WO2012133671A1 - 表面処理鋼板及びその製造方法 - Google Patents
表面処理鋼板及びその製造方法 Download PDFInfo
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- WO2012133671A1 WO2012133671A1 PCT/JP2012/058410 JP2012058410W WO2012133671A1 WO 2012133671 A1 WO2012133671 A1 WO 2012133671A1 JP 2012058410 W JP2012058410 W JP 2012058410W WO 2012133671 A1 WO2012133671 A1 WO 2012133671A1
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- steel sheet
- plating
- treated steel
- layer
- film
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
-
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
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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
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2350/00—Pretreatment of the substrate
- B05D2350/60—Adding a layer before coating
- B05D2350/65—Adding a layer before coating metal layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/51—One specific pretreatment, e.g. phosphatation, chromatation, in combination with one specific coating
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12472—Microscopic interfacial wave or roughness
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12785—Group IIB metal-base component
- Y10T428/12792—Zn-base component
- Y10T428/12799—Next to Fe-base component [e.g., galvanized]
Definitions
- the present invention relates to a surface-treated steel sheet excellent in corrosion resistance and paint adhesion and a method for producing the same.
- electrogalvanized steel sheets having an electrogalvanized layer
- electrogalvanized steel sheets have been used in various fields such as home appliances, building materials, and automobiles.
- electrogalvanized steel sheets have been required to further improve corrosion resistance.
- As a method for improving the corrosion resistance of the electrogalvanized steel sheet it is conceivable to increase the plating amount (weight per unit area) of the galvanized layer.
- the basis weight of the galvanized layer is increased, the manufacturing cost increases, or the workability and weldability decrease.
- Patent Document 1 As a method for improving the corrosion resistance and appearance of an electrogalvanized steel sheet, a technique for forming a coating film on the surface has been widely used (for example, Patent Document 1). However, if the adhesion (coating adhesion) between the coating layer of the electrogalvanized steel sheet and the coating film is insufficient, the effect of forming the coating film is sufficiently obtained even if the coating film is formed on the surface. I can't. For this reason, while improving the corrosion resistance of an electrogalvanized steel plate, improving paint adhesion is requested
- the corrosion resistance decreases.
- the roughness of the plating layer largely depends on the roughness of the steel plate before plating. Therefore, in the conventional electrogalvanized steel sheet, if the steel sheet roughness is high, the roughness of the plating layer is inevitably high, and the corrosion resistance is deteriorated. In order to prevent such deterioration of corrosion resistance, it is conceivable to improve the steel sheet roughness by reducing the roughness of the plating layer, but this is not desirable from the viewpoint of manufacturing cost. Therefore, in recent years, it is required to improve the corrosion resistance without depending on the roughness of the steel plate.
- Non-Patent Documents 1 to 4 describe techniques for performing composite electrodeposition of Zn—V oxide on the surface of a copper plate as a cathode.
- a surface-treated steel sheet in which one or more coatings are formed on the surface of a steel sheet (electroplated steel sheet) on which a plating layer containing zinc and vanadium oxide is formed was examined. .
- the present inventors have intensively studied as described below. That is, the present inventors pay attention to the adhesion amount (weight per unit area), vanadium content, and crystal structure in the plating layer containing zinc and vanadium formed on the steel plate surface by the electroplating method, and using various methods. A plating bath was brought into contact with the steel plate surface, and the relationship between the corrosion resistance of the obtained plating layer and the coating adhesion was investigated.
- the trunk of the dendritic columnar crystal is referred to as a primary arm
- the branch is referred to as a secondary arm
- the primary arm and secondary arm are collectively referred to as an arm.
- the obtained plating layer was a high-roughness plating layer whose surface roughness is 1.0 micrometer or more and 4.0 micrometers or less by centerline average roughness Ra.
- the plating layer which has a dendritic columnar crystal was not formed. Therefore, compared with the case where the plating bath is brought into contact with the steel plate in a fluid state, cracks are likely to occur on the surface of the plating layer.
- the plating bath In the flowing state, the plating bath is flowing at a substantially uniform flow rate with respect to the steel plate. Therefore, compared with a stationary state and a stirring state, ion is continuously supplied uniformly from the plating bath to the steel plate surface. As a result, it is estimated that a uniform plating layer was formed on the steel plate surface.
- ions are concentrated and consumed locally in the plating bath near the surface of the steel sheet, which is the cathode, and ions used for deposition of the plating layer near the steel sheet are deficient. Therefore, it is estimated that cracks are likely to occur.
- the present inventors contacted the surface of the steel sheet in a fluidized state with the plating bath and electrodeposited for a period of 1 second to 30 seconds, and the vanadium content and basis weight contained in the plating layer formed, and this plating
- the relationship with the corrosion resistance of the surface-treated steel sheet having a layer was investigated.
- the vanadium content is 1% to 20% and the basis weight is 3 g / m 2. It was found that sufficient corrosion resistance can be obtained by setting the amount to 40 g / m 2 or less.
- the inventors of the present invention include zinc and vanadium formed by bringing a plating bath into contact with the steel plate surface in a fluid state, the vanadium content is 1% to 20%, and the basis weight is 3 g / m 2 to 40 g / m 2.
- a plurality of coating materials were respectively applied to the following plating layers, and the adhesion (coating adhesion) between the plating layer and the coating film was examined. As a result, it was found that the surface-treated steel sheet having such a plating layer has excellent paint adhesion as compared with the conventional electrogalvanized steel sheet.
- the present inventors formed a plating layer containing zinc and vanadium in the same manner as in the case of the steel sheet using the copper plate used for the cathode in Non-Patent Documents 1 to 4 instead of the steel sheet, and the coating adhesion and The corrosion resistance was examined. As a result, the plating layer formed on the surface of the copper plate could not obtain sufficient corrosion resistance when the vanadium content and the basis weight were small. On the other hand, in order to ensure sufficient paint adhesion, when a plating layer having a vanadium content of 3% or more and a basis weight of 3 g / m 2 or more is formed on the surface of the copper plate, between the plating layer and the copper plate The adhesiveness of was insufficient. Thus, it is difficult to form a plating layer on the copper plate surface that has sufficient corrosion resistance, excellent paint adhesion, and good adhesion between the plating layer and the copper plate. there were.
- the inventors of the present invention contact a plating bath with the surface of a steel sheet in a fluid state, and include zinc and vanadium by an electroplating method.
- the vanadium content is 1% to 20% and the basis weight is 1%.
- a plating layer of 3 g / m 2 or more and 40 g / m 2 or less was formed on the steel plate.
- the surface-treated steel sheet having such a plating layer was hard to generate cracks on the surface, and had a plurality of dendritic columnar crystals grown in the thickness direction of the steel sheet.
- the ratio x / y between the adjacent columnar crystals that is, the vanadium content x existing outside the arm and the vanadium content y existing inside the columnar crystal, ie, the arm, is 1.1 or more in terms of vanadium element. It was 3.0 or less, and was excellent in corrosion resistance and paint adhesion.
- a resin film is further formed on the surface of the plating layer having excellent corrosion resistance and coating adhesion, and if necessary, metal oxide particles and a lubricant are added to the resin film, and the corrosion resistance of the resin film is increased.
- the conductivity of the surface-treated steel sheet having a resin film formed on the surface of the surface-treated steel sheet having a high-roughness plating layer was also investigated, the film thickness was in the range of 0.5 to 5.0 ⁇ m. It has been found that sufficient conductivity can be obtained without depending on the thickness.
- the present inventors totaled a film containing an inhibitor obtained by applying and drying an aqueous metal surface treatment agent containing a silane coupling agent on the plating layer of the surface-treated steel sheet having the above plating layer.
- the surface-treated steel sheet formed to have a film thickness of 0.5 to 4.0 ⁇ m was examined for the same corrosion resistance and conductivity as described above. As a result, it has been found that the film has sufficient corrosion resistance, and that sufficient conductivity can be ensured even when the film thickness is thick. Furthermore, conventionally, it has been difficult to obtain good workability (work adhesion) even when a film is formed on the surface of the galvanized layer not containing vanadium.
- the surface-treated steel sheet in which the plating layer containing zinc and vanadium oxide is formed on the surface of the steel sheet as described above exhibits a black appearance.
- the plating layer in order to use it as a designable material having a black appearance, on the plating layer in order to conceal fine appearance unevenness of the plating surface or to give scratch resistance necessary for press working. Furthermore, it may be necessary to form a thick black film.
- the present inventors have a polyester resin (A1), a curing agent (B1), and a colorant (C1) containing a sulfonic acid group on the plating layer of the surface-treated steel sheet having the plating layer.
- An organic resin film made of an organic resin containing was formed, and coating adhesion at the time of processing, corrosion resistance and scratch resistance, gloss, and L * value were examined.
- the plating layer contains zinc and vanadium in the plating layer, and has a plurality of dendritic columnar crystals grown in the thickness direction of the plate, so that the gloss is high. It had an appearance with a low suppressed L * value. Furthermore, excellent adhesion was obtained at the interface between the plating layer and the organic resin film. Furthermore, since the above organic resin film is one in which the colorant (C1) containing the color pigment containing carbon black in the organic resin film is uniformly dispersed, the film thickness is reduced to reduce coating adhesion. Even without it, an appearance with a sufficiently low L * value with sufficiently reduced gloss was obtained, and excellent scratch resistance was obtained.
- the above-mentioned organic resin film is a dense one obtained by curing a polyester resin (A1) containing a sulfonic acid group with a curing agent (B1). Therefore, by forming the above-mentioned organic resin film on the above-mentioned plating layer, the synergistic effect of the excellent corrosion resistance and paint adhesion due to the above-mentioned plating layer and the corrosion resistance improving effect by the dense and thin organic resin film And a surface-treated steel sheet having very excellent corrosion resistance is obtained.
- the present inventors formed a plating layer containing zinc and vanadium and a colored coating layer containing a color pigment layer in this order on one or both surfaces of the surface-treated steel sheet having the plating layer. As a result, a surface-treated steel sheet excellent in corrosion resistance and workability was obtained.
- the present invention has been completed based on the above findings.
- the present invention employs the following means. (1) That is, the surface-treated steel sheet according to an aspect of the present invention includes a steel sheet and a plating layer formed on one or both surfaces of the steel sheet and containing zinc and vanadium; the plating layer includes the vanadium. And having a plurality of dendrite-like arms grown in the thickness direction of the steel sheet, and having a basis weight of 3 g / m 2 or more and 40 g / m 2 or less; The ratio x / y of the vanadium content x existing outside the arm with respect to the vanadium content y is 1.1 or more and 3.0 or less in terms of vanadium element.
- the plating layer has an emissivity of 0.30 or more and 0.95 in the region of wave number 600 to 3000 cm ⁇ 1 measured under the condition that the surface temperature is 100 ° C. It may be the following.
- the surface roughness of the plating layer is 1.0 ⁇ m or more in terms of the centerline average roughness Ra specified by JIS B 0601: 2001. It may be 0.0 ⁇ m or less.
- one or more films may be further formed on the plated layer.
- the film may contain an organic resin.
- the film is a resin film, and 5 to 50 parts by mass of metal oxide particles with respect to 100 parts by mass of the solid content of the resin film;
- the resin film may contain 0.1 to 30% by mass of a lubricant with respect to 100% by mass of the solid content.
- the organic resin has in its structure at least one of a carboxyl group, a hydroxyl group, a sulfonic acid group, and a silanol group; a polyester resin containing a sulfonic acid group And; a curing agent; and a coloring pigment containing carbon black.
- the coating may be obtained by applying an aqueous metal surface treatment agent containing a silane coupling agent to the steel sheet and drying it.
- the composite film may further contain an inhibitor component having a fluoro metal complex compound having at least one selected from titanium and zirconium as an essential component.
- the coating may be a composite coating containing a polyether polyurethane resin and a color pigment containing carbon black.
- the coating may be a colored coating layer including a colored pigment layer.
- the colored coating layer includes a primer coating layer, and the primer coating layer is formed between the plating layer and the coloring pigment layer.
- a rust inhibitor may be included.
- the colored coating layer may be formed in contact with the plating layer.
- the surface-treated steel sheet according to any one of (11) and (12) may further include a chemical conversion treatment layer between the colored coating layer and the plating layer.
- a method for producing a surface-treated steel sheet according to an aspect of the present invention is a method for producing a surface-treated steel sheet comprising a plating step of forming a plating layer containing zinc and vanadium on the surface of the steel sheet by electroplating.
- the steel sheet is immersed in a plating bath, and the current density in the plating bath is set to 20 to 150 A / dm 2 and electrodeposition is performed for a time period of 1 second to 30 seconds to perform the plating layer.
- the plating bath contains a zinc compound and a vanadium compound, and contains at least one of vanadium ions or vanadyl ions in a total content of 0.01 mol / l or more and less than 1.0 mol / l, nitric acid
- the ion content is limited to less than 0.0005 mol / l
- the plating bath is formed by moving a steel plate in a circulating plating bath or a plating bath.
- the plating layer has a vanadium content of 1% to 20% and a basis weight of 3 g / m 2 to 40 g. / M 2 or less.
- the average flow rate of the plating bath in the plating tank may be in the range of 20 to 300 m / min.
- the plating bath may contain sodium ions in an amount of 0.1 mol / l to 4.0 mol / l.
- the plating bath may contain 0.01 mol / l or more and 1.0 mol / l or less of nickel ions.
- the surface-treated steel sheet according to the present embodiment has a vanadium content of 1% to 20% and a basis weight of 3 g / m 2 to 40 g / m 2 , and a plurality of dendritic arms grown in the thickness direction of the steel sheet. And a ratio x / y to vanadium content y existing in the arm of vanadium content x existing outside the arm is 1.1 to 3.0 in terms of vanadium element. ing. Therefore, it is excellent in corrosion resistance and paint adhesion.
- the steel sheet in the plating step, is immersed in a fluidized plating bath, and the electrodeposition is performed for 1 second to 30 seconds, and the vanadium content is 1% to 20%.
- a plating layer having a basis weight of 3 g / m 2 or more and 40 g / m 2 or less is formed. Thereby, it is hard to generate
- a surface-treated steel sheet in which a coating such as a resin coating, a composite coating, or a colored coating layer is further formed on the plating layer has more excellent characteristics such as corrosion resistance, conductivity, and appearance.
- FIG. 1 is a schematic view showing an example of a plating apparatus used in the method for producing a surface-treated steel sheet according to this embodiment.
- symbol 1 shows a steel plate
- symbol 2 shows a plating bath
- symbol 21 shows a plating tank
- symbol 3 has shown the anode.
- the method for producing a surface-treated steel sheet according to the present embodiment includes a plating process for forming a plating layer containing zinc and vanadium on the surface of the steel sheet 1 by electroplating.
- the steel plate 1 on which the plating layer is formed is not particularly limited.
- extremely low carbon type ferrite main structure
- low carbon type structure containing pearlite in ferrite
- two-phase structure type for example, structure containing martensite in ferrite, structure containing bainite in ferrite
- Any type of steel sheet may be used, such as a processing-induced transformation type (a structure containing retained austenite in ferrite) or a fine crystal type (a ferrite main structure).
- reference numerals 4 and 5 denote rolls for moving the steel plate 1 in the direction of the arrow in FIG.
- the roll 4 disposed on the upper portion of the steel plate 1 functions as a connecting member (conductor) that electrically connects the power source (not shown) and the steel plate 1.
- the steel plate 1 is a cathode by being electrically connected to the roll 4.
- the plating tank 21 shown in FIG. 1 is used in the plating step.
- the plating tank 21 has an upper tank 21 a disposed at the upper part of the steel plate 1 and a lower tank 21 b disposed at the lower part of the steel plate 1.
- a plurality of anodes 3 made of platinum or the like are disposed at a predetermined interval between the steel plates 1 at positions adjacent to the steel plates 1 in the upper tank 21 a and the lower tank 21 b. Yes.
- the surface of each anode 3 facing the steel plate 1 is arranged so as to be substantially parallel to the surface of the steel plate 1.
- Each anode 3 is electrically connected to a power source (not shown) by a connecting member (not shown).
- the inside of the upper tank 21a and the lower tank 21b are filled with the plating bath 2.
- the steel plate 1 which moves by making the surface direction substantially horizontal is disposed.
- the steel plate 1 passing through the plating tank 21 by the rolls 4 and 5 in the direction of the arrow (the right side in the drawing) is immersed in the plating bath 2 in the upper tank 21a and the lower tank 21b. Therefore, in this embodiment, the steel plate 1 is moved by the rolls 4 and 5, and the steel plate 1 is moved in the plating bath 2, so that the plating bath 2 flows relatively to the steel plate 1. It has become.
- the upper tank 21a is provided with an upper supply pipe 2a for supplying the plating bath 2 to the upper tank 21a so as to penetrate the upper surface of the upper tank 21a.
- the upper supply pipe 2a is branched into a plurality of outer branch paths 2c and a plurality of intermediate branch paths 2d (only one is shown in FIG. 1) in the upper tank 21a.
- a plurality of intermediate branch paths 2d are arranged along the width direction of the steel plate 1 between the adjacent anodes 3 in plan view, and the plating bath 2 is supplied between the electrodes 3 (anode) and the steel plate 1 on both sides.
- An opening is provided.
- a plurality of outer peripheral branch paths 2 c are arranged along the width direction of the steel plate 1 between the anode 3 and the roll 4 in a plan view, and an opening for supplying the plating bath 2 between the electrode 3 and the steel plate 1. Department.
- the upper tank 21a is provided with a discharge port (not shown) for discharging the plating bath 2, and is connected to the upper supply pipe 2a via a pipe (not shown) provided with a pump. Therefore, in the upper tank 21a, the plating bath 2 is supplied from the upper supply pipe 2a. Thereafter, the gas is discharged from the discharge port, and is again supplied from the upper supply pipe 2a through the pipe and circulated by the pump.
- the lower tank 21b is provided with a lower supply pipe 2b for supplying the plating bath 2 to the lower tank 21b so as to penetrate the lower surface of the lower tank 21b.
- the lower supply pipe 2b is branched into a plurality of outer peripheral branch paths 2e and a plurality of intermediate branch paths 2f (only one is shown in FIG. 1) in the lower tank 21b.
- a plurality of intermediate branch paths 2f are arranged along the width direction of the steel plate 1 between the anodes 3 adjacent in plan view, and an opening for supplying the plating bath 2 between the electrodes 3 and the steel plate 1 on both sides. It has.
- a plurality of outer peripheral branch paths 2 e are arranged along the width direction of the steel plate 1 between the anode 3 and the roll 5 in a plan view, and an opening for supplying the plating bath 2 between the electrode 3 and the steel plate 1. Department.
- the lower tank 21b is provided with a discharge port (not shown) for discharging the plating bath 2, and is connected to the lower supply pipe 2b via a pipe (not shown) provided with a pump. Therefore, in the lower tank 21b, the plating bath 2 is supplied from the lower supply pipe 2b. Thereafter, the gas is discharged from the discharge port, and is again supplied from the lower supply pipe 2b through the pipe and circulated by the pump.
- the number of electrodes 3 may be any number.
- the number of electrodes 3 is appropriately determined according to the size of the plating tank 21, the steel plate 1, the electrode 3, the arrangement of the upper supply pipe 2 a and the lower supply pipe 2 b, the average flow rate of the plating bath 2 in the plating tank 21, and the like. it can.
- the arrangement and shape of the upper supply pipe 2a and the lower supply pipe 2b can also be appropriately changed according to the shape of the electrode 3, the average flow rate of the plating bath 2 in the plating tank 21, and the like.
- the plating bath is in a fluidized state in which the plating bath is circulated, and in a fluidized state in which the plating bath 2 flows relatively to the steel plate 1 by moving the steel plate 1 in the plating bath 2.
- the steel plate 1 is immersed in the bath 2, the current density in the plating bath is set to 20 to 150 A / dm 2 , and the electrodeposition is performed for 1 second to 30 seconds to form a plating layer containing zinc and vanadium. It is a process to do.
- the surface of the steel plate 1 less than 20% and basis weight 1% or more vanadium content of 3 g / m 2 or more 40 g / m 2 or less of dendritic columnar crystals
- a plating layer having (primary arm and secondary arm) is formed.
- the circulating plating bath 2 is in a fluidized state, and the plating bath 2 is fluidized relative to the steel plate 1 by passing the steel plate 1 through the plating bath 2.
- the steel plate 1 is immersed in the plating bath 2. Therefore, ions are sufficiently supplied between the steel plate 1 and the electrode 3.
- the ratio x of vanadium content x existing inside the arm has a plurality of dendrite-like arms grown in the thickness direction of the steel sheet and exists outside the arm x
- a surface-treated steel sheet having a plating layer having a / y of 1.1 or more and 3.0 or less in terms of vanadium element is obtained.
- the plating bath 2 of the plating tank 21 shown in FIG. 1 is in a fluidized state in which the plating bath 2 flows relative to the steel plate 1 by moving the steel plate 1 in the plating bath 2. Even without circulating 2, ions can be sufficiently supplied between the steel plate 1 and the electrode 3.
- a surface-treated steel sheet having a sufficient corrosion resistance with a vanadium content of the plating layer formed by the plating step being 1% or more and 20% or less and a basis weight being 3 g / m 2 or more and 40 g / m 2 or less.
- the vanadium content of the plating layer is preferably 2% or more in order to further improve the corrosion resistance and paint adhesion.
- the vanadium content of the plating layer is 20% or less. More preferably, it is 15% or less.
- the basis weight of the plating layer is 3 g / m 2 or more. However, when the corrosion resistance and coating adhesion are further improved, it is preferably 5 g / m 2 or more.
- the basis weight of the plating layer is preferably 40 g / m 2 or less, and more preferably 15 g / m 2 or less. When the basis weight of the plating layer is 40 g / m 2 or less, not only the manufacturing cost increases, but also the plating adhesion (powdering property) deteriorates.
- the amount of metal to be deposited can be reduced as compared with conventional electrogalvanizing (usually about 20 g / m 2 ), etc., and the metal cost for forming the plating layer It is economically superior from the viewpoint of power costs.
- the plating layer obtained in the present embodiment exhibits a black appearance because vanadium elements are present in the form of dendrites as oxides in zinc. Therefore, when the surface-treated steel sheet according to the present embodiment is used as a material for a product having a black appearance, for example, it has a preferable appearance. Moreover, when apply
- the electrodeposition time is 1 second or longer in order to obtain a sufficient basis weight.
- the electrodeposition time is 30 seconds or less from the viewpoint of not impairing productivity. Preferably, it is 1 second or more and 15 seconds or less.
- the current density is 20 to 150 A / dm 2 .
- the plating layer of this embodiment having a vanadium content of 1% to 20% and a basis weight of 3 g / m 2 to 40 g / m 2 can be easily formed.
- the current density is less than 20 A / dm 2, it is difficult to secure a predetermined vanadium content and / or basis weight. If the current density exceeds 150 A / dm 2 , the adhesion between the plating layer and the steel sheet 1 may be reduced.
- the steel plate 1 is immersed in the fluidized plating bath 2 to form a plating layer. Therefore, in order to ensure a sufficiently high vanadium content, the plating bath is placed on the steel plate surface in a stationary state and a stirred state. It is necessary to increase the current density as compared with the case of contact. This is because, when the steel plate 1 is immersed in the plating bath 2 in a fluidized state, ions are uniformly and continuously supplied from the plating bath 2 to the surface of the steel plate 1. This is because it is difficult for vanadium to be taken in.
- the average flow rate of the plating bath 2 in the plating tank 21 is preferably in the range of 20 to 300 m / min, and more preferably in the range of 40 to 200 m / min.
- the average flow rate of the plating bath 2 is in the range of 20 to 300 m / min, generation of cracks in the plating layer can be more effectively prevented.
- the average flow velocity of the plating bath 2 is less than the above range, the effect of circulating the plating bath 2 to a fluid state may be insufficient.
- the average flow velocity of the plating bath 2 exceeds the above range, there is a possibility that the supply of ions from the plating bath 2 to the surface of the steel plate 1 may be hindered.
- the plating bath 2 contains a V compound and a Zn compound.
- the plating bath 2 is not a V compound and a Zn compound, such as a pH adjuster such as H 2 SO 4 or NaOH, or a Ni compound such as NiSO 4 .6H 2 O, if necessary.
- a pH adjuster such as H 2 SO 4 or NaOH
- a Ni compound such as NiSO 4 .6H 2 O
- Other metal compounds and additives such as Na 2 SO 4 that stabilize the conductivity of the plating bath 2 may be added.
- the plating bath 2 reliably forms dendritic columnar crystals, the nitrate ion content is limited to less than 0.0005 mol / l.
- Examples of the Zn compound used in the plating bath 2 include metal Zn, ZnSO 4 .7H 2 O, ZnCO 3 and the like. These may be used alone or in combination of two or more.
- Examples of the V compound used in the plating bath 2 include ammonium metavanadate (V), potassium metavanadate (V), sodium metavanadate (V), VO (C 5 H 7 O 2 ) 2 (vanadyl acetylacetonate (IV)). ), VOSO 4 ⁇ 5H 2 O ( vanadyl sulfate (IV)) and the like. These may be used alone or in combination of two or more.
- the plating bath 2 preferably contains Zn 2+ and VO 2+ or V 4+ as the V compound and the Zn compound.
- the plating bath 2 contains either or both of VO 2+ and V 4+ , these are contained in the plating bath 2 in a total of 0.01 mol / l or more and less than 1.0 mol / l.
- a plating layer having a vanadium content of 1% to 20% and a basis weight of 3 g / m 2 to 40 g / m 2 is obtained. Can be easily formed.
- Plating bath 2 may include a Zn 2+, preferably comprises Zn 2+ 0.1 ⁇ 1.5mol / l, more preferably contains 0.35 ⁇ 1.2mol / l.
- the plating bath 2 contains 0.1 mol / l or more of sodium ions.
- the conductivity of the plating bath 2 can be increased, and the plating layer of this embodiment can be easily formed.
- the concentration is 4.0 mol / l or more
- the plating bath 2 preferably contains 0.01 mol / l or more of nickel ions. In this case, vanadium is likely to precipitate, and the plating layer of this embodiment can be easily formed.
- setting it to 1.0 mol / l or more is not desirable because there is a concern that the corrosion resistance and plating adhesion of the surface-treated steel sheet may deteriorate.
- the temperature of the plating bath 2 is not particularly limited, but is preferably in the range of 40 to 60 ° C. in order to easily and efficiently form the plating layer of this embodiment.
- the pH of the plating bath 2 has a dendritic columnar crystal and is in the range of 1 to 5 in order to easily form the plating layer of the present embodiment having the vanadium content and the basis weight. The range of 1.5 to 4 is more preferable.
- the surface roughness of the plating layer is preferably 1.0 ⁇ m or more and 4.0 ⁇ m or less in terms of the centerline average roughness Ra specified by JIS B 0601: 2001. Conventionally, it has been considered that corrosion resistance is secured by lowering the surface roughness of the plating layer. However, in the present invention, since the plating layer has sufficient corrosion resistance, Ra has a high roughness of 1.0 ⁇ m or more. Even as a layer, the corrosion resistance does not deteriorate. Furthermore, by increasing the surface roughness of the plating layer, not only can the conductivity when a film is formed later be secured, but also the work adhesion can be improved.
- Ra if Ra exceeds 4.0 ⁇ m, the rubber and pass roll of the roll coater are scraped and may adhere to the product as dust, so the upper limit is set to 4.0 ⁇ m. In addition, More preferably, they are 1.1 micrometers or more and 3.0 micrometers or less.
- FIG. 3A and 3B are scanning electron micrographs of a plating layer as an example of the surface-treated steel sheet according to the present embodiment.
- FIG. 3A is a photograph viewed from above
- FIG. 3B is a photograph of a cross section.
- the plating layer 11 is free from cracks (gap) reaching the steel plate 1 and has a plurality of fine and dense dendritic columnar crystals 12 (arms) grown in the thickness direction of the steel plate 1. have.
- Each columnar crystal 12 grows from the surface of the steel plate 1 not only in the thickness direction but also in the surface direction of the steel plate 1. Therefore, as shown in FIG. 3B, at least a part of the columnar crystals 12 is separated at the base 12a in contact with the steel plate 1 and is integrated with the adjacent columnar crystals 12 at the portion 12b away from the steel plate 1. It has become.
- a region 13 (a dark gray portion in FIG. 3B) having a large amount of is formed.
- the ratio x / y of the vanadium content x existing outside the arm to the vanadium content y existing inside the arm is 1.1 or more in terms of vanadium element. From the viewpoint of corrosion resistance, the ratio x / y is more preferably 1.2 or more. When x / y exceeds 3.0, it is necessary to add V excessively, resulting in high cost. When the ratio x / y is in the range of 1.2 to 2.0, better corrosion resistance can be obtained at low cost.
- the surface-treated steel sheet according to this embodiment has a plurality of fine and dense dendritic columnar crystals 12 grown in the thickness direction of the steel sheet 1 as shown in FIGS. 3A and 3B. Then, at least a part of the columnar crystals 12 is separated at the base portion 12a, and a plating layer 11 having a shape integrated with the adjacent columnar crystals 12 is formed at a portion 12b away from the steel plate 1, and excellent coating is achieved. Adhesion. This is presumably because the columnar crystal 12 functions as an anchor effect. In this embodiment, as shown in FIG. 3A and FIG.
- the plating layer 11 has a vanadium content of 1% or more and 20% or less, a basis weight of 3 g / m 2 or more and 40 g / m 2 or less, and a plurality of layers grown in the thickness direction of the steel sheet 1.
- the dendrite-like columnar crystal 12 is included.
- the plating layer formed in the present embodiment has an emissivity of 0.30 or more in a region of wave number 600 to 3000 cm ⁇ 1 measured at 100 ° C. Since the emissivity is the same as the absorptance of an object at a constant temperature, a material with a high emissivity also has a high heat absorption.
- the emissivity of the plating layer 11 is preferably 0.30 or more, and more preferably 0.60 or more in order to sufficiently obtain the heat absorption effect and the heat dissipation effect.
- the above emissivity tends to be less than 0.30. If the emissivity of the plating layer 11 is less than 0.30, the heat absorption effect and the heat dissipation effect may not be sufficiently obtained.
- the radiation absorption in the wave number region of less than 600 cm ⁇ 1 or more than 3000 cm ⁇ 1 has a very small effect on the heat absorption of the surface-treated steel sheet and the temperature lowering effect. Emissivity is inadequate.
- the temperature at which the emissivity is measured was set to 100 ° C. in consideration of the operating temperature of an electronic circuit such as an IC chip used for home appliances.
- the plating layer 11 having an emissivity of 0.30 or more in the region of wave number 600 to 3000 cm ⁇ 1 measured at 100 ° C. is formed on the surface of the steel sheet 1.
- This heat can be absorbed well and can be efficiently dissipated.
- it can be suitably used as a heat sink for electronic components.
- FIG. 2 is a schematic view showing another example of a plating apparatus used in the method for producing a surface-treated steel sheet according to the present embodiment.
- reference numeral 10 indicates a steel plate
- reference numeral 32 indicates a plating bath
- reference numeral 22 indicates a plating tank
- reference numeral 23 indicates an anode.
- the steel plate 10 shown in FIG. 2 has a planar shape that is smaller than the planar shape of the plating tank 22.
- the steel plate 10 is not particularly limited, and one made of the same material as the steel plate 1 used in the first embodiment can be used.
- As the plating bath 32 the thing similar to the plating bath 2 used in 1st Embodiment can be used.
- the plating process which forms the plating layer containing zinc and vanadium on the surface of the steel plate 10 by the electroplating method is performed using the plating tank 22 shown in FIG.
- a discharge port 32c is provided on one side surface 32a of the plating tank 22 facing each other.
- a supply port 32d is provided on the other side surface 32b.
- the discharge port 32c and the supply port 32d are connected by a pipe 32e, and the pump P is connected to the pipe 32e.
- an anode 23 made of platinum or the like is disposed at the bottom of the plating tank 22.
- the inside of the plating tank 22 is filled with a plating bath 32, and the steel plate 10 serving as a cathode is immersed in the plating bath 32 with the surface direction arranged substantially horizontally.
- the plating bath 32 is discharged from the discharge port 32c of the plating tank 22, and the plating bath 32 is supplied from the supply port 32d through the piping 32e by the pump P and circulated.
- the steel sheet 10 is immersed in the fluidized plating bath 32 to form a plating layer containing zinc and vanadium.
- the surface of the steel sheet 10 less than 20% and basis weight 1% or more vanadium content of 3 g / m 2 or more 40 g / m 2 or less dendritic columnar crystals A plating layer is formed.
- the steel plate 10 is immersed in the circulating fluidized plating bath 32, so that ions are sufficiently supplied between the steel plate 10 and the electrode (anode) 23.
- the vanadium content rate x having a plurality of dendritic arms (columnar crystals) grown in the thickness direction of the steel sheet 10 and existing outside the arms (between adjacent columnar crystals)
- a surface-treated steel sheet having a plating layer in which the ratio x / y to vanadium content y existing in the arm (in the columnar crystal) is 1.1 or more and 3.0 or less in terms of vanadium element is obtained.
- the steel plate 1 When the steel plate is immersed in a circulating fluidized plating bath as in the first embodiment and the second embodiment, the steel plate 1 is applied to the steel plate 1 like the plating bath 2 in the plating tank 21 of the first embodiment.
- the plating bath 2 may be relatively fluidized, and the steel plate may not be moved in the plating bath as in the second embodiment.
- the circulating plating bath 32 since the circulating plating bath 32 is circulated, the plating bath is relatively flowed with respect to the steel plate, and sufficient ions can be supplied between the steel plate 10 and the electrode 23. .
- one or more films are further formed on the upper surface of the plated layer of the surface-treated steel sheet obtained in the first embodiment or the second embodiment. An example will be described.
- the surface-treated steel sheet in which a resin film is formed on the surface-treated steel sheet having a plating layer containing zinc and vanadium obtained in the first embodiment or the second embodiment will be described.
- this resin film it may be called the resin film which concerns on this embodiment.
- the plating layer of the surface-treated steel sheet used in this embodiment may be referred to as a plating layer according to this embodiment.
- one or more resin films (A) are formed on the upper surface of the plating layer according to this embodiment.
- the thickness of at least one layer of the plurality of resin films (A) is preferably 0.5 to 5.0 ⁇ m.
- the thickness of the resin film (A) is more preferably 0.5 ⁇ m or more, and even more preferably 1.0 ⁇ m or more. Further, from the viewpoint of conductivity, the thickness of the resin film (A) is more preferably 5.0 ⁇ m or less, and further preferably 4.0 ⁇ m or less.
- the resin film (A) includes a water-soluble resin and a resin (water-dispersible resin) that is inherently insoluble in water but can be finely dispersed in water like an emulsion or suspension.
- the type of the resin film (A) is not particularly limited.
- at least one selected from the group consisting of polyester resins, polyurethane resins, acrylic resins, epoxy resins, polyolefin resins, and modified resins thereof may be used.
- the polyester resin is not particularly limited.
- polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, 1,6-hexanediol, neopentyl glycol, triethylene glycol, bisphenol hydroxypropyl ether, glycerin, trimethylol ethane, trimethylol propane and phthalic anhydride
- Dehydration condensation with polybasic acids such as isophthalic acid, terephthalic acid, succinic anhydride, adipic acid, sebacic acid, maleic anhydride, itaconic acid, fumaric acid, hymic anhydride, etc., neutralize with ammonia, amine compounds, etc. Those obtained by dispersing in water can be used.
- the polyurethane resin is not particularly limited.
- polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, 1,6-hexanediol, neopentyl glycol, triethylene glycol, bisphenol hydroxypropyl ether, glycerin, trimethylol ethane, trimethylol propane and hexamethylene diisocyanate,
- a compound obtained by reacting with a diisocyanate compound such as isophorone diisocyanate or tolylene diisocyanate, extending the chain with diamine or the like, and dispersing in water can be used.
- the acrylic resin is not particularly limited.
- unsaturated monomers such as styrene, alkyl (meth) acrylates, (meth) acrylic acid, hydroxyalkyl (meth) acrylates, and alkoxysilane (meth) acrylates are used in an aqueous solution with a polymerization initiator. Those obtained by radical polymerization can be used.
- the polymerization initiator is not particularly limited, and for example, persulfates such as potassium persulfate and ammonium persulfate, azo compounds such as azobiscyanovaleric acid and azobisisobutyronitrile can be used.
- the epoxy resin is not particularly limited.
- bisphenol A type epoxy resin bisphenol F type epoxy resin, resorcinol type epoxy resin, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, resorcinol type epoxy resin, novolac type epoxy resin, etc.
- an amine compound such as N-methylethanolamine and neutralization with an organic or inorganic acid, or after radical polymerization of a high acid value acrylic resin in the presence of the epoxy resin, ammonia or amine
- examples thereof include those obtained by neutralizing with a compound or the like and dispersing in water.
- the polyolefin resin is not particularly limited.
- ethylene and unsaturated carboxylic acid such as methacrylic acid, acrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid under high temperature and high pressure, ammonia, amine compounds, KOH, NaOH, LiOH, etc.
- a metal compound or a product obtained by neutralizing with an ammonia or amine compound containing the above metal compound and dispersing in water can be used.
- a phenol resin can be used as a kind of the said resin film (A).
- the phenol resin is not particularly limited.
- phenol resins such as methylolated phenol resin obtained by addition reaction of aromatics such as phenol, resorcin, cresol, bisphenol A, paraxylylene dimethyl ether and formaldehyde in the presence of a reaction catalyst are diethanolamine, N-methylethanolamine.
- a compound obtained by reacting with an amine compound such as, etc., and neutralizing with an organic acid or an inorganic acid can be used.
- the resin film according to the present embodiment preferably contains metal oxide particles and a lubricant.
- the content of the metal oxide particles (B) is 5 to 50% by mass with respect to 100% by mass of the solid content of the resin film (A).
- the amount exceeds 50% by mass the resin film becomes brittle and the effect of improving the corrosion resistance of the processed part is small.
- the type of the metal oxide particles (B) is not particularly limited. Examples thereof include those composed of at least one metal element selected from the group consisting of Si, Ti, Al and Zr. More specifically, silica particles, titania particles, alumina particles, zirconia particles, etc. may be used. it can.
- the metal oxide particles (B) preferably have an average particle diameter of about 1 to 300 nm. These may be used alone or in combination of two or more.
- the content of the lubricant (H) is preferably 0.1 to 30% by mass with respect to 100% by mass of the solid content of the resin film (A). If it is less than 0.1%, the workability improvement effect is small, and if it exceeds 30%, the corrosion resistance improvement effect may not be obtained.
- the lubricity of the resin film is improved by containing the lubricant (H) as described above. As a result, it is effective in improving workability during press molding, preventing wrinkles due to molds and handling, and preventing wear and scratches during transportation of molded products and coils.
- the lubricant (H) is not particularly limited. Known fluorine-based, hydrocarbon-based, fatty acid amide-based, ester-based, alcohol-based, metal soap-based and inorganic lubricants can be used.
- the selection criteria for selecting a lubricant additive for improving processability is to select a material that exists on the surface of the resin film rather than being dispersed in the resin film on which the added lubricant is formed. This is effective in that the friction between the surface of the object and the mold is reduced to maximize the lubrication effect.
- the surface friction coefficient is high, the resin film is easily broken, and the powdery material is peeled and deposited, resulting in poor appearance and reduced workability, which is called powdering phenomenon.
- a substance that exists on the surface of the resin film a substance that is incompatible with the resin and has a small surface energy is selected.
- a polyolefin wax as the lubricant (H) because the dynamic friction coefficient of the surface is lowered, the workability is greatly improved, and the corrosion resistance after processing is also improved.
- the wax include hydrocarbon waxes such as paraffin, microcrystalline, and polyethylene.
- the melting point of the wax is more preferably 70 to 160 ° C. If it is less than 70 degreeC, it may soften and melt at the time of a process, and the outstanding characteristic as a lubricant may not be exhibited.
- the melting point exceeds 160 ° C., hard particles are present on the surface and the friction characteristics are deteriorated, so that high moldability may not be obtained.
- the particle diameter of these waxes is more preferably 0.1 to 5 ⁇ m. If the thickness exceeds 5 ⁇ m, the distribution of the solidified wax may be non-uniform, or the resin-based film may fall off. Moreover, when it is less than 0.1 ⁇ m, workability may be insufficient.
- the resin film (A) according to this embodiment preferably further contains a phosphoric acid compound (C).
- a phosphate layer is formed on the surface of the plating layer and is passivated, so that the corrosion resistance is improved.
- Examples of the phosphoric acid compound (C) include phosphoric acids such as orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid and salts thereof; aminotri (methylenephosphonic acid), 1-hydroxyethylidene-1 Phosphonic acids such as 1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) and salts thereof; and organic phosphoric acids such as phytic acid and salts thereof.
- the cation species of the salt is not particularly limited, and examples thereof include Cu, Co, Fe, Mn, Sn, V, Mg, Ba, Al, Ca, Sr, Nb, Y, Ni, and Zn. These may be used alone or in combination of two or more.
- the phosphoric acid compound (C) is preferably contained in an amount of 0.01 to 20% by mass with respect to 100% by mass of the solid content of the resin film (A).
- the content is less than 0.01% by mass, the content may be small and the effect of improving the corrosion resistance may not be obtained.
- the content exceeds 20% by mass the resin film becomes brittle and the effect of improving the corrosion resistance of the processed part cannot be obtained. There is.
- the resin film (A) according to this embodiment may further contain at least one crosslinking agent (D) selected from the group consisting of a silane coupling agent, a crosslinkable zirconium compound, and a crosslinkable titanium compound. preferable. These may be used alone or in combination of two or more.
- D crosslinking agent
- cross-linking agent (D) selected from the group consisting of the silane coupling agent, cross-linkable zirconium compound and cross-linkable titanium compound is contained, the adhesion between the plating layer and the resin film (A) is improved. Further improve.
- the silane coupling agent is not particularly limited.
- the crosslinkable zirconium compound is not particularly limited as long as it is a zirconium-containing compound having a plurality of functional groups capable of reacting with a carboxyl group or a hydroxyl group.
- a compound that is soluble in water or an organic solvent is preferable, and a water-soluble zirconium compound is more preferable.
- An example of such a compound is zirconyl ammonium carbonate.
- the crosslinkable titanium compound is not particularly limited as long as it is a titanium-containing compound having a plurality of functional groups capable of reacting with a carboxyl group or a hydroxyl group.
- the solid content of the aqueous resin (A) is 100% by mass.
- the content is preferably 0.1 to 50% by mass. If the amount is less than 0.1% by mass, the content may be small and the effect of improving the adhesion may not be obtained. If the amount exceeds 50% by mass, the stability of the aqueous composition may be lowered.
- the resin film (A) according to this embodiment further contains at least one crosslinking agent (E) selected from the group consisting of amino resins, polyisocyanate compounds, block bodies thereof, epoxy compounds, and carbodiimide compounds. It is preferable. These crosslinking agents may be used alone or in combination of two or more.
- crosslinking agent (E) selected from the group consisting of the amino resin, polyisocyanate compound, block body thereof, epoxy compound and carbodiimide compound is contained, the crosslinking density increases and the barrier property of the resin-based film Improves the corrosion resistance further.
- the amino resin is not particularly limited.
- melamine resin benzoguanamine resin, urea resin, glycoluril resin and the like can be used.
- the polyisocyanate compound is not particularly limited.
- hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, tolylene diisocyanate and the like can be used.
- the blocked product is a blocked product of the polyisocyanate compound.
- the epoxy compound is not particularly limited as long as it is a compound having a plurality of oxirane rings.
- adipic acid diglycidyl ester phthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, sorbitan polyglycidyl ether, pentaerythritol polyglycidyl ether, glycerin polyglycidyl ether, trimethylpropane polyglycidyl ether, neopentyl glycol polyglycidyl ether, ethylene Glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol glycol diglycidyl ether, polypropylene glycol glycol diglycidyl ether, 2,2-bis- (4'-glycidyloxyphenyl) propane, tris (2,3-epoxypropyl) Isocyanurate, bisphenol A diglycidyl ether, hydrogenated bis
- the carbodiimide compound for example, after synthesizing an isocyanate-terminated polycarbodiimide by a condensation reaction involving decarbonization of a diisocyanate compound such as aromatic diisocyanate, aliphatic diisocyanate, and alicyclic diisocyanate, the reactivity with an isocyanate group is further increased. And a compound to which a hydrophilic segment having a functional group is added.
- a diisocyanate compound such as aromatic diisocyanate, aliphatic diisocyanate, and alicyclic diisocyanate
- At least one crosslinking agent (E) selected from the group consisting of the amino resin, the polyisocyanate compound, its block, an epoxy compound, and a carbodiimide compound is 0.001% relative to 100% by mass of the solid content of the resin film (A).
- the content is preferably 1 to 50% by mass. If the amount is less than 0.1% by mass, the content may be small and the effect of improving the corrosion resistance may not be obtained. If the amount exceeds 50% by mass, the resin film becomes brittle and the effect of improving the corrosion resistance of the processed part may not be obtained.
- the resin film (A) according to this embodiment may further contain at least one (F) selected from the group consisting of a vanadium compound, a tungsten compound, and a molybdenum compound. These may be used alone or in combination of two or more.
- the corrosion resistance of the resin film according to this embodiment is improved by containing at least one (F) selected from the group consisting of the vanadium compound, the tungsten compound, and the molybdenum compound.
- the vanadium compound is not particularly limited. Conventionally known vanadium-containing compounds can be used. For example, vanadate and ammonium vanadate, vanadate such as sodium vanadate, phosphovanadate such as phosphovanadate and ammonium phosphovanadate, and the like can be used. .
- the tungsten compound is not particularly limited. Conventionally known tungsten-containing compounds can be used. For example, tungstic acid and ammonium tungstate, tungstate such as sodium tungstate, phosphotungstic acid such as phosphotungstic acid and ammonium phosphotungstate, and the like can be used. .
- the molybdenum compound is not particularly limited.
- a conventionally well-known molybdenum containing compound can be used, for example, molybdate etc. can be used.
- the molybdate is not limited in its skeleton and degree of condensation, and examples thereof include orthomolybdate, paramolybdate, and metamolybdate.
- all salts, such as a single salt and a double salt, are included, and phosphoric acid molybdate etc. can be used as a double salt.
- the total amount is 0.01 to 20% by mass with respect to 100% by mass of the solid content of the resin film (A). It is preferable that If it is less than 0.01% by mass, the content may be small and the effect of improving corrosion resistance may not be obtained. On the other hand, if the amount exceeds 20% by mass, the resin-based film becomes brittle, and the effect of improving the corrosion resistance of the processed part may not be obtained.
- the resin film (A) according to this embodiment may further contain a polyphenol compound (G).
- the inclusion of the polyphenol compound (G) improves the corrosion resistance of the resin film and the adhesion of the post-coating film when used for post-coating applications.
- the polyphenol compound (G) is a compound having two or more phenolic hydroxyl groups bonded to a benzene ring or a condensate thereof.
- the compound having two or more phenolic hydroxyl groups bonded to the benzene ring include gallic acid, pyrogallol, catechol and the like.
- the condensate of the compound having two or more phenolic hydroxyl groups bonded to the benzene ring is not particularly limited, and for example, a polyphenol compound or the like widely distributed in the plant kingdom usually called tannic acid can be used. Tannic acid is a general term for aromatic compounds having a complex structure having a large number of phenolic hydroxyl groups widely distributed in the plant kingdom.
- the tannic acid may be hydrolyzable tannic acid or condensed tannic acid.
- the tannic acid is not particularly limited.
- hamelian tannin, oyster tannin, chatannin, pentaploid tannin, gallic tannin, myrobalan tannin, dibidi tannin, argarovira tannin, valonia tannin, catechin tannin and the like can be used.
- tannic acid examples include commercially available ones such as “tannic acid extract A”, “B tannic acid”, “N tannic acid”, “industrial tannic acid”, “purified tannic acid”, “Hi tannic acid”, “F tannic acid”, “local tannic acid” (all manufactured by Dainippon Pharmaceutical Co., Ltd.), “tannic acid: AL” (manufactured by Fuji Chemical Industry Co., Ltd.) and the like can also be used.
- the said polyphenol compound may be used independently and may use 2 or more types together.
- the polyphenol compound (G) is preferably contained in an amount of 0.1 to 50% by mass with respect to 100% by mass of the solid content of the resin film (A). If the amount is less than 0.1% by mass, the content may be small and the effect of improving the corrosion resistance may not be obtained. If the amount exceeds 50% by mass, the stability of the aqueous composition may be lowered.
- the resin film according to the present embodiment may further contain other additives.
- a pigment may be blended.
- the pigment include titanium oxide (TiO 2 ), zinc oxide (ZnO), calcium carbonate (CaCO 3 ), barium sulfate (BaSO 4 ), alumina (Al 2 O 3 ), kaolin clay, carbon black, and iron oxide.
- Inorganic pigments such as (Fe 2 O 3 , Fe 3 O 4 ) and various colored pigments such as organic pigments can be used.
- an aqueous composition as a raw material for the resin film (A) is applied to the surface of the plated steel sheet to form a film.
- the application method is not particularly limited. For example, generally used roll coat, air spray, airless spray, immersion, etc. can be appropriately employed.
- any method such as hot air, induction heating, near infrared, far infrared, etc. may be used, or they may be used in combination.
- the heating temperature of the object to be coated is 50 to 250 ° C, preferably 70 to 220 ° C.
- the heating temperature is less than 50 ° C.
- the evaporation rate of water is slow and sufficient film forming properties cannot be obtained, and the corrosion resistance may be lowered.
- the temperature exceeds 250 ° C.
- the resin is thermally decomposed to deteriorate the corrosion resistance, and the appearance is deteriorated due to yellowing or the like.
- the drying time when heat drying after coating is preferably 1 second to 5 minutes.
- resin is hardened
- aqueous metal surface treatment agent further containing an organosilicon compound (W) containing a silane coupling agent (I) on the upper surface of the plating layer of the surface-treated steel sheet obtained in the first embodiment or the second embodiment.
- organosilicon compound (W) containing a silane coupling agent (I) on the upper surface of the plating layer of the surface-treated steel sheet obtained in the first embodiment or the second embodiment.
- One or more layers of a film obtained by coating and drying were formed.
- the organosilicon compound (W) which is an essential component of a water-system metal surface treating agent is a silane which contains one or more amino groups in a molecule
- the blending ratio of the silane coupling agent (I) and the silane coupling agent (J) is preferably 0.5 to 1.7 in terms of solid content mass ratio [(I) / (J)]. 7 to 1.7 is more preferable, and 0.9 to 1.1 is most preferable.
- the silane coupling agent (I) containing one or more amino groups in the molecule in the present embodiment is not particularly limited.
- 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane and the like can be exemplified, and examples of the silane coupling agent (J) containing one or more glycidyl groups in the molecule include 3-glycidide.
- Xylpropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and the like can be used.
- the method for producing the organosilicon compound (W) is not particularly limited, but the water adjusted to pH 4 is mixed with the silane coupling agent (I) and the silane coupling agent (J). Are sequentially added and stirred for a predetermined time.
- the formula —SiR 1 R 2 R 3 (wherein R 1 , R 2 and R 3 each independently represents an alkoxy group or a hydroxyl group, at least one of which is an alkoxy group) At least one hydrophilic function selected from two or more functional groups (a) represented by a group), a hydroxyl group (separate from those which can be included in the functional group (a)) and an amino group.
- the number of functional groups (a) containing one or more groups (b) is preferably 2 or more.
- the number of functional groups (a) is one, the adhesion to the surface of the metal material and the film-forming property are lowered, so that there is a possibility that the black residue resistance is lowered.
- the number of carbon atoms of the alkoxy group in the definition of R 1 , R 2 and R 3 of the functional group (a) is not particularly limited, but is preferably 1 to 6, more preferably 1 to 4, more preferably 1 or 2. Most preferably.
- the existing ratio of the functional group (b) may be one or more in one molecule.
- the average molecular weight of the organosilicon compound (W) is preferably 1000 to 10,000, and more preferably 1300 to 6000.
- the molecular weight here is not particularly limited, and either direct measurement by TOF-MS method or conversion measurement by chromatography method may be used.
- the average molecular weight is less than 1000, the water resistance of the formed film is remarkably lowered.
- the average molecular weight is greater than 10,000, it is difficult to stably dissolve or disperse the organosilicon compound.
- the coating according to the present embodiment preferably contains an inhibitor component having a fluoro metal complex compound having at least one selected from titanium and zirconium as an essential component.
- an inhibitor component having a fluoro metal complex compound having at least one selected from titanium and zirconium as an essential component.
- the corrosion inhibiting effect of the surface-treated steel sheet can be greatly improved.
- the solid content mass ratio [(N) / (W)] of the organosilicon compound (W) and the fluorometal complex compound (N) is 0.02 to 0.07 is preferable, 0.03 to 0.06 is more preferable, and 0.04 to 0.05 is most preferable.
- the solid content mass ratio [(Y) / (W)] of the organosilicon compound (W) and phosphoric acid (Y) is 0.03 to 0.12. Preferably, it is 0.05 to 0.12, more preferably 0.09 to 0.1. If the solid content mass ratio [(Y) / (W)] of the organosilicon compound (W) and phosphoric acid (Y) is less than 0.03, the addition effect is not exhibited, which is not preferable. On the other hand, if it exceeds 0.12, the film becomes extremely water-soluble, which is not preferable.
- the vanadium compound (Z) is preferably contained in the coating according to this embodiment.
- the solid content mass ratio [(Z) / (W)] of the organosilicon compound (W) and the vanadium compound is 0.05 to 0.17, It is more preferably 0.07 to 0.15, further preferably 0.09 to 0.14, and most preferably 0.11 to 0.13. If the solid content mass ratio [(Z) / (W)] of the organosilicon compound (W) and the vanadium compound is less than 0.05, the effect of addition is not exhibited, which is not preferable. On the other hand, if it exceeds 0.17, the stability is extremely lowered, which is not preferable.
- the vanadium compound (Z) is not particularly limited.
- a pentavalent vanadium compound is formed by an organic compound having at least one functional group selected from the group consisting of a hydroxyl group, a carbonyl group, a carboxyl group, a primary to tertiary amino group, an amide group, a phosphoric acid group, and a phosphonic acid group. Those reduced to tetravalent to divalent can also be used.
- solid content mass ratio [(Z) / (N)] of fluoro metal complex compound (N) and vanadium compound (Z) Is required to be 1.3 to 6.0, preferably 1.3 to 3.5, more preferably 2.5 to 3.3, and 2.8 to 3.0. Most preferred. If the mass ratio [(Z) / (N)] of the solid content of the fluoro compound (N) and the vanadium compound (Z) is less than 1.3, the effect of adding the vanadium compound (Z) is not preferable. On the other hand, if it exceeds 6.0, bath stability and black residue resistance are lowered, which is not preferable.
- the fluorometal complex compound (N) include titanium hydrofluoric acid (O) and zircon hydrofluoric acid (P).
- the film according to this embodiment preferably contains at least one metal component selected from Mg, Co, and W.
- the metal component can function as an inhibitor for elution, and corrosion of the surface-treated steel sheet can be suppressed.
- a cobalt compound (Co) is preferably at least one cobalt compound selected from the group consisting of cobalt sulfate, cobalt nitrate, and cobalt carbonate.
- the blending ratio is preferably such that the solid content mass ratio [(Co) / (W)] of the organosilicon compound (W) to the cobalt compound (Co) is 0.01 to 0.1, It is more desirably 02 to 0.07, and most desirably 0.03 to 0.05. If the solid content mass ratio [(Co) / (W)] of the organosilicon compound (W) and the cobalt compound (Co) is less than 0.01, the effect of adding the cobalt compound (Co) is not preferable. . Conversely, if it is larger than 0.1, the effect of improving the corrosion resistance cannot be obtained, which is not preferable.
- the surface-treated steel sheet according to the present embodiment is coated with the above-described aqueous metal surface treatment agent and dried at a temperature higher than 50 ° C. and lower than 250 ° C., and the film thickness after drying is 0.05 to 2.0 ⁇ m.
- the drying temperature is preferably higher than 50 ° C. and lower than 250 ° C., more preferably 70 ° C. to 150 ° C., and most preferably 100 ° C. to 140 ° C.
- An ultimate temperature of 50 ° C. or lower is not preferable because the solvent for the aqueous metal surface treatment agent does not completely evaporate. Conversely, when the temperature is 250 ° C.
- the film thickness is preferably 0.05 to 2.0 ⁇ m, more preferably 0.2 to 1.0 ⁇ m, and most preferably 0.3 to 0.6 ⁇ m. If the film thickness is less than 0.05 ⁇ m, the surface of the metal material cannot be covered, and the effect of improving corrosion resistance may not be obtained. On the other hand, if it is larger than 2.0 ⁇ m, the conductivity and the work adhesion are lowered, which is not preferable.
- the water-based metal surface treatment agent used in the present invention includes a leveling agent, a water-soluble solvent, a metal stabilizer, an etching inhibitor, a pH adjuster, and the like for improving the coating properties within a range that does not impair the effects of the present invention. It is possible to use.
- the film of the present invention may further contain polyethylene wax (Q) as a lubricant.
- Q polyethylene wax
- the lubricity of the coating is improved, workability improvement during press molding, prevention of wrinkles due to molds and handling, etc., and prevention of abrasion scratches during transportation of molded products and coils effective.
- the polyethylene wax (Q) is preferably contained in an amount of 0.1 to 10% by mass with respect to 100% by mass of the solid content of the film. If it is less than 0.1%, the effect of improving workability is small, and if it exceeds 10%, the corrosion resistance may be lowered.
- the particle diameter of these waxes is more preferably 0.1 to 5 ⁇ m. If it exceeds 5 ⁇ m, the distribution of the solidified wax may be non-uniform, or the resin-based film may fall off. Moreover, when it is less than 0.1 ⁇ m, the workability may be insufficient.
- the organosilicon compound (W) includes a silane coupling agent (I) containing at least one amino group in the molecule and a silane coupling agent (J) containing at least one glycidyl group in the molecule. It is obtained by blending at a solid content mass ratio [(I) / (J)].
- the blending ratio of the silane coupling agent (I) and the silane coupling agent (J) is preferably a ratio of 0.50 to 0.75 in terms of solid content mass ratio [(I) / (J)]. 0.50 to 0.65 is more preferable, and 0.55 to 0.65 is most preferable.
- the solid content mass ratio [(I) / (J)] is less than 0.50, the hydrophobicity and self-crosslinking property of the organosilicon compound (W) become strong, so that the stability of the treating agent is remarkably lowered.
- the solid content mass ratio [(I) / (J)] exceeds 0.75, the hydrophilicity of the organosilicon compound (W) becomes too strong, and the water resistance of the resulting film is significantly lowered.
- the silane coupling agent (I) containing one or more amino groups in the molecule is not particularly limited.
- 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, and the like can be used.
- silane coupling agent (J) having one or more glycidyl groups in the molecule for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, etc. can be used. .
- the method for producing the organosilicon compound (W) is not particularly limited.
- silane coupling agent (I) and silane coupling agent (J) are sequentially added to water adjusted to pH 4 and stirred for a predetermined time.
- the number of functional groups (a) in the organosilicon compound (W) is preferably 2 or more.
- the adhesion to the surface of the zinc-based plating material, the self-crosslinking property of the organosilicon compound (W), the binding property to the polyether polyurethane resin (K) described later May decrease and a film may not be sufficiently formed. In that case, the effect by forming a composite film on a plating layer is not acquired.
- the carbon number of the alkyl group and alkoxy group in the definition of R1, R2 and R3 of the functional group (a) is not particularly limited, but is preferably 1 to 6, more preferably 1 to 4. Or 2 is most preferred.
- a compound of formula —SiR 1 R 2 R 3 (wherein R 1 , R 2 and R 3 independently represent an alkoxy group or a hydroxyl group, and at least one of The proportion of the functional group (b) represented by (representing an alkoxy group) may be one or more in one molecule.
- the average molecular weight is preferably 1000 to 10,000, more preferably 1300 to 6000.
- the molecular weight here is not particularly limited, but can be measured using either direct measurement by TOF-MS method or conversion measurement by chromatography method.
- the average molecular weight determined by the same method is less than 1000, the water solubility of the organosilicon compound is increased, so that the water resistance of the formed film is significantly reduced.
- the average molecular weight exceeds 10,000, it becomes difficult to stably dissolve or disperse the organosilicon compound (W).
- polyether polyurethane resin (K) a structural unit (L1) represented by the following general formula [1], an alicyclic structure having 4 to 6 carbon atoms (L2), and an aromatic ring structure having 6 carbon atoms (L3) It is desirable to have at least one structural unit (L) selected from the group consisting of The structural unit (L1) acts as a reaction point with the organosilicon compound (W). Therefore, when the structural unit (L1) is included, the degree of crosslinking is increased, and the corrosion resistance and the detergent resistance are remarkably improved.
- polyester polyurethane resin is not preferable because it is hydrolyzed by acid or alkali.
- Polycarbonate polyurethane is not preferred because it is easy to form a hard and brittle film and is inferior in adhesion during processing and corrosion resistance of the processed part.
- R9, R10 and R11 in the structural unit (L1) are not particularly limited, but R9 is a monovalent organic residue selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group and an aralkyl group, R10 R11 is preferably a functional group independently selected from the group consisting of an alkoxyl group, an acyloxy group, a hydroxyl group and a halogen atom, R9 is most preferably an alkyl group, and R10 and R11 are hydroxyl groups. Is most preferred.
- the number m of ethylene chains in the structural unit (L1) is not particularly limited, but is preferably 1 to 5, and most preferably 2 or 3.
- the polyether polyurethane resin (K) according to this embodiment is not particularly limited.
- Polyurethane a urethane resin that is a polycondensation product of a polyether polyol and an aliphatic, alicyclic or aromatic polyisocyanate, and obtained by using a polyol having a (substituted) amino group as a part of the polyol to be used.
- polyether polyols ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, saccharose, methylene glycol as initiators
- a compound obtained by addition polymerization of one or more compounds such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrohydrofuran, and cyclohexylene using glycerin can be used.
- tolylene diisocyanate diphenylmethane diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate and the like can be used.
- the structural unit (L1) is a primary amine at the stage where the skeleton end of the polyether polyurethane resin (K) is an isocyanate. It can be obtained by reacting the terminal isocyanate of the polyether polyurethane resin (K) with a primary amine using an organic compound having both trialkoxysilane. Examples of organic compounds having both primary amines and trialkoxysilanes include 3-aminopropyltriethoxysilane and 3-aminopropyltrimethoxysilane.
- the composite film according to this embodiment preferably contains a cationic phenol resin (M).
- the cationic phenol resin (M) desirably has a bisphenol A skeleton.
- the above-mentioned cationic phenol resin (M) is not particularly limited, but is a novolak type phenol resin having bisphenol A condensed with bisphenol A as a main skeleton structure, and is not only a linear compound but also three-dimensional. A compound in a condensed form may be included.
- the cationic property of the cationic phenol resin (M) is not particularly limited.
- —CH 2 NHCH 2 OH and / or —CH 2 NHCH 2 OC 2 H 5 to which hydrogen atoms bonded to carbon atoms constituting the aromatic ring are lost and added are sulfate ions.
- Those expressed by neutralization with inorganic acid ions such as phosphate ions or organic acid ions such as acetate ions and formate ions to form quaternary ammonium salts are preferred.
- the acid to be neutralized is most preferably phosphoric acid.
- the composite coating according to this embodiment preferably contains an inhibitor component (d) containing a fluorometal complex compound (N) having at least one selected from titanium and zirconium as an essential component.
- an inhibitor component (d) containing a fluorometal complex compound (N) having at least one selected from titanium and zirconium as an essential component By containing such an inhibitor component, the corrosion inhibiting effect of the surface-treated steel sheet is greatly improved.
- the fluoro metal complex compound (N) having titanium is, for example, titanium hydrofluoric acid (O)
- the fluoro metal complex compound (N) having zirconium is, for example, zircon hydrofluoric acid (P).
- the inhibitor component (d) contains both titanium hydrofluoric acid (O) and zircon hydrofluoric acid (P)
- the amount of Ti contained in titanium hydrofluoric acid (O) with respect to the blending ratio thereof The metal component mass ratio [(M o ) / (M p )] of the amount of Zr (M p ) contained in (M o ) and zircon hydrofluoric acid (P) is in the range of 0.5 to 0.8. It is preferably 0.6 to 0.8, more preferably 0.6 to 0.7.
- phosphoric acid (Y) is not particularly limited.
- the elution of phosphoric acid can be controlled, and the corrosion resistance retention time can be extended.
- phosphoric acid or magnesium biphosphate is preferable because a greater effect of improving corrosion resistance can be obtained. More preferably, phosphoric acid and magnesium biphosphate are used in combination.
- the composite film according to this embodiment preferably contains a vanadium compound (Z).
- the vanadium compound (Z) is not particularly limited.
- vanadium of compounds such as vanadium pentoxide [V 2 O 5 ], metavanadate [HVO 3 ], ammonium metavanadate [NH 4 VO 3 ], sodium metavanadate [NaVO 3 ], vanadium oxytrichloride [VOCl 3 ], and the like.
- V an alcohol, which was reduced to vanadium (IV) with a reducing agent such as organic acids, vanadium dioxide [VO 2], vanadium oxy acetylacetonate [VO (C 5 H 7 O 2) 2], Vanadium (IV) -containing compounds such as vanadium oxysulfate [VOSO 4 ], vanadium acetylacetonate [V (C 5 H 7 O 2 ) 3 ], vanadium trioxide [V 2 O 3 ], vanadium trichloride [VCl 3 ]
- adium (III) of a compound such as Oxidized ones may be used.
- the aqueous metal surface treatment agent described above preferably contains a polyethylene wax (Q) described later in addition to the film-forming component (c) and the inhibitor component (d), and is made of an aqueous medium and preferably has a pH of 4 to 6. .
- the polyethylene wax (Q) is not particularly limited, but the number average particle diameter is preferably 0.1 to 4.0 ⁇ m, more preferably 0.2 to 3.0 ⁇ m, most preferably 0.3 to 2.5 ⁇ m. preferable. If the number average particle diameter is less than 0.1 ⁇ m, the amount of polyethylene wax exposed on the surface of the film is reduced, and the friction coefficient is increased, which is not preferable. On the other hand, when the thickness exceeds 4.0 ⁇ m, the polyethylene wax becomes remarkably large with respect to the film thickness, and the wax is not held in the film and falls off by slight sliding, so that the effect of reducing the friction coefficient is not exhibited.
- the density of the polyethylene wax (Q) is preferably 0.90 ⁇ 0.96g / m 2, more preferably 0.90 ⁇ 0.94g / m 2, most preferably 0.91 ⁇ 0.93g / m 2 .
- the density is less than 0.90 g / m 2 , the softening point and hardness are lowered, the film itself is softened, and the workability is lowered, which is not preferable.
- it exceeds 0.96 g / m 2 the static friction coefficient becomes too low, so that roll slip and coil crushing occur and the operability is lowered.
- the pH of the above-mentioned aqueous metal surface treatment agent is preferably 4-6.
- the pH is less than 4, the material is excessively etched, the material is dissolved in the drug, and the stability of the drug is lowered.
- it exceeds 6 the solubility of the above-mentioned inhibitor component (d) is remarkably lowered, and the stability is lowered.
- the organosilicon compound (W) and the organic resin (GB) polyether polyurethane resin (K) are used.
- the solid content mass ratio [(GB ⁇ K) / (W)] of (K) is preferably 0.33 to 0.90, more preferably 0.33 to 0.80, Most preferred is ⁇ 0.70. If the solid content mass ratio [(GB ⁇ K) / (W)] is less than 0.33, the barrier property of the film-forming component (c) is lowered, which is not preferable. On the other hand, when it exceeds 0.90, the adhesiveness with the raw material due to the organosilicon compound (W) is remarkably lowered, so that various performances are lowered.
- the organic resin (GB) polyether polyurethane resin (K) and the cationic phenol resin (M) to the solid content are used.
- the solid content mass ratio [(M) / (GB ⁇ K)] of the phenol resin (M) is preferably 0.010 to 0.030, more preferably 0.010 to 0.025, Most preferably, it is from 010 to 0.022. If this mass ratio [(M) / (GB ⁇ E)] is less than 0.010, the addition effect of the cationic phenol resin (M) is not manifested, and the corrosion resistance and solvent resistance are lowered. If it exceeds 0.030, the film is colored slightly yellow with a phenolic resin, and a remarkable yellowing occurs in a high-humidity environment or an ultraviolet exposure environment, which is not preferable.
- Total metal component mass ratio [(M o + M p ) / (Si W )] is preferably 0.08 to 0.20, more preferably 0.08 to 0.17, Most preferably, it is from 0.08 to 0.15.
- this metal component mass ratio [(M o + M p ) / (Si W )] is less than 0.08, titanium and zirconium produced from titanium hydrofluoric acid and zircon hydrofluoric acid or their The production amount of the compound film is reduced, and the corrosion resistance is lowered.
- it exceeds 0.20 the surface coverage of the material by the film of titanium and zirconium or its oxide increases, and the number of reaction points with the material of the organosilicon compound (W) decreases, so that the organosilicon compound (W ) Reduces the adhesion-imparting effect. In that case, the overall effect of the composite film formation is reduced.
- the solid content mass ratio [(Y) / (W)] of the organosilicon compound (W) and phosphoric acid (Y) is preferably 0.020 to 0.110, preferably 0.030 to 0. 110 is more preferable, and 0.040 to 0.100 is most preferable.
- this solid content mass ratio [(Y) / (W)] is less than 0.020, the effects of improving the alkali resistance and corrosion resistance, which are the effects of adding phosphoric acid (Y), are not exhibited.
- it exceeds 0.110 the drug stability decreases.
- the solid content mass ratio [(Z) / (W)] of the organosilicon compound (W) and the vanadium compound (Z) is preferably 0.020 to 0.060, and preferably 0.025 to 0. 0.060 is more preferable, and 0.030 to 0.055 is most preferable.
- the solid content mass ratio [(Z) / (W)] is less than 0.020, the inhibitor effect due to the vanadium compound (Z) cannot be obtained.
- it exceeds 0.060 the film tends to be yellow-colored at high humidity due to the complex compound of the vanadium compound and the organic substance contained in the film.
- the polyether polyurethane resin (K) is related to the compounding ratio of the organosilicon compound (W) and the polyether polyurethane resin (K).
- structural units contained in) (L1) and from the Si (Si K), organic silicon compound (W) from the Si (Si W) and structural units contained in the polyether polyurethane resin (K) (L) derived from Si weight ratio of the sum of (Si K) [(Si K ) / (Si W + Si K)] is preferably from 0.015 to 0.045, more preferably 0.015 to 0.040, 0 20 to 0.040 is most preferred.
- the dispersion stability of the polyether polyurethane resin (K) is improved, the reaction between the organosilicon compound (W) with the functional group (a) and the reaction between the organosilicon compound (W) and the material occur in a well-balanced manner. Therefore, sufficient adhesion can be obtained.
- the mass ratio [(Q) / (W)] of the organosilicon compound (W) and the solid content of the polyethylene wax (Q) is preferably 0.05 to 0.30, and 0.07 Is more preferably from ⁇ 0.30, most preferably from 0.10 to 0.25.
- the mass ratio [(Q) / (W)] is less than 0.05, sufficient lubricity is not exhibited.
- it is 0.30 or more, the continuity of the coating is inhibited by the polyethylene wax, the coating tends to break, and the corrosion resistance may be lowered.
- the composite film according to this embodiment preferably includes a color pigment containing carbon black (P1).
- the addition amount of the color pigment is preferably 5 to 35% by mass. By setting it within the range, the emissivity of the obtained surface-treated steel sheet can be increased and blackening can be achieved. If the addition amount is less than 5% by mass, the emissivity is not sufficiently improved, which is not preferable. Moreover, when the addition amount is more than 35% by mass, it is not preferable because the storage stability and corrosion resistance of the metal surface treatment agent are deteriorated.
- the composite film according to this embodiment preferably contains at least one metal component selected from Mg, Co, and W.
- these metal components can function as an inhibitor for elution, and the corrosion resistance of the surface-treated steel sheet can be improved.
- a cobalt compound is preferably at least one cobalt compound selected from the group consisting of cobalt sulfate, cobalt nitrate, and cobalt carbonate.
- the above-described aqueous metal surface treatment agent is applied and dried at an ultimate temperature of 50 to 250 ° C.
- the drying temperature is preferably 50 ° C. to 250 ° C. at the ultimate temperature, more preferably 70 ° C. to 150 ° C., and most preferably 100 ° C. to 140 ° C.
- the reached temperature is less than 50 ° C.
- the solvent of the aqueous metal surface treatment agent is not completely volatilized.
- it exceeds 250 ° C. a part of the organic chain of the film formed with the aqueous metal surface treatment agent is decomposed.
- the film formed on the plating layer is a composite film containing the organic silicon compound (W) and the organic resin (GB), the film can be formed thick. As a result, the corrosion resistance can be greatly improved. Moreover, even if the film is thickened, the composite film can be maintained without deteriorating the conductivity. Furthermore, conventionally, it has been considered that the formation of such a composite film on the galvanized layer may deteriorate the work adhesion, but the target for forming the composite film is zinc as described above. By using a plating layer containing vanadium, excellent process adhesion can be ensured.
- the film thickness of the composite film is preferably 0.3 to 4.0 ⁇ m, more preferably 0.5 to 3.0 ⁇ m, and 1.0 to 2 Most preferably, it is 0.0 ⁇ m. If the film thickness of the composite film is less than 0.3 ⁇ m, the surface of the steel sheet cannot be coated, and the effect of improving corrosion resistance cannot be obtained. On the other hand, if it exceeds 4.0 ⁇ m, the electrical conductivity and the adhesiveness deteriorate.
- the aqueous metal surface treatment agent used in the present embodiment is a leveling agent, a water-soluble solvent, a metal stabilizer, and an etching inhibitor for improving coating properties within a range that does not impair the effect of the composite film according to the present embodiment. It is possible to use an agent or the like.
- leveling agents include nonionic or cationic surfactants such as polyethylene oxide or polypropylene oxide adducts and acetylene glycol compounds.
- water-soluble solvents include alcohols such as ethanol, isopropyl alcohol, t-butyl alcohol, and propylene glycol.
- Cellosolves such as ethylene glycol monobutyl ether and ethylene glycol monoethyl ether, esters such as ethyl acetate and butyl acetate, and ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone.
- the metal stabilizer include chelate compounds such as EDTA and DTPA
- the etching inhibitor include amine compounds such as ethylenediamine, triethylenepentamine, guanidine, and pyrimidine. In particular, those having two or more amino groups in one molecule are more preferable because they are effective as a metal stabilizer.
- FIG. 7 is an enlarged cross-sectional view for explaining an example of the surface-treated steel sheet according to the fifth embodiment.
- the surface-treated steel sheet according to this embodiment includes a plating layer 73 formed by the method of Embodiment 1 or 2 on both surfaces of the steel sheet 71, and a single organic resin film formed as an upper layer of the plating layer 73. 72.
- the organic resin film 72 may be referred to as an organic resin film according to the present embodiment.
- an L * value of 10 to 35 is preferable because it can be used for various purposes as a material having a black appearance.
- the L * value exceeds 35, it is difficult to use as a material having a black appearance.
- the coating adhesion between the plating layer 73 and the organic resin film 72 is sufficient by increasing the thickness of the organic resin film or increasing the pigment concentration in the film. May not be obtained and corrosion resistance may be reduced. Therefore, the surface-treated steel sheet according to the present embodiment desirably has an L * value representing lightness of 10 to 35.
- the surface-treated steel sheet of this embodiment preferably has a 60 degree gloss value representing gloss of 50 or less.
- the gloss value of the surface-treated steel sheet is 50 or less, it can be used for various applications as a material having a black appearance.
- the gloss value exceeds 50, scratches at the time of handling or press working become conspicuous and may not be used as a designable material.
- the organic resin film 72 according to this embodiment will be described.
- the organic resin film 72 of the present embodiment is made of an organic resin containing a polyester resin (A1) containing a sulfonic acid group, a curing agent (B1), and a colorant (C1) that is a color pigment containing carbon black,
- a black water-based paint containing a polyester resin (A1) containing a sulfonic acid group, a curing agent (B1), and a colorant (C1) is applied and cured by baking and drying.
- the thickness of the organic resin film 72 is preferably as thin as possible within a range where a predetermined appearance with sufficiently low gloss and L * value can be obtained so that excellent paint adhesion can be obtained. Specifically, it is preferably 1 to 10 ⁇ m, more preferably 2 to 5 ⁇ m. If the thickness of the organic resin film 72 is less than 1 ⁇ m, a predetermined appearance with sufficiently low gloss and L * value may not be obtained, or fine unevenness on the plating surface may not be concealed, resulting in a skate-like appearance. On the other hand, when the thickness of the organic resin film 72 exceeds 10 ⁇ m, there is a possibility that problems such as a decrease in coating adhesion and a tendency to cause cracks during film formation may occur.
- the thickness of the organic resin film 72 can be measured by using a cross-sectional observation, an electromagnetic film thickness meter, or the like.
- the mass of the coating film adhered per unit area may be calculated by dividing by the specific gravity of the coating film or the specific gravity after drying of the coating material.
- the coating mass is the mass difference before and after the formation of the coating film, the mass difference before and after peeling the coating film, or the X-ray fluorescence analysis of the coating film, and the content in the coating film is known in advance. What is necessary is just to select from existing methods appropriately, such as measuring the abundance of an element.
- the specific gravity of the paint film or the specific gravity after drying of the paint is measured by measuring the volume and mass of the isolated paint film, measuring the volume and mass after taking an appropriate amount of paint in a container and drying it, or paint film. What is necessary is just to select suitably from the existing method, such as calculating from the compounding quantity of a structural component, and the known specific gravity of each component.
- polyester resin containing sulfonic acid groups (A1) The polyester resin itself is hydrophobic, but exhibits high hydrophilicity when the polyester resin contains a sulfonic acid group. For this reason, the polyester resin (A1) containing a sulfonic acid group can be stably dissolved or dispersed in the water-based paint. In addition, the polyester resin (A1) containing a sulfonic acid group improves the compatibility between carbon black having a hydrophobic surface and water, and plays an important role in uniformly and stably dispersing the carbon black in the water-based paint. Is responsible. This is due to the effect obtained by orienting the hydrophobic polyester resin main skeleton to carbon black.
- the surface-treated steel sheet according to the present embodiment carbon black is uniformly dispersed in the organic resin film 72, and even if the thickness of the organic resin film 72 is small, it has extremely excellent design properties (colorability and concealment). is doing.
- the water-based paint for forming the organic resin film 72 of this embodiment may not contain a surface hydrophilization treatment or a surfactant in order to improve the dispersibility of carbon black. Therefore, there is no concern that the corrosion resistance of the organic resin film 72 is lowered by the surface hydrophilization treatment or the surfactant.
- the sulfonic acid group contained in the polyester resin (A1) has an effect of improving the adhesion with the plating layer 73 disposed in contact with the organic resin film 72. For this reason, the surface-treated steel sheet of this embodiment is extremely excellent in the adhesion between the organic resin film 72 and the plating layer 73.
- the polyester resin (A1) containing a sulfonic acid group is not particularly limited as long as it contains a sulfonic acid group.
- a sulfonic acid group For example, what was obtained by melt-dispersing in water what was obtained by polycondensing the polyester raw material which consists of a polycarboxylic acid component and a polyol component can be used.
- the polycarboxylic acid component is not particularly limited, and examples thereof include terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, azelaic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, dimer acid, trimellitic anhydride, pyromellitic anhydride and the like. These can use 1 type (s) or 2 or more types arbitrarily.
- the polyol component is not particularly limited.
- the sulfonic acid group contained in the polyester resin (A1) refers to a functional group represented by —SO 3 H, and may be neutralized with alkali metals, amines containing ammonia, or the like.
- the neutralized sulfonic acid group may be an already neutralized sulfonic acid group incorporated into the polyester resin, or may be neutralized after the sulfonic acid group is incorporated into the resin. Good.
- sulfonic acid metal bases neutralized with alkali metals such as Li, Na, and K exhibit higher hydrophilicity, and thus are suitable for improving the dispersibility of carbon black and obtaining high designability.
- the sulfonic acid group is preferably a sulfonic acid metal base neutralized with an alkali metal, and most preferably a sulfonic acid Na base.
- the polyester resin (A1) containing a sulfonic acid group preferably contains a urethane bond in the skeleton.
- the method for introducing a urethane bond into the skeleton of the polyester resin (A1) containing a sulfonic acid group is not particularly limited.
- it can be obtained by reacting a hydroxyl group contained in a polyester resin with a diisocyanate compound such as hexamethylene diisocyanate, isophorone diisocyanate, or tolylene diisocyanate.
- the organic resin film 72 preferably further contains an acrylic resin (A3) in addition to the polyester resin (A1) containing a sulfonic acid group.
- an acrylic resin (A3) in addition to the polyester resin (A1) containing a sulfonic acid group.
- the kind of acrylic resin (A3) is not particularly limited.
- a polymerization initiator in an aqueous solution of unsaturated monomers such as styrene, alkyl (meth) acrylates, (meth) acrylic acid, hydroxyalkyl (meth) acrylates, alkoxysilane (meth) acrylates, etc.
- unsaturated monomers such as styrene, alkyl (meth) acrylates, (meth) acrylic acid, hydroxyalkyl (meth) acrylates, alkoxysilane (meth) acrylates, etc.
- radical polymerization can be used.
- persulfates such as potassium persulfate and ammonium persulfate
- azo compounds such as azobis cyano valeric acid and azo bisiso ptyronitrile, etc. can be used.
- the content thereof is preferably 0.5 to 10% by mass with respect to 100% by mass of the polyester resin (A1) containing a sulfonic acid group.
- the amount is less than 0.5% by mass, the effect of containing the acrylic resin (A3) may not be sufficiently obtained.
- the amount exceeds 10% by mass the corrosion resistance and workability are not included. May decrease.
- the organic resin film 72 preferably further contains a polyurethane resin (A2) containing a carboxyl group.
- a polyurethane resin (A2) containing a carboxyl group By further containing the polyurethane resin (A2) containing a carboxyl group, the corrosion resistance and the adhesion between the organic resin film 72 and the plating layer 73 can be improved.
- the kind of polyurethane resin (A2) containing a carboxyl group is not particularly limited as long as it contains a carboxyl group.
- polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, 1,6-hexanediol, neopentyl glycol, triethylene glycol, bisphenol hydroxypropyl ether, glycerin, trimethylol ethane, trimethylol propane, and hexamethylene diisocyanate.
- a compound obtained by reacting with a diisocyanate compound such as isophorone diisocyanate or tolylene diisocyanate, extending the chain with diamine or the like, and dispersing in water can be used.
- Chain extension with diamines can increase the molecular weight of the resin and generate urea groups from the reaction of isocyanate groups with amino groups.
- a urea group having a high cohesive energy in the resin By including a urea group having a high cohesive energy in the resin, the cohesive strength of the coating film can be further increased, and the corrosion resistance and scratch resistance of the organic resin film 72 can be further increased.
- the content of the polyurethane resin (A2) is preferably 5 to 100% by mass with respect to 100% by mass of the polyester resin (A1) containing a sulfonic acid group.
- the content is less than 5% by mass, the effect of containing the polyurethane resin (A2) may not be sufficiently obtained.
- the content is more than 100% by mass, the workability may be reduced as compared with the case where it is not contained. is there.
- the organic resin film 72 of this embodiment is obtained by curing a polyester resin having high ductility and excellent workability with a curing agent (B1). Therefore, the deterioration of the film forming property due to the inclusion of the colorant (C1) containing carbon black is suppressed and becomes dense. As a result, the organic resin film 72 of this embodiment is excellent in moisture resistance, corrosion resistance, scratch resistance, and chemical resistance.
- curing agent (B1) will not be specifically limited if the polyester resin (A1) containing a sulfonic acid group is hardened.
- melamine resin or polyisocyanate compound for example, melamine resin or polyisocyanate compound.
- a melamine resin a resin obtained by etherifying a part or all of methylol groups of a product obtained by condensing melamine and formaldehyde with a lower alcohol such as methanol, ethanol, or butanol can be used.
- the content of the melamine resin is preferably 30 to 100% by mass in the curing agent (B1). If it is less than 30% by mass, the effect of containing a melamine resin may not be sufficiently obtained.
- the polyisocyanate compound is not particularly limited.
- the blocked product include a blocked product of hexamethylene diisocyanate, a blocked product of isophorone diisocyanate, a blocked product of xylylene diisocyanate, and a blocked product of tolylene diisocyanate, which are blocked products of the polyisocyanate compound.
- These curing agents may be used alone or in combination of two or more.
- the content of the curing agent (B1) is 5 to 35 masses with respect to 100 mass% of the total organic resin (when the organic resin film 72 includes a resin other than the polyester resin (A1)). % Is preferred. If it is less than 5% by mass, the bake-curing may be insufficient and the effect of improving the corrosion resistance may not be obtained, or the moisture resistance, scratch resistance, and chemical resistance may be lowered. On the other hand, if it exceeds 35% by mass, bake hardening becomes excessive, and the corrosion resistance and workability may be lowered.
- the colorant (C1) includes a color pigment containing carbon black. Carbon black is inexpensive and has high hiding properties. In addition to carbon black, colored inorganic pigments such as titanium dioxide, carbon black, graphite and iron oxide, colored organic pigments such as phthalocyanine blue, phthalocyanine green, quinacridone, azo orange, azo yellow, azo red, aluminum powder, dioxide Bright materials such as titanium-coated mica powder and titanium dioxide-coated glass powder may also be included. Although there is no restriction
- the carbon black preferably has a number average particle size of 20 to 300 nm in a state dispersed in the coating film in consideration of the design properties (colorability, hiding properties) and corrosion resistance of the organic resin coating 72.
- the absolute amount of carbon black is the content of carbon black contained in the organic resin film 72 (X % By mass) and the coating thickness (Y ⁇ m).
- the product of X and Y which is the absolute amount of carbon black contained in the organic resin film 72, is preferably 18 or more. . If the product of X and Y is less than 18, the designability (colorability and concealment) may not be sufficiently improved.
- the organic resin film 72 preferably further contains silica (D1) in order to improve the corrosion resistance and scratch resistance.
- Silica (D1) is not particularly limited, but silica fine particles such as colloidal silica and fumed silica having a primary particle diameter of 5 to 50 nm are preferable. From the viewpoint of corrosion resistance and workability, the silica fine particles are preferably dispersed in the organic resin film 72 while maintaining the primary particle diameter (number average particle diameter) of 5 to 50 nm.
- the content of silica (D1) is preferably 5 to 30% by mass in the organic resin film 72. If it is less than 5% by mass, the effect of containing silica (D1) may not be sufficiently obtained, and if it exceeds 30% by mass, moisture resistance, workability and the like may be deteriorated.
- the organic resin film 72 preferably further contains a lubricant (E1).
- a lubricant (E1) By including the lubricant (E1), the scratch resistance is improved.
- the lubricant (E1) is not particularly limited, and a known lubricant can be used, but it is more preferable to use at least one selected from a fluororesin system and a polyolefin resin system.
- fluororesin systems include polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluorobroylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), and polytarolotrifluoro.
- Ethylene PCTFE
- PVDF polyvinylidene fluoride
- PVF polyvinyl fluoride
- ETFE ethylene-tetrafluoroethylene copolymer
- ECTFE ethylene-chlorotrifluoroethylene copolymer
- the polyolefin resin system is not particularly limited.
- hydrocarbon waxes such as paraffin, microcrystalline, and polyethylene, and derivatives thereof can be used.
- a polyethylene resin is more preferable.
- the derivative is not particularly limited, and for example, carboxylated polyolefin, chlorinated polyolefin and the like can be used. Of these, one type may be used alone, or two or more types may be used in combination.
- a polyethylene resin it is preferable that the organic resin film 72 is dispersed with particles having a number average particle diameter of 0.5 to 2 ⁇ m from the viewpoint of corrosion resistance and scratch resistance.
- the content of the lubricant (E1) is preferably 0.5 to 10% by mass in the organic resin film 72. If the amount is less than 0.5% by mass, the effect of containing the lubricant (E) may not be sufficiently obtained. If the amount exceeds 10% by mass, the effect of improving the corrosion resistance may not be obtained. Workability may be reduced.
- the surface-treated steel sheet according to this embodiment is excellent in corrosion resistance and paint adhesion, has a sufficiently low gloss, has a sufficiently low L * value, has excellent adhesion and scratch resistance during processing, and is beautiful. Appearance.
- the surface-treated steel sheet according to this embodiment has an appearance with sufficiently suppressed gloss, a film containing a matting agent is formed on the surface of the organic resin film 72, or a matting agent is applied to the organic resin film 72. There is no need to contain it, and low gloss can be realized with a thin film.
- the adhesion between the organic resin film 72 and the plating layer 73 is excellent, it is not necessary to provide a base layer between the organic resin film 72 and the plating layer 73, and it can be easily manufactured.
- the surface-treated steel sheet provided with one layer of the organic resin film 72 has been described as an example.
- the organic resin film 72 may be one layer or more, and may be two layers or more.
- the total thickness of the organic resin films is preferably 1 to 10 ⁇ m.
- the organic resin film according to the present embodiment forms a black water-based paint including a polyester resin (A1) containing a sulfonic acid group, a curing agent (B1), and carbon black as a colorant (C1). It is obtained by applying to the steel plate 71 and baking and drying.
- the method for producing the water-based paint is not particularly limited.
- a polyester resin (A1) containing a sulfonic acid group that is a component of the organic resin film 72 in water, a curing agent (B1), and carbon black as a colorant (C1) can be added and stirred with a disper to dissolve or disperse.
- the method for applying the water-based paint is not particularly limited, and for example, known roll coating, curtain coating, die coating, spray coating, bar coating, dipping, electrostatic coating, and the like can be appropriately used.
- the baking and drying method is not particularly limited, and the steel plate 71 on which the plating layer 73 is formed is heated in advance, the steel plate 71 on which the plating layer 73 is formed after application of the water-based paint, or a combination thereof. And may be dried.
- the baking drying temperature is preferably 150 to 250 ° C., more preferably 160 to 230 ° C., and most preferably 180 to 220 ° C. in terms of ultimate temperature. If the ultimate temperature is less than 150 ° C., the bake hardening is insufficient, and the effect of improving the corrosion resistance may not be sufficiently obtained. On the other hand, when it exceeds 250 ° C., the bake hardening becomes excessive, and the effect of improving the corrosion resistance may not be obtained or the workability may be deteriorated.
- the baking and drying time is preferably 1 to 60 seconds, and more preferably 3 to 20 seconds. If it is less than 1 second, bake hardening may be insufficient, and if it exceeds 60 seconds, the productivity is lowered.
- FIG. 8A is an enlarged cross-sectional view for explaining an example of the surface-treated steel sheet according to the sixth embodiment.
- a surface-treated steel plate 81a shown in FIG. 8A is manufactured by the method of the first or second embodiment, and includes the colored pigment layer 16 formed on and in contact with the plated layer 82 on both surfaces of the surface-treated steel plate 81 having the plated layer.
- a colored coating layer is formed.
- FIG. 8A is an enlarged cross-sectional view for explaining an example of the surface-treated steel sheet according to the sixth embodiment.
- a surface-treated steel plate 81a shown in FIG. 8A is manufactured by the method of the first or second embodiment, and includes the colored pigment layer 16 formed on and in contact with the plated layer 82 on both surfaces of the surface-treated steel plate 81 having the plated layer.
- a colored coating layer is formed.
- the case where the plating layer 82 and the colored coating layer (colored pigment layer 16) are formed on both surfaces of the steel sheet 81 will be described as an example. Moreover, the plating layer 82 and the colored coating film layer may be formed. In addition, it is preferable that the same layer is formed on one surface and the other surface of the steel plate 81 because it is easy to manufacture, but separate layers may be formed.
- the colored pigment layer 16 includes a pigment and a resin, and does not include a rust preventive agent.
- the adhesion between the plating layer 82 and the colored coating film layer is excellent, so that the surface-treated steel sheet 81a is sufficiently high. Corrosion resistance can be secured.
- the color pigment layer 16 contains a rust preventive agent such as a rust preventive pigment, the color pigment layer 16 becomes brittle and the workability of the surface-treated steel sheet 81a is lowered.
- excellent processability can be ensured as compared with the case where a rust preventive agent such as a rust preventive pigment is contained.
- pigment used in the colored pigment layer 16 one or more generally known pigments can be used and are not particularly limited.
- titanium oxide which is a white pigment
- carbon black which is a black pigment, or the like can be used.
- the resin used for the colored pigment layer 16 one or more kinds of generally known resins such as polyester resin, urethane resin, acrylic resin, epoxy resin, fluorine resin, and silicon resin can be used.
- the curing agent for forming the color pigment layer 16 generally known coating curing agents such as melamine and isocyanate can be used.
- the resin used for the colored pigment layer 16 when a polyester resin cross-linked with melamine or a polyester resin cross-linked with isocyanate is used, more excellent processability is obtained, which is more preferable. .
- the resin used for the color pigment layer 16 may be a polyester resin crosslinked with a melamine curing agent or a polyester resin crosslinked with an isocyanate curing agent. Sufficient coating adhesion can be ensured, and the colored pigment layer 16 does not peel off even when severe processing such as binding or bending is performed.
- the plating layer 82 has excellent paint adhesion to the coating film formed thereon. Therefore, the effect of improving the corrosion resistance by forming the color pigment layer 16 on the plating layer 82 is effectively exhibited. Therefore, the thickness of the color pigment layer 16 can be reduced as compared with the conventional case.
- the surface-treated steel plate 81a of this embodiment has excellent adhesion between the plating layer 82 and the color pigment layer 16, a chemical conversion treatment layer or a primer coating layer is provided between the plating layer 82 and the color pigment layer 16. High corrosion resistance and workability can be ensured without forming.
- the colored pigment layer 16 (colored coating film layer) may be formed in contact with the plating layer 82 as in the surface-treated steel plate 81a shown in FIG. 8A.
- the manufacturing process can be simplified and the manufacturing process can be performed at a low cost.
- the process of forming a colored coating layer composed of the colored pigment layer 16 in contact with the plating layer 82 will be described.
- the colored pigment layer 16 can be formed by applying a paint containing a pigment and a resin on the plating layer 82 of the surface-treated steel sheet obtained by the method of the first embodiment or the second embodiment.
- FIG. 8B is an enlarged cross-sectional view for explaining another example of the surface-treated steel sheet according to the sixth embodiment.
- the colored coating layer 15 includes a primer coating layer 14 formed between the plating layer 82 and the colored pigment layer 16.
- the primer coating layer 14 is formed between the plating layer 82 and the color pigment layer 16, and thus even better corrosion resistance can be obtained.
- the primer coating layer 14 shown in FIG. 8B includes a resin and a rust inhibitor.
- the resin used for the primer coating 14 include the same resins that can be used for the colored coating layer 16.
- the resin used for the primer coating film 14 and the resin used for the colored coating film layer 16 may be the same or different.
- the rust preventive agent contained in the primer coating layer 14 is more preferably a non-chromium type containing no hexavalent chromium from the viewpoint of environmental friendliness.
- the non-chromium-based rust preventive agent preferably contains one or both of Si and P. In this case, even better corrosion resistance can be obtained.
- the rust preventive agent may contain a rust preventive pigment, may not contain a rust preventive pigment, or may be only a rust preventive pigment.
- Examples of the rust inhibitor containing one or both of Si and P include, for example, silica-based rust preventive pigments, zinc phosphate-based rust preventive pigments, aluminum phosphate-based rust preventive pigments, and magnesium phosphate-based rust preventive pigments.
- Examples of commercially available rust preventives include “SHIELDEX” (registered trademark) series, which is a calcium-adsorbed silica manufactured by GRACE, and “K-WHITE” (registered trademark) series, which is aluminum trihydrogen phosphate, manufactured by Teika. Can be used.
- the content of the rust inhibitor in the primer coating layer 14 is preferably 5 to 30% by mass in terms of solid content.
- the content of the rust preventive pigment in the primer coating layer 14 is within the above range, further excellent corrosion resistance can be obtained while ensuring processability.
- the rust preventive agent is a rust preventive pigment, if the content of the rust preventive agent in the primer coating layer 14 is less than 5% by mass, the effect of including the rust preventive agent may not be sufficiently exhibited. .
- the primer coating layer 14 becomes brittle, and when the forming process is performed, the coating film of the processed part is easily peeled off, and the workability of the surface-treated steel sheet is improved There is a risk of hindrance.
- the primer coating layer 14 is formed on the surface-treated steel plate 81 having a plating layer on the plating layer 82.
- the primer coating layer 14 is formed by applying a coating containing a resin and a rust inhibitor on the plating layer 82 to form a coating, drying, baking, and water cooling.
- the colored pigment layer 16 is formed on both surfaces of the steel plate 81 on which the plating layer 82 and the primer coating layer 14 are formed in the same manner as the surface-treated steel plate 81a shown in FIG. 8A. As a result, a colored coating layer 15 composed of the colored pigment layer 16 and the primer coating layer 14 is formed.
- the surface-treated steel sheet 81b of this embodiment has excellent coating adhesion to the coating film formed on the plating layer 82, the primer coating layer of the plating layer 82 and the colored coating layer 15 High corrosion resistance and workability can be secured without forming a chemical conversion treatment layer between the two. Therefore, the primer coating layer 14 can be formed in contact with the plating layer 82 as in the surface-treated steel plate 81b shown in FIG. 8B. In the surface-treated steel sheet 81b shown in FIG. 8B, the manufacturing process can be simplified and can be manufactured at a low cost as compared with the case of forming the chemical conversion treatment layer.
- FIG. 8C is an enlarged cross-sectional view for explaining another modified example of the surface-treated steel sheet according to the sixth embodiment.
- the surface-treated steel plate 81c shown in FIG. 8C is different from the surface-treated steel plate 81b shown in FIG. 8B in that the chemical conversion treatment layer 17 is formed between the colored coating layer 15 and the plating layer 82. Since the surface-treated steel plate 81c shown in FIG. 8C includes the chemical conversion treatment layer 17 formed between the colored coating layer 15 and the plating layer 82, further excellent corrosion resistance is obtained.
- the chemical conversion treatment layer 17 shown in FIG. 8C is preferably obtained by chemical conversion treatment using a treatment liquid containing silica, a silane coupling agent, and a resin.
- the chemical conversion treatment layer 17 excellent in the adhesion between the colored coating layer 15 and the plating layer 82 can be obtained.
- the resin contained in the chemical conversion treatment liquid generally known resins such as a polyester resin, an acrylic resin, a urethane resin, and an epoxy resin can be used. These resins are more preferably water-soluble or water-dispersed types because the treatment liquid used for the chemical conversion treatment can be easily handled.
- silica contained in the chemical conversion treatment liquid generally known silica can be used.
- silica having a fine particle diameter is more preferable because it can maintain stability when dispersed in a chemical treatment liquid.
- Commercially available silica may be used as the silica contained in the treatment liquid. Examples of commercially available silica include “Snowtex N”, “Snowtex C”, “Snowtex UP”, “Snowtex PS” (all manufactured by Nissan Chemical Industries), “Adelite AT-20Q” (Asahi Denka Kogyo) Silica gel such as Aerosil # 300 (manufactured by Nippon Aerosil Co., Ltd.) or the like.
- silane coupling agent contained in the chemical conversion treatment liquid examples include ⁇ - (2-aminoethyl) aminopropyltrimethoxysilane, ⁇ - (2-aminoethyl) aminopropylmethyldimethoxysilane, and ⁇ - (2-amino).
- Ethyl) aminopropyltriethoxysilane ⁇ - (2-aminoethyl) aminopropylmethyldiethoxysilane, ⁇ - (2-aminoethyl) aminopropylmethyldimethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -methacryloxy Propylmethyldimethoxysilane, ⁇ -methacryloxypropyltriethoxysilane, ⁇ -methacryloxypropylmethyldiethoxysilane, N- ⁇ - (N-vinylbenzylaminoethyl) - ⁇ -aminopropyltrimethoxysilane, N- ⁇ - ( N-vinylbenzylamino Ethyl) - ⁇ -aminopropylmethyldimethoxysilane, N- ⁇ - (N-vinylbenzylaminoethyl) - ⁇ -aminopropyltriethoxysilane
- the chemical conversion treatment layer may contain a rust inhibitor containing one or more selected from tannin, tannic acid, a zirconium compound, and a titanium compound.
- silica silica, a silane coupling agent, and a resin are formed on the plating layer 82 of the surface-treated steel sheet obtained by the method of the first embodiment or the second embodiment.
- a chemical conversion treatment is performed by applying a treatment liquid containing the above and dried and allowed to cool to form a chemical conversion treatment film.
- the chemical conversion treatment liquid contains a zirconium compound
- zirconium compound zirconyl ammonium carbonate, zircon hydrofluoric acid, zircon ammonium fluoride, potassium zircon fluoride, sodium zircon fluoride, zirconium acetylacetonate, zirconium butoxide 1-butanol solution
- a zirconium compound zirconyl ammonium carbonate, zircon hydrofluoric acid, zircon ammonium fluoride, potassium zircon fluoride, sodium zircon fluoride, zirconium acetylacetonate, zirconium butoxide 1-butanol solution
- titanium compound is titanium hydrofluoric acid, ammonium titanium fluoride, titanium potassium oxalate, titanium isopropoxide, isopropyl titanate, titanium ethoxide, or titanium 2-ethyl.
- Commonly known materials such as 1-hexanolate, tetraisopropy
- the primer coating layer 14 and the color pigment layer 16 are colored in the same manner as the surface-treated steel plate 81b shown in FIG. 8B.
- a coating layer 15 is formed.
- the surface-treated steel sheet 81c according to the present embodiment has excellent coating adhesion of the plating layer 82, and the chemical conversion treatment layer 17 is formed between the colored coating layer 15 and the plating layer 82, so that it is very high. Corrosion resistance and workability.
- Example 1 “Example m1 to Example m73, Comparative Example x1, Comparative Example x5 to Comparative Example x15”
- a surface-treated steel sheet was formed by the method shown below using the plating apparatus shown in FIG.
- a plating bath having the composition, pH, and temperature shown in Tables 1 to 3 is discharged from the discharge port 2c, supplied from the supply port 2d, and circulated at the average flow rate shown in Tables 1 to 3.
- a steel plate as a cathode shown in Tables 1 to 3 was immersed in the plating bath.
- Example 1 The materials shown in Tables 1 to 3 were used as anodes, and zinc and vanadium were included on the surface of the steel sheet by electroplating at the current densities and times (electrodeposition times) shown in Tables 1 to 3 (Comparative Example 1)
- Comparative example x2 An electroplated copper plate was formed by the method shown below using the plating apparatus shown in FIG. A plating bath having the composition, pH, and temperature shown in Table 3 is discharged from the discharge port 2c, supplied from the supply port 2d, and circulated at an average flow rate shown in Table 3. The copper plate which is a cathode shown in 3 was immersed. Using the material shown in Table 3 as the anode, a plating layer of Comparative Example x2 containing zinc and vanadium was formed on the surface of the copper plate by electroplating at the current density and time shown in Table 3.
- Comparative Example x3 A surface-treated steel sheet was formed by the method shown below using the plating apparatus shown in FIG.
- the steel plate which is the cathode shown in Table 3, was immersed in a stationary plating bath without circulating the plating bath having the composition, pH, and temperature shown in Table 3.
- a plating layer of Comparative Example x3 containing zinc and vanadium was formed on the surface of the steel sheet by electroplating at the current density and time shown in Table 3.
- Comparative Example 4 Comparative Example x4 is the same as Comparative Example x3 except that the plating bath in the plating tank is not circulated and is stirred (stirred) by a stirrer (stirrer) disposed at the bottom of the plating tank. The plating layer was formed.
- the basis weight, vanadium content, and surface roughness Ra of the plating layers of Examples m1 to m73 and Comparative Examples x1 to x15 thus obtained were determined by the following methods.
- the basis weight of the plating layer was the total mass per unit area of V element and Zn element detected by fluorescent X-rays.
- the vanadium content was calculated as a percentage by dividing the amount of V element detected by fluorescent X-rays by the basis weight.
- the surface roughness Ra (centerline average roughness) of the plating layer was measured based on JIS B 0601: 2001. The results are shown in Tables 4-6.
- the vanadium content is 1% to 20% and the basis weight is 3 g. / M 2 or more and 40 g / m 2 or less.
- the vanadium content was less than 1%.
- the basis weight was less than 3 g / m 2 .
- Example m1 to Example m73 and Comparative Example x1 to Comparative Example x15 are observed using a scanning electron microscope and have a plurality of dendritic columnar crystals grown in the thickness direction of the steel plate (copper plate). Confirmed whether or not.
- the results are shown in FIGS. 3A to 6B.
- the white portion on the uppermost surface is a gold layer provided to facilitate observation of the plating layer.
- FIGS. 3A and 3B are scanning electron micrographs of the plated layer of the surface-treated steel sheet of Example m23.
- FIG. 3A is a photograph viewed from above
- FIG. 3B is a photograph of a cross section.
- the plating layer of Example m23 had no cracks (gap) reaching the steel plate, and had a plurality of dendritic columnar crystals grown in the thickness direction of the steel plate.
- the plating layers of the surface-treated steel sheets of Example m1 to Example m73 and Comparative Example x5 to Comparative Example x8 are free of cracks (gap) reaching the steel sheet and are grown in the thickness direction of the steel sheet. Of dendritic columnar crystals.
- FIGS. 4A and 4B are scanning electron micrographs of the plated layer of the surface-treated steel sheet of Comparative Example x3.
- 4A is a photograph viewed from above
- FIG. 4B is a photograph of a cross section.
- the plating layer of Comparative Example x3 formed using the plating bath in a stationary state did not have dendritic columnar crystals.
- the deep crack (gap) which reaches a steel plate was formed in the plating layer of the comparative example x3 on the surface.
- the plating layer of Comparative Example x4 formed using a stirred plating bath has a crystal structure similar to that of Comparative Example x3, and a deep crack (gap) reaching the steel plate is formed on the surface. It did not have a columnar crystal. Further, even in Comparative Example x15 in which 0.01% of nitrate ions were included in the plating bath, no dendritic columnar crystals were present.
- FIGS. 5A and 5B are scanning electron micrographs of the plating layer of the electroplated copper plate of Comparative Example x2.
- FIG. 5A is a photograph viewed from above
- FIG. 5B is a photograph of a cross section.
- the plating layer of Comparative Example x2 formed on the surface of the copper plate had gathered granular crystals, and did not have dendritic columnar crystals.
- FIGS. 6A and 6B are scanning electron micrographs of the plated layer of the surface-treated steel sheet of Comparative Example x1.
- FIG. 6A is a photograph viewed from above
- FIG. 6B is a photograph of a cross section.
- the plating layer of Comparative Example x1 not containing vanadium did not have dendritic columnar crystals.
- the plating layers of Comparative Example x9 to Comparative Example x14 having a vanadium content of less than 1% had the same crystal structure as that of Comparative Example x1, and did not have dendritic columnar crystals.
- Example m1 to Example m73 and Comparative Example x1 to Comparative Example x15 examples m1 to Example m73 and Comparative Examples x5 to Comparative Example x8 in which the plating layer has dendritic columnar crystals.
- a plurality of vanadium contents x existing between adjacent columnar crystals and a plurality of vanadium contents y existing in the columnar crystals were measured using EPMA (Electron
- the plating layers of the surface-treated steel sheets of Example m1 to Example m73 and Comparative Example x5 to Comparative Example x8 have a x / y ratio x / y of 1 in terms of vanadium element. It was 1 or more and 3.0 or less.
- the salt spray test JIS Z 2371 was performed by tape-sealing the edges and back of the test piece cut out from the surface-treated steel sheet. And the white rust generation
- the white rust generation area ratio is a percentage of the area of the white rust generation site to the area of the observation site.
- (Standard) 6 White rust generation area ratio is less than 3%, 5: White rust generation area ratio 3% or more, less than 10%, 4: White rust generation area ratio 10% or more, less than 25%, 3: White rust generation area ratio 25% or more, less than 50%, 2: White rust generation area ratio 50% or more, less than 75%, 1: White rust generation area ratio 75% or more
- Powdering property adheresion between plating layer and steel plate
- a 60 ° V bending mold was used for the powdering test. Using a die with a radius of curvature of 1 mm at the tip so that the evaluation surface of the test piece cut out from the surface-treated steel plate is inside the bent part, it is bent at 60 °, and tape is attached to the inside of the bent part. The tape was peeled off. The powdering property was evaluated according to the following criteria from the peeled state of the plating layer peeled off with the tape.
- the test piece cut out from the surface-treated steel plate was coated with a paint (Amirac # 1000, manufactured by Kansai Paint Co., Ltd.) and baked at 140 ° C. for 20 minutes to form a film having a dry film thickness of 25 ⁇ m.
- the obtained coated plate was immersed in boiling water for 30 minutes and then left in a room temperature room for 24 hours. After that, 100 squares of 1 mm square were cut into the test piece with an NT cutter, and after extruding 7 mm with an Erichsen tester, the extruding convex part was subjected to a peel test with an adhesive tape. The paint adhesion was evaluated.
- the corrosion resistance standard is 4 or more
- the powdering standard is A or more
- the coating adhesion standard is A or more
- Comparative Example x1 in which the plating layer does not contain vanadium, the powdering property is excellent, but the plating layer having a dendrite-like columnar crystal cannot be obtained, and the corrosion resistance and the coating adhesion are low. It was insufficient.
- Comparative Example x2 in which a plating layer was formed on the surface of the copper plate, a plating layer having dendritic columnar crystals could not be obtained, and powdering properties, corrosion resistance, and coating adhesion were all insufficient.
- Comparative Example x3 in which a plating layer was formed using a plating bath that was in a stationary state
- Comparative Example x4 in which a plating layer was formed using a plating bath that was in a stirring state, a plating layer having dendritic columnar crystals was obtained.
- the coating adhesion was good, but the powdering and corrosion resistance were insufficient.
- Comparative Example x5 to Comparative Example x8 in which the weight per unit area of the plating layer was less than 3 g / m 2 , the corrosion resistance was insufficient.
- Comparative Example x9 to Comparative Example x14 in which the vanadium content of the plating layer is less than 1%, the powdering property is excellent, but the plating layer having dendritic columnar crystals cannot be obtained, and the corrosion resistance is very low. Paint adhesion was also insufficient.
- Example 2 the composition shown in Tables 8 to 10 was prepared by using the resin film chemicals shown in Table 7 on the surface-treated steel plate (copper plate) having a plating layer containing zinc and vanadium oxide produced in Example 1.
- the resin film raw material having the above was applied to the surface of the plated steel plate and baked and dried to form a resin film.
- processed part corrosion resistance, conductivity, emissivity, and scratch resistance were evaluated.
- the emissivity was evaluated in the same manner as in Example 1 with the same criteria.
- the processed part corrosion resistance, electrical conductivity, and scratch resistance were evaluated as follows.
- the results are shown in Tables 11-13.
- the content in the resin film is all mass% with respect to the solid content of the resin film.
- surface has shown the number of the used surface treatment steel plate, and respond
- the blank indicates that it is not intentionally contained.
- the interlayer resistance value ( ⁇ ⁇ cm 2 ) is measured by the measurement method specified in JIS C 2550, and the conductivity is measured according to the following criteria. Evaluated and made C or more suitable.
- Interlayer resistance value is less than 1.0 ⁇ ⁇ cm 2 A: Interlayer resistance value is 1.0 ⁇ ⁇ cm 2 or more and less than 1.5 ⁇ ⁇ cm 2 B: Interlayer resistance value is 1.5 ⁇ ⁇ cm 2 or more and 2.0 ⁇ ⁇ Less than cm 2 C: Interlayer resistance value is 2.0 ⁇ ⁇ cm 2 or more and less than 2.5 ⁇ ⁇ cm 2 D: Interlayer resistance value is 2.5 ⁇ ⁇ cm 2 or more and less than 3.0 ⁇ ⁇ cm 2 E: Interlayer resistance value is 3 .0 ⁇ ⁇ cm 2 or more
- the surface-treated steel sheets of Examples s1 to s40 were excellent in processed part corrosion resistance of 3 or more, conductivity of C or more, and scratch resistance of 3 or more.
- Example 3 a water-based metal having a composition shown in Tables 15 to 17 was used on the surface of the surface-treated steel sheet having a plating layer containing zinc and vanadium oxide produced in Example 1, using a chemical as shown in Table 14. A surface treatment agent was applied and baked and dried to form a film. And as performance after film formation, with respect to processed part corrosion resistance, conductivity, workability (work adhesion), and emissivity, except for workability, evaluation is performed in the same manner as in Example 2 and on the same basis. It was. The workability was evaluated as shown below. The results are shown in Tables 18-20.
- the test piece cut out from the surface-treated steel sheet on which the film was formed was subjected to a 180 ° bending process, and then a tape peeling test was performed on the outside of the bent portion.
- the appearance of the tape peeling part was observed with a magnifying glass having a magnification of 10 times and evaluated according to the following evaluation criteria.
- the bending process was performed in an atmosphere of 20 ° C. with a 0.5 mm spacer interposed therebetween.
- the surface-treated steel sheets of Examples t1 to t49 were excellent in the processed portion corrosion resistance of 3 or more, the conductivity of B or more, and the scratch resistance of 3 or more.
- Example 4 an organic resin film was formed on the surface of the surface-treated steel sheet having a plating layer containing zinc and vanadium oxide produced in Example 1 by the method described below, and Examples r1 to r87 were compared.
- the surface-treated steel plates (copper plates) of Example f1 to Comparative Example f9 were formed. That is, the resin (A1) shown in Table 21, the curing agent (B1) shown in Table 22, the colorant (C1) shown in Table 23, and the silica (D1) and Table 25 shown in Table 24 as needed.
- An organic resin is obtained by applying a black water-based paint containing one or both of the lubricants (E1) shown on the surface of a surface-treated steel plate (copper plate) having a plating layer containing vanadium oxide and baking and drying. A film was formed.
- the water-based paint contains a resin, a curing agent (B1), a colorant (C1), and, if necessary, one or both of silica (D1) and a lubricant (E1) in water. It was manufactured by stirring with a disper and dissolving or dispersing. A roll coat was used for applying the water-based paint.
- As the baking and drying method a method of heating the steel plate (copper plate) on which the plating layer was formed after application of the water-based paint to the ultimate temperatures (reach plate temperatures) shown in Tables 29 to 31 was used.
- test pieces each having a length of 50 mm and a width of 100 mm were cut out, and the appearance (concealing property, L * value, gloss) as a performance after film formation by the following method. ), Processing adhesion, processed part corrosion resistance, and scratch resistance. The results are shown in Tables 29 to 31.
- the concealment evaluation was 3 or more, the L * value was 35 or less, and the 60 ° gloss value was 50 or less. was gotten.
- the evaluation of the processing adhesion is 4 or more, the evaluation of the processing portion corrosion resistance is 3 or more after any test time, the evaluation of the scratch resistance is 3 or more, the processing adhesion, the processing portion corrosion resistance, the scratch resistance. was excellent.
- Example 5 A colored coating layer containing a colored pigment layer was formed on the surface of the surface-treated steel sheet having a plating layer containing zinc and vanadium oxide produced in Example 1 by the method shown below.
- a primer coating layer is formed between the plating layer on one side and the coloring pigment layer by the method shown below, and the coloring pigment layer and the primer coating layer are formed.
- a colored coating layer composed of a film layer was formed.
- the chemical conversion treatment layer was formed by the method shown below between the plating layer of one surface and the colored coating film layer as needed.
- a chemical conversion treatment film was formed by applying a treatment liquid shown below with a roll coater at an adhesion amount of 100 mg / m 2 . Then, the chemical conversion treatment film was dried in a hot air oven under the condition that the temperature of the steel sheet reached 60 ° C. and allowed to cool, thereby obtaining a chemical conversion treatment layer.
- “Chemical treatment liquid” An aqueous solution containing 5 g / L of silane coupling agent, 1.0 g / L of silica, and 25 g / L of resin was prepared and used as a treatment liquid for chemical conversion treatment. Note that ⁇ -glycidoxypropyltrimethoxysilane is used as the silane coupling agent, “Snowtex-N” manufactured by Nissan Chemical Co., Ltd., which is water-dispersed fine silica, is used as the silica, and the water-based acrylic resin is used as the resin. Polyacrylic acid was used.
- a primer coater shown below is applied with a film thickness of 5 ⁇ m with a roll coater, A primer coating was formed. Thereafter, the primer coating film was dried and baked under the condition that the temperature of the steel sheet reached 210 ° C. in an induction heating oven, and water-cooled to obtain a primer coating film layer.
- polyester resin “Byron (registered trademark) 29CS (amorphous polyester resin“ Byron (registered trademark) 290 ”) manufactured by Toyobo Co., Ltd. was dissolved in an organic solvent to form a liquid with a solid content concentration of 30% by mass. And a glass transition point (hereinafter Tg) of 72 ° C., a number average molecular weight (hereinafter referred to as MN) of 17,000) ”and a melamine resin“ Cymel (Mitsui Cytec Co., Ltd.) ”as a curing agent. (Registered trademark) 303 "was used.
- Tg glass transition point
- MN number average molecular weight
- Cymel Mitsubishi Chemical Cytec Co., Ltd.
- the primer paint is obtained by adding 0.5% by mass of an acidic catalyst “Catalyst TM600” manufactured by Mitsui Cytec Co., Ltd. to a mixed solution of a polyester resin and a melamine resin mixed at the above mixing ratio, and stirring.
- an acidic catalyst Catalyst TM600” manufactured by Mitsui Cytec Co., Ltd.
- P-Al anti-corrosive pigments
- polyester resin “Green (registered trademark) C300 (amorphous polyester resin, cyclohexanone / solvesso dissolved type, Tg 7 ° C., number average molecular weight (MN) 23,000)” manufactured by Toyobo Co., Ltd. is used.
- a melamine resin “Cymel (registered trademark) 303” manufactured by Mitsui Cytec Co., Ltd. was used as a curing agent. The mixing ratio of the polyester resin and the melamine resin was such that the mass ratio of the resin solids was polyester resin: melamine resin 80: 20.
- the colored paint was obtained by adding 0.5% by mass of an acidic catalyst “Catalyst TM600” manufactured by Mitsui Cytec Co., Ltd. to a mixed solution of a polyester resin and a melamine resin mixed at the above mixing ratio, and stirring.
- an acidic catalyst “Catalyst TM600” manufactured by Mitsui Cytec Co., Ltd.
- To the clear paint add a white pigment, titanium oxide “Typaque (registered trademark) CR-95” manufactured by Ishihara Sangyo Co., Ltd. or carbon black “Toka Black # 7350” manufactured by Tokai Carbon Co., Ltd., which is a black pigment, and stir.
- a white pigment titanium oxide “Typaque (registered trademark) CR-95” manufactured by Ishihara Sangyo Co., Ltd. or carbon black “Toka Black # 7350” manufactured by Tokai Carbon Co., Ltd., which is a black pigment, and stir.
- FIG. 9 is a schematic perspective view for explaining a bending process in the bending workability test.
- the evaluation surface 41a one surface of the surface-treated steel plate 41 is placed outside in a 20 ° C. atmosphere so that the 180 ° bending process (generally called “0T bending process”) is performed.
- the processed part was observed with a 20-fold magnifier, and the presence or absence of cracks in the coating film was examined.
- the tape was affixed and peeled on the processed part of the bent steel plate 41, and the remaining state of the coating film after the tape peeling was observed.
- the case where the coating film was not peeled off at all on the processed part was evaluated as A
- the case where the coating film was peeled off at a part of the processed part was evaluated as B
- the case where the entire coated part was peeled off was evaluated as C.
- FIG. 10 is a schematic perspective view showing a cup-shaped molded body in the drawing workability test.
- the molded body 42 shown in FIG. 10 was immersed in boiling water for 1 hour, and the coating film after immersion was observed.
- A shows that the coating film is not peeled off from the molded body 42
- B shows that there is peeling within a coating film peeling width of 5 mm from the molded body end surface 42a of the molded body 42 shown in FIG.
- a film having a peeling width exceeding 5 mm was evaluated as C.
- the salt spray test was performed on the sample thus obtained by the method described in 9.1 of JIS K 5400.
- the salt water was sprayed so that it wiped on one side (surface).
- the test time was 240 hours. In this test, cut scratches that reach the sample substrate (steel plate) from above the coating film were not provided.
- the average swell width and maximum swell width of the end face of the long side of the sample are measured, S when the average swell width is 2 mm or less, A when 2 mm or more and 3 mm or less, B when 3 mm or less and 5 mm or less, B, 5 mm or more.
- the case was evaluated as C.
- the average swollen width of the end face is determined by dividing the long side of the sample having a length of 150 mm into 10 mm sections (15 sections in total), measuring the maximum swollen width in each section, and measuring the maximum swollen width of each section. A value obtained by dividing the total value by the total number of sections (15) was defined as the average swollen width.
- the surface-treated steel sheet according to the present invention comprises a plurality of dendrite-like arms having a vanadium content of 1% to 20% and a basis weight of 3 g / m 2 to 40 g / m 2 and grown in the thickness direction of the steel sheet. And a plating layer having a ratio x / y to vanadium content y existing inside the arm of vanadium content x existing outside the arm is 1.1 or more and 3.0 or less in terms of vanadium element. Yes. Therefore, it is excellent in corrosion resistance and paint adhesion.
Abstract
Description
電気亜鉛めっき鋼板の耐食性を向上させる方法としては、亜鉛めっき層のめっき量(目付け量)を増加させることが考えられる。しかしながら、亜鉛めっき層の目付け量を増加させた場合、製造コストが増大する、または、加工性や溶接性が低下する。
また、塗膜を形成した電気亜鉛めっき鋼板においては、上述したような耐食性のほかに、導電性(以下、アース性ともいう。)を向上させることが要求されている。導電性の向上には塗膜を薄くすることが有効な手段であるが、上述したように、薄膜にすると耐食性の向上が図れない。
このように、従来は、電気亜鉛めっき鋼板において、表面にさらに皮膜を形成しても、耐食性と導電性の両特性を満足させることは非常に困難であった。
また、本発明は、鋼板の表面に、亜鉛とバナジウム酸化物とを含むめっき層が形成された耐食性および塗装密着性に優れた表面処理鋼板を提供することを目的とする。
すなわち、本発明者らは、電気めっき法で鋼板表面に形成した亜鉛とバナジウムとを含むめっき層における付着量(目付け量)とバナジウム含有率と結晶構造とに着目し、種々の方法を用いて鋼板表面にめっき浴を接触させて、得られためっき層の耐食性と塗装密着性との関係を調べた。
さらに、上記めっき層中のアーム外に存在するバナジウム含有率xの前記アーム内に存在するバナジウム含有率yに対する比、すなわち、x/yを調査した結果、バナジウム元素換算で1.1以上3.0以下であることを見出した。なお、得られためっき層は、表面粗度が中心線平均粗さRaで1.0μm以上4.0μm以下である高粗度なめっき層であった。
これに対し、静止状態および攪拌状態で鋼板表面に接触させた場合、デンドライト状の柱状結晶を有するめっき層が形成されなかった。そのため、めっき浴を流動状態で鋼板に接触させた場合と比較して、めっき層の表面にクラックが発生しやすかった。
その結果、このようなめっき層を有する表面処理鋼板は、従来の電気亜鉛めっき鋼板と比較して、優れた塗装密着性を有していることが分かった。
さらに、高粗度なめっき層を有する表面処理鋼板の表面に樹脂皮膜を形成した表面処理鋼板の導電性についても調査したところ、皮膜厚さが0.5~5.0μmの範囲で皮膜の膜厚に依存することなく、十分な導電性が得られることを見出した。つまり、皮膜が薄膜の場合は当然ながら、厚膜であった場合であっても、十分な導電性を有していた。
つまり、従来は耐食性と導電性の両特性を満足させた表面処理鋼板を提供することは非常に困難であると考えられてきたが、上述したようなめっき層を有する表面処理鋼板に樹脂皮膜を形成することにより、耐食性と導電性の特性をいずれも向上させることができることを見出した。
さらに、従来、バナジウムを含んでいない亜鉛めっき層表面へ皮膜を形成しても、良好な加工性(加工密着性)を得ることは困難であった。しかしながら、バナジウムを含有しためっき層の場合、この加工密着性の劣化を抑制できることを見出した。つまり、耐食性と導電性の特性を両立、そして優れた加工密着性を確保できることを見出した。
したがって、亜鉛とバナジウムとを含む上記のめっき層の上層に、厚い黒色皮膜を形成することなく、めっき表面の微細な外観ムラを隠蔽し、光沢が十分に抑えられ、L*値(明度)が十分に低く、耐キズ付性および加工時の密着性に優れ、更に美麗な外観を有する鋼板があれば、その価値は高い。
上記課題を解決して係る目的を達成するために、本発明は以下の手段を採用した。
(1)すなわち、本発明の一態様に係る表面処理鋼板は、鋼板と、前記鋼板の片面または両面に形成されてかつ、亜鉛及びバナジウムを含むめっき層とを備え;前記めっき層は、前記バナジウムの含有率が1%以上20%以下かつ目付け量が3g/m2以上40g/m2以下であり、前記鋼板の厚み方向に成長した複数のデンドライト状のアームを有し;前記アーム内に存在する前記バナジウムの含有率yに対する前記アーム外に存在する前記バナジウムの含有率xの比x/yが、バナジウム元素換算で1.1以上3.0以下である。
「第1実施形態」
図1に示すめっき装置を用いて、本実施形態に係る表面処理鋼板の製造方法により本実施形態に係る表面処理鋼板を製造する場合を例に挙げて説明する。
本実施形態に係る表面処理鋼板の製造方法は、鋼板1の表面に、電気めっき法により亜鉛とバナジウムとを含むめっき層を形成するめっき工程を備えている。
図1に示すように、上部槽21a内および下部槽21b内の鋼板1に隣接する位置には、白金などからなる複数の陽極3が鋼板1との間に所定の間隔を空けて配置されている。各陽極3の鋼板1に対向する面は、鋼板1の表面と略平行となるように配置されている。各陽極3は、不図示の接続部材によって、電源(不図示)に電気的に接続されている。
本実施形態においては、このめっき工程を行うことにより、鋼板1の表面に、バナジウム含有率が1%以上20%以下かつ目付け量が3g/m2以上40g/m2以下のデンドライト状の柱状結晶(一次アーム及び二次アーム)を有するめっき層を形成する。
めっき層のバナジウム含有率は、耐食性および塗装密着性をより一層向上させるために2%以上であることが好ましい。めっき層と鋼板1との間で良好な密着性を得るため、めっき層のバナジウム含有率は、20%以下とする。より好ましくは、15%以下である。
また、めっき工程においては、電流密度を20~150A/dm2とする。電流密度を上記範囲内とすることで、バナジウム含有率が1%以上20%以下かつ目付け量が3g/m2以上40g/m2以下である本実施形態のめっき層を容易に形成できる。電流密度が20A/dm2未満であると、所定のバナジウム含有率および/または目付け量を確保しにくくなる。電流密度が150A/dm2を超えると、めっき層と鋼板1との間の密着性が低下する恐れがある。
めっき浴2に用いられるZn化合物としては、金属Zn、ZnSO4・7H2O、ZnCO3などが挙げられる。これらは単独で用いてもよく、2種類以上を併用しても良い。
めっき浴2に用いられるV化合物としては、メタバナジン酸アンモン(V)、メタバナジン酸カリウム(V)、メタバナジン酸ソーダ(V)、VO(C5H7O2)2(バナジルアセチルアセトネート(IV))、VOSO4・5H2O(硫酸バナジル(IV))などが挙げられる。これらは単独で用いてもよく、2種類以上を併用しても良い。
めっき浴2が、VO2+または、V4+をいずれか、もしくは両方含む場合、めっき浴2中にこれらを合計で0.01mol/l以上1.0mol/l未満含有させる。VO2+または、V4+を上記範囲内で含むめっき浴2を用いることで、バナジウム含有率が1%以上20%以下かつ目付け量が3g/m2以上40g/m2以下であるめっき層を容易に形成できる。めっき浴2に含まれるVO2+または、V4+の含有量が上記範囲未満である場合、鋼板1の厚み方向に複数のデンドライト状の柱状結晶12が成長しにくくなり、バナジウム含有率が低下する。また、めっき浴2に含まれるVO2+または、V4+の含有量が上記範囲を超えると、高価なバナジウムをめっき浴2中に多く使用することになるため経済的に不利となる。
めっき浴2が、Zn2+を含む場合、Zn2+を0.1~1.5mol/l含むことが好ましく、0.35~1.2mol/l含むことがより好ましい。
めっき浴2がNi化合物を含む場合、めっき浴2中にニッケルイオンを0.01mol/l以上含むことが好ましい。この場合、バナジウムが析出しやすくなり、本実施形態のめっき層を容易に形成できる。ただし、1.0mol/l以上とすることは、表面処理鋼板の耐食性やめっき密着性が劣化することが懸念されるため望ましくない。
本実施形態においては、図3Aおよび図3Bに示すように、鋼板1に達するクラック(隙間)がなく、隣接する柱状結晶12間(アーム外)に柱状結晶12内(アーム内)と比較してバナジウム含有量の多い領域13が形成されている。従って、バナジウムを含有させることによる耐食性を向上させる効果が、より効果的に発揮されると推定される。
放射率は一定温度では物体の吸収率と同じになるので、放射率の高いものは熱吸収性も高くなる。めっき層11の上記放射率は、熱吸収性効果および放熱効果を十分に得るために、0.30以上であることが好ましく、0.60以上であることがより好ましい。
なお、波数600cm-1未満、もしくは、3000cm-1超の波数領域の放射線吸収は、表面処理鋼板の熱吸収性に与える影響および温度低下効果が非常に小さいため、これらの波数領域の放射線を含めた放射率は不適である。また、放射率を測定する温度は、家電製品に使用されるICチップ等の電子回路の稼働温度を考慮して100℃とした。
図2に示すめっき装置を用いて、第2実施形態に係る表面処理鋼板及びその製造方法について説明する。
図2は、本実施形態に係る表面処理鋼板の製造方法において用いられるめっき装置の他の例を示した概略図である。図2において、符号10は鋼板、符号32はめっき浴、符号22はめっき槽、符号23は陽極を示している。
めっき浴32としては、第1実施形態において用いためっき浴2と同様のものを用いることができる。
図2に示すように、めっき槽22の底部には、白金などからなる陽極23が配置されている。めっき槽22内は、めっき浴32で満たされており、めっき浴32には、陰極である鋼板10が面方向を略水平に配置して浸漬されている。
本実施形態においても、めっき工程を行うことにより、鋼板10の表面に、バナジウム含有率が1%以上20%以下かつ目付け量が3g/m2以上40g/m2以下のデンドライト状の柱状結晶を有するめっき層が形成される。
第1実施形態または第2実施形態で得られた亜鉛とバナジウムとを含むめっき層を有する表面処理鋼板に、樹脂皮膜を形成させた表面処理鋼板について説明する。なお、この樹脂皮膜について、本実施形態に係る樹脂皮膜と言う場合がある。また、本実施形態で用いた表面処理鋼板が有するめっき層について、本実施形態に係るめっき層と言う場合がある。
本実施形態に係る樹脂皮膜(A)は、本実施形態に係るめっき層の上面に、樹脂皮膜(A)が1層以上形成されている。これら複数の樹脂皮膜(A)の少なくとも1層の厚みは0.5~5.0μmが望ましい。従来では、皮膜の薄膜化、及びめっき層の高粗度化は、耐食性の劣化を招くと考えられてきた。しかしながら、上述したように、本実施形態に係るめっき層は、非常に高い耐食性を有しているため、めっき層が高粗度であっても、上述の皮膜の厚みで、十分な耐食性を確保することができる。さらに、本実施形態に係るめっき層は高粗度であるため、上述の皮膜厚みで十分な導電性を確保することができる。耐食性の観点から、樹脂皮膜(A)の厚みを0.5μm以上とすることがより好ましく、1.0μm以上とすることがよりさらに好ましい。また、導電性の観点から、樹脂皮膜(A)の厚みを5.0μm以下とすることがより好ましく、4.0μm以下とすることがさらに好ましい。
なお、フェノール樹脂としては特に限定されない。例えば、フェノール、レゾルシン、クレゾール、ビスフェノールA、パラキシリレンジメチルエーテル等の芳香族類とホルムアルデヒドとを反応触媒の存在下で付加反応させたメチロール化フェノール樹脂等のフェノール樹脂をジエタノールアミン、N-メチルエタノールアミン等のアミン化合物類と反応させ、有機酸又は無機酸で中和することによって得られるもの等を用いることができる。
上記の第1実施形態または第2実施形態で得られた表面処理鋼板のめっき層の上面に、更に、シランカップリング剤(I)を含む有機ケイ素化合物(W)を含有する水系金属表面処理剤を塗布し乾燥することにより得られる皮膜を1層以上形成させた。
本実施形態において水系金属表面処理剤の必須成分である有機ケイ素化合物(W)は、分子中にアミノ基を1つ以上含有するシランカップリング剤(I)と、分子中にグリシジル基を1つ以上含有するシランカップリング剤(J)を配合して得ることができる。シランカップリング剤(I)とシランカップリング剤(J)の配合比率としては、固形分質量比〔(I)/(J)〕で0.5~1.7であることが好ましく、0.7~1.7がより好ましく、0.9~1.1であることが最も好ましい。固形分質量比〔(I)/(J)〕が0.5未満であると、耐指紋性および浴安定性、耐黒カス性が著しく低下するため好ましくない。逆に1.7を超えると、耐水性が著しく低下するため好ましくない。
有機ケイ素化合物(W)の平均の分子量は1000~10000であることが好ましく、1300~6000であることがより好ましい。ここでいう分子量は、特に限定するものではないが、TOF-MS法による直接測定およびクロマトグラフィー法による換算測定のいずれかを用いて良い。平均の分子量が1000未満であると、形成された皮膜の耐水性が著しく低くなる。一方、平均の分子量が10000より大きいと、前記有機ケイ素化合物を安定に溶解または分散させることが困難になる。
本発明のフルオロ金属錯化合物(N)の配合量に関しては、前記有機ケイ素化合物(W)とフルオロ金属錯化合物(N)の固形分質量比〔(N)/(W)〕が0.02~0.07であることが好ましく、0.03~0.06がより好ましく、0.04~0.05であることが最も好ましい。前記有機ケイ素化合物(W)とフルオロ金属錯化合物(N)の固形分質量比〔(N)/(W)〕が0.02未満であると、添加効果が発現しないため好ましくない。逆に0.07より大きいと導電性が低下するため好ましくない。
皮膜の膜厚に関しては、0.05~2.0μmであることが好ましく、0.2~1.0μmであることが更に好ましく、0.3~0.6μmであることが最も好ましい。膜厚が0.05μm未満であると、該金属材の表面を被覆できないため耐食性向上効果が得られない場合がある。逆に2.0μmより大きいと、導電性と加工密着性が低下するため好ましくない。
上述の皮膜においては、シランカップリング剤(I)を含む有機ケイ素化合物(W)と、さらに、有機樹脂(GB)とを含んだ水系金属表面処理剤を塗布して乾燥することにより得られる複合皮膜としてもよい。その場合、後述のようであることが望ましい。なお、この複合皮膜について、本実施形態に係る複合皮膜という場合がある。
ポリエーテルポリウレタン樹脂(K)を用いる場合、下記一般式[1]で表される構造単位(L1)、炭素数4~6の脂環構造(L2)および炭素数6の芳香環構造(L3)からなる群から選ばれる少なくとも一つの構造単位(L)を有することが望ましい。構造単位(L1)は、前記有機ケイ素化合物(W)との反応点として作用する。そのため、構造単位(L1)を有すると、架橋度上がり耐食性や耐洗浄剤性が著しく向上する。また、炭素数4~6の脂環構造(L2)を有すると、造膜時に有機ケイ素化合物(W)と絡合し、架橋した場合と同様の効果が得られる。また、芳香環構造(L3)を有すると、芳香環の有するバリア性がポリエーテルポリウレタン樹脂(K)に付与されるため、架橋反応や絡合反応は生じないものの、これらと同様の効果が得られる。
チタンを有するフルオロ金属錯化合物(N)としては、例えばチタンフッ化水素酸(O)であり、ジルコニウムを有するフルオロ金属錯化合物(N)としては、例えばジルコンフッ化水素酸(P)である。
着色顔料の添加量は5~35質量%であることが好ましい。範囲内とすることにより、得られた表面処理鋼板の放射率を高め黒色化を図ることができる。添加量が5質量%未満であると放射率の向上が不十分であるため好ましくない。また、添加量が35質量%超であると、金属表面処理剤の貯蔵安定性や耐食性の劣化のため好ましくない。
図7は、第5実施形態に係る表面処理鋼板の一例を説明するための拡大断面図である。本実施形態に係る表面処理鋼板は、鋼板71の両方の表面にそれぞれ、実施形態1または2の方法で形成されためっき層73と、めっき層73の上層に形成された1層の有機樹脂皮膜72とを有するものである。なお、以下において有機樹脂皮膜72について、本実施形態に係る有機樹脂皮膜と言う場合がある。
ポリエステル樹脂自身は疎水性であるが、ポリエステル樹脂にスルホン酸基が含有されている場合、高い親水性を示す。このため、スルホン酸基を含有するポリエステル樹脂(A1)は水系塗料中に安定して溶解もしくは分散することができる。加えて、スルホン酸基を含有するポリエステル樹脂(A1)は、疎水性表面を有するカーボンブラックと水との相溶性を向上させ、カーボンブラックを水系塗料中に均一に安定して分散させる重要な役割を担っている。これは、疎水性を示すポリエステル樹脂主骨格が、カーボンブラックに配向することで得られる効果による。
本実施形態の有機樹脂皮膜72を形成するための水系塗料は、カーボンブラックの分散性を高めるために、表面親水化処理や界面活性剤を含有させなくてもよい。それ故、表面親水化処理や界面活性剤によって、有機樹脂皮膜72の耐食性が低下する懸念がない。
スルホン酸基を含有するポリエステル樹脂(A1)骨格中へのウレタン結合の導入方法については、特に限定されない。例えば、ポリエステル樹脂に含まれる水酸基とヘキサメチレンジイソシアネート、イソホロンジイソシアネート、トリレンジイソシアネート等のジイソシアネート化合物とを反応させること等によって得られる。
本実施形態の有機樹脂皮膜72は、延性が高く加工性に優れるポリエステル樹脂を硬化剤(B1)で硬化させて得られたものである。そのため、カーボンブラックを含有する着色剤(C1)を含むことによる造膜性の低下が抑制され、緻密なものとなっている。その結果、本実施形態の有機樹脂皮膜72は、耐湿性、耐食性、耐傷付き性、耐薬品性に優れている。
メラミン樹脂としては、メラミンとホルムアルデヒトとを縮合して得られる生成物のメチロール基の一部またはすべてをメタノール、エタノール、ブタノールなどの低級アルコールでエーテル化した樹脂を用いることができる。
着色剤(C1)は、カーボンブラックを含有する着色顔料を含む。カーボンブラックは、安価で高い隠蔽性を有する。カーボンブラックに加えて更に、二酸化チタン、カーボンブラック、グラファイト、酸化鉄等の着色無機顔料や、フタロシアニンブルー、フタロシアニングリーン、キナクリドン、アゾオレンジ、アゾイエロー、アゾレッド等の着色有機顔料や、アルミニウム粉、二酸化チタンコーティングマイカ粉、二酸化チタンコーティングガラス粉等の光輝材などを含んでもよい。
カーボンブラックとしては、特に制限はないが、例えば、ファーネスブラック、ケッチエンプラック、アセチレンブラック、チャンネルブラック等、公知のカーボンブラックを使用することができる。また、公知のオゾン処理、プラズマ処理、液相酸化処理されたカーボンブラックも使用することができる。
ポリエチレン樹脂を使用する場合、耐食性や耐傷付き性の観点から、有機樹脂皮膜72中に数平均粒子径0.5~2μmの粒子で分散されていることが好ましい。
水系塗料の塗布方法は、特に制限されるものではなく、例えば、公知のロールコート、カーテンコート、ダイコート、スプレー塗布、バーコート、浸漬、静電塗布等を適宜使用することができる。
焼付乾燥方法は特に制限はなく、あらかじめ、めっき層73の形成された鋼板71を加熱しておくか、水系塗料の塗布後にめっき層73の形成された鋼板71を加熱するか、或いはこれらを組み合わせて乾燥を行ってもよい。
以下、図面を参照して上記の第1実施形態または第2実施形態で得られた表面処理鋼板のめっき層の上面に、更に、着色顔料層を含む着色塗膜層を形成した場合について説明する。
図8Aは、第6実施形態に係る表面処理鋼板の一例を説明するための拡大断面図である。図8Aに示す表面処理鋼板81aは、本実施形態1または2の方法で製造され、めっき層を有する表面処理鋼板81の両面において、めっき層82上に接して形成された着色顔料層16からなる着色塗膜層が形成されている。
図8Aに示す表面処理鋼板においては、鋼板81の両面に、めっき層82と着色塗膜層(着色顔料層16)とが形成されている場合を例に挙げて説明するが、鋼板の片面のみに、めっき層82と着色塗膜層とが形成されていてもよい。また、鋼板81の一方の面と、他方の面とに同じ層が形成されていることが、容易に製造でき好ましいが、別々の層が形成されているものであってもよい。
着色顔料層16に防錆顔料などの防錆剤を含有させると、着色顔料層16が脆くなり、表面処理鋼板81aの加工性が低下する。本実施形態では、着色顔料層16が防錆剤を含まないので、防錆顔料などの防錆剤を含有させた場合と比較して、優れた加工性を確保できる。
これに対し、本実施形態に係る表面処理鋼板では、着色顔料層16に用いる樹脂として、ポリエステル樹脂をメラミン硬化剤で架橋したものや、ポリエステル樹脂をイソシアネート硬化剤で架橋したもののみを用いても、十分な塗装密着性を確保することができ、縛り加工や曲げ加工などの厳しい加工を施しても着色顔料層16が剥離しない。
本実施形態に係る表面処理鋼板は、上述した図8Aに示す例に限定されない。図8Bは、第6実施形態に係る表面処理鋼板の他の例を説明するための拡大断面図である。図8Bに示す表面処理鋼板81bは、8Aに示す表面処理鋼板81aと異なり、着色塗膜層15が、めっき層82と着色顔料層16との間に形成されたプライマー塗膜層14を含む。図8Bに示す表面処理鋼板81bは、めっき層82と着色顔料層16との間にプライマー塗膜層14が形成されているので、より一層優れた耐食性が得られる。
プライマー塗膜14に用いる樹脂としては、着色塗膜層16に使用できる樹脂と同様のものが挙げられる。プライマー塗膜14に用いる樹脂と着色塗膜層16に用いる樹脂とは同じであってもよいし、異なっていてもよい。
本実施形態に係る表面処理鋼板においては、より一層耐食性を向上させるために、必要に応じて、着色塗膜層とめっき層との間に化成処理層が形成されていてもよい。
図8Cは、第6実施形態に係る表面処理鋼板の他の変形例を説明するための拡大断面図である。図8Cに示す表面処理鋼板81cは、図8Bに示す表面処理鋼板81bと異なり、着色塗膜層15とめっき層82との間に化成処理層17が形成されている。図8Cに示す表面処理鋼板81cは、着色塗膜層15とめっき層82との間に形成された化成処理層17を含むものであるので、より一層優れた耐食性が得られる。
化成処理の処理液に含まれる樹脂としては、ポリエステル樹脂、アクリル樹脂、ウレタン樹脂、エポキシ樹脂等の一般に公知のものを用いることができる。これらの樹脂は、水溶性もしくは水に分散したタイプであると、化成処理に用いる処理液の取り扱いが容易となるため、より好適である。
また、化成処理の処理液がチタニウム化合物を含むものである場合、チタニウム化合物として、チタンフッ化水素酸、チタンフッ化アンモニウム、シュウ酸チタンカリウム、チタンイソプロポキシド、チタン酸イソプロピル、チタンエトキシド、チタン2-エチル1‐ヘキサノラート、チタン酸テトライソプロピル、チタン酸テトラn-ブチルチタンフッ化カリウム、チタンフッ化ナトリウム等の一般に公知のものを使用できる。
本実施形態に係る表面処理鋼板81cは、めっき層82の塗装密着性が優れており、着色塗膜層15とめっき層82との間に化成処理層17が形成されているので、非常に高い耐食性および加工性を有する。
「実施例m1~実施例m73、比較例x1、比較例x5~比較例x15」
図2に示すめっき装置を用いて、以下に示す方法により、表面処理鋼板を形成した。
表1~表3に示すめっき浴組成、pH、温度のめっき浴を、排出口2cから排出し、供給口2dから供給して、表1~表3に示す平均流速で循環させてなる流動状態のめっき浴に、表1~表3に示す陰極である鋼板を浸漬させた。陽極として表1~表3に示す材料を用い、表1~表3に示す電流密度および時間(電析時間)で、電気めっき法により鋼板の表面に亜鉛とバナジウムとを含む(比較例1については亜鉛のみからなる)実施例m1~実施例m73、比較例x1、比較例x5~比較例x15のめっき層を形成した。
なお、鋼板としては、JIS G 3141記載の一般冷延鋼板の絞り用であるSPCDで板厚0.8mmのものを用いた。
図2に示すめっき装置を用いて、以下に示す方法により、電気めっき銅板を形成した。
表3に示すめっき浴組成、pH、温度のめっき浴を、排出口2cから排出し、供給口2dから供給して、表3に示す平均流速で循環させてなる流動状態のめっき浴に、表3に示す陰極である銅板を浸漬させた。陽極として表3に示す材料を用い、表3に示す電流密度および時間で、電気めっき法により銅板の表面に亜鉛とバナジウムとを含む比較例x2のめっき層を形成した。
図2に示すめっき装置を用いて、以下に示す方法により、表面処理鋼板を形成した。
表3に示すめっき浴組成、pH、温度のめっき浴を循環させず、静止状態とされためっき浴に、表3に示す陰極である鋼板を浸漬させた。陽極として表3に示す材料を用い、表3に示す電流密度および時間で、電気めっき法により鋼板の表面に亜鉛とバナジウムとを含む比較例x3のめっき層を形成した。
めっき槽内のめっき浴を循環させず、めっき槽の底部に配置した攪拌子(スターラー)によって攪拌されている状態(攪拌状態)としたこと以外は、比較例x3と同様にして、比較例x4のめっき層を形成した。
めっき層の目付量は、蛍光X線により検出されるV元素およびZn元素の単位面積当たりの合計質量とした。バナジウム含有率は、蛍光X線により検出されたV元素量を前記目付量で除して百分率で算出した。めっき層の表面粗さRa(中心線平均粗さ)は、JIS B 0601:2001に基づいて測定した。
その結果を表4~表6に示す。
これに対し、表6に示すように、比較例x1、比較例x9~比較例x14の表面処理鋼板では、バナジウム含有率が1%未満であった。また、比較例x5~比較例x8、比較例x12の表面処理鋼板では、目付け量が3g/m2未満であった。
また、攪拌状態とされためっき浴を用いて形成した比較例x4のめっき層は、比較例x3と同様の結晶構造であり、表面に鋼板に達する深いクラック(隙間)が形成されており、デンドライト状の柱状結晶を有していなかった。また、めっき浴中に硝酸イオンが0.01%含まれた比較例x15でも、デンドライト状の柱状結晶を有していなかった。
また、バナジウム含有率が1%未満である比較例x9~比較例x14のめっき層は、比較例x1と同様の結晶構造であり、デンドライト状の柱状結晶を有していなかった。
上記の測定結果を基に、隣接する柱状結晶間(アーム外)に存在するバナジウム含有率xと柱状結晶内(アーム内)に存在するバナジウム含有率yのそれぞれの平均値を算出し、xとyの比x/yを求めた。その結果を表4~表6に示す。
表面処理鋼板から切り出した試験片のエッジおよび裏面をテープシールして、塩水噴霧試験(JIS Z 2371)を行った。そして、24時間後の非シール部分の白錆発生面積率を目視で観察し、以下の基準で評価した。白錆発生面積率とは、観察部位の面積に対する白錆発生部位の面積の百分率である。
6:白錆発生面積率3%未満、
5:白錆発生面積率3%以上、10%未満、
4:白錆発生面積率10%以上、25%未満、
3:白錆発生面積率25%以上、50%未満、
2:白錆発生面積率50%以上、75%未満、
1:白錆発生面積率75%以上
パウダリング試験には、60°V曲げ金型を用いた。表面処理鋼板から切り出した試験片の評価面が曲げ部の内側となるように、先端の曲率半径が1mmである金型を用いて、 60°に曲げ加工し、曲げ部の内側にテープを貼り、テープを引き剥がした。テープと共に剥離しためっき層の剥離状況から、パウダリング性を以下の基準で評価した。
S:剥離幅2mm未満
A:剥離幅2mm以上3mm未満
B:剥離幅3mm以上5mm未満
C:剥離幅5mm以上
日本分光社製のフーリエ変換赤外分光光度計「VALOR-III」を用いて、表面処理鋼板の温度を100℃にしたときの波数600~3000cm-1の領域における赤外発光スペクトルを測定し、これを標準黒体の発光スペクトルと比較することにより、算出した。なお、標準黒体としては、鉄板にタコスジャパン社販売(オキツモ社製造)の「THI-1B黒体スプレー」を30±2μmの膜厚でスプレー塗装したものを用いた。
表面処理鋼板から切り出した試験片に塗料(関西ペイント株式会社製、アミラック♯1000)をバーコート塗布し、140℃で20分間焼付を行い、乾燥膜厚で25μmの皮膜を形成した。得られた塗装板を沸騰水に30分浸漬後、常温の室内に24時間放置した。その後、試験片に対して1mm角100個の碁盤目をNTカッターで切り入れ、これをエリクセン試験機で7mm押し出した後、この押し出し凸部に粘着テープによる剥離テストを行い、以下の基準にて塗装密着性を評価した。
S:剥離無し
A:剥離個数1個以上、10個未満
B:剥離個数10個以上、50個未満
C:剥離個数50個以上
銅板の表面にめっき層を形成した比較例x2では、デンドライト状の柱状結晶を有するめっき層が得られず、パウダリング性、耐食性、塗装密着性のいずれも不十分であった。
めっき層のバナジウム含有率が1%未満である比較例x9~比較例x14では、パウダリング性に優れているが、デンドライト状の柱状結晶を有するめっき層が得られず、耐食性が非常に低く、塗装密着性も不十分であった。
次に、実施例1で製造した亜鉛とバナジウム酸化物とを含むめっき層を有する表面処理鋼板(銅板)に、表7に示すような樹脂皮膜の薬剤を用いて、表8~10に示す組成を有する樹脂皮膜の原料を、上記めっきを施した鋼板表面に塗布し、焼付乾燥して樹脂皮膜を形成した。そして、皮膜形成後の性能として、加工部耐食性、導電性、放射率、耐傷付き性を評価した。放射率については、実施例1と同様の方法で、同様の基準にて評価を行った。加工部耐食性、導電性、耐傷付き性については、以下のように評価を行った。結果を表11~13に示す。
なお、以下、樹脂皮膜中の含有量は、全て樹脂皮膜の固形分に対する質量%である。また、表中のめっきとは、用いた表面処理鋼板の番号を示しており、実施例1の番号に対応している。また、空欄は、意図的には含有させていないことを示している。
試験片の中央部にエリクセン試験機(JIS Z 2247のA寸法に準拠)にて6mm押し出し加工したのち、端面をテープシールしてJIS Z 2371に準拠した塩水噴霧試験(SST)を24時間、72時間、及び120時間行い、押し出し加工を施した部分の各々の試験時間後における錆発生状況を観察し、下記の評価基準で評価した。
5:白錆発生面積が1%未満
4:白錆発生面積が1%以上、5%未満
3:白錆発生面積が5%以上、10%未満
2:白錆発生面積が10%以上、30%未満
1:白錆発生面積が30%以上
樹脂皮膜を形成した表面処置鋼板から切り出した試験片を用いて、JIS C 2550に規定されている測定方法で、層間抵抗値(Ω・cm2)を測定し、以下の基準にて導電性を評価し、C以上を好適とした。
S:層間抵抗値が1.0Ω・cm2未満
A:層間抵抗値が1.0Ω・cm2以上1.5Ω・cm2未満
B:層間抵抗値が1.5Ω・cm2以上2.0Ω・cm2未満
C:層間抵抗値が2.0Ω・cm2以上2.5Ω・cm2未満
D:層間抵抗値が2.5Ω・cm2以上3.0Ω・cm2未満
E:層間抵抗値が3.0Ω・cm2以上
試験片をラビングテスター(大平理化工業社製)に設置後、ラビングテスターの摺動冶具先端に前記試験片と平行になるように縦30mm、横30mmの大きさの段ボール紙を取り付け、その段ボール紙を9.8N(1.0kgf)の荷重で5往復、及び10往復擦った後の皮膜状態を下記の評価基準で評価した。
(基準)
5:擦り面に全く痕跡が認められない
4:擦り面に極僅かに摺動傷が付く(目を凝らして何とか摺動傷が判別できるレベル)
3:擦り面に僅かに摺動傷が付く(目を凝らすと容易に摺動傷が判別できるレベル)
2:擦り面に明確な摺動傷が付く(瞬時に摺動傷が判別できるレベル)
1:擦り面の皮膜が脱落し、下地の金属板が露出する
次に、実施例1で製造した亜鉛とバナジウム酸化物とを含むめっき層を有する表面処理鋼板の表面に、表14に示すような薬剤を用いて、表15~17に示す組成を有する水系金属表面処理剤を、塗布し、焼付乾燥して皮膜を形成した。
そして、皮膜形成後の性能として、加工部耐食性、導電性、加工性(加工密着性)、放射率について、加工性以外は、実施例2と同様の方法で、同様の基準にて評価を行った。加工性は、以下に示すように評価を行った。結果を表18~20に示す。
皮膜を形成した表面処置鋼板から切り出した試験片に180°折り曲げ加工を施した後、折り曲げ部の外側に対してテープ剥離試験を実施した。テープ剥離部の外観を拡大率10倍のルーペで観察し、下記の評価基準で評価した。折り曲げ加工は20℃の雰囲気中で0.5mmのスペーサーを間に挟んで実施した。
5:塗膜に剥離は認められない
4:極一部の塗膜に剥離が認められる(剥離面積≦2%)
3:一部の塗膜に剥離が認められる(2%<剥離面積≦10%)
2:塗膜に剥離が認められる(10%<剥離面積≦20%)
1:塗膜に剥離が認められる(剥離面積>20%)
次に、実施例1で製造した亜鉛とバナジウム酸化物とを含むめっき層を有する表面処理鋼板の表面に、以下に示す方法により、有機樹脂皮膜を形成し、実施例r1~実施例r87、比較例f1~比較例f9の表面処理鋼板(銅板)を形成した。
すなわち、表21に示す樹脂(A1)と、表22に示す硬化剤(B1)と、表23に示す着色剤(C1)と、必要に応じて表24に示すシリカ(D1)と表25に示す潤滑剤(E1)のいずれか一方または両方を含む黒色の水系塗料を、バナジウム酸化物とを含むめっき層を有する表面処理鋼板(銅板)の表面に塗布し、焼付乾燥することにより、有機樹脂皮膜を形成した。
水系塗料は、水中に有機樹脂皮膜の成分である樹脂と硬化剤(B1)と着色剤(C1)と、必要に応じてシリカ(D1)と潤滑剤(E1)のいずれか一方または両方とをディスパーで攪拌し、溶解もしくは分散させることにより製造した。また、水系塗料の塗布には、ロールコートを使用した。また、焼付乾燥方法としては、水系塗料の塗布後にめっき層の形成された鋼板(銅板)を表29~表31に示す到達温度(到達板温度)に加熱する方法を用いた。
試験片を目視観察し、塗膜の隠蔽性を下記の評価基準で評価した。
(基準)
5:黒色、表面艶ともに均一である。下地も全く透けて見えない。
4:黒色は均一であるが、表面艶が不均一である。下地は全く透けて見えない。
3:黒色、表面艶ともに不均一である。下地は全く透けて見えない。
2:黒色、表面艶ともに不均一であり容易に確認できる。下地がやや透けている。
1:黒色、表面艶ともに不均一であり容易に確認できる。下地が明らかに透けている。
光沢測定装置(商品名:Uni Gloss 60Plus (コニカミノルタ社製))を用いて、試験片の60度光沢値を測定した。
「L*値」
色彩色差計CR-400(コニカミノルタ社製)を用いて、試験片のL*値を測定した。
実施例1で製造した亜鉛とバナジウム酸化物とを含むめっき層を有する表面処理鋼板の表面に、以下に示す方法により、着色顔料層を含む着色塗膜層を形成した。
また、必要に応じて、一方の面のめっき層と着色塗膜層との間に、以下に示す方法により、化成処理層を形成した。
めっき層の形成された鋼板の一方の面に化成処理を施す場合、ロールコーターにて以下に示す処理液を付着量100mg/m2で塗布する化成処理を行って化成処理皮膜を形成した。その後、化成処理皮膜を、熱風オーブンにて鋼板の温度が60℃に到達する条件で乾燥させ、放冷することにより、化成処理層を得た。
シランカップリング剤5g/Lとシリカ1.0g/Lと樹脂25g/Lとを含む水溶液を作製し、化成処理の処理液とした。なお、シランカップリング剤にはγ-グリシドキシプロピルトリメトキシシランを用い、シリカには水分散微粒シリカである日産化学社製「スノーテックス-N」を用い、樹脂には水系アクリル樹脂であるポリアクリル酸を用いた。
めっき層の形成された鋼板の一方の面または、めっき層上に化成処理層の形成された鋼板の一方の面に、ロールコーターにて以下に示すプライマー塗料を5μmの膜厚で塗布して、プライマー塗膜を形成した。その後、プライマー塗膜を、誘導加熱オーブンにて鋼板の温度が210℃に到達する条件で乾燥・焼付し、水冷することにより、プライマー塗膜層を得た。
樹脂として、ポリエステル樹脂をメラミンで架橋したものを用いた。ポリエステル樹脂としては、東洋紡績社製の「バイロン(登録商標)29CS(非晶性ポリエステル樹脂である「バイロン(登録商標)290」を有機溶剤に溶解して液状にした固形分濃度30質量%のものでありシクロヘキサノン/ソルベッソ溶解型でガラス転移点(以降、Tg)72℃、数平均分子量(以降、MN)17,000である)」を用い、硬化剤として三井サイテック社製メラミン樹脂「サイメル(登録商標)303」を用いた。ポリエステル樹脂とメラミン樹脂との混合比は、樹脂固形分の質量比で、ポリエステル樹脂:メラミン樹脂=80:20となるようにした。
めっき層の形成された鋼板の一方の面または、めっき層上に化成処理層および/またはプライマー塗膜層の形成された鋼板の一方の面に、カーテンコーターにて以下に示す着色塗料を15μmの膜厚で塗布し、着色塗膜を形成した。その後、着色塗膜を、誘導加熱オーブンにて鋼板の温度が230℃に到達する条件で乾燥・焼付し、水冷することにより、着色顔料層を得た。
樹脂として、ポリエステル樹脂をメラミンで架橋したものを用いた。ポリエステル樹脂としては、東洋紡績社製の「バイロン(登録商標)C300(非晶性ポリエステル樹脂でありシクロヘキサノン/ソルベッソ溶解型でTg7℃、数平均分子量(MN)23,000である)」を用い、硬化剤として三井サイテック社製メラミン樹脂「サイメル(登録商標)303」を用いた。ポリエステル樹脂とメラミン樹脂との混合比は、樹脂固形分の質量比で、ポリエステル樹脂:メラミン樹脂=80:20となるようにした。
なお、着色塗料を塗布する際には、有機溶剤(シクロヘキサノンとソルベッソ150とを質量比でシクロヘキサノン:ソルベッソ150=1:1で混合したもの)で適宜希釈し、粘度を調整した。
めっき層の形成された鋼板81の他方の面に、ロールコーターにて市販のポリエステル系上塗り塗料である日本ペイント社製「FL100HQ」を5μmの膜厚で塗布し、グレー色系の着色塗膜を形成した。その後、着色塗膜を、誘導加熱オーブンにて鋼板の温度が210℃に到達する条件で乾燥・焼付し、水冷することにより、他方の面の着色顔料層を得た。
図9は、曲げ加工性試験における折り曲げ加工を説明するための概略斜視図である。図9に示すように、20℃雰囲気中で表面処理鋼板41の評価面41a(一方の面)が外側になるようにして、180°折り曲げ加工(一般に「0T曲げ加工」と呼ばれる密着曲げ加工)を実施し、加工部を20倍ルーペで観察し、塗膜の割れの有無を調べた。
更に、折り曲げ加工された鋼板41の加工部上にテープを貼り付けて剥離し、テープ剥離後の塗膜の残存状態を観察した。そして、加工部全面において塗膜が全く剥離していない場合をA、加工部の一部で塗膜が剥離している場合をB、塗膜の全面が剥離している場合をCと評価した。
エリクセン型の20tプレス試験機を用いて、表面処理鋼板を以下に示す条件でプレス加工して成形体を形成する円筒絞り試験を行った。金型のダイス肩Rを3mm、ポンチ肩Rを3mm、ポンチ径をφ50mmとし、絞り比2.0、しわ押さえ圧1t、潤滑油無しの条件で絞り抜くまでプレス加工し、図10に示すカップ状の成形体42を得た。
図10は、絞り加工性試験におけるカップ状の成形体を示した概略斜視図である。図10に示す成形体42を沸騰水中に1時間浸漬し、浸漬後の塗膜を観察した。そして、成形体42から塗膜が全く剥離していないものをA、図10に示す成形体42の成形体端面42aから塗膜剥離巾5mm以内の剥離があるものをB、成形体端面42aから塗膜剥離巾5mm超の剥離があるものをCと評価した。
得られた表面処理鋼板を横70mm×縦150mmのサイズに切断し、耐食性試験用のサンプルとした。なお、表面処理鋼板を切断する際に、サンプルの長辺となる端面部については、切断時の返り(バリ)が他方の面(裏面)に来るように(下バリとなるように)した。また、サンプルの短辺の端面部については、切断後にテープにてシールした。
2、32 めっき浴
21、22 めっき槽
3、23 陽極
4、5 ロール
2a 上部供給用配管
2b 下部供給用配管
21a 上部槽
21b 下部槽
32c 排出口
32d 供給口
32e 配管
P ポンプ
11 めっき層
12 柱状結晶
Claims (18)
- 鋼板と、
前記鋼板の片面または両面に形成されてかつ、亜鉛及びバナジウムを含むめっき層とを備え;
前記めっき層は、前記バナジウムの含有率が1%以上20%以下かつ目付け量が3g/m2以上40g/m2以下であり、前記鋼板の厚み方向に成長した複数のデンドライト状のアームを有し;
前記アーム内に存在する前記バナジウムの含有率yに対する前記アーム外に存在する前記バナジウムの含有率xの比x/yが、バナジウム元素換算で1.1以上3.0以下である;
ことを特徴とする表面処理鋼板。 - 前記めっき層が、その表面温度が100℃の条件において測定した波数600~3000cm-1の領域における放射率が0.30以上0.95以下であることを特徴とする請求項1に記載の表面処理鋼板。
- 前記めっき層の表面粗度が、JIS B 0601:2001で規定される中心線平均粗さRaで1.0μm以上、4.0μm以下であることを特徴とする請求項1または2に記載の表面処理鋼板。
- 前記めっき層の上にさらに皮膜が1層以上形成されていることを特徴とする請求項1または2に記載の表面処理鋼板。
- 前記皮膜が、有機樹脂を含有することを特徴とする請求項4に記載の表面処理鋼板。
- 前記皮膜が、樹脂皮膜であり、
前記樹脂皮膜の固形分100質量部に対して、5~50質量部の金属酸化物粒子と;
更に、前記樹脂皮膜の固形分100質量%に対して0.1~30質量%の潤滑材と;
を含有することを特徴とする請求項5に記載の表面処理鋼板。 - 前記有機樹脂が、
カルボキシル基、水酸基、スルホン酸基、シラノール基の少なくとも1種を構造中に有し;
スルホン酸基を含有するポリエステル樹脂と;
硬化剤と;
カーボンブラックを含有する着色顔料を含む;
ことを特徴とする請求項5に記載の表面処理鋼板。 - 前記皮膜が、シランカップリング剤を含有する水系金属表面処理剤を前記鋼板に塗布して乾燥させることにより得られることを特徴とする請求項4に記載の表面処理鋼板。
- 前記皮膜が、更に、チタンおよびジルコニウムから選ばれる少なくとも1種を有するフルオロ金属錯化合物を必須成分とするインヒビター成分を含有する
ことを特徴とする請求項8に記載の表面処理鋼板。 - 前記皮膜が、
ポリエーテルポリウレタン樹脂と;
カーボンブラックを含有する着色顔料と;
を含む複合皮膜であることを特徴とする請求項8に記載の表面処理鋼板。 - 前記皮膜が、着色顔料層を含む着色塗膜層であることを特徴とする請求項5に記載の表面処理鋼板。
- 前記着色塗膜層が、プライマー塗膜層を含み、前記プライマー塗膜層は、前記めっき層と前記着色顔料層との間に形成されて、かつ防錆剤を含むことを特徴とする請求項11に記載の表面処理鋼板。
- 前記着色塗膜層が前記めっき層上に接して形成されていることを特徴とする請求項11に記載の表面処理鋼板。
- 前記着色塗膜層と前記めっき層との間に、化成処理層をさらに含むことを特徴とする請求項11に記載の表面処理鋼板。
- 鋼板の表面に、電気めっき法により亜鉛とバナジウムとを含むめっき層を形成するめっき工程を備えた表面処理鋼板の製造方法であって、
前記めっき工程において、めっき浴に前記鋼板を浸漬させ、前記めっき浴中の電流密度を20~150A/dm2として、1秒以上30秒以下の時間、電析を行って前記めっき層を形成し;
前記めっき浴は、亜鉛化合物及びバナジウム化合物を含有し、かつ、バナジウムイオンまたはバナジルイオンの少なくとも1種を合計含有量で0.01mol/l以上1.0mol/l未満含有し、硝酸イオン含有量を0.0005mol/l未満に制限し、さらに、前記めっき浴は、循環させためっき浴または、めっき浴中で鋼板を移動させることにより前記鋼板に対して前記めっき浴が相対的に流動されるめっき浴の少なくとも一方であり;
前記めっき層は、バナジウム含有率が1%以上20%以下、かつ目付け量が3g/m2以上40g/m2以下である;
ことを特徴とする表面処理鋼板の製造方法。 - めっき槽内における前記めっき浴の平均流速を20~300m/minの範囲とすることを特徴とする請求項15に記載の表面処理鋼板の製造方法。
- 前記めっき浴が、ナトリウムイオンを0.1mol/l以上4.0mol/l以下含むことを特徴とする請求項15または16に記載の表面処理鋼板の製造方法。
- 前記めっき浴が、ニッケルイオンを0.01mol/l以上1.0mol/l以下含むことを特徴とする請求項15または16に記載の表面処理鋼板の製造方法。
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KR20200096281A (ko) | 2017-12-20 | 2020-08-11 | 닛폰세이테츠 가부시키가이샤 | 프리코트 강판 |
WO2020110750A1 (ja) * | 2018-11-29 | 2020-06-04 | 日本製鉄株式会社 | 表面処理鋼板、及び表面処理鋼板の製造方法 |
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JP5273316B2 (ja) | 2013-08-28 |
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CN103459677A (zh) | 2013-12-18 |
US9428823B2 (en) | 2016-08-30 |
CN103459677B (zh) | 2015-04-08 |
JP2013108183A (ja) | 2013-06-06 |
KR20130114275A (ko) | 2013-10-16 |
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KR101413812B1 (ko) | 2014-06-30 |
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