Technical field
[0001]The present invention relates to a zinc-based electroplated steel sheet.
This application, on October 12, 2017, claiming priority on Japanese Patent Application No. 2017-198465 filed in Japanese, which is incorporated herein by reference.
BACKGROUND
[0002]Electrical equipment, building materials, and, as the beginning of the automobile, the article touches in the eyes of the people, generally design resistance is required. As a method of enhancing the design property, a method or paste film or painted to the surface of the article is generally in recent years, mainly in Western nature-oriented, the material utilizing the texture of metal application is increasing. From the viewpoint of taking advantage of the texture of the metal, the paint or resin coating for impairing the texture of the metal, as a material for an article, stainless steel or aluminum material excellent in corrosion resistance it is left unpainted are used. In order to improve the design of the stainless steel and aluminum materials, to attach the arc-shaped fine irregularities called vibrations, but such embossing or subjected to impart fine linear irregularities called hairline appearance, is frequently used particularly favored by.
[0003]
　Brushed (HL finish), as one of a surface finish of stainless steel, JIS G4305: In 2012, is defined as "that finished by polishing as continuous polishing th stick with abrasive appropriate particle size" ing.
[0004]
　However, since stainless steel or aluminum material is expensive, inexpensive material alternative to these stainless steel or aluminum material is desired. One such alternative materials, with similar high design quality and moderate corrosion resistance stainless steel and aluminum material, and suitable for use in electrical equipment and building materials, metal texture having a hairline appearance there is an excellent steel material (metallic feeling).
[0005]
　As a technique for imparting an appropriate corrosion resistance steel, galvanized superior in sacrificial protection against steel, or a technique of applying zinc alloy plating has been widely used. Such galvanized or zinc alloy plating (hereinafter collectively and galvanized and zinc alloy plating, also referred to as "zinc-based plating".) Hairline design as a technique relating to steel granted to, for example, perpendicular to the hairline direction hairline perpendicular direction of the surface roughness Ra to the surface of the (arithmetic mean roughness) plating layer is 0.1 ~ 1.0 .mu.m, a film layer plating layer having an adhesive layer and the transparent having translucency that (see Patent Document 1 below.) technique for forming with or, Zn-Al-Mg-based hot dip plated layer hairline direction and hairline perpendicular direction of the roughness parameter which is formed on the surface layer of the (Ra and PPI) specific in the range, and, (see the following Patent Document 2.) technique for forming a transparent resin coating layer on the surface of the Zn-Al-Mg-based hot dip plated layer and, rolling the Zn and Zn alloy plating To steel sheet transferring the texture (see the following Patent Document 3.) Technique to coat the resin as the surface roughness is within a predetermined range has been proposed.
CITATION
Patent Document
[0006]
Patent Document 1: Japanese Unexamined Japanese Patent Registered Utility Model No. 3192959
Patent Document 2: Japanese Patent 2006-124824 JP
Patent Document 3: Japanese Kohyo 2013-536901 JP
Patent Document 4: WO 2015/125887
Summary of the Invention
Problems that the Invention is to Solve
[0007]
　However, as proposed in the Patent Documents 1 to 3, in the technology for coating the organic resin to steel sheet hairline design has been applied, it can be realized hairline design, and to express a certain corrosion resistance although it is possible, there is a problem that metallic feeling (metallic luster) is poor.
[0008]
　As a method for forming a hairline, a steel sheet rolling method of rolling a plated steel sheet to be formed hairline by rolling roll or the like having a predetermined roughness, a plating grinding method for grinding the surface of the plated steel sheet to be formed hairline , there is. Lack of metallic effect as described above (metal luster), in particular, the hairline is formed on the plated original plate in steel sheet rolling method of the above, then, it was in significant plated steel sheet forming the hairline by performing electroplating . Although the lack of a sense metallic is why is not clear noticeable, the plated steel sheet was produced by applying to be plated a hairline of a steel plate rolling method, the unevenness of the plating of crystal grains present at the outermost surface of the plating layer, light entering it is considered to be due to irregular reflection in the plating layer surface. Further, as the case of forming the hairline by steel rolling method with respect to the steel sheet after plating as described in Patent Document 2, since the unevenness of the plating of the crystal grains are crushed by rolling, metallic feeling is insufficient by diffused reflection of light there is no problem, but a problem that the plating surface is insufficient adhesion to the resin film to be smoothed occurs.
[0009]
　As a method for improving the gloss, by adding a predetermined organic additive electroplating solution, a method of refining the plating grains are known (e.g., see Patent Document 4.). However, refining the crystal grains of the plating, the plating layer when coated with resin, processability adhesion with the resin film is lowered. In the method described in Patent Document 4, it is necessary to use organic additives in order to obtain a smooth plating, drag out (waste) treatment costs of the plating solution is disadvantageously increased.
[0010]
　Incidentally, stainless steel, for corrosion resistance of stainless steel itself with the oxide film present on the surface is good, paint for improving corrosion resistance is not required. That is, the metal matrix itself since it can be used on the surface, does not require basically the resin coating. On the other hand, when applying a resin coating for stainless steel, it is an object to impart coloration and another texture. Therefore, in stainless steel, the loss of metallic effect as the present inventors have findings had a problem. Such a situation is the same for the aluminum material.
[0011]
　The present invention has been made in view of the above problems, it is an object of the present invention is provided with a predetermined corrosion resistance while using inexpensive steel, have a hairline appearance and, metallic feeling, and excellent processability adhesion is to provide a zinc-based electroplated steel sheet.
Means for Solving the Problems
[0012]
　The present inventors have intensively studied a method for improving the feeling metallic, if it is possible to suppress the irregular reflection at the outermost surface of the plating layer, even if the plating layer comprising at upon resin coating, improve the sense of metallic I thought that it is possible to be. Finding that the present inventors have, as a result of the original further study of such idea, in order to suppress the irregular reflection, it is possible to suppress the irregular reflection by providing the smoothing unit with reduced unevenness of crystal grains of the plating It led to obtain. Meanwhile, the portion unevenness of plating the crystal grains remaining on the surface of the plating layer becomes coarse portion, it is possible to obtain a processing adhesion with the resin coating. Therefore, the proportion of such coarse portions and the smoothing unit by appropriately adjusting, could be obtained knowledge that can both metallic feeling and processability adhesion.
[0013]
　Although zinc-based plating is excellent in sacrificial protection property, fingerprint resistance, processability, and, in order to ensure corrosion resistance, it is preferable to perform the resin coating. Therefore, the present inventors have found that the resin-coated plated steel, were considered separately. As a result, the degree of gloss measured in the hairline direction G60 (Gl) of 70 to 400, and, with respect to the degree of gloss measured in the hairline direction perpendicular G60 (Gc), 0.3 ≦ Gc / Gl ≦ 0.7 when a, can feel a sense of good metallic, it has become known that the metallic effect is Moi If out of this range. That is, the present inventors have found that a person "has a hairline appearance, and, excellent metallic feeling" a sense of feel, and succeeded in for the first time quantified.
[0014]
　The present inventors have found that under various findings as described above, conducted intensive study for the percentage of the coarse portion and the smooth portion, even if the organic resin coating layer on the upper layer of the zinc-based electroplated layer is present, and metallic effect, conceive condition for achieving both a processing adhesion of the organic resin coating layer and the zinc-based electroplated layers, and have completed the present invention.
　Summary of the completed invention based on this finding is as follows.
[0015]
[1] and the steel plate, at least one of located on the surface, and a zinc-based electroplated layer hairline is formed as a recess extending in a predetermined direction, the zinc-based electroplated layer of the steel sheet, crude unit (a) and the smooth portion becomes from the (B), the rough part (a) has an average surface roughness Ra a comprises a region is 200nm exceeds 2000nm or less, wherein the smooth portion (B) has an average surface roughness Ra B include is 5nm exceed 200nm or less area, the boundary between the rough part (a) and the smooth portion (B), a hairline orthogonal direction orthogonal to the predetermined direction and a thickness direction cross-section in the highest point H of the zinc-based electroplated layer in the range of the observation width 1cm along the hair line perpendicular to the direction 1 the lowest point H from 0 1/3 height a and the hairline of the maximum height Ry obtained by subtracting the parallel to the orthogonal direction When to be in a virtual straight line which forms a same area unit together, the rough part area (A) S A and the smoothing unit area of (B) S B is taken as the area ratio S B / S a is in the range from 0.6 to 10.0, the average height difference between the rough part (a) and the smooth portion adjacent to the rough part (a) and (B), 0 it is a .3μm ~ 3.0μm, zinc-based electroplated steel sheet.
[2] The average surface roughness Ra of the rough part (A) AThere is a total area of the region is 200nm exceeds 2000nm or less, the area S of the coarse portion (A) A is at least 85%, and the average surface roughness Ra of the smooth portion (B) B 5 nm is the total area of the at excess 200nm or less area, the area S of the smooth portion (B) B 65% or more with respect to a zinc-based electroplated steel sheet according to [1].
[3] The crude unit (A) is formed in the hair line, the average length along the extending direction of the hairline is at 1cm or more, [1] or zinc-based electroplated steel sheet according to [2].
[4] the smooth portion (B) is formed in the hair line, the average length along the extending direction of the hairline is at 1cm or more, [1] or zinc-based electroplated steel sheet according to [2].
[5] The hair line is in the range of any 1cm width along the hairline orthogonal direction, present at a frequency of three / cm ~ 80 present / cm on average, according to [3] or [4] zinc-based electroplated steel sheet.
[6] In the surface of the steel sheet, at a position corresponding to the hairline in the zinc-based electroplated layer, a recessed portion is formed, [1] to zinc-based electroplating according to any one of [5] steel sheet.
[7] The average coating weight of the zinc-based electroplated layer, 5 g / m 2 - 40 g / m 2 in the range of [1] zinc electroplated steel sheet according to any one of to [6] .
[8] The zinc-based electroplated layer, Fe, Ni, and any one or more additive elements selected from the group consisting of Co, 5 mass% to 20 mass% in total; the balance Zn and an impurity; containing, [1] zinc electroplated steel sheet according to any one of - [7].
[9] The density of the coarse portion (A) plating a particle size of more than 0.3μm in the particle, 10 10 pieces / m 2 at least, zinc-based electroplated steel sheet according to [8].
　Here, for example, when the zinc-based electroplated layer contains Fe as the additive element, the particle size of the coarse portion (A) is the density of more than plated particles 0.5 [mu] m, 3 × 10 10 pieces / m 2 ~ 5 × 10 14 cells / m 2 is.
　Or, when the zinc-based electroplated layer contains Ni as the additive element, the density of the rough part (A) plating a particle size of more than 0.3μm in the particle, 5 × 10 10 cells / m 2 ~ 7 × 10 14 pieces / m 2 is.
　Or, when the zinc-based electroplated layer contains Co as the additive element, the density of the rough part (A) plating a particle size of more than 0.6μm in the particle is, 1 × 10 10 pieces / m 2 ~ 3 × 10 14 cells / m 2 is.
[10] The zinc-based electroplated layer is made of Zn, include hexagonal laminate set crystals in a surface layer of the zinc-based electroplated layer of zinc according to any one of [1] to [7] system electroplated steel sheet.
[11] on the surface of the zinc-based electroplated layer further comprises an organic resin coating layer having a light transmitting property, [1] zinc electroplated steel sheet according to any one of - [10].
The invention's effect
[0016]
　According to the present invention described above, includes a predetermined corrosion resistance while using inexpensive steel, have a hairline appearance and, excellent in metallic luster and processability adhesion, to provide a zinc-based electroplated steel sheet it becomes possible.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017]
[Figure 1A] is an explanatory view schematically showing an example of the structure of a zinc-based electroplated steel sheet according to the embodiment of the present invention, is a cross-sectional view along the thickness direction.
[Figure 1B] is an explanatory view schematically showing an example of the structure of a zinc-based electroplated steel sheet according to the embodiment, a cross-sectional view along the thickness direction.
[Figure 2] is an explanatory diagram for explaining an example of the zinc-based electroplated layer according to the embodiment, an enlarged fragmentary cross-sectional view along the thickness direction.
3 is a graph for explaining an example of the zinc-based electroplated layer according to the embodiment.
It is a graph for explaining an example of FIG. 4 zinc-based electroplated layer according to the embodiment.
5 is a graph for explaining an example of the zinc-based electroplated layer according to the embodiment.
[6] an explanatory view for explaining another example of the zinc-based electroplated layer according to the embodiment, an enlarged fragmentary cross-sectional view along the thickness direction.
[Figure 7A] is an explanatory diagram of another example of the structure of the zinc-based electroplated steel sheet according to the embodiment shown schematically, a cross-sectional view along the thickness direction.
[Figure 7B] is an explanatory diagram of another example of the structure of the zinc-based electroplated steel sheet according to the embodiment shown schematically, a cross-sectional view along the thickness direction.
[FIG 8A] is an example of the surface electron microscopic observation was the time of the microscopic image of the zinc-based electroplated layer zinc-based electroplated steel sheet according to the embodiment has.
[FIG 8B] is an example of the surface electron microscopic observation was the time of the microscopic image of the zinc-based electroplated layer zinc-based electroplated steel sheet according to the embodiment has.
[FIG 9] (A) is an example of a microscopic image when the surface of the zinc-based electroplated layer zinc-based electroplated steel sheet according to the embodiment has been observed with an electron microscope, (B) and (C) the it is a partially enlarged view.
FIG. 10 is a graph showing an example of measurement of the surface height of the zinc-based electroplated layer zinc-based electroplated steel sheet according to the embodiment has.
[FIG. 11] (A) is an example of a microscopic image when the surface of the zinc-based electroplated layer having general zinc-based electroplated steel sheet was observed with an electron microscope, is a partially enlarged diagram (B) .
A cross-sectional view for explaining an imaginary line forming the boundary between [12] crude unit and a smoothing unit, (A) indicates the case of the embodiment shown in FIG. 2, shown in FIG. 6 (B) It was shown in the case of form.
DESCRIPTION OF THE INVENTION
[0018]
　Reference will now be described in detail preferred embodiments of the present invention. In the specification and the drawings, components having substantially the same function and structure are a repeated explanation thereof by referring to the figures.
[0019]
(Overall configuration of a zinc-based electroplated steel sheet)
　In the following, first, with reference to FIGS. 1A and 1B, will be described in detail the overall structure of the zinc-based electroplated steel sheet according to the embodiment of the present invention. 1A and 1B are explanatory views of an example of the structure of the zinc-based electroplated steel sheet according to the embodiment shown schematically.
[0020]
　Zinc-based electroplated steel sheet 1 according to this embodiment, as schematically shown in Figure 1A, the steel sheet 11 as a base material, a zinc-based electroplated layer 13 located on one surface with a steel plate 11, at least it has. Further, as shown in FIG. 1B, zinc-based electroplated steel sheet 1 according to this embodiment, the surface side of the zinc-based electroplated layer 13, and further has an organic resin coating layer 15 having a light transmitting property it is preferable.
[0021]

　steel sheet 11 as a base material for the zinc-based electroplated steel sheet according to the present embodiment is not limited in particular, the mechanical strength required for the zinc-based electroplated steel sheet (e.g., tensile strength, etc.) etc. depending on the various types of known steel (mild steel, mild steel, high tensile steel, etc.) can be appropriately used.
[0022]

　On one surface of the steel sheet 11 as described above, zinc-based electroplated layer 13 is formed. Zinc-based electroplated layer 13 according to this embodiment, as schematically shown in Figure 1A, (the case of FIG. 1A, the direction perpendicular to the paper surface) predetermined direction the recess 101 to form a hairline extending in a non hairline It has a section 103, a. In zinc-based electroplated layer 13 according to this embodiment, in a recess 101 which forms a hairline, it is formed rough unit such as described in detail below, and, in the non hairline unit 103, as detailed below smooth portion may be formed such. Or, in the zinc-based electroplated layer 13 according to this embodiment, in a recess 101 which forms a hairline, a smoothing unit, such as described in detail below is formed, and the non hairline unit 103, described in detail below rough portion may be formed as. In either case, the average length along the extending direction of the hairline is preferably 1cm or more.
[0023]
　The hairline depth, it is exemplified zinc is 50% or less than 5% the average plating thickness of the electroplating layer 13. More specific examples of the hair line depth, it is exemplified in the range of 0.2μm or more 2.5μm or less. Further, hairline cross-sectional shape in a cross section perpendicular to the extending direction of the hairline is predominantly V-shape, it may include a U-shape.
[0024]
　In the following description, the "direction in which the hairline is drawn", abbreviated as "hairline direction", to a "direction orthogonal to the extending direction of the hairline", abbreviated as "hairline orthogonal direction" . Also, the rough part and the smooth part of the above will be described in detail later.
[0025]
[For type and composition of the zinc-based electroplated layer]
　As the zinc-based electroplated layer 13 according to this embodiment, electro-galvanized or electro zinc alloy plating (hereinafter, collectively referred to as "zinc-based electroplating.") to use.
[0026]
　First, with respect to the plating metal, a plating other than zinc-plated, in order to poor sacrificial protection property, cut edge when use is not suitable for applications which are exposed unavoidably. Further, since the zinc concentration in the plating film loss of the sacrificial protection ability too low, zinc alloy plating, based on the total weight of the plating film, it is preferable to contain zinc than 65 mass%.
[0027]
　Specifically, Zn content in the zinc-based plating, based on the total weight of the plating film is preferably the aforementioned manner 65 mass% or more, more preferably 70 mass% or more, particularly preferably 80 the weight% or more. On the other hand, the upper limit of the Zn content in the zinc-based plating is 100 mass%.
[0028]
　As the plating method, in addition to the electroplating, there are such hot dipping or spraying method or a vapor deposition plating method. However, in the hot dipping method, a dross inevitably mixed coagulation patterns and plating layer such as spangle, have poor appearance quality is not suitable. Further, in the spray method, can not ensure the uniformity of the appearance by a gap inside the plated film is unsuitable. Further, vapor deposition method, since poor productivity because the deposition rate is slow, is not suitable. Therefore, the zinc-based electroplated steel sheet 1 according to this embodiment, in order to perform the zinc-based plated steel material surface, utilizes electroplating.
[0029]
　Here, electrolytic zinc alloy plating to be used as a zinc-based electroplated layer 13 according to this embodiment, Co, Cr, Cu, Fe, Ni, P, Sn, Mn, Mo, V, W, the element group consisting of Zr and at least one additive element selected from preferably contains, and Zn. In particular, electrolytic zinc alloy plating, Fe, Ni, and at least one additive element selected from the element group consisting of Co, it is preferable to contain a total of 5 to 20 mass%. Electrolytic zinc alloy plating, Fe, Ni, at least one additional element of Co by containing in the range of the total content of the above, to achieve better corrosion resistance (耐白 rust resistance / barrier properties) it is possible.
[0030]
　Moreover, electro-galvanized and electro zinc alloy plating may contain impurities as balance. Here, the impurities, not that with intentionally added as a zinc-based electroplated components, or mixed in the raw material, or is intended to be mixed in the manufacturing process, Al, Mg, Si, Ti, B it can include S, N, C, Nb, Pb, Cd, Ca, Pb, Y, La, Ce, Sr, Sb, O, F, Cl, Zr, Ag, W, and H or the like. Further, in practicing the electrolytic zinc plating, depending on the breed of electroplating steel produced in the same manufacturing facility, Co, Cr, Cu, Fe , Ni, P, Sn, Mn, Mo, V, W, there is a case where Zr is mixed as an impurity. In the present embodiment, impurities, the presence of about 1% by weight in total based on the mass of the total plating, effects obtained by plating is not impaired.
　Incidentally, it can be determined and Fe, Ni, Co was intentionally added, Fe were mixed as impurities, Ni, and the Co, the concentration of the zinc-based electroplated layer 13. That is, it determines Fe, Ni, since the lower limit of the total content of Co is 5 weight%, as an impurity if the total content is less than 5 wt% in the case of intentionally added.
[0031]
　The composition of the zinc-based electroplated layer as described above, can be analyzed, for example, by the following method. That is, the solvent or remover does not attack the plating (e.g., Neoriba S-701: San Cai manufactured Kako Co., Ltd.) dissolved in zinc-based electroplated layer such as hydrochloric acid inhibitors containing after removing the organic resin coating layer with a release agent such as to. Then, the dissolved solution ICP: analyzed by (Inductively Coupled Plasma) emission spectrometer. As the inhibitor, Asahi Chemical Industry Co., Ltd. of NO. 700AS can be used.
[0032]
[The average coating weight of the zinc-based electroplated layer 13]
　The average adhesion amount of the zinc-based electroplated layer 13 according to this embodiment, 5 g / m 2 or more 40 g / m 2 is preferably less. The average coating weight of the zinc-based electroplated layer 13 is 5 g / m 2 of less than, when hairline grant, the base steel (i.e., steel plate 11) may possibly be exposed. On the other hand, the average adhesion amount of the zinc-based electroplated layer 13 is 40 g / m 2 for the case where more than the hairline formed by grinding or rolling the steel plate 11, may become less conspicuous by zinc-based electroplating layer 13 , which is not preferable. The lower limit of the average coating weight of the zinc-based electroplated layer 13, more preferably 7 g / m 2 is, more preferably 10 g / m 2 is. The upper limit of the average coating weight of the zinc-based electroplated layer 13 is more preferably 35 g / m 2 or less, more preferably 30 g / m 2 is.
[0033]

　surface of above-described hair line design zinc electroplated layer 13 which has been granted, as schematically shown in FIG. 1B, if a transparent resin (i.e., a light-transmitting it is preferably coated with a resin). That is, the surface side of the zinc-based electroplated layer 13 according to this embodiment, it is preferable that the organic resin coating layer 15 is provided. Here, in the present embodiment, "resin having translucency", through the organic resin coating layer 15 formed on the surface of the zinc-based electroplated layer 13, that zinc-based electroplated layer 13 can be visually observed means.
[0034]
[Organic resin for components of the coating layer]
　resin used for forming the organic resin coating layer 15, sufficient transparency, chemical resistance, corrosion resistance, workability, preferably those with a like耐疵with resistance. Examples of such resins include polyester resins, epoxy resins, urethane resins, polyester resins, phenolic resins, polyether sulfone-based resin, melamine-alkyd resins, acrylic resins, polyamide resins, polyimide system resins, silicone resins, polyvinyl acetate resins, polyolefin resins, polystyrene resins, vinyl chloride resins, vinyl acetate resins are available.
[0035]
　Furthermore, as a means for improving the adhesion between the organic resin coating layer 15 and the zinc-based electroplated layer 13, within a range not to impair the appearance, against plated steel consisting of the steel plate 11 and the zinc-based electroplated layer 13 it may be subjected to inorganic treatment and organic-inorganic composite treatment and surface modification treatment. Here, "disfigurement", or reduce the transparency, or cause uneven gloss, such or cause abnormal crude convex feeling, means reducing the feeling metallic. The process of improving the adhesion, for example, a Zr oxide treatment, or Zn oxide treatment, silane coupling agent treatment or mild acid immersion treatment and include weak alkali immersion treatment.
[0036]
　Further, in order to add the desired performance to the organic resin coating layer 15, a range not impairing the transparency and appearance, and, without departing from the scope defined by the present invention, the organic resin coating layer various additives 15 it may be contained in the. The performance to be added to the organic resin coating layer 15, for example, corrosion resistance, sliding properties, 耐疵 with, conductivity, color tone and the like. For example, if the corrosion resistance, may be contained, such as rust inhibitors or inhibitors, if the sliding property and 耐疵 with resistance, may be contained and waxes and beads, if conductive, conductive agent it may be contained and, if tones may contain a known colorant such as a pigment or dye.
[0037]
　Incidentally, the organic resin coating layer 15 according to this embodiment, when to incorporate a known colorant such as pigments and dyes, it is preferred to incorporate a coloring agent to the extent that hair line is visible.
[0038]
[The thickness of the organic resin coating layer]
　The average thickness of the organic resin coating layer 15 according to this embodiment is preferably 10μm or less. If the average thickness of the organic resin coating layer 15 is more than 10 [mu] m, light is reflected light decreases by the distance through the organic resin coating layer 15 becomes longer, the gloss is likely to decrease. Further, the deformation of the resin due to the processing, and texture of the surface of the zinc-based electroplated layer 13, the deviation between the shape of the surface of the organic resin coating layer 15, tends to occur. For the above reasons, the average thickness of the organic resin coating layer 15 is preferably 10μm or less, and more preferably 8μm or less.
[0039]
　On the other hand, from the viewpoint of corrosion resistance, the thickness of the thinnest portion when viewed from the cross section of the organic resin coating layer 15 (i.e., the minimum value of the thickness of the organic resin coating layer 15), and at 0.1μm or more and an organic resin coating the average thickness of the layer 15, is preferably 1.0μm or more. Here, "the thinnest part" means the minimum value of the film thickness to create a sectional samples cut out a length of 5mm at an arbitrary position in the direction perpendicular to the hairline was measured at 20 points at 100μm intervals and, the "average thickness" means an average of 20 points. And the thickness of the thinnest portion of the organic resin coating layer 15 is 0.5μm or more and more preferably the average thickness of the organic resin coating layer 15 is 3.0μm or more.
[0040]
　While the overall structure of the zinc-based electroplated steel sheet 1 according to this embodiment has been described in detail. In FIG. 1A and 1B, are illustrated for the case where one zinc-based electroplated layer 13 on the surface of and the organic resin coating layer 15 of the steel sheet 11 is formed, the two surfaces forming the front and back each other of the steel sheet 11 zinc-based electroplated layer 13 and an organic resin coating layer 15 may be formed thereon.
[0041]
(For the surface shape of the zinc-based electroplated layer 13)
　Next, with reference to FIGS. 2-6, the surface shape of the zinc-based electroplated layer 13 according to the present embodiment will be described in detail. Figure 2 is an explanatory diagram for explaining an example of the zinc-based electroplated layer according to the present embodiment. 3 to 5 are graphs for explaining an example of the zinc-based electroplated layer according to the present embodiment. Figure 6 is an explanatory diagram for explaining another example of the zinc-based electroplated layer according to the present embodiment.
[0042]
　Zinc-based electroplated layer 13 according to this embodiment, as prior mentioned, the surface layer portion, and a recess 101 which forms a hairline, the non-hairline unit 103, a. Moreover, focusing on the surface shape of the different microscopic zinc-based electroplated layer 13 and the hairline, zinc-based electroplated layer 13 according to this embodiment includes an area average surface roughness Ra of 200nm exceeds 2000nm or less a coarse portion 111, an average surface roughness Ra has a smoothing unit 113 including a region is 5nm exceed 200nm or less, a.
[0043]
　In the zinc-based electroplated layer 13 according to this embodiment, to the coarse portion 111 as described above may be formed in a hair line, the smooth portion 113 as described above may be formed on the inner hairline . That is, the coarse portion 111 as described above, is formed in the recess 101 to form a hairline, and may have a mode where the smoothing unit 113 as described above is formed into a non hairline 103 and, or, the smooth portion 113 as described above, is formed in the recess 101 to form a hairline, and have a mode where coarse portion 111 as described above is formed into a non hairline 103 it may be.
[0044]
　Here, the area ratio of the coarse portion and the flat portion in the present embodiment, it is also possible to determine by measuring the actual surface state was observed like in SEM each area ratio of the present invention the roughness profile is measured by a laser microscope as described later, it sets the crude corresponding part and the smoothing corresponding part by the boundary line by a virtual straight line based thereon, to be used and the area ratio.
　The boundaries between the coarse portion 111 and the smoothing unit 113 in this embodiment, defined as follows.
　First, as shown in FIG. 2 and FIG. 12 (A), the in zinc-based electroplated layer 13 according to this embodiment, the coarse portion 111 is formed in the recess 101 to form a hairline, and smoothing unit 113 is mainly focusing when formed into non hairline portion 103. In this case, display resolution in the height direction is not less 1nm or more, and laser microscope display resolution in the width direction is 1nm or more (i.e., a laser microscope display resolution in the height direction and the width direction is better than 1nm) is used to measure the surface height of the zinc-based electroplated layer 13 in the region of the plan view 1 cm × 1 cm in 500 times magnification. If the observation field of the laser microscope is less than 1 cm, and observing the multiple field-of-view may measure the surface height by connecting them.
[0045]
　Then, along the hairline direction in 100μm interval, the lowest point of the surface height is plotted, height in its cross-section of the hair line perpendicular directions a and thickness direction of the cross-section (FIG. 12 (A)) (H 0 ) and the highest point (H 1 identifies a), respectively. "Smoothing unit 113" is the lowest point (H 0 ) the height from the (H 1 -H 0 was) × 1/3 region defined by a set of at which point more. On the other hand, "coarse portion 111" is the lowest point (H 0 height from) is (H 1 -H 0 and an area defined by a set of) × is a point less than 1/3. That is, the boundary between the coarse portion 111 and the smoothing unit 113, in each of the hairline orthogonal directions a and thickness direction of the cross-section (FIG. 12 (A)), within the scope of the observation width 1cm along the hairline orthogonal direction zinc highest point H of the electroplated layer 13 1 from the lowest point H 0 present on the virtual straight line BL which extends parallel to the height a and the hairline direction perpendicular 1/3 of the maximum height Ry obtained by subtracting the.
[0046]
　Coarse portion 111, after the formation of the zinc-based electroplated layer 13, corresponding to the portion unaffected by the processing of grinding or rolling or the like. Therefore, the surface of the zinc-based electroplated layer 13 when microscopic observation, the coarse portion 111, the crystal grains can be confirmed with a height. The height defined grain is as described above.
　The crystal grain shape in the case where the rough portion 111 in plan view is polygonal structure, in the case of pure zinc containing no additive element zinc electroplated layer 13, crystal shape due to zinc dense hexagonal ( take a hexagonal laminate set crystal).
[0047]
　Further, when containing an additional element to the zinc-based electroplated layer 13, the crystal grain size is, the additional element contained different plating conditions (current density, the relative flow rate of the plating solution and the steel sheet) by the like.
[0048]
　The average particle diameter D indicates the size of the crystal grains (plating particles) ave is determined by the following method.
　First, to observe the surface of the zinc-based electroplated layer 13 by SEM. Field magnification at this time is in the range of 1,000 to 10,000-fold, when not even be confirmed plated particles with 10,000 times the maximum magnification counts the number is zero. Then, from the contour of the plated particles, obtaining the plane area S per one plated particles. Then, assuming a circle having the same plane area and its plane area, determine its diameter, as the representative diameter D by the following equation (1). Then, optionally select 10 plating particles in the observation field of view, to obtain a mean value of the representative diameter D thereof 10 plating particles, an average particle diameter D ave is obtained.
[0049]
　= 2 × D (S / [pi) 0.5 · · · Equation (1)
　where, D is, the unit a typical size in the plan view of the plating particles is [mu] m. Further, S is, the unit is circular corresponding area in plan view of the plating particles [mu] m 2 is.
[0050]
　The density of the crystal grains is determined by the following method.
　First, SEM observation of the surface of the zinc-based electroplated layer 13 as described above, by counting the granule径閾value or more plating particles is a number in the range of 10 [mu] m × 10 [mu] m, determined density of the plating particles It is. The particle径閾value is different for each alloy, when a Zn-Ni is 0.1 [mu] m ~ 2.5 [mu] m, if a Zn-Fe is 0.3 [mu] m ~ 3.0 [mu] m, are Zn-Co If you are a 0.4μm ~ 8.0μm.
　In the case where even if the magnification of the SEM to the maximum magnification (10,000 times) can not be confirmed plated particles counts the number is zero.
[0051]
　If zinc-based electroplated layer 13 is Zn-Fe, an average particle diameter D of the crystal grains in the coarse portion 111 (plating particles) ave will be in the range of 0.5 [mu] m ~ 2.2 .mu.m. The density of the crystal grains in the coarse portion 111, 3 × 10 10 cells / m 2 ~ 5 × 10 14 cells / m 2 falls within the range of. As an example of actual measurement, when zinc-based electroplated layer 13 is Zn-Fe, the crystal grains in the coarse portion 111, an average particle diameter D ave is and density of 6.5 × 10 a 1.78Myuemu 13 pieces / M 2 was.
[0052]
　Further, if the zinc-based electroplated layer 13 is Zn-Co, the average particle diameter D of the crystal grains in the coarse portion 111 (plating particles) ave will be in the range of 0.6 .mu.m ~ 6.0 .mu.m. The density of the crystal grains in the coarse portion 111, 1 × 10 10 pieces / m 2 ~ 3 × 10 14 cells / m 2 falls within the range of. As an example of actual measurement, when zinc-based electroplated layer 13 is Zn-Co, the crystal grains in the coarse portion 111, an average particle diameter D ave is 10 and the density at 5.13μm is 2.2 × 12 pieces / M 2 was.
[0053]
　Further, if the zinc-based electroplated layer 13 is Zn-Ni, average particle diameter D of the crystal grains in the coarse portion 111 (plating particles) ave will be in the range of 0.3 [mu] m ~ 2.0 .mu.m. The density of the crystal grains in the coarse portion 111, 5 × 10 10 cells / m 2 ~ 7 × 10 14 pieces / m 2 falls within the range of. As an example of actual measurement, when zinc-based electroplated layer 13 is Zn-Ni, the crystal grains in the coarse portion 111, an average particle diameter D ave is and density of 4.4 × 10 a 0.6 .mu.m 12 pieces / M 2 was.
[0054]
　In summary of the above, as an additional element in the zinc-based electroplated layer 13, Fe, Ni, and, if it contains any one or more elements selected from the group consisting of Co, particle size in the coarse portion 111 is 0. the density of plated particles is 3μm or more, 10 10 pieces / m 2 becomes higher.
[0055]
　Next, as shown in FIG. 6 and FIG. 12 (B), the in zinc-based electroplated layer 13 according to the present embodiment, the smooth portion 113 is formed in the recess 101 to form a hairline, and the coarse portion 111 mainly focused when formed into a non hairline unit 103. In this case, display resolution in the height direction is not less 1nm or more, and laser microscope display resolution in the width direction is 1nm or more (i.e., a laser microscope display resolution in the height direction and the width direction is better than 1nm) is used to measure the surface height of the zinc-based electroplated layer 13 in the region of the plan view 1 cm × 1 cm in 500 times magnification. If the observation field of the laser microscope is less than 1 cm, and observing the multiple field-of-view may measure the surface height by connecting them.
[0056]
　Then, along the hairline direction in 100μm intervals, plotting the surface height of the cross section of the hair line perpendicular direction a and the thickness direction, the lowest point of the height at the cross-section (H 0 ) and the highest point (H 1 ) are specific, respectively. "Coarse portion 111" is the lowest point (H 0 height from) is (H 1 -H 0 becomes) × 1/3 region defined by a set of at which point more. On the other hand, "smoothing unit 113" is the lowest point (H 0 height from) is (H 1 -H 0 becomes) × 1 / region defined across at the set of points less than 3. The boundary between these coarse portion 111 and the smoothing unit 113, in each cross section of the hair line perpendicular direction a and the thickness direction, the highest point of the zinc-based electroplated layer in the range of the observation width 1cm along the hairline orthogonal direction H 1 from the lowest point H 0 present on the virtual straight line BL which extends parallel to the height a and the hairline direction perpendicular 1/3 of the maximum height Ry obtained by subtracting the.
[0057]
　In zinc-based electroplated layer 13 according to this embodiment, the coarse portion 111 as described above, corresponds to the portion where unevenness of the plating of the crystal grains are present, the smoothing unit 113 as described above, the coarse portion 111 corresponding to irregularities small portion of the plating of the crystal grains than. In the zinc-based electroplated layer 13 according to this embodiment, the coarse portion 111 of the unevenness of the plating of the crystal grains are present, a smoothing unit 113 unevenness of the plating of the crystal grains is less than the coarse portion 111, an appropriate It is made to present in a proportion. Thus, while realizing an improvement in metallic effect in smoothing unit 113, the coarse portion 111, be provided in the upper layer of the zinc-based electroplated layer 13 is preferably realized machining adhesiveness between the organic resin coating layer 15.
[0058]
　Hereinafter, for even when the organic resin coating layer 15 is present in the upper layer of the zinc-based electroplated layer 13 to balance the metallic feeling and processability adhesion, the various conditions required for the zinc-based electroplated layer 13, It will be described in detail. In the following, the coarse portion 111 is formed in the recess 101 constituting the hairline, and the case where the smoothing unit 113 is formed in the non hairline unit 103 as an example, will be referred to.
[0059]
[The difference between the average surface height of the average surface height and the smooth portion of the crude unit]
　zinc electroplated layer 13 according to this embodiment, as described above, has both the coarse portion 111 and the smoothing unit 113 since, as schematically shown in FIG. 2, for each of the coarse portion 111 and the smoothing unit 113 are adjacent to each other, the average surface height of the coarse portion 111, and to consider the average surface height of the smooth portion 113 can. At this time, the zinc-based electroplated layer 13 according to this embodiment, a rough portion 111, a smoothing unit 113 adjacent to such coarse portion 111, adjacent to the average height difference (crude unit 111 according coarse portion 111 of the smoothing the difference in the average surface height of the part 113) is in the range of 0.3 [mu] m ~ 3.0 [mu] m. That is, in the zinc-based electroplated layer 13 according to this embodiment, substantially all of the coarse portion 111 of the recess 101 to form a hairline, if substantially all of the non-hair line portion 103 is smooth portion 113, the recesses 101 and the non the average height difference between the hairline portion 103, in the range of 0.3 [mu] m ~ 3.0 [mu] m.
[0060]
　In the example shown in FIG. 2, for example, crude unit A is formed in a recess 101 which forms a hairline 2 and, smoothing portion B formed in the non hairline portion 103 3 and are adjacent to each other, the coarse portion a 2 and smoothing unit B 3 average height difference can be identified by known measurement methods. In this case, the smooth portion B 3 and the average surface height of the crude unit A 2 height difference between the average surface height of the (Delta] h in FIG. 2) has a range of 0.3 [mu] m ~ 3.0 [mu] m. The same relationship is coarse portion A 2 and the smoothing unit B 2 and between the coarse portion A 1 and the smoothing unit B 2 and between the coarse portion A 1 and the smoothing unit B 1 also holds between the are doing.
[0061]
　When the average height difference between the smooth portion 113 adjacent the coarse portion 111 is less than 0.3μm each other, hairline becomes inconspicuous, it is wasted where the hair line process in zinc-based electroplated layer 13. On the other hand, when the average height difference between the smooth portion 113 and the coarse portion 111 adjacent to each other is more than 3.0μm is not a beautiful hairline to hairline becomes too rough, the design of the hairline is impaired. The lower limit of the average height difference of the smoothing unit 113 and the coarse portion 111 adjacent to each other, preferably 0.8 [mu] m, more preferably 1.0 .mu.m. Further, the upper limit of the average height difference of the smoothing unit 113 and the coarse portion 111 adjacent to each other, preferably 2.6 [mu] m, more preferably from 2.2 .mu.m.
[0062]
　The average height difference between the coarse portion 111 and the smoothing unit 113, for example, by measuring the surface of the zinc-based electroplated layer 13 by a laser microscope, can be measured. At this time, in each of the plurality of locations of the zinc-based electroplated layer 13, the reference high crude unit 111 Satoshi, measures the height difference of up to smoothing unit 113. Then, the average height difference obtained by averaging the plurality of height difference Delta] h, by further averaging by dividing the number of measurement points, can be a coarse portion 111 and the average height difference between the smooth portion 113.
[0063]
Area Ratio of the area of the area and the smooth portion of the crude unit]
　Also, the zinc-based electroplated layer 13 according to this embodiment, the area of the coarse portion 111 (total plane area of the corresponding area in the coarse portion 111) S A and then, the area of the smooth portion 113 (total plane area of the region corresponding to the smoothing unit 113) S B is taken as the area ratio S in the same area unit together B / S a is a 0.6 to 10.0 It is within the range. In this case, for example, in the range shown in FIG. 2, the coarse portion A 1 plane area and the coarse portion A of 2 total area of the area S of the coarse portion 111 within the range shown in FIG. 2 A , and the smooth portion B 1 of the area and the smooth portion B 2 of the area and the smooth portion B 3 total area of the area S of the smooth portion 113 within the range shown in FIG. 2 B becomes. Note that the plane area, as shown in FIG. 8B, the area when viewed area when viewed in plan, that is, as an image when observed the electric microscope.
[0064]
　Hereinafter, the area ratio S as described above B / S A reason why it is important, with reference to FIGS. 3 to 5 will be specifically described.
[0065]
　3, the area ratio S B / S A case where, fix the value of 2.0, was changed the surface roughness Ra of the smooth portion 113 (JIS B 0601 to a defined arithmetic mean roughness Ra) a, using a commercially available glossmeter shows the results of measurement of 60 degree gloss (G60). 3, the horizontal axis is the surface roughness Ra of the smooth portion 113, the vertical axis is the measurement result of the 60 degree gloss. Further, in FIG. 3, hairline in the stretching direction (hereinafter, hairline direction) and a direction perpendicular to the hairline (hereinafter, hairline orthogonal direction) shows the measurement results in each of the.
[0066]
　As apparent from FIG. 3, in both measurements hairline direction and hairline orthogonal directions, larger the surface roughness Ra of the smooth portion 113 (in other words, from the smoothing unit 113 as smoothness will be lost) , the value of the 60-degree gloss continue to decrease, it can be seen that the metallic effect decreases. From these results, by providing the smoothing unit 113, and suppressing the irregular reflection of light that has reached the surface of the zinc-based electroplated layer 13, it is understood that it is possible to improve the gloss.
[0067]
　Next, FIG. 4, by adjusting the surface roughness Ra of the smooth portion 113 to 20 ± 5 nm, the area ratio S B / S A in the case of changing the using commercially available gloss meter, 60 degree gloss (G60) illustrates the results of measuring the. 4, the horizontal axis, the area ratio S B / S A is the vertical axis, the measurement results of the 60 degree gloss.
[0068]
　As apparent from FIG. 4, the area ratio S B / S A a by 0.6 or more, the case without the smoothing section 113 (area ratio S B / S A as compared with the case where = 0) , it is possible to achieve approximately 5 times more gloss at hairline direction, it becomes possible to realize a three times or more glossiness at the hair line perpendicular direction.
[0069]
　On the other hand, the organic resin coating layer 15 provided on the same surface of the sample as that used in the measurement of Fig. 4, a result of evaluation of the processability adhesion is FIG. The evaluation of the processability adhesion were performed in the same manner as described in the following examples, a rating of 5, which means excellent processing adhesion, to score 1 means that poor processability adhesion, in five stages evaluated. As is apparent from FIG. 5, the area ratio S B / S A The sample is 10 or less, processability adhesion whereas evaluates to score 5, the area ratio S B / S A sample exceeds 10 in machining adhesion it is rapidly lowered.
[0070]
　The surface roughness Ra of the smooth portion 113, while changing in the range of 5 nm ~ 200 nm, measurement was carried out in the same manner as FIGS. Also in this case, the area ratio S B / S A With the 0.6 or more, the case without the smoothing section 113 (area ratio S B / S A better dramatically than when a = 0) can be realized glossiness, the area ratio S B / S a when exceeds 10, the processing adhesion is rapidly lowered.
[0071]
　From the above results, in the zinc-based electroplated layer 13 according to this embodiment, the area ratio S B / S A be a be in the range of 0.6 to 10.0 important, revealed . In zinc-based electroplated layer 13 according to this embodiment, the area ratio S B / S A lower limit of preferably 1.5, more preferably 2.5. Further, the area ratio S B / S A upper limit of is preferably 8.0, more preferably 6.5.
[0072]
　Here, (a total plane area of the region corresponding to the coarse portion 111) S area of the coarse portion 111 A , and, S (total plane area of the area corresponding to the smooth portion 113) the area of the smooth portion 113 B has a height display resolution of direction is not less 1nm or more, and binarizes the height data display resolution in the width direction is measured by a laser microscope is 1nm or more, the known image processing on the obtained binary data by applying, it can be measured.
[0073]
　The above-described as the average height difference between the coarse portion 111 and the smoothing unit 113, and the area ratio S of the coarse portion 111 and the smoothing portion 113 B / S A condition for the shown in FIG. 2 Do, coarse portion 111 is formed in the recess 101 constituting the hairline, and not only when the smoothing section 113 is formed in the non hairline unit 103, as schematically shown in FIG. 6, the smoothing unit 113 is formed in the recess 101 constituting the hairline, and it was confirmed that the established similarly also when the coarse portion 111 is formed in the non hairline unit 103.
[0074]
[The surface roughness of the rough portion]
　As prior mentioned, the zinc-based electroplated layer 13 according to this embodiment, by coarse portion 111 is present in the appropriate proportions, the zinc-based electroplated layer 13 the organic resin coating layer 15 is secured processability adhesion when provided on an upper layer. Here, in order to ensure the processability adhesion by the coarse portion 111, the coarse portion 111, by having regions with suitable size having an appropriate surface roughness, the contact area between the organic resin coating layer 15 it is preferable to increase.
[0075]
　Therefore, the zinc-based conductive base plated layer 13 according to this embodiment, the coarse portion 111, display resolution in the height direction is not less 1nm or more, and a laser microscope display resolution in the width direction is 1nm or more using when measured Te, the surface roughness Ra a thinking region is 200nm ultra 2000nm or less, the total area of such regions, the area S of the coarse portion 111 a with respect to, it is preferable that a 85% or more.
[0076]
　Surface roughness Ra of a portion in contact with the organic resin coating layer 15 A that is 200nm ultra 2000nm or less, capable of realizing excellent processing adhesion, more reliable contact between the organic resin coating layer 15 it is possible to realize in. Total area of such regions, the area S of the coarse portion 111 A with respect to the case where less than 85%, the zinc-based electroplated steel sheet 1 according to the present embodiment realizes excellent processability adhesion that it may be difficult. Therefore, the zinc-based electroplated steel sheet 1 according to this embodiment, area S of the coarse portion 111 A of the ratio of the total area to preferably set to 85% or more.
[0077]
　The area S of the coarse portion 111 A for a surface roughness Ra A ratio of the total area of the region is 200nm ultra 2000nm or less, the higher the better, preferably 90% or more, more preferably 95% or more. The area S of the coarse portion 111 A upper limit of the proportion of the total area to the not particularly defined, it may be 100%.
[0078]
[The surface roughness of the smoothing unit]
　Further, as prior mentioned, the zinc-based electroplated layer 13 according to this embodiment, by smoothing unit 113 is present in the appropriate proportions, according to the present embodiment It is realized the metallic effect of the zinc-based electroplated steel sheet 1. In order to achieve the effect of improving the metallic effect by smoothing unit 113, as also illustrated in FIG. 4, the smoothing unit 113, to have a region suitable size having an appropriate surface roughness preferable.
[0079]
　Therefore, the zinc-based conductive base plated layer 13 according to the present embodiment, the smoothing unit 113, display resolution in the height direction is not less 1nm or more and using a laser microscope display resolution in the width direction is 1nm or more when measured Te, the surface roughness Ra B thinking region is 5nm super 200nm or less, the total area of such regions, the area S of the smooth portion 113 B respect, it is preferable that a 65% or more.
[0080]
　Surface roughness Ra of the smooth portion 113 B that is 5nm super 200nm or less, it is possible to more surely achieve excellent gloss. Total area of such regions, the area S of the smooth portion 113 B relative to the case where less than 65%, the zinc-based electroplated steel sheet 1 according to this embodiment, to realize a sense of good metallic it may be difficult. Therefore, the zinc-based electroplated steel sheet 1 according to this embodiment, area S of the smooth portion 113 B is the ratio of the total area for 65% or more.
[0081]
　The area S of the smooth portion 113 B ratio of the total area for the higher good, is preferably 70% or more, more preferably 75% or more. The area S of the smooth portion 113 B upper limit of the proportion of the total area for the not particularly defined, it may be 100%.
[0082]
　Incidentally, the total area as described above, display resolution in the height direction is not less 1nm or more and using a laser microscope display resolution in the width direction is 1nm or more, the surface roughness of the smooth portion 113 or the rough part 111 is the Ra was measured at 1μm intervals along the hairline and the same direction, it can be obtained by the following equation (2) and (3). Since the thus measured local surface roughness when measured length of Ra is too short, the measurement length is set to more than 50 [mu] m. If the observation field of the laser microscope is less than 50 [mu] m, it observed multiple field of view may be obtained Ra by connecting a plurality of field.
[0083]
　Crude unit total area: S A × (Ra is the number / total number of measurements was less than 2000nm or 200nm) · · · (2)
　smoothing unit total area: S B × (number of Ra is less than 200nm or 20nm / total number of measurements) equation (3)
[0084]
About hairline forming Frequency
　Moreover, in the zinc-based electroplated layer 13 according to this embodiment, the recess 101 containing the crude unit 111 or the smoothing unit 113 as described above, any 1cm width along the hairline orthogonal direction in the range, it is preferably present at a frequency of three / cm ~ 80 present / cm. The hair line frequency of forming the hairline orthogonal directions, that is in the range of three / cm ~ 80 present / cm, it is possible to provide a better design. If hairline formation frequency in hairline orthogonal directions is less than three / cm, the density of the hairline is too low, more likely not be able to recognize the hairline. On the other hand, when the hairline forming frequency in hairline orthogonal directions exceeds 80 present / cm is not a beautiful hairline too high density of the hairline is, there is a possibility that the design property is impaired as hairline .
[0085]
　The lower limit of the frequency of presence of the recess 101 in the region of any 1cm width along the hairline orthogonal direction is more preferably ten / cm, more preferably from 15 present / cm. The upper limit of the frequency of presence of the recess 101 in the region of any 1cm width along the hairline direction perpendicular, more preferably 70 yarns / cm, more preferably from 65 present / cm.
[0086]
　Incidentally, the presence frequency of such recesses 101, the surface of the zinc-based electroplated layer 13, display resolution in the height direction is not less 1nm or more and observed with a laser microscope display resolution in the width direction is 1nm or more, the range of any 1mm width, can be identified by counting the number of the recesses 101. That is, the surface of the zinc-based electroplated layer 13, the range of any 1mm width measured over 20 points, by dividing the sum of the number of recesses 101 in each range measurement point number, the average frequency of the recess 101 it can be determined.
[0087]
　Above with reference to FIGS. 2-6, the surface shape of the zinc-based electroplated layer 13 according to the present embodiment has been described in detail.
[0088]
(Zinc another configuration example of an electric plated steel sheet)
　Here, in FIGS. 1A and 1B, it was illustrated for the case where the concave portion 101 only in the zinc-based electroplated layer 13 is provided. However, the zinc-based electroplated steel sheet 1 according to this embodiment, as shown in FIGS. 7A and 7B, also with respect to the surface of the steel sheet 11, a concave portion is provided 105 which forms a hairline that extends in a predetermined direction it may be.
[0089]
　More specifically, as shown in FIGS. 7A and 7B, the surface of the steel sheet 11, hairline in the zinc-based electroplated layer 13 (i.e., recess 101) in positions corresponding to, may be provided with recesses 105.
[0090]
　Here, as shown in FIGS. 1A and 1B, the case where zinc-based electroplated layer 13 only providing the recess 101, as shown in FIGS. 7A and 7B, is provided a recess 105 on the surface of the steel sheet 11 in in the case, for producing a zinc-based electroplated steel sheet 1, the timing of the hair line process is different. The differences between the timing of the hair line processing will be described again in detail below.
[0091]
　Of the surface of the steel sheet 11, whether the recess 105 is present in a position corresponding to the recess 101 formed in the zinc-based electroplated layer 13, it is possible to check in a known manner. As such confirmation method, for example, a method of observing a zinc-based electroplated steel sheet 1 from a cross-sectional direction, and photograph of the zinc-based electroplated layer 13 from the surface, only the zinc-based electroplated layer 13 with hydrochloric acid was added to the inhibitor removal a photograph taken from the surface after, there may be employed a method to compare like.
[0092]
(Method of manufacturing the zinc-based electroplated steel sheet)
　Next, a manufacturing method of the zinc-based electroplated steel sheet according to the present embodiment as described above will be briefly described.
[0093]

　Hereinafter, first, a method of manufacturing the zinc-based electroplated steel sheet 1 having the structure as shown in FIGS. 1A and 1B, will be described briefly.
　In such a case, first, to adjust steel plate 11 of the surface roughness is subjected to a pickling with acid using a degreasing by alkali solution and hydrochloric or sulfuric acid. Then, a zinc-based electroplated layer 13 on the surface of the steel sheet 11. Here, adjustment of the surface roughness of the steel sheet 11 can be a conventional method, for example, the surface roughness is adjusted to a desired range roll steel sheet 11 rolled to the surface method of transferring a roughness, it is possible to use a method such as.
[0094]
　As the method of forming the zinc-based electroplated layer 13 may be a known electroplating process. The electroplating bath, for example, sulfuric acid bath, a chloride bath, a zincate bath, cyanide bath, pyrophosphate bath, a boric acid bath, citric acid bath, other complex bath, and combinations thereof and the like can be used. Further, the electrolytic zinc alloy plating bath, in addition to Zn ion, Co, Cr, Cu, Fe, Ni, P, Sn, Mn, Mo, V, W, 1 or more single ion or complex selected from Zr the addition of ions can be formed Co, Cr, Cu, Fe, Ni, P, Sn, Mn, Mo, V, W, an electrolytic zinc alloy plating layer 13 to a desired amount containing Zr. In order to control the stabilization and plating properties of the ions in the plating bath, the addition of additives to said plating bath is more preferred.
[0095]
　The composition of the electroplating bath, temperature, flow rate and, a current density and the energization pattern like during plating may be appropriately selected so that the desired plating composition, but is not particularly limited. The control of the thickness of the zinc plating layer and the electrolytic zinc alloy plating layer by adjusting a current value and a time within the range of current density as a desired composition, can be carried out.
[0096]
　To the plated steel sheet 11 comprising a zinc-based electroplated layer 13 obtained as described above, to form a hairline of the present embodiment. The method of imparting hairline, is not particularly limited, it is possible to use various known methods. Such known methods, for example, as in the case of imparting hairline stainless steel, a method of polishing with the abrasive belt, the method of polishing with abrasive brushes, a method of transferring a roll which imparted with a texture, predetermined grinding equipment in a method for grinding, and the like.
[0097]
　The depth and frequency of hairline, the polishing belt or abrasive brush size and roll texture depth, and, by adjusting the rolling force and the relative speed and the number of times can be controlled to a desired state.
[0098]
　Above a manner the surface of the zinc-based electroplated layer 13 forming the hairline is like, unevenness due to crystal grains of the plating are present. Therefore, in the manufacturing method of the zinc-based electroplated steel sheet according to the present embodiment, after the hair line formation, to the surface shape of the zinc-based electroplated layer 13 is the surface shape satisfying the various conditions as described prior, known or by grinding the surface of the zinc-based electroplated layer 13 by a method, polishing or, or rolled in a roll having an adjusted surface roughness.
[0099]
　Here, the grinding treatment as described above, polishing treatment, or in the rolling process, as part of unevenness of the plating of the crystal grains is left corresponds to the hairline portion, the non hairline portion surrounding the such remaining portion optionally, grinding, polishing, or continue to the process of rolling. As a result, as shown schematically in Figure 2, the process was carried out portion becomes smooth portion 113 irregularities are suppressed plating crystal grains, while the recess 101 to form a hairline not undergone the process , the coarse portion 111 of the unevenness of the plating of the crystal grains remains.
[0100]
　Conversely, grinding treatment such as described above, polishing treatment, or, in the rolling process, selectively grind only the portion serving as a hairline portion, polishing, when the process of rolling, schematically shown in FIG. 6 such a recess 101 which forms a hairline becomes the smooth portion 113 of the unevenness of the plating of the crystal grains is suppressed. On the other hand, non hairline portion receiving no treatment, the coarse portion 111.
[0101]
　Such, the case is formed by grinding with abrasive brush configuration shown in FIG. Surface of the zinc-based electroplated layer 13 before hairline formation, while a flat is in a state covered with the unevenness of the plating of the crystal grains. In this state, by polishing the surface of the zinc-based electroplated layer 13 with abrasive brushes, scraped portion becomes hairline (recess 101). Moreover, in this hairline, the convex portions of the plated crystal grains is also scraped by the polishing, the surface roughness is smoothed lower than the original state. That is, the surface roughness adjustment in hairline formation and hair line are simultaneously performed. On the other hand, of the surface of the zinc-based electroplated layer 13, the flat portion not cut by the abrasive brush (non hairline unit 103) is in a state where irregularities remained of the original street plated crystal grains.
　Thus, as shown in FIG. 6, the non-hairline portion 103 processability adhesion backed coarse portion 111 is dominantly present to a high smoothing unit 113 is a dominantly present to gloss recess 101 bet is to coexist.
[0102]
　On the surface of the zinc-based electroplated layer 13 imparted with hairline as described above, as required, to cover the organic resin. Here, the paint used for forming the organic resin coating layer 15, the instant coated on zinc-based electroplated layer 13 to follow the surface shape of the zinc-based electroplated layer 13, once, the zinc-based electroplated layer 13 it is preferred leveling after reflecting the surface shape is slowest. That is, a high shear rate in the low viscosity, it is desirable that the paint is high viscosities at low shear rates. Specifically, shear rate 0.1 [1 / sec] in has a 10 [Pa · s] or more viscosity, shear rate 1000 [1 / sec] in 0.01 [Pa · s] following it is desirable to have a shear viscosity.
[0103]
　To adjust the shear viscosity in the range as described above, for example, if the coating material using an aqueous emulsion resin may be adjusted by adding hydrogen bonding of the viscosity modifier. Such hydrogen bonding of the viscosity modifier, because at the time of low shear rate mutually constrained to one another by hydrogen bonds, since it can increase the viscosity of the coating, the hydrogen bond is cleaved at high shear rates, lowering the viscosity to. Thus, it is possible to adjust the shear viscosity in accordance with the coating conditions to be obtained.
[0104]
　Note that the method of coating an organic resin, is not particularly limited, it is possible to use a known method. For example, after coating with using a viscosity was adjusted paint as described above, spraying method, a roll coater method or curtain coater method or die coater method or a dipping pulling method, be formed by air drying or baking drying it can. The drying temperature and the drying time, as well as the baking temperature and baking time, the organic resin coating layer 15 to be formed to include a desired performance, may be appropriately determined. At this time, when the heating rate is slow, the time from the softening point of the resin component to the baking completion will proceed leveling longer heating rate, faster it is preferable.
[0105]

　Next, a method of manufacturing the zinc-based electroplated steel sheet having a structure as shown in FIGS. 7A and 7B, will be briefly described.
　In this case, the - use of the steel plate ended up adjustment of the to surface roughness similar to the "manufacturing method 1". Then, the steel sheet, by forming a hairline before plating treatment, the steel sheet 11 is obtained. The method of applying the hair line to the steel sheet is not particularly limited, a method of polishing with the abrasive belt, the method of polishing with abrasive brushes, a method of transferring a roll which imparted with a texture, grinding at a predetermined grinding equipment it is preferred to use a method in which. Thus, the surface of the steel sheet 11, the coarse portion 105, as shown in FIGS. 7A and 7B are formed.
[0106]
　Then, a zinc-based electroplated layer 13 with respect to the steel plate 11 formed of hairline. Method of forming a zinc-based electroplated layer 13, the - for "a method of manufacturing 1" and can be carried out in the same manner, the detailed description is omitted below. By performing electroplating against hairline of the formed steel plate 11, while maintaining the surface shape of the steel sheet 11 formed of hairline, so that the zinc-based electroplated layer 13 is formed. That is, the zinc-based electroplated layer 13 having a hair line position and shape corresponding to the hairline of the steel sheet 11 in plan view is formed.
[0107]
　On the surface of the zinc-based electroplated layer 13 formed as described above, the - like the "manufacturing method 1", the crystal grains of the plating exists. That is, the surface of the zinc-based electroplated layer 13 at this point, both of the recesses 101 and non hairline portion 103 is in a state covered with the unevenness of the plating of the crystal grains.
　The present manufacturing method, after the formation of the zinc-based electroplated layer 13, zinc to the surface shape of the electroplated layer 13 is the surface shape satisfying the various conditions as described prior, zinc by known methods or by grinding the surface of the electroplated layer 13, abrasive or, or rolled in a roll having an adjusted surface roughness. Accordingly, the - like the "manufacturing method 1", on the surface of the zinc-based electroplated layer 13, the coarse portion 111 and the smoothing portion 113 is formed.
[0108]
　More specifically, for example, when polishing with abrasive brushes, of the surface of the zinc-based electroplated layer 13, only the main non hairline portion 103 is gradually polished. As a result, the convex portion of the non-hair line 103 in the crystal grains are polished by abrasive brush is scraped becomes smooth becomes low surface roughness than the original state, the smoothing unit 113 is dominantly present . On the other hand, the recess 101 forms an abrasive brush hard to reach recesses have substantially original street, in a state where irregularities remained plating crystal grains. Thus, the coarse portion 113 non hairline unit 103 processability adhesion backed dominantly exists to is a recess 101 having high gloss will coexist smoothing unit 111 exists dominantly.
[0109]
　Subsequently, as shown in FIG. 7B, the surface of the zinc-based electroplated layer 13 imparted with hairline, as necessary, to cover the organic resin. Formation of the organic resin coating layer 15, the - for "a method of manufacturing 1" and can be carried out in the same manner, the detailed description is omitted below.
[0110]
　It has been described above manufacturing method of the zinc-based electroplated steel sheet according to the present embodiment.
　As the zinc-based electroplated steel sheet 1, when comparing the embodiment shown in form and Figure 7A shown in FIG. 1A, the direction of the form shown in Figure 7A, smoothing in the depth direction as well plane parts are formed, since the depth is generated in the hairline, high gloss (texture) is easily obtained. For the same reason, even when comparing the embodiment shown in form and 7B shown in FIG. 1B, a high gloss towards forms (texture) is easily obtained as shown in Figure 7B.
[0111]
(A specific example of the zinc-based electroplated layer)
　Subsequently, more is formed by the method described, a specific example of the zinc-based electroplated layer 13 according to this embodiment, with reference to FIGS. 8A ~ 11 , it will be briefly described.
　Figure 8A ~ 9 are the surface of the zinc-based electroplated layer 13 which is an example of a microscopic image when the electron microscopic observation. Figure 10 is a graph showing an example of measurement of the surface height of the zinc-based electroplated layer 13 to zinc-based electroplated steel sheet 1 according to this embodiment has. Figure 11 is a surface of the zinc-based electroplated layer common zinc-based electroplated steel sheet has an example of a microscopic image when the electron microscopic observation. A specific example is shown below, consists of a recess 101 is coarse portion 111 to form a hairline, and non hairline unit 103 is a specific example of a case composed of a smooth portion 113.
[0112]
　It can be formed when a zinc-based electroplated layer 13 in the manufacturing method described form, a zinc-based electroplated layer 13 having a surface shape as shown in FIG. 8A or more, for example. In electron micrograph shown in FIG. 8A, the region corresponding to the recess 101, and a region corresponding to the non-hair line 103 are distributed as shown in FIG. 8B. Incidentally, in FIG. 8B, a region corresponding to the non-hair line portion 103 is shown by hatching.
[0113]
　9, in the zinc-based electroplated layer 13 shown in FIG. 8A, and an enlarged view of a portion of the recess 101, and an enlarged view of a part of the non-hair line portion 103, shown together. 9 Looking at (B) is an enlarged view of the recess 101 in FIG. 9 (A), the it is understood that those of particulate are present many in central photograph. Object of this particulate is crystalline particles of plating. On the other hand, looking at FIG. 9 (C) is an enlarged view of a non-hair line 103 in FIG. 9 (A), the unevenness due to the plating of the crystal particles, such as are present in the enlarged view of the recess 101, it exists at all no it can be seen.
[0114]
　Further, FIG. 10 is a measurement result of the surface height in a portion recess 101 and the non hairline portion 103 are continuous, the horizontal axis of FIG. 10 is a measuring length, the vertical axis of FIG. 10, the surface height is the difference. As it is clear from looking at Figure 10, the height difference between the non-hair line portion 103 and the recess 101 is about 0.8 [mu] m. The average height difference between the recesses 101 in each portion and the non-hairline unit 103, it is understood that the 0.3μm or more.
[0115]
　On the other hand, when the surface of the zinc-based electroplated layer common zinc-based electroplated steel sheet has to electron microscopy, as shown in FIG. 11 (A), zinc-based electroplated layer 13 according to this embodiment has it can be seen that non hairline unit 103 such as that does not exist. Further, as shown in FIG. 11 (B), on the surface of a typical zinc-based electroplated layer, it can be seen that the crystal grains of the plating is widely distributed.
Example
[0116]
　Hereinafter, the effects of the present invention will be specifically described by the invention examples. The area S in Table 1 and Table 3 below A and S B , respectively, are each of an area in the case where the entire area of the observation field is 1.0 (although dimensionless value), the area S A + S B = 1.0. Also, among the column "RaA total area of less than 200nm exceeds 2000nm" in Table 1 and Table 3, left column area S A is the ratio of roughness satisfying area among the (maximum 1.0), right column is the roughness satisfy actual area. Therefore, the area S A × [left column] = become [right column. Similarly, of the column "RaB total area of less than 5nm excess 200nm" in Table 1 and Table 3, left column area S B have a ratio of roughness satisfying area among the (maximum 1.0) , right column is the roughness satisfy actual area. Therefore, the area S B becomes × [left column] = [the right column. The average height difference in Tables 1 and 3 are the average values of △ h shown in FIG. 2 or FIG. That is, the average surface height of a crude unit 111 calculates a difference △ h between the average surface height of the smooth portion 113 adjacent to the crude unit 111, which, for each of the combinations of the coarse portion 111 and the smoothing unit 113 Ask. Then, the average value of the △ h determined determined, which was defined as the average height difference of Tables 1 and 3.
　Note that the contents described in the examples below, but the present invention is limited.
[0117]
(Experimental Example 1: the rough part forms a hairline)
　thickness of 0.6 mm, as the steel sheet is of the throttle among cold-rolled steel sheet defined in JIS G 3141 SPCD, concentration Na of 30 g / L 4 SiO 4 using the treatment liquid, the treatment liquid 60 ° C., a current density of 20A / dm 2 , and electrolytic degreasing under the conditions of processing time of 10 seconds and washed with water. Then the steel material with a electrolytic degreasing, H is the concentration 50 g / L of 60 ° C. 2 SO 4 was immersed for 10 seconds in an aqueous solution, by washing with water, was subjected to pre-plating treatment.
[0118]
　Then, No. shown in Table 1 below 1 ~ No. The steel sample 20, before the formation of the zinc-based electroplated layer 13, by rolling, to form a hairline on the surface of the steel sheet. Incidentally, the rolling method was the method of reduction of the rolling rolls subjected to pattern on the surface on the design surface. Rolling speed was 200Mpm, rolling roll diameter was 500 mm. In addition, No. 21 ~ No. For 23 of the steel samples, before the formation of the zinc-based electroplated layer 13, by grinding, to form a hairline on the surface of the steel sheet.
[0119]
　Then, for all steel samples subjected to zinc-based electroplating having the composition shown in Table 1 below, to form a zinc-based electroplated layer 13. Here, in Table 1 below, added elements that are listed in the "plating composition" is an element which is added to the electroplating solution composed mainly of zinc, in this case field is blank means that which has been subjected to electro-galvanized.
[0120]
　Zn-Ni plating film (Table 1: No.1 ~ 13,17 ~ 21), the bath temperature 50 ° C., a current density of 50A / dm 2 when plated with, a ratio such that the composition shown in Table 1 below adjusting the sulfuric Zn heptahydrate and sulfuric Ni hexahydrate, pH 2, including the 1.2M in total and sulfuric Zn heptahydrate and sulfuric Ni hexahydrate, and anhydrous sodium sulfate 50 g / L, the using a plating bath of 2.0, the amount of adhesion to the values shown in Table 1 was formed by adjusting the plating time.
[0121]
　Zn-Fe plating film (Table 1: No.14) is bath temperature 50 ° C., a current density of 50A / dm 2 when plated in the following sulphate Zn heptahydrate in an becomes such a ratio composition shown in Table 1 pH2 including the adjusted sulfate Fe (II) heptahydrate, and 1.2M in total and sulfuric Zn heptahydrate and sulfate Fe (II) heptahydrate, and anhydrous sodium sulfate 50 g / L, the using a plating bath of 2.0, the amount of adhesion to the values shown in Table 1 was formed by adjusting the plating time.
[0122]
　Zn-Co plating film (Table 1: No.15) is bath temperature 50 ° C., a current density of 50A / dm 2 when plated in the following sulphate Zn heptahydrate in an becomes such a ratio composition shown in Table 1 and adjusting the sulfuric Co heptahydrate, and 1.2M in total and sulfuric Zn heptahydrate sulfate Co heptahydrate, and anhydrous sodium sulfate 50 g / L, the plating bath of pH2.0 containing used, the amount of adhesion to the values shown in Table 1 was formed by adjusting the plating time.
[0123]
　Zn plating film (Table 1: No.16) uses a 1.2M sulfuric acid Zn heptahydrate, and anhydrous sodium sulfate 50 g / L, the plating bath of pH2.0 containing a bath temperature 50 ° C., current density 50A / dm 2 when plated with, the amount of adhesion to the values shown in Table 1 was formed by adjusting the plating time.
　Ni, examples and additional element of Fe No. In 22, bath temperature 50 ° C., a current density of 50A / dm 2 when plated in the following sulphate Zn seven in a ratio such that the composition shown in Table 1 hydrate and sulfuric Ni hexahydrate sulfate Fe (II ) was adjusted heptahydrate, and 1.2M in total and sulfuric Zn heptahydrate and sulfuric Ni hexahydrate sulfate Fe (II) heptahydrate, and anhydrous sodium sulfate 50 g / L, the using a plating bath pH2.0 containing, deposited amount to a value shown in Table 1 was formed by adjusting the plating time.
　Examples for Ni, Fe, and additive element Co No. In 23, bath temperature 50 ° C., a current density of 50A / dm 2 when plated in the following sulphate Zn seven at become such a ratio composition of Table monohydrate and sulfuric Ni hexahydrate sulfate Co Nanamizu a hydrate and sulfuric acid Fe (II) heptahydrate were adjusted, the total sulfate Zn heptahydrate and the sulfuric Ni hexahydrate sulfate Fe (II) heptahydrate sulfate Co heptahydrate and 1.2M in, using the plating bath of pH2.0 containing sodium sulfuric anhydride 50 g / L, the deposition amount is such that the values shown in Table 1 was formed by adjusting the plating time.
[0124]
　Note that when all of the plating process described above, as the relative velocity with respect to the steel sheet is 1 m / sec, was flowing a plating solution. Further, the composition of the obtained plating film, plated steel sheet inhibitor is immersed in (Asahi Chemical Industry Co., Ltd. NO.700AS) 10 wt% of containing hydrochloric acid dissolved peeled, dissolved solution by ICP analysis confirmed.
[0125]
　Further, the reagents are all common reagents used (zinc sulfate heptahydrate, anhydrous sodium sulfate, hydrochloric acid, sulfuric acid (pH adjustment)).
[0126]
　In addition, No. 1 ~ No. For 23 of the steel samples, after formation of the zinc-based electroplated layer 13, the surface of the zinc-based electroplated layer 13 is polished brush, so that the surface shape of the recess 101 and the non hairline unit 103 shown in Table 1 , polishing conditions (abrasive paper size, rolling force, polishing times, etc.) were suitably adjusted. Thus, configured recess 101 in the rough portion 111, such as non hairline unit 103 is constituted by the smoothing section 113, to form a surface shape of the zinc-based electroplated layer 13.
　Incidentally, the boundary between the coarse portion 111 and the smoothing unit 113 in a and the thickness direction of the cross hair line perpendicular direction, the highest point H of the zinc-based electroplated layer 13 within the range of the observation width 1cm along the hairline orthogonal direction 1 lowest point H from 0 was located on a virtual straight line which extends parallel to the height and the hair line perpendicular to the direction of 1/3 of the maximum height Ry obtained by subtracting the.
[0127]
　The various surface roughness of the zinc-based electroplated layer 13 shown in Table 1, the surface height, hairline number, area ratio or the like is a display resolution in the height direction is 1nm or more and displayed in the width direction resolution using Keyence Corporation laser microscope / VK-9710 is 1nm or more measured with reference to the above-described method, coating weight, the inhibitor (Asahi chemical industry Co., Ltd. NO.700AS) 10 wt% of containing hydrochloric acid It was calculated from the weight difference before and after dissolving peeled and immersed in.
[0128]
　To the above coated steel sheet imparted with hairline, to form a transparent organic resin coating layer. Transparent organic resin was formed by the following method. That is, a urethane-based resin (ADEKA Co., HUX-232) and an isocyanate (manufactured by Dai-ichi Kogyo Seiyaku Co., ELASTRON BN69) and curing catalyst (manufactured by Dai-ichi Kogyo Seiyaku Co., Elastron CAT-21) and a solid content mass ratio is 100: 10 were mixed so that 0.5. Thereafter, a polyethylene wax (manufactured by Mitsui Chemicals, Inc., Chemipearl W500), and dry film concentration is added in an amount of 2 wt% and stirred. Further, the resulting mixture was diluted with water to prepare a treatment liquid having a different density and viscosity. These treatment solution was applied on the surface of the steel sheet by a roll coater. At this time, the dry film thickness was adjusted to a thickness shown in Table 1 below. It was maintained for 30 seconds painted steel sheet in a hot air oven maintained at 280 ° C.. Temperature reached the steel plate was set to 210 ° C., after heating, it was cooled by spraying with water.
[0129]
[Table 1]

[0130]
　Before forming the organic resin coating layer 15, and, for each of the after forming, the gloss G60 glossmeter (manufactured by Suga Test Instruments: Gloss Meter UGV-6P) was measured by. Note that when measurements were measured two hairline direction glossiness (Gl) and hairline direction perpendicular glossiness (Gc). The resulting thereof, are summarized in Table 2 below.
[0131]
　Corrosion resistance of the resultant zinc-based electroplated steel sheet was evaluated by the following methods.
　That is, from each of the zinc-based electroplated steel sheet thus obtained, thereby manufacturing a test piece of width 70 mm × length 150 mm. Edge and backside with sealing tape was subjected salt spray test (JIS Z 2371). Then, it was visually observed to white rust area ratio of the non-sealed portion after 24 hours was evaluated according to the following evaluation criteria. The white rust area ratio, a percentage of the area of white rust site to the area of the observed region. The results obtained are summarized in Table 2 below.
[0132]
(Evaluation
　　criteria) 5: White rust occurrence rate 10% less than
　　4: White rust occurrence rate 10% or more less than 25%
　　3: White rust occurrence rate 25% 50% or more than
　　2: White rust occurrence rate 50% or more and less than 75%
　　1 : white rust occurrence rate of 75% or more
[0133]
　Further, as for a process adhesion of the resultant zinc-based electroplated steel sheet (adhesion to the organic resin coating layer) was evaluated by the following methods.
　That is, from each of the zinc-based electroplated steel sheet thus obtained, to prepare a test piece of width 50 mm × length 50 mm. It was subjected to bending of 180 ° with respect to the obtained test pieces were conducted to a tape peeling test with respect to the outside of the bent portion. Observing the appearance of the tape peeling unit with magnification 10x loupe and evaluated according to the following evaluation criteria. Bending, in an atmosphere of 20 ° C., it was performed in between the 0.5mm spacer. The results obtained are summarized in Table 2 below.
[0134]
(Evaluation criteria)
　　5: no peeling of the coating film was observed
　　4: observed peeling a small part of the coating film (peeling area ≦ 2%)
　　3: Peeling is observed on a part of the coating (2% < peeling area ≦
　　10%) 2: peeling of the coating film is observed (10% 20%)
[0135]
[Table 2]

[0136]
　No. 1 ~ No. Of 23 of the steel sample, No. In 2 of the comparative example, both the average height difference and the area ratio does not meet the prescribed resulted with low processability adhesion. In addition, No. In Comparative Example 5, both the average height difference and the area ratio does not meet the prescribed, resulted with low corrosion resistance. In addition, No. In Comparative example 13, it does not meet the provisions Gc / Gl, resulted in a poor metal feeling.
[0137]
　As is apparent from Table 2, the zinc-based electroplated steel sheet according to an embodiment of the present invention is provided with a predetermined corrosion resistance while using inexpensive steel, have a hairline appearance and, metallic feeling and processability adhesion it can be seen that excellent.
[0138]
(Experimental Example 2 Example smoothing unit forms a hairline)
　as steel, it is for a throttle of the cold-rolled steel sheet defined in JIS G 3141 SPCD (thickness 0.6 mm), the concentration of 30 g / L Na 4 SiO 4 using the treatment liquid, the treatment liquid 60 ° C., a current density of 20A / dm 2 , and electrolytic degreasing under the conditions of processing time of 10 seconds and washed with water. Then the steel material with a electrolytic degreasing, H is the concentration 50 g / L of 60 ° C. 2 SO 4 was immersed for 10 seconds in an aqueous solution, by washing with water, was subjected to pre-plating treatment.
[0139]
　Then, for all steel samples subjected to zinc-based electroplating having the composition shown in Table 3 below, to form a zinc-based electroplated layer 13. Here, in Table 3 below, "additive element" described in the column of "plating composition" is a the added element in the electroplating solution. If such a column is blank (Table 3: No.33) to means that subjected to electro-galvanized.
[0140]
　Also, Zn-Ni plating film (Table 3: No.31,32,34 ~ 40), the bath temperature 50 ° C., a current density of 50A / dm 2 when plated with, such that the composition shown in Table 3 below adjusting the sulfuric Zn heptahydrate and sulfuric Ni hexahydrate in a ratio, and 1.2M in total and sulfuric Zn heptahydrate and sulfuric Ni hexahydrate, and anhydrous sodium sulfate 50 g / L, the using a plating bath pH2.0 containing coating weight after hairline formed such that the values shown in Table 3 was formed by adjusting the plating time.
[0141]
　Zn-Fe plating film (Table 1: No.41) is bath temperature 50 ° C., a current density of 50A / dm 2 when plated in the following sulphate Zn heptahydrate in an becomes such a ratio the compositions shown in Table 3 pH2 including the adjusted sulfate Fe (II) heptahydrate, and 1.2M in total and sulfuric Zn heptahydrate and sulfate Fe (II) heptahydrate, and anhydrous sodium sulfate 50 g / L, the using a plating bath of 2.0, coating weight after hairline formed such that the values shown in Table 3 was formed by adjusting the plating time.
　Zn-Co plating film (Table 1: No.42) is bath temperature 50 ° C., a current density of 50A / dm 2 when plated in the following sulphate Zn heptahydrate in an becomes such a ratio the compositions shown in Table 3 and adjusting the sulfuric Co heptahydrate, and 1.2M in total and sulfuric Zn heptahydrate sulfate Co heptahydrate, and anhydrous sodium sulfate 50 g / L, the plating bath of pH2.0 containing used, the coating weight after the hair line formed such that the values shown in Table 3 was formed by adjusting the plating time.
[0142]
　Ni, examples and additional element of Fe No. In 43, bath temperature 50 ° C., a current density of 50A / dm 2 when plated in the following sulphate Zn seven in a ratio such that the composition shown in Table 3 hydrate and sulfuric Ni hexahydrate sulfate Fe (II ) was adjusted heptahydrate, and 1.2M in total and sulfuric Zn heptahydrate and sulfuric Ni hexahydrate sulfate Fe (II) heptahydrate, and anhydrous sodium sulfate 50 g / L, the using a plating bath pH2.0 containing coating weight after hairline formed such that the values shown in Table 3 was formed by adjusting the plating time.
　Examples for Ni, Fe, and additive element Co No. In 44, bath temperature 50 ° C., a current density of 50A / dm 2 when plated in the following sulphate Zn seven in a ratio such that the composition shown in Table 3 hydrate and sulfuric Ni hexahydrate sulfate Co Nanamizu a hydrate and sulfuric acid Fe (II) heptahydrate were adjusted, the total sulfate Zn heptahydrate and the sulfuric Ni hexahydrate sulfate Fe (II) heptahydrate sulfate Co heptahydrate and 1.2M in, using the plating bath of pH2.0 containing sodium sulfuric anhydride 50 g / L, a, as coating weight after hairline formation becomes a value shown in Table 3, by adjusting the plating time the formed.
[0143]
　Note that when all of the plating process described above, as the relative velocity with respect to the steel sheet is 1 m / sec, was flowing a plating solution. Further, the composition of the obtained plating film, plated steel sheet inhibitor is immersed in (Asahi Chemical Industry Co., Ltd. NO.700AS) 10 wt% of containing hydrochloric acid dissolved peeled, dissolved solution by ICP analysis confirmed.
[0144]
　Further, the reagents are all common reagents used (zinc sulfate heptahydrate, anhydrous sodium sulfate, hydrochloric acid, sulfuric acid (pH adjustment)).
[0145]
　Then, No. shown in Table 3 below 31 ~ No. For 34 of the steel sheet samples, after formation of the zinc-based electroplated layer 13, by rolling, to form a hairline on the surface of the zinc-based electroplated steel sheet 1. Incidentally, the rolling method, the mill roll subjected to pattern on the surface, the design surface of the zinc-based electroplated steel sheet 1 (i.e., the surface of the zinc-based electroplated layer 13) was a method of reduction to. Rolling rate was 50mpm. The rolling roll surface, to secure a commercial belt sander for sandpaper grinder, by rotating the roll to impart a continuous abrasive wire as a pattern. The number of hairline is adjusted by the interval of such abrasive line, hairline depth was adjusted by roughness and rolling load of sandpaper. The abrasive grains, using a commercially available SiC.
[0146]
　Also, No. shown in Table 3 below 35 ~ No. The steel samples 38, 41 and 44, after the formation of the zinc-based electroplated layer 13, by grinding, to form a hairline on the surface of the steel sheet. Incidentally, the grinding method, while rotating the roll subjected to pattern on the surface, the design surface with a zinc-based electroplated layer 13 (i.e., the surface of the zinc-based electroplated layer 13) was a method of reduction to. Grinding brush was rotated in the sheet passing direction opposite direction of the steel sheet samples. Hairline depth, brush material, the rotational speed and brush - was adjusted by the load between the steel plates. Further, hairline density was adjusted by the yarn diameter and density of the brush.
[0147]
　By the above procedure, the recess 101 is formed by the smoothing unit 113, such as non hairline unit 103 is constituted by a rough section 111, to form a surface shape of the zinc-based electroplated layer 13.
　Further, for reference, a comparative example of a case where the steel sheet is temper rolling was then hairline is formed by brushing or rolling to No. 39, No. 40 were also provided.
　Incidentally, the boundary between the coarse portion 111 and the smoothing unit 113 in a and the thickness direction of the cross hair line perpendicular direction, the highest point H of the zinc-based electroplated layer 13 within the range of the observation width 1cm along the hairline orthogonal direction 1 lowest point H from 0 was located on a virtual straight line which extends parallel to the height and the hair line perpendicular to the direction of 1/3 of the maximum height Ry obtained by subtracting the.
[0148]
　Here, various surface roughness of the zinc-based electroplated layer 13 shown in Table 3, the surface height, hairline number, area ratio or the like is a display resolution in the height direction is 1nm or more and, in the width direction using Keyence Corporation laser microscope / VK-9710 display resolution is 1nm or more measured with reference to the above-described method, coating weight, the inhibitor (Asahi chemical industry Co., Ltd. NO.700AS) containing 10 wt% It was calculated from the weight difference before and after dissolving peeled and immersed in hydrochloric acid.
[0149]
　To the above coated steel sheet imparted with hairline, to form a transparent organic resin coating layer. Transparent organic resin was formed by the following method. That is, a urethane-based resin (ADEKA Co., HUX-232) and an isocyanate (manufactured by Dai-ichi Kogyo Seiyaku Co., ELASTRON BN69) and curing catalyst (manufactured by Dai-ichi Kogyo Seiyaku Co., Elastron CAT-21) and a solid content mass ratio is 100: 10 were mixed so that 0.5. Thereafter, a polyethylene wax (manufactured by Mitsui Chemicals, Inc., Chemipearl W500), and dry film concentration is added in an amount of 2 wt% and stirred. Further, the resulting mixture was diluted with water to prepare a treatment liquid having a different density and viscosity. These treatment solution was applied on the surface of the steel sheet by a roll coater. At this time, the dry film thickness was adjusted to a thickness shown in Table 1 below. It was maintained for 30 seconds painted steel sheet in a hot air oven maintained at 280 ° C.. Temperature reached the steel plate was set to 210 ° C., after heating, it was cooled by spraying with water.
[0150]
[table 3]

[0151]
　For each of the zinc-based electroplated steel sheet obtained as described above, in the same manner as in Experimental Example 1, glossiness, corrosion resistance, and was evaluated processability adhesion. Evaluation methods and evaluation criteria are the same as in Experimental Example 1. The results obtained are summarized in Table 4 below.
[0152]
[Table 4]

[0153]
　No. 31 ~ No. Of 44 of the steel sample, No. In comparative example 34, both average height difference and the area ratio does not meet the prescribed resulted with low processability adhesion. In addition, No. In Comparative example 36, the area ratio does not meet the prescribed, resulted with low adhesion.
　No. In Comparative example 38, the area ratio and Gc / Gl does not meet the prescribed, resulted in a poor metal feeling.
　No. Comparative example 39 is obtained by brush graining after tone chamber rolling, No. 40 is obtained by rolling after the control room rolling. These both processability adhesion to unevenness of plating particles have disappeared becomes the result of the extremely low.
[0154]
　As it is apparent from Table 4, zinc-based electroplated steel sheet according to the present invention includes a predetermined corrosion resistance while using inexpensive steel, have a hairline appearance and, excellent in metallic appearance and processability adhesion it can be seen that you are.
[0155]
　Having described in detail preferred embodiments of the present invention with reference to the accompanying drawings, the present invention is not limited to such an example. It would be appreciated by those skilled in the relevant field of technology of the present invention, within the scope of the technical idea described in the claims, it is intended to cover various changes and modifications , also such modifications are intended to fall within the technical scope of the present invention.
Industrial Applicability
[0156]
　According to the present invention, it includes a predetermined corrosion resistance while using inexpensive steel, have a hairline appearance and, excellent in metallic luster and processability adhesion, it is possible to provide a zinc-based electroplated steel sheet .
DESCRIPTION OF SYMBOLS
[0157]
　　　1 zinc electroplated steel sheet
　　11 steel
　　13 zinc-based electroplated layer
　　15 organic resin coating layer
　101, 105 recess
　103 non hairline portion
　111 coarse portion
　113 smooth portion

The scope of the claims

[Requested item 1]And the steel sheet,
　at least one of located on the surface, the zinc-based electroplated layer hairline is formed as a recess extending in a predetermined direction of the steel sheet
provided with,
　the zinc-based electroplated layer is rough part ( becomes from a) and a smoothing section (B), and
　the rough part (a) has an average surface roughness Ra a comprises a region is 200nm exceeds 2000nm or less,
　wherein the smooth portion (B) has an average surface roughness Ra B comprises a region is 5nm exceed 200nm or less,
　the boundary between the rough part (a) and the smooth portion (B),
　　in the hair line perpendicular to the direction in and the thickness direction of the cross section perpendicular to the predetermined direction, the the highest point H of the zinc-based electroplated layer in the range of the observation width 1cm along the hairline direction orthogonal 1 from the lowest point H 0 to the height a and the hairline direction perpendicular 1/3 of the maximum height Ry obtained by subtracting the form a parallel When to be in a virtual straight line,
　in the same unit of area from each other, the rough portions of the surface area of the (A) S A and the smoothing unit area of (B) S B is taken as the area ratio S B / S AThere is in the range of 0.6 to 10.0,
　the average height difference between the rough part (A) and the smooth portion adjacent to the rough part (A) and (B), 0.3 [mu] m ~ is 3.0μm,
zinc-based electroplated steel sheet.
[Requested item 2]
　The average surface roughness Ra of the rough part (A) A total area of the region is 200nm exceeds 2000nm or less, the area S of the coarse portion (A) A 85% or more with respect to, and
　the smoothing the average surface roughness Ra in part (B) B total area of is 5nm exceed 200nm or less area, the area S of the smooth portion (B) B 65% or more with respect,
according to claim 1 zinc-based electroplated steel sheet.
[Requested item 3]
　The crude unit (A) is formed in the hair line,
　the average length along the extending direction of the hairline is at 1cm or more,
the zinc-based electroplated steel sheet according to claim 1 or 2.
[Requested item 4]
　The smoothing unit (B) is formed in the hair line,
　the average length along the extending direction of the hairline is at 1cm or more,
the zinc-based electroplated steel sheet according to claim 1 or 2.
[Requested item 5]
　The hairline is in the range of any 1cm width along the hairline orthogonal direction, present at a frequency of three / cm ~ 80 present / cm on average,
zinc electroplated steel sheet according to claim 3 or 4 .
[Requested item 6]
　The surface of the steel sheet, at a position corresponding to the hairline in the zinc-based electroplated layer, a recessed portion is formed,
a zinc-based electroplated steel sheet according to any one of claims 1 to 5.
[Requested item 7]
　The average coating weight of the zinc-based electroplated layer, 5 g / m 2 ~ 40 g / m 2 in the range of,
zinc-based electroplated steel sheet according to any one of claims 1-6.
[Requested item 8]
　The zinc-based electroplated layer,
　　Fe, Ni, and any one or more additive elements selected from the group consisting of Co, 5 mass% to 20 mass% in total;
　　and Zn and impurities the balance ;
containing,
zinc electroplated steel sheet according to any one of claims 1 to 7.
[Requested item 9]
　The particle size of the coarse portion (A) is the density of 0.3μm or more plated particles, 10 10 pieces / m 2 at least,
zinc-based electroplated steel sheet of claim 8.
[Requested item 10]
　The zinc-based electroplated layer is made of Zn,
　the hexagonal laminate set crystals contained in the surface layer of the zinc-based electroplated layer,
a zinc-based electroplated steel sheet according to any one of claims 1 to 7.
[Requested item 11]
　On the surface of the zinc-based electroplated layer further comprises an organic resin coating layer having a light-zinc electroplated steel sheet according to any one of claims 1 to 10.