WO2022091850A1 - 溶融Al-Zn-Si-Mg系めっき鋼板、表面処理鋼板及び塗装鋼板 - Google Patents
溶融Al-Zn-Si-Mg系めっき鋼板、表面処理鋼板及び塗装鋼板 Download PDFInfo
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- WO2022091850A1 WO2022091850A1 PCT/JP2021/038479 JP2021038479W WO2022091850A1 WO 2022091850 A1 WO2022091850 A1 WO 2022091850A1 JP 2021038479 W JP2021038479 W JP 2021038479W WO 2022091850 A1 WO2022091850 A1 WO 2022091850A1
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Images
Classifications
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- 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
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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- C—CHEMISTRY; METALLURGY
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- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
- C22C18/04—Alloys based on zinc with aluminium as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/10—Alloys based on aluminium with zinc as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
- C22C30/06—Alloys containing less than 50% by weight of each constituent containing zinc
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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
- 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
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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
- 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
- C23C2/12—Aluminium or alloys based thereon
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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
- 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
Definitions
- the present invention relates to a molten Al-Zn-Si-Mg-based plated steel sheet, a surface-treated steel sheet and a coated steel sheet having stable and excellent corrosion resistance.
- hot-dip Al-Zn-based plated steel sheets represented by 55% Al-Zn-based steel sheets exhibit high corrosion resistance among hot-dip galvanized steel sheets because they have both the sacrificial corrosion resistance of Zn and the high corrosion resistance of Al. Has been done. Therefore, due to its excellent corrosion resistance, hot-dip Al-Zn plated steel sheets are mainly used in the field of building materials such as roofs and walls that are exposed to the outdoors for a long period of time, and in the field of civil engineering and construction such as guardrails, wiring pipes, and noise barriers. ..
- the plating film of the molten Al-Zn-based plated steel sheet consists of the portion where Al containing Zn oversaturated is solidified into a dendrite ( ⁇ -Al phase) and the Zn-Al eutectic structure existing in the dendrite gap (interdrendlite). It is characterized by having a structure in which a plurality of ⁇ -Al phases are laminated in the film thickness direction of the plating film. Due to such a characteristic film structure, the corrosion progress path from the surface becomes complicated, so that the corrosion does not easily proceed, and the hot-dip Al-Zn-based plated steel sheet becomes a hot-dip galvanized steel sheet having the same plating film thickness. It is also known that better corrosion resistance can be achieved.
- Patent Document 1 contains an Al-Zn-Si alloy containing Mg in a plating film, and the Al-Zn-Si alloy is 45 to An alloy containing 60% by weight elemental aluminum, 37-46% by weight elemental zinc and 1.2-2.3% by weight Si, wherein the Mg concentration is 1-5% by weight, molten Al-Zn-Si-. Mg-based plated steel sheets are disclosed.
- the plating film contains at least one of 2 to 10% Mg and 0.01 to 10% Ca to improve corrosion resistance and protect the base steel sheet after it is exposed.
- a molten Al-Zn-Si-Mg-based plated steel sheet for the purpose of enhancing the above-mentioned is disclosed.
- Mg: 1 to 15%, Si: 2 to 15%, Zn: 11 to 25% are contained in mass%, and the balance forms a coating layer composed of Al and unavoidable impurities.
- Molten Al-Zn-Si-Mg system with improved corrosion resistance of flat plate and end face by reducing the size of intermetallic compounds such as Mg 2 Si phase and Mg Zn 2 phase present in the plating film to 10 ⁇ m or less. Plated steel plates are disclosed.
- Patent Document 4 discloses a molten Al-Zn-Si-Mg-based plated steel sheet in which wrinkle-like unevenness defects are suppressed by containing 0.01 to 10% Sr in the plating film.
- Patent Document 5 also discloses a molten Al-Zn-Si-Mg-based plated steel sheet in which mottled defects are suppressed by containing 500 to 3000 ppm of Sr in the plating film.
- Patent Document 6 discloses a molten Al-Zn-Si-Mg-based plated steel sheet in which 0.001 to 1.0% of Sr is contained in the plating film to achieve both surface appearance and corrosion resistance.
- Patent Document 7 also describes a molten Al-Zn-Si-Mg-based plated steel sheet in which 0.001 to 1.0% of Sr is contained in the plating film to achieve both surface appearance and corrosion resistance between the flat plate portion and the processed portion. Is disclosed.
- Patent Document 8 also discloses a molten Al-Zn-Si-Mg-based plated steel sheet that achieves both surface appearance and corrosion resistance by containing 0.01 to 0.2% Sr in the plating film. .. Further, Patent Document 9 discloses a molten Al-Zn-Si-Mg-based plated steel sheet having improved corrosion resistance by controlling the Si and Mg concentrations in the plating film at a specific ratio.
- Patent Document 10 describes molten Al-Zn-Si in which the mass ratio of Mg in the Si-Mg phase to the total amount of Mg in the plating layer is optimized for the purpose of improving the white rust resistance of the processed portion. -Mg-based plated steel sheets are disclosed.
- Patent Document 11 blackening resistance and white rust resistance are improved by forming a chemical conversion film containing a urethane resin on the plating film of a molten Al-Zn-Si-Mg-based plated steel sheet.
- the technology is disclosed.
- a coated steel sheet in which a chemical conversion film, primer coating film, topcoat coating film, etc. is formed on the surface of a molten Al-Zn-based plated steel sheet can be bent 90 degrees or 180 degrees by press forming, roll forming, or embossing. Various processing is applied, and long-term coating film durability is required.
- the molten Al-Zn-based plated steel sheet forms a chromate-containing chemical conversion film
- the primer coating film also contains a chromate-based rust-preventive pigment, and on top of that, a heat-curable polyester-based film.
- Patent Document 12 describes aluminum-zinc alloy plating containing Al, Zn, Si and Mg on the surface of a steel material and adjusting the content of these elements.
- the layer ( ⁇ ) is plated, and a film ( ⁇ ) containing at least one compound (A) selected from a titanium compound and a zirconium compound as a film-forming component is formed as an upper layer thereof, and an aluminum-zinc alloy plated layer ( ⁇ ) is formed.
- a surface-treated hot-dip plated steel material in which the mass ratio of the Si—Mg phase in ⁇ ) to the total amount of Mg in the plating layer is adjusted to 3% or more is disclosed.
- the technique of containing Mg in the plating film as disclosed in Patent Documents 1 to 3 does not always bring about the improvement of corrosion resistance uniquely.
- the corrosion resistance is improved only by containing Mg in the plating component.
- the characteristics of the intermetallic phase were not considered, and it was not possible to uniformly talk about the superiority or inferiority of corrosion resistance. Therefore, even when a molten Al-Zn-Si-Mg-based plated steel sheet is manufactured using the same plating bath composition, the corrosion resistance varies when the corrosion acceleration test is carried out, and the Al-Zn-based plated steel sheet to which Mg is not added is present.
- Bottom dross FeAl-based compounds (bottom dross) containing iron that are unevenly distributed in the middle or bottom may be generated, and these dross adhere to the surface of the plating film and cause convex defects, which impairs the appearance of the surface of the plating film. There was also a fear.
- the coated steel sheet has long-term coating film durability performance in a state where it has been subjected to various processing such as 90 degree bending and 180 degree bending by press forming, roll forming, embossing, etc.
- various processing such as 90 degree bending and 180 degree bending by press forming, roll forming, embossing, etc.
- Patent Document 12 can always obtain stable corrosion resistance and surface appearance after processing.
- the corrosion resistance of the coated steel sheet is affected by the corrosion resistance of the plated steel sheet used as the base, and as for the surface appearance, the height difference of the unevenness of the wrinkle-like defect is as much as several tens of ⁇ m. Even if the surface is smoothed, the unevenness is not completely eliminated, and it is considered that the appearance of the coated steel sheet cannot be improved.
- the coating film becomes thin in the convex portion, there is a concern that the corrosion resistance is locally deteriorated. Therefore, in order to obtain a coated steel sheet having excellent corrosion resistance and surface appearance, it is important to improve the corrosion resistance and surface appearance of the underlying plated steel sheet.
- an object of the present invention to provide a molten Al-Zn-Si-Mg-based plated steel sheet having stable and excellent corrosion resistance. Another object of the present invention is to provide a surface-treated steel sheet having stable and excellent corrosion resistance and white rust resistance. Further, it is an object of the present invention to provide a coated steel sheet having stable and excellent corrosion resistance and corrosion resistance of a processed portion.
- the present inventors have found the Mg 2 Si phase, Mg Zn 2 phase, and Si phase formed in the plating film of the molten Al-Zn-Si-Mg-based plated steel sheet. It was found that the amount of precipitation increases or decreases depending on the balance of each component in the plating film and the formation conditions of the plating film, the abundance ratio changes, and one of the phases may not precipitate depending on the balance of the composition. In addition, the corrosion resistance of the molten Al-Zn-Si-Mg-based plated steel sheet changes depending on the abundance ratio of these phases, and the corrosion resistance is stable especially when there are more MgZn 2 phases than Mg 2 Si phase or Si phase. Investigated to improve.
- Mg 2 Si phase and Si phase a general method such as a scanning electron microscope is used to observe the secondary electron image or backscattered electron image of the plating film from the surface or cross section. It is known that it is very difficult to distinguish the difference between the phases.
- a method for more detailed analysis it is possible to obtain microscopic information by observing with a transmission electron microscope, but Mg 2 Si phase and Si phase that influence macroscopic information such as corrosion resistance and appearance. It was not possible to grasp the abundance ratio of. Therefore, as a result of further diligent research, the present inventors focused on the X-ray diffraction method and quantified the phase abundance ratio by using the intensity ratio of specific diffraction peaks for the Mg 2 Si phase and the Si phase.
- the present inventors control the abundance ratio of Mg 2 Si phase, Si phase, etc. in the molten Al-Zn-Si-Mg-based plated steel sheet, and then control the Sr concentration in the bath to wrinkle. It was also found that a plated steel sheet with excellent surface appearance can be obtained by reliably suppressing the occurrence of irregularities.
- the present inventors also studied the chemical conversion film formed on the plating film, and formed the chemical conversion film from a specific resin and a specific metal compound to form a plating film of the chemical conversion film. It was also found that the affinity of the white rust and the rust preventive effect were enhanced, and the stable improvement of the white rust resistance was improved.
- the present inventors have also studied the chemical conversion film and the primer coating film formed on the plating film, and while forming the chemical conversion film with a specific resin and a specific inorganic compound, the primer coating film is formed. It has also been found that, by being composed of a specific polyester resin and an inorganic compound, the barrier property and adhesion of the coating film can be enhanced, and excellent post-processing corrosion resistance can be realized even if it is chromate-free.
- the present invention has been made based on the above findings, and the gist thereof is as follows.
- 1. A molten Al-Zn-Si-Mg-based plated steel sheet with a plating film.
- the plating film contains Al: 45 to 65% by mass, Si: 1.0 to 4.0% by mass and Mg: 1.0 to 10.0% by mass, and has a composition in which the balance is Zn and unavoidable impurities.
- Si (111): Diffraction intensity of Si (111) plane (plane spacing d 0.3135 nm)
- Mg 2 Si (111): Diffraction intensity of Mg 2 Si (111) plane (plane spacing d 0.3668 nm)
- Si (111) 0 ⁇ ⁇ ⁇ (2)
- Si (111): Diffraction intensity of Si (111) plane (plane spacing d 0.3135 nm)
- a surface-treated steel sheet comprising the plating film according to any one of 1 to 6 and a chemical conversion film formed on the plating film.
- the chemical conversion film comprises at least one resin selected from epoxy resin, urethane resin, acrylic resin, acrylic silicon resin, alkyd resin, polyester resin, polyalkylene resin, amino resin and fluororesin, and P compound, Si compound and Co.
- a surface treatment comprising at least one metal compound selected from a compound, a Ni compound, a Zn compound, an Al compound, an Mg compound, a V compound, a Mo compound, a Zr compound, a Ti compound and a Ca compound. Steel plate.
- the chemical conversion film contains (a): an anionic polyurethane resin having an ester bond and (b): an epoxy resin having a bisphenol skeleton in a total amount of 30 to 50% by mass, and contains the (a) and the (b).
- the ratio ((a): (b)) is in the range of 3:97 to 60:40 in mass ratio, 2 to 10% by mass of vanadium compound, 40 to 60% by mass of zirconium compound and 0.5 to 0.5.
- the coating film has at least a primer coating film, and the primer coating film contains a polyester resin having a urethane bond and an inorganic compound containing a vanadium compound, a phosphoric acid compound and magnesium oxide. , Painted steel plate.
- the present invention it is possible to provide a molten Al-Zn-Si-Mg-based plated steel sheet having stable and excellent corrosion resistance. Further, according to the present invention, it is possible to stably provide a surface-treated steel sheet having excellent corrosion resistance and white rust resistance. Further, according to the present invention, it is possible to stably provide a coated steel sheet having excellent corrosion resistance and corrosion resistance of a processed portion.
- the molten Al-Zn-Si-Mg-based plated steel sheet of the present invention has a plating film on the surface of the steel sheet.
- the plating film contains Al: 45 to 65% by mass, Si: 1.0 to 4.0% by mass and Mg: 1.0 to 10.0% by mass, and has a composition in which the balance is Zn and unavoidable impurities.
- the Al content in the plating film is 45 to 65% by mass, preferably 50 to 60% by mass, from the viewpoint of the balance between corrosion resistance and operation. This is because if the Al content in the plating film is at least 45% by mass, dendrite solidification of Al occurs, and a plating film structure mainly composed of the dendrite solidified structure of the ⁇ -Al phase can be obtained.
- the corrosion progress path becomes complicated and the corrosion resistance of the plating film itself is improved. Further, the more the dendrite portions of the ⁇ -Al phase are laminated, the more complicated the corrosion progress path becomes, and the more difficult it is for corrosion to reach the base steel sheet.
- the corrosion resistance is improved, and the Al content is 50 mass. % Or more is preferable.
- the Al content in the plating film exceeds 65% by mass, most of Zn changes to a structure that is solid-dissolved in ⁇ -Al, and the dissolution reaction of the ⁇ -Al phase cannot be suppressed, so that Al-Zn -The corrosion resistance of Si-Mg plating deteriorates. Therefore, the Al content in the plating film needs to be 65% by mass or less, preferably 60% by mass or less.
- Si in the plating film mainly suppresses the growth of the Fe-Al-based and / or Fe-Al-Si-based interfacial alloy layer generated at the interface with the underlying steel sheet, and does not deteriorate the adhesion between the plating film and the steel sheet.
- Added for the purpose When a steel plate is actually immersed in an Al-Zn-based plating bath containing Si, Fe on the surface of the steel plate and Al or Si in the bath undergo an alloying reaction, and Fe-Al-based and / or Fe-Al-Si-based.
- the metal-metal compound layer is formed at the base steel plate / plating film interface.
- the Fe-Al-Si alloy has a slower growth rate than the Fe-Al alloy, so the ratio of the Fe-Al-Si alloy is high.
- the higher the value the more the growth of the entire interfacial alloy layer is suppressed. Therefore, the Si content in the plating film needs to be 1.0% by mass or more.
- the Si content in the plating film exceeds 4.0% by mass, not only the above-mentioned growth suppressing effect of the interfacial alloy layer is saturated, but also corrosion is promoted due to the presence of an excess Si phase in the plating film. Therefore, the Si content should be 4.0% or less.
- the content of Si in the plating film is preferably 3.0% or less from the viewpoint of suppressing the presence of an excessive Si phase.
- the Si content is preferably 1.0 to 3.0% by mass from the viewpoint of easily satisfying the relational expression (1) described later in relation to the Mg content described later.
- the plating film contains 1.0 to 10.0% of Mg.
- Mg in the plating film, the above-mentioned Si can be present in the form of an intermetallic compound of Mg 2 Si phase, and the promotion of corrosion can be suppressed.
- MgZn 2 phase which is an intermetallic compound, is also formed in the plating film, and the effect of further improving the corrosion resistance can be obtained.
- Mg content in the plating film is less than 1.0% by mass, Mg is used for solid solution to the ⁇ -Al phase, which is the main phase, rather than the formation of the intermetallic compounds (Mg 2 Si, MgZn 2 ). Therefore, sufficient corrosion resistance cannot be ensured.
- the Mg content in the plating film is set to 10.0% or less.
- the Mg content in the plating film is preferably 5.0% by mass or less from the viewpoint of suppressing the generation of dross during plating formation and facilitating the management of the plating bath. From the viewpoint of easily satisfying the relational expression (1) described later in relation to the Si content, the Mg content is preferably 3.0% by mass, and compatibility with dross suppression is taken into consideration. Then, it is more preferable to set the Mg content to 3.0 to 5.0% by mass.
- the above-mentioned intermetallic compound dissolves preferentially over the ⁇ -Al phase, and as a result, Mg is formed in the vicinity of the corrosive product.
- Mg is formed in the vicinity of the corrosive product.
- the protective effect of the plating film is enhanced.
- the effect of improving the protective effect of the plating film is more reliably expressed when Si in the plating film exists as the Mg 2 Si phase instead of the Si phase, so that the abundance ratio of the Si phase to the Mg 2 Si phase is lowered. Is considered to be effective.
- the abundance ratio of Mg 2 Si and Si in the plating film has a relationship (1): Si (111) / Mg 2 Si (111) ⁇ 0.8 using the diffraction peak intensity obtained by the X-ray diffractometry. It is necessary to satisfy, but when the abundance ratio of Mg 2 Si and Si in the plating film does not satisfy the relationship (1), that is, when Si (111) / Mg 2 Si (111)> 0.8, the plating is performed. Since the amount of Si phase present in the film increases, it is not possible to obtain the above-mentioned Mg-rich environment in the vicinity of corrosion products, and it becomes difficult to obtain the effect of improving the protective effect of the plating film.
- the abundance ratio of Si to Mg 2 Si (Si (111) / Mg 2 Si (111)) is preferably 0.5 or less, more preferably 0.3 or less, and 0.2 or less. Is particularly preferable.
- the composition of the plating film tentatively satisfies the range of the present invention (Al: 45 to 65% by mass, Si: 1.0 to 4.0% by mass and Mg: Even if it contains 1.0 to 10.0% by mass and the balance consists of Zn and unavoidable impurities), if the abundance ratio of Mg 2 Si and Si does not satisfy the relationship (1), the plating film according to the present invention. It is not possible to sufficiently obtain the effect of improving the protective effect of.
- Mg 2 Si (111) is (111) of Mg 2 Si.
- Diffraction intensity of the plane (plane spacing d 0.3668 nm).
- Si (111) / Mg 2 Si (111) can be obtained.
- the amount of plating film (amount to scrape off the plating film) required for powder X-ray diffraction measurement is 0.1 g or more from the viewpoint of accurately measuring Si (111) and Mg 2 Si (111). It may be sufficient, preferably 0.3 g or more.
- the plating film when the plating film is scraped off, steel plate components other than the plating film may be contained in the powder, but these intermetallic compound phases are contained only in the plating film, and the above-mentioned peak strength can be obtained. It has no effect. Further, the reason why the plating film is powdered and X-ray diffraction is performed is that when X-ray diffraction is performed on the plating film formed on the plated steel sheet, it is affected by the plane orientation of the solidification structure of the plating film and has the correct phase ratio. This is because it is difficult to perform the calculation.
- the diffraction intensity of Si in the plating film by the X-ray diffraction method is as follows because the corrosion resistance can be improved more stably. It is preferable to satisfy the relationship (2).
- Si (111) 0 ⁇ ⁇ ⁇ (2)
- Si (111): Diffractive intensity of Si (111) plane (plane spacing d 0.3135 nm)
- the Si phase is present as a cathode site, so that the surroundings Since it is known to promote the dissolution of the ⁇ -Al phase, reducing the Si phase is also effective from the viewpoint of suppressing the dissolution of the ⁇ -Al phase, and among them, Si as described in the relationship (2).
- a phase-free film (setting the diffraction peak intensity of Si (111) to zero) is the most excellent for stabilizing corrosion resistance.
- the method for measuring the diffraction peak intensity of the (111) plane of Si by X-ray diffraction is as described above.
- the method for satisfying the above-mentioned relationship (1) and relationship (2) is not particularly limited.
- the balance between the Si content, the Mg content and the Al content in the plating film is adjusted to obtain Mg 2 Si and Si.
- the abundance ratio (diffraction intensity of Mg 2 Si (111) and Si (111)) can be controlled.
- the balance between the Si content, the Mg content and the Al content in the plating film does not necessarily satisfy the relationship (1) and the relationship (2) if the content ratio is set to a certain level. For example, it is necessary to change the content ratio of Mg and Al depending on the content (mass%) of Si.
- the conditions for forming the plating film (for example, cooling conditions after plating) can be adjusted.
- the diffraction intensity of Mg 2 Si (111) and Si (111) can be controlled so as to satisfy the relationship (1) and the relationship (2).
- the molten Al-Zn-Si-Mg-based plated steel sheet of the present invention contains Zn and unavoidable impurities.
- the unavoidable impurities contain Fe.
- This Fe is inevitably contained in the plating bath due to elution of the steel sheet and the equipment in the bath, and is supplied by diffusion from the base steel sheet during the formation of the interfacial alloy layer, and as a result, it is inevitably contained in the plating film. Will be included.
- the Fe content in the plating film is usually about 0.3 to 2.0% by mass.
- Other unavoidable impurities include Cr, Ni, Cu and the like.
- the total content of the unavoidable impurities is not particularly limited, but if it is excessively contained, it may affect various characteristics of the plated steel sheet, so that the total content is preferably 5.0% by mass or less.
- the plating film contains 0.01 to 1.0% by mass of Sr.
- Sr When the plating film contains Sr, it is possible to more reliably suppress the occurrence of surface defects such as wrinkle-like uneven defects, and it is possible to realize good surface appearance.
- the wrinkle-like defect is a wrinkle-like uneven defect formed on the surface of the plating film, and is observed as a whitish streak on the surface of the plating film. Such wrinkle-like defects are likely to occur when a large amount of Mg is added to the plating film.
- the abundance ratios of Si and Mg 2 Si in the above-mentioned plating film satisfy the relationship (1), and the plating film has a mass of 0.01 to 1.0 mass. It is preferable to contain% Sr. Thereby, the effect of improving the surface appearance by the above-mentioned Sr can be further enjoyed. The cause of this is not clear, but it is presumed that when the amount of Si in the plating film increases, oxidation of the plating surface layer is difficult to be suppressed in the first place, which affects the effect of improving the appearance when Sr is added. ..
- the Sr content in the plating film is less than 0.01% by mass, it is difficult to obtain the effect of suppressing the occurrence of the wrinkle-like defects described above, and the Sr content in the plating film exceeds 1.0% by mass.
- the Sr content in the plating film should be 0.01 to 1.0% by mass because Sr is excessively incorporated into the interfacial alloy layer and may affect the plating adhesion more than the appearance improving effect. Is preferable.
- the plating film can improve the stability of the corrosion product and delay the progress of corrosion in the same manner as the above-mentioned Mg, Cr and Mn in total of 0.01 to 10% by mass.
- V, Mo, Ti, Ca, Ni, Co, Sb and B are preferably selected from one or more. The reason why the total content of the above-mentioned components is set to 0.01 to 10% by mass is that a sufficient corrosion delay effect can be obtained and the effect is not saturated.
- the amount of the plating film adhered is preferably 45 to 120 g / m 2 per side from the viewpoint of satisfying various characteristics.
- the adhesion amount of the plating film is 45 g / m 2 or more, sufficient corrosion resistance can be obtained even for applications that require long-term corrosion resistance such as building materials, and the adhesion amount of the plating film is 120 g / m / m. This is because when m 2 or less, excellent corrosion resistance can be realized while suppressing the occurrence of plating cracks during processing.
- the amount of the plating film adhered is more preferably 45 to 100 g / m 2 .
- the amount of the plating film adhered is calculated from the difference in the weight of the steel sheet before and after peeling by dissolving and peeling the plating film of a specific area with a mixed solution of hydrochloric acid and hexamethylenetetramine shown in JIS H0401: 2013, for example. Can be derived.
- it can be determined by sealing with tape so that the plating surface of the non-target surface is not exposed, and then performing the above-mentioned dissolution.
- the component composition of the plating film can be confirmed, for example, by immersing the plating film in hydrochloric acid or the like to dissolve the plating film, and confirming the solution by ICP emission spectroscopic analysis, atomic absorption spectroscopy, or the like.
- This method is merely an example, and any method can be used as long as the component composition of the plating film can be accurately quantified, and the method is not particularly limited.
- the plating film of the molten Al-Zn-Si-Mg-based plated steel sheet obtained by the present invention has almost the same composition as the plating bath as a whole. Therefore, the composition of the plating film can be controlled accurately by controlling the composition of the plating bath.
- the base steel sheet constituting the molten Al-Zn-Si-Mg-based plated steel sheet of the present invention is not particularly limited, and a cold-rolled steel sheet, a hot-rolled steel sheet, or the like may be appropriately used according to the required performance and specifications. Can be used.
- the method for obtaining the base steel plate is not particularly limited.
- a steel sheet that has undergone a hot-rolling step and a pickling step can be used, and in the case of the cold-rolled steel sheet, it can be manufactured by further adding a cold-rolling step.
- the method for producing the molten Al-Zn-Si-Mg-based plated steel sheet of the present invention is not particularly limited.
- it can be manufactured by washing, heating, and immersing the base steel sheet in a plating bath in a continuous hot-dip plating facility.
- recrystallization annealing is performed to control the structure of the base steel sheet itself, and in order to prevent oxidation of the steel sheet and reduce a trace amount of oxide film existing on the surface, a nitrogen-hydrogen atmosphere, etc. Heating in the reducing atmosphere of is effective.
- the composition of the plating film is almost the same as the composition of the plating bath as a whole. Therefore, it is possible to use one containing Al: 45 to 65% by mass, Si: 1.0 to 4.0% by mass and Mg: 1.0 to 10.0% by mass, and the balance having a composition of Zn, Fe and unavoidable impurities. ..
- the bath temperature of the plating bath is not particularly limited, but is preferably in the temperature range of (melting point + 20 ° C.) to 650 ° C.
- the lower limit of the bath temperature is set to a melting point of + 20 ° C., because the bath temperature must be equal to or higher than the freezing point in order to perform the hot-dip plating treatment. This is to prevent coagulation due to a local decrease in bath temperature.
- the upper limit of the bath temperature is set to 650 ° C. If the temperature exceeds 650 ° C, rapid cooling of the plating film becomes difficult, and the interfacial alloy layer formed between the plating film and the steel sheet may become thick. Because.
- the temperature of the base steel plate that penetrates into the plating bath is not particularly limited, but from the viewpoint of ensuring the plating characteristics and preventing the change in the bath temperature in the continuous hot-dip plating operation, the plating bath is described. It is preferable to control the temperature within ⁇ 20 ° C.
- the immersion time of the steel sheet in the plating bath is 0.5 seconds or more. This is because if it takes less than 0.5 seconds, a sufficient plating film may not be formed on the surface of the base steel sheet.
- the upper limit of the dipping time is not particularly limited, but it is preferably within 8 seconds because the interfacial alloy layer formed between the plating film and the steel sheet may become thicker if the dipping time is lengthened.
- the precipitation start temperature of the simple substance Si phase and Mg2Si in the plating film is 500 to 490 ° C for the simple substance Si phase and 520 to 500 ° C for Mg2Si. Therefore, by increasing the residence time in the temperature range of 520 to 500 ° C where only Mg2Si precipitates, the precipitation of Mg2Si is promoted and the precipitation of the simple substance Si phase is suppressed. This is because it is easier to fill.
- the molten Al-Zn-Si-Mg-based plated steel sheet can form a coating film on the plating film directly or via an intermediate layer, depending on the required performance.
- the method for forming the coating film is not particularly limited and can be appropriately selected according to the required performance.
- a forming method such as roll coater coating, curtain flow coating, spray coating and the like can be mentioned.
- After painting a paint containing an organic resin it is possible to heat and dry it by means such as hot air drying, infrared heating, and induction heating to form a coating film.
- the intermediate layer is not particularly limited as long as it is a layer formed between the plating film of the hot-dip galvanized steel sheet and the coating film.
- the surface-treated steel sheet of the present invention includes a plating film on the surface of the steel sheet and a chemical conversion film formed on the plating film.
- the composition of the plating film is the same as that of the above-mentioned plating film of the molten Al-Zn-Si-Mg-based plated steel sheet of the present invention.
- a chemical conversion film is formed on the plating film.
- the chemical conversion film may be formed on at least one side of the surface-treated steel sheet, and may be formed on both sides of the surface-treated steel sheet depending on the application and required performance.
- the chemical conversion film is selected from at least one of epoxy resin, urethane resin, acrylic resin, acrylic silicon resin, alkyd resin, polyester resin, polyalkylene resin, amino resin and fluororesin.
- One kind of resin and at least one kind of metal selected from P compound, Si compound, Co compound, Ni compound, Zn compound, Al compound, Mg compound, V compound, Mo compound, Zr compound, Ti compound and Ca compound. It is characterized by containing a compound and.
- the resin constituting the chemical conversion film is selected from among epoxy resin, urethane resin, acrylic resin, acrylic silicon resin, alkyd resin, polyester resin, polyalkylene resin, amino resin and fluororesin from the viewpoint of improving corrosion resistance. At least one selected is used. From the same viewpoint, the resin preferably contains at least one of urethane resin and acrylic resin.
- the resin constituting the chemical conversion film also includes an addition polymer of the above-mentioned resin.
- the epoxy resin is, for example, a glycidyl etherified epoxy resin such as bisphenol A type, bisphenol F type, or novolak type, or a bisphenol A type epoxy resin to which propylene oxide, ethylene oxide, or polyalkylene glycol is added.
- a glycidyl etherified product, an aliphatic epoxy resin, an alicyclic epoxy resin, a polyether epoxy resin, or the like can be used.
- urethane resin for example, an oil-modified polyurethane resin, an alkyd-based polyurethane resin, a polyester-based polyurethane resin, a polyether-based polyurethane resin, a polycarbonate-based polyurethane resin, or the like can be used.
- acrylic resin for example, polyacrylic acid and its copolymer, polyacrylic acid ester and its copolymer, polymethacrylic acid and its copolymer, polymethacrylic acid ester and its copolymer, urethane-acrylic acid.
- examples thereof include copolymers (or urethane-modified acrylic resins) and styrene-acrylic acid copolymers, and those obtained by modifying these resins with other alkyd resins, epoxy resins, phenol resins and the like can be used.
- acrylic silicon resin examples include a resin having a hydrolyzable alkoxysilyl group at the side chain or the end of an acrylic copolymer as a main agent, to which a curing agent is added. Further, when an acrylic silicone resin is used, excellent weather resistance can be expected in addition to corrosion resistance.
- an oil-modified alkyd resin for example, an oil-modified alkyd resin, a rosin-modified alkyd resin, a phenol-modified alkyd resin, a styrene-modified alkyd resin, a silicon-modified alkyd resin, an acrylic-modified alkyd resin, an oil-free alkyd resin, a high-molecular-weight oil-free alkyd resin, and the like.
- an oil-modified alkyd resin for example, an oil-modified alkyd resin, a rosin-modified alkyd resin, a phenol-modified alkyd resin, a styrene-modified alkyd resin, a silicon-modified alkyd resin, an acrylic-modified alkyd resin, an oil-free alkyd resin, a high-molecular-weight oil-free alkyd resin, and the like.
- the polyester resin is a polycondensate synthesized by dehydrating and condensing a polyvalent carboxylic acid and a polyalcohol to form an ester bond.
- the polyvalent carboxylic acid include terephthalic acid, 2, 6-Naphthalenedicarboxylic acid and the like are used, and examples of the polyalcohol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,4-cyclohexanedimethanol and the like.
- examples of the polyester include polyethylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate. Further, acrylic-modified polyester resins can also be used.
- the polyalkylene resin may be, for example, an ethylene-based copolymer such as an ethylene-acrylic acid copolymer, an ethylene-methacrylic acid copolymer, or a carboxyl-modified polyolefin resin, an ethylene-unsaturated carboxylic acid copolymer, or an ethylene-based ionomer. Further, those obtained by modifying these resins with other alkyd resins, epoxy resins, phenol resins and the like can be used.
- an ethylene-based copolymer such as an ethylene-acrylic acid copolymer, an ethylene-methacrylic acid copolymer, or a carboxyl-modified polyolefin resin, an ethylene-unsaturated carboxylic acid copolymer, or an ethylene-based ionomer.
- the amino resin is a thermosetting resin produced by the reaction of an amine or an amide compound with an aldehyde, and examples thereof include melamine resin, guanamine resin, and thiourea resin, but from the viewpoint of corrosion resistance, weather resistance, adhesion, and the like. , It is preferable to use a melamine resin.
- the melamine resin is not particularly limited, and examples thereof include butylated melamine resin, methylated melamine resin, and aqueous melamine resin.
- fluororesin examples include fluoroolefin polymers and copolymers of fluoroolefins with alkyl vinyl ethers, synchroalkyl vinyl ethers, carboxylic acid-modified vinyl esters, hydroxyalkylallyl ethers, tetrafluoropropyl vinyl ethers and the like. When these fluororesins are used, not only corrosion resistance but also excellent weather resistance and excellent hydrophobicity can be expected.
- a curing agent for the purpose of improving corrosion resistance and processability.
- the curing agent include urea resin (butylated urea resin, etc.), melamine resin (butylated melamine resin, butyl etherified melamine resin, etc.), butylated urea / melamine resin, amino resin such as benzoguanamine resin, blocked isocyanate, and oxazoline compound. Phenol resin or the like can be used as appropriate.
- the metal compounds constituting the chemical conversion film among P compounds, Si compounds, Co compounds, Ni compounds, Zn compounds, Al compounds, Mg compounds, V compounds, Mo compounds, Zr compounds, Ti compounds and Ca compounds. At least one selected from is used. From the same viewpoint, the metal compound preferably contains at least one of a P compound, a Si compound and a V compound.
- the P compound can be contained in the chemical conversion film to improve corrosion resistance and sweat resistance.
- the P compound is a compound containing P, and can contain, for example, one or two or more selected from inorganic phosphoric acid, organic phosphoric acid and salts thereof.
- the inorganic phosphoric acid includes phosphoric acid, primary phosphate, secondary phosphate, tertiary phosphate, pyrophosphoric acid, pyrophosphate, tripolyphosphoric acid, tripolyphosphate, phosphite, and subphosphoric acid. It is preferable to use one or more selected from acid salt, hypophosphite, and hypophosphite.
- phosphonic acid phosphonic acid compound
- the phosphonic acid it is preferable to use one or more selected from nitrilotris methylenephosphonic acid, phosphonobtantricarboxylic acid, methyldiphosphonic acid, methylenephosphonic acid, and ethylidene diphosphonic acid.
- the salt is preferably a salt of Group 1 to Group 13 elements in the periodic table, more preferably a metal salt, and an alkali metal salt and an alkaline earth. It is preferably one or more selected from among the metal salts.
- the chemical conversion treatment liquid containing the above P compound When the chemical conversion treatment liquid containing the above P compound is applied to a molten Al-Zn-Si-Mg-based plated steel sheet, the surface of the plating film is etched by the action of the P compound, and Al, Zn, which are constituent elements of the plating film, A concentrated layer in which Si and Mg are incorporated is formed on the plating film side of the chemical conversion film. By forming the concentrated layer, the bond between the chemical conversion film and the surface of the plating film is strengthened, and the adhesion of the chemical conversion film is improved.
- the concentration of the P compound in the chemical conversion treatment liquid is not particularly limited, but may be 0.25% by mass to 5% by mass.
- the concentration of the P compound is less than 0.25% by mass, the etching effect is insufficient and the adhesion to the plating interface is lowered, not only the corrosion resistance of the flat surface portion is lowered, but also the plating generated in the defective portion, the cut end face portion, the processing, etc. Corrosion resistance and sweat resistance of damaged parts of the film may also decrease.
- the concentration of the P compound is preferably 0.35% by mass or more, more preferably 0.50% by mass or more.
- the concentration of the P compound exceeds 5% by mass, not only the life of the chemical conversion treatment liquid is shortened, but also the appearance when the film is formed tends to be uneven, and the amount of P eluted from the chemical conversion film.
- the concentration of the P compound is preferably 3.5% by mass or less, more preferably 2.5% by mass or less.
- the content of the P compound in the chemical conversion film for example, by applying and drying a chemical conversion treatment solution having a concentration of the P compound of 0.25% by mass to 5% by mass, P adheres to the chemical conversion film after drying.
- the amount can be 5 to 100 mg / m 2 .
- the Si compound is a component that forms a skeleton that forms a chemical conversion film together with the resin, and can enhance the affinity with the plating film and uniformly form the chemical conversion film.
- the Si compound is a compound containing Si, and preferably contains, for example, one or more selected from silica, trialkoxysilane, tetraalkoxysilane, and a silane coupling agent.
- the silica is not particularly limited and any silica can be used.
- the silica for example, at least one of wet silica and dry silica can be used.
- the colloidal silica which is a kind of the wet silica for example, Snowtex O, C, N, S, 20, OS, OXS, NS and the like manufactured by Nissan Chemical Industries, Ltd. can be preferably used.
- the dry silica for example, AEROSIL 50, 130, 200, 300, 380 manufactured by Nippon Aerosil Co., Ltd. can be preferably used.
- trialkoxysilane any one can be used without particular limitation.
- the general formula: R 1 Si (OR 2 ) 3 (in the formula, R 1 is hydrogen or an alkyl group having 1 to 5 carbon atoms, and R 2 is an alkyl group having the same or different carbon atoms of 1 to 5 carbon atoms. ) Is preferably used.
- Examples of such trialkoxysilanes include trimethoxysilane, triethoxysilane, and methyltriethoxysilane.
- tetraalkoxysilane any one can be used without particular limitation.
- R is an alkyl group having the same or different carbon atoms of 1 to 5.
- tetraalkoxysilanes include tetramethoxysilane, tetraethoxysilane, and tetrapropoxysilane.
- any one can be used without particular limitation.
- the Si compound By containing the Si compound in the chemical conversion film, the Si compound is dehydrated and condensed to form an amorphous chemical conversion film having a siloxane bond having a high barrier effect that shields the corrosive factor. Further, by binding with the above-mentioned resin, a chemical conversion film having a higher barrier property is formed. Furthermore, in a corroded environment, dense and stable corrosion products are formed in the defective parts and damaged parts of the plating and film caused by processing, and the combined effect with the plating film also has the effect of suppressing the corrosion of the underlying steel sheet. be. From the viewpoint of having a high effect of forming a stable corrosion product, it is preferable to use at least one of colloidal silica and dry silica as the Si compound.
- the concentration of the Si compound in the chemical conversion treatment liquid for forming the chemical conversion film is 0.2% by mass to 9.5% by mass.
- concentration of the Si compound in the chemical conversion treatment liquid is 0.2% by mass or more, the barrier effect due to the siloxane bond can be obtained, and as a result, in addition to the corrosion resistance of the flat surface portion, the damage caused by the defective portion, the cut portion, the processing and the like can be obtained. Corrosion resistance and sweat resistance in the part are improved.
- the concentration of the Si compound is 9.5% by mass or less, the life of the chemical conversion treatment liquid can be extended.
- the Co compound and the Ni compound can be contained in the chemical conversion film to improve blackening resistance. It is considered that this is because Co and Ni have the effect of delaying the elution of the water-soluble component from the film in a corrosive environment. Further, the Co and the Ni are elements that are less likely to be oxidized than Al, Zn, Si, Mg and the like. Therefore, by concentrating at least one of the Co compound and the Ni compound at the interface between the chemical conversion film and the plating film (forming a concentrated layer), the concentrated layer becomes a barrier against corrosion. As a result, blackening resistance can be improved.
- Co By using a chemical conversion treatment liquid containing the Co compound, Co can be contained in the chemical conversion film and incorporated into the concentrated layer. It is preferable to use a cobalt salt as the Co compound. As the cobalt salt, it is more preferable to use 1 or 2 or more selected from cobalt sulfate, cobalt carbonate and cobalt chloride. Further, by using a chemical conversion treatment liquid containing the Ni compound, Ni can be contained in the chemical conversion film and incorporated into the concentrated layer. It is preferable to use a nickel salt as the Ni compound. As the nickel salt, it is more preferable to use 1 or 2 or more selected from nickel sulfate, nickel carbonate and nickel chloride.
- the concentration of the Co compound and / or the Ni compound in the chemical conversion treatment liquid is not particularly limited, but may be 0.25% by mass to 5% by mass in total.
- concentration of the Co compound and / or the Ni compound is less than 0.25% by mass, the interfacial concentrated layer becomes non-uniform, and not only the corrosion resistance of the flat surface portion is lowered, but also the plating caused by the defective portion, the cut end face portion, the processing, etc. And the corrosion resistance of the damaged part of the film may also decrease. From the same viewpoint, it is preferably 0.5% by mass or more, more preferably 0.75% by mass or more.
- the concentration of the Co compound and / or the Ni compound exceeds 5% by mass, the appearance when the film is formed tends to be non-uniform, and the corrosion resistance may decrease. From the same viewpoint, it is preferably 4.0% by mass or less, more preferably 3.0% by mass or less.
- a chemical conversion treatment solution having a total concentration of the Co compound and / or Ni compound of 0.25% by mass to 5% by mass, the total amount of Co and Ni adhered to the dried chemical conversion film is 5 to 100 mg. Can be / m 2 .
- a concentrated layer containing at least one of Al, Zn and Mg can be formed on the plating film side of the chemical conversion coating. ..
- the formed concentrated layer can improve the corrosion resistance.
- the Al compound, the Zn compound, and the Mg compound are not particularly limited as long as they are compounds containing Al, Zn, and Mg, respectively, but are preferably inorganic compounds, and salts, chlorides, and the like. It is preferably an oxide or a hydroxide.
- Examples of the Al compound include one or more selected from aluminum sulfate, aluminum carbonate, aluminum chloride, aluminum oxide and aluminum hydroxide.
- Examples of the Zn compound include one or more selected from zinc sulfate, zinc carbonate, zinc chloride, zinc oxide and zinc hydroxide.
- Examples of the Mg compound include one or more selected from magnesium sulfate, magnesium carbonate, magnesium chloride, magnesium oxide and magnesium hydroxide.
- the concentration of the Al compound, Zn compound and / or Mg compound in the chemical conversion treatment liquid for forming the chemical conversion film is preferably 0.25% by mass to 5% by mass in total.
- the total concentration is 0.25% by mass or more, the concentrated layer can be formed more effectively, and as a result, the corrosion resistance can be further improved.
- the total concentration is 5% by mass or less, the appearance of the chemical conversion film becomes more uniform, and the corrosion resistance of the flat surface portion, the defective portion, the damaged portion of the plating or the film caused by processing, etc. is further improved.
- V When the V compound is contained in the chemical conversion film, V is appropriately eluted in a corrosive environment and combined with zinc ions and the like of plating components that are also eluted in a corrosive environment to form a dense protective film. ..
- the formed protective film can further enhance the corrosion resistance not only to the flat surface portion of the steel sheet but also to the defective portion, the damaged portion of the plating film caused by processing, the corrosion progressing from the cut end face to the flat surface portion, and the like.
- the V compound is a V-containing compound, and examples thereof include one or more selected from sodium metavanadate, vanadyl sulfate, and vanadium acetylacetonate.
- the V compound in the chemical conversion treatment liquid for forming the chemical conversion film is preferably 0.05% by mass to 4% by mass.
- concentration of the V compound is 0.05% by mass or more, it is easy to elute in a corrosive environment to form a protective film, and the corrosion resistance of the defective part, the cut end face part, and the damaged part of the plating film caused by processing is improved. improves.
- concentration of the V compound exceeds 4% by mass, the appearance when the chemical conversion film is formed tends to be non-uniform, and the blackening resistance is also lowered.
- the Mo compound is a compound containing Mo and can be obtained by adding one or both of molybdic acid and molybdate to the chemical conversion treatment liquid.
- the molybdate include one or more selected from sodium molybdate, potassium molybdate, magnesium molybdate, and zinc molybdate.
- the concentration of the Mo compound in the chemical conversion treatment liquid for forming the chemical conversion film is preferably 0.01% by mass to 3% by mass.
- concentration of the Mo compound is 0.01% by mass or more, the formation of oxygen-deficient zinc oxide is further suppressed, and the blackening resistance can be further improved.
- concentration of the Mo compound is 3% by mass or less, the life of the chemical conversion treatment liquid is further extended, and the corrosion resistance can be further improved.
- the corrosion factor is less likely to permeate the chemical conversion film, and the corrosion resistance can be improved.
- the Zr compound is a compound containing Zr, and for example, one or more selected from zirconyl acetate, zirconyl sulfate, potassium zirconyl carbonate, sodium zirconyl carbonate and ammonium zirconyl carbonate can be used.
- the organic titanium chelate compound is suitable because when the chemical conversion treatment liquid is dried to form a film, the film is densified and more excellent corrosion resistance can be obtained.
- the Ti compound is a compound containing Ti, and is one or more selected from, for example, titanium sulfate, titanium chloride, titanium hydroxide, titanium acetylacetonate, titanium octylene glycolate, and titanium ethylacetoacetate. Can be used.
- the concentration of the Zr compound and / or the Ti compound in the chemical conversion treatment liquid for forming the chemical conversion film is preferably 0.2% by mass to 20% by mass in total.
- the concentration of the Zr compound and / or the Ti compound is 0.2% by mass or more, the effect of suppressing the permeation of the corrosive factor is enhanced, and not only the corrosion resistance of the flat surface portion but also the defect portion, the cut end face portion, and the plating film damage due to processing are damaged. The corrosion resistance of the part can be further improved.
- the total concentration of the Zr compound and / or the Ti compound is 20% by mass or less, the life of the chemical conversion treatment liquid can be further extended.
- the Ca compound is a compound containing Ca, and examples thereof include an oxide of Ca, a nitrate of Ca, a sulfate of Ca, and an intermetallic compound containing Ca. More specifically, examples of the Ca compound include CaO, CaCO 3 , Ca (OH) 2 , Ca (NO 3 ) 2.4H 2 O, CaSO 4.2H 2 O and the like.
- the content of the Ca compound in the chemical conversion film is not particularly limited.
- the chemical conversion film can contain various known components usually used in the paint field, if necessary.
- various surface conditioners such as leveling agents and defoamers, dispersants, anti-settling agents, ultraviolet absorbers, light stabilizers, silane coupling agents, various additives such as titanate coupling agents, coloring pigments, and extender pigments.
- Various pigments such as bright materials, curing catalysts, organic solvents, lubricants and the like.
- the chemical conversion film does not contain harmful components such as hexavalent chromium, trivalent chromium and fluorine. This is because the chemical conversion treatment liquid for forming the chemical conversion film does not contain these harmful components, so that the safety is high and the amount is small to the environment.
- the amount of the chemical conversion film adhered is not particularly limited.
- the adhesion amount of the chemical conversion film is preferably 0.1 to 3.0 g / m 2 , preferably 0.5 to 2.5 g / m 2 . It is more preferable to do so. Corrosion resistance can be ensured more reliably by setting the adhesion amount of the chemical conversion film to 0.1 g / m 2 or more, and cracking or peeling of the chemical conversion film by setting the adhesion amount of the chemical conversion film to 3.0 g / m 2 or less. Can be prevented.
- the amount of the chemical conversion film adhered may be obtained by a method appropriately selected from existing methods such as a method of measuring the abundance of an element whose content in the film is known in advance by fluorescent X-ray analysis of the film. ..
- the method for forming the chemical conversion film is not particularly limited, and can be appropriately selected according to the required performance, manufacturing equipment, and the like.
- a chemical conversion treatment liquid is continuously applied onto the plating film with a roll coater or the like, and then, using hot air or induction heating, the plate temperature reaches about 60 to 200 ° C. (Peak Metal Temperature: PMT). It can be formed by drying.
- PMT Peak Metal Temperature
- a known method such as an airless spray, an electrostatic spray, a curtain flow coater or the like can be appropriately adopted in addition to the roll coater.
- the chemical conversion film may be either a single-layer film or a multi-layer film as long as it contains the resin and the metal compound, and is not particularly limited.
- the surface-treated steel sheet of the present invention can also form a coating film on the chemical conversion film, if necessary.
- the coated steel sheet of the present invention is a coated steel sheet in which a coating film is formed directly on the plating film or via a chemical conversion film.
- the composition of the plating film is the same as that of the above-mentioned plating film of the molten Al-Zn-Si-Mg-based plated steel sheet of the present invention.
- the coated steel sheet of the present invention can form a chemical conversion film on the plating film.
- the chemical conversion film may be formed on at least one side of the coated steel sheet, and may be formed on both sides of the coated steel sheet depending on the application and required performance.
- the chemical conversion film contains (a): an anionic polyurethane resin having an ester bond and (b): an epoxy resin having a bisphenol skeleton in a total amount of 30 to 50% by mass.
- a resin component having a content ratio ((a): (b)) of a) and the (b) in the range of 3:97 to 60:40 by mass ratio, and a vanadium compound of 2 to 10% by mass, 40 to It is characterized by containing an inorganic compound containing 60% by mass of a zirconium compound and 0.5 to 5% by mass of a fluorine compound.
- the resin component constituting the chemical conversion film contains (a): an anionic polyurethane resin having an ester bond and (b): an epoxy resin having a bisphenol skeleton.
- the anionic polyurethane resin having the (a) ester bond a resin obtained by copolymerizing a polyester polyol with a diisocyanate or a polyisocyanate having two or more isocyanate groups and a dimethylolalkyl acid is obtained.
- a chemical conversion treatment liquid can be obtained by dispersing it in a liquid such as water by a known method.
- the polyester polyol includes a polyester obtained by a dehydration condensation reaction from a glycol component and an acid component such as an ester-forming derivative of hydroxylcarboxylic acid, a polyester obtained by a ring-opening polymerization reaction of a cyclic ester compound such as ⁇ -caprolactone, and these.
- Examples of the polyisocyanate include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates.
- aromatic polyisocyanate examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-xylene diisocyanate, diphenylmethane diisocyanate, 2,4-diphenylmethane diisocyanate, 2,2-diphenylmethane diisocyanate, and triphenyl.
- aromatic polyisocyanate examples include methanetriisocyanate, polymethylene polyphenyl polyisocyanate, naphthalenediocyanate, and derivatives thereof (for example, prepolymers obtained by reaction with polyols, modified polyisocyanates such as carbodiimide compounds of diphenylmethane diisocyanate, etc.).
- dimethylolalkyl acid examples include dimethylolalkyl acids having 2 to 6 carbon atoms, and more specifically, dimethylolethaneic acid, dimethylolpropaneic acid, dimethylolbutanoic acid, and dimethylolheptan. Acids and dimethylolhexaneic acid and the like can be mentioned.
- the epoxy resin having the (b) bisphenol skeleton a known epoxy resin can be used.
- a known epoxy resin can be used.
- bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin and the like can be mentioned.
- These epoxy resins can be obtained by reacting bisphenol compounds such as bisphenol A, bisphenol F, bisphenol AD, and bisphenol S with epichlorohydrin in the presence of an alkaline catalyst.
- the component [A] preferably contains a bisphenol A type epoxy resin or a bisphenol F type epoxy resin, and more preferably contains a bisphenol A type epoxy resin.
- the epoxy resin having the (b) bisphenol skeleton can be dispersed in a liquid such as water by a known method to obtain a chemical conversion treatment liquid.
- the resin component acts as a binder for the chemical conversion film, but the anionic polyurethane resin having the (a) ester bond constituting the binder is flexible, so that the chemical conversion film is destroyed when processed ().
- the effect of making it difficult to peel off) can be achieved, and the epoxy resin having the bisphenol skeleton described in (b) can have the effect of improving the adhesion to the underlying zinc-based plated steel plate and the upper primer coating film.
- the resin component is contained in the chemical conversion film in a total amount of 30 to 50% by mass. If the content of the resin component is less than 30% by mass, the binder effect of the chemical conversion film is lowered, and if it exceeds 50% by mass, the function of the inorganic component shown below, for example, the inhibitory action is lowered. From the same viewpoint, the content of the resin component in the chemical conversion film is preferably 35 to 45% by mass.
- the content ratio ((a): (b)) of the anionic polyurethane resin having the (a) ester bond and the epoxy resin having the (b) bisphenol skeleton is 3:97 by mass ratio. It must be in the range of ⁇ 60: 40. This is because when the above (a): (b) is out of the above range, sufficient corrosion resistance cannot be obtained due to a decrease in flexibility and adhesion as a chemical conversion coating film. From the same viewpoint, the above (a): (b) is preferably 10:90 to 55:45.
- the resin component includes a resin (other resin component) other than the above-mentioned (a) anionic polyurethane resin having an ester bond and (b) an epoxy resin having a bisphenol skeleton, depending on the required performance. be able to.
- the other resin components are not particularly limited, and are, for example, at least one or two or more selected from acrylic resin, acrylic silicon resin, alkyd resin, polyester resin, polyalkylene resin, amino resin and fluororesin. Can be used in combination.
- the total content of the (a) anionic polyurethane resin having an ester bond and the (b) epoxy resin having a bisphenol skeleton is preferably 50% by mass or more. It is more preferably 75% by mass or more. This is to ensure that the flexibility and adhesion of the film to be treated are reduced.
- the chemical conversion film contains 2 to 10% by mass of vanadium compound, 40 to 60% by mass of zirconium compound and 0.5 to 5% by mass of fluorine compound as inorganic compounds. By including these compounds, the corrosion resistance of the chemical conversion film can be enhanced.
- the vanadium compound is added to the chemical conversion treatment liquid and acts as a rust preventive (inhibitor).
- the vanadium compound is contained in the chemical conversion film, the vanadium compound is appropriately eluted in a corrosive environment and combined with zinc ions or the like of a plating component that also elutes in a corrosive environment to form a dense protective film. ..
- the formed protective film can further enhance the corrosion resistance not only to the flat surface portion of the steel sheet but also to the defective portion, the damaged portion of the plating film caused by processing, the corrosion progressing from the cut end face to the flat surface portion, and the like.
- vanadium compound examples include vanadium pentoxide, metavanadic acid, ammonium metavanadate, vanadium oxytrichloride, vanadium trioxide, vanadium dioxide, magnesium vanadate, vanadyl acetylacetonate, and vanadium acetylacetonate.
- vanadium pentoxide metavanadic acid
- ammonium metavanadate vanadium oxytrichloride
- vanadium trioxide vanadium dioxide
- magnesium vanadate vanadyl acetylacetonate
- vanadium acetylacetonate vanadium acetylacetonate
- the content of the vanadium compound in the chemical conversion treatment film is 2 to 10% by mass. If the content of the vanadium compound in the chemical conversion coating is less than 2% by mass, the inhibitory effect is not sufficient, resulting in a decrease in corrosion resistance. On the other hand, if the content of the vanadium compound exceeds 10% by mass, the moisture resistance of the chemical conversion coating is reduced. This is because it causes a decrease in.
- the zirconium compound is contained in the chemical conversion coating, and can be expected to improve the strength and corrosion resistance of the chemical conversion coating by reacting with the plating metal and coexisting with the resin component. Furthermore, the zirconium compound itself is a dense chemical conversion coating. It contributes to the formation of zirconium and is rich in coating properties, so a barrier effect can be expected. Examples of the zirconium compound include neutralizing salts such as zirconium sulfate, zirconium carbonate, zirconium nitrate, zirconium lactate, zirconium acetate, and zirconium chloride.
- the content of the zirconium compound in the chemical conversion treatment film is 40 to 60% by mass. If the content of the zirconium compound in the chemical conversion coating is less than 40% by mass, the strength and corrosion resistance of the chemical conversion coating are deteriorated, and if the content of the zirconium compound exceeds 60% by mass, the chemical conversion coating is brittle. This is because the chemical conversion treatment film is destroyed or peeled off when it is subjected to severe processing.
- the fluorine compound is contained in the chemical conversion film and acts as an adhesive-imparting agent with the plating film. As a result, it is possible to improve the corrosion resistance of the chemical conversion film.
- a fluoride salt such as an ammonium salt, a sodium salt or a potassium salt, or a fluorine compound such as ferrous fluoride or ferric fluoride can be used. Among these, it is preferable to use ammonium fluoride or a fluoride salt such as sodium fluoride and potassium fluoride.
- the content of the fluorine compound in the chemical conversion treatment film is 0.5 to 5% by mass. If the content of the fluorine compound in the chemical conversion treatment film is less than 0.5% by mass, sufficient adhesion at the processed portion cannot be obtained, and if the content of the fluorine compound exceeds 5% by mass, the moisture resistance of the chemical conversion treatment film becomes high. This is because it decreases.
- the amount of the chemical conversion film adhered is not particularly limited.
- the amount of the chemical conversion film adhered may be obtained by a method appropriately selected from existing methods such as a method of measuring the abundance of an element whose content in the film is known in advance by fluorescent X-ray analysis of the film. ..
- the method for forming the chemical conversion film is not particularly limited, and can be appropriately selected according to the required performance, manufacturing equipment, and the like.
- a chemical conversion treatment liquid is continuously applied onto the plating film with a roll coater or the like, and then, using hot air or induction heating, the plate temperature reaches about 60 to 200 ° C. (Peak Metal Temperature: PMT). It can be formed by drying.
- PMT Peak Metal Temperature
- a known method such as an airless spray, an electrostatic spray, a curtain flow coater or the like can be appropriately adopted in addition to the roll coater.
- the chemical conversion film may be either a single-layer film or a multi-layer film as long as it contains the resin and the metal compound, and is not particularly limited.
- the coated steel sheet of the present invention has a coating film formed on the plating film directly or via a chemical conversion film, and the coating film has at least a primer coating film.
- the primer coating film contains a polyester resin having a urethane bond and an inorganic compound containing a vanadium compound, a phosphoric acid compound and magnesium oxide.
- the primer coating film contains a polyester resin having a urethane bond as a main component. Since the polyester resin having a urethane bond has both flexibility and strength, it is possible to obtain an effect that cracks are less likely to occur in the primer coating film when it is processed, and a chemical conversion treatment film containing a urethane resin is obtained. Since it has a high affinity with, it can contribute to the improvement of corrosion resistance of the processed portion.
- the term "main component" as used herein means that the component has the highest content among the components in the primer coating film.
- polyester resin having a urethane bond a known resin such as a resin obtained by reacting a polyester polyol with a diisocyanate or a polyisocyanate having two or more isocyanate groups can be used. Further, a resin obtained by reacting the polyester polyol with the diisocyanate or the polyisocyanate in a state of excess hydroxylate (urethane-modified polyester resin) and cured with a blocked polyisocyanate can also be used.
- the polyester polyol can be obtained by a known method using a dehydration condensation reaction between a polyhydric alcohol component and a polybasic acid component.
- the polyhydric alcohol include glycols and trihydric or higher polyhydric alcohols.
- the glycols include, for example, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, hexylene glycol, 1,3-butanediol, 1,4.
- a polyvalent carboxylic acid is usually used, but a monovalent fatty acid or the like can be used in combination if necessary.
- the polyvalent carboxylic acid include phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, 4-methylhexahydrophthalic acid, bicyclo [2,2,1] heptane-2,3-dicarboxylic acid, trimellitic acid, and the like.
- polyisocyanate for example, aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, dimerate diisocyanate, and xylylene diisocyanate (XDI), metaxylylene diisocyanate, tolylene diisocyanate (TDI), 4, 4 -Aromatic diisocyanates such as diphenylmethane diisocyanate (MDI), cyclic aliphatic diisocyanates such as isophorone diisocyanate, hydride XDI, hydride TDI, hydride MDI, and adducts, biurets, isocyanurates and the like thereof. Will be. These polyisocyanates can be used alone or in combination of two or more.
- aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, dimerate diisocyanate, and
- the hydroxyl value of the polyester resin having a urethane bond is not particularly limited, but is preferably 5 to 120 mgKOH / g, more preferably 7 to 100 mgKOH / g from the viewpoint of solvent resistance, processability, and the like. It is g, more preferably 10 to 80 mgKOH / g. Further, the number average molecular weight of the polyester resin having a urethane bond is preferably 500 to 15,000, more preferably 700 to 12,000, still more preferably 800 to 10,000 from the viewpoint of solvent resistance, processability and the like. Is.
- the content of the polyester resin having a urethane bond in the primer coating film is preferably 40 to 88% by mass. If the content of the polyester resin having a urethane bond is less than 40% by mass, the binder function as a primer coating film may be deteriorated, while if the content of the polyester resin having a urethane bond exceeds 88% by mass, the binder function may be deteriorated.
- the functions of the following inorganic substances, such as inhibitory action, may be reduced.
- the vanadium compound which is one of the inorganic compounds, acts as an inhibitor.
- the vanadium compound include vanadium pentoxide, metavanadic acid, ammonium metavanadate, vanadium oxytrichloride, vanadium trioxide, vanadium dioxide, magnesium vanadate, vanadyl acetylacetonate, and vanadium acetylacetonate.
- the vanadium compound added to the primer coating film may be the same as or different from the vanadium compound added to the chemical conversion treatment film.
- vanazic acid compound vanadic acid ions that gradually elute to the moisture that invades from the outside react with the ions on the surface of the galvanized steel sheet to form a passivation film with good adhesion, which protects and prevents exposed metal parts. It is believed that rusting is manifested.
- the content of the vanadium compound in the primer coating film is not particularly limited, but is preferably 4 to 20% by mass from the viewpoint of achieving both corrosion resistance and moisture resistance. If the content of the vanadium compound is less than 4% by mass, the inhibitory effect may be lowered and the corrosion resistance may be lowered, and if the content of the vanadium compound is more than 20% by mass, the moisture resistance of the primer coating film may be lowered. There is a risk.
- the phosphoric acid compound which is one of the inorganic compounds, also acts as an inhibitor.
- the phosphoric acid compound for example, phosphoric acid, an ammonium salt of phosphoric acid, an alkali metal salt of phosphoric acid, an alkaline earth metal salt of phosphoric acid and the like can be used.
- an alkali metal salt of phosphoric acid such as calcium phosphate can be preferably used.
- the content of the phosphoric acid compound in the primer coating film is not particularly limited, but is preferably 4 to 20% by mass from the viewpoint of achieving both corrosion resistance and moisture resistance. If the content of the phosphoric acid compound is less than 4% by mass, the inhibitory effect may be lowered and the corrosion resistance may be lowered, and if the content of the phosphoric acid compound is more than 20% by mass, the moisture resistance of the primer coating film may be lowered. May be invited.
- Magnesium oxide which is one of the above-mentioned inorganic compounds, produces a product containing Mg by initial corrosion, and has the effect of stabilizing as a sparingly soluble magnesium salt and improving corrosion resistance.
- the content of the magnesium oxide in the primer coating film is not particularly limited, but is preferably 4 to 20% by mass from the viewpoint of achieving both corrosion resistance and corrosion resistance of the processed portion. If the magnesium oxide content is less than 4% by mass, the effect may be lowered and the corrosion resistance may be lowered, and if the magnesium oxide content is more than 20% by mass, the flexibility of the primer coating film may be deteriorated. The corrosion resistance of the processed portion may decrease due to the decrease in the amount of
- the primer coating film may contain components other than the polyester resin having a urethane bond and the inorganic compound described above.
- a cross-linking agent used when forming a primer coating film can be mentioned.
- the cross-linking agent reacts with the polyester resin having a urethane bond to form a cross-linked coating film, and is, for example, an oxazoline compound, an epoxy compound, a melamine compound, an isocyanate-based compound, a carbodiimide-based compound, a silane coupling compound, or the like. It is also possible to use two or more kinds of cross-linking agents in combination.
- a blocked polyisocyanate compound or the like can be preferably used from the viewpoint of corrosion resistance of the processed portion of the obtained coated steel sheet.
- the blocked polyisocyanate include alcohols such as butanol, oximes such as methylethylketooxime, lactams such as ⁇ -caprolactam, and diketones such as acetoacetic acid diester, using the isocyanate group of the polyisocyanate compound.
- examples thereof include those blocked by imidazoles such as imidazole and 2-ethylimidazole, or phenols such as m-cresol.
- the primer coating film may contain various known components usually used in the paint field, if necessary.
- various surface conditioners such as leveling agents and antifoaming agents, dispersants, anti-sedimentants, ultraviolet absorbers, light stabilizers, silane coupling agents, various additives such as titanate coupling agents, etc.
- various pigments such as coloring pigments and extender pigments, bright materials, curing catalysts, and organic solvents.
- the thickness of the primer coating film is preferably 1.5 ⁇ m or more. By setting the thickness of the primer coating film to 1.5 ⁇ m or more, it is possible to more reliably obtain the effect of improving corrosion resistance and the effect of improving the adhesion with the chemical conversion treatment film or the top coat film formed on the primer coating film. Because it can be done.
- the method for forming the primer coating film is not particularly limited. Further, as for the coating method of the coating composition constituting the primer coating film, the coating composition can be preferably applied by a method such as roll coater coating or curtain flow coating. After the coating composition is coated, it can be baked by heating means such as hot air heating, infrared heating, and induction heating to obtain a primer coating film. The baking treatment is usually carried out with a maximum plate temperature of about 180 to 270 ° C. and about 30 seconds to 3 minutes in this temperature range.
- a topcoat coating film is further formed on the primer coating film.
- the topcoat coating film can impart aesthetics such as color, luster, and surface condition to the coated steel sheet, and also has various performances such as workability, weather resistance, chemical resistance, stain resistance, water resistance, and corrosion resistance. Can be enhanced.
- the composition of the topcoat coating film is not particularly limited, and the material, thickness, and the like can be appropriately selected according to the required performance.
- the topcoat coating film can be formed by using a polyester resin-based paint, a silicon polyester resin-based paint, a polyurethane resin-based paint, an acrylic resin-based paint, a fluororesin-based paint, or the like.
- the top coat is a titanium oxide, a valve handle, mica, carbon black or various other coloring pigments; metallic pigments such as aluminum powder and mica; extender pigments composed of carbonates and sulfates; silica fine particles and nylon resins.
- Various fine particles such as beads and acrylic resin beads; a curing catalyst such as p-toluenesulfonic acid and dibutyltin dilaurate; wax; and other additives can be contained in an appropriate amount.
- the thickness of the topcoat coating film is preferably 5 to 30 ⁇ m from the viewpoint of achieving both appearance and processability.
- the thickness of the topcoat coating film is 5 ⁇ m or more, the color tone appearance can be more reliably stabilized, and when the thickness of the topcoat coating film is 30 ⁇ m or less, the workability is deteriorated (topcoat coating). The generation of cracks in the film) can be suppressed more reliably.
- the coating method of the coating composition for forming the topcoat coating film is not particularly limited.
- the coating composition can be applied by a method such as roll coater coating or curtain flow coating. After the coating composition is coated, it can be baked by heating means such as hot air heating, infrared heating, and induction heating to form a topcoat coating film.
- the baking treatment is usually carried out with a maximum plate temperature of about 180 to 270 ° C. and about 30 seconds to 3 minutes in this temperature range.
- Samples 1 to 44> A cold-rolled steel sheet with a thickness of 0.8 mm manufactured by a conventional method is used as a base steel sheet, and annealing and plating are performed with a hot-dip plating simulator manufactured by Resuka Co., Ltd. to obtain hot-dip plated steel sheets under the conditions shown in Table 1.
- Samples 1-44 were prepared. Regarding the composition of the plating bath used for manufacturing the hot-dip plated steel sheet, the composition of the plating bath was Al: 30 to 75% by mass and Si: 0.5 to 4.5 so as to be the composition of the plating film of each sample shown in Table 1. It was varied in the range of% by mass, Mg: 0 to 10% by mass, and Sr: 0.00 to 0.15% by mass.
- the bath temperature of the plating bath is 590 ° C when Al: 30 to 60% by mass and 630 ° C when Al: more than 60% by mass, and the plating penetration plate temperature of the base steel sheet is the same as the plating bath temperature. It was controlled to be. Furthermore, the plating treatment was carried out under the condition that the plate temperature was cooled to a temperature range of 520 to 500 ° C. in 3 seconds. The amount of the plating film adhered was controlled to be 85 ⁇ 5 g / m 2 per side for the samples 1 to 41 and 51 to 125 g / m 2 per side for the samples 42 to 44.
- composition of plating film (adhesion amount, composition, X-ray diffraction intensity)
- punch 100 mm ⁇ seal the non-measurement surface with tape, then dissolve and peel the plating with a mixed solution of hydrochloric acid and hexamethylenetetramine shown in JIS H 0401: 2013, and the mass of the sample before and after peeling. From the difference, the amount of adhesion of the plating film was calculated. Table 1 shows the amount of adhesion of the plating film obtained as a result of the calculation. Then, the stripping solution was filtered, and the filtrate and solid content were analyzed respectively. Specifically, components other than insoluble Si were quantified by ICP emission spectroscopic analysis of the filtrate.
- the solid content was dried and incinerated in a heating furnace at 650 ° C., and then melted by adding sodium carbonate and sodium tetraborate. Furthermore, insoluble Si was quantified by dissolving the melt with hydrochloric acid and ICP emission spectroscopic analysis of the solution.
- the Si concentration in the plating film is the sum of the soluble Si concentration obtained by the filtrate analysis and the insoluble Si concentration obtained by the solid content analysis. Table 1 shows the composition of the plating film obtained as a result of the calculation.
- the plating film on the evaluation symmetric plane is mechanically scraped until the underlying steel plate appears, the obtained powder is mixed well, and then 0.3 g is taken out and X is taken out.
- the diffraction intensity of d 0.3135 nm) was measured. The measurement results are shown in Table 1.
- Corrosion loss of 3 samples is 45 g / m 2 or less ⁇ : Corrosion loss of 3 samples is 70 g / m 2 or less ⁇ : Corrosion loss of 1 sample or more exceeds 70 g / m 2
- each sample of the example of the present invention is superior to each sample of the comparative example in terms of corrosion resistance, surface appearance, processability, and bath stability in a well-balanced manner.
- Example 2 Samples 1-112> (1) Plating shown in Tables 3 and 4 is performed by using a cold-rolled steel sheet with a thickness of 0.8 mm manufactured by a conventional method as a base steel sheet and performing an annealing treatment and a plating treatment with a hot-dip plating simulator manufactured by Resuka Co., Ltd. A sample of a hot-dip plated steel sheet with film conditions was prepared. Regarding the composition of the plating bath used for manufacturing the hot-dip plated steel sheet, the composition of the plating bath was Al: 30 to 75% by mass and Si: 0.5 to 4.5 so as to be the composition of the plating film of each sample shown in Table 2.
- the bath temperature of the plating bath is 590 ° C when Al: 30 to 60% by mass and 630 ° C when Al: more than 60% by mass, and the plating penetration plate temperature of the base steel sheet is the same as the plating bath temperature. It was controlled to be. Furthermore, the plating treatment was carried out under the condition that the plate temperature was cooled to a temperature range of 520 to 500 ° C. in 3 seconds.
- the amount of the plating film adhered was controlled to be 85 ⁇ 5 g / m 2 per side for samples 1 to 82 and 95 to 112, and 51 to 125 g / m 2 per side for samples 83 to 94.
- a chemical conversion treatment liquid is applied on the plating film of each sample of the prepared hot-dip galvanized steel sheet with a bar coater, and dried in a hot air furnace (heating rate: 60 ° C / s, PMT: 120 ° C).
- a chemical conversion film was formed in 1 and each sample of the surface-treated steel sheet shown in Tables 3 and 4 was prepared.
- the chemical conversion treatment liquid surface treatment liquids A to F in which each component was dissolved in water as a solvent were prepared.
- each component (resin, metal compound) contained in the surface treatment liquid are as follows.
- Urethane resin Superflex 130, Superflex 126 (Daiichi Kogyo Seiyaku Co., Ltd.)
- Acrylic resin Boncoat EC-740EF (DIC Corporation)
- Metal compound P compound: aluminum dihydrogen dihydrogen tripolyphosphate Si compound: silica
- V compound sodium metavanadate Mo compound: molybdic acid
- Zr compound Zirconyl potassium carbonate
- Table 2 shows the compositions of the prepared chemical conversion treatment liquids A to F and the amount of the formed chemical conversion film adhered.
- the concentration of each component in Table 2 of the present specification is the concentration of solid content (mass%).
- composition of plating film (adhesion amount, composition, X-ray diffraction intensity)
- 100 mm ⁇ is punched out, the non-measurement surface is sealed with tape, and then the plating is melted and peeled off with a mixed solution of hydrochloric acid and hexamethylenetetramine shown in JIS H 0401: 2013.
- the amount of adhesion of the plating film was calculated from the mass difference.
- the amount of adhesion of the obtained plating film is shown in Tables 3 and 4. Then, the stripping solution was filtered, and the filtrate and solid content were analyzed respectively.
- components other than insoluble Si were quantified by ICP emission spectroscopic analysis of the filtrate.
- the solid content was dried and incinerated in a heating furnace at 650 ° C., and then melted by adding sodium carbonate and sodium tetraborate.
- insoluble Si was quantified by dissolving the melt with hydrochloric acid and ICP emission spectroscopic analysis of the solution.
- the Si concentration in the plating film is the sum of the soluble Si concentration obtained by the filtrate analysis and the insoluble Si concentration obtained by the solid content analysis.
- the composition of the plating film obtained as a result of the calculation is shown in Tables 3 and 4.
- the plating film on the evaluation symmetric plane is mechanically scraped until the underlying steel plate appears, the obtained powder is mixed well, and then 0.3 g is taken out and X is taken out.
- the diffraction intensity of d 0.3135 nm) was measured. The measurement results are shown in Tables 3 and 4.
- Corrosion loss of 3 samples is 30 g / m 2 or less
- Corrosion loss of 3 samples is 50 g / m 2 or less
- Corrosion loss of 1 sample or more exceeds 50 g / m 2
- each sample of the example of the present invention is superior in balance in corrosion resistance, white rust resistance, surface appearance, processability and bath stability as compared with each sample of the comparative example. You can see that there is. Further, from the results in Table 4, it can be seen that the white rust resistance of each sample subjected to the chemical conversion treatments A to D is excellent.
- Example 3 Samples 1 to 44> (1)
- the plating film conditions shown in Table 6 are obtained by using a cold-rolled steel sheet with a thickness of 0.8 mm manufactured by a conventional method as a base steel sheet and performing an annealing treatment and a plating treatment with a hot-dip plating simulator manufactured by Resuka Co., Ltd.
- a sample of the hot-dip plated steel sheet was prepared.
- the composition of the plating bath used for manufacturing the hot-dip plated steel sheet the composition of the plating bath was Al: 30 to 75% by mass and Si: 0.5 to 4.5 so as to be the composition of the plating film of each sample shown in Table 6.
- the bath temperature of the plating bath is 590 ° C when Al: 30 to 60% by mass and 630 ° C when Al: more than 60% by mass, and the plating penetration plate temperature of the base steel sheet is the same as the plating bath temperature. It was controlled to be. Furthermore, the plating treatment was carried out under the condition that the plate temperature was cooled to a temperature range of 520 to 500 ° C. in 3 seconds. The amount of the plating film adhered was controlled to be 85 ⁇ 5 g / m 2 per side for the samples 1 to 41 and 42 to 125 g / m 2 per side for the samples 42 to 44.
- the chemical conversion treatment liquid shown in Table 5 is applied on the plating film of each sample of the prepared hot-dip galvanized steel sheet with a bar coater, and dried in a hot air drying furnace (reached plate temperature: 90 ° C.). A chemical conversion-treated film having an adhesion of 0.1 g / m 2 was formed.
- the chemical conversion treatment liquid used a chemical conversion treatment liquid having a pH of 8 to 10 prepared by dissolving each component in water as a solvent was used.
- the types of each component (resin component, inorganic compound) contained in the chemical conversion treatment liquid are as follows.
- a primer paint is applied on the chemical conversion film formed as described above with a bar coater, and the steel sheet is baked under the conditions of an ultimate temperature of 230 ° C. and a baking time of 35 seconds.
- a primer coating film having the above was formed.
- the topcoat coating composition is applied on the primer coating film formed as described above with a bar coater, and the steel sheet is baked under the conditions of reaching temperature of 230 ° C to 260 ° C and baking time of 40 seconds, as shown in Table 5.
- a topcoat coating film having the resin conditions and film thickness shown was formed, and a coated steel sheet of each sample was produced.
- the primer paint was obtained by mixing each component and then stirring with a ball mill for about 1 hour.
- Resin component Urethane-modified polyester resin (a product obtained by reacting 455 parts by mass of polyester resin and 45 parts by mass of isophorone diisocyanate, having a resin acid value of 3, a number average molecular weight of 5,600, and a hydroxyl value of 36). , The one cured with blocked isocyanate was used. The urethane resin to be urethane-modified was produced under the following conditions.
- a flask equipped with a stirrer, a rectification tower, a water separator, a cooling tube and a thermometer was charged with 320 parts by mass of isophthalic acid, 200 parts by mass of adipic acid, 60 parts by mass of trimethylolpropane and 420 parts by mass of cyclohexanedimethanenol.
- Heat and stir, and while distilling the generated condensed water out of the system raise the temperature from 160 ° C to 230 ° C over 4 hours at a constant rate, and after reaching the temperature of 230 ° C, gradually add 20 parts by mass of xylene.
- Resin I Melamine-cured polyester paint ("Precolor HD0030HR” manufactured by BASF Japan Ltd.)
- Resin II Organosol-based baking-type fluororesin-based paint with a mass ratio of polyvinylidene fluoride and acrylic resin of 80:20 (“Precolor No. 8800HR” manufactured by BASF Japan Ltd.)
- composition of plating film (adhesion amount, composition, X-ray diffraction intensity)
- 100 mm ⁇ is punched out, the non-measurement surface is sealed with tape, and then the plating is melted and peeled off with a mixed solution of hydrochloric acid and hexamethylenetetramine shown in JIS H 0401: 2013.
- the amount of adhesion of the plating film was calculated from the mass difference.
- Table 6 shows the amount of adhesion of the plating film obtained as a result of the calculation.
- the stripping solution was filtered, and the filtrate and solid content were analyzed respectively. Specifically, components other than insoluble Si were quantified by ICP emission spectroscopic analysis of the filtrate.
- the solid content was dried and incinerated in a heating furnace at 650 ° C., and then melted by adding sodium carbonate and sodium tetraborate. Furthermore, insoluble Si was quantified by dissolving the melt with hydrochloric acid and ICP emission spectroscopic analysis of the solution.
- the Si concentration in the plating film is the sum of the soluble Si concentration obtained by the filtrate analysis and the insoluble Si concentration obtained by the solid content analysis. Table 6 shows the composition of the plating film obtained as a result of the calculation.
- the plating film on the evaluation symmetric plane is mechanically scraped until the underlying steel plate appears, the obtained powder is mixed well, and then 0.3 g is taken out and X is taken out.
- the diffraction intensity of d 0.3135 nm) was measured. The measurement results are shown in Table 6.
- the corrosion acceleration test was started from wetting, samples were taken out every 20 cycles, washed with water and dried, and then visually observed to confirm the occurrence of red rust on the sheared end face on one side that was not tape-sealed. Then, the number of cycles when red rust was confirmed was evaluated according to the following criteria. The evaluation results are shown in Table 6. ⁇ : Number of red rust generation cycles of 3 samples ⁇ 600 cycles ⁇ : 600 cycles > Number of red rust generation cycles of 3 samples ⁇ 500 cycles ⁇ : Number of red rust generation cycles of at least 1 sample ⁇ 500 cycles
- each sample of the example of the present invention is superior to each sample of the comparative example in terms of corrosion resistance, appearance after painting, processability after painting, and bath stability in a well-balanced manner. I understand.
- the present invention it is possible to provide a molten Al-Zn-Si-Mg-based plated steel sheet having stable and excellent corrosion resistance. Further, according to the present invention, it is possible to stably provide a surface-treated steel sheet having excellent corrosion resistance and white rust resistance. Further, according to the present invention, it is possible to stably provide a coated steel sheet having excellent corrosion resistance and corrosion resistance of a processed portion.
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Abstract
Description
このような溶融Al-Zn-Si-Mg系めっき鋼板としては、例えば特許文献1に、めっき皮膜中にMgを含むAl-Zn-Si合金を含み、該Al-Zn-Si合金が、45~60重量%の元素アルミニウム、37~46重量%の元素亜鉛及び1.2~2.3重量%のSiを含有する合金であり、該Mgの濃度が1~5重量%である、溶融Al-Zn-Si-Mg系めっき鋼板が開示されている。
また、特許文献2には、めっき皮膜中に2~10%のMg、0.01~10%のCaの1種以上を含有させることで耐食性の向上を図るとともに、下地鋼板が露出した後の保護作用を高めることを目的とした溶融Al-Zn-Si-Mg系めっき鋼板が開示されている。
さらに、特許文献3には、質量%で、Mg:1~15%、Si:2~15%、Zn:11~25%を含有し、残部がAl及び不可避的不純物からなる被覆層を形成し、めっき皮膜中に存在するMg2Si相やMgZn2相などの金属間化合物の大きさを10μm以下とすることで、平板及び端面の耐食性の改善を図った溶融Al-Zn-Si-Mg系めっき鋼板が開示されている。
例えば特許文献4には、めっき皮膜中に0.01~10%のSrを含有させることで、しわ状の凹凸欠陥を抑制した溶融Al-Zn-Si-Mg系めっき鋼板が開示されている。
さらに、特許文献5にも、めっき皮膜中に500~3000ppmのSrを含有させることで、まだら欠陥を抑制した溶融Al-Zn-Si-Mg系めっき鋼板が開示されている。
また、特許文献6には、めっき皮膜中に0.001~1.0%のSrを含有させることで、表面外観性と耐食性を両立させた溶融Al-Zn-Si-Mg系めっき鋼板が開示されている。
さらに、特許文献7にも、めっき皮膜中に0.001~1.0%のSrを含有させることで、表面外観性と平板部と加工部の耐食性を両立させた溶融Al-Zn-Si-Mg系めっき鋼板が開示されている。
さらにまた、特許文献8にも、めっき皮膜中に0.01~0.2%のSrを含有させることで、表面外観性と耐食性を両立させた溶融Al-Zn-Si-Mg系めっき鋼板が開示されている。
また、特許文献9には、めっき皮膜中のSiとMg濃度を特定の比率で制御することで、耐食性を向上させた溶融Al-Zn-Si-Mg系めっき鋼板が開示されている。
例えば特許文献10には、加工部の耐白錆性を改善させることを目的として、Si-Mg相中のMgの、めっき層中のMg全量に対する質量比率を適正化した溶融Al-Zn-Si-Mg系めっき鋼板が開示されている。
また、特許文献11には、溶融Al-Zn-Si-Mg系めっき鋼板のめっき皮膜上にウレタン樹脂を含有する化成皮膜を形成することで、耐黒変性や耐白錆性の改善を図った技術が開示されている。
しかし、昨今このような塗装鋼板について、環境負荷物質であるクロメートを使用することが問題視されており、クロメートフリーであっても耐食性や表面外観を改善できる塗装鋼板の開発が強く望まれている。
これらの要求に対応した技術として、例えば特許文献12には、鋼材の表面上に、Al、Zn、Si及びMgを含み、且つ、これらの元素の含有量について調整を図ったアルミニウム・亜鉛合金めっき層(α)をめっきし、更にその上層として、チタン化合物およびジルコニウム化合物から選ばれる少なくとも1種の化合物(A)を造膜成分とする皮膜(β)を形成し、アルミニウム・亜鉛合金めっき層(α)中のSi-Mg相の、めっき層中のMg全量に対する質量比率を3%以上に調整した表面処理溶融めっき鋼材が開示されている。
特許文献1~3に開示された溶融Al-Zn-Si-Mg系めっき鋼板では、めっき成分にMgを含有させることのみで耐食性の向上を図っているが、めっき皮膜を構成する金属相・金属間化合物相の特徴については考慮されておらず、耐食性の優劣について一律に語ることができなかった。そのため、同じめっき浴組成を用いて溶融Al-Zn-Si-Mg系めっき鋼板を製造した場合でも、腐食促進試験を実施するとその耐食性にばらつきが存在し、Mgを添加しないAl-Zn系めっき鋼板に対して必ずしも優位にはならない、という問題があった。
同様に、めっき外観性の改善においても、めっき皮膜中にSrを添加したのみでは、必ずしもシワ状の凹凸欠陥を消滅させることができる訳ではなく、特許文献4~8に開示された溶融Al-Zn-Si-Mg系めっき鋼板についても、耐食性と外観を両立できていない場合があった。加えて、Mgが酸化しやすい元素であるため、めっき浴中に含有されるMgが浴面近傍に酸化物(トップドロス)を発生させたり、溶融めっきの場合、時間の経過とともにめっき浴の浴中又は底部に偏在する鉄を含んだFeAl系化合物(ボトムドロス)が発生することがあり、これらのドロスが、めっき皮膜の表面に付着して凸形状の欠陥を引き起こし、めっき皮膜表面の外観を損ねるおそれもあった。
特許文献9に開示された溶融Al-Zn-Si-Mg系めっき鋼板では、SiとMgの濃度を特定の比率で管理し、めっき皮膜中のSi相の析出を無くすことで耐食性の改善を図っているが、必ずしもSi相の抑制ができるとは言えず、めっき皮膜中におけるSi相の形成を抑制できた場合においても優れた耐食性が得られない場合がある等、技術的に不完全なものであった。
塗装鋼板の耐食性は、下地とするめっき鋼板の耐食性に影響されることはいうまでもなく、表面外観についても、しわ状欠陥の凹凸の高低差は数十μmにも及ぶことから、塗膜により表面が平滑化しても凹凸の完全解消には至らず、塗装鋼板としての外観改善は望めないと考えられる。さらに、凸部では塗膜が薄くなるため、局部的に耐食性が低下する懸念もある。そのため、耐食性と表面外観に優れた塗装鋼板を得るには、下地であるめっき鋼板の耐食性と表面外観を改善することが重要である。
また、本発明は、安定的に優れた耐食性及び耐白錆性を有する表面処理鋼板を提供することを目的とする。
さらに、本発明は、安定的に優れた耐食性及び加工部耐食性を有する塗装鋼板を提供することを目的とする。
ただし、これらのMg2Si相及びSi相については、一般的な手法、例えば走査型電子顕微鏡を活用し、めっき皮膜を表面または断面から二次電子像あるいは反射電子像などの観察を実施しても相の違いを判別することは非常に困難であることが知られている。より詳細な解析ができる手法として、透過型電子顕微鏡を用いて観察を行うことでミクロな情報を得ることは可能であるが、耐食性や外観といったマクロな情報を左右するMg2Si相及びSi相の存在比率まで把握することはできなかった。
そのため、本発明者らはさらに鋭意研究を重ねた結果、X線回折法に着目し、Mg2Si相及びSi相について特定の回折ピークの強度比を利用することによって、相の存在比率を定量的に規定できること、さらに、めっき皮膜中にMg2Si相とSi相が特定の存在比率を満足すると安定的に優れた耐食性を実現できることに加え、ドロスの発生を抑えて良好な表面外観性も確保できることを見出した。
さらにまた、本発明者らは、溶融Al-Zn-Si-Mg系めっき鋼板の、Mg2Si相、Si相等の存在比率を制御した上で、浴中のSr濃度を制御することで、シワ状の凹凸欠陥の発生を確実に抑え、表面外観性に優れためっき鋼板が得られることも知見した。
1.めっき皮膜を備える溶融Al-Zn-Si-Mg系めっき鋼板であって、
前記めっき皮膜は、Al:45~65質量%、Si:1.0~4.0質量%及びMg:1.0~10.0質量%を含有し、残部がZn及び不可避的不純物からなる組成を有し、
前記めっき皮膜中のSi 及びMg2SiのX線回折法による回折強度が、以下の関係(1)を満足することを特徴とする、溶融Al-Zn-Si-Mg系めっき鋼板。
Si (111)/Mg2Si (111)≦0.8 ・・・(1)
Si (111):Siの(111)面(面間隔d=0.3135nm)の回折強度、
Mg2Si (111):Mg2Siの(111)面(面間隔d=0.3668nm)の回折強度
Si (111)=0 ・・・(2)
Si (111):Siの(111)面(面間隔d=0.3135nm)の回折強度
前記化成皮膜は、エポキシ樹脂、ウレタン樹脂、アクリル樹脂、アクリルシリコン樹脂、アルキド樹脂、ポリエステル樹脂、ポリアルキレン樹脂、アミノ樹脂及びフッ素樹脂から選択される少なくとも一種の樹脂と、P化合物、Si化合物、Co化合物、Ni化合物、Zn化合物、Al化合物、Mg化合物、V化合物、Mo化合物、Zr化合物、Ti化合物及びCa化合物から選択される少なくとも一種の金属化合物と、を含有することを特徴とする、表面処理鋼板。
前記化成皮膜は、(a):エステル結合を有するアニオン性ポリウレタン樹脂及び(b):ビスフェノール骨格を有するエポキシ樹脂を合計で30~50質量%含有し、該(a)と該(b)の含有比率((a):(b))が、質量比で3:97 ~60:40の範囲である樹脂成分と、2~10質量%のバナジウム化合物、40~60質量%のジルコニウム化合物及び0.5~5量%のフッ素化合物を含む無機化合物と、を含有し、
前記塗膜は、プライマー塗膜を少なくとも有し、該プライマー塗膜が、ウレタン結合を有するポリエステル樹脂と、バナジウム化合物、リン酸化合物及び酸化マグネシウムを含む無機化合物と、を含有することを特徴とする、塗装鋼板。
また、本発明によれば、安定的に優れた耐食性及び耐白錆性を有する表面処理鋼板を提供できる。
さらに、本発明によれば、安定的に優れた耐食性及び加工部耐食性を有する塗装鋼板を提供できる。
本発明の溶融Al-Zn-Si-Mg系めっき鋼板は、鋼板表面にめっき皮膜を備える。そして、該めっき皮膜は、Al:45~65質量%、Si:1.0~4.0質量%及びMg:1.0~10.0質量%を含有し、残部がZn及び不可避的不純物からなる組成を有する。
また、前記めっき皮膜中にMgを含有すると、めっき皮膜中に金属間化合物であるMgZn2相も形成され、より耐食性を向上させる効果が得られる。前記めっき皮膜中のMg含有量が1.0質量%未満の場合、前記金属間化合物(Mg2Si、MgZn2)の生成よりも、主要相であるα-Al相への固溶にMgが使用されるため、十分な耐食性が確保できない。一方、前記めっき皮膜中のMg含有量が多くなると、耐食性の向上効果が飽和することに加え、α-Al相の脆弱化に伴い加工性が低下するため、含有量は10.0%以下とする。さらに、前記めっき皮膜中のMg含有量は、めっき形成時のドロス発生を抑制し、めっき浴管理を容易にする観点から、5.0質量%以下とすることが好ましい。なお、前記Siの含有量との関係で、後述の(1)の関係式を満たしやすい観点からは、前記Mgの含有量を3.0質量%とすることが好ましく、ドロス抑制との両立性を考慮すると、前記Mgの含有量を3.0~5.0質量%とすることがより好ましい。
Si (111)/Mg2Si (111)≦0.8 ・・・(1)
Si (111):Siの(111)面(面間隔d=0.3135nm)の回折強度、Mg2Si (111):Mg2Siの(111)面(面間隔d=0.3668nm)の回折強度
なお、前記めっき皮膜中のMg2SiとSiとの存在比率については、仮にめっき皮膜の組成が本発明の範囲を満たす(Al:45~65質量%、Si:1.0~4.0質量%及びMg:1.0~10.0質量%を含有し、残部がZn及び不可避的不純物からなる)場合であっても、Mg2Si及びSiの存在比率が関係(1)を満たさない場合には、本発明によるめっき皮膜の保護作用向上効果を十分に得ることができない。
前記X線回折によりSi (111)及びMg2Si (111)を測定する方法としては、前記めっき皮膜の一部を機械的に削り出し、粉末にした状態でX線回折を行うこと(粉末X線回折測定法)で算出することができる。回折強度の測定については、面間隔d=0.3135nmに相当するSiの回折ピーク強度、面間隔d=0.3668nmに相当するMg2Siの回折ピーク強度を測定し、これらの比率を算出することでSi (111)/Mg2Si (111)を得ることができる。
なお、粉末X線回折測定を実施する際に必要なめっき皮膜の量(めっき皮膜を削り出す量)は、精度良くSi (111)及びMg2Si (111)を測定する観点から、0.1g以上あればよく、0.3g以上あることが好ましい。また、前記めっき皮膜を削り出す際に、めっき皮膜以外の鋼板成分が粉末に含まれる場合もあるが、これらの金属間化合物相はめっき皮膜のみに含まれるものであり、また前述したピーク強度に影響することはない。さらに、前記めっき皮膜を粉末にしてX線回折を行うのは、めっき鋼板に形成されためっき皮膜に対してX線回折を行うと、めっき皮膜凝固組織の面方位の影響を受け正しい相比率の計算を行うことが困難なためである。
Si (111)=0 ・・・(2)
Si (111):Siの(111)面(面間隔d=0.3135nm)の回折強度
一般的に、Al合金の水溶液中への溶解反応においては、Si相がカソードサイトとして存在することで周辺のα-Al相の溶解を促進することが知られていることから、Si相を少なくすることはα-Al相の溶解を抑制する観点でも有効であり、その中でも関係(2)のようにSi相が存在しない皮膜とすること(前記Si(111)の回折ピーク強度をゼロとすること)が耐食性の安定化のために最も優れている。
なお、X線回折によりSiの(111)面の回折ピーク強度の測定方法は、上述した通りである。
また、前記めっき皮膜中のSiの含有量、Mgの含有量及びAlの含有量のバランスを調整する他にも、めっき皮膜形成時の条件(例えば、めっき後の冷却条件)を調整することによって、関係(1)や関係(2)を満たすように、Mg2Si (111)及びSi (111)の回折強度を制御できる。
このうち、前記不可避的不純物はFeを含有する。このFeは、鋼板や浴中機器がめっき浴中に溶出することで不可避的に含まれるものと界面合金層の形成時に下地鋼板からの拡散によって供給される結果、前記めっき皮膜中に不可避的に含まれることとなる。前記めっき皮膜中のFe含有量は、通常0.3~2.0質量%程度である。その他の不可避的不純物としては、Cr、Ni、Cu等が挙げられる。前記不可避的不純物の総含有量については、特に限定はされないが、過剰に含有した場合、めっき鋼板の各種特性に影響を及ぼす可能性があるため、合計で5.0質量%以下であることが好ましい。
なお、前記シワ状欠陥とは、前記めっき皮膜の表面に形成されたシワ状の凹凸になった欠陥であり、前記めっき皮膜表面において白っぽい筋として観察される。このようなシワ状欠陥は、前記めっき皮膜中にMgを多く添加した場合に、発生しやすくなる。そのため、前記溶融めっき鋼板では、前記めっき皮膜中にSrを含有させることによって、前記めっき皮膜表層においてSrをMgよりも優先的に酸化させ、Mgの酸化反応を抑制することで、前記シワ状欠陥の発生を抑えることが可能となる。
前記浴温の下限を、融点+20℃としたのは、溶融めっき処理を行うためには、前記浴温を凝固点以上にすることが必要であり、融点+20℃とすることで、前記めっき浴の局所的な浴温低下による凝固を防止するためである。一方、前記浴温の上限を650℃としたのは、650℃を超えると、前記めっき皮膜の急速冷却が難しくなり,めっき皮膜と鋼板との間に形成する界面合金層が厚くなるおそれがあるためである。
本発明の表面処理鋼板は、鋼板表面にめっき皮膜と、該めっき皮膜上に形成された化成皮膜と、を備える。
このうち、前記めっき皮膜の構成は、上述した本発明の溶融Al-Zn-Si-Mg系めっき鋼板のめっき皮膜と同様である。
なお、前記化成皮膜は、表面処理鋼板の少なくとも片面に形成されればよく、用途や要求される性能に応じて、表面処理鋼板の両面に形成することもできる。
上述した化成皮膜をめっき皮膜上に形成することよって、めっき皮膜との親和性を高め、前記めっき皮膜上に化成皮膜を均一に形成することが可能になることに加え、化成皮膜の防錆効果やバリア効果を高めることができる。その結果、本発明の表面処理鋼板の安定的な耐食性及び耐白錆性の実現が可能となる。
なお、前記P化合物が塩である場合、当該塩は、周期表における第1族~第13族元素の塩であることが好ましく、金属塩であることがより好ましく、アルカリ金属塩及びアルカリ土類金属塩のうちから選択される1つ以上であることが好ましい。
前記化成処理液中のP化合物の濃度は、特に限定はされないが、0.25質量%~5質量%とすることができる。前記P化合物の濃度が0.25質量%未満では、エッチング効果が不足してめっき界面との密着力が低下し、平面部耐食性が低下するだけでなく、欠陥部、切断端面部、加工などで生じるめっきや皮膜の損傷部の耐食性、耐汗性も低下するおそれがある。同様の観点から、P化合物の濃度は、好ましくは0.35質量%以上、より好ましくは0.50質量%以上である。一方、前記P化合物の濃度が5質量%を超えると化成処理液の寿命が短くなるだけでなく、皮膜を形成した際の外観が不均一になりやすく、また、化成皮膜からのPの溶出量が多くなり、耐黒変性が低下するおそれもある。同様の観点から、P化合物の濃度は、好ましくは3.5質量%以下、より好ましくは2.5質量%以下である。前記化成皮膜中のP化合物の含有量については、例えば、P化合物の濃度を0.25質量%~5質量%とした化成処理液を、塗布、乾燥することにより、乾燥後の化成皮膜におけるPの付着量を5~100mg/m2とすることができる。
また、前記Ni化合物を含む化成処理液を用いることにより、Niを、前記化成皮膜中に含有させ、前記濃化層中に取り込ませることができる。前記Ni化合物としては、ニッケル塩を用いることが好ましい。前記ニッケル塩としては、硫酸ニッケル、炭酸ニッケル及び塩化ニッケルのうちから選択される1又は2以上を用いることがより好ましい。
なお、前記Al化合物、前記Zn化合物及び前記Mg化合物は、それぞれ、Al、Zn及びMgを含有する化合物のことであれば、特に限定されないが、無機化合物であることが好ましく、塩、塩化物、酸化物又は水酸化物であることが好ましい。
前記Zn化合物としては、例えば、硫酸亜鉛、炭酸亜鉛、塩化亜鉛、酸化亜鉛及び水酸化亜鉛のうちから選択される1つ以上が挙げられる。
前記Mg化合物としては、例えば、硫酸マグネシウム、炭酸マグネシウム、塩化マグネシウム、酸化マグネシウム及び水酸化マグネシウムのうちから選択される1つ以上が挙げられる。
なお、前記モリブデン酸塩としては、例えば、モリブテン酸ナトリウム、モリブテン酸カリウム、モリブテン酸マグネシウム及びモリブテン酸亜鉛のうちから選択される1つ以上が挙げられる。
前記化成皮膜付着量は、皮膜を蛍光X 線分析して予め皮膜中の含有量が分かっている元素の存在量を測定する方法のような、既存の手法から適切に選択した方法で求めればよい。
本発明の塗装鋼板は、めっき皮膜上に、直接又は化成皮膜を介して、塗膜が形成された塗装鋼板である。
このうち、前記めっき皮膜の構成は、上述した本発明の溶融Al-Zn-Si-Mg系めっき鋼板のめっき皮膜と同様である。
なお、前記化成皮膜は、塗装鋼板の少なくとも片面に形成されればよく、用途や要求される性能に応じて、塗装鋼板の両面に形成することもできる。
上述した化成皮膜をめっき皮膜上に形成することよって、化成皮膜の強度及び密着性を高めつつ、耐食性も向上させることができる。
前記ポリイソシアネートとしては、芳香族ポリイソシアネート、脂肪族ポリイソシアネート、脂環式ポリイソシアネート等が挙げられる。前記芳香族ポリイソシアネートとしては、例えば、2,4-トリレンジイソシアネート、2,6-トリレンジイソシアネート、m-キシレンジイソシアネート、ジフェニルメタンジイソシアネート、2,4-ジフェニルメタンジイソシアネート、2,2-ジフェニルメタンジイソシアネート、トリフェニルメタントリイソシアネート、ポリメチレンポリフェニルポリイソシアネート、ナフタレンジイソシアネート、およびこれらの誘導体(例えばポリオール類との反応により得られたプレポリマー類、ジフェニルメタンジイソシアネートのカルボジイミド化合物等の変性ポリイソシアネート類等)等が挙げられる。
前記樹脂成分は、前記化成皮膜中に合計で30~50質量%含まれる。前記樹脂成分の含有量が30質量%未満では化成皮膜のバインダー効果が低下し、50質量%を超えると、下記に示す無機成分による機能、例えばインヒビター作用が低下する。同様の観点から、前記化成皮膜における前記樹脂成分の含有量は、35~45質量%であることが好ましい。
前記樹脂成分がその他の樹脂を含む場合、前記(a)エステル結合を有するアニオン性ポリウレタン樹脂及び前記(b)ビスフェノール骨格を有するエポキシ樹脂の合計含有量が、50質量%以上であることが好ましく、75質量%以上であることがより好ましい。成処理皮膜としての可撓性の低下や密着性をより確実に得るためである。
これらの化合物を含むことによって、化成皮膜の耐食性を高めることができる。
前記バナジウム化合物については、例えば、五酸化バナジウム、メタバナジン酸、メタバナジン酸アンモニウム、オキシ三塩化バナジウム、三酸化バナジウム、二酸化バナジウム、バナジン酸マグネシウム、バナジルアセチルアセトネート、バナジウムアセチルアセトネート等が挙げられる。特に、これらの中でも、4価のバナジウム化合物又は還元若しくは酸化することによって得られる4価のバナジウム化合物を用いることが望ましい。
前記ジルコニウム化合物としては、硫酸ジルコニウム、炭酸ジルコニウム、硝酸ジルコニウム、乳酸ジルコニウム、酢酸ジルコニウム、塩化ジルコニウムなどの中和塩等が挙げられる。
前記フッ素化合物としては、例えば、アンモニウム塩、ナトリウム塩、カリウム塩などのフッ化物塩、又は、フッ化第一鉄、フッ化第二鉄等のフッ素化合物を用いることができる。これらの中でも、フッ化アンモニウムや、フッ化ナトリウム及びフッ化カリウム等のフッ化物塩を用いることが好ましい。
前記化成皮膜付着量は、皮膜を蛍光X 線分析して予め皮膜中の含有量が分かっている元素の存在量を測定する方法のような、既存の手法から適切に選択した方法で求めればよい。
前記プライマー塗膜が、前記ウレタン結合を有するポリエステル樹脂と前記無機化合物を含有することによって、塗膜の密着性を高めつつ、耐食性を向上させることができる。
なお、ここでいう「主成分」とは、プライマー塗膜中の各成分中最も含有量が多い成分であることを意味する。
前記多価アルコールとしては、グリコール及び3価以上の多価アルコールが挙げられる。前記グリコールは、例えば、エチレングリコール、プロピレングリコール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、ジプロピレングリコール、ポリエチレングリコール、ポリプロピレングリコール、ネオペンチルグリコール、ヘキシレングリコール、1,3-ブタンジオール、1,4-ブタンジオール、1,5-ペンタンジオール、1,6-ヘキサンジオール、2-ブチル-2-エチル-1,3-プロパンジオール、メチルプロパンジオール、シクロヘキサンジメタノール、3,3-ジエチル-1,5-ペンタンジオール等が挙げられる。また、前記3価以上の多価アルコールは、例えば、グリセリン、トリメチロールエタン、トリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール等が挙げられる。これらの多価アルコールは、単独で使用することもでき、2種以上組み合わせて使用することもできる。
前記多塩基酸は、通常は多価カルボン酸が使用されるが、必要に応じて1価の脂肪酸などを併用することができる。前記多価カルボン酸として、例えば、フタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、4-メチルヘキサヒドロフタル酸、ビシクロ[2,2,1]ヘプタン-2,3-ジカルボン酸、トリメリット酸、アジピン酸、セバシン酸、コハク酸、アゼライン酸、フマル酸、マレイン酸、イタコン酸、ピロメリット酸、ダイマー酸など、及びこれらの酸無水物、並びに1,4-シクロヘキサンジカルボン酸、イソフタル酸、テトラヒドロイソフタル酸、ヘキサヒドロイソフタル酸、ヘキサヒドロテレフタル酸等が挙げられる。これらの多塩基酸は、単独で使用することもでき、2種以上組み合わせて使用することもできる。
さらに、前記ウレタン結合を有するポリエステル樹脂の数平均分子量は、耐溶剤性、加工性などの点から、好ましくは500~15,000であり、より好ましくは、700~12,000であり、さらに好ましくは800~10,000である。
前記プライマー塗膜中に添加するバナジウム化合物は、前記化成処理皮膜に添加するバナジウム化合物と同種であっても異種であってもよい。バナジン酸化合物は、外部から侵入してくる水分に徐々に溶出するバナジン酸イオンと亜鉛系めっき鋼板表面のイオンが反応し、密着性の良い不働態皮膜を形成し、金属露出部を保護し防錆作用が現れると考えられている。
例えば、プライマー塗膜を形成する際に用いられる架橋剤が挙げられる。前記架橋剤は、前記ウレタン結合を有するポリエステル樹脂と反応して架橋塗膜を形成するものであり、例えば、オキサゾリン化合物、エポキシ化合物、メラミン化合物、イソシアネート系化合物、カルボジイミド系化合物、シランカップリング化合物等が挙げられ、2種類以上の架橋剤を併用することも可能である。なかでも得られる塗装鋼板の加工部耐食性の観点から、好ましくはブロック化ポリイソシアネート化合物等を用いることができる。該ブロック化ポリイソシアネートとしては、例えば、ポリイソシアネート化合物のイソシアネート基を、例えば、ブタノールなどのアルコール類、メチルエチルケトオキシムなどのオキシム類、ε-カプロラクタム類などのラクタム類、アセト酢酸ジエステルなどのジケトン類、イミダゾール、2-エチルイミダゾールなどのイミダゾール類、又は、m-クレゾールなどのフェノール類などによりブロックしたものが挙げられる。
前記上塗塗膜は、塗装鋼板に色彩や光沢、表面状態等の美観を付与することができることに加え、加工性、耐候性、耐薬品性、耐汚染性、耐水性、耐食性等の各種性能を高めることができる。
例えば、前記上塗塗膜を、ポリエステル樹脂系塗料、シリコンポリエステル樹脂系塗料、ポリウレタン樹脂系塗料、アクリル樹脂系塗料、フッ素樹脂系塗料等を用いて形成することができる。
さらに、前記上塗塗膜は、酸化チタン、弁柄、マイカ、カーボンブラック又はその他の各種着色顔料;アルミニウム粉やマイカなどのメタリック顔料;炭酸塩や硫酸塩等からなる体質顔料;シリカ微粒子、ナイロン樹脂ビーズ、アクリル樹脂ビーズ等の各種微粒子;p-トルエンスルホン酸、ジブチル錫ジラウレート等の硬化触媒;ワックス;その他の添加剤を適量含有することができる。
常法で製造した板厚0.8mmの冷延鋼板を下地鋼板として用い、(株)レスカ製の溶融めっきシミュレーターで、焼鈍処理、めっき処理を行うことで、表1に示す条件の溶融めっき鋼板のサンプル1~44を作製した。
なお、溶融めっき鋼板製造に用いためっき浴の組成については、表1に示す各サンプルのめっき皮膜の組成となるように、めっき浴の組成をAl:30~75質量%、Si:0.5~4.5質量%、Mg:0~10質量%、Sr:0.00~0.15質量%の範囲で種々変化させた。また、めっき浴の浴温は、Al:30~60質量%の場合は590℃、Al:60質量%超の場合は630℃とし、下地鋼板のめっき浸入板温がめっき浴温と同温度となるように制御した。さらに、板温が520~500℃の温度域に3秒で冷却する条件でめっき処理を実施した。
また、めっき皮膜の付着量は、サンプル1~41では、片面あたり85±5g/m2、サンプル42~44では、片面あたり51~125g/m2となるように制御した。
上記のように得られた溶融めっき鋼板の各サンプルについて、以下の評価を行った。評価結果を表1に示す。
めっき後の各サンプルについて、100mmφを打ち抜き、非測定面をテープでシーリングした後、JIS H 0401:2013に示される塩酸とヘキサメチレンテトラミンの混合液でめっきを溶解剥離し、剥離前後のサンプルの質量差から、めっき皮膜の付着量を算出した。算出の結果、得られためっき皮膜の付着量を表1に示す。
その後、剥離液をろ過し、ろ液と固形分をそれぞれ分析した。具体的に、ろ液をICP発光分光分析することで、不溶Si以外の成分を定量化した。
また、固形分は650℃の加熱炉内で乾燥・灰化した後、炭酸ナトリウムと四ホウ酸ナトリウムを添加することで融解させた。さらに、塩酸で融解物を溶解し、溶解液をICP発光分光分析することで、不溶Siを定量化した。めっき皮膜中のSi濃度は、ろ液分析によって得た可溶Si濃度に、固形分分析によって得た不溶Si濃度を加算したものである。算出の結果、得られためっき皮膜の組成を表1に示す。
さらに、各サンプルについて、100mm×100mmのサイズに剪断後、評価対称面のめっき皮膜を下地鋼板が現れるまで機械的に削り出し、得られた粉末をよく混ぜ合わせた後、0.3gを取出し、X線回折線装置(株式会社リガク製「SmartLab」)を用いて、使用X線:Cu-Kα(波長=1.54178Å)、Kβ線の除去:Niフィルター、管電圧:40kV、管電流:30mA、スキャニング・スピード:4°/min、サンプリング・インターバル:0.020°、発散スリット:2/3°、ソーラースリット:5°、検出器:高速一次元検出器(D/teX Ultra)の条件で、上記粉末の定性分析を行った。各ピーク強度からベース強度を差し引いた強度を各回折強度(cps)とし、Mg2Siの(111)面(面間隔d=0.3668nm)の回折強度、及び、Siの(111)面(面間隔d=0.3135nm)の回折強度を測定した。測定結果を、表1に示す。
得られた溶融めっき鋼板の各サンプルについて、120mm×120mmのサイズに剪断後、評価対象面の各エッジから10mmの範囲、及び、サンプルの端面と評価非対象面をテープでシーリングし、評価対象面を100mm×100mmのサイズで露出させた状態のものを、評価用サンプルとして用いた。なお、該評価用サンプルは同じものを3つ作製した。
上記のように作製した3つの評価用サンプルに対して、いずれも図1に示すサイクルで腐食促進試験を実施した。腐食促進試験を湿潤からスタートし、300サイクル後まで行った後、各サンプルの腐食減量をJIS Z 2383及びISO8407に記載の方法で測定し、下記の基準で評価した。評価結果を表1に示す。
◎:サンプル3個の腐食減量が全て45g/m2以下
○:サンプル3個の腐食減量が全て70g/m2以下
×:サンプル1個以上の腐食減量が70g/m2越え
(3)表面外観性
得られた溶融めっき鋼板の各サンプルについて、目視によって、めっき皮膜の表面を観察した。
そして、観察結果を、以下の基準に従って評価した。評価結果を表1に示す。
◎:シワ状欠陥が全く観察されなかった
○:エッジから50mmの範囲のみにシワ状欠陥が観察された
×:エッジから50mmの範囲以外でシワ状欠陥が観察された
得られた溶融めっき鋼板の各サンプルについて、70mm×150mmのサイズに剪断後、同板厚の板を内側に8枚挟んで180°曲げの加工(8T曲げ)を施した。折り曲げ後の曲げ部外面にセロテープ(登録商標)を強く貼りつけた後、引き剥がした。曲げ部外面のめっき皮膜の表面状態、及び、使用したテープの表面におけるめっき皮膜の付着(剥離)の有無を目視で観察し、下記の基準で加工性を評価した。評価結果を表1に示す。
〇:めっき皮膜にクラックと剥離が共に認められない
△:めっき皮膜にクラックがあるが、剥離が認められない
×:めっき皮膜にクラックと剥離が共に認められる
溶融めっき鋼板の各サンプルの製造時、めっき浴の浴面の状態を目視で確認し、溶融Al-Zn系めっき鋼板を製造する際に用いるめっき浴の浴面(Mg含有酸化物のない浴面)と比較した。評価は、以下の基準で行い、評価結果を表1に示す。
〇:溶融Al-Zn系めっき浴(55質量%Al-残部Zn-1.6質量%浴)と同程度
△:溶融Al-Zn系めっき浴(55質量%Al-残部Zn-1.6質量%浴)に比べて白色酸化物が多い
×:めっき浴中に黒色酸化物の形成が認められる
(1)常法で製造した板厚0.8mmの冷延鋼板を下地鋼板として用い、(株)レスカ製の溶融めっきシミュレーターで、焼鈍処理、めっき処理を行うことで、表3及び4に示すめっき皮膜条件の溶融めっき鋼板のサンプルを作製した。
なお、溶融めっき鋼板製造に用いためっき浴の組成については、表2に示す各サンプルのめっき皮膜の組成となるように、めっき浴の組成をAl:30~75質量%、Si:0.5~4.5質量%、Mg:0~10質量%、Sr:0.00~0.15質量%の範囲で種々変化させた。また、めっき浴の浴温は、Al:30~60質量%の場合は590℃、Al:60質量%超の場合は630℃とし、下地鋼板のめっき浸入板温がめっき浴温と同温度となるように制御した。さらに、板温が520~500℃の温度域に3秒で冷却する条件でめっき処理を実施した。
また、めっき皮膜の付着量は、サンプル1~82、95~112では、片面あたり85±5g/m2、サンプル83~94では、片面あたり51~125g/m2となるように制御した。
(2)その後、作製した溶融めっき鋼板の各サンプルのめっき皮膜上に、バーコーターで化成処理液を塗布し、熱風炉で乾燥(昇温速度:60℃/s、PMT:120℃)させることで化成皮膜を形成し、表3及び4に示す表面処理鋼板の各サンプルを作製した。
なお、化成処理液は、各成分を溶媒としての水に溶解させた表面処理液A~Fを調製した。表面処理液に含有する各成分(樹脂、金属化合物)の種類については、以下のとおりである。
(樹脂)
ウレタン樹脂:スーパーフレックス130、スーパーフレックス126(第一工業製薬株式会社)
アクリル樹脂:ボンコートEC-740EF(DIC株式会社)
(金属化合物)
P化合物:トリポリリン酸二水素アルミニウム
Si化合物:シリカ
V化合物:メタバナジン酸ナトリウム
Mo化合物:モリブデン酸
Zr化合物:炭酸ジルコニルカリウム
調製した化成処理液A~Fの組成及び形成された化成皮膜の付着量を表2に示す。なお、本明細書の表2における各成分の濃度は、固形分の濃度(質量%)である。
上記のように得られた溶融めっき鋼板及び表面処理鋼板の各サンプルについて、以下の評価を行った。評価結果を表3及び4に示す。
溶融めっき鋼板の各サンプルについて、100mmφを打ち抜き、非測定面をテープでシーリングした後、JIS H 0401:2013に示される塩酸とヘキサメチレンテトラミンの混合液でめっきを溶解剥離し、剥離前後のサンプルの質量差から、めっき皮膜の付着量を算出した。算出の結果、得られためっき皮膜の付着量を表3及び4に示す。
その後、剥離液をろ過し、ろ液と固形分をそれぞれ分析した。具体的に、ろ液をICP発光分光分析することで、不溶Si以外の成分を定量化した。
また、固形分は650℃の加熱炉内で乾燥・灰化した後、炭酸ナトリウムと四ホウ酸ナトリウムを添加することで融解させた。さらに、塩酸で融解物を溶解し、溶解液をICP発光分光分析することで、不溶Siを定量化した。めっき皮膜中のSi濃度は、ろ液分析によって得た可溶Si濃度に、固形分分析によって得た不溶Si濃度を加算したものである。算出の結果、得られためっき皮膜の組成を表3及び4に示す。
さらに、各サンプルについて、100mm×100mmのサイズに剪断後、評価対称面のめっき皮膜を下地鋼板が現れるまで機械的に削り出し、得られた粉末をよく混ぜ合わせた後、0.3gを取出し、X線回折線装置(株式会社リガク製「SmartLab」)を用いて、使用X線:Cu-Kα(波長=1.54178Å)、Kβ線の除去:Niフィルター、管電圧:40kV、管電流:30mA、スキャニング・スピード:4°/min、サンプリング・インターバル:0.020°、発散スリット:2/3°、ソーラースリット:5°、検出器:高速一次元検出器(D/teX Ultra)の条件で、上記粉末の定性分析を行った。各ピーク強度からベース強度を差し引いた強度を各回折強度(cps)とし、Mg2Siの(111)面(面間隔d=0.3668nm)の回折強度、及び、Siの(111)面(面間隔d=0.3135nm)の回折強度を測定した。測定結果を、表3及び4に示す。
溶融めっき鋼板及び表面処理鋼板の各サンプルについて、120mm×120mmのサイズに剪断後、評価対象面の各エッジから10mmの範囲、及び、サンプルの端面と評価非対象面をテープでシーリングし、評価対象面を100mm×100mmのサイズで露出させた状態のものを、評価用サンプルとして用いた。なお、該評価用サンプルは同じものを3つ作製した。
上記のように作製した3つの評価用サンプルに対して、いずれも図1に示すサイクルで腐食促進試験を実施した。腐食促進試験を湿潤からスタートし、300サイクル後まで行った後、各サンプルの腐食減量をJIS Z 2383及びISO8407に記載の方法で測定し、下記の基準で評価した。評価結果を表3及び4に示す。
◎:サンプル3個の腐食減量が全て30g/m2以下
○:サンプル3個の腐食減量が全て50g/m2以下
×:サンプル1個以上の腐食減量が50g/m2越え
溶融めっき鋼板及び表面処理鋼板の各サンプルについて、120mm×120mmのサイズに剪断後、評価対象面の各エッジから10mmの範囲、及び、サンプルの端面と評価非対象面をテープでシーリングし、評価対象面を100mm×100mmのサイズで露出させた状態のものを、評価用サンプルとして用いた。
上記評価用サンプルを用いて、JIS Z 2371に記載の塩水噴霧試験を90時間実施し、下記の基準で評価した。評価結果を表3及び4に示す。
◎:平板部に白錆なし
○:平板部の白錆発生面積10%未満
×:平板部の白錆発生面積10%以上
溶融めっき鋼板の各サンプルについて、目視によって、めっき皮膜の表面を観察した。
そして、観察結果を、以下の基準に従って評価した。評価結果を表3及び4に示す。
◎:シワ状欠陥が全く観察されなかった
○:エッジから50mmの範囲のみにシワ状欠陥が観察された
×:エッジから50mmの範囲以外でシワ状欠陥が観察された
溶融めっき鋼板の各サンプルについて、70mm×150mmのサイズに剪断後、同板厚の板を内側に8枚挟んで180°曲げの加工(8T曲げ)を施した。折り曲げ後の曲げ部外面にセロテープ(登録商標)を強く貼りつけた後、引き剥がした。曲げ部外面のめっき皮膜の表面状態、及び、使用したテープの表面におけるめっき皮膜の付着(剥離)の有無を目視で観察し、下記の基準で加工性を評価した。評価結果を表3及び4に示す。
〇:めっき皮膜にクラックと剥離が共に認められない
△:めっき皮膜にクラックがあるが、剥離が認められない
×:めっき皮膜にクラックと剥離が共に認められる
溶融めっき時、めっき浴の浴面の状態を目視で確認し、溶融Al-Zn系めっき鋼板を製造する際に用いるめっき浴の浴面(Mg含有酸化物のない浴面)と比較した。評価は、以下の基準で行い、評価結果を表3及び4に示す。
〇:溶融Al-Zn系めっき浴(55質量%Al-残部Zn-1.6質量%浴)と同程度
△:溶融Al-Zn系めっき浴(55質量%Al-残部Zn-1.6質量%浴)に比べて白色酸化物が多い
×:めっき浴中に黒色酸化物の形成が認められる
また、表4の結果から、化成処理A~Dを実施した各サンプルの耐白錆性が優れた結果を示すことがわかる。
(1)常法で製造した板厚0.8mmの冷延鋼板を下地鋼板として用い、(株)レスカ製の溶融めっきシミュレーターで、焼鈍処理、めっき処理を行うことで、表6に示すめっき皮膜条件の溶融めっき鋼板のサンプルを作製した。
なお、溶融めっき鋼板製造に用いためっき浴の組成については、表6に示す各サンプルのめっき皮膜の組成となるように、めっき浴の組成をAl:30~75質量%、Si:0.5~4.5質量%、Mg:0~10質量%、Sr:0.00~0.15質量%の範囲で種々変化させた。また、めっき浴の浴温は、Al:30~60質量%の場合は590℃、Al:60質量%超の場合は630℃とし、下地鋼板のめっき浸入板温がめっき浴温と同温度となるように制御した。さらに、板温が520~500℃の温度域に3秒で冷却する条件でめっき処理を実施した。
また、めっき皮膜の付着量は、サンプル1~41では、片面あたり85±5g/m2、サンプル42~44では、片面あたり42~125g/m2となるように制御した。
なお、用いた化成処理液は、各成分を溶媒としての水に溶解させて調製したpHが8~10の化成処理液を用いた。化成処理液に含有する各成分(樹脂成分、無機化合物)の種類については、以下のとおりである。
(樹脂成分)
樹脂A:(a)エステル結合を有するアニオン性ポリウレタン樹脂(第一工業製薬(株)製「スーパーフレックス210」と、(b)ビスフェノール骨格を有するエポキシ樹脂(吉村油化学(株)製「ユカレジンRE-1050」)とを、含有質量比(a):(b)=50:50で混合したもの
樹脂B:アクリル樹脂(DIC(株)製「ボンコートEC-740EF」)
(無機化合物)
バナジウム化合物:アセチルアセトンでキレート化した有機バナジウム化合物
ジルコニウム化合物:炭酸ジルコニウムアンモニウム
フッ素化合物:フッ化アンモニウム
なお、プライマー塗料については、各成分を混合した後、ボールミルで約1時間攪拌することにより得た。プライマー塗膜を構成する樹脂成分及び無機化合物は、以下のものを用いた。
(樹脂成分)
樹脂α:ウレタン変性ポリエステル樹脂(ポリエステル樹脂455質量部、イソホロンジイソシアネート45質量部を反応させて得たものであり、樹脂酸価は3、数平均分子量は5,600、水酸基価は36である。)を、ブロック化イソシアネートで硬化させたものを用いた。
なお、ウレタン変性させるポリエステル樹脂については、次の条件で作製した。攪拌機、精留塔、水分離器、冷却管及び温度計を備えたフラスコに、イソフタル酸320質量部、アジピン酸200量部、トリメチロールプロパン60質量部、シクロヘキサンジメタンノール420質量部を仕込み、加熱、攪拌し、生成する縮合水を系外へ留去させながら、160℃ から230℃ まで一定速度で4時間かけて昇温させ、温度230℃ に到達した後、キシレン20質量部を徐々に添加し、温度を230℃ に維持した状態で縮合反応を続け、酸価が5以下になった時に反応を終了させ、100℃まで冷却した後、ソルベッソ100(エクソンモービル社製、商品名、高沸点芳香族炭化水素系溶剤) 120質量部、ブチルセロソルブ100質量部を加えることで、ポリエステル樹脂溶液を得た。
樹脂β:ウレタン硬化ポリエステル樹脂(関西ペイント(株)製「エバクラッド4900」)
(無機化合物)
バナジウム化合物:バナジン酸マグネシウム
リン酸化合物:リン酸カルシウム
酸化マグネシウム化合物:酸化マグネシウム
また、上塗塗膜に用いた樹脂については、以下の塗料を用いた。
樹脂I: メラミン硬化ポリエステル塗料(BASFジャパン(株)製「プレカラーHD0030HR」)
樹脂II: ポリフッ化ビニリデンとアクリル樹脂が質量比で80:20であるオルガノゾル系焼付型フッ素樹脂系塗料(BASFジャパン(株)製「プレカラーNo.8800HR」)
上記のように得られた塗装鋼板の各サンプルについて、以下の評価を行った。評価結果を表6に示す。
溶融めっき鋼板の各サンプルについて、100mmφを打ち抜き、非測定面をテープでシーリングした後、JIS H 0401:2013に示される塩酸とヘキサメチレンテトラミンの混合液でめっきを溶解剥離し、剥離前後のサンプルの質量差から、めっき皮膜の付着量を算出した。算出の結果、得られためっき皮膜の付着量を表6に示す。
その後、剥離液をろ過し、ろ液と固形分をそれぞれ分析した。具体的に、ろ液をICP発光分光分析することで、不溶Si以外の成分を定量化した。
また、固形分は650℃の加熱炉内で乾燥・灰化した後、炭酸ナトリウムと四ホウ酸ナトリウムを添加することで融解させた。さらに、塩酸で融解物を溶解し、溶解液をICP発光分光分析することで、不溶Siを定量化した。めっき皮膜中のSi濃度は、ろ液分析によって得た可溶Si濃度に、固形分分析によって得た不溶Si濃度を加算したものである。算出の結果、得られためっき皮膜の組成を表6に示す。
さらに、各サンプルについて、100mm×100mmのサイズに剪断後、評価対称面のめっき皮膜を下地鋼板が現れるまで機械的に削り出し、得られた粉末をよく混ぜ合わせた後、0.3gを取出し、X線回折線装置(株式会社リガク製「SmartLab」)を用いて、使用X線:Cu-Kα(波長=1.54178Å)、Kβ線の除去:Niフィルター、管電圧:40kV、管電流:30mA、スキャニング・スピード:4°/min、サンプリング・インターバル:0.020°、発散スリット:2/3°、ソーラースリット:5°、検出器:高速一次元検出器(D/teX Ultra)の条件で、上記粉末の定性分析を行った。各ピーク強度からベース強度を差し引いた強度を各回折強度(cps)とし、Mg2Siの(111)面(面間隔d=0.3668nm)の回折強度、及び、Siの(111)面(面間隔d=0.3135nm)の回折強度を測定した。測定結果を、表6に示す。
塗装鋼板の各サンプルについて、120mm×120mmのサイズに剪断後、評価対象面の任意に選んだ3辺のエッジから10mmの範囲、及び、サンプルの同3辺の端面と評価非対象面をテープでシーリングし、評価対象面を100mm×100mmのサイズで露出させた状態のものを、評価用サンプルとして用いた。なお、該評価用サンプルは同じものを3つ作製した。
上記のように作製した3つの評価用サンプルに対して、いずれも図1に示すサイクルで腐食促進試験を実施した。腐食促進試験を湿潤からスタートし、20サイクル毎にサンプルを取出し、水洗及び乾燥させた後に目視により観察し、テープシールしていない1辺の剪断端面に赤錆の発生について確認を行った。
そして、赤錆が確認されたときのサイクル数を、下記の基準に従って評価した。評価結果を表6に示す。
◎:サンプル3個の赤錆発生サイクル数≧600サイクル
○:600サイクル>サンプル3個の赤錆発生サイクル数≧500サイクル
×:少なくとも1個のサンプルの赤錆発生サイクル数<500サイクル
塗装鋼板の各サンプルについて、目視によって表面を観察した。
そして、観察結果を、以下の基準に従って評価した。評価結果を表6に示す。
◎:シワ状欠陥が全く観察されなかった
○:エッジから50mmの範囲のみにシワ状欠陥が観察された
×:エッジから50mmの範囲以外でシワ状欠陥が観察された
塗装鋼板の各サンプルについて、70mm×150mmのサイズに剪断後、同板厚の板を内側に8枚挟んで180°曲げの加工(8T曲げ)を施した。折り曲げ後の曲げ部外面にセロテープ(登録商標)を強く貼りつけた後、引き剥がした。曲げ部外面の塗膜の表面状態、及び、使用したテープの表面における塗膜の付着(剥離)の有無を目視で観察し、下記の基準で加工性を評価した。評価結果を表6に示す。
〇:めっき皮膜にクラックと剥離が共に認められない
△:めっき皮膜にクラックがあるが、剥離が認められない
×:めっき皮膜にクラックと剥離が共に認められる
溶融めっき時、めっき浴の浴面の状態を目視で確認し、溶融Al-Zn系めっき鋼板を製造する際に用いるめっき浴の浴面(Mg含有酸化物のない浴面)と比較した。評価は、以下の基準で行い、評価結果を表6に示す。
〇:溶融Al-Zn系めっき浴(55質量%Al-残部Zn-1.6質量%浴)と同程度
△:溶融Al-Zn系めっき浴(55質量%Al-残部Zn-1.6質量%浴)に比べて白色酸化物が多い
×:めっき浴中に黒色酸化物の形成が認められる
また、本発明によれば、安定的に優れた耐食性及び耐白錆性を有する表面処理鋼板を提供できる。
さらに、本発明によれば、安定的に優れた耐食性及び加工部耐食性を有する塗装鋼板を提供できる。
Claims (8)
- めっき皮膜を備える溶融Al-Zn-Si-Mg系めっき鋼板であって、
前記めっき皮膜は、Al:45~65質量%、Si:1.0~4.0質量%及びMg:1.0~10.0質量%を含有し、残部がZn及び不可避的不純物からなる組成を有し、
前記めっき皮膜中のSi 及びMg2SiのX線回折法による回折強度が、以下の関係(1)を満足することを特徴とする、溶融Al-Zn-Si-Mg系めっき鋼板。
Si (111)/Mg2Si (111)≦0.8 ・・・(1)
Si (111):Siの(111)面(面間隔d=0.3135nm)の回折強度、
Mg2Si (111):Mg2Siの(111)面(面間隔d=0.3668nm)の回折強度 - 前記めっき皮膜中の前記SiのX線回折法による回折強度が、以下の関係(2)を満足することを特徴とする、請求項1に記載の溶融Al-Zn-Si-Mg系めっき鋼板。
Si (111)=0 ・・・(2) - 前記めっき皮膜が、さらにSr:0.01~1.0質量%を含有することを特徴とする、請求項1又は2に記載の溶融Al-Zn-Si-Mg系めっき鋼板。
- 前記めっき皮膜中のAlの含有量が、50~60質量%であることを特徴とする、請求項1~3のいずれか1項に記載の溶融Al-Zn-Si-Mg系めっき鋼板。
- 前記めっき皮膜中のSiの含有量が、1.0~3.0質量%であることを特徴とする、請求項1~4のいずれか1項に記載の溶融Al-Zn-Si-Mg系めっき鋼板。
- 前記めっき皮膜中のMgの含有量が、1.0~5.0質量%であることを特徴とする、請求項1~5のいずれか1項に記載の溶融Al-Zn-Si-Mg系めっき鋼板。
- 請求項1~6のいずれか1項に記載のめっき皮膜と、該めっき皮膜上に形成された化成皮膜と、を備える表面処理鋼板であって、
前記化成皮膜は、エポキシ樹脂、ウレタン樹脂、アクリル樹脂、アクリルシリコン樹脂、アルキド樹脂、ポリエステル樹脂、ポリアルキレン樹脂、アミノ樹脂及びフッ素樹脂から選択される少なくとも一種の樹脂と、P化合物、Si化合物、Co化合物、Ni化合物、Zn化合物、Al化合物、Mg化合物、V化合物、Mo化合物、Zr化合物、Ti化合物及びCa化合物から選択される少なくとも一種の金属化合物と、を含有することを特徴とする、表面処理鋼板。 - 請求項1~6のいずれか1項に記載のめっき皮膜上に、直接又は化成皮膜を介して、塗膜が形成された塗装鋼板であって、
前記化成皮膜は、(a):エステル結合を有するアニオン性ポリウレタン樹脂及び(b):ビスフェノール骨格を有するエポキシ樹脂を合計で30~50質量%含有し、該(a)と該(b)の含有比率((a):(b))が、質量比で3:97 ~60:40の範囲である樹脂成分と、2~10質量%のバナジウム化合物、40~60質量%のジルコニウム化合物及び0.5~5量%のフッ素化合物を含む無機化合物と、を含有し、
前記塗膜は、プライマー塗膜を少なくとも有し、該プライマー塗膜が、ウレタン結合を有するポリエステル樹脂と、バナジウム化合物、リン酸化合物及び酸化マグネシウムを含む無機化合物と、を含有することを特徴とする、塗装鋼板。
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WO2023132327A1 (ja) * | 2022-01-06 | 2023-07-13 | Jfeスチール株式会社 | 溶融Al-Zn-Si-Mg系めっき鋼板及びその製造方法、表面処理鋼板及びその製造方法、並びに、塗装鋼板及びその製造方法 |
WO2023166858A1 (ja) * | 2022-03-04 | 2023-09-07 | Jfeスチール株式会社 | 溶融Al-Zn系めっき鋼板、その製造方法、表面処理鋼板及び塗装鋼板 |
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