Title of invention: Zinc-based electroplated steel sheet
Technical field
[0001]
The present invention relates to a zinc-based electroplated steel sheet.
The present application claims priority based on Japanese Patent Application No. 2018-071944 filed in Japan on April 3, 2018, the contents of which are incorporated herein by reference.
Background technology
[0002]
Generally, design is required for articles that people can see, such as electrical equipment, building materials, and automobiles. As a method of enhancing the design, a method of painting or attaching a film to the surface of an article is common, but in recent years, mainly in Europe and the United States, which are nature-oriented, the application of materials utilizing the texture of metal Is increasing. From the viewpoint of utilizing the texture of metal, coating or resin coating impairs the texture of metal. Therefore, stainless steel or aluminum that is excellent in corrosion resistance even when unpainted is used as the material of the article. In addition, in order to improve the design of stainless steel and aluminum materials, fine arc-shaped irregularities called vibrations are added, and embossing is applied, but fine linear irregularities called hairlines are added. The appearance is particularly preferred and heavily used.
[0003]
The hairline finish (HL finish) is defined as one of the surface finishes of stainless steel materials in JIS G4305:2012, which is "finished by polishing with an abrasive having an appropriate grain size so as to have continuous polishing". ing.
[0004]
However, since stainless steel and aluminum are expensive, inexpensive materials that replace these stainless steel and aluminum are desired. As one of such alternative materials, a metal having a hairline appearance, which has high designability and appropriate corrosion resistance similar to stainless steel materials and aluminum materials and is suitable for use in electric devices and building materials, etc. There are steel materials that have an excellent texture (metallic luster or metallic feeling; hereinafter referred to as “metallic feeling”).
[0005]
As a technique for imparting appropriate corrosion resistance to steel materials, a technique for imparting zinc plating or zinc alloy plating, which is excellent in sacrificial corrosion resistance, to steel materials is widely used. As a technique related to a steel material in which a hairline design is added to such zinc plating or zinc alloy plating (hereinafter, zinc plating and zinc alloy plating may be collectively referred to as "zinc-based plating"), for example, hairline An adhesive layer having a light-transmitting property and a film layer-plating layer having a light-transmitting property with respect to the surface of the plating layer having a surface roughness Ra (arithmetic mean roughness) of 0.1 to 1.0 μm in a direction perpendicular to (See Patent Document 1 below) and the roughness parameters (Ra and PPI) in the hairline direction and in the direction orthogonal to the hairline formed on the surface layer of the Zn—Al—Mg-based hot-dip plating layer. A technique for forming a transparent resin film layer on the surface of a Zn—Al—Mg-based hot-dip plating layer (see Patent Document 2 below) and a texture transferred to Zn and Zn-based alloy plating by rolling. A technique of coating a steel plate with a resin so that the surface roughness is within a certain range (see Patent Document 3 below) has been proposed.
Prior art documents
Patent documents
[0006]
Patent Document 1: Japanese Utility Model No. 3192959 gazette
Patent Document 2: Japanese Unexamined
Patent Publication No. 2006-124824 Patent Document 3: Japanese Special Table 2013-536901
Patent Document 4: International Publication No. 2015/125887
Summary of the invention
Problems to be Solved by the Invention
[0007]
However, the technique of coating an organic resin on a steel plate provided with a hairline design as proposed in Patent Documents 1 to 3 above can realize a hairline design and exhibit a certain corrosion resistance. However, there is a problem that the metallic feeling is lost due to the resin coating.
[0008]
Here, as a method for forming a hairline, a steel plate rolling method of rolling a plated steel sheet on which a hairline is desired to be formed by a rolling roll having a predetermined roughness, and a plating grinding method for grinding the surface of the plated steel sheet at which a hairline is desired to be formed. 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 above-mentioned steel sheet rolling method. It is not clear why the loss of metallic appearance is significant, but in plated steel sheets where the hairline is made by the steel sheet rolling method, the incident light is caused by the crystal grains of the plating present on the outermost surface of the plating layer. It is thought that this is due to diffuse reflection at. Therefore, when it is assumed that the surface of the plated steel sheet on which the hairline is formed is coated with the resin as described below, it is considered that the formation of the hairline by the steel sheet rolling method is not appropriate.
[0009]
As a method for improving the glossiness, a method is known in which a predetermined organic additive is added to the electroplating solution to make the plating crystal grains fine (for example, refer to Patent Document 4 above). However, when the crystal particles of the plating are miniaturized, there is a problem that the processing adhesion with the resin film is lowered when the upper layer of the plating is coated with the resin. Further, the method described in Patent Document 4 has a problem in that it is necessary to use an organic substance additive in order to obtain smooth plating, which increases the cost of dragout (waste solution) treatment of the plating solution.
[0010]
Since the stainless steel material itself has good corrosion resistance due to the oxide film existing on the surface of the stainless steel material, coating for improving the corrosion resistance is unnecessary. That is, since the metal base 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. On the other hand, when a resin coating is applied to a stainless steel material, the purpose is to impart coloring or another texture. Therefore, in stainless steel materials, the loss of metallic feeling as found by the present inventors did not pose a problem. The same applies to aluminum materials.
[0011]
Further, depending on the application, a matte appearance having a metallic feeling and suppressed gloss may be preferred as a calm texture. As described above, the hairline is usually formed by polishing/grinding the surface with a polishing/grinding belt or rolling with a rolling roll. It is difficult to realize a matte appearance with low gloss because the area where the roughness becomes low due to ().
[0012]
Further, a zinc-based plated steel sheet is often coated with a resin in order to maintain corrosion resistance and maintain aesthetics, but the adhesion between the zinc-based plated layer and the resin coating may be reduced due to the formation of hairlines. It was.
[0013]
Therefore, the present invention has been made in view of the above problems, and an object of the present invention is to suppress an increase in gloss while having a hairline appearance, and to form a resin film on the upper layer of plating. It is an object of the present invention to provide a zinc-based electroplated steel sheet capable of achieving high film adhesion while maintaining a metallic feeling.
Means for solving the problems
[0014]
The present inventors diligently studied a method for improving a metallic feeling, and if diffused reflection on the outermost surface of the plating layer can be suppressed, even if the surface of the plating layer is coated with a resin, a metallic feeling is obtained. Thought that it is possible to improve. As a result of further studies based on such an idea, the present inventors provided a smooth portion having a surface roughness in a microscopic range of a predetermined threshold value or less on the plating layer surface in order to suppress diffused reflection. Then, we came to the knowledge that diffuse reflection can be suppressed.
Further, the inventors of the present invention appropriately adjust the ratio of the rough portion and the smooth portion whose surface roughness in the microscopic range is greater than a predetermined threshold value on the surface of the plating layer to obtain a metallic feeling and film adhesion. It was found that it is possible to suppress an excessive increase in gloss while achieving both. The "surface roughness in the microscopic range" will be described later.
[0015]
Based on the above-mentioned various findings, the present inventors diligently studied the distribution state of the rough portion and the smooth portion, and provided an organic resin coating layer on the upper layer of the zinc-based electroplating layer. The present invention has been completed by coming up with the conditions for suppressing an excessive increase in gloss while achieving both a metallic feeling and film adhesion.
The gist of the present invention completed based on such findings is as follows.
[0016]
(1) In the zinc-based electroplated steel sheet according to one aspect of the present invention, a steel sheet and a zinc-based electroplated layer that is located on at least one surface of the steel sheet and has a hairline that extends in a predetermined direction on the surface. The zinc-based electroplating layer is defined by a microscopic rough portion having a three-dimensional average surface roughness Sa (1 μm) h of more than 200 nm and 2000 nm or less defined in (A) below, and (B) below. It has a microscopic smooth portion having a three-dimensional average surface roughness Sa (1 μm) s of more than 5 nm and 200 nm or less.
In the zinc-based electroplating layer, the three-dimensional average surface roughness Sa in a region of 50 μm×50 μm is provided along each of the hairline direction in which the hairline extends and the hairline orthogonal direction orthogonal to the hairline direction. (50 μm) is continuously measured to calculate R50, which is the ratio of Sa (50 μm) in the adjacent region formed by the two adjacent regions, and the R50 is less than 0.667 or 1.500 or more. When the adjacent region A is defined as 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 μm) h means a roughness profile having a length of 1000 μm in the hairline direction, and 10 points of the convex peaks at the highest position among the convex peaks in the roughness profile. The three-dimensional average surface roughness Sa (1 μm) of the region of 1 μm × 1 μm was measured around the apex of each of the convex portions, and the minimum value of the measured three-dimensional average surface roughness Sa (1 μm) was measured. Represents
(B) Sa (1 μm) s is a roughness profile having a length of 1000 μm in the hairline direction, and the 10 points of the concave apex at the lowest position among the concave apex in the roughness profile are defined. The three-dimensional average surface roughness Sa (1 μm) in a region of 1 μm×1 μm centering on the apex of each recess is measured, and the maximum value of the measured three-dimensional average surface roughness Sa (1 μm) is shown.
(2) The zinc-based electroplated steel sheet according to (1) may further include an organic resin coating layer having translucency and a thickness of 10 μm or less as an upper layer of the zinc-based electroplated layer. Good.
(3) In the zinc-based electroplated steel plate according to (2), 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 set to 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 light removal method using a color difference meter using the light source D65 .
(4) In the zinc-based electroplated steel sheet according to (2) or (3), in the state where the organic resin coating layer is present, a surface roughness Ra(CC) measured along the hairline orthogonal direction, and The surface roughness Ra (MC) of the zinc-based electroplating layer measured along the direction orthogonal to the hairline after peeling off the organic resin coating layer satisfies the relationship represented by the following formula (1). You may.
Ra(CC)
The steel sheet 11 which is the base material of the zinc-based electroplated steel sheet 1 according to the present embodiment is not particularly limited, and mechanical properties required for the zinc-based electroplated steel sheet (for example, tensile strength and the like). ) Etc., various known steel plates can be appropriately used.
[0025]
[Regarding Surface Shape of Base Material] In the
zinc-based electroplated steel sheet 1 according to the present embodiment, the zinc-based electroplated layer 13, or the organic resin coating layer 15 and the zinc-based electroplated layer 15 located on the upper side of the zinc-based electroplated layer 13. The surface roughness Ra of the steel sheet 11 after removing both the electroplating layers 13 is preferably 1.0 μm or more and 1.7 μm or less. Here, Ra is the arithmetic mean roughness defined in JIS B 0601:2013. When the surface roughness Ra is less than 1.0 μm, it may be difficult to provide the zinc-based electroplating layer 13 having the surface shape as described in detail below, which is not preferable. When the surface roughness Ra exceeds 1.7 μm, it is recognized that the hairline extends in a predetermined direction even if the zinc-based electroplating layer 13 having a surface shape as described in detail below is provided. This is not preferable because it may become difficult.
In the steel sheet 11 according to the present embodiment, the steel sheet 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 surface roughness Ra of 11 is more preferably 1.1 μm or more and 1.5 μm or less.
In the present invention, the surface roughness Ra is not significantly different between the direction in which the hairline is visually recognized as being stretched and the direction orthogonal to the hairline, but with respect to the range of the surface roughness Ra. Is measured in the direction perpendicular to the hairline.
[0026]
Further, the surface roughness Ra of the steel sheet 11 is determined 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. In the above, it is preferable that the thickness is 60% or less of the thickness of the zinc-based electroplating layer 13. When the surface roughness Ra is more than 60% of the thickness of the zinc-based electroplating layer 13, corrosion resistance may be impaired when the zinc-based electroplating layer 13 having a surface shape as described in detail below is provided. It is not preferable because it has properties.
In the steel sheet 11 according to the present embodiment, the steel sheet 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 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 obtained 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 adhesion of the zinc-based electroplating layer 13 thus obtained and the specific gravity of the metal contained in the zinc-based electroplating layer 13.
[0027]
The surface roughness Ra of the steel sheet 11 after removing the zinc-based electroplating layer 13, or both 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 In the above range, the surface roughness Ra of the steel sheet 11 before forming the zinc-based electroplating layer 13 and the organic resin coating layer 15 is also in the above range.
[0028]
The surface roughness Ra as described above can be measured with a stylus type roughness meter. Here, when the surface roughness of the steel sheet 11 is measured after forming the zinc-based electroplating layer 13 and the organic resin coating layer 15 to be described later, a zinc-based electroplating agent such as a solvent or a remover that does not attack the steel sheet is used. After removing the plating layer 13 and the organic resin coating layer 15, the surface roughness Ra may be measured.
[0029]
A
zinc-based electroplating layer is formed on one surface of the steel plate 11 as described above. As schematically shown in FIG. 1A, the zinc-based electroplating layer 13 according to the present embodiment has a smooth portion 103 that is visually recognized as a hairline extending in a predetermined direction (the direction indicated by an arrow at the bottom of FIG. 1A). And rough portions 101a and 101b that are visually recognized as portions that are not hairlines. Here, in the following description, the "direction in which the hairline is visually recognized as being stretched" is abbreviated as the "hairline direction", and the "direction orthogonal to the direction in which the hairline is stretched and visually recognized" is abbreviated. Is abbreviated as "hairline orthogonal direction".
[0030]
In FIG. 1A, the rough portion 101a is a recessed portion and is a portion that is free from the influence of polishing and the like accompanying hairline processing. Further, the rough portion 101b is a portion of the zinc-based electroplating layer 13 that remains after the hairline processing even though the surface thereof is located at a position away from the surface of the steel plate 11 in the depth direction, and is usually rough. The portion 101b is also continuous in the hairline direction over a certain range. In the rough portion 101b of FIG. 1A, it is schematically shown that the rough portion may exist also on the surface portion of the zinc-based electroplating layer 13. The rough portion and the smooth portion will be described in detail below.
[0031]
[Type and composition of zinc-based electroplating layer]
The zinc-based electroplating layer 13 according to the present embodiment is electrogalvanized or electrozinc alloy plating (hereinafter collectively referred to as "zinc-based electroplating"). To use.
[0032]
First, regarding plating metal, plating other than zinc-based plating is inferior in sacrificial corrosion resistance, and is therefore not suitable for applications where the cut end face is inevitably exposed during use. Further, if the zinc concentration in the zinc-based electroplating layer 13 becomes too low, the sacrificial anticorrosive ability is lost. It is preferable to do so.
[0033]
As the plating method, in addition to electroplating, there are hot-dip plating method, thermal spraying method, vapor deposition plating method and the like. However, 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. Further, the thermal spraying method is not suitable because the uniformity of appearance cannot be guaranteed due to the voids inside the plating film. In addition, the vapor deposition method is unsuitable because the film formation rate is low and the productivity is poor.
Therefore, in the zinc-based electroplated steel sheet 1 according to this embodiment, electroplating is used to apply zinc-based plating to the steel sheet surface.
[0034]
Here, when the zinc-based electroplating layer 13 according to the present embodiment is formed by using electrozinc alloy plating, the electrozinc alloy plating includes Co, Cr, Cu, Fe, Ni, P, Sn, Mn, It is preferable to contain at least one element selected from the element group consisting of Mo, V, W, and Zr, and Zn. In particular, it is preferable that the electrogalvanic alloy plating contains at least one element selected from the group consisting of Fe, Ni, and Co in a total amount of 5% by mass or more and 20% by mass or less. By containing one or more elements selected from the element group consisting of Fe, Ni, and Co within the range of the above total content, the electrogalvanized alloy plating can realize more excellent corrosion resistance. ..
[0035]
The electrolytic zinc plating and the electrolytic zinc alloy plating may contain impurities. Here, the impurities are not intentionally added as zinc-based electroplating components, but are mixed in the raw material or mixed in the manufacturing process, and are mixed in Al, Mg, Si, Ti, B. , S, N, C, Nb, Pb, Cd, Ca, Pb, Y, La, Ce, Sr, Sb, O, F, Cl, Zr, Ag, W, H and the like. Further, when performing electrogalvanizing, although it depends on the type of electroplated steel sheet manufactured in the same manufacturing facility, Co, Cr, Cu, Fe, Ni, P, Sn, Mn, Mo, V, W and Zr may be mixed as impurities. In the present embodiment, even if impurities are present in a total amount of about 1% by mass with respect to the total mass of the plating, the effect obtained by the plating is not impaired.
[0036]
In the zinc-based electroplating layer 13 of the present invention, if the Zn content is excessively reduced, the sacrificial anticorrosive ability is reduced. Therefore, the Zn content in the zinc-based electroplating layer 13 is the same as that of the zinc-based electroplating layer 13. With respect to the mass, it is preferably 65% or more, more preferably 70% or more, and particularly preferably 80% or more, as described above.
[0037]
The composition of the zinc-based electroplating layer 13 can be analyzed by the following method, for example. That is, after removing the organic resin coating layer with a solvent that does not attack the plating or a release agent such as a remover (for example, Neo River S-701: manufactured by Sansai Kako Co., Ltd.), the zinc-based electroplating layer is formed with hydrochloric acid containing an inhibitor. After melting, the composition of the zinc-based electroplating layer 13 may be analyzed by an ICP (Inductively Coupled Plasma) emission spectroscopy analyzer.
[0038]
[Regarding the Adhesion Amount of Zinc-Based Electroplating Layer 13]
The attachment amount of the zinc-based electroplating layer according to this embodiment is preferably 10 g/m 2 or more. As long as the desired corrosion resistance can be ensured, the amount of adhesion of the zinc-based electroplating layer does not matter, but if the amount of adhesion of the zinc-based electroplating layer is less than 10 g / m 2 , the base iron exposure rate is 5% when the hairline is applied. It is not preferable because the possibility of exceeding it increases.
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 upper limit of the adhesion amount of the zinc-based electroplating layer is not particularly specified, and may be appropriately determined in consideration of the manufacturing cost of the plated steel sheet according to the present embodiment, for example, about 60 g / m 2. can do.
[0039]
[About Base Iron Exposure Rate]
The zinc-based electroplated steel sheet 1 according to the present embodiment is premised on that the surface of the zinc-based electroplated layer 13 is subjected to hairline processing such as polishing. Therefore, a part of the zinc-based electroplating layer 13 may be removed in a process step such as polishing, and the base metal (that is, the steel plate 11) may be partially exposed depending on the polishing/grinding thickness.
[0040]
The base iron exposure rate of the zinc-based electroplating layer 13 according to the present embodiment is preferably less than 5%. In the present embodiment, the corrosion resistance is sufficiently ensured by zinc or zinc alloy plating, but if the base iron is exposed at the time of applying the hairline, the long-term corrosion resistance may be lowered due to the influence of galvanic corrosion, which is not preferable. .. In the present embodiment, the zinc-based electroplating layer 13 has a base iron exposure rate of less than 5%, and thus has excellent corrosion resistance because it has excellent long-term corrosion resistance in addition to the appropriate corrosion resistance generally required for steel sheets. ..
The exposure rate of the base metal of the zinc-based electroplating layer 13 is more preferably 3% or less, and further preferably 0%.
The base iron exposure rate is an area in which Zn is not detected with respect to the analysis area after the organic resin coating layer 15 is removed with a solvent that does not attack the plating or a remover such as a remover, and then EPMA analysis is performed on five arbitrary 1 mm square areas. The rate can be obtained by image analysis.
[0041]
Since 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 the hairline processing. Such a surface shape will be described in detail below.
[0042]
As shown schematically in FIG. 1B, the surface of the zinc-based electroplating layer 13 to which the hairline is provided as described above has a transparent resin (in other words, has translucency). It is preferably coated with a resin). That is, the organic resin coating layer 15 is preferably provided on the surface side of the zinc-based electroplating layer 13 according to this embodiment. Here, in the present embodiment, “the resin has a light-transmitting property” means that the surface of the zinc-based electroplated steel sheet 1 is illuminated and the zinc-based electroplated steel sheet 1 is observed at an angle of 10° from the vertical direction. At this time, it means that the hairline applied to the zinc-based electroplating layer 13 can be visually recognized.
[0043]
[Regarding Components of
Organic Resin Coating Layer ] The resin used for forming the organic resin coating layer 15 is not particularly limited as long as it has sufficient transparency. Examples of resins used for forming the organic resin coating layer 15 include polyester resins, epoxy resins, urethane resins, polyester resins, phenol resins, polyether sulfone resins, melamine alkyd resins, and acrylic resins. Examples thereof include resins, polyamide-based resins, polyimide-based resins, silicone-based resins, polyvinyl acetate-based resins, polyolefin-based resins, polystyrene-based resins, vinyl chloride-based resins, and vinyl acetate-based resins.
[0044]
Further, as a means for improving the adhesion between the organic resin coating layer 15 and the zinc-based electroplating layer 13, the steel sheet 11 and the zinc-based electroplating layer 13 are coated with each other within a range that does not impair the appearance. , Inorganic treatment, organic-inorganic composite treatment, surface modification treatment, etc. may be performed. Here, “impairing the appearance” means reducing a metallic feeling such as a decrease in transparency, uneven gloss, and abnormal unevenness. Examples of such treatment include Zr oxide treatment, Zn oxide treatment, silane coupling agent treatment, weak acid immersion treatment, and weak alkali immersion treatment.
[0045]
In order to add the desired performance to the organic resin coating layer 15, various additives may be contained within a range that does not impair the translucency and appearance and does not deviate from the range specified in the present invention. .. The properties added to the organic resin coating layer 15 include, for example, corrosion resistance, slidability, scratch resistance, conductivity, and color tone. For example, if it is corrosion resistant, it may contain a rust preventive agent, an inhibitor, etc., if it is slidable or scratch resistant, it may contain wax or beads, and if it is conductive, it may be a conductive agent. And the like may be contained, and if it is a color tone, a known colorant such as a pigment or a dye may be contained.
[0046]
When a known coloring agent such as a pigment or a dye is added to the organic resin coating layer 15 according to the present embodiment, the coloring agent is added to the extent that the hairline is visible and the metallic feeling is not lost. Is preferable. Here, the degree to which the hairline can be visually recognized and the metallic feeling is not lost is the color tone (L * a * b) of the organic resin coating layer 15 in a 10-degree field of view by a commercially available color difference meter using the CIE standard light source D65. * 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. ..
[0047]
[Thickness of Organic Resin Coating Layer]
The thickness of the organic resin coating layer 15 according to this embodiment is preferably 10 μm or less. When the thickness of the organic resin coating layer 15 exceeds 10 μm, the distance through which the light passes through the organic resin coating layer 15 becomes long, the reflected light decreases, and the glossiness in the hairline direction decreases, resulting in difficulty in visually recognizing the hairline. It is not preferable because the possibility that In addition, the deformation of the resin due to the processing easily causes a deviation between the texture of the surface of the zinc-based electroplating layer 13 and the shape of the surface of the organic resin coating layer 15, which is not preferable.
For the above reasons, the thickness of the organic resin coating layer 15 is preferably 10 μm or less, and more preferably 8 μm or less.
[0048]
On the other hand, from the viewpoint of corrosion resistance, the thickness of the thinnest portion (that is, the minimum value of the thickness of the organic resin coating layer 15) as viewed from the cross section of the organic resin coating layer 15 is 0.1 μm or more, and the organic resin coating is The average thickness of the layer 15 is preferably 1.0 μm or more. Here, the "thinnest part" means the minimum value of the film thickness measured at 20 points at 100 μm intervals by cutting out a length of 5 mm at an arbitrary position in the direction orthogonal to the hairline to prepare a cross-sectional sample. However, the "average thickness" means the average of 20 points.
The thickness of the thinnest portion of the organic resin coating layer 15 is more preferably 0.5 μm or more, and the average thickness of the organic resin coating layer 15 is more preferably 3.0 μm or more.
[0049]
The overall configuration of the zinc-based electroplated steel sheet 1 according to this embodiment has been described above in detail. Although FIGS. 1A and 1B show a case where the zinc-based electroplating layer 13 and the organic resin coating layer 15 are formed on one surface of the steel sheet 11, they are on two surfaces of the steel sheet 11 facing each other. The zinc-based electroplating layer 13 and the organic resin coating layer 15 may be formed on.
[0050]
(Regarding Surface Shape of Zinc Based Electroplated Layer 13)
Next, the surface shape of the zinc based electroplated layer 13 according to the present embodiment will be described in detail with reference to FIG. 1A.
[0051]
As described above, the zinc-based electroplating layer 13 according to this embodiment has the smooth portion 103 forming the hairline and the rough portions 101a and 101b in the surface layer portion. The rough portions 101a and 101b are caused by the microscopic surface shape of the zinc-based electroplating layer 13.
In the present embodiment, the rough portions 101a and 101b are portions where the three-dimensional roughness Sa (1 μm) of the 1 μm×1 μm microscopic region is more than 200 nm and 2000 nm or less, and the detection frequency of the microscopic rough portions is high. The smoothing portion 103 is a portion where the three-dimensional roughness Sa (1 μm) of the microscopic region of 1 μm × 1 μm is more than 5 nm and 200 nm or less, and the detection frequency of the microscopic smoothing portion is high.
[0052]
Here, the three-dimensional roughness Sa is the arithmetic mean height defined by ISO 25178, which is an extension of Ra (arithmetic mean height of the line) defined by JIS B0601: 2013 to a surface.
[0053]
Here, in the present embodiment, the "microscopic coarse portion", the "microscopic smooth portion", the "coarse portion 101a, 101b" and the "smooth portion 103" are defined as follows.
[0054]
First, in the zinc-based electroplating layer 13 according to the present embodiment, 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 is observed in a range of 1 cm × 1 cm at a magnification of 500 times using a laser microscope having a display resolution of more than 10 nm. Here, when the observation visual field of the laser microscope is less than 1 cm×1 cm, a plurality of visual fields may be observed, and the surface may be observed by connecting these plural visual fields.
[0055]
Next, the region where the three-dimensional roughness Sa (1 μm) h of the region of 1 μm × 1 μm is more than 200 nm and 2000 nm or less is defined as a “microscopic rough portion”. Similarly, the region where the three-dimensional roughness Sa (1 μm) s of the region of 1 μm × 1 μm became more than 5 nm and 200 nm or less with the formation of the hairline was defined as a “microscopic smoothing portion”.
[0056]
Here, the above-mentioned three-dimensional roughness Sa (1 μm) h is defined as the following (A), and the three-dimensional roughness Sa (1 μm) s is defined as the following (B).
[0057]
(A) Sa (1 μm) h means measuring a roughness profile having a length of 1000 μm in the hairline direction, and measuring 10 roughness points at the highest position among the projection height points in the profile. The three-dimensional average surface roughness Sa (1 μm) in a region of 1 μm × 1 μm centered on the apex of the convex portion is measured, and represents the minimum value of the measured three-dimensional average surface roughness Sa (1 μm).
(B) Sa (1 μm) s is a roughness profile having a length of 1000 μm measured in the hairline direction, and each of the 10 recessed peaks at the lowest position among the recessed peaks in the profile is the respective recessed peak. The three-dimensional average surface roughness Sa (1 μm) in the region of 1 μm × 1 μm is measured around the center, and the maximum value of the measured three-dimensional average surface roughness Sa (1 μm) is represented.
[0058]
1A and 1B which are schematic diagrams, the above definition means that a part of Sa(1 μm) s exceeds 200 nm exists in a part of the smooth portion indicated by reference numeral 103, and reference numerals 101a and 101b. It is not excluded that a portion where Sa (1 μm) h is lower than 200 nm exists in a part of the rough portion indicated by.
[0059]
In the zinc-based electroplating layer 13 according to the present embodiment, the rough portions 101a and 101b correspond to the portions where the crystal particles of the plating are present as they are or in a state close to being electrodeposited. The smooth portion 103 corresponds to a portion where the crystal particles of the plating are crushed due to the formation of the hairline, or a portion where the shape of the crystal particles does not exist.
In the zinc-based electroplating layer 13 according to the present embodiment, the coarse portions 101a and 101b in which the minute regions (that is, the microscopic rough portions) in which the crystal particles as they are plated remain are frequently present and plated. A smoothing portion 103 having a high frequency of existence of a minute region (that is, a microscopic smoothing portion) in which the shape of the crystal particles as it is does not remain is present at an appropriate ratio and position as described later. As a result, in the smooth portion 103, the metallic feeling is improved, and in the rough portions 101a and 101b, it is preferable that the roughened portions 101a and 101b are provided in the upper layer of the zinc-based electroplating layer 13. And to suppress excessive rise in gloss.
[0060]
In the following, even when the organic resin coating layer 15 is present on the zinc-based electroplating layer 13, in order to achieve both a suitable metallic feeling, a suitable adhesion to the processed portion, and an excessive increase in gloss. Various conditions required for the zinc-based electroplating layer 13 will be described in detail.
[0061]
[Distribution state of rough portion and smooth portion] In the
zinc-based electroplating layer 13 according to the present embodiment, if the smooth portion 103 is continuously present over a long distance in the hairline direction, the gloss becomes too high, which is not preferable. .. On the other hand, if the rough portions 101a and 101b are excessively continuous, the continuity of the hairline is impaired, which is not preferable. Therefore, it is important that the rough portions 101a and 101b divide the smooth portion 103 forming the hairline at an appropriate ratio.
[0062]
When the three-dimensional average surface roughness Sa (50 μm) in a region of 50 μm×50 μm 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 μm) of the region where there are many microscopic smooth portions and few microscopic rough portions are calculated to be low. On the contrary, the three-dimensional average surface roughness Sa (50 μm) of a region where many microscopic rough portions exist and few microscopic smooth portions exist is calculated to be high. Therefore, when the region where the three-dimensional average surface roughness Sa (50 μm) is high or the region where the three-dimensional average surface roughness Sa (50 μm) is low is continuous, the smooth portion 103 or the rough portions 101a and 101b are continuous. It can be judged that it is.
[0063]
Here, "a region having a high three-dimensional average surface roughness Sa (50 μm) or a region having a low three-dimensional average surface roughness Sa (50 μm) is continuous" means along the hairline direction or the hairline orthogonal direction. Then, when the three-dimensional average surface roughness Sa (50 μm) is continuously measured, the ratio of the three-dimensional average surface roughness Sa (50 μm) between two adjacent regions (hereinafter, sometimes referred to as adjacent regions) When the R50 is calculated, the value of R50 is in the range of 0.667 or more and less than 1.500.
[0064]
In the zinc-based electroplating layer 13 according to the present embodiment, the three-dimensional average surface roughness Sa (50 μm) is measured at n points in the hairline direction, and the three-dimensional average surface roughness Sa (50 μm) is measured in the adjacent region in the hairline direction. When the value of the ratio R50 is calculated at the point (n-1), it is out of the range of 0.667 or more and less than 1.500 (in other words, when the value of the ratio R50 is less than 0.667 or 1.500 or more. A certain ratio of the number of adjacent regions (the adjacent region having a value of the ratio R50 of less than 0.667 or 1.500 or more may be referred to as an adjacent region A) is 30% or more (that is, (adjacent region)). The number of regions A) / (n-1) is 0.3 or more). In other words, the number ratio of adjacent regions (hereinafter, may be referred to as adjacent regions B) in which R50 is 0.667 or more and less than 1.500 is less than 70%.
When the number ratio of the adjacent regions A in the hairline direction is less than 30% (that is, the number ratio of the adjacent regions B is 70% or more), the smooth portion 103 is too continuous and the gloss is too high, and the organic When the resin coating layer 15 is provided, the adhesion of the processed portion is lowered, or the rough portions 101a and 101b are too continuous to be recognized as continuous hairlines, and the glossiness in the hairline direction is too low. This is not preferable because it impairs the metallic feeling.
On the other hand, there is no upper limit to the number ratio of the adjacent areas 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, glossiness can be appropriately suppressed without impairing the metallic feeling, and excellent film adhesion can be realized. The number ratio is preferably 35% or more, and more preferably 40% or more.
[0065]
In the direction orthogonal to the hairline, the number ratio of the adjacent regions A is 30% or more as in the hairline direction. Even when the number ratio of the adjacent regions A in the direction orthogonal to the hairline is less than 30%, the smooth portion 103 is too continuous and the gloss becomes too high, and the adhesion of the processed portion when the organic resin coating layer 15 is provided is high. It is not preferable because it is lowered 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 on 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, gloss can be appropriately suppressed without impairing the metallic feel, and excellent coating adhesion can be realized.
The number ratio is preferably 35% or more, and more preferably 40% or more.
[0066]
In the present invention, the number ratio of the adjacent regions A in the hairline direction and the hairline orthogonal direction is set to 30% or more, and as shown in FIG. 1A, for example, the cross-sectional shape of the zinc-based electroplating layer 13 is provided with irregularities to form the hairline. As a method for breaking the continuity, as will be described later, the polishing / grinding thickness with respect to the steel sheet roughness is limited to a predetermined ratio. 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.
[0067]
[Surface Roughness in Rough Parts 101a and 101b]
As described above, in the zinc-based electroplating layer 13 according to the present embodiment, the number ratio of the adjacent regions A is set to 30% or more. Regions where a large number of rough portions are present and few microscopic smooth portions are present (that is, the rough portions 101a and 101b) are present at an appropriate ratio. This ensures film adhesion when the organic resin coating layer 15 is provided on the zinc-based electroplating layer 13.
[0068]
Therefore, the zinc-based electroplating layer 13 according to the present embodiment has an area of 1 μm×1 μm 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. When the three-dimensional average surface roughness Sa (1 μm) of the above is measured, it has a microscopic rough portion in which Sa (1 μm) h defined in the above (A) is more than 200 nm and 2000 nm or less.
In the zinc-based electroplated steel sheet 1 according to the present embodiment, as described above, it is preferable that the surface roughness Ra of the steel sheet 11 as the base material be within a specific range. As a result, the electroplating layer is deposited in the valley portion (concave portion) of the roughness curve (roughness profile), and the portion is protected from polishing or the like. This is to be secured.
[0069]
When Sa (1 μm) h of the above-mentioned microscopic rough portion is more than 200 nm and 2000 nm or less, the contact state with the organic resin coating layer 15 which can realize excellent film adhesion is more reliably realized. can do.
[0070]
[Surface Roughness in Smooth Portion] Further
, as mentioned earlier, in the zinc-based electroplating layer 13 according to the present embodiment, the smooth portion 103 is present in an appropriate ratio, and thus the present embodiment relates to the present embodiment. The zinc-based electroplated steel sheet 1 has a suitable metallic feeling. Here, in order to realize the effect of improving the metallic feeling by the smooth portion 103, it is preferable that the smooth portion 103 has an appropriate surface roughness and a region having an appropriate width.
[0071]
Therefore, for the zinc-based electroplating layer 13 according to the present embodiment, the smooth portion 103 is formed by 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. When the three-dimensional average roughness Sa (1 μm) in the area of 1 μm×1 μm is measured, Sa(1 μm)s defined in the above (B) has a microscopic smoothing portion of more than 5 nm and 200 nm or less.
[0072]
Since the smoothing portion 103 frequently detects the microscopic smoothing portion, it is possible to achieve both a suitable metallic feeling and a suitable glossiness.
[0073]
[Surface Roughness of Zinc-based Electroplating Layer Before and After Formation of Organic Resin Coating Layer] Further
, in the zinc-based electroplating layer 13 according to the present embodiment, in the state where the organic resin coating layer 15 is present, in the direction orthogonal to the hairline. The surface roughness Ra (CC) [unit: μm] measured along the surface roughness Ra (MC) of the zinc-based electroplating layer 13 measured along the direction orthogonal to the hairline after the organic resin coating layer 15 was peeled off. ) [Unit: μm] preferably satisfy the relationship represented by the following formula (101).
[0074]
Ra(CC) For the
Zn plating film, a plating bath having a pH of 2.0 containing 1.0 M of Zn heptahydrate sulfate and 50 g / L of anhydrous sodium sulfate was used. The bath time was 50° C., the current density was 50 A/dm 2 , and the plating time was adjusted so that the adhesion amount was the value shown in the table.
[0099]
When plated at a
bath temperature of 50° C. and a current density of 50 A/dm 2 , the composition is shown in the “plating type” column of the table. The mixing ratio of Zn heptahydrate sulfate and Ni hexahydrate sulfate was adjusted. Adhesion amount using a plating bath of pH 2.0 containing Zn heptahydrate sulfate, Ni hexahydrate sulfate (1.2 M in total) adjusted by the above mixing ratio, and anhydrous sodium sulfate 50 g / L. Was formed by adjusting the plating time so that
[0100]
When plated at a
bath temperature of 50° C. and a current density of 50 A/dm 2 , the composition is shown in the “plating type” column of the table. The mixing ratio of Zn heptahydrate sulfate and Fe (II) sulphate heptahydrate was adjusted. A plating bath having a pH of 2.0 containing Zn sulfate heptahydrate and Fe(II) sulfate heptahydrate (total of 1.2 M) adjusted at the above mixing ratio and 50 g/L of anhydrous sodium sulfate was used. The plating time was adjusted so that the adhered amount was the value shown in the table.
[0101]
When plated at a
bath temperature of 50 ° C. and a current density of 50 A / dm 2 , the composition is as described in the "Plating type" column of the table. In addition, the mixing ratio of Zn sulfate heptahydrate and Co sulfate heptahydrate was adjusted. Using a plating bath having a pH of 2.0 containing Zn sulfate heptahydrate and Co sulfate heptahydrate (total of 1.2 M) adjusted at the above mixing ratio, and anhydrous sodium sulfate 50 g/L, the amount of deposition Was formed by adjusting the plating time so that the value becomes as shown in the table.
[0102]
When plated at a
bath temperature of 50 ° C. and a current density of 50 A / dm 2 , the composition is as described in the "Plating type" column of the table. The mixing ratio of Zn sulphate heptahydrate, Ni sulphate hexahydrate and Fe(II) sulphate heptahydrate was adjusted. PH 2 containing Zn sulfate heptahydrate, Ni sulfate hexahydrate, Fe(II) sulfate heptahydrate (total of 1.2M) and 50 g/L of anhydrous sodium sulfate adjusted in the above mixing ratio It was formed by using a plating bath of .0 and adjusting the plating time so that the amount of adhesion was as shown in the table.
[0103]
When plated at a
bath temperature of 50° C. and a current density of 50 A/dm 2 , the composition is shown in the “plating species” column of the table. The mixing ratio of Zn sulfate heptahydrate, Co sulfate heptahydrate and sodium molybdate dihydrate was adjusted. Zn sulfate heptahydrate, Co sulfate heptahydrate and sodium molybdate dihydrate (1.2M in total) adjusted with the above-mentioned mixing ratio, sodium formate 25 g/L, and boric acid 50 g/L, It was formed by using a plating bath having a pH of 4.0 containing the above, and adjusting the plating time so that the amount of adhesion was the value shown in the table.
[0104]
In all of the above plating treatments, the plating solution was made to flow so that the relative flow rate was 1 m/sec.
[0105]
The composition of the
obtained plating film was determined by immersing the plated steel sheet in 10 mass% hydrochloric acid containing an inhibitor (NO.700AS manufactured by Asahi Chemical Industry Co., Ltd.), peeling it off, and dissolving the solution by ICP. Confirmed by analysis.
[0106]
As the above reagents, general reagents were used.
[0107]
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 grain size of the polishing paper, the pressing force, and the number of times of polishing were adjusted to form a hairline so that the polishing/grinding ratio shown in the table was obtained.
As for the polishing/grinding ratio, the hairline was applied to one of two 100 mm widths adjacent to each other in the width direction of the steel sheet, and the coating amount of each was obtained without applying the hairline to the other side. It was calculated from the difference between the amount of plating adhesion and the amount of adhesion after the other hairline was applied. Further, the value of the plating specific gravity at this time was 7.1.
The plating roughness and the amount of plating adhesion after applying the hairline are as shown in the table.
[0108]
The surface roughness Ra of
the steel sheet after removing the plating layer is measured by a three-dimensional surface roughness measuring machine (Surfcom 1500DX3 manufactured by Tokyo Seimitsu Co., Ltd.), and the three-dimensional surface roughness Sa of the plated steel sheet is measured. Was measured according to the above method using a laser microscope / VK-9710 manufactured by Keyence Co., Ltd., which 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.
[0109]
The coating amount of coating layer before applying hairline was obtained by immersing the steel plate after forming the plating layer in 10 mass% hydrochloric acid containing an inhibitor (NO.700AS manufactured by Asahi Chemical Co., Ltd.). It was calculated from the weight difference before and after dissolution and peeling.
[0110]
< Measurement of Microscopic Rough Section Sa A and Microscopic Smooth Section Sa B >
The microscopic rough section Sa A in each table was determined as follows. First, a roughness profile having a length of 1000 μm in the hairline direction was measured using the laser microscope used for measuring the three-dimensional surface roughness Sa. Sa (1 μm) of a region of 1 μm×1 μm centering on the apex of the 10 protrusions at the highest position among the apexes of the profile was measured. The minimum value among them (that is, the value of Sa (1 μm) h) is shown as Sa A in the table .
The microscopic smoothing portion Sa B in each table was obtained as follows. First, using the laser microscope used for the measurement of Sa, a height profile having a length of 1000 μm in the hairline direction was measured. For the 10 concave vertices at the lowest position among the concave vertices in the profile, Sa (1 μm) in a region of 1 μm × 1 μm centered on the concave vertices was measured. The maximum value among them (that is, the value of Sa (1 μm) s) is described as Sa B in the table .
[0111]
The three-dimensional average surface roughness Sa (50 μm) in the region of 50 μm × 50 μm was continuously measured at 21 points in the hairline direction and 21 points in the hairline orthogonal direction. The ratio R50 of the three-dimensional average surface roughness Sa (50 μm) in the adjacent areas was calculated in a total of 20 adjacent areas. Among the 20 adjacent regions in total, the number ratio of the adjacent regions A having R50 of less than 0.667 or 1.500 or more is shown in each table.
[0112]
The adhesion amount of the plating layer after hairline addition was measured in the same manner as the measurement of the plating layer adhesion amount before hairline addition.
Here, the difference in the adhesion amount of the plating layer before and after applying the hairline corresponds to the amount of decrease in the plating layer in the process of applying the hairline.
[0113]
The
plated steel sheet obtained by the above-mentioned manufacturing method was cut out and the image was analyzed with EPMA (JXA8230 manufactured by JEOL Ltd.) in 5 fields of view of 1 mm square. By the image analysis, the area where Zn is not detected and Fe is detected is considered to have exposed the ground iron, and the area ratio of the area is defined as the ground iron exposure rate. The EPMA analysis was performed under the conditions of an acceleration voltage of 15 kV and an irradiation current of 30 nA. It is judged that Zn is not detected in the region where the detection intensity of Zn is 1/16 or less when the standard sample (pure Zn) is measured, and the detection intensity of Fe is 14 / when the standard sample (pure Fe) is measured. It was judged that Fe was detected in a region exceeding 16.
[0114]
These results obtained are shown in the table.
[0115]
A
transparent organic resin coating layer was formed on the plated steel sheet having the hairline. As the treatment liquid for forming the organic resin, treatment liquids having various concentrations and viscosities in which a urethane resin (HUX-232 manufactured by ADEKA Co., Ltd.) was dispersed in water were used. The treatment liquid was scooped up with a roll and transferred to a 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 liquid was transferred was placed in a furnace kept at 250°C, held for 1 minute to 5 minutes until the ultimate temperature of the steel sheet reached 210°C, then taken out and cooled. In addition, No. For 62 to 69, carbon black (manufactured by Mitsubishi Chemical Corporation: # 850) and cyanine blue (manufactured by Dainichiseika Kogyo: AF Blue E-2B) were added to the organic resin coating layer as colorants.
[0116]
BYK-425 (manufactured by Big Chemie) is added to the organic resin forming treatment liquid as a viscosity adjusting agent, and at a shear rate of 0.1 [1/sec], 10 [Pa·s] or more. It was adjusted to have a shear viscosity of 0.01 [Pa · s] or less at a shear rate of 1000 [1 / sec]. The viscosity adjuster is not added only to the treatment liquids corresponding to the conditions 6, 9, 25, 39 and 53, and the viscosity is adjusted to be less than 10 [Pa · s] at a shear rate of 0.1 [1 / sec]. did.
[0117]
The surface roughness Ra (CC) of the organic resin coating layer is 3 as in the measurement of the surface roughness Ra of the steel plate after the plating layer is removed. It was measured with a dimensional surface roughness measuring device (Surfcom 1500DX3 manufactured by Tokyo Seimitsu Co., Ltd.).
[0118]
The 60 ° glossiness G60 of the plated steel sheet after forming the organic resin coating layer is measured in the L direction (rolling direction of the steel sheet) and the C direction (rolling direction of the steel sheet) by a glossiness meter (manufactured by Suga Test Instruments Co., Ltd .: Gross Meter UGV-6P). (Perpendicular to the rolling direction). The obtained G60 value is shown in the table.
When the glossiness G60 (Gl) measured in the hairline direction (which represents the same direction as the L direction because the hairline is formed along the L direction in the sample used) is 70 or more and 150 or less, an appropriate glossiness is obtained. It was judged that it was obtained.
[0119]
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 forming the organic resin coating layer is exposed to the light of a fluorescent lamp from an angle of 45 °, observed from a distance of 15 cm at an angle of 10 ° from the vertical direction to the steel sheet, and evaluated as follows. 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.
[0120]
(Evaluation criteria)
A: Hairline with
a length of 20 mm or more can be clearly seen B: Hairline with a length of 20 mm or more with an unclear outline can be seen
C: Hairline with a length of 20 mm or more cannot be seen
D: Hairline cannot be seen at all
[0121]
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 forming the organic resin coating layer. After bending the obtained test piece at 180 °, a tape peeling test was performed on the outside of the bent portion. The appearance of the tape peeling portion was observed with a magnifying glass having a magnification of 10 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.
In addition, No. In SUS, since the organic resin coating layer was not formed, the film adhesion was not evaluated. Therefore, No. The evaluation result of the film adhesion of SUS is shown by "-".
[0122]
(Evaluation criteria)
A: No peeling of the organic resin coating layer and / or zinc-based electroplating layer is observed on
the adhesive surface of the tape. B: Organic resin coating layer and / or zinc-based electroplating on a very small part of the adhesive surface of the tape. Peeling of the plating layer is recognized (peeling area ≤ 2%)
C: Peeling of the organic resin coating layer and/or the zinc-based electroplating layer is recognized on a part of the adhesive surface of the tape (2% 20%)
[0123]
When evaluating
the corrosion resistance (more specifically, long-term corrosion resistance) of the zinc-based electroplated steel sheet after forming the organic resin coating layer, first, the obtained sample was cut into a size of 75 mm×100 mm. The end faces and the back face were protected with tape seals. A sample whose end face and back surface were protected with a tape seal was subjected to a salt spray test (JIS Z 2371: 2015) of 35 ° C.-5% NaCl. A sample having a rust generation rate of 5% or less after 240 hours was regarded as OK, and a sample exceeding 5% was regarded as NG. The results obtained are shown in the table.
[0124]
The metallic feeling of
the zinc-based electroplated steel sheet after forming the organic resin coating layer was evaluated by the following method.
Using a glossiness G60 (Gl) measured in the hairline direction, a G60 (Gc) value measured in the direction orthogonal to the hairline, and a spectrocolorimeter (manufactured by Konica Minolta: CM-2600d) under CIE standard light source D65 conditions. The metallic feeling was evaluated by the following evaluation criteria using the values of a * and b * obtained by measuring the color tone of the L * a * b * color system 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.
[0125]
(Evaluation Criteria)
A: 0.3≦Gc/Gl≦0.75 and (a *2 +b *2 ) 0.5 ≦5
B: 0.3≦Gc/Gl≦0.85 and 5<(a * 2 +b *2 ) 0.5 ≤ 10 or 0.75 Gc/Gl, or Gc/Gl>0.85, or 10<(a *2 +b *2 ) 0.5
[0126]
[table 1]
[0127]
[Table 2]
[0128]
[Table 3]
[0129]
[Table 4]
[0130]
[Table 5]
[0131]
[Table 6]
[0132]
As is clear from Tables 1 to 6, the zinc-based electroplated steel sheet according to the examples of the present invention has excellent translucency, has an appropriate glossiness, and has an excellent metallic feeling and a coating film. It can be seen that it has adhesiveness. On the other hand, in the zinc-based electroplated steel sheet corresponding to the comparative example of the present invention, excellent results could not be obtained in at least one of the items of translucency, glossiness, metallic feeling and coating adhesion.
[0133]
The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited to these examples. It is clear that anyone with ordinary knowledge in the field of technology to which the present invention belongs can come up with various modifications or modifications within the scope of the technical ideas described in the claims. Of course, it is understood that these also belong to the technical scope of the present invention.
Explanation of symbols
[0134]
1 Zinc-based electroplated steel sheet
11 Steel sheet
13 Zinc-based electroplated layer
15 Organic resin coating layers
101a, 101b Rough part
103 Smooth part
The scope of the claims
[Claim 1]
The
zinc-based electroplating layer
includes a steel plate; a zinc-based electroplating layer located on at least one surface of the steel plate and having a hairline extending in a predetermined direction on the surface; the
zinc-based electroplating layer is
defined by the following (A). A microscopic rough portion having a three-dimensional average surface roughness Sa (1 μm) h of more than 200 nm and 2000 nm or less;
a three-dimensional average surface roughness Sa (1 μm) s of more than 5 nm and 200 nm or less defined in (B) below. a microscopic smoothing section is;
has,
in the zinc-based electroplated layer, hairline direction in which the hairline is stretched, and, along each of hairline direction orthogonal to the hairline direction, The three-dimensional average surface roughness Sa (50 μm) of a 50 μm×50 μm region is continuously measured to calculate R50 which is the ratio of the Sa (50 μm) in the adjacent region formed by the two adjacent regions. When the adjacent region having R50 of less than 0.667 or 1.500 or more is defined as 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
zinc-based electroplated steel plate characterized by being.
(A) Sa (1 μm) h means a roughness profile having a length of 1000 μm in the hairline direction, and 10 points of the convex peaks at the highest position among the convex peaks in the roughness profile. The three-dimensional average surface roughness Sa (1 μm) of the region of 1 μm × 1 μm was measured around the apex of each of the convex portions, and the minimum value of the measured three-dimensional average surface roughness Sa (1 μm) was measured. Represents
(B) Sa (1 μm) s is a roughness profile having a length of 1000 μm in the hairline direction, and the 10 points of the concave apex at the lowest position among the concave apex in the roughness profile are defined. The three-dimensional average surface roughness Sa (1 μm) in a region of 1 μm×1 μm centering on the apex of each recess is measured, and the maximum value of the measured three-dimensional average surface roughness Sa (1 μm) is shown.
[Claim 2]
The zinc-based electroplated steel sheet according to claim 1, further comprising an organic resin coating layer having translucency and a thickness of 10 μm or less as an upper layer of the zinc-based electroplated layer .
[Claim 3]
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 measured by a normal reflected light removal method using a color difference meter using a CIE standard light source D65. The zinc-based electroplated steel sheet according to claim 2, wherein a value of (a *2 +b *2 ) 0.5 indicating saturation when measured is 10 or less
.
[Claim 4]
The surface roughness Ra (CC) measured along the hairline orthogonal direction in the presence of the organic resin coating layer and the surface roughness Ra (CC) measured along the hairline orthogonal direction after the organic resin coating layer was peeled off. The zinc-based
electroplated steel sheet according to claim 2 or 3, wherein the surface roughness Ra (MC) of the zinc-based electroplated layer satisfies the relationship represented by the following formula (1). ..
Ra (CC)