3가 크롬
화합물trivalent chromium
compound 		산도
조절제acidity
regulator 		밀착성
향상제adhesion
enhancer 		내식성
개선제corrosion resistance
improver 		점상 부식
개선제Petechiae
improver 		조용제Joongjae 용제solvent
발명예 1Invention Example 1 5555 0.50.5 33 55 0.50.5 33 3333
발명예 2Invention example 2 2323 44 1212 99 33 33 4646
발명예 3 Inventive example 3 4343 88 55 88 22 99 2525
발명예 4Inventive Example 4 4949 0.30.3 66 99 1One 55 29.729.7
발명예 5Inventive Example 5 2525 44 22 1010 1One 2020 3838
발명예 6Inventive example 6 2222 66 1818 1212 1One 1515 2626
발명예 7Inventive Example 7 4040 99 33 1818 1One 88 2121
발명예 8Inventive Example 8 5050 22 1818 22 33 77 1818
발명예 9Inventive Example 9 2323 22 1111 88 0.10.1 1One 54.954.9
발명예 10Inventive Example 10 5656 33 1One 22 2.82.8 55 30.230.2
발명예 11Inventive Example 11 2828 1010 77 1111 1One 22 4141
발명예 12Inventive Example 12 3333 1One 44 66 1One 1818 3737
비교예 1Comparative Example 1 1515 88 33 1717 1One 1010 4646
비교예 2Comparative Example 2 6565 1One 1010 22 1One 22 1919
비교예 3Comparative Example 3 4949 00 1515 88 1One 55 2222
비교예 4Comparative Example 4 5757 1111 22 1One 1One 99 1919
비교예 5Comparative Example 5 3838 33 0.10.1 1212 22 55 39.939.9
비교예 6Comparative Example 6 4141 33 2222 77 33 66 1818
비교예 7Comparative Example 7 3232 44 1818 0.20.2 1One 33 41.841.8
비교예 8Comparative Example 8 2626 99 66 2323 33 44 2929
비교예 9Comparative Example 9 3434 66 1212 2020 00 66 2222
비교예 10Comparative Example 10 4545 55 1616 1616 44 88 66
비교예 11Comparative Example 11 4747 22 1313 66 1One 00 3131
비교예 12Comparative Example 12 3232 33 77 66 1One 3030 2121
용액 안정성solution stability
제조된 용액 조성물이 일정 조건에서 용액의 안정성이 유지되는지 확인하기 위해 다음과 같은 실험을 수행하였다. The following experiment was performed to confirm whether the prepared solution composition maintains the stability of the solution under certain conditions.
상기 발명예 1 내지 12 및 비교예 1 내지 12의 각 용액 조성물의 초기 점도(Vi)를 측정한 다음, 50℃의 오븐에 120시간 동안 보관하였다가 25℃로 냉각시켜, 25℃ 에서의 점도(VI)를 측정하였다. 각각 측정된 점도 값을 아래 수학식 1에 대입하여 계산된 값(△V)에 따라 용액 안정성을 평가하였다. 그 결과는 아래 표 3에 나타내었다.The initial viscosity (Vi) of each solution composition of Inventive Examples 1 to 12 and Comparative Examples 1 to 12 was measured, stored in an oven at 50 ° C for 120 hours, cooled to 25 ° C, and the viscosity at 25 ° C ( VI) was measured. The stability of the solution was evaluated according to the value (ΔV) calculated by substituting each measured viscosity value into Equation 1 below. The results are shown in Table 3 below.
[수학식 1][Equation 1]
△V = (Vl - Vi)/ Vi × 100 (%)ΔV = (Vl - Vi)/Vi × 100 (%)
<용액 안정성 평가 기준><Solution stability evaluation criteria>
○: ΔV 값이 20(%) 미만이거나, 육안 관찰시 겔화 현상이 보이지 않음○: ΔV value is less than 20 (%) or no gelation phenomenon is observed with the naked eye
×: ΔV 값이 20(%) 이상이거나, 육안 관찰시 겔화 현상이 보임×: ΔV value of 20 (%) or more, or a gelation phenomenon is observed upon visual observation
[표면처리된 강판의 제조][Manufacture of surface-treated steel sheet]
다음으로, 상기 제조된 용액 조성물을 강판 표면에 바 코팅법으로 도포한 다음, 인덕션 오븐에서 건조처리를 수행하여, 각각의 표면처리된 강판을 획득하였다. 상기 바 코팅시 조성물의 부착량이 Cr을 기준으로 약 35mg/m2이 되도록 실시하였다.Next, the prepared solution composition was applied to the surface of the steel sheet by a bar coating method, and then dried in an induction oven to obtain each surface-treated steel sheet. The bar coating was carried out so that the adhesion amount of the composition was about 35 mg/m 2 based on Cr.
이때, 용액 조성물을 도포하기 위한 강판으로는 Zn-Mg-Al계 합금 용융아연도금강판(도금층: Mg 5.4중량%, Al 12.6중량%, 잔부 Zn 및 불가피한 불순물, [관계식 1]의 값: 0.40)을 이용하였으며, 7cm×15cm(가로×세로)로 절단하여 탈지처리한 시편으로 제작하였다.At this time, the steel sheet for applying the solution composition is a Zn-Mg-Al alloy hot-dip galvanized steel sheet (plating layer: Mg 5.4% by weight, Al 12.6% by weight, balance Zn and unavoidable impurities, value of [Relationship 1]: 0.40) was used, and it was cut into 7cm × 15cm (width × length) and manufactured as a degreased specimen.
상기 표면처리시 건조처리 온도와 형성된 코팅층의 두께에 대해서는 아래 표 2에 나타내었다.The drying treatment temperature and the thickness of the coating layer formed during the surface treatment are shown in Table 2 below.
구분division 열처리 온도(℃)Heat treatment temperature (℃) 코팅층 두께(㎛)Coating layer thickness (㎛)
발명예 1Invention example 1 6060 0.50.5
발명예 2Invention example 2 6060 0.50.5
발명예 3Inventive example 3 6060 0.50.5
발명예 4Inventive Example 4 6060 0.50.5
발명예 5Inventive Example 5 6060 0.50.5
발명예 6Inventive example 6 6060 0.50.5
발명예 7Inventive Example 7 6060 0.50.5
발명예 8Inventive Example 8 160160 0.50.5
발명예 9Inventive Example 9 160160 0.50.5
발명예 10Inventive Example 10 160160 1.11.1
발명예 11Inventive Example 11 220220 1.11.1
발명예 12Inventive example 12 220220 1.11.1
비교예 1Comparative Example 1 6060 1.11.1
비교예 2Comparative Example 2 6060 1.11.1
비교예 3Comparative Example 3 6060 1.11.1
비교예 4Comparative Example 4 6060 1.11.1
비교예 5Comparative Example 5 6060 1.11.1
비교예 6Comparative Example 6 160160 1.11.1
비교예 7Comparative Example 7 160160 1.11.1
비교예 8Comparative Example 8 160160 1.11.1
비교예 9Comparative Example 9 220220 1.11.1
비교예 10Comparative Example 10 220220 1.11.1
비교예 11Comparative Example 11 220220 0.50.5
비교예 12Comparative Example 12 220220 0.50.5
상기에 따라 제조된 표면처리된 강판의 물성을 측정하기 위하여, 다음과 같은 방법 및 기준으로 평판 내식성, 가공부 내식성, 조관유 침해성, 내알칼리성, 점상 부식 내식성, 이물 결함 등을 측정하였다. 각 결과는 하기 표 3에 나타내었다.In order to measure the physical properties of the surface-treated steel sheet manufactured according to the above, the following methods and standards were used to measure plate corrosion resistance, processed part corrosion resistance, pipe formation oil invasion resistance, alkali resistance, point corrosion resistance, foreign matter defects, and the like. Each result is shown in Table 3 below.
평판 내식성plate corrosion resistance
ASTM B117에서 규정한 방법에 의거하여, 각 강판(시편)에 대해 용액 조성물을 처리한 후 시간 경과에 따라 강판의 백청 발생율을 측정하였다.Based on the method specified in ASTM B117, after treating each steel sheet (specimen) with the solution composition, the white rust generation rate of the steel sheet was measured over time.
<평판 내식성 평가 기준><Platform corrosion resistance evaluation criteria>
○: 백청 발생 시간이 144시간 이상○: White rust generation time is 144 hours or more
△: 백청 발생 시간이 96시간 이상 144시간 미만△: White rust generation time is 96 hours or more and less than 144 hours
×: 백청 발생 시간이 96시간 미만×: White rust generation time is less than 96 hours
가공부 내식성Processed part corrosion resistance
상기에 따라 표면처리된 강판(시편)을 에릭슨 테스터(Erichsen tester)를 이용하여 6mm의 높이로 밀어 올린 후, 24시간 경과하였을 때 백청 발생 정도를 측정하였다.After pushing the surface-treated steel sheet (specimen) according to the above to a height of 6 mm using an Erichsen tester, the degree of white rust generation was measured when 24 hours elapsed.
<가공부 내식성 평가 기준><Evaluation Criteria for Corrosion Resistance of Processed Parts>
○: 백청 발생 없거나, 발생하더라도 상당히 미세한 경우○: When there is no white rust, or if it occurs, it is very fine
△: 원에 백청이 발생하여 일부 흘렀으나, 밖으로 흘러나가지 않은 경우△: When white rust occurred on the circle and partially flowed, but did not flow out
×: 백청이 발생하여 원 밖으로 흘러나간 경우×: When white rust occurs and flows out of the circle
조관유 침해성Crude Oil Invasiveness
상기에 따라 표면처리된 강판(시편)을 상온에서 조관유에 침적하여 24시간 유지 후, 침적 전/후의 색차를 측정하였다. 이때, 조관유는 국내 범우 BW WELL MP-411을 10% 물에 희석하여 사용하였다.The surface-treated steel sheet (specimen) according to the above was immersed in pipe-forming oil at room temperature and maintained for 24 hours, and then the color difference before/after immersion was measured. At this time, crude oil was used by diluting domestic Beomwoo BW WELL MP-411 in 10% water.
<조관유 침해성 평가 기준><Crude oil invasiveness evaluation criteria>
○: ΔE ≤ 2○: ΔE ≤ 2
△: 2 < ΔE ≤ 3Δ: 2 < ΔE ≤ 3
×: 3 < ΔE×: 3 < ΔE
내알칼리성alkali resistance
상기에 따라 표면처리된 강판(시편)을 60℃의 탈지용액에 2분간 침적한 후 수세, 에어 블로잉(air blowing)한 후, 전/후의 색차를 측정하였다. 이때, 알칼리 탈지 용액은 파카라이징사의 Finecleaner L 4460 A: 20g/2.4L + L 4460 B: 12g/2.4L (pH=12)를 사용하였다.After immersing the surface-treated steel sheet (specimen) in a degreasing solution at 60° C. for 2 minutes, washing with water and air blowing, the color difference between before and after was measured. At this time, as the alkali degreasing solution, Finecleaner L 4460 A: 20g/2.4L + L 4460 B: 12g/2.4L (pH=12) from Parraising Co., Ltd. was used.
<내알칼리성 평가 기준><Criteria for evaluation of alkali resistance>
○: ΔE ≤ 2○: ΔE ≤ 2
△: 2 < ΔE ≤ 4Δ: 2 < ΔE ≤ 4
×: 4 < ΔE×: 4 < ΔE
점상 부식 내식성petechiae corrosion resistance
상기에 따라 표면처리된 강판(시편)의 표면에 분무기를 이용하여 이슬이 맺히도록 한 다음, 상기 분무 처리된 강판 두 장을 서로 맞대어 포장한 후 항온항습기에 넣어 고온 습도(42℃, 95%)에서 6시간, 저온 습도(15℃, 60%)에서 6시간을 1사이클로 하여 총 8사이클(cycle) 동안 행한 후, 표면의 점상 결함 개수를 측정하였다. 이때, 강판의 스캔 면적을 150×50mm2로 설정하고, 이를 100배로 확대하여 부식성 점상 결함 면적이 29500㎛2 이상인 것의 개수만을 세었다.Dew is formed on the surface of the steel sheet (specimen) treated as described above using a sprayer, and then the two spray-treated steel sheets are packed facing each other and put in a thermo-hygrostat at high temperature and humidity (42℃, 95%). 6 hours at low temperature and humidity (15° C., 60%) for 6 hours as one cycle for a total of 8 cycles, and then the number of point defects on the surface was measured. At this time, the scan area of the steel sheet was set to 150×50 mm 2 , and only the number of corrosive point defects having an area of 29500 μm 2 or more was counted by magnifying it 100 times.
<점상 부식 내식성 평가 기준><Standards for Evaluating Petechiae Corrosion Resistance>
○: 점상 개수 ≤ 20○: number of dots ≤ 20
△: 20 < 점상 개수 ≤ 40△: 20 < number of dots ≤ 40
×: 40 < 점상 개수×: 40 < number of dots
이물 결함foreign body defect
상기에 따라 표면처리된 강판(시편)의 이물 결함을 평가하기 위하여, 표면적이 약 4cm2인 탐침에 흰색 거즈를 씌운 뒤 탐침 위에 무게 10kg의 추를 올려놓은 다음, 이 탐침을 상기 강판 표면에 100회 왕복 마찰시킨 후 마찰 전/후의 거즈의 백색도 값(ΔL=Lbefore-Lafter)을 측정하였다. 이때, 고습 조건을 모사하기 위하여 습도 챔버 내에 상기 강판과 탐침을 위치시키고, 상기 챔버 내를 가습기를 이용하여 95% 이상의 습도를 유지시킨 다음 마찰 평가를 진행하였다.In order to evaluate foreign matter defects of the steel sheet (specimen) treated as described above, a probe having a surface area of about 4 cm 2 was covered with white gauze, a weight of 10 kg was placed on the probe, and then the probe was placed on the surface of the steel sheet at 100 After rubbing back and forth twice, the whiteness value (ΔL=L before -L after ) of the gauze before/after rubbing was measured. At this time, in order to simulate the high humidity condition, the steel plate and the probe were placed in a humidity chamber, and a humidity of 95% or more was maintained in the chamber using a humidifier, and then friction evaluation was performed.
<이물 결함 평가 기준><Criteria for Evaluation of Foreign Matter Defects>
○: ΔL ≤ 2.5○: ΔL ≤ 2.5
△: 2.5 < ΔL ≤ 5.0Δ: 2.5 < ΔL ≤ 5.0
×: 5.0 < ΔL×: 5.0 < ΔL
구분division 용액
안정성solution
stability 		평판
내식성reputation
corrosion resistance 		가공부
내식성processing department
corrosion resistance 		조관유
침해성Cho Kwan-Yoo
invasive 		내
알칼리성my
alkalinity 		점상 부식 내식성petechiae corrosion resistance 이물 결함foreign body defect
발명예 1Invention example 1 ○○ ○○ ○○ ○○ ○○ ○○ ○○
발명예 2Invention example 2 ○○ ○○ ○○ ○○ ○○ ○○ ○○
발명예 3Inventive example 3 ○○ ○○ ○○ ○○ ○○ ○○ ○○
발명예 4Inventive example 4 ○○ ○○ ○○ ○○ ○○ ○○ ○○
발명예 5Inventive Example 5 ○○ ○○ ○○ ○○ ○○ ○○ ○○
발명예 6Inventive example 6 ○○ ○○ ○○ ○○ ○○ ○○ ○○
발명예 7Inventive Example 7 ○○ ○○ ○○ ○○ ○○ ○○ ○○
발명예 8Inventive Example 8 ○○ ○○ ○○ ○○ ○○ ○○ ○○
발명예 9Inventive Example 9 ○○ ○○ ○○ ○○ ○○ ○○ ○○
발명예 10Inventive Example 10 ○○ ○○ ○○ ○○ ○○ ○○ ○○
발명예 11Inventive Example 11 ○○ ○○ ○○ ○○ ○○ ○○ ○○
발명예 12Inventive Example 12 ○○ ○○ ○○ ○○ ○○ ○○ ○○
비교예 1Comparative Example 1 ○○ ×× ×× ○○ ○○ ×× ○○
비교예 2Comparative Example 2 ○○ ○○ ○○ ○○ ○○ ○○ ××
비교예 3Comparative Example 3 ×× ×× ×× ○○ ○○ ×× ○○
비교예 4Comparative Example 4 ○○ ×× ×× ○○ ○○ ×× ○○
비교예 5Comparative Example 5 ○○ ○○ ○○ ○○ ○○ ○○ ××
비교예 6Comparative Example 6 ○○ ×× ×× ○○ ○○ ×× ○○
비교예 7Comparative Example 7 ○○ ×× ×× ○○ ○○ ×× ○○
비교예 8Comparative Example 8 ×× ○○ ○○ ○○ ×× ○○ ××
비교예 9Comparative Example 9 ○○ ○○ ○○ ○○ ○○ ×× ○○
비교예 10Comparative Example 10 ×× ○○ ×× ○○ ○○ ○○ ○○
비교예 11Comparative Example 11 ○○ ×× ×× ○○ ○○ ×× ○○
비교예 12Comparative Example 12 ×× ○○ ×× ○○ ○○ ○○ ○○
상기 표 3에 나타낸 바와 같이, 발명예 1 내지 12의 용액 조성물은 용액 안정성이 우수하며, 이러한 용액 조성물로 표면처리된 강판 역시 모든 평가 결과에서 매우 우수한 결과를 보였다.As shown in Table 3, the solution compositions of Examples 1 to 12 were excellent in solution stability, and the steel sheets surface-treated with these solution compositions also showed excellent results in all evaluation results.
반면, 비교예 1은 3가 크롬 화합물의 함량이 부족한 경우로, 베리어 효과에 의한 내식성이 충분하지 못하여 평판 내식성, 가공부 내식성, 점상 부식 내식성이 열위하였다.On the other hand, in Comparative Example 1, when the content of the trivalent chromium compound was insufficient, the corrosion resistance due to the barrier effect was not sufficient, and thus the corrosion resistance of the plate, the corrosion resistance of the processed part, and the corrosion resistance of the point corrosion were inferior.
비교예 2는 3가 크롬 화합물의 함량이 과도하게 높은 경우로, 이물 결함이 발생한 것을 알 수 있다.In Comparative Example 2, the content of the trivalent chromium compound was excessively high, and it can be seen that foreign matter defects occurred.
비교예 3은 산도 조절제의 함량이 불충분하여 용액 안정성이 열위하였으며, 이러한 용액 조성물을 표면처리한 강판의 평판 내식성, 가공부 내식성, 점상 부식 내식성이 열위하였다.In Comparative Example 3, the solution stability was inferior due to insufficient acidity regulator content, and plate corrosion resistance, processed part corrosion resistance, and point corrosion resistance of the steel sheet surface-treated with this solution composition were inferior.
비교예 4는 산도 조절제의 함량이 과도한 경우로, 용액 내에 잔류하는 산이 많아져 표면처리된 강판의 평판 내식성, 가공부 내식성, 점상 부식 내식성이 열위하였다.In Comparative Example 4, when the content of the acidity regulator was excessive, the acid remaining in the solution increased, resulting in inferior plate corrosion resistance, processed section corrosion resistance, and point corrosion resistance of the surface-treated steel sheet.
비교예 5는 밀착성 향상제의 함량이 불충분한 경우로, 이물 결함이 발생하였다.In Comparative Example 5, the content of the adhesion improver was insufficient, and foreign matter defects occurred.
비교예 6은 밀착성 향상제의 함량이 지나치게 높은 경우로, 잔존하는 미반응 실란으로 인해 표면처리된 강판의 평판 내식성, 가공부 내식성, 점상 부식 내식성이 열위하였다.In Comparative Example 6, the content of the adhesion improver was excessively high, and the plate corrosion resistance, corrosion resistance of the processed part, and pitting corrosion resistance of the surface-treated steel sheet were inferior due to the remaining unreacted silane.
비교예 7은 내식성 개선제의 함량이 부족한 경우로서, 내식성이 충분하지 못하여 평판 내식성, 가공부 내식성, 점상 부식 내식성이 열위하였다.Comparative Example 7 was a case where the content of the corrosion resistance improver was insufficient, and the corrosion resistance was not sufficient, resulting in inferior plate corrosion resistance, processing corrosion resistance, and point corrosion resistance.
비교예 8은 내식성 개선제의 함량이 과도한 경우로, 지나치게 많아진 고형분으로 인해 용액 안정성이 열위하였으며, 표면처리된 강판의 내알칼리성이 열위하고, 이물 결함이 발생하였다.In Comparative Example 8, when the content of the corrosion resistance improver was excessive, the solution stability was inferior due to the excessively increased solid content, the alkali resistance of the surface-treated steel sheet was inferior, and foreign matter defects occurred.
비교예 9는 점상 부식 개선제의 함량이 부족한 경우로, 표면처리된 강판의 점상 부식 내식성이 열위하였다.Comparative Example 9 is a case where the content of the petechiae corrosion improver was insufficient, and the petechiae corrosion resistance of the surface-treated steel sheet was inferior.
비교예 10은 점상 부식 개선제의 함량이 과도한 경우로서, 용액 안정성이 부족하고, 표면처리된 강판의 가공부 내식성이 발생하였다.In Comparative Example 10, the content of the petechial corrosion improver was excessive, and solution stability was insufficient, and corrosion resistance of the surface-treated steel sheet occurred.
비교예 11은 조용제의 함량이 불충분한 경우로, 표면처리된 강판의 평판 내식성, 가공부 내식성 및 점상 부식 내식성이 열위하였다.In Comparative Example 11, the content of the co-solvent was insufficient, and the surface-treated steel sheet had poor plate corrosion resistance, processed part corrosion resistance, and pitting corrosion resistance.
비교예 12는 조용제의 함량이 과도한 경우로, 용액 안정성이 부족하고, 표면처리된 강판의 가공부 내식성이 열위하였다.In Comparative Example 12, the content of the co-solvent was excessive, and the stability of the solution was insufficient, and the corrosion resistance of the processed part of the surface-treated steel sheet was inferior.
도 1은 본 발명의 따른 용액 조성물을 이용하여 표면처리된 강판(발명예 1)의 표면 형상과 종래의 조성물에 의해 표면처리된 강판의 표면 형상을 관찰하여 나타낸 것이다.1 shows the surface shape of a steel sheet surface-treated using a solution composition according to the present invention (Inventive Example 1) and the surface shape of a steel sheet surface-treated with a conventional composition.
도 1에 나타낸 바와 같이, 종래의 용액 조성물로 표면처리된 강판(a)은 에지부에서 점상 부식 결함이 발생한 반면, 본 발명의 용액 조성물로 표면처리된 강판은 결함없이 에지부까지 표면이 매끈함을 알 수 있다.As shown in FIG. 1, the surface-treated steel sheet (a) with the conventional solution composition has point corrosion defects at the edge, whereas the surface-treated steel sheet with the solution composition of the present invention has a smooth surface up to the edge without defects. Able to know.

Claims (14)

  1. (a) 3가 크롬 화합물 20~60중량%,(a) 20 to 60% by weight of a trivalent chromium compound;
    (b) 산도 조절제 0.1~10중량%,(b) 0.1 to 10% by weight of an acidity regulator;
    (c) 밀착성 향상제 1~20중량%,(c) 1 to 20% by weight of an adhesion improver;
    (d) 내식성 개선제 1~20중량%,(d) 1 to 20% by weight of a corrosion resistance improver;
    (e) 점상 부식 개선제 0.01~3.0중량%,(e) 0.01 to 3.0% by weight of a petechial corrosion improver;
    (f) 조용제 1~20중량% 및(f) 1 to 20% by weight of a co-solvent; and
    (g) 잔부 용제를 포함하는 강판 표면처리용 용액 조성물.(g) A solution composition for surface treatment of steel sheet containing a residual solvent.
  2. 제 1항에 있어서,According to claim 1,
    상기 3가 크롬 화합물은 황산크롬, 질산크롬, 인산크롬, 불화크롬, 염화크롬 및 이들의 혼합물로 이루어진 군에서 선택된 하나 이상의 것인 강판 표면처리용 용액 조성물.The trivalent chromium compound is at least one selected from the group consisting of chromium sulfate, chromium nitrate, chromium phosphate, chromium fluoride, chromium chloride, and mixtures thereof.
  3. 제 1항에 있어서,According to claim 1,
    상기 산도 조절제는 인산, 질산, 황산, 불산, 염산, (NH4)H2PO4, (NH4)2HPO4, NaH2PO4, Na2HPO4, 피트산(Phytic acid), 글리콜릭산, 젖산, 초산, 옥살릭산 및 이들의 혼합물로 이루어진 군에서 선택된 하나 이상의 것인 강판 표면처리용 용액 조성물. The acidity regulator is phosphoric acid, nitric acid, sulfuric acid, hydrofluoric acid, hydrochloric acid, (NH 4 )H 2 PO 4 , (NH 4 ) 2 HPO 4 , NaH 2 PO 4 , Na 2 HPO 4 , phytic acid, glycolic acid , lactic acid, acetic acid, oxalic acid, and at least one solution composition for steel sheet surface treatment selected from the group consisting of mixtures thereof.
  4. 제 1항에 있어서,According to claim 1,
    상기 밀착성 향상제는 비닐메톡시 실란, 비닐트리메톡시 실란(VTMS), 비닐에폭시 실란, 비닐트리에폭시 실란, 3-아미노프로필트리에폭시 실란, 3-글리시독시프로필트리메톡시 실란, 3-메타글리옥시프로필트리메톡시 실란, γ-글리시독시프로필트리에톡시실란, γ-글리시독시트리메틸디메톡시실란, 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)propylmethyldiethoxysilane, 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) 및 이들의 혼합물로 이루어진 군에서 선택된 하나 이상의 것인 강판 표면처리용 용액 조성물. The adhesion improver is vinyl methoxy silane, vinyl trimethoxy silane (VTMS), vinyl epoxy silane, vinyl triepoxy silane, 3-aminopropyltriepoxy silane, 3-glycidoxypropyltrimethoxy silane, 3-metaglycyl Oxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxytrimethyldimethoxysilane, 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)propylmethyldiethoxysilane, 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 at least one solution composition for surface treatment of steel sheet selected from the group consisting of mixtures thereof.
  5. 제 1항에 있어서,According to claim 1,
    상기 내식성 개선제는 바나딜 아세틸아세토네이트(Vanadyl acetylacetonate), 메타바나딘산암모늄(Ammonium metavanadate), 메타바나딘산칼륨(Potassium metavanadate), 메타바나딘산나트륨(Sodium metavanadate), 바나듐 삼산화물(Vanadium trioxide), 바나듐 아세틸아세테이트, 암모늄 메타바나데이트, 산화규소 및 이들의 혼합물로 이루어진 군에서 선택된 하나 이상의 것인 강판 표면처리용 용액 조성물. The corrosion resistance improving agent is vanadyl acetylacetonate, ammonium metavanadate, potassium metavanadate, sodium metavanadate, vanadium trioxide ), vanadium acetylacetate, ammonium metavanadate, silicon oxide, and at least one solution composition for surface treatment of steel sheet selected from the group consisting of mixtures thereof.
  6. 제 1항에 있어서,According to claim 1,
    상기 점상 부식 개선제는 에틸렌다이아민, 헥사메틸렌다이아민, 트리메틸아민, 메틸아민, 디페닐아민, 에틸렌아민, 아닐린, 톨루이딘, 피페리딘, 아지리딘, 피리딘, 알라닌, 프로필아민, 디이소프로필아민, 모노이소프로필아민, 디부틸아민, 디프로필아민 및 이들의 혼합물로 이루어진 군에서 선택된 하나 이상의 것인 강판 표면처리용 용액 조성물.The petechiae corrosion improver is ethylenediamine, hexamethylenediamine, trimethylamine, methylamine, diphenylamine, ethyleneamine, aniline, toluidine, piperidine, aziridine, pyridine, alanine, propylamine, diisopropylamine, A solution composition for surface treatment of steel sheet, which is at least one selected from the group consisting of monoisopropylamine, dibutylamine, dipropylamine, and mixtures thereof.
  7. 제 1항에 있어서,According to claim 1,
    상기 조용제는 에탈올, 이소프로필알코올, 메탄올, 탈로우 알코올(Tallow alcohol), 2-부톡시에탄올(2-butoxyethanol), 디에틸렌 글리콜 모노부틸 에테르(Diethylene glycol monobutyl ether) 및 이들의 혼합물로 이루어진 군에서 선택된 하나 이상의 것인 강판 표면처리용 용액 조성물.The co-agent is a group consisting of ethanol, isopropyl alcohol, methanol, tallow alcohol, 2-butoxyethanol, diethylene glycol monobutyl ether, and mixtures thereof A solution composition for surface treatment of steel sheet, which is at least one selected from
  8. 제 1항에 있어서,According to claim 1,
    상기 용제는 물인 강판 표면처리용 용액 조성물.The solvent is water, a solution composition for surface treatment of steel sheet.
  9. 강판;grater;
    상기 강판의 적어도 일면에 형성된 Zn-Mg-Al계 도금층; 및a Zn-Mg-Al-based plating layer formed on at least one surface of the steel sheet; and
    상기 도금층 상에 형성된 표면처리 코팅층을 포함하며,Including a surface treatment coating layer formed on the plating layer,
    상기 표면처리 코팅층은 제 1항 내지 제 8항 중 어느 한 항의 조성물로 형성된 코팅층인 표면처리된 도금강판.The surface-treated coated steel sheet is a coating layer formed of the composition of any one of claims 1 to 8.
  10. 제 9항에 있어서,According to claim 9,
    상기 Zn-Mg-Al계 도금층은 중량%로 마그네슘(Mg): 4.0~7.0%, 알루미늄(Al): 11.0~19.5%, 잔부 Zn 및 기타 불가피한 불순물을 포함하고,The Zn-Mg-Al-based plating layer includes magnesium (Mg): 4.0 to 7.0%, aluminum (Al): 11.0 to 19.5%, the balance Zn and other unavoidable impurities in weight%,
    하기 관계식 1을 만족하는 것을 특징으로 하는 표면처리된 도금강판.A surface-treated coated steel sheet, characterized in that it satisfies the following relational expression 1.
    [관계식 1][Relationship 1]
    0.26 ≤ I(110)/I(103) ≤ 0.650.26 ≤ I(110)/I(103) ≤ 0.65
    (관계식 1에서, I(110)은 MgZn2상에 대한 (110)면 결정 피크의 X선 회절 적분 강도를 나타내고, 상기 I(103)은 MgZn2상에 대한 (103)면 결정의 X선 회절 적분 강도를 나타낸다.)(In relational expression 1, I(110) represents the X-ray diffraction integrated intensity of the (110) plane crystal peak for the MgZn 2 phase, and I(103) represents the X-ray diffraction of the (103) plane crystal for the MgZn 2 phase represents the integral strength.)
  11. 제 9항에 있어서,According to claim 9,
    상기 표면처리 코팅층은 0.1~2.0㎛의 두께를 가지는 것인 표면처리된 도금강판.The surface treatment coating layer is a surface-treated coated steel sheet having a thickness of 0.1 ~ 2.0㎛.
  12. 강판의 적어도 일면에 용융아연도금처리하여 Zn-Mg-Al계 도금층을 형성하는 단계;forming a Zn-Mg-Al-based plating layer by hot-dip galvanizing treatment on at least one surface of the steel sheet;
    상기 도금층 상에 제 1항 내지 제 8항 중 어느 한 항의 조성물을 코팅처리하는 단계; 및coating the composition of any one of claims 1 to 8 on the plating layer; and
    상기 코팅처리된 강판을 건조처리하는 단계를 포함하는 표면처리된 도금강판의 제조방법.A method of manufacturing a surface-treated coated steel sheet comprising the step of drying the coated steel sheet.
  13. 제 12항에 있어서,According to claim 12,
    상기 코팅처리는 바코팅, 롤코팅, 스프레이, 침적, 스프레이 스퀴징 및 침적 스퀴징으로 이루어진 군에서 선택된 어느 하나의 방법으로 행해지는 것인 표면처리된 도금강판의 제조방법.The method of manufacturing a surface-treated coated steel sheet wherein the coating treatment is performed by any one method selected from the group consisting of bar coating, roll coating, spraying, dipping, spray squeezing, and dipping squeezing.
  14. 제 12항에 있어서,According to claim 12,
    상기 건조는 강판의 최종도달온도(PMT) 기준으로 40~280℃의 온도 범위에서 행해지는 것인 표면처리된 도금강판의 제조방법.The method of manufacturing a surface-treated coated steel sheet in which the drying is performed in a temperature range of 40 to 280 ° C. based on the final temperature (PMT) of the steel sheet.
PCT/KR2022/020708 2021-12-21 2022-12-19 Solution composition for steel sheet surface treatment, steel sheet surface-treated using same, and manufacturing method therefor WO2023121175A1 (en)

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