WO2019194229A1 - 亜鉛系電気めっき鋼板 - Google Patents
亜鉛系電気めっき鋼板 Download PDFInfo
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- WO2019194229A1 WO2019194229A1 PCT/JP2019/014830 JP2019014830W WO2019194229A1 WO 2019194229 A1 WO2019194229 A1 WO 2019194229A1 JP 2019014830 W JP2019014830 W JP 2019014830W WO 2019194229 A1 WO2019194229 A1 WO 2019194229A1
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- Prior art keywords
- zinc
- hairline
- layer
- steel sheet
- surface roughness
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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
- C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
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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
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
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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
- B05D7/16—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 using synthetic lacquers or varnishes
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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
Definitions
- the present invention relates to a zinc-based electroplated steel sheet.
- Hairline finish is defined as “finished by polishing with a suitable grain size of abrasive material” in JIS G4305: 2012 as one of the surface finishes of stainless steel materials. ing.
- stainless steel materials and aluminum materials are expensive, inexpensive materials that replace these stainless steel materials and aluminum materials are desired.
- it has a high design and moderate corrosion resistance similar to stainless steel and aluminum materials, and is suitable for use in electrical equipment and building materials, etc.
- steel materials with excellent texture metallic luster, metallic feeling, hereinafter referred to as “metallic feeling”.
- zinc plating and zinc alloy plating may be collectively referred to as “zinc-based plating”.
- a hairline direction formed on the surface layer of the Zn—Al—Mg-based hot-plated layer and roughness parameters (Ra and PPI) orthogonal to the hairline are specified.
- Patent Document 2 a technique for forming a transparent resin film layer on the surface of the Zn—Al—Mg-based hot-plated layer (see Patent Document 2 below), and rolling to texture Zn and Zn-based alloy plating.
- Patent Document 3 Technique to coat the resin as the surface roughness is within a predetermined range has been proposed.
- a steel plate rolling method for rolling a plated steel sheet for which a hairline is to be formed by a rolling roll having a predetermined roughness a plating grinding method for grinding the surface of the plated steel sheet for which a hairline is to be formed, and There is.
- the loss of metallic feeling as described above was particularly remarkable in the plated steel sheet in which the hairline was formed by the steel sheet rolling method described above.
- the reason why the loss of metallic feeling is remarkable is not certain, but in the case of a plated steel sheet in which the hairline is made by rolling the steel sheet, the incident light is incident on the entire surface of the plating layer due to the crystal grains of the plating present on the outermost surface of the plating layer. This is thought to be due to irregular reflection. Therefore, when it is assumed that the resin coating described below is performed on the surface of the plated steel plate on which the hairline is formed, it is considered that the formation of the hairline by the steel plate rolling method is not appropriate.
- the stainless steel material itself has good corrosion resistance due to the oxide film present on the surface, the coating for improving the corrosion resistance is unnecessary. That is, since the metal substrate itself can be used on the surface, the problem of loss of metallic feeling due to the resin coating does not exist in the first place.
- the object is to impart coloring or another texture. Therefore, in the stainless steel material, the loss of metallic feeling as found by the present inventors has not been a problem. This situation is the same for aluminum materials.
- the hairline is usually formed by polishing / grinding the surface with a polishing / grinding belt or the like, or rolling with a rolling roll, but polishing / grinding (hereinafter referred to as “polishing etc.”).
- polishing / grinding hereinafter referred to as “polishing etc.”.
- the portion whose roughness is lowered due to the above is inevitably high gloss, and it is difficult to realize a matte appearance with low gloss.
- zinc-based plated steel sheets are often coated with a resin to maintain corrosion resistance and aesthetics.
- the adhesion between the zinc-based plated layer and the resin film may decrease with the formation of the hairline. It was.
- the present invention has been made in view of the above problems, and the object of the present invention is to prevent an increase in gloss while having a hairline appearance, and to form a resin film on the plating upper layer.
- An object of the present invention is to provide a zinc-based electroplated steel sheet capable of realizing high coating adhesion while maintaining a metallic feeling.
- the present inventors diligently studied a method for improving the metallic feeling, and if the irregular reflection on the outermost surface of the plating layer can be suppressed, the metallic feeling can be obtained even when the surface of the plating layer is coated with a resin. We thought that it was possible to improve. As a result of further studies based on such an idea, the present inventors provide a smooth portion having a microscopic surface roughness of a predetermined threshold or less on the plating layer surface in order to suppress irregular reflection. As a result, it has been found that diffuse reflection can be suppressed.
- the present inventors appropriately adjust the ratio of the rough portion and the smooth portion where the surface roughness in the microscopic range is greater than a predetermined threshold on the surface of the plating layer, so that the metallic feeling and the film adhesion can be achieved. It was possible to obtain knowledge that an excessive increase in gloss can be suppressed while satisfying the above.
- the “surface roughness in the microscopic range” will be described later.
- the present inventors have intensively studied the distribution state of the rough portion and the smooth portion, and a case where the organic resin coating layer is provided on the zinc-based electroplating layer.
- the present inventors have completed the present invention by conceiving conditions for suppressing an excessive increase in gloss while achieving both a metallic feel and film adhesion.
- the gist of the present invention completed based on such findings is as follows.
- a steel sheet and a zinc-based electroplated layer having a hairline located on at least one surface of the steel sheet and extending in a predetermined direction on the surface is defined by a microscopic rough portion having a three-dimensional average surface roughness Sa (1 ⁇ m) h defined by (A) below of 200 nm to 2000 nm and below (B): And a microscopic smooth portion having a three-dimensional average surface roughness Sa (1 ⁇ m) s of more than 5 nm and not more than 200 nm.
- the three-dimensional average surface roughness Sa of a region of 50 ⁇ m ⁇ 50 ⁇ m along each of the hairline direction in which the hairline extends and the hairline orthogonal direction orthogonal to the hairline direction (50 ⁇ m) is continuously measured to calculate R50 which is the ratio of the Sa (50 ⁇ m) in the adjacent region formed by the two adjacent regions, and the R50 is less than 0.667 or more than 1.500
- the adjacent region is the adjacent region A
- the number ratio of the adjacent regions A is 30% or more in both the hairline direction and the hairline orthogonal direction.
- (A) Sa (1 ⁇ m) h is a roughness profile having a length of 1000 ⁇ m measured in the hairline direction, and the ten convex vertices at the highest position among the convex vertices in the roughness profile ,
- the three-dimensional average surface roughness Sa (1 ⁇ m) of the region of 1 ⁇ m ⁇ 1 ⁇ m centered on each convex vertex is measured, and the minimum value among the measured three-dimensional average surface roughness Sa (1 ⁇ m) Represents.
- (B) Sa (1 ⁇ m) s is a roughness profile having a length of 1000 ⁇ m in the hairline direction, and about the 10 recess vertices at the lowest position among the recess vertices in the roughness profile,
- the three-dimensional average surface roughness Sa (1 ⁇ m) of a region of 1 ⁇ m ⁇ 1 ⁇ m is measured around each vertex of the recess, and represents the maximum value of the measured three-dimensional average surface roughness Sa (1 ⁇ m).
- the zinc-based electroplated steel sheet according to (1) may further include an organic resin coating layer having translucency and a thickness of 10 ⁇ m or less as an upper layer of the zinc-based electroplating layer. Good.
- the organic resin coating layer contains a colorant, and the color tone of the organic resin coating layer according to the L * a * b * color system is determined by the CIE standard.
- the value of (a * 2 + b * 2 ) 0.5 indicating the saturation may be 10 or less when measured by the specular reflection removal method using a color difference meter using the light source D65.
- the surface roughness Ra (CC) measured along the hairline orthogonal direction, and the The surface roughness Ra (MC) of the zinc-based electroplating layer measured along the direction orthogonal to the hairline after peeling the organic resin coating layer satisfies the relationship represented by the following formula (1) May be.
- the base iron exposure rate of the zinc-based electroplated layer may be less than 5%.
- the adhesion amount of the zinc-based electroplated layer may be 10 g / m 2 to 60 g / m 2. .
- the zinc-based electroplated layer or the organic resin coating layer provided as an upper layer of the zinc-based electroplated layer And the surface roughness Ra of the said steel plate after removing both the said zinc-type electroplating layer may be 1.0 micrometer or more and 1.7 micrometers or less.
- the zinc-based electroplated layer is any one selected from the group consisting of Fe, Ni, and Co.
- the above elements may be contained in a total amount of 5% by mass to 20% by mass.
- the surface roughness Ra of the said steel plate after removing both of the said zinc-type electroplating layers may be 60% or less of the thickness of the said zinc-type electroplating layer.
- an excessive increase in gloss is suppressed while having a hairline appearance and excellent metallic feeling, and the film adhesion when a resin film is formed on the plating upper layer is realized. Is possible.
- FIG. 1A and FIG. 1B are explanatory views schematically showing an example of the structure of a zinc-based electroplated steel sheet according to this embodiment.
- the zinc-based electroplated steel sheet according to the present embodiment has at least a steel sheet as a base material and a zinc-based electroplated layer located on one surface of the steel sheet, and the surface of the zinc-based electroplated layer. Hairline processing is given to.
- a smooth portion corresponding to a hairline (that is, a portion crushed and smoothed by hairline processing) is provided so as to be physically continuous along a predetermined direction.
- the connection is recognized as a hairline.
- the hairline processing applied to the surface of the zinc-based electroplating layer according to the present embodiment is performed by a person regardless of whether the smooth portion is physically continuous. When the surface is observed, the hairline is recognized as being connected in a predetermined direction.
- the zinc-based electroplated steel sheet according to this embodiment having such characteristics will be described in detail.
- the zinc-based electroplated steel sheet 1 includes a steel plate 11 as a base material, a zinc-based electroplated layer 13 located on one surface of the steel plate 11, At least.
- the zinc-based electroplated steel sheet 1 according to the present embodiment further includes a light-transmitting organic resin coating layer 15 on the surface side of the zinc-based electroplated layer 13. It is preferable.
- the steel plate 11 which is a base material of the zinc-based electroplated steel sheet 1 according to the present embodiment is not particularly limited, and depends on mechanical characteristics (for example, tensile strength, etc.) required for the zinc-based electroplated steel sheet. Various known steel plates can be used as appropriate.
- the zinc-based electroplated layer 13 or both the organic resin coating layer 15 and the zinc-based electroplated layer 13 located on the upper layer side of the zinc-based electroplated layer 13 are removed.
- the surface roughness Ra of the steel plate 11 after being processed is preferably 1.0 ⁇ m or more and 1.7 ⁇ m or less.
- Ra is the arithmetic average roughness specified in JIS B 0601: 2013.
- the surface roughness Ra is less than 1.0 ⁇ m, there is a possibility that it may be difficult to provide the zinc-based electroplating layer 13 having the surface shape as described in detail below.
- the surface roughness Ra exceeds 1.7 ⁇ m, it is recognized that the hairline extends in a predetermined direction even if the zinc-based electroplating layer 13 having the surface shape as described in detail below is provided. Since it may become difficult, it is not preferable.
- the surface roughness Ra of 11 is more preferably 1.1 ⁇ m or more and 1.5 ⁇ m or less.
- the surface roughness Ra is not significantly different between the direction in which the hairline is visible and the direction perpendicular to the hairline, but with respect to the range of the surface roughness Ra. Is measured in the direction perpendicular to the hairline.
- the surface roughness Ra of the steel plate 11 is obtained after removing both the zinc-based electroplating layer 13 or the organic resin coating layer 15 and the zinc-based electroplating layer 13 located on the upper layer side of the zinc-based electroplating layer 13.
- the thickness is preferably 60% or less of the thickness of the zinc-based electroplating layer 13.
- the corrosion resistance may be impaired when the zinc-based electroplating layer 13 having the surface shape described in detail below is provided. It is not preferable because of its properties.
- the surface roughness Ra of 11 is more preferably 40% or less of the thickness of the zinc-based electroplating layer 13.
- the thickness of the zinc-based electroplating layer 13 is determined as follows. First, the plated steel sheet is immersed in an acid solution containing an inhibitor to dissolve the zinc-based electroplating layer 13. Next, the thickness of the zinc-based electroplating layer 13 is converted from the amount of the zinc-based electroplating layer 13 thus obtained and the specific gravity of the metal contained in the zinc-based electroplating layer 13.
- the surface roughness Ra of the steel plate 11 after removing both the zinc-based electroplating layer 13 or the organic resin coating layer 15 formed as the upper layer of the zinc-based electroplating layer 13 and the zinc-based electroplating layer 13 is as follows. When it falls within the above range, the surface roughness Ra of the steel plate 11 before forming the zinc-based electroplating layer 13 and the organic resin coating layer 15 also falls within the above range.
- the surface roughness Ra as described above can be measured with a stylus type roughness meter.
- a zinc-based electroplating agent such as a solvent or a remover that does not attack the steel plate is used.
- the surface roughness Ra may be measured after removing the plating layer 13 and the organic resin coating layer 15.
- the zinc-based electroplating layer 13 is a smooth portion 103 that is visually recognized as a hairline extending in a predetermined direction (the direction indicated by the arrow at the bottom of FIG. 1A). And rough portions 101a and 101b that are visually recognized as portions that are not hairlines.
- hairline direction direction in which the hairline is visually recognized as being stretched
- hairline orthogonal direction direction orthogonal direction
- the rough portion 101a is a recessed portion and is a portion that is free from the influence of polishing or the like associated with hairline processing.
- the rough portion 101b is a portion remaining in the zinc-based electroplating layer 13 after the hairline processing even though the surface thereof is at a position away from the surface of the steel plate 11 in the depth direction.
- the part 101b is also continuous over a certain range in the hairline direction.
- the rough portion 101b in FIG. 1A schematically shows that the rough portion may exist also on the surface portion of the zinc-based electroplating layer 13. Further, the rough portion and the smooth portion will be described in detail later.
- zinc-based electroplating layer 13 As the zinc-based electroplating layer 13 according to the present embodiment, electrogalvanizing or electrozinc alloy plating (hereinafter collectively referred to as “zinc-based electroplating”) is used.
- plating other than zinc plating is inferior in sacrificial corrosion resistance, so it is not suitable for applications in which the cut end face is unavoidably exposed during use. Moreover, since the sacrificial anticorrosive ability is lost when the zinc concentration in the zinc-based electroplating layer 13 becomes too low, the zinc alloy plating contains 65% by mass or more of zinc with respect to the total mass of the zinc-based electroplating layer 13. It is preferable to do.
- the plating method there are a hot dipping method, a thermal spraying method, a vapor deposition plating method and the like in addition to electroplating.
- the hot dipping method is not suitable because the appearance quality is inferior due to solidification patterns such as spangles and dross inevitably mixed in the plating layer.
- the thermal spraying method is not suitable because the uniformity of the appearance cannot be ensured due to the voids inside the plating film.
- the vapor deposition method is not suitable because the productivity is poor because the film formation rate is low. Therefore, in the zinc-based electroplated steel sheet 1 according to the present embodiment, electroplating is used to perform zinc-based plating on the steel sheet surface.
- the electrozinc alloy plating includes Co, Cr, Cu, Fe, Ni, P, Sn, Mn, It is preferable to include Zn and at least one element selected from the element group consisting of Mo, V, W, and Zr.
- the electrozinc alloy plating preferably contains a total of 5% by mass or more and 20% by mass or less of one or more elements selected from the element group consisting of Fe, Ni, and Co.
- the electrozinc alloy plating contains one or more elements selected from the element group consisting of Fe, Ni, and Co within the above-described total content range, it is possible to achieve better corrosion resistance. .
- the electrogalvanization and the electrozinc alloy plating may contain impurities.
- the impurity is not intentionally added as a zinc-based electroplating component, but is mixed in the raw material or mixed in the manufacturing process.
- Co, Cr, Cu, Fe, Ni, P, Sn, Mn, Mo, V, W and Zr may be mixed as impurities. In this embodiment, even if impurities are present in a total amount of about 1% by mass with respect to the mass of all plating, the effect obtained by plating is not impaired.
- the sacrificial anticorrosive ability is lowered.
- it is preferably 65% or more, more preferably 70% or more, and particularly preferably 80% or more with respect to the mass.
- the composition of the zinc-based electroplating layer 13 can be analyzed, for example, by the following method. That is, after removing the organic resin coating layer with a release agent such as a solvent that does not attack plating or a remover (eg, Neo River S-701, manufactured by Sansai Kako Co., Ltd.), the zinc-based electroplating layer is then added with hydrochloric acid containing an inhibitor. What is necessary is just to melt
- ICP Inductively Coupled Plasma: Inductively Coupled Plasma
- the adhesion amount of the zinc-based electroplating layer 13 is preferably 10 g / m 2 or more. If the desired corrosion resistance can be ensured, the amount of adhesion of the zinc-based electroplating layer is not limited, but if the amount of adhesion of the zinc-based electroplating layer is less than 10 g / m 2 , the exposure rate of the ground iron is 5% when the hairline is applied. Since the possibility of exceeding is increased, it is not preferable.
- the adhesion amount of the zinc-based electroplating layer is more preferably 15 g / m 2 or more, and further preferably 20 g / m 2 or more.
- the zinc-based electroplated steel sheet 1 according to the present embodiment is premised on performing a hairline process on the surface of the zinc-based electroplated layer 13 by polishing or the like. Therefore, a part of the zinc-based electroplating layer 13 is removed in a process step such as polishing, and depending on the polishing / grinding thickness, the ground iron (that is, the steel plate 11) may be partially exposed.
- the base metal exposure rate of the zinc-based electroplating layer 13 according to the present embodiment is less than 5%.
- long-term corrosion resistance may be reduced due to the influence of galvanic corrosion when the base iron is exposed at the time of applying a hairline, which is not preferable.
- the exposure rate of the base iron of the zinc-based electroplating layer 13 is less than 5%, in addition to the moderate corrosion resistance generally required for a steel sheet, it has excellent long-term corrosion resistance, and therefore has extremely good corrosion resistance.
- the ground iron exposure rate of the zinc-based electroplating layer 13 is more preferably 3% or less, and further preferably 0%.
- the exposure rate of the ground iron is an area where Zn is not detected relative to the analysis area by removing the organic resin coating layer 15 with a remover such as a solvent or a remover that does not affect plating, and then EPMA analyzing five arbitrary 1 mm squares.
- the rate can be obtained by image analysis.
- the surface of the zinc-based electroplating layer 13 according to the present embodiment is subjected to specific hairline processing, the surface has a characteristic surface shape associated with hairline processing. Such a surface shape will be described in detail later.
- the organic resin coating layer 15 is preferably provided on the surface side of the zinc-based electroplating layer 13 according to the present embodiment.
- the resin has translucency means that light is applied to the surface of the zinc-based electroplated steel sheet 1 and the zinc-based electroplated steel sheet 1 is observed at an angle of 10 ° from the vertical direction. In this case, it means that the hairline applied to the zinc-based electroplating layer 13 can be visually recognized.
- the resin used for forming the organic resin coating layer 15 is not particularly limited as long as it retains sufficient transparency.
- the resin used for forming the organic resin coating layer 15 include a polyester resin, an epoxy resin, a urethane resin, a polyester resin, a phenol resin, a polyether sulfone resin, a melamine alkyd resin, and an acrylic resin.
- examples include resins, polyamide resins, polyimide resins, silicone resins, polyvinyl acetate resins, polyolefin resins, polystyrene resins, vinyl chloride resins, vinyl acetate resins.
- the plated steel sheet comprising the steel plate 11 and the zinc-based electroplating layer 13 is within a range that does not impair the appearance.
- inorganic treatment, organic-inorganic composite treatment, surface modification treatment, or the like may be performed.
- “deteriorating the appearance” means reducing the metallic feeling, such as reducing the transparency, causing uneven glossiness, or causing abnormal unevenness.
- examples of such treatment include Zr oxide treatment, Zn oxide treatment, silane coupling agent treatment, weak acid immersion treatment, weak alkali immersion treatment, and the like.
- various additives may be contained within a range that does not impair the translucency and appearance and does not deviate from the range defined by the present invention.
- Examples of the performance added to the organic resin coating layer 15 include corrosion resistance, slidability, scratch resistance, conductivity, and color tone.
- corrosion resistant it may contain a rust preventive or inhibitor
- if it is slidable or wrinkle resistant it may contain wax, beads, etc.
- a color tone a known colorant such as a pigment or a dye may be contained.
- the organic resin coating layer 15 which concerns on this embodiment contain well-known coloring agents, such as a pigment and dye
- a coloring agent is included so that a hairline can be visually recognized and a metallic feeling is not lost. It is preferable.
- the extent to which the hairline can be visually recognized and the metallic feeling is not lost means that the color tone (L * a * b) of the organic resin coating layer 15 is viewed in a 10-degree field by a commercially available color difference meter using the CIE standard light source D65. * It means the range in which the relationship of saturation (a * 2 + b * 2 ) 0.5 ⁇ 10 is established when the color tone of the color system is measured by the SCE (Specular Component Excluded) method. .
- the thickness of the organic resin coating layer 15 is preferably 10 ⁇ m or less.
- the thickness of the organic resin coating layer 15 exceeds 10 ⁇ m, the distance through which the light passes through the organic resin coating layer 15 is increased, the reflected light is reduced, and the glossiness in the hairline direction is lowered. As a result, the hairline is difficult to visually recognize. This is not preferable because the possibility of becoming higher becomes higher.
- the deformation of the resin accompanying the processing is not preferable because the texture between the surface of the zinc-based electroplating layer 13 and the shape of the surface of the organic resin coating layer 15 are likely to occur.
- the thickness of the organic resin coating layer 15 is preferably 10 ⁇ m or less, and more preferably 8 ⁇ m or less.
- the thickness of the thinnest portion as viewed from the cross section of the organic resin coating layer 15 (that is, the minimum thickness of the organic resin coating layer 15) is 0.1 ⁇ m or more, and the organic resin coating It is preferable that the average thickness of the layer 15 is 1.0 ⁇ m or more.
- the “thinnest part” means the minimum value of the film thickness obtained by cutting a length of 5 mm at an arbitrary position in a direction orthogonal to the hairline to create a cross-sectional sample and measuring 20 points at 100 ⁇ m intervals.
- Average thickness means an average of 20 points.
- the thickness of the thinnest part of the organic resin coating layer 15 is more preferably 0.5 ⁇ m or more, and the average thickness of the organic resin coating layer 15 is more preferably 3.0 ⁇ m or more.
- FIG. 1A and FIG. 1B the case where the zinc-based electroplating layer 13 and the organic resin coating layer 15 are formed on one surface of the steel plate 11 is illustrated. Further, the zinc-based electroplating layer 13 and the organic resin coating layer 15 may be formed.
- the zinc-based electroplating layer 13 has the smooth portion 103 that forms the hairline and the rough portions 101a and 101b in the surface layer portion.
- the rough portions 101 a and 101 b are caused by the microscopic surface shape of the zinc-based electroplating layer 13.
- the rough portions 101a and 101b are portions where the microscopic rough portion in which the three-dimensional roughness Sa (1 ⁇ m) of the microscopic region of 1 ⁇ m ⁇ 1 ⁇ m is greater than 200 nm and less than or equal to 2000 nm is high.
- the smoothing part 103 is a part where the microscopic smoothing part in which the three-dimensional roughness Sa (1 ⁇ m) of the microscopic area of 1 ⁇ m ⁇ 1 ⁇ m is more than 5 nm and not more than 200 nm is detected frequently.
- the three-dimensional roughness Sa is an arithmetic average height defined by ISO 25178, which is an expansion of Ra (arithmetic average height) defined by JIS B0601: 2013.
- microscopic rough portion “microscopic smooth portion”, “rough portions 101a and 101b”, and “smooth portion 103” are defined as follows.
- a laser microscope having a display resolution in the height direction of 10 nm or more and a display resolution in the width direction of 10 nm or more (that is, the height direction and the width direction).
- the surface of the zinc-based electroplating layer 13 in the range of 1 cm ⁇ 1 cm is observed at a magnification of 500 times using a laser microscope whose display resolution is better than 10 nm.
- the observation field of view of the laser microscope is less than 1 cm ⁇ 1 cm, a plurality of fields of view may be observed and the surface may be observed by connecting these fields of view.
- a region where the three-dimensional roughness Sa (1 ⁇ m) h of the region of 1 ⁇ m ⁇ 1 ⁇ m is more than 200 nm and not more than 2000 nm is defined as a “microscopic rough portion”.
- the region in which the three-dimensional roughness Sa (1 ⁇ m) s of the region of 1 ⁇ m ⁇ 1 ⁇ m with the formation of the hairline is more than 5 nm and not more than 200 nm is defined as a “microscopic smooth portion”.
- the above-mentioned three-dimensional roughness Sa (1 ⁇ m) h is defined as (A) below, and the three-dimensional roughness Sa (1 ⁇ m) s is defined as (B) below.
- (A) Sa (1 ⁇ m) h is a roughness profile with a length of 1000 ⁇ m in the hairline direction, and for each of the 10 convex vertices at the highest position among the convex vertices in the profile, The three-dimensional average surface roughness Sa (1 ⁇ m) of a region of 1 ⁇ m ⁇ 1 ⁇ m with the convex portion apex as the center is measured, and represents the minimum value of the measured three-dimensional average surface roughness Sa (1 ⁇ m).
- (B) Sa (1 ⁇ m) s is a roughness profile having a length of 1000 ⁇ m in the hairline direction, and each of the 10 recessed vertices at the lowest position among the recessed vertices in the profile
- the three-dimensional average surface roughness Sa (1 ⁇ m) of a region of 1 ⁇ m ⁇ 1 ⁇ m is measured, and the maximum value of the measured three-dimensional average surface roughness Sa (1 ⁇ m) is represented.
- 1A and 1B which are schematic diagrams, show that there is a portion where Sa (1 ⁇ m) s exceeds 200 nm in a part of the smoothing portion indicated by reference numeral 103, and reference numerals 101a and 101b. This does not exclude the presence of a portion where Sa (1 ⁇ m) h is less than 200 nm in a part of the rough portion indicated by.
- the rough portions 101a and 101b correspond to portions where the crystal grains of plating are present in an electrodeposition state or close to the electrodeposition state.
- the smooth portion 103 corresponds to a portion where the crystal grains of the plating are crushed with the formation of the hairline or a portion where the shape of the crystal particles does not exist.
- rough portions 101a and 101b having a high presence frequency of minute regions (that is, microscopic rough portions) in which crystal particles that have been plated remain, and plating are provided.
- the smooth portion 103 having a high frequency of existence of minute regions (that is, microscopic smooth portions) in which the shape of the remaining crystal grains does not remain is present at an appropriate ratio and position.
- the three-dimensional average surface roughness Sa (50 ⁇ m) of a 50 ⁇ m ⁇ 50 ⁇ m region is measured using a laser microscope having a display resolution in the height direction of 10 nm or more and a display resolution in the width direction of 10 nm or more.
- the three-dimensional average surface roughness Sa (50 ⁇ m) is calculated to be low in a region where there are many microscopic smooth portions and few microscopic rough portions.
- the three-dimensional average surface roughness Sa (50 ⁇ m) in a region where there are many microscopic rough portions and few microscopic smooth portions is calculated to be high.
- the smooth portion 103 or the rough portions 101a and 101b are continuous. Can be judged.
- the region where the three-dimensional average surface roughness Sa (50 ⁇ m) is high or the region where the three-dimensional average surface roughness Sa (50 ⁇ m) is low is continuous is along the hairline direction or the direction orthogonal to the hairline.
- the ratio of the three-dimensional average surface roughness Sa (50 ⁇ m) in two adjacent regions hereinafter sometimes referred to as adjacent regions.
- the three-dimensional average surface roughness Sa (50 ⁇ m) is measured at n points in the hairline direction, and the three-dimensional average surface roughness Sa (50 ⁇ m) is measured in the adjacent region in the hairline direction.
- the value of the ratio R50 is calculated at (n ⁇ 1) places, it is out of the range of 0.667 or more and less than 1.500 (in other words, the value of the ratio R50 is less than 0.667 or 1.500 or more.
- the ratio of the number of adjacent regions is 30% or more (that is, (adjacent The number of regions A) / (n-1) is 0.3 or more).
- the number ratio of adjacent regions (hereinafter, may be referred to as adjacent regions B) where R50 is 0.667 or more and less than 1.500 is less than 70%.
- the adhesion of the processed part when the resin coating layer 15 is provided decreases, or the rough parts 101a and 101b are too continuous to be recognized as a continuous hairline, and the glossiness in the hairline direction is too low. This is not preferable because the metallic feeling is impaired.
- there is no upper limit of the number ratio of the adjacent regions A in the hairline direction and the number ratio may be 100%. By setting the number ratio of the adjacent regions A in the hairline direction to 30% or more, it is possible to moderately suppress the gloss without impairing the metallic feeling and realize excellent film adhesion.
- the number ratio is preferably 35% or more, more preferably 40% or more.
- the number ratio of the adjacent regions A is set to 30% or more as in the hairline direction. Even when the number ratio of the adjacent areas A in the direction orthogonal to the hairline is less than 30%, the smooth part 103 is too continuous and the gloss becomes too high, and the processed part adhesion when the organic resin coating layer 15 is provided is high. It is not preferable because it decreases or the rough portions 101a and 101b are too continuous to be recognized as a hairline. On the other hand, there is no upper limit for the number ratio of the adjacent regions A in the hairline orthogonal direction, and the number ratio may be 100%. By setting the number ratio to 30% or more, it is possible to moderately suppress the gloss without impairing the metallic feeling and realize excellent film adhesion.
- the number ratio is preferably 35% or more, more preferably 40% or more.
- the ratio of the number of adjacent regions A in the hairline direction and the direction orthogonal to the hairline is 30% or more, for example, as shown in FIG.
- the polishing / grinding thickness with respect to the steel plate roughness is limited to a predetermined ratio as described later. Further, as described above, it is preferable to set the surface roughness Ra of the steel plate 11 as the base material within a specific range.
- the zinc-based electroplating layer 13 has a 1 ⁇ m ⁇ 1 ⁇ m region using a laser microscope having a display resolution in the height direction of 1 nm or more and a display resolution in the width direction of 1 nm or more.
- Sa (1 ⁇ m) h defined by (A) above has a microscopic rough portion that is more than 200 nm and not more than 2000 nm.
- the surface roughness Ra of the steel sheet 11 that is the base material is preferably set within a specific range.
- an electroplating layer is deposited on a valley portion (concave portion) in the roughness curve (roughness profile), and the portion is protected from polishing or the like.
- a microscopic rough portion is present. This is because it is secured.
- Sa (1 ⁇ m) h of the above-mentioned microscopic rough portion is more than 200 nm and not more than 2000 nm, thereby realizing a more reliable contact state with the organic resin coating layer 15 capable of realizing excellent film adhesion. can do.
- the smooth portion 103 is present at an appropriate ratio, so that the zinc-based electroplated steel sheet 1 according to the present embodiment is suitable. Has a metallic feel.
- the smooth portion 103 has an appropriate surface roughness and an appropriate area.
- the zinc-based electroplating layer 13 uses a laser microscope in which the smooth portion 103 has a display resolution in the height direction of 1 nm or more and a display resolution in the width direction of 1 nm or more.
- the microscopic smooth portion has Sa (1 ⁇ m) s defined in (B) above more than 5 nm and not more than 200 nm.
- the smoothing part 103 has a high detection frequency of the microscopic smoothing part, it is possible to achieve both a suitable metallic feeling and a suitable glossiness.
- the surface roughness Ra (CC) [unit: ⁇ m] measured along the hairline orthogonal direction in the state where the organic resin coating layer 15 is present
- the organic resin The surface roughness Ra (MC) [unit: ⁇ m] of the zinc-based electroplating layer 13 measured along the direction orthogonal to the hairline after peeling the coating layer 15 is represented by the following formula (101). It is preferable to satisfy the relationship.
- each Ra in the above formula (101) is an average value of Ras at six locations obtained by measuring arbitrary 10 locations and excluding 2 locations on the maximum side and 2 locations on the minimum side.
- the surface roughness Ra (MC) and Ra (CC) more preferably satisfy the relationship represented by the following formula (103).
- the surface roughness Ra in each direction can be measured with a stylus type roughness meter.
- the organic resin coating layer 15 is removed with a release agent such as a solvent or a remover that does not attack plating. Measurement may be performed after removal.
- the manufacturing method of the zinc-type electroplating steel plate which has a structure as shown to FIG. 1A and FIG. 1B is demonstrated easily.
- a steel sheet adjusted to have a surface roughness within a predetermined range is degreased with an alkaline solution and pickled with an acid such as hydrochloric acid or sulfuric acid to form a zinc-based electroplating layer.
- the adjustment of the surface roughness of the steel sheet can use a known method, for example, a method of rolling and transferring with a roll adjusted so that the surface roughness is in a desired range, etc. This method can be used.
- the electroplating bath As a method for forming the zinc-based electroplating layer 13, a known electroplating method can be used.
- the electroplating bath that can be used include a sulfuric acid bath, a chloride bath, a zincate bath, a cyanide bath, a pyrophosphoric acid bath, a boric acid bath, a citric acid bath, other complex baths, and combinations thereof.
- the electrozinc alloy plating bath contains one or more single ions or complex ions selected from Co, Cr, Cu, Fe, Ni, P, Sn, Mn, Mo, V, W, and Zr.
- an electrozinc alloy plating layer containing a desired amount of Co, Cr, Cu, Fe, Ni, P, Sn, Mn, Mo, V, W, and Zr.
- an additive it is more preferable to add an additive to the plating bath.
- composition, temperature, flow rate, current density and current pattern during plating may be selected as appropriate so as to obtain a desired plating composition, and are not particularly limited.
- the thickness of the galvanized layer and the electrogalvanized plated layer should be controlled by adjusting the current value and the time within the range of the current density where the galvanized layer and the electrogalvanized plated layer have a desired composition. Can do.
- the hairline which concerns on this embodiment is formed with respect to the steel plate 11 provided with the obtained zinc system electroplating layer 13.
- FIG. Examples of the method for applying the hairline include a method of polishing with a polishing belt, a method of polishing with an abrasive brush, a method of polishing with a polishing / grinding device, and the like.
- the depth and frequency of the hairline can be controlled to a desired state by adjusting the particle size of the polishing belt and the abrasive brush, the rolling force, the relative speed, and the number of times.
- the concave portion where the crystal particles as plated are present is held as it is, or the concave portion is appropriately ground or the like, which is schematically shown in FIGS. 1A and 1B.
- the rough portions 101a and 101b can exist so as to divide the smooth portion 103 as shown in FIG.
- the polishing / grinding thickness (that is, the polishing / grinding rate) at the time of forming the hairline with respect to the surface roughness Ra of the steel plate 11 is set to 10 to 80%.
- a desired hairline can be formed.
- the polishing / grinding rate is the length in the depth direction starting from the surface of the zinc-based electroplating layer 13 as to how much the zinc-based electroplating layer 13 is polished / ground with respect to the surface roughness of the steel sheet. It is the amount expressed in size.
- the polishing / grinding thickness can be changed by adjusting the grain size of the polishing paper, the rolling force, and the number of times of polishing.
- the hairline By forming the hairline at a polishing / grinding rate of 10 to 80%, the hairline is formed with the unevenness on the surface of the steel plate 11 as the base remaining, so the smooth portion is physically continuous. In spite of not doing, the hairline which is connected in the predetermined direction can be formed.
- the polishing / grinding rate is less than 10%, the number ratio of the adjacent regions A in the hairline direction and / or the hairline orthogonal direction is likely to be less than 30%, which is not preferable.
- the polishing / grinding rate is 10% or more, preferably 20% or more, more preferably 30% or more.
- the polishing / grinding rate exceeds 80%, the number ratio of the adjacent regions A in the hairline direction and / or the hairline orthogonal direction is likely to be less than 30%, which is not preferable.
- the polishing / grinding rate is 80% or less, preferably 70% or less, more preferably 60% or less.
- the surface roughness Ra of the steel plate 11 can be measured with a palpation type roughness meter.
- the polishing / grinding rate is calculated from the difference in the amount of plating adhesion between the two adjacent portions, with one having a hairline and the other having no hairline.
- a specific gravity of 7.1 is used when converting the amount of adhesion to the length.
- the surface of the zinc-based electroplating layer 13 provided with a hairline is covered with an organic resin.
- the coating material used for forming the organic resin coating layer 15 follows the surface shape of the zinc-based electroplating layer 13 at the moment when it is applied to the zinc-based electroplating layer 13, and once the surface of the zinc-based electroplating layer 13 is applied.
- the leveling after reflecting the shape is preferably slow. That is, it is desirable that the paint has a low viscosity at a high shear rate and a high viscosity at a low shear rate.
- the shear viscosity in order to adjust the shear viscosity within the above range, for example, in the case of a paint using a water-based emulsion resin, it can be adjusted by adding a hydrogen bonding viscosity modifier.
- a hydrogen bonding viscosity modifier Such hydrogen bondable viscosity modifiers restrain each other by hydrogen bonds at low shear rates, so the viscosity of the paint can be increased, but at high shear rates, the hydrogen bonds are broken and the viscosity decreases. To do. This makes it possible to adjust the shear viscosity according to the required coating conditions.
- the method for coating the organic resin is not particularly limited, and a known method can be used. For example, using a paint adjusted to the viscosity as described above, after applying by a spraying method, a roll coater method, a curtain coater method, a die coater method or a dip pulling method, it may be formed by natural drying or baking drying. it can. In addition, what is necessary is just to determine a drying temperature and drying time, and a baking temperature and baking time suitably so that the organic resin coating layer 15 to form may have desired performance. At this time, if the rate of temperature rise is slow, the time from the softening point of the resin component to the completion of baking becomes long and leveling proceeds, so that the rate of temperature rise is preferably fast.
- FIG. 2A is an example of an image when the surface of the zinc-based electroplating layer included in the zinc-based electroplated steel sheet according to the present embodiment is observed with an SEM.
- FIG. 2B is an image taken with a normal camera so that the surface of the zinc-based electroplating layer 13 shown in FIG.
- the zinc-based electroplating layer 13 having the surface shape as shown in FIG. 2A can be formed.
- the photo height direction corresponds to the hairline direction
- the photo width direction corresponds to the hairline orthogonal direction.
- the smooth portion 103 is not necessarily continuously distributed along the hairline direction, and is a rough portion. As can be seen from FIG.
- a steel plate having a thickness of 0.6 mm which has been annealed and temper-rolled (as a component composition, in mass%, C: 0.05%, Si: 0.001%, Mn: 0.15 %, P: 0.01%, S: 0.01%, sol.Al: 0.04%, respectively, and the balance is an Al killed steel sheet made of Fe and impurities).
- the above steel plate was electrolytically degreased and washed with water using a Na 4 SiO 4 treatment solution having a concentration of 30 g / L under the conditions of a treatment solution of 60 ° C., a current density of 20 A / dm 2 , and a treatment time of 10 seconds.
- the electrolytically degreased steel plate was immersed in an aqueous solution of H 2 SO 4 having a concentration of 50 g / L at 60 ° C. for 10 seconds, and further washed with water, thereby performing plating pretreatment.
- the surface roughness Ra (arithmetic mean roughness) of the steel sheet was as shown in the table.
- a commercially available SUS304 steel plate (B4 bright finish steel plate) provided with a hairline with # 180 abrasive grains was used as a comparative material (indicated as “No. SUS”). No. In SUS, a zinc-based electroplating layer was not formed, and no hairline was imparted. No. In SUS, an organic resin coating layer was not formed.
- the steel sheet was plated as shown in the table to form a zinc-based electroplating layer.
- a Zn plating film As the zinc-based electroplating layer, a Zn plating film, a Zn—Ni plating film, a Zn—Fe plating film, a Zn—Co plating film, a Zn—Ni—Fe plating film, and a Zn—Co—Mo plating film were used.
- the formation conditions of each plating film are as follows.
- ⁇ Zn plating film (No. 1-15, 62, 66)>
- a pH 2.0 plating bath containing Zn sulfate heptahydrate 1.0M and anhydrous sodium sulfate 50 g / L was used, the bath temperature was 50 ° C., and the current density was 50 A / dm 2.
- the plating time was adjusted so that the value indicated in the table was obtained.
- ⁇ Zn—Co plating film (No. 44 to 57, 65, 69)> Mixing of Zn sulfate heptahydrate and Co sulfate heptahydrate so that when plating is performed at a bath temperature of 50 ° C. and a current density of 50 A / dm 2 , the composition described in the “plating type” column of the table is obtained. The ratio was adjusted.
- the plating solution was flowed so that the relative flow rate was 1 m / sec.
- composition of the obtained plating film was confirmed by immersing the plated steel plate in 10% by mass hydrochloric acid containing an inhibitor (No. 700AS manufactured by Asahi Chemical Co., Ltd.), dissolving and peeling it, and analyzing the dissolved solution by ICP.
- a hairline was applied to the obtained plated steel sheet along the L direction (rolling direction) of the steel sheet.
- the hairline was formed by pressing abrasive paper against the steel plate.
- the hairline was formed so as to achieve the polishing / grinding rate shown in the table by adjusting the grain size, rolling force and number of polishings of the abrasive paper.
- the polishing / grinding rate is determined by giving a hairline to one of two 100 mm width adjacent to the width direction of the steel sheet, and determining the amount of each plating without giving a hairline to the other, and before applying the hairline. It calculated from the difference of the adhesion amount after the plating adhesion amount and the other hairline provision. Moreover, 7.1 of the value of the plating specific gravity at this time was used.
- the plating roughness after the hairline is applied and the plating adhesion amount are as shown in the table.
- the surface roughness Ra of the steel sheet after removing the plating layer is measured with a three-dimensional surface roughness measuring machine (Surfcom 1500DX3, manufactured by Tokyo Seimitsu), and the three-dimensional surface roughness Sa of the plated steel sheet is determined by the display resolution in the height direction.
- a three-dimensional surface roughness measuring machine Sudfcom 1500DX3, manufactured by Tokyo Seimitsu
- the three-dimensional surface roughness Sa of the plated steel sheet is determined by the display resolution in the height direction.
- the plating adhesion amount before applying the hairline was calculated from the difference in weight before and after the steel sheet after forming the plating layer was immersed in 10% by mass hydrochloric acid containing an inhibitor (No. 700AS manufactured by Asahi Chemical) and dissolved and peeled off.
- the microscopic rough portion Sa A in each table was determined as follows. First, a roughness profile having a length of 1000 ⁇ m in the hairline direction was measured using the laser microscope used for measuring the three-dimensional surface roughness Sa. Sa (1 ⁇ m) of an area of 1 ⁇ m ⁇ 1 ⁇ m centered on the convex vertices was measured for the ten convex vertices at the highest position among the convex vertices in the profile. The minimum value (namely, the value of Sa (1 micrometer) h) was described as Sa A in the table
- Sa (1 ⁇ m) of an area of 1 ⁇ m ⁇ 1 ⁇ m centered on the concave vertex was measured for the ten concave concave vertices at the lowest position among the concave vertices in the profile.
- the maximum value (that is, the value of Sa (1 ⁇ m) s) among them is shown as Sa B in the table.
- the three-dimensional average surface roughness Sa (50 ⁇ m) of a 50 ⁇ m ⁇ 50 ⁇ m region was continuously measured at 21 locations in the hairline direction and 21 locations in the hairline orthogonal direction.
- the ratio R50 of the three-dimensional average surface roughness Sa (50 ⁇ m) in the adjacent region was calculated in a total of 20 adjacent regions.
- the ratio of the number of adjacent regions A with R50 less than 0.667 or 1.500 or more out of the total 20 adjacent regions is shown in each table.
- a transparent organic resin coating layer was formed on the plated steel sheet provided with the hairline.
- As the organic resin-forming treatment liquid treatment liquids having various concentrations and viscosities in which urethane resin (manufactured by ADEKA Corporation, HUX-232) was dispersed in water were used. The treatment liquid was scooped up with a roll and transferred to the plated steel sheet so as to have the thickness shown in the table after baking and drying. The plated steel sheet to which the treatment solution was transferred was placed in a furnace maintained at 250 ° C., held for 1 to 5 minutes until the steel sheet reached 210 ° C., and then removed and cooled. No.
- BYK-425 (manufactured by Big Chemie) is added as a viscosity modifier to the organic resin forming treatment liquid, and has a viscosity of 10 [Pa ⁇ s] or more at a shear rate of 0.1 [1 / sec] and a shear rate of 1000 [ 1 / sec] was adjusted to have a shear viscosity of 0.01 [Pa ⁇ s] or less.
- the viscosity adjusting agent is not added only to the treatment liquids corresponding to conditions 6, 9, 25, 39, and 53, and the viscosity at a shear rate of 0.1 [1 / sec] is adjusted to be lower than 10 [Pa ⁇ s]. did.
- the surface roughness Ra (CC) of the organic resin coating layer was measured with a three-dimensional surface roughness measuring machine (Surfcom 1500DX3, manufactured by Tokyo Seimitsu) in the same manner as the surface roughness Ra of the steel sheet after the plating layer was removed. .
- the 60 ° gloss G60 of the plated steel sheet after the organic resin coating layer is formed is measured in the L direction (rolling direction of the steel sheet) and C direction (direction perpendicular to the rolling direction) by a gloss meter (Suga Test Instruments: Gross meter UGV-6P). ).
- the obtained G60 values are shown in the table.
- the glossiness G60 (Gl) measured in the hairline direction is 70 to 150, the appropriate glossiness It was judged that it was obtained.
- the translucency of the zinc-based electroplated steel sheet after forming the organic resin coating layer was evaluated by the following method.
- the zinc-based electroplated steel sheet after the formation of the organic resin coating layer was irradiated with light from a fluorescent lamp from an angle of 45 °, and was observed from a distance of 15 cm at an angle of 10 ° from the vertical direction with respect to the steel sheet.
- the translucency was evaluated by the standard. Those evaluated as A or B were regarded as acceptable. The results obtained are shown in the table.
- a hairline with a length of 20 mm or more can be clearly seen
- the film adhesion of the zinc-based electroplated steel sheet after forming the organic resin coating layer was evaluated by the following method.
- a test piece having a width of 50 mm and a length of 50 mm was prepared from the zinc-based electroplated steel sheet after the organic resin coating layer was formed.
- the obtained test piece was subjected to a bending process of 180 °, and then a tape peeling test was performed on the outside of the bent part.
- 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. Those evaluated as A or B were regarded as acceptable.
- the results obtained are shown in the table.
- No. In SUS since the organic resin coating layer was not formed, the film adhesion was not evaluated. Therefore, no.
- the evaluation result of SUS film adhesion is indicated by “ ⁇ ”.
- the metallic feeling of the zinc-based electroplated steel sheet after forming the organic resin coating layer was evaluated by the following method. Using the value of G60 (Gl) measured in the hairline direction and G60 (Gc) measured in the direction orthogonal to the hairline, and using a spectrocolorimeter (manufactured by Konica Minolta: CM-2600d) under the conditions of CIE standard light source D65 The metallic feeling was evaluated according to the following evaluation criteria, using the values of a * and b * , in which the color tone based on the L * a * b * color system was measured by the SCE (Specular Component Excluded) method. Those evaluated as A or B were regarded as acceptable. The results obtained are shown in the table.
- the zinc-based electroplated steel sheet corresponding to the examples of the present invention has excellent translucency, moderate glossiness, and excellent metallic feel and coating. It turns out that it has adhesiveness.
- the zinc-based electroplated steel sheet corresponding to the comparative example of the present invention could not obtain excellent results with respect to at least any of the items of translucency, glossiness, metallic feeling, and film adhesion.
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JP2022515160A (ja) * | 2018-12-19 | 2022-02-17 | ポスコ | 表面外観に優れた電気めっき鋼板及びその製造方法 |
WO2022196318A1 (ja) * | 2021-03-19 | 2022-09-22 | 日本製鉄株式会社 | テクスチャ付きめっき鋼板の製造方法及びテクスチャ付きめっき鋼板の製造装置 |
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WO2022196318A1 (ja) * | 2021-03-19 | 2022-09-22 | 日本製鉄株式会社 | テクスチャ付きめっき鋼板の製造方法及びテクスチャ付きめっき鋼板の製造装置 |
WO2023068303A1 (ja) * | 2021-10-19 | 2023-04-27 | 日本製鉄株式会社 | めっき鋼板 |
KR20230084519A (ko) * | 2021-12-03 | 2023-06-13 | 닛폰세이테츠 가부시키가이샤 | Zn계 도금 강판 |
KR102620034B1 (ko) | 2021-12-03 | 2024-01-03 | 닛폰세이테츠 가부시키가이샤 | Zn계 도금 강판 |
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JP6733839B2 (ja) | 2020-08-05 |
KR102393728B1 (ko) | 2022-05-04 |
CN111699282A (zh) | 2020-09-22 |
CN111699282B (zh) | 2023-01-20 |
JPWO2019194229A1 (ja) | 2020-04-30 |
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