KR20210152501A - galvanized steel - Google Patents

Abstract

A plated steel sheet according to one embodiment of the present invention includes a base steel sheet having a base material texture on its surface, a galvanized layer formed on the surface having a base material texture of the base steel sheet, and a colored resin layer formed on the galvanized layer, , on the surface of the galvanized layer, a plating texture is formed, the colored resin layer contains a colorant, the plating texture includes a plurality of convex portions and a plurality of concave portions, and the concave bottom three-dimensional average roughness Sas is 200 It is more than nm and 2000 nm or less, DKmin x CK is 15.0 or less, (DKmax-DKmin) x CK is larger than 1.0. A coated steel sheet according to another aspect of the present invention is provided with a base steel sheet, a zinc plating layer formed on the surface of the base steel sheet, and a colored resin layer formed on the zinc plating layer, the surface of the zinc plating layer extending in one direction texture is formed, the colored resin layer contains a colorant, the three-dimensional average roughness Saave' is more than 5 nm and 200 nm or less, DKmin' x CK' is 15.0 or less, (DKmax'-DKmin') x CK' is greater than 1.0.

Description

galvanized steel

The present invention relates to a plated steel sheet.

This application is patent application No. 2019-171166, filed in Japan on September 20, 2019, Patent application No. 2019-171137, filed in Japan on September 20, 2019, and Japanese patent application No. Priority is claimed based on the filed Patent Application No. 2019-098050, and the content is incorporated herein by reference.

Articles such as electric equipment, building materials, and automobiles may be required to have design properties. As a method of improving the designability of an article, there exist a method of coating the surface of an article, and the method of sticking a film.

In recent years, materials utilizing the texture of metal tend to be preferred, mainly in nature-oriented Europe and America. In the case of making use of the texture of the metal, a stainless steel sheet or an aluminum sheet having excellent corrosion resistance is used as a material even without being painted. In addition, for the purpose of further enhancing the metallic feeling of the stainless steel sheet and the aluminum sheet, a stainless steel sheet or an aluminum sheet having a texture represented by a hairline formed on the surface is also provided. However, a stainless steel plate or an aluminum plate is expensive. Therefore, an inexpensive material which replaces a stainless steel plate or an aluminum plate is calculated|required.

As one of the alternative materials for such a stainless steel sheet or an aluminum sheet, the plated steel sheet provided with the zinc plating layer on the surface is examined. In this specification, a zinc plating layer also includes a zinc alloy plating layer. A plated steel plate is equipped with moderate corrosion resistance similarly to a stainless steel plate and an aluminum plate, and is excellent also in workability. Therefore, a plated steel sheet is suitable for uses, such as an electric device and a building material. Then, for the purpose of improving the designability of a plated steel sheet, various proposals are made.

For example, in Unexamined-Japanese-Patent No. 2006-124824 (patent document 1), after giving a hairline finish to a galvanized steel sheet, the transparent resin film is formed in the surface of the galvanizing layer in which the hairline was formed. Thereby, the surface of a plating layer is made visually visible, maintaining corrosion resistance, and designability is improved.

Further, in Japanese Patent Publication No. 2013-536901 (Patent Document 2), after rolling a galvanized steel sheet to form a texture on the surface of the galvanized layer, an organic film (resin) having a surface roughness within a certain range. ) to coat the surface of the galvanized layer. Thereby, the surface of a plating layer is made visually visible, maintaining corrosion resistance, and designability is improved.

Japanese Patent Laid-Open No. 2006-124824 Japanese Patent Publication No. 2013-536901

In recent years, a material having a colored appearance while making use of the metal texture is starting to be demanded. More specifically, a plated steel sheet in which the texture of the surface of the galvanized layer can be visually recognized while having a colored appearance is desired.

An object of the present invention is to provide a plated steel sheet capable of visually recognizing the texture of the surface of the galvanized layer while having a colored appearance.

(1) A plated steel sheet according to one aspect of the present invention includes a base steel sheet having a base material texture on its surface, a galvanized layer formed on the surface having the base material texture of the base steel sheet, and formed on the zinc plating layer, a colored resin layer with a galvanized layer, wherein the galvanized layer has a plating texture on its surface, the colored resin layer contains a colorant, the plating texture includes a plurality of convex portions and a plurality of concave portions, When the rolling direction of the base steel sheet is defined as the first direction, and the direction orthogonal to the first direction on the surface of the plated steel sheet is defined as the second direction, the plated steel sheet has the following (A) to ( C) is satisfied.

(A) When the roughness profile in the range of the length of 1000 µm in the second direction of the plating texture is measured, and the lowest position in each of the recesses in the measured roughness profile is defined as the bottom point of the recess , three-dimensionality of a micro-region of 1 μm×1 μm centered on the specified bottom points of the recesses, and specifying 10 bottom points of the recesses in the lowest order among the bottom points of the plurality of recesses of the roughness profile. When the average roughness Sa is measured and the arithmetic mean of the ten measured three-dimensional average roughness Sa is defined as the three-dimensional average roughness Sas at the bottom of the recess, the three-dimensional average roughness Sas at the bottom of the recess is greater than 200 nm and less than or equal to 2000 nm.

(B) In the range of 100 μm length in the second direction, the minimum thickness (μm) of the colored resin layer is defined as DKmin, and the content (area%) of the coloring agent in the colored resin layer is defined as CK, , when F1 is defined by Formula (1), F1 is 15.0 or less.

F1=DKmin×CK (1)

(C) In the range of the length of 100 µm in the second direction, when the maximum thickness (µm) of the colored resin layer is defined as DKmax and F2 is defined by the formula (2), the F2 is greater than 1.0.

F2=(DKmax-DKmin)×CK (2)

(2) The plated steel sheet according to (1) above may further satisfy the following (D).

(D) When the roughness profile in the range of the length of 1000 µm in the second direction of the plating texture is measured, and the highest position in each of the convex portions in the measured roughness profile is defined as the convex portion apex , 10 of the convex vertices of the roughness profile are specified in the highest order, and three-dimensionality of a minute region of 1 μm×1 μm centered on the specified convex vertex. When the average roughness Sa is measured and the arithmetic mean value of the ten measured three-dimensional average roughness Sa is defined as the convex part normal three-dimensional average roughness Sas, the convex part normal three-dimensional average roughness Sah is more than 5 nm and 200 nm or less.

(3) In the plated steel sheet according to (2), the plurality of convex portions and the plurality of concave portions extend in the first direction, and the plurality of convex portions and the plurality of concave portions extend in the second direction may be arranged as

(4) In the plated steel sheet described in (3) above, the base material texture is a hairline, the plating texture is a hairline, and the plated steel sheet may further satisfy the following (E) and (F).

(E) The surface roughness Ra of the colored resin layer in the first direction is defined as Ra(CL), the surface roughness Ra of the colored resin layer in the second direction is defined as Ra(CC), and F3 is defined as the formula When defined by (3), the F3 is 1.10 or more.

F3=Ra(CC)/Ra(CL) (3)

(F) When the surface roughness of the galvanized layer in the second direction is defined as Ra(MC), Ra(MC) is 0.30 µm or more.

(5) In the plated steel sheet according to any one of (1) to (4), the brightness L*(SCI) of the plated steel sheet when viewed from the colored resin layer side may be 45 or less.

(6) In the plated steel sheet according to any one of (1) to (5), F1 may be 13.5 or less.

(7) In the plated steel sheet according to any one of (1) to (6), F2 may be larger than 2.0.

(8) In the plated steel sheet according to any one of (4) to (7), the F3 may be 1.15 or more.

(9) In the plated steel sheet according to any one of (1) to (8), the ferrous iron exposure rate of the galvanized layer may be less than 5%.

(10) In the plated steel sheet according to (2), the plurality of convex portions are formed by polishing the surface of the galvanized layer, and the plurality of concave portions may not be polished.

(11) A plated steel sheet according to another aspect of the present invention includes a base steel sheet, a galvanized layer formed on a surface of the base steel sheet, and a colored resin layer formed on the galvanized layer, the galvanized layer comprising: , has a texture extending in one direction on its surface, the colored resin layer contains a colorant, and satisfies all of the following (A') to (C').

(A') Measure the roughness profile in the range of a length of 1000 μm in the direction perpendicular to the extension direction of the texture, and among the measured locations on the roughness profile, 10 specific positions in the order of height are selected as the bottom point of the recess Among the positions on the measured roughness profile, 10 specific positions in the order of height are defined as convex vertices, and 1 μm × 1 μm centered at the bottom of each concave portion and each convex vertex is defined as When the three-dimensional average roughness Sa' of the microregion is measured and the arithmetic mean value of the measured three-dimensional average roughness Sa' is defined as the three-dimensional average roughness Saave', the three-dimensional average roughness Saave' is greater than 5 nm and less than or equal to 200 nm.

(B') In the range of a length of 100 µm in a direction orthogonal to the extending direction of the texture, the minimum thickness (µm) of the colored resin layer is defined as DKmin', and the content (area) of the colorant in the colored resin layer %) is defined as CK', Equation (1') is satisfied.

DKmin'×CK'≤15.0 (1')

(C') Expression (2') is satisfied when the maximum thickness (µm) of the colored resin layer is defined as DKmax' in a range of 100 µm in length in a direction perpendicular to the extension direction of the texture.

(DKmax'-DKmin')×CK'>1.0 (2')

(12) In the plated steel sheet according to (11), the texture is a hairline, and the following (D') and (E') may be satisfied.

(D') The surface roughness Ra of the colored resin layer in the extending direction of the texture is defined as Ra(CL)', and the surface roughness Ra of the colored resin layer in the direction perpendicular to the extending direction of the texture is Ra(CC). )', Equation (3') is satisfied.

Ra(CC)'≥Ra(CL)'×1.10 (3')

(E') When the surface roughness of the galvanized layer in the direction orthogonal to the extending direction of the texture is defined as Ra(MC)', Ra(MC)' is 0.30 µm or more.

(13) In the plated steel sheet according to the above (11) or (12), the ferrous iron exposure rate of the galvanized layer may be less than 5%.

(14) In the plated steel sheet according to any one of (1) to (13), the colored resin layer is a laminated resin layer, and the laminated resin layer includes a plurality of laminated resin layers in a direction normal to the surface of the base steel sheet. A colored resin layer is provided, and in the plurality of colored resin layers, the sum of the product of the content (area %) of the coloring agent in the colored resin layer and the thickness (μm) of the colored resin layer is 15.0 area%·μm or less and, among the plurality of colored resin layers, the colored resin layer in which the product of the content (area %) of the coloring agent in the colored resin layer and the thickness (㎛) of the colored resin layer is the largest is defined as the deepest colored colored resin layer, , When the product of the content of the coloring agent in the colored resin layer and the thickness of the colored resin layer having the second largest color resin layer is defined as the second hyperchromic colored resin layer, the content C of the coloring agent in the deepest colored resin layer _1ST (area %), thickness D _{1ST (μm) of the deepest color resin layer, content C 2ND} (area%) of the colorant in the second hyperchromic color resin layer, and thickness D _{2ND of the second hyperchromic color resin layer} (micrometer) may satisfy Formula (4).

1.00<(C _1ST ×D _1ST )/(C _2ND ×D _2ND )≤4.00 (4)

(15) In the plated steel sheet according to (14), the thickness of the laminated resin layer may be 10.0 µm or less.

(16) In the plated steel sheet according to (14) or (15) above, the laminated resin layer further includes one or a plurality of transparent resin layers not containing the colorant, and the laminated resin layer comprises: A plurality of colored resin layers and one or more transparent resin layers may be laminated and formed.

The plated steel sheet according to the present disclosure can visually recognize the texture of the surface of the galvanized layer while having a colored appearance.

BRIEF DESCRIPTION OF THE DRAWINGS In the plated steel sheet of 1st Embodiment, it is a schematic diagram of the cross section perpendicular|vertical to a 1st direction.
It is sectional drawing of the plated steel plate of 1st Embodiment.
It is an enlarged view of the colored resin layer shown in FIG.
4 is a plan view of a galvanized layer having a hairline formed on the surface thereof as a texture.
5 is a view showing a roughness profile of a plating texture formed on a surface of a galvanized layer.
It is a schematic diagram for demonstrating the micro recessed part bottom area in the surface of a zinc plating layer.
It is a schematic diagram for demonstrating the top area|region of the minute convex part in the surface of a zinc plating layer.
7 is a cross-sectional view perpendicular to the first direction in a portion near the surface of the galvanized layer.
Fig. 8 is a cross-sectional view perpendicular to the first direction in a portion near the surface of the galvanized layer according to the first embodiment.
9 is a schematic diagram of a cross section perpendicular to the extending direction of a texture in the plated steel sheet according to the second embodiment.
It is sectional drawing of the plated steel plate of 2nd Embodiment.
It is an enlarged view of the colored resin layer shown in FIG.
12 is a plan view of a galvanized layer having a hairline formed on the surface thereof as a texture.
13 is a view showing a roughness profile of a texture formed on a surface of a galvanized layer.
It is a schematic diagram for demonstrating the micro recessed part area|region in the surface of a zinc plating layer.
It is a schematic diagram for demonstrating the micro convex part area|region in the surface of a zinc plating layer.
15A is a schematic diagram of a cross-section CS.
15B is a schematic diagram of a cross-section CS.
It is a schematic diagram for demonstrating the evaluation method of color nonuniformity in the case where the surface of the galvanized layer of the designable galvanized steel sheet of this embodiment has a hairline as a texture.
It is a schematic diagram for demonstrating the evaluation method of color fluctuations in the case where the surface of the galvanized layer of the designable galvanized steel sheet of this embodiment has a hairline as a texture.

(First embodiment)

MEANS TO SOLVE THE PROBLEM The present inventors examined the plated steel plate which can visually recognize the texture (henceforth a plating texture) of the surface of a galvanized layer while it is a colored external appearance. As described in Patent Documents 1 and 2, a galvanized steel sheet in which a transparent resin layer is formed on a galvanized layer has already been proposed. Therefore, the present inventors first attempted to manufacture a colored galvanized steel sheet by containing a colorant including a pigment and/or dye in a resin layer formed on the zinc plating layer.

As a result, it became clear that the plating texture formed on the surface of a galvanizing layer may not visually recognize depending on conditions when a coloring agent is made to contain in a resin layer. Then, the present inventors investigated and investigated the factor which affects the visibility of a plating texture, when resin contains a coloring agent. As a result, the present inventors acquired the following knowledge. In the following description, the rolling direction of the base steel sheet is defined as the first direction RD. In addition, in the surface of a plated steel sheet, the direction (width direction of a plated steel sheet) orthogonal to a 1st direction is defined as 2nd direction WD. A direction (thickness direction of the plated steel sheet) orthogonal to the first direction RD and the second direction WD is defined as a third direction TD.

When the colored resin layer containing a coloring agent is formed on the zinc plating layer in which the plating texture was formed in the surface, the coloring agent content in a colored resin layer and the thickness of a colored resin layer affect the visibility of a plating texture. When there is too much content of the coloring agent in a colored resin layer specifically, it will become impossible to visually recognize a plating texture. Moreover, when a colored resin layer is too thick, it will become impossible to visually recognize a plating texture.

Moreover, in the cross section perpendicular to the 1st direction RD, the thickness of the resin formed on the plating texture fluctuates according to the unevenness|corrugation of the plating texture. BRIEF DESCRIPTION OF THE DRAWINGS In the plated steel sheet of 1st Embodiment, it is a schematic diagram of the cross section perpendicular|vertical to 1st direction RD. Referring to FIG. 1 , a plated steel sheet 1 includes a base steel sheet 100 , a galvanized layer 10 , and a colored resin layer 11 . The base steel sheet 100 has a texture 100S on its surface. Hereinafter, the texture 100S is referred to as a base material texture 100S. The zinc plating layer 10 has a plating texture 10S on its surface. The plating texture 10S includes a plurality of convex portions 10CO (Convex) and a plurality of concave portions 10RE (Recess). The convex portions 10CO and the concave portions 10RE are alternately arranged. In FIG. 1 , the plurality of convex portions 10CO and the plurality of concave portions 10RE are alternately arranged in the second direction WD.

The colored resin layer 11 is formed on the surface of the zinc plating layer 10 . Therefore, the surface 11S of the colored resin layer 11 reflects the uneven patterns (shapes of the concave portions 10RE and the convex portions 10CO) of the plating texture 10S to some extent, but the plating texture 10S rather than flattened. Concretely, the convex part 11CO is formed in the part corresponding to the convex part 10CO of the plating texture 10S among the surface 11S of the colored resin layer 11. As shown in FIG. The height of the convex portion 11CO is lower than the height of the convex portion 10CO. That is, the surface 11S of the colored resin layer 11 is flatter than the surface of the plating texture 10S.

Here, in the range of 100 micrometers length of 2nd direction WD, the maximum thickness (micrometer) of the colored resin layer 11 is defined as DKmax. In addition, the minimum thickness (micrometer) of the colored resin layer 11 is defined as DKmin. Even when colored with the colored resin layer 11, in order to make the plating texture 10S visually visible, the coloring agent content CK (area %) in the colored resin layer 11 and the colored resin layer ( 11) limits the thickness to some extent. And under the limited conditions, the difference between the maximum thickness DKmax and the minimum thickness DKmin of the colored resin layer 11 is reflected in the brightness difference in which the plating texture can be visually recognized. Specifically, by increasing the difference between the maximum thickness DKmax and the minimum thickness DKmin of the colored resin layer 11 to some extent, a difference in brightness occurs in the concave portion 10RE and the convex portion 10CO of the plating texture 10S. As a result, even when the colored resin layer 11 is formed, the plating texture 10S can be visually recognized.

Moreover, it is preferable that the adhesiveness with respect to the galvanizing layer 10 of the colored resin layer 11 is high. Then, the present inventors examined the method of improving the adhesiveness with respect to the galvanizing layer 10 of the colored resin layer 11. FIG. As a result, the surface roughness of the convex portion 10CO and the concave portion 10RE of the plating texture 10S, particularly in the minute region in the concave portion 10RE, is roughened to some extent (specifically, the bottom of the concave portion to be described later). It discovered that the adhesiveness with respect to the galvanizing layer 10 of the colored resin layer 11 could be improved by three-dimensional average roughness Sas being more than 200 nm and 2000 nm or less.

Based on the above findings, the present inventors (A) roughen the surface roughness of the minute regions in the concave portion 10RE among the convex portions 10CO and the concave portions 10RE of the plating texture 10S to some extent, (B) adjust the thickness and colorant content of the colored resin layer 11, (C) the difference between the maximum thickness DKmax and the minimum thickness DKmin of the colored resin layer 11 in the cross section orthogonal to the first direction to some extent It has been discovered that, by adjusting the size, it is possible to obtain a plated steel sheet having a colored appearance, the plating texture on the surface of the galvanized layer can be visually recognized, and excellent in adhesion of the colored resin layer.

The plated steel sheet of 1st Embodiment completed based on the above knowledge has the following structure.

The plated steel sheet of [1] is,

A base steel sheet having a base material texture on the surface, and

a galvanized layer formed on the surface of the base steel sheet having the base material texture;

and a colored resin layer formed on the galvanized layer;

The zinc plating layer has a plating texture on its surface,

The colored resin layer contains a colorant,

The plating texture is

a plurality of convex portions;

comprising a plurality of recesses;

When the rolling direction of the base steel sheet is defined as the first direction, and the direction orthogonal to the first direction on the surface of the plated steel sheet is defined as the second direction, the plated steel sheet has the following (A) to ( C) is satisfied.

(A) When the roughness profile in the range of the length of 1000 µm in the second direction of the plating texture is measured, and the lowest position in each of the recesses in the measured roughness profile is defined as the bottom point of the recess , three-dimensionality of a micro-region of 1 μm×1 μm centered on the specified bottom points of the recesses, and specifying 10 bottom points of the recesses in the lowest order among the bottom points of the plurality of recesses of the roughness profile. When the average roughness Sa is measured and the arithmetic mean of the ten measured three-dimensional average roughness Sa is defined as the three-dimensional average roughness Sas at the bottom of the recess, the three-dimensional average roughness Sas at the bottom of the recess is greater than 200 nm and less than or equal to 2000 nm.

(B) In the range of 100 μm length in the second direction, the minimum thickness (μm) of the colored resin layer is defined as DKmin, and the content (area%) of the coloring agent in the colored resin layer is defined as CK, , when F1 is defined by Formula (1), F1 is 15.0 or less.

F1=DKmin×CK (1)

(C) In the range of the length of 100 µm in the second direction, when the maximum thickness (µm) of the colored resin layer is defined as DKmax and F2 is defined by the formula (2), the F2 is greater than 1.0.

F2=(DKmax-DKmin)×CK (2)

The plated steel sheet of [2] is,

The plated steel sheet according to [1], and the following (D) may be satisfied.

(D) When the roughness profile in the range of the length of 1000 µm in the second direction of the plating texture is measured, and the highest position in each of the convex portions in the measured roughness profile is defined as the convex portion apex , 10 of the convex vertices of the roughness profile are specified in the highest order, and three-dimensionality of a minute region of 1 μm×1 μm centered on the specified convex vertex. When the average roughness Sa is measured and the arithmetic mean value of the ten measured three-dimensional average roughness Sa is defined as the convex part normal three-dimensional average roughness Sas, the convex part normal three-dimensional average roughness Sah is more than 5 nm and 200 nm or less.

The roughness of the plating texture affects the visibility of the plating texture. When the plating texture is formed on the surface of the zinc plating layer, not only the unevenness of the plating texture but also minute unevenness (roughness) resulting from the crystal of the zinc plating on the surface of the plating texture exist on the surface of the zinc plating layer. When the minute unevenness|corrugation resulting from the crystal|crystallization of zinc plating is small, the diffuse reflection of the light by the micro unevenness|corrugation resulting from the crystal|crystallization of zinc plating is suppressed. In this case, the gloss of the plating texture is increased, and whitening of the plating texture is suppressed. In the plated steel sheet of [2], roughness in the microscopic region of the concave portion among the plating textures is maintained at 200 nm or more, and the roughness in the microscopic region of the convex portion is suppressed to 200 nm or less. Therefore, the visibility of a plating texture can be improved more by a convex part, maintaining the adhesiveness of a colored resin layer by the recessed part of a plating texture.

The plated steel sheet of [3] is,

It is the plated steel sheet according to [2],

The plurality of convex portions and the plurality of concave portions may extend in the first direction,

The plurality of the convex portions and the plurality of the concave portions may be arranged in the second direction.

The plated steel sheet of [4] is,

It is the plated steel sheet described in [3],

The base material texture may be a hairline,

The plating texture may be a hairline,

The plated steel sheet is also

The following (E) and (F) may be satisfied.

(E) The surface roughness Ra of the colored resin layer in the first direction is defined as Ra(CL), the surface roughness Ra of the colored resin layer in the second direction is defined as Ra(CC), and F3 is defined as the formula When defined by (3), the F3 is 1.10 or more.

F3=Ra(CC)/Ra(CL) (3)

(F) When the surface roughness of the galvanized layer in the second direction is defined as Ra(MC), Ra(MC) is 0.30 µm or more.

The plated steel sheet of [5] is,

It is the plated steel sheet according to any one of [1] to [4],

45 or less may be sufficient as the brightness L*(SCI) at the time of seeing the said plated steel sheet from the said colored resin layer side.

The plated steel sheet of [6] is,

It is the plated steel sheet according to any one of [1] to [5],

F1 may be 13.5 or less.

The plated steel sheet of [7] is,

It is the plated steel sheet according to any one of [1] to [6],

F2 may be greater than 2.0.

The plated steel sheet of [8] is,

It is the plated steel sheet according to any one of [4] to [7],

1.15 or more may be sufficient as said F3.

The plated steel sheet of [9] is,

It is the plated steel sheet according to any one of [1] to [8],

The ferrous iron exposure rate of the galvanized layer may be less than 5%.

The plated steel sheet of [10] is,

It is the plated steel sheet according to [2],

The plurality of convex portions may be formed by polishing the surface of the galvanized layer,

The plurality of concave portions may not be polished.

Hereinafter, the plated steel sheet of 1st Embodiment is demonstrated in detail.

[About the plated steel sheet (1)]

2 : is sectional drawing of the plated steel plate 1 of 1st Embodiment. Referring to FIG. 2 , the plated steel sheet 1 of the first embodiment includes a base steel sheet 100 , a galvanized layer 10 , and a colored resin layer 11 . The galvanized layer 10 is formed on the base material texture 100S of the surface of the base steel sheet 100 . The colored resin layer 11 is formed on the surface (texture) 10S of the zinc plating layer 10 . The galvanized layer 10 is disposed between the base steel sheet 100 and the colored resin layer 11 . Hereinafter, the base steel sheet 100, the galvanized layer 10, and the colored resin layer 11 are demonstrated.

[About the base steel plate 100]

The base steel sheet 100 may use a known steel sheet applied to the coated steel sheet according to each mechanical property (eg, tensile strength, workability, etc.) required for the plated steel sheet to be manufactured. For example, as the base steel sheet 100 , a steel sheet for electrical equipment applications may be used, or a steel sheet for automobile exterior panels may be used. The base steel sheet 100 may be a hot rolled steel sheet or a cold rolled steel sheet.

A texture 100S (base material texture 100S) is formed on the surface of the base steel sheet 100 . That is, the base steel sheet 100 has a texture 100S (base material texture 100S) on its surface. The plating texture 10S to be described later may be formed along the base material texture 100S. In this case, the shape of the plating texture 10S is similar to the shape of the base material texture 100S. For example, when the base material texture 100S is less, the plating texture 10S is also less. When the base material texture 100S is a hairline, the plating texture 10S is also a hairline. On the other hand, the base material texture 100S and the plating texture 10S may have different shapes. For example, the base material texture 100S is less, and the plating texture 10S may be a hairline.

[About the galvanized layer 10]

The galvanized layer 10 is formed on the surface of the base steel sheet 100 . In the first embodiment, the galvanized layer 10 is disposed between the base steel sheet 100 and the colored resin layer 11 . The zinc plating layer 10 is formed by a well-known zinc plating treatment method. Specifically, the zinc plating layer 10 is formed by, for example, an electroplating method. In this specification, the zinc plating layer 10 also includes a zinc alloy plating layer.

It is sufficient that the galvanized layer 10 has a known chemical composition. For example, the Zn content in the chemical composition of the galvanized layer 10 may be 65% or more by mass%. When Zn content is 65% or more in mass %, a sacrificial corrosion protection function is exhibited remarkably, and the corrosion resistance of the plated steel sheet 1 becomes remarkably high. A preferable lower limit of the Zn content in the chemical composition of the galvanized layer 10 is 70%, more preferably 80%.

The chemical composition of the galvanized layer 10 is one or two elements selected from the group consisting of Al, Co, Cr, Cu, Fe, Ni, P, Si, Sn, Mg, Mn, Mo, V, W, and Zr. It is preferable to contain more than an element and Zn. In the case where the galvanized layer 10 is an electrogalvanized layer, the chemical composition further preferably contains 5 to 20% by mass in total of at least one element selected from the group consisting of Fe, Ni, and Co. Further, in the case where the galvanized layer 10 is a hot-dip galvanized layer, it is more preferable that the chemical composition contains 5 to 20% by mass in total of at least one element selected from the group consisting of Mg, Al, and Si. In these cases, the galvanized layer 10 also exhibits excellent corrosion resistance.

The galvanized layer 10 may contain impurities. Here, an impurity mixes in a raw material, or mixes in a manufacturing process. Impurities are, for example, Ti, B, S, N, C, Nb, Pb, Cd, Ca, Pb, Y, La, Ce, Sr, Sb, O, F, Cl, Zr, Ag, W, H, etc. to be. The chemical composition of the galvanized layer 10 WHEREIN: It is preferable that the total content of impurities is 1 % or less.

The chemical composition of the galvanized layer 10 can be measured by the following method, for example. The colored resin layer 11 of the plated steel sheet 1 is washed with a release agent such as a solvent that does not invade the galvanized layer 10 or a remover (for example, Sansai Kaco Co., Ltd. trade name: Neoliver S-701). Remove. Thereafter, the galvanized layer 10 is dissolved using hydrochloric acid containing the inhibitor. The solution is subjected to ICP analysis using an ICP (Inductively Coupled Plasma) emission spectrometer to determine the Zn content. If the calculated|required Zn content is 65 % or more, it is judged that the plating layer to be measured is the zinc plating layer 10 .

[About the adhesion amount of the galvanized layer 10]

The adhesion amount in particular of the galvanizing layer 10 is not restrict|limited, A well-known adhesion amount is sufficient. The preferable adhesion amount of the galvanized layer 10 is 5.0-120.0 g/m<2>. If the adhesion amount of the galvanized layer 10 is 5.0 g/m 2 or more, exposure of the base iron (base steel sheet 100 ) can be suppressed when a plating texture described later is provided to the galvanized layer 10 . A more preferable lower limit of the adhesion amount of the galvanized layer 10 is 7.0 g/m 2 , and still more preferably 10.0 g/m 2 . There is no restriction|limiting in particular about the upper limit of the adhesion amount of the galvanizing layer 10. From the viewpoint of economical efficiency, in the case of the galvanized layer 10 by the electroplating method, the upper limit of the preferable adhesion amount is 40.0 g/m2, more preferably 35.0 g/m2, and still more preferably 30.0 g/m2.

[About the colored resin layer 11]

The colored resin layer 11 is formed on the surface (plating texture) 10S of the galvanized layer 10 . 3 : is an enlarged view of the colored resin layer 11 shown in FIG. Referring to FIG. 3 , the colored resin layer 11 includes a resin 31 and a colorant 32 . The colorant 32 is contained in the resin 31 . Hereinafter, the resin 31 and the coloring agent 32 are demonstrated.

[About resin (31)]

The resin 31 is a light-transmitting resin. In the first embodiment, the "resin having light transmittance" refers to a colored resin layer 11 containing a colorant 32 and a resin 31 in an environment equivalent to sunlight in the morning on a clear sky (illuminance about 65000 lux). When the provided plated steel sheet 1 is placed, it means that the plating texture 10S of the galvanized layer 10 can be visually recognized. The resin 31 functions as a binder for fixing the colorant 32 .

The resin 31 will not be specifically limited as long as it is resin which has the light-transmitting property of the above-mentioned definition, A well-known natural resin or a well-known synthetic resin can be used. The resin 31 is, for example, an epoxy-based resin, a urethane-based resin, a polyester-based resin, a phenol-based resin, a polyethersulfone-based resin, a melamine alkyd-based resin, an acrylic resin, a polyamide-based resin, a polyimide-based resin, or a silicone-based resin. It is 1 type, or 2 or more types selected from the group which consists of resin, polyvinyl acetate type resin, polyolefin type resin, polystyrene type resin, vinyl chloride type resin, and vinyl acetate type resin.

[About the colorant (32)]

The coloring agent 32 colors the colored resin layer 11 by being contained in the resin 31 mentioned above. The colorant 32 is well known. The colorant 32 has a chromatic color. A chromatic color means a color having properties of hue, brightness, and saturation. The colorant 32 is made of, for example, at least one selected from the group consisting of inorganic pigments, organic pigments, and dyes. From the viewpoint of durability against ultraviolet rays, it is more preferable that the colorant 32 is a pigment type (inorganic pigment and/or organic pigment).

When the colorant 32 is an inorganic pigment, the colorant 32 is, for example, a neutralized precipitation pigment (sulfate, carbonate, etc.), and/or a calcined pigment (metal sulfide, metal oxide, polyvalent metal complex oxide, etc.). When the colorant 32 is an organic pigment, the colorant 32 is, for example, a chlorine pigment, an azo pigment (solvent azolake pigment, insoluble azo pigment, etc.), an acid condensed pigment, a polycyclic pigment (phthalocyanine-based pigment, indigo). It is at least one selected from the group consisting of type pigments, quinacridone type pigments, anthraquinone type pigments, etc.) and metal complex pigments (azo chelate pigments, transition metal complex pigments, etc.). When the colorant 32 is a dye, the colorant 32 is, for example, at least one selected from the group consisting of azo dyes, indigo dyes, anthraquinone dyes, sulfide dyes and carbonium dyes.

The color of the colorant 32 is not particularly limited. The colorant 32 is black, such as carbon black (C) and iron black (Fe ₃ O ₄ ), for example. However, the colorant 32 is not limited to black, and may be a colorant 32 of another color (white, magenta, yellow, cyan, red, orange, yellow, green, blue, indigo, purple, etc.).

When the colorant 32 is a pigment, the particle diameter is not particularly limited. The maximum value of the primary particle diameter in case the colorant 32 is a pigment is 3 nm - 1000 nm, for example.

[About the plating texture 10S formed on the surface of the galvanized layer 10]

A plating texture 10S is formed on the surface of the galvanized layer 10 of the plated steel sheet 1 . That is, the galvanized layer 10 of the plated steel sheet 1 has a plating texture 10S on its surface. In the first embodiment, "texture" means an uneven pattern formed on the surface of the base steel sheet 100 and/or the surface of the galvanized layer 10 by a physical or chemical method. That is, the texture (base material texture 100S, plating texture 10S) has a plurality of convex portions and a plurality of concave portions. The convex portion and the concave portion may or may not extend in one direction. The texture is less, for example, the hairline. A preferable texture is a hairline. The hairline is a linear concavo-convex shape extending in one direction.

[When the plating texture (10S) is a hairline]

4 : is a top view of the galvanizing layer 10 in which the hairline is formed as the plating texture 10S on the surface. Referring to FIG. 4 , the hairline 10S has a linear concavo-convex shape formed on the surface of the zinc plating layer 10 . The hairline 10S includes a plurality of grooves 10L extending in the first direction. The extending directions of the plurality of grooves 10L of the hairline 10S are substantially the same. The substantially same direction as used herein means the second orthogonal to the extending direction of the groove 10L of the hairline 10S when the galvanized layer 10 is viewed in the thickness direction TD (that is, when viewed in the same plane as in FIG. 4 ). It means that 90% or more of the angles between the grooves 10L adjacent to each other arranged in the direction WD are less than ±5°.

[About requirements (A) to (C)]

The plated steel sheet 1 of the first embodiment having the above-described configuration further satisfies the following (A) to (C).

Requirement (A):

Measure the roughness profile in the range of the length of 1000 μm in the second direction WD of the plating texture 10S, and define the lowest position in each recess 10RE in the measured roughness profile as the bottom of the recess, Among the plurality of bottom points of the roughness profile, 10 bottom points of the recesses are specified in the lowest order, and the three-dimensional average roughness Sa of a minute area of 1 μm × 1 μm centered on the specified bottom point of the recess is measured. And, when the arithmetic mean value of the ten measured three-dimensional average roughness Sa is defined as the three-dimensional average roughness Sas at the bottom of the recess, the three-dimensional average roughness Sas at the bottom of the recess is greater than 200 nm and less than or equal to 2000 nm.

Requirement (B):

In the range of 100 µm length in the second direction WD, the minimum thickness (µm) of the colored resin layer 11 is defined as DKmin, and the content (area%) of the colorant 32 in the colored resin layer 11 is CK , and when F1 is defined by Equation (1), F1 is 15.0 or less.

F1=DKmin×CK (1)

Requirement (C):

The range of the length of 100 micrometers of 2nd direction WD WHEREIN: When the maximum thickness (micrometer) of the colored resin layer 11 is defined as DKmax and F2 is defined by Formula (2), F2 is larger than 1.0.

F2=(DKmax-DKmin)×CK (2)

Hereinafter, each requirement is demonstrated in detail.

[About the roughness of the textured surface]

FIG. 5 is a diagram showing the roughness profile of the plating texture 10S formed on the surface of the zinc plating layer 10 . Referring to FIG. 5 , an arbitrary 1000 μm length range in the second direction WD of the plating texture 10S is selected. In the selected 1000 μm length range, the roughness profile of the plating texture 10S is measured. It is assumed that the obtained roughness profile has a shape as shown in FIG. 5 .

[About the three-dimensional average roughness Sas of the bottom of the recess]

Pay attention to each concave portion 10RE in the measured roughness profile. In each recessed part 10RE, the position with the lowest height is defined as the recessed part bottom point PRE. Among the plurality of recess bottom PREs in the roughness profile in the 1000 μm length range, from the lowest recess bottom PRE1, 10 recess bottom points PRE1, PRE2, ... , specify PRE10.

As shown in Fig. 6A, when the surface of the galvanized layer 10 is viewed in a plan view, the bottom region of the minute recesses of 1 μm × 1 μm centered on the defined bottom points PREk of each recess (k is 1 to 10). (200) is specified. In FIG. 6A , the vertical direction of the micro-recess bottom region 200 is parallel to the extension direction RD of the plating texture 10S, and the horizontal direction of the micro-recess bottom region 200 is parallel to the width direction WD. However, as long as the micro-recess bottom region 200 is a surface including the extension direction RD and the width direction WD, each side of the micro-recess bottom region 200 does not need to be parallel to the extension direction RD or the width direction WD.

In each of the ten micro concave bottom regions 200 specified by the above method, the three-dimensional average roughness Sa is measured. The three-dimensional average roughness Sa is an arithmetic mean roughness prescribed in ISO 25178, in which Ra (arithmetic mean roughness of a line) prescribed in JIS B 0601 (2013) is extended to a surface. An arithmetic mean value of the ten measured three-dimensional average roughness Sa is defined as the three-dimensional average roughness Sas of the bottom of the recess.

[About the convex portion normal three-dimensional average roughness Sah]

Referring to FIG. 5 , attention is paid to each convex portion 10CO in the roughness profile in an arbitrary 1000 μm length range in the second direction WD of the plating texture 10S. In each convex part 10CO, the position with the highest height is defined as the convex part apex PCO. Among the plurality of convex apex PCOs in the roughness profile in the 1000 µm length range, from the highest convex apex PCO1, 10 convex vertices PCO1, PCO2, ... , PCO10 is specified.

As shown in Fig. 6B, when the surface of the galvanized layer 10 is viewed in a plan view, the top region of the minute convex portions of 1 μm × 1 μm centered on the defined apex PCok of each convex portion (k is 1 to 10). (300) is specified. In FIG. 6B , the vertical direction of the micro-convex part top region 300 is parallel to the extending direction RD of the plating texture 10S, and the horizontal direction of the micro-convex part top region 300 is parallel to the width direction WD. However, if the minute convex portion top region 300 is a surface including the extension direction RD and the width direction WD, each side of the minute convex portion top region 300 does not need to be parallel to the extension direction RD or the width direction WD.

The three-dimensional average roughness Sa is measured in each of the ten minute convex-portion top regions 300 specified by the above method. The three-dimensional average roughness Sa is an arithmetic mean roughness prescribed in ISO 25178, in which Ra (arithmetic mean roughness of a line) prescribed in JIS B 0601 (2013) is extended to a surface. An arithmetic mean value of the ten measured three-dimensional average roughness Sa is defined as a convex part normal three-dimensional average roughness Sah.

[About requirement (A)]

The three-dimensional average roughness Sas of the bottom of the concave portion obtained by the above definition is 200 nm and less than 2000 nm (requirement (A)). This roughness can be made based on the crystal|crystallization of zinc plating. Therefore, the plurality of recessed portions of the zinc plating need not be polished. In the unevenness of the plating texture 10S, at least the three-dimensional average roughness Sas of the bottom of the recess is rough to some extent, and if it is more than 200 nm and not more than 2000 nm, the adhesion of the colored resin layer 11 to the galvanized layer 10 can be improved have. A preferable lower limit of the concave bottom three-dimensional average roughness Sas is 250 nm, more preferably 300 nm. A preferable upper limit of the concave bottom three-dimensional average roughness Sas is 1500 nm, more preferably 1000 nm, still more preferably 800 nm.

Among the plating textures 10S, the value of the convex part normal three-dimensional average roughness Sah is not particularly limited as long as at least the bottom three-dimensional roughness Sas of the concave portion exceeds 200 nm and is less than or equal to 2000 nm. The convex part normal three-dimensional average roughness Sah is 2000 nm or less, for example. As long as Sah is not limited, the plurality of convex portions may be formed by polishing the surface of the galvanized layer, or may not be polished. The shape of the unevenness|corrugation of the plating texture 10S is also not specifically limited.

7 is a cross-sectional view perpendicular to the first direction RD in the portion near the surface of the galvanized layer 10 . Referring to FIG. 7 , in the concave portion 10RE and the convex portion 10CO of the plating texture 10S formed on the surface of the galvanized layer 10, before polishing, the surface of the concave portion 10RE and the convex portion ( 10CO), minute concavities and convexities (micro concavities SRE and micro convexities SCO) at the nanometer level due to plating crystals exist. In this case, the three-dimensional average roughness Sas at the bottom of the concave portion and the three-dimensional average roughness Sah at the top of the convex portions are both greater than 200 nm and less than or equal to 2000 nm.

[About requirement (B)]

Referring to FIG. 1 , attention is paid to a cross section in an arbitrary 100 μm length range in the second direction WD orthogonal to the first direction RD of the plating texture 10S. A cross section (FIG. 1) of this 100 µm length range is defined as an observation cross section. Observation cross section WHEREIN: Among the thicknesses of the colored resin layer 11, the minimum thickness is defined as DKmin (micro|micron|mu). Observation cross section WHEREIN: Among the thickness of the colored resin layer 11, the largest thickness is defined as DKmax (micrometer).

In addition, in an observation cross section, content (area %) of the coloring agent in the colored resin layer 11 is defined as CK. As mentioned above, in this specification, colorant content CK is represented by the area ratio (area %) of the colorant in an observation cross section.

Here, F1 is defined by Equation (1).

F1=DKmin×CK (1)

At this time, F1 is 15.0 or less.

F1 is an index of the color concentration of the colored resin layer 11 . When F1 exceeds 15.0, the thickness of the colored resin layer 11 is too thick, or there is too much coloring agent content CK. In this case, the coloring of the colored resin layer 11 is too dark, and it is difficult to visually recognize the plating texture 10S of the galvanizing layer 10. If F1 is 15.0 or less, on the condition that the requirements (A) and (C) are satisfied, while the appearance colored with the colored resin layer 11 , the plating texture 10S of the surface of the galvanized layer 10 is sufficiently obtained can admit The preferable upper limit of F1 is 14.0, more preferably 13.5, still more preferably 13.0, still more preferably 12.5. In addition, the lower limit of F1 is not specifically limited. The lower limit of F1 is, for example, 4.0.

The thickness of the colored resin layer 11 is measured by the following method. A sample having a cross section orthogonal to the first direction RD of the plating texture 10S on the surface is taken. Among the samples, an observation cross section in a length range of 100 µm in the second direction WD is observed with a reflection electron image (BSE) at a magnification of 2000 times using a scanning electron microscope (SEM). Observation in a reflection electron image (BSE) of a scanning electron microscope (SEM) WHEREIN: The base steel plate 100, the galvanizing layer 10, and the colored resin layer 11 can be discriminate|determined easily by contrast. Observation cross section WHEREIN: The thickness of the colored resin layer 11 is measured by 0.5 micrometer pitch in 2nd direction WD. Among the measured thicknesses, the minimum thickness is defined as the minimum thickness DKmin (μm). Among the measured thicknesses, the maximum thickness is defined as the maximum thickness DKmax (μm). When it is necessary to determine whether it is the colored resin layer 11 (that is, whether the resin contains a coloring agent), you may judge whether it is the colored resin layer 11 by TEM observation mentioned later.

Colorant content CK (area %) in the colored resin layer 11 is calculated|required by the following method. A sample having a cross section orthogonal to the first direction RD of the plating texture 10S on the surface is taken. Among the samples, a cross section orthogonal to the first direction RD of the plating texture 10S is defined as an observation surface. From the sample, a thin film sample in which the colored resin layer 11 and the zinc plating layer 10 of the observation surface can be observed is produced using a converging ion beam apparatus (FIB: Focused Ion Beam). The thickness of the thin film sample is 50 to 200 nm. Among the observation surfaces of the produced thin film sample, the length in the direction perpendicular to the thickness direction of the colored resin layer 11 (ie, the second direction WD) is 3 µm, and the thickness direction of the colored resin layer (ie, the third direction) is In direction TD), the visual field which has the length including the whole colored resin layer is observed using a transmission electron microscope (TEM:Transmission Electron Microscope). TEM observation WHEREIN: The resin 31 and the coloring agent 32 in the colored resin layer 11 are distinguishable by contrast. ^{The total area A1 (micrometer 2} ) of several coloring agents in the colored resin layer 11 in the said visual field is calculated|required. ^{Moreover, the area (micrometer 2} ) of the colored resin layer 11 in the said visual field is calculated|required. Based on the calculated|required total area A1 and area A0, content (area %) of the coloring agent in the colored resin layer 11 is calculated|required by following formula.

CK=A1/A0×100

[About requirement (C)]

It is a cross section perpendicular to the 1st direction RD of the plating texture 10S, and it is an observation cross section of 100 micrometers length range of the 2nd direction WD of the plating texture 10S. WHEREIN: F2 is defined by Formula (2).

F2=(DKmax-DKmin)×CK (2)

At this time, F2 is greater than 1.0.

F2 is a contrast index of the brightness in the colored resin layer 11 . If F2 is 1.0 or less, the contrast of the brightness in the colored resin layer 11 is low. In this case, the brightness contrast of the colored resin layer 11 cannot fully be utilized for visual recognition of the plating texture 10S. Therefore, it is difficult to visually recognize the plating texture 10S under the colored resin layer 11 .

When F2 is higher than 1.0, the contrast of the brightness in the colored resin layer 11 is high enough. In this case, the brightness contrast of the colored resin layer 11 can be fully utilized for visual recognition of the plating texture 10S. As a result, on the premise that the requirements (A) and (B) are satisfied, the plating texture 10S under the colored resin layer 11 can be sufficiently visually recognized.

A preferred lower limit of F2 is 2.0 or greater than 2.0, more preferably 2.2, still more preferably 2.4. In addition, the upper limit of F2 is not specifically limited. The upper limit of F2 is, for example, 15.0.

[Lightness L*(SCI) when the plated steel sheet is viewed from the colored resin layer side]

As for the plated steel sheet 1 of the first embodiment, as long as F2, which is a contrast index of brightness in the concave portion and the convex portion, etc. satisfies the above requirements, the brightness on the entire surface thereof is not particularly specified. Therefore, the upper and lower limit values of the brightness L*(SCI) at the time of seeing a plated steel plate from the colored resin layer side are not specifically prescribed|regulated. In addition, 45 or less may be sufficient as the brightness L*(SCI) at the time of seeing a plated steel plate from the colored resin layer side. As the brightness L*(SCI) of the coated steel sheet is lower, the blackness of the coated steel sheet as seen with the naked eye increases. In a normal plated steel sheet, when the brightness L*(SCI) of the surface is 45 or less, the visibility of the plating texture becomes difficult. On the other hand, since the plated steel sheet 1 of the first embodiment satisfies the above requirements (A) to (C), even if the brightness L*(SCI) when the plated steel sheet is viewed from the colored resin layer side is 45 or less, zinc The texture of the surface of the plating layer can be visually recognized.

Brightness L*(SCI) is the brightness measured by the SCI system. The SCI method is referred to as a method including specular light, and refers to a method of measuring color without removing specular light. The brightness measurement method according to the SCI method is prescribed in JIS Z 8722 (2009). In the SCI method, since the measurement is performed without removing the specular light, it becomes the color of the real object (so-called object color). The CIELAB display color is a uniform color space specified in JIS Z 8781 (2013). The three coordinates of CIELAB are represented by L* value, a* value, and b* value. L* value represents lightness and is represented by 0-100. When the L* value is 0, it means black, and when the L* value is 100, it means the diffuse color of white.

[About the thickness of the colored resin layer 11]

In the plated steel sheet 1 of 1st Embodiment, Preferably, the average thickness of the colored resin layer 11 is 10.0 micrometers or less. When the thickness of the colored resin layer 11 exceeds 10.0 µm, it becomes easy to smooth (level) only the colored resin layer 11, and the impression of reflection on the surface of the colored resin layer 11 and the plating texture that can be visually recognized The discrepancy in the impression of (10S) increases. In this case, the metallic feeling of the plated steel sheet 1 falls. If the average thickness of the colored resin layer 11 is 10.0 μm or less, on the premise that all of the above requirements (A) to (C) are satisfied, the plating texture 10S of the galvanized layer 10 can be visually recognized, In addition, the metallic feeling is sufficiently increased. The more preferable upper limit of the average thickness of the colored resin layer 11 is 9.0 micrometers, More preferably, it is 8.0 micrometers.

In addition, the preferable minimum of the average thickness of the colored resin layer 11 is 0.5 micrometer. Corrosion resistance becomes still higher that the average thickness of the colored resin layer 11 is 0.5 micrometer or more. The minimum with more preferable average thickness of the colored resin layer 11 is 0.7 micrometers, More preferably, it is 1.0 micrometer, More preferably, it is 2.0 micrometers, More preferably, it is 3.0 micrometers.

The average thickness of the colored resin layer 11 is measured by the following method. The arithmetic mean value of the thickness measured at 0.5 micrometer pitch in 2nd direction WD in the observation cross section mentioned above is defined as the average thickness (micrometer) of the colored resin layer 11. As shown in FIG.

[About requirement (D)]

In the plated steel sheet 1 of the first embodiment, preferably, the convex portion normal three-dimensional average roughness Sah is more than 5 nm and 200 nm or less (requirement (D)).

Referring to FIG. 7 , in the concave portion 10RE and the convex portion 10CO of the plating texture 10S formed on the surface of the galvanized layer 10, before polishing, the surface of the concave portion 10RE and the convex portion ( 10CO), minute concavities and convexities (micro concavities SRE and micro convexities SCO) at the nanometer level due to plating crystals exist. That is, the roughness of the micro concavities and convexities (micro concavities SRE and micro protrusions SCO) in the convex portion 10CO is the roughness of the micro concavities and convexities (micro concavities SRE and micro protrusions SCO) in the concave portion 10RE. equally rough with Therefore, in the convex portion 10CO, light is diffusely reflected due to the minute irregularities, as in the concave portion 10RE.

Then, in the requirement (D), the convex part normal three-dimensional average roughness Sah is made smaller than the recessed part bottom three-dimensional average roughness Sas. Specifically, as described above, the concave bottom three-dimensional average roughness Sas is 200 nm or more, whereas the convex portion normal three-dimensional average roughness Sah may be more than 5 nm and 200 nm or less. In this case, light is easily diffused in the concave portion 10RE, whereas in the convex portion 10CO, the illuminance is lower than in the concave portion 10RE, and light is less diffusely reflected in the convex portion 10CO. Accordingly, in the plating texture 10S of the galvanized layer 10 , the convex portion 10CO is in a state in which it is easy to visually recognize. For example, as shown in FIG. 8, the top of the convex part 10CO is grind|polished, and the convex part 10CO is made into trapezoid shape. As a result, the roughness of the minute concavities and convexities in the convex portion 10CO (micro concavities SRE and minute convexities SCO) is higher than the roughness of the micro concavities and convexities (micro concavities SRE and micro protrusions SCO) in the concavities 10RE. can be made small

If the convex part normal three-dimensional average illuminance Sah is 200 nm or less, diffuse reflection of light in the vicinity of the apex of the convex part can be suppressed. In this case, in the plated steel sheet 1 of 1st Embodiment which has the colored resin layer 11, it becomes easy to visually recognize the plating texture 10S further. Moreover, it is so preferable that the convex part normal three-dimensional average roughness Sah is small. However, it is very difficult to make the three-dimensional average roughness Sah of the convex part normal to 5 nm or less. Therefore, in 1st Embodiment, the convex part normal three-dimensional average roughness Sah is more than 5 nm and 200 nm or less. The preferable upper limit of the convex part normal three-dimensional average roughness Sah is 190 nm, More preferably, it is 180 nm, More preferably, it is 170 nm.

[About other forms of colored resin layer 11]

The colored resin layer 11 of the plated steel sheet 1 of the first embodiment may further contain an additive in order to impart corrosion resistance, slidability, conductivity, and the like to the colored resin layer 11 . Additives for imparting corrosion resistance are, for example, well-known rust inhibitors and inhibitors. Additives for imparting sliding properties are, for example, well-known waxes and beads. The additive for providing electroconductivity is a well-known electrically conductive agent, for example.

[About the surface shape of the colored resin layer 11 in the case where the plating texture 10S is a hairline (referring to the requirement (E))]

The colored resin layer 11 may have a surface shape as described in detail below due to the type of the plating texture 10S formed on the surface of the zinc plating layer 10 as the lower layer.

Here, it is assumed that the plating texture 10S is a hairline. The surface roughness Ra of the colored resin layer 11 in the 1st direction RD of the plating texture 10S is defined as Ra(CL). The surface roughness Ra of the colored resin layer 11 in the 2nd direction WD of the plating texture 10S is defined as Ra(CC). And, F3 is defined by Equation (3).

F3=Ra(CC)/Ra(CL)

In this case, F3 may be 1.10 or more.

F3 is an index regarding the metallic feeling of the plated steel sheet in the case where the plating texture 10S is a hairline. When F3 is less than 1.10, the difference between the impression received from the plating texture 10S (hairline) in the state without the colored resin layer 11 and the reflection impression of the light on the surface of the colored resin layer 11 becomes large too much. In this case, the metallic feeling is lost. When the plating texture 10S is a hairline, if F3 is 1.10 or more, the impression received from the plating texture 10S (hairline) in the absence of the colored resin layer 11 and the surface of the colored resin layer 11 It is possible to suppress the discrepancy in the reflection impression of light. Therefore, a sufficient metallic feeling is obtained. A preferable lower limit of F3 is 1.15, more preferably 1.20, still more preferably 1.25.

Surface roughness Ra(CL) is measured by the measuring method of the arithmetic mean roughness prescribed|regulated to JISB0601 (2013). Specifically, in the surface 11S of the colored resin layer 11, ten arbitrary places are made into a measurement location. In each measurement location, the arithmetic mean roughness Ra is measured from the evaluation length extended in the 1st direction RD of the plating texture 10S. The evaluation length is set to 5 times the reference length (cut-off wavelength). The arithmetic mean roughness Ra is measured using a stylus type roughness meter, and the measurement speed is 0.5 mm/sec. Among the 10 obtained arithmetic mean roughness Ra, 6 arithmetic mean roughness Ra, excluding the largest arithmetic mean roughness Ra, the second largest arithmetic mean roughness Ra, the smallest arithmetic mean roughness Ra, and the second smallest arithmetic mean roughness Ra, An arithmetic mean value is defined as surface roughness Ra(CL).

Similarly, surface roughness Ra (CC) is measured by the measuring method of the arithmetic mean roughness prescribed|regulated to JISB0601 (2013). Specifically, in the surface 11S of the colored resin layer 11, ten arbitrary places are made into a measurement location. In each measurement location, the arithmetic mean roughness Ra is measured in the evaluation length extended in the 2nd direction WD of the plating texture 10S. The evaluation length is set to 5 times the reference length (cut-off wavelength). The arithmetic mean roughness Ra is measured using a stylus type roughness meter, and the measurement speed is 0.5 mm/sec. Among the 10 obtained arithmetic mean roughness Ra, 6 arithmetic mean roughness Ra, excluding the largest arithmetic mean roughness Ra, the second largest arithmetic mean roughness Ra, the smallest arithmetic mean roughness Ra, and the second smallest arithmetic mean roughness Ra, An arithmetic mean value is defined as surface roughness Ra(CC).

[Regarding the surface shape of the galvanized layer 10 when the plating texture 10S is a hairline (referring to the requirement (F))]

Similar to the requirement (E), the requirement (F) is a requirement in the case where the plating texture 10S is a hairline. The surface roughness Ra of the surface of the galvanized layer 10 on which the plating texture 10S is formed in the second direction WD is defined as Ra(MC). When the plating texture 10S is a hairline, the surface roughness Ra (MC) may be 0.30 µm or more. When the plating texture 10S is viewed from the colored resin layer 11 as surface roughness Ra(MC) is 0.30 µm or more, a sufficient metallic feeling is obtained. The preferable lower limit of surface roughness Ra(MC) is 0.35 micrometer, More preferably, it is 0.40 micrometer. The upper limit of surface roughness Ra(MC) is not specifically limited. However, it may be difficult on industrial production to raise surface roughness Ra(MC) excessively. Therefore, the upper limit of surface roughness Ra(MC) is 2.00 micrometers, for example. The upper limit of the surface roughness Ra(MC) may be, for example, 1.00 µm.

Surface roughness Ra (MC) is measured by the measuring method of the arithmetic mean roughness prescribed|regulated to JISB0601 (2013). Specifically, a solvent that does not invade the galvanized layer 10 or a release agent such as a remover (for example, Sansai Kaco Co., Ltd. trade name: Neoliver S-701), etc. Remove the strata 11 . In the plating texture 10S of the galvanized layer 10 after the colored resin layer 11 has been removed, ten arbitrary places are set as measurement locations. Each measurement location WHEREIN: The arithmetic mean roughness Ra is measured with the evaluation length extended in the 2nd direction WD. The evaluation length is set to 5 times the reference length (cut-off wavelength). The arithmetic mean roughness Ra is measured using a stylus type roughness meter, and the measurement speed is 0.5 mm/sec. Among the 10 obtained arithmetic mean roughness Ra, 6 arithmetic mean roughness Ra, excluding the largest arithmetic mean roughness Ra, the second largest arithmetic mean roughness Ra, the smallest arithmetic mean roughness Ra, and the second smallest arithmetic mean roughness Ra, An arithmetic mean value is defined as surface roughness Ra (MC).

[About Ji-cheol Exposure Rate]

Preferably, the base iron exposure rate of the galvanized layer 10 of the plated steel sheet 1 is less than 5%. In the first embodiment, corrosion resistance is sufficiently ensured by the zinc plating layer 10 (zinc plating or zinc alloy plating). However, as a result of grinding the surface of the galvanized layer 10 at the time of application of the plating texture 10S, when the ferrous iron is exposed, the corrosion resistance (long-term corrosion resistance) in a long period of time may decrease due to the influence of galvanic corrosion. . In many cases, such a fall in long-term corrosion resistance becomes remarkable when the iron exposure rate is 5% or more. Therefore, in the first embodiment, the preferred ferrite exposure rate is less than 5%.

When the ferrous iron exposure rate of the galvanized layer 10 is less than 5%, in addition to the moderate corrosion resistance generally obtained for steel materials, very good corrosion resistance such as excellent long-term corrosion resistance is obtained. A preferable upper limit of the iron exposure rate of the galvanized layer 10 is 3% or less, more preferably 2%, still more preferably 1%, still more preferably 0%.

The iron exposure rate is measured by the following method. Specifically, a solvent that does not invade the galvanized layer 10 or a release agent such as a remover (for example, Sansai Kaco Co., Ltd. trade name: Neoliver S-701), etc. Remove the strata 11 . On the surface of the galvanized layer 10, 5 arbitrary rectangular areas of 1 mm x 1 mm are selected. EPMA analysis is performed on the selected rectangular area. By image analysis, a region in which Zn is not detected (Zn undetected region) in each rectangular region is specified. In the first embodiment, a region in which the detection intensity of Zn is 1/16 or less when a standard sample (pure Zn) is measured is regarded as a Zn undetected region. The ratio (area %) of the total area of the Zn undetected region among the five rectangular regions to the total area of the five rectangular regions is defined as the iron exposure rate (area %).

[About other coatings]

In addition, in the plated steel sheet 1 of the first embodiment, an inorganic coating film or an organic-inorganic composite coating film may be formed between the colored resin layer 11 and the galvanizing layer 10 for the purpose of improving corrosion resistance or adhesion. The inorganic film has light-transmitting properties. The inorganic film is, for example, an amorphous silica film, a zirconia film, or a phosphate film. The organic-inorganic composite film has light-transmitting properties. The organic-inorganic composite film contains, for example, a silane coupling agent and an organic resin. The organic-inorganic composite film has light-transmitting properties.

[About the shape of the texture]

In FIG. 4, the hairline was shown as an example of a texture. However, as described above, the shape of the texture is not limited to the hairline. The texture may have a plurality of convex portions and a plurality of concave portions. Accordingly, the convex portion and the concave portion may or may not extend in one direction. The texture may be a hairline, may be less, or may have another form. As for the texture, the uneven pattern should just be formed.

[Manufacturing method]

An example of the manufacturing method of the plated steel sheet 1 of 1st Embodiment is demonstrated. The manufacturing method demonstrated later is an example for manufacturing the plated steel sheet 1 of 1st Embodiment. Accordingly, the plated steel sheet 1 having the above-described configuration may be manufactured by a manufacturing method other than the manufacturing method described later. However, the manufacturing method demonstrated later is a preferable example of the manufacturing method of the plated steel sheet 1 of 1st Embodiment.

The manufacturing method of the first embodiment includes a preparatory step (S1) of preparing the base steel sheet 100, and a base material surface texture forming step (S2) of forming a base material texture 100S on the surface of the base steel sheet 100; A zinc plating treatment step (S3) of forming the galvanized layer 10 on the base steel sheet 100 and an optional step, the zinc plating surface texture performed when the surface of the zinc plating layer 10 is further textured Formation process (S4), it is an arbitrary process, and grinding|polishing process (S5) which grind|polishes the top of the convex part 10CO of the galvanizing layer 10 as needed, and the colored resin layer 11 on the galvanizing layer 10 ) is included in the colored resin layer forming step (S6). Hereinafter, each process is demonstrated.

[Preparation process (S1)]

In the preparation step S1 , the base steel sheet 100 is prepared. A steel plate may be sufficient as the base material steel plate 100, and another shape may be sufficient as it. When the base steel sheet 100 is a steel sheet, the base steel sheet 100 may be a hot rolled steel sheet or a cold rolled steel sheet.

[Base material surface texture forming process (S2)]

In the base material surface texture forming process ( S2 ), the base material texture 100S is formed on the base material surface. At this time, a plated steel plate becomes the structure shown in FIG. In the base material surface texture forming step S2 , the base material texture 100S is formed on the surface of the base steel sheet 100 by performing known texturing on the surface of the base steel sheet 100 . When the base material texture 100S is a hairline, well-known hairline processing is performed. The hairline processing method is, for example, a method of forming a hairline by polishing the surface with a well-known abrasive belt, a method of forming a hairline by polishing the surface with a well-known abrasive brush, and rolling and transferring with a roll to which a hairline shape is given. There is a method of forming a hairline, and the like. The length, depth, and frequency of a hairline can be adjusted by adjusting the particle size of a well-known abrasive belt, the particle size of a well-known abrasive-grain brush, and the surface shape of a roll.

[Galvanizing process (S3)]

In the zinc plating treatment step S3 , a zinc plating treatment is performed on the prepared base steel sheet 100 to form the zinc plating layer 10 on the surface of the base steel sheet 100 .

What is necessary is just to implement a galvanizing process by a well-known method. For example, the zinc plating layer 10 is formed using a well-known electroplating method. In this case, it is sufficient to use a well-known bath for an electrogalvanizing bath and an electrozinc alloy plating bath. The electroplating bath is, for example, a sulfuric acid bath, a chloride bath, a zincate bath, a cyanide bath, a pyrophosphoric acid bath, a boric acid bath, a citric acid bath, other complex baths, and combinations thereof. The electro zinc alloy plating bath contains, for example, one or more monoions or complex ions selected from Co, Cr, Cu, Fe, Ni, P, Sn, Mn, Mo, V, W, and Zr in addition to Zn ions. do.

The chemical composition, temperature, flow rate, and conditions (current density, energization pattern, etc.) of an electrogalvanizing bath and an electrozinc alloy plating bath in an electrogalvanizing process can be adjusted suitably. The thickness of the galvanizing layer 10 in the electro galvanizing process can be adjusted by adjusting the current value and time within the range of the current density in the electro galvanizing process.

A base material texture 100S is formed in the base steel sheet 100 . Therefore, if the base steel sheet 100 is galvanized and the galvanized layer 10 is formed, a plating texture 10S corresponding to the base material texture 100S is formed on the surface of the galvanized layer 10. . By the above manufacturing process, the plated steel sheet provided with the base material steel plate 100 in which the base material texture 100S is formed, and the zinc plating layer 10 in which the plating texture 10S was formed is manufactured.

[About the galvanized surface texture forming process (S4) and polishing process (S5)]

Both the galvanizing surface texture forming process ( S4 ) and the polishing process ( S5 ) are arbitrary processes. That is, it is not necessary to perform the galvanizing surface texture forming process (S4) and the polishing process (S5). It is not necessary to perform the galvanizing surface texture formation process (S4) and perform the grinding|polishing process (S5). The polishing step (S5) may be performed without performing the zinc plating surface texture forming step (S4). You may perform a zinc plating surface texture formation process (S4) and a grinding|polishing process (S5). When performing the zinc plating surface texture formation process (S4) and the grinding|polishing process (S5), you may perform either first. Both the zinc plating surface texture forming step S4 and the polishing step S5 are steps of reducing the calculation of the convex portion 10CO of the plating texture 10S of the zinc plating layer 10 . Hereinafter, each process is demonstrated.

[Galvanized surface texture forming process (S4)]

The galvanized surface texture forming process S4 is an optional process. That is, the zinc plating surface texture forming step (S4) may or may not be performed. In the case of carrying out, in the galvanizing surface texture forming step S4, the calculation of the convex portion 10CO among the surface plating textures 10S of the galvanized layer 10 shown in FIG. 7 is reduced, and as shown in FIG. It is set as the trapezoidal shape like a bar, and let the convex part normal three-dimensional average roughness Sah be more than 5 nm and 200 nm or less. Specifically, in the galvanizing surface texture forming step S4, a known texturing is performed on the surface (plating texture 10S) of the galvanized layer 10 of the plated steel sheet to form convex portions of the plating texture 10S. Let the normal three-dimensional average illuminance Sah exceed 5 nm and be 200 nm or less. At this time, the concave portion of the plating texture 10S is hardly cut. Therefore, the three-dimensional average roughness Sas of the bottom of the recess is maintained at more than 200 nm and not more than 2000 nm.

When the plating texture 10S is a hairline, well-known hairline processing is performed. The hairline processing method is, for example, a method of forming a hairline by polishing the surface with a well-known abrasive belt, a method of forming a hairline by polishing the surface with a well-known abrasive brush, and rolling and transferring with a roll to which a hairline shape is given. There is a method of forming a hairline, and the like. The grinding degree of the peak of the convex portion 10CO of the surface plating texture 10S of the galvanized layer 10 can be adjusted by adjusting the particle size of the known abrasive belt, the particle size of the known abrasive brush, and the surface shape of the roll. do. That is, by adjusting the particle size of the known abrasive belt, the particle size of the well-known abrasive brush, and the surface shape of the roll, while maintaining the three-dimensional average roughness Sas of the bottom of the concave portion from more than 200 nm to not more than 2000 nm, the normal three-dimensional roughness Sah for the convex portions can be adjusted to more than 5 nm and less than or equal to 200 nm. In the case of performing hairline processing in the galvanizing surface texture forming step (S4), the convex portion normal three-dimensional average roughness Sah exceeds 5 nm while maintaining the bottom three-dimensional average roughness Sas of the concave portion to be more than 200 nm and not more than 2000 nm. Not only can it be adjusted to 200 nm or less, but a new hairline can also be given to the plating texture 10S. In addition, abrasive iron exposure rate can also be adjusted by adjusting the particle size of the well-known abrasive belt in the galvanizing surface texture formation process S4, the particle size of a well-known abrasive-grain brush, and the surface shape of a roll.

[Polishing process (S5)]

The grinding|polishing process S5 is an arbitrary process. That is, the grinding|polishing process S5 does not need to be implemented. When carrying out, in the grinding|polishing process S5, the top of the convex part 10CO of the surface plating texture 10S of the galvanizing layer 10 shown in FIG. 7 is grind|polished, and a trapezoid shape as shown in FIG. And let the convex part normal three-dimensional average roughness Sah be more than 5 nm and 200 nm or less. By this polishing process, the convex part top three-dimensional average roughness Sah is made into more than 5 nm and 200 nm or less, maintaining concave part bottom three-dimensional average roughness Sas to more than 200 nm and 2000 nm or less. The polishing treatment includes, for example, a method of polishing the surface with a known abrasive belt, a method of polishing the surface with a known abrasive brush, and the like. The shape of the convex portion 10CO and the roughness of the surface of the convex portion 10CO can be adjusted by adjusting the particle size of a known abrasive belt or a known abrasive brush. That is, the convex part normal three-dimensional average roughness Sah can be adjusted by adjusting the particle size of a well-known abrasive belt, and the particle size of a well-known abrasive-grain brush. The grinding process (S5) has a smaller amount of grinding (polishing amount) than the galvanizing surface texture forming process (S4). Moreover, the abrasive iron exposure rate can also be adjusted by adjusting the particle size of the well-known abrasive belt in grinding|polishing process S5, and the particle size of a well-known abrasive-grain brush.

The polishing step (S5) may be performed simultaneously with the above-described zinc plating surface texture forming step (S4). By carrying out at the same time, production efficiency can be improved.

[Colored resin layer forming step (S6)]

In a colored resin layer formation process S6, the colored resin layer 11 is formed on the galvanizing layer 10 of the plated steel sheet in which the plating texture 10S was formed. Hereinafter, a colored resin layer formation process (S6) is demonstrated in detail.

It is preferable that the paint used for formation of the colored resin layer 11 tracks the surface shape of steel materials at the moment it apply|coats to a plated steel plate, and it is a slow thing after leveling once reflecting the surface shape of steel materials. That is, when the shear rate is fast, the viscosity is low, and when the shear rate is slow, it is preferable that the coating material has a high viscosity. Specifically, when the shear rate is 0.1 [1/sec], it has a viscosity of 10 [Pa s] or more, and when the shear rate is 1000 [1/sec], it has a shear viscosity of 0.01 [Pa s] or less It is desirable to have

Adjustment of the shear viscosity of the paint can be performed by the following method. When the paint is a water-based emulsion paint, it can be adjusted by adding a known viscosity modifier having hydrogen bonding properties. Such hydrogen-bonding viscosity modifiers bind to each other by hydrogen bonding at a low shear rate. Therefore, the viscosity of a coating material can be raised. On the other hand, hydrogen bonds are cleaved at high shear rates. Therefore, the viscosity of a coating material falls.

By adjusting the shear viscosity of the coating material used for formation of the colored resin layer 11, the surface shape of the colored resin layer 11 mentioned above can be adjusted.

The method of forming the colored resin layer 11 on the galvanizing layer 10 may be a well-known method. For example, the coating material whose viscosity is adjusted is apply|coated on the galvanizing layer 10 by the spraying method, the roll coater method, the curtain coater method, or the immersion pulling method. Then, natural drying or baking drying is performed with respect to the coating material on the galvanizing layer 10, and the colored resin layer 11 is formed. Drying temperature, drying time, baking temperature, and baking time can be adjusted suitably. The three-dimensional average roughness Saave, the minimum thickness DKmin of the colored resin layer 11, and the maximum thickness DKmax are adjusted by adjusting the shear viscosity of the coating material used for formation of the colored resin layer 11, the amount of application on the galvanized layer 10, and the like. can Moreover, by adjusting content of the coloring agent in a coating material, coloring agent content CK in the colored resin layer 11 can be adjusted.

According to the above manufacturing process, the plated steel sheet 1 of 1st Embodiment can be manufactured. In addition, the plated steel sheet 1 of 1st Embodiment is not limited to the said manufacturing method, As long as the plated steel sheet 1 which has the above-mentioned structure can be manufactured, it is 1st Embodiment by manufacturing method other than the said manufacturing method. You may manufacture the plated steel sheet 1 of However, the said manufacturing method is suitable for manufacture of the plated steel sheet 1 of 1st Embodiment.

(Second embodiment)

In the plated steel sheet which concerns on 1st Embodiment, it tried to improve both the adhesiveness of a colored resin layer, and the texture visibility of the surface of a zinc plating layer. However, depending on the use of a plated steel sheet, the direction of texture visibility may give priority to the adhesiveness of a colored resin layer. MEANS TO SOLVE THE PROBLEM The present inventors examined the galvanized steel plate which is the colored external appearance and the texture visibility of the surface of a galvanized layer still higher. As described in Patent Documents 1 and 2, a galvanized steel sheet in which a transparent resin layer is formed on a galvanized layer has already been proposed. Therefore, the present inventors first tried to manufacture a colored galvanized steel sheet by containing a colorant in the resin layer formed on the galvanized layer.

As a result, it became clear that the texture formed on the surface of a galvanizing layer may not be visually recognized depending on conditions when a coloring agent is made to contain in a resin layer. Then, the present inventors investigated and investigated the factor which affects the visual recognition of a texture, when resin contains a coloring agent. As a result, the present inventors acquired the following knowledge.

When the colored resin layer containing the coloring agent is formed on the galvanized layer in which the texture is formed on the surface, the coloring agent content in the colored resin layer and the thickness of the colored resin layer affect the visibility of the texture. When there is too much content of the coloring agent in a colored resin layer specifically, it will become impossible to visually recognize a texture. Moreover, when a colored resin layer is too thick, a texture will become impossible to visually recognize.

In addition, the shape of the texture also affects the visibility of the texture. When the texture is formed on the surface of the galvanized layer, not only the unevenness of the texture but also minute unevenness due to the crystal of the zinc plating exist on the surface of the galvanized layer. When the minute irregularities resulting from the zinc plating crystals are large, the light is diffusely reflected by the minute irregularities resulting from the zinc plating crystals. In this case, the gloss of the texture is lowered and the texture is whitened. Therefore, when the colored resin layer is formed on the zinc plating layer, it becomes difficult to visually recognize a texture. Therefore, from the viewpoint of further improving the visibility of the texture, it is preferable to suppress the illuminance (slight irregularities) in the microscopic region at the top (convex portion) or the bottom (concave portion) of the texture extending in one direction.

In addition, in the cross section perpendicular to the extending direction of the texture, the thickness of the resin formed on the texture varies according to the unevenness of the texture. 9 : is a schematic diagram of the cross section perpendicular|vertical to the extending direction of a texture in the plated steel sheet of this embodiment. Referring to FIG. 9 , the plated steel sheet includes a galvanized layer 10 ′ and a colored resin layer 11 ′. A texture 10S' is formed on the surface of the galvanized layer 10'. The texture 10S' includes a convex portion 10CO' (Convex) and a concave portion 10RE' (Recess).

The colored resin layer 11' is formed on the surface of the zinc plating layer 10'. Therefore, although the unevenness|corrugation of the texture 10S' is reflected to some extent in the surface 11S' of the colored resin layer 11', it is flattened rather than the texture 10S'. Concretely, the convex part 11CO' is formed in the part corresponding to the convex part 10CO' of the texture 10S' among the surface 11S' of the colored resin layer 11'. The height of the convex portion 11CO' is lower than the height of the convex portion 10CO'. That is, the surface 11S' of the colored resin layer 11' is flatter than the surface of the texture 10S'.

Here, in the range of the length of 100 µm in the direction perpendicular to the extending direction of the texture 10S', the maximum thickness (µm) of the colored resin layer 11' is defined as DKmax'. In addition, the minimum thickness (micrometer) of the colored resin layer 11' is defined as DKmin'. Even when colored with the colored resin layer 11', in order to make the texture 10S' visually recognizable, as described above, the content of the coloring agent in the colored resin layer 11' and the colored resin layer 11' to some extent limit the thickness of And under the limited conditions, the difference between the maximum thickness DKmax' and the minimum thickness DKmin' of the colored resin layer 11' is reflected in the brightness difference. Specifically, by increasing the difference between the maximum thickness DKmax' and the minimum thickness DKmin' of the colored resin layer 11' to some extent, the brightness in the concave portion 10RE' and the convex portion 10CO' of the texture 10S'. a car occurs in As a result, even when the colored resin layer 11' is formed, the texture 10S' can be visually recognized.

Based on the above findings, the present inventors (A') adjust the roughness in the minute regions of the convex portion 10CO' and the concave portion 10RE' of the texture 10S', (B') the colored resin layer (C') The difference between the maximum thickness DKmax' and the minimum thickness DKmin' of the colored resin layer 11' in the cross section orthogonal to the extending direction of the texture 10S' by adjusting the thickness and the colorant content of (11') It has been discovered that, by making the galvanized steel sheet into a certain size, it is possible to obtain a plated steel sheet in which the texture of the surface of the galvanized layer can be visually recognized while having a colored appearance.

The plated steel sheet of 2nd Embodiment completed based on the above knowledge has the following structure.

The plated steel sheet of [11] is,

base steel plate,

a galvanized layer formed on the surface of the base steel sheet;

and a colored resin layer formed on the galvanized layer;

The galvanized layer has a texture extending in one direction on its surface,

The colored resin layer contains a colorant,

All of the following (A') to (C') are satisfied.

(A') Measure the roughness profile in the range of a length of 1000 μm in a direction perpendicular to the extension direction of the texture, and among the measured locations on the roughness profile, 10 specific positions in the order of height are selected as the bottom point of the recess Among the positions on the measured roughness profile, 10 specific positions in the order of height are defined as convex vertices, and 1 μm × 1 μm centered at the bottom of each concave portion and each convex vertex is defined as When the three-dimensional average roughness Sa' of the microregion is measured and the arithmetic mean value of the measured three-dimensional average roughness Sa' is defined as the three-dimensional average roughness Saave', the three-dimensional average roughness Saave' is greater than 5 nm and less than or equal to 200 nm.

(B') In the range of a length of 100 µm in a direction orthogonal to the extending direction of the texture, the minimum thickness (µm) of the colored resin layer is defined as DKmin', and the content (area) of the colorant in the colored resin layer %) is defined as CK', Equation (1') is satisfied.

DKmin'×CK'≤15.0 (1')

(C') Expression (2') is satisfied when the maximum thickness (µm) of the colored resin layer is defined as DKmax' in a 100 µm length range in a direction perpendicular to the extension direction of the texture.

(DKmax'-DKmin')×CK'>1.0 (2')

The plated steel sheet of [12] is,

It is the plated steel sheet according to [11],

The texture may be a hairline,

The following (D') and (E') may be satisfied.

(D') The surface roughness Ra of the colored resin layer in the extending direction of the texture is defined as Ra(CL)', and the surface roughness Ra of the colored resin layer in the direction perpendicular to the extending direction of the texture is Ra(CC). )', Equation (3') is satisfied.

Ra(CC)'≥Ra(CL)'×1.10 (3')

(E') When the surface roughness of the galvanized layer in the direction orthogonal to the extending direction of the texture is defined as Ra(MC)', Ra(MC)' is 0.30 µm or more.

The plated steel sheet of [13] is,

It is the plated steel sheet according to [11] or [12],

The ferrous iron exposure rate of the galvanized layer may be less than 5%.

Hereinafter, the plated steel sheet of 2nd Embodiment is demonstrated in detail.

[About the plated steel plate (1')]

10 : is sectional drawing of the plated steel plate 1' of 2nd Embodiment. In Fig. 10, the direction perpendicular to the paper is defined as the extending direction of the texture 10S' (that is, the rolling direction of the plated steel sheet 1') RD'. The thickness direction of the plated steel sheet 1' is defined as thickness direction TD'. Among the plated steel sheets 1', a direction perpendicular to the texture extension direction RD' and the thickness direction TD' is defined as the width direction WD'. In addition, RD', TD', and WD' by this definition have substantially the same concept as RD, TD, and WD in 1st Embodiment.

With reference to FIG. 10, the plated steel plate 1' of 2nd Embodiment is equipped with the base steel plate 100', the galvanized layer 10', and the colored resin layer 11'. The galvanized layer 10' is formed on the surface of the base steel sheet 100'. The colored resin layer 11' is formed on the surface (texture) 10S' of the zinc plating layer 10'. The galvanized layer 10' is disposed between the base steel sheet 100' and the colored resin layer 11'. Hereinafter, the base steel sheet 100', the galvanized layer 10', and the colored resin layer 11' are demonstrated.

[About the base steel plate (100')]

The base steel sheet 100 ′ is a plated steel sheet (electro galvanized steel sheet, electro galvanized steel sheet, hot-dip galvanized steel sheet, etc.) according to each mechanical property (eg, tensile strength, workability, etc.) required for the plated steel sheet to be manufactured. , alloyed hot-dip galvanized steel sheet, etc.) may be used. For example, as the base steel sheet 100', a steel sheet for electrical equipment applications may be used, or a steel sheet for automobile exterior panels may be used. The base steel sheet 100' may be a hot rolled steel sheet or a cold rolled steel sheet.

[About the galvanized layer 10']

The galvanized layer 10' is formed on the surface of the base steel sheet 100'. In the second embodiment, the galvanized layer 10' is disposed between the base steel sheet 100' and the colored resin layer 11'. The zinc plating layer 10' is formed by a well-known zinc plating method. Specifically, the zinc plating layer 10' is formed by, for example, any plating method of an electroplating method or a hot-dip plating method. In this specification, the zinc plating layer 10' also includes a zinc alloy plating layer. More specifically, the galvanized layer 10' is a concept including an electrogalvanized layer, an electrozinc alloy plated layer, a hot-dip galvanized layer, and an alloyed hot-dip galvanized layer.

It is sufficient if the zinc plating layer 10' in 2nd Embodiment has a well-known chemical composition. For example, the Zn content in the chemical composition of the galvanized layer 10' may be 65% or more by mass%. When the Zn content is 65% or more in terms of mass%, the sacrificial anticorrosion function is remarkably exhibited, and the corrosion resistance of the plated steel sheet 1' is remarkably increased. A preferable lower limit of the Zn content in the chemical composition of the galvanized layer 10' is 70%, more preferably 80%.

The chemical composition of the galvanized layer 10' is one element selected from the group consisting of Al, Co, Cr, Cu, Fe, Ni, P, Si, Sn, Mg, Mn, Mo, V, W, and Zr, or It is preferable to contain two or more elements and Zn. The chemical composition of the galvanized layer 10' when the galvanized layer 10' is an electrogalvanized layer is 5 to 20% by mass in total of at least one element selected from the group consisting of Fe, Ni, and Co. It is more preferable that it contains Zn and impurities with the remainder. In the case where the galvanized layer 10' is a hot-dip galvanized layer, the chemical composition of the galvanized layer 10' is 5 to 20% by mass in total of at least one element selected from the group consisting of Mg, Al, and Si. It is more preferable that it contains Zn and impurities. In these cases, the galvanized layer 10' also exhibits excellent corrosion resistance.

The galvanized layer 10' may contain impurities. Here, an impurity mixes in a raw material, or mixes in a manufacturing process. Impurities are, for example, Ti, B, S, N, C, Nb, Pb, Cd, Ca, Pb, Y, La, Ce, Sr, Sb, O, F, Cl, Zr, Ag, W, H, etc. to be. In the chemical composition of the galvanized layer 10', the total content of impurities is preferably 1% or less.

The chemical composition of the galvanized layer 10' can be measured by the following method, for example. The colored resin layer 11 of the plated steel sheet 1' with a release agent such as a solvent that does not invade the zinc plating layer 10' or a remover (for example, Sansai Kaco Co., Ltd. trade name: Neoliver S-701) ') is removed. Thereafter, the galvanized layer 10' is dissolved using hydrochloric acid containing the inhibitor. The solution is subjected to ICP analysis using an ICP (Inductively Coupled Plasma) emission spectrometer to determine the Zn content. If the calculated|required Zn content is 65 % or more, it is judged that the plating layer to be measured is the zinc plating layer 10'.

[About the adhesion amount of the galvanized layer 10']

The adhesion amount in particular of the zinc plating layer 10' is not restrict|limited, A well-known adhesion amount is sufficient. The preferable adhesion amount of the zinc plating layer 10' is 5.0-120.0 g/m<2>. When the adhesion amount of the galvanized layer 10' is 5.0 g/m 2 or more, when a texture to be described later is provided to the galvanized layer 10', exposure of the base iron (base steel sheet 100') can be suppressed. A more preferable lower limit of the adhesion amount of the galvanized layer 10' is 7.0 g/m 2 , and still more preferably 10.0 g/m 2 . The upper limit of the adhesion amount of the galvanized layer 10' is not particularly limited. From the viewpoint of economical efficiency, in the case of the galvanized layer 10' by the electroplating method, the upper limit of the preferable adhesion amount is 40.0 g/m2, the more preferable upper limit is 35.0 g/m2, and still more preferably 30.0 g/m2.

[About the colored resin layer 11']

The colored resin layer 11' is formed on the surface (texture) 10S' of the zinc plating layer 10'. 11 : is an enlarged view of the colored resin layer 11' shown in FIG. Referring to FIG. 11 , the colored resin layer 11 ′ includes a resin 31 ′ and a colorant 32 ′. The colorant 32' is contained in the resin 31'. Hereinafter, the resin 31' and the coloring agent 32' are demonstrated.

[About resin (31')]

The resin 31' is a light-transmitting resin. In the second embodiment, the "resin having translucency" refers to a colored resin layer 11 containing a colorant 32' and a resin 31' in an environment equivalent to sunlight in the morning on a clear sky (illuminance about 65000 lux). ') means that the texture 10S' of the galvanized layer 10' can be visually recognized when the plated steel sheet 1' having the ') is placed. The resin 31' functions as a binder for fixing the colorant 32'.

The resin 31' is not particularly limited as long as it is a resin having the above-described light-transmitting properties, and a known natural resin or a known synthetic resin can be used. The resin 31' in the second embodiment is, for example, an epoxy-based resin, a urethane-based resin, a polyester-based resin, a phenol-based resin, a polyethersulfone-based resin, a melamine alkyd-based resin, an acrylic resin, or a polyamide-based resin. It is 1 type or 2 or more types selected from the group which consists of resin, polyimide type resin, silicone type resin, polyvinyl acetate type resin, polyolefin type resin, polystyrene type resin, vinyl chloride type resin, and vinyl acetate type resin.

[About the colorant (32')]

The coloring agent 32' colors the colored resin layer 11' by being contained in the resin 31' mentioned above. The colorant 32' in the second embodiment is a well-known one, and includes widely used inorganic pigments, organic pigments, dyes, and the like to color a resin layer formed on the surface of a steel sheet. The colorant 32' is a chromatic colorant. A chromatic color means a color having properties of hue, brightness, and saturation. The colorant 32' is made of, for example, at least one selected from the group consisting of inorganic pigments, organic pigments, and dyes. In addition, from the viewpoint of durability against ultraviolet rays, the colorant 32' is more preferably a pigment-based pigment (inorganic pigment and/or organic pigment).

When the colorant 32' is an inorganic pigment, the colorant 32' is, for example, a neutralized precipitation pigment (sulfate, carbonate, etc.), and/or a calcined pigment (metal sulfide, metal oxide, polyvalent metal complex oxide, etc.) to be. When the colorant 32' is an organic pigment, the colorant 32' is, for example, a chlorine pigment, an azo pigment (solvent azolake pigment, insoluble azo pigment, etc.), an acid condensed pigment, a polycyclic pigment (phthalocyanine-based pigment, etc.) , indigo pigments, quinacridone pigments, anthraquinone pigments, etc.) and metal complex pigments (azo chelate pigments, transition metal complex pigments, etc.). When the colorant 32' is a dye, the colorant 32' is, for example, at least one selected from the group consisting of azo dyes, indigo dyes, anthraquinone dyes, sulfide dyes, and carbonium dyes.

The color of the colorant 32' is not particularly limited. The colorant 32' is, for example, black of carbon black (C') or iron black (Fe ₃ O ₄ ). However, the colorant 32' is not limited to black, and may be a colorant 32' of another color (white, magenta, yellow, cyan, red, orange, yellow, green, blue, indigo, purple, etc.).

When the colorant 32' is a pigment, the particle diameter is not particularly limited. The maximum value of the primary particle diameter when the colorant 32' is a pigment is, for example, 3 nm to 1000 nm.

[About the texture 10S' formed on the surface of the galvanized layer 10']

A texture 10S' is formed on the surface of the galvanized layer 10' of the plated steel sheet 1'. That is, the galvanized layer 10' of the plated steel sheet 1' has a texture 10S' on its surface. The texture 10S' extends in one direction. In the second embodiment, "texture" means the uneven pattern formed on the surface of the galvanized layer 10' by a physical or chemical method. A preferable texture is a hairline. The hairline is a linear concavo-convex shape extending in one direction.

[When the texture (10S') is a hairline]

12 is a plan view of a galvanized layer 10' having a hairline formed on its surface as a texture 10S'. Referring to FIG. 12 , the hairline 10S' has a linear concavo-convex shape formed on the surface of the galvanized layer 10'. The extension direction RD' of the hairline 10S' is the same direction. The same direction as used herein refers to the direction WD' perpendicular to the extension direction RD' of the hairline 10S' when the galvanized layer 10' is viewed in the thickness direction TD' (that is, when viewed in the same plane as in FIG. 12). It means that 90% or more of the angles between the arranged and adjacent hairlines are less than ±5°.

[About requirements (A') to (C')]

The plated steel sheet 1' of the second embodiment having the above-described configuration further satisfies all of the following (A') to (C').

Requirement (A'):

The roughness profile in the range of length of 1000 µm in the direction WD' orthogonal to the extension direction RD' of the texture 10S' is measured, and among the positions on the measured roughness profile, 10 specific positions in the order of the height are the recesses. It is defined as the bottom point, and among the positions on the measured roughness profile, 10 specific positions in the order of height are defined as the convex vertices. The three-dimensional average roughness Sa' of a minute region of 1 μm×1 μm centered on the bottom point of each concave portion and the apex of each convex portion is measured. An arithmetic mean value of the measured three-dimensional average roughness Sa' is defined as three-dimensional average roughness Saave'. At this time, the three-dimensional average illuminance Saave' is greater than 5 nm and less than or equal to 200 nm.

Requirement (B'):

In the range of the length of 100 µm in the direction WD' orthogonal to the extension direction RD' of the texture 10S', the minimum thickness (µm) of the colored resin layer 11' is defined as DKmin'. In addition, content (area %) of the coloring agent 32' in the colored resin layer 11' is defined as CK'. At this time, the minimum thickness DKmin' of the colored resin layer 11' and content CK' of the coloring agent 32' satisfy Formula (1').

DKmin'×CK'≤15.0 (1')

Requirement (C'):

In the range of the length of 100 µm in the direction WD' orthogonal to the extension direction RD' of the texture 10S', the maximum thickness (µm) of the colored resin layer 11' is defined as DKmax'. At this time, the maximum thickness DKmax' of the colored resin layer 11', the minimum thickness DKmin' of the colored resin layer 11', and content CK' of the coloring agent 32' satisfy Formula (2').

(DKmax'-DKmin')×CK'>1.0 (2')

Hereinafter, each requirement is demonstrated in detail.

[About requirement (A')]

13 is a diagram showing the roughness profile of the texture 10S' formed on the surface of the galvanized layer 10'. Referring to FIG. 13 , an arbitrary 1000 μm length range in the direction WD′ orthogonal to the extension direction RD′ of the texture 10S′ is selected. In the selected 1000 μm length range, the roughness profile of the texture 10S' is measured. Assume that the obtained roughness profile has a shape as shown in FIG. 13 .

Among the positions on the measured roughness profile, ten positions are specified in the order of height from the lowest position to the lowest position. The specified position, in descending order of height, the bottom of the recess PRE1', PRE2', ... , is defined as PRE10'. Moreover, among the positions on the measured roughness profile, ten points|pieces are specified in order of height from a position with the highest height to a position with a high height. The specified position, in the order of height, the convex vertices PCO1', PCO2', ... , PCO10' is defined.

As shown in Fig. 14A, when the surface of the galvanized layer 10' is viewed in a plan view, a minute concavity of 1 µm x 1 µm centered on the defined bottom point PREk' (k is 1 to 10) of each concave portion. The region 200' is specified. In Fig. 14A, the longitudinal direction of the micro concavity region 200' is parallel to the extension direction RD' of the texture 10S', and the horizontal direction of the micro concavity region 200' is parallel to the width direction WD'. have. However, if the minute concave portion region 200' is a surface including the extension direction RD' and the width direction WD', each side of the minute concave portion region 200' is parallel to the extension direction RD' or the width direction WD'. You do not have to do.

Similarly, as shown in Fig. 14B, when the surface of the galvanized layer 10' is viewed in a plan view, micro-convexities of 1 mu m x 1 mu m centered on the defined apex of each convex portion PCOk' (k is 1 to 10). The sub-region 300' is specified. In Fig. 14B, the longitudinal direction of the micro-convex region 300' is parallel to the extension direction RD' of the texture 10S', and the horizontal direction of the micro-convex region 300' is parallel to the width direction WD'. have. However, if the minute convex portion region 300' is a surface including the extension direction RD' and the width direction WD', each side of the minute convex portion region 300' is parallel to the extension direction RD' or the width direction WD'. You do not have to do.

The three-dimensional average roughness Sa' is measured in the ten minute concave portion regions 200' and the ten minute convex portion regions 300' specified by the above method. The three-dimensional average roughness Sa' is an arithmetic mean height prescribed in ISO 25178 by extending Ra (arithmetic mean height of a line) prescribed in JIS B 0601 (2013) to a plane. An arithmetic mean value of 20 measured three-dimensional average roughness Sa' is defined as three-dimensional average roughness Saave'. At this time, the arithmetic mean roughness Saave' is greater than 5 nm and less than or equal to 200 nm.

In the portion near the apex of the convex portion or the portion near the bottom of the concave portion of the texture 10S', minute irregularities (hereinafter referred to as micro irregularities) at the nanometer level due to the galvanized crystal exist. When the minute irregularities are of a certain size, light is diffusely reflected by the minute irregularities. In this case, the gloss of the texture is lowered and the texture is whitened. Therefore, when the colored resin layer is formed on the zinc plating layer, it becomes difficult to visually recognize a texture. Accordingly, from the viewpoint of further improving the visibility of the texture, it is preferable that the minute irregularities in the minute regions 200' and 300' be as small as possible.

In 2nd Embodiment, the three-dimensional average roughness Saave' based on the said definition is more than 5 nm and 200 nm or less. When the three-dimensional average illuminance Saave' is 200 nm or less, diffuse reflection of light in the vicinity of the apex of the convex portion and the vicinity of the bottom of the concave portion can be further suppressed. In this case, in the plated steel sheet 1' of the second embodiment having the colored resin layer 11', the texture 10S' is further easily visually recognized. In addition, the three-dimensional average roughness Saave' is so preferable that it is small. However, it is very difficult to make three-dimensional average roughness Saave' into 5 nm or less. Therefore, in 2nd Embodiment, three-dimensional average roughness Saave' is more than 5 nm and 200 nm or less. The preferable upper limit of three-dimensional average roughness Saave' is 190 nm, More preferably, it is 180 nm, More preferably, it is 170 nm.

[About requirement (B')]

Referring to Fig. 9, attention is paid to a cross section in an arbitrary 100 mu m length range in a direction WD' orthogonal to an extension direction RD' of the texture 10S'. A cross section (FIG. 9) of this 100 µm length range is defined as an observation cross section. Observation cross section WHEREIN: Among the thicknesses of the colored resin layer 11', the minimum thickness is defined as DKmin' (μ). Observation cross section WHEREIN: Among the thicknesses of the colored resin layer 11', the largest thickness is defined as DKmax' (micrometer).

In addition, in an observation cross section, content (area %) of the coloring agent in the colored resin layer 11' is defined as CK'. As mentioned above, in this specification, colorant content CK' is represented by the area ratio (area %) of the colorant in an observation cross section.

As described above, when the minimum thickness DKmin' (µm), the maximum thickness DKmax' (µm), and the colorant content CK' (area%) of the colored resin layer 11' are defined, the minimum of the colored resin layer 11' Thickness DKmin' and content CK' of the coloring agent 32' satisfy Formula (1').

DKmin'×CK'≤15.0 (1')

When the formula (1') is not satisfied, that is, when the product of the minimum thickness DKmin' and the colorant content CK' exceeds 15.0, the thickness of the colored resin layer 11' is too thick or the colorant content CK' is too high many. In this case, the coloring of the colored resin layer 11' is too dark, and it is difficult to visually recognize the texture 10S' of the galvanized layer 10'. If the product of the minimum thickness DKmin' and the colorant content CK' is 15.0 or less, on condition that the requirements (A') and (C') are satisfied, the appearance colored by the colored resin layer 11' and the galvanized layer The texture 10S' of the surface of (10') can be sufficiently visually recognized. The preferable upper limit of DKmin' x CK' is 14.0, More preferably, it is 13.0, More preferably, it is 12.0. In addition, the lower limit of DKmin' x CK' is not specifically limited. The lower limit of DKmin' x CK' is 4.0, for example.

The thickness of the colored resin layer 11' in 2nd Embodiment is measured by the following method. A sample having a cross section orthogonal to the extending direction RD' of the texture 10S' on the surface is taken. Among the samples, an observation cross-section in a length range of 100 µm in a direction WD' orthogonal to the extension direction RD' of the texture 10S' was taken as a reflection electron image (BSE) at a magnification of 2000 using a scanning electron microscope (SEM). Observe. In observation with a reflected electron image (BSE) of a scanning electron microscope (SEM), the base steel sheet 100', the galvanized layer 10', and the colored resin layer 11' can be easily discriminated by contrast. do. In the observation cross section, the thickness of the colored resin layer 11' is measured at a pitch of 0.5 µm in the direction WD'. Among the measured thicknesses, the minimum thickness is defined as the minimum thickness DKmin' (㎛). Among the measured thicknesses, the maximum thickness is defined as the maximum thickness DKmax' (μm). When it is necessary to determine whether or not it is the colored resin layer 11' (that is, whether the resin contains a coloring agent), it may be determined whether it is the colored resin layer 11' by TEM observation to be described later.

Colorant content CK' (area %) in colored resin layer 11' is calculated|required by the following method. A sample having a cross section orthogonal to the extending direction RD' of the texture 10S' on the surface is taken. Among the samples, a cross section orthogonal to the extension direction RD' of the texture 10S' is defined as an observation surface. From the sample, a thin film sample in which the colored resin layer 11' and the zinc plating layer 10' of the observation surface can be observed is produced using a Converged Ion Beam (FIB). The thickness of the thin film sample is 50 to 200 nm. Among the observation surfaces of the produced thin film sample, the length in the direction perpendicular to the thickness direction of the colored resin layer 11' (that is, the direction WD') is 3 µm, and the thickness direction of the colored resin layer 11' ( That is, in direction TD', the visual field which has the length including the colored resin layer 11' whole is observed using a transmission electron microscope (TEM:Transmission Electron Microscope). TEM observation WHEREIN: The resin 31' and the colorant 32' in the colored resin layer 11' can be discriminated by contrast. ^{The total area A1' (micrometer 2} ) of the some coloring agent 32' in the colored resin layer 11' in the said visual field is calculated|required. ^{Moreover, area A0' (micrometer 2} ) of the colored resin layer 11' in the said visual field is calculated|required. Based on the calculated|required total area A1' and area A0', the coloring agent content (area %) in the colored resin layer 11' is calculated|required by the following formula.

CK=A1'/A0'×100

[About requirement (C')]

The colored resin layer 11' is a cross-section perpendicular to the extension direction RD' of the texture 10S', and in an observation cross-section in a 100 µm length range in a direction WD' orthogonal to the extension direction RD' of the texture 10S'. The maximum thickness DKmax' of , the minimum thickness DKmin' of the colored resin layer 11', and the content CK' of the coloring agent 32' satisfy Formula (2').

(DKmax'-DKmin')×CK'>1.0 (2')

(DKmax'-DKmin') x CK' is a contrast index of the brightness in the colored resin layer 11'. When (DKmax'-DKmin') x CK' is 1.0 or less, the contrast of the brightness in the colored resin layer 11' is low. In this case, the contrast of the brightness of the colored resin layer 11' cannot be sufficiently utilized for visual recognition of the texture 10S'. Therefore, it is difficult to visually recognize the texture 10S' under the colored resin layer 11'.

When (DKmax'-DKmin') x CK' is higher than 1.0, the contrast of the brightness in the colored resin layer 11' is sufficiently high. In this case, the contrast of the brightness of the colored resin layer 11' can be fully utilized for visual recognition of the texture 10S'. As a result, on the premise that the requirements (A') and (B') are satisfied, the texture 10S' under the colored resin layer 11' can be sufficiently visually recognized.

The preferable lower limit of (DKmax'-DKmin')xCK' is 1.2, More preferably, it is 1.5, More preferably, it is 1.8, More preferably, it is 2.0. In addition, the upper limit of (DKmax'-DKmin')xCK' is not specifically limited. The upper limit of (DKmax'-DKmin') x CK' is 15.0, for example.

[About the thickness of the colored resin layer 11']

In the plated steel sheet 1' of the second embodiment, preferably, the average thickness of the colored resin layer 11' is 10.0 µm or less. When the thickness of the colored resin layer 11' exceeds 10.0 µm, it becomes easy to smooth (level) only with the colored resin layer 11', and the impression of reflection on the surface of the colored resin layer 11' and visual recognition can be achieved. The difference in impressions of the existing textures 10S' increases. In this case, the metallic feeling of the plated steel sheet 1' is reduced. When the average thickness of the colored resin layer 11' is 10.0 µm or less, on the premise that all of the above requirements (A') to (C') are satisfied, the texture 10S' of the galvanized layer 10' can be visually recognized, and the metallic feeling is sufficiently increased. The more preferable upper limit of the average thickness of the colored resin layer 11' is 9.0 micrometers, More preferably, it is 8.0 micrometers.

In addition, the preferable minimum of the average thickness of the colored resin layer 11' is 0.5 micrometer. If the average thickness of the colored resin layer 11' is 0.5 micrometer or more, corrosion resistance will become still higher. The minimum with more preferable average thickness of the colored resin layer 11' is 0.7 micrometers, More preferably, it is 1.0 micrometer, More preferably, it is 2.0 micrometers, More preferably, it is 3.0 micrometers.

The average thickness of the colored resin layer 11' is measured by the following method. The arithmetic mean value of the thickness measured at 0.5 micrometer pitch in direction WD' in the observation cross section mentioned above is defined as the average thickness (micrometer) of the colored resin layer 11'.

[About other forms of colored resin layer 11']

The colored resin layer 11' of the plated steel sheet 1' of the second embodiment may further contain an additive in order to impart corrosion resistance, slidability, conductivity, and the like to the colored resin layer 11'. Additives for imparting corrosion resistance are, for example, well-known rust inhibitors and inhibitors. Additives for imparting sliding properties are, for example, well-known waxes and beads. The additive for providing electroconductivity is a well-known electrically conductive agent, for example.

[About the surface shape of the preferable colored resin layer 11' (refer to the requirement (D'))]

Preferably, the colored resin layer 11' has a surface shape as described in detail below due to the type of the texture 10S' formed on the surface of the galvanized layer 10' as the lower layer.

The surface roughness Ra of the colored resin layer 11' in the extending direction RD' of the texture 10S' is defined as Ra(CL)'. When the texture 10S' is a hairline, the surface roughness Ra of the colored resin layer 11' in the direction WD' orthogonal to the extension direction RD' of the texture 10S' is defined as Ra(CC)'. do. At this time, preferably, the surface roughness Ra(CC)' and the surface roughness Ra(CL)' satisfy the formula (3').

Ra(CC)'≥Ra(CL)'×1.10 (3')

When the surface roughness Ra(CC)' of the colored resin layer 11' is less than 1.10 times the surface roughness Ra(CL)', the impression received from the texture 10S' in the absence of the colored resin layer 11' And the difference of the reflection impression of the light on the surface of the colored resin layer 11' becomes large too much. In this case, the metallic feeling is lost. When the surface roughness Ra(CC)' is 1.10 times or more with respect to the surface roughness Ra(CL)', the impression received from the texture 10S' in the absence of the colored resin layer 11' and the colored resin layer 11' ), it is possible to suppress the deviation of the reflection impression of light on the surface. Therefore, a sufficient metallic feeling is obtained. More preferably, the surface roughness Ra(CC)' of the colored resin layer 11' is 1.15 times or more of the surface roughness Ra(CL)', more preferably 1.20 times or more, and still more preferably 1.25 times or more. to be.

Surface roughness Ra(CL)' is measured by the measuring method of the arithmetic mean roughness prescribed|regulated to JISB0601 (2013). Specifically, in the surface 11S' of the colored resin layer 11', ten arbitrary places are made into a measurement location. In each measurement location, the arithmetic mean roughness Ra is measured by the evaluation length extended in the extending direction RD' of the texture 10S'. The evaluation length is set to 5 times the reference length (cut-off wavelength). The arithmetic mean roughness Ra is measured using a stylus type roughness meter, and the measurement speed is 0.5 mm/sec. Among the 10 obtained arithmetic mean roughness Ra, 6 arithmetic mean roughness Ra, excluding the largest arithmetic mean roughness Ra, the second largest arithmetic mean roughness Ra, the smallest arithmetic mean roughness Ra, and the second smallest arithmetic mean roughness Ra, An arithmetic mean value is defined as surface roughness Ra(CL)'.

Similarly, surface roughness Ra(CC)' is measured by the measuring method of the arithmetic mean roughness prescribed|regulated to JISB0601 (2013). Specifically, in the surface 11S' of the colored resin layer 11', ten arbitrary places are made into a measurement location. In each measurement location, the arithmetic mean roughness Ra is measured by the evaluation length extended in the direction WD' orthogonal to the extending direction RD' of the texture 10S'. The evaluation length is set to 5 times the reference length (cut-off wavelength). The arithmetic mean roughness Ra is measured using a stylus type roughness meter, and the measurement speed is 0.5 mm/sec. Among the 10 obtained arithmetic mean roughness Ra, 6 arithmetic mean roughness Ra, excluding the largest arithmetic mean roughness Ra, the second largest arithmetic mean roughness Ra, the smallest arithmetic mean roughness Ra, and the second smallest arithmetic mean roughness Ra, An arithmetic mean value is defined as surface roughness Ra(CC)'.

[About the surface shape of the galvanized layer 10' (refer to the requirement (E'))]

The surface roughness Ra of the surface of the galvanized layer 10' on which the texture 10S' is formed in the direction WD' orthogonal to the extending direction of the texture 10S' is defined as Ra(MC)'. When the texture 10S' is a hairline, the surface roughness Ra(MC)' is preferably 0.30 µm or more. When the surface roughness Ra(MC)' is less than 0.30 µm, it is difficult to visually recognize the texture 10S' from the colored resin layer 11'. When surface roughness Ra(MC)' is 0.30 micrometer or more, texture 10S' can fully be visually recognized from the colored resin layer 11'. A more preferable lower limit of the surface roughness Ra(MC)' is 0.35 µm, still more preferably 0.40 µm. The upper limit of surface roughness Ra(MC)' is not specifically limited. However, it may be difficult in industrial production to raise surface roughness Ra(MC)' excessively. Therefore, the upper limit of surface roughness Ra(MC)' is 2.00 micrometers, for example. The upper limit of the surface roughness Ra(MC)' may be, for example, 1.00 µm.

Surface roughness Ra(MC)' is measured by the measuring method of the arithmetic mean roughness prescribed|regulated to JISB0601 (2013). Specifically, a solvent that does not invade the galvanized layer 10' or a release agent such as a remover (for example, Sansai Kako Co., Ltd. trade name: Neoliver S-701) is used to remove the plated steel sheet 1'. The colored resin layer 11' is removed. Texture 10S' of galvanized layer 10' after removing colored resin layer 11' WHEREIN: Let arbitrary ten places be a measurement location. In each measurement location, the arithmetic mean roughness Ra is measured by the evaluation length extended in the direction WD' orthogonal to the extending direction RD' of the texture 10S'. The evaluation length is set to 5 times the reference length (cut-off wavelength). The arithmetic mean roughness Ra is measured using a stylus type roughness meter, and the measurement speed is 0.5 mm/sec. Among the 10 obtained arithmetic mean roughness Ra, 6 arithmetic mean roughness Ra, excluding the largest arithmetic mean roughness Ra, the second largest arithmetic mean roughness Ra, the smallest arithmetic mean roughness Ra, and the second smallest arithmetic mean roughness Ra, An arithmetic mean value is defined as surface roughness Ra(MC)'.

[About Ji-cheol Exposure Rate]

Preferably, the iron exposure rate of the galvanized layer 10' of the plated steel sheet 1' is less than 5%. In the second embodiment, corrosion resistance is sufficiently ensured by the zinc plating layer 10' (galvanizing or zinc alloy plating). However, as a result of grinding the surface of the galvanized layer 10' upon application of the texture 10S', when the ferrous iron is exposed, the corrosion resistance (long-term corrosion resistance) in a long period of time decreases due to the influence of galvanic corrosion. have. Such a fall in long-term corrosion resistance becomes remarkable with a base iron exposure rate of 5% or more in many cases. Therefore, in the second embodiment, the preferred ferrite exposure rate is less than 5%.

When the iron exposure rate of the galvanized layer 10' is less than 5%, in addition to the moderate corrosion resistance generally required for steel materials, very good corrosion resistance such as excellent long-term corrosion resistance is obtained. A preferable upper limit of the iron exposure rate of the galvanized layer 10' is 3% or less, more preferably 2%, still more preferably 1%, still more preferably 0%.

The iron exposure rate is measured by the following method. Specifically, a solvent that does not invade the galvanized layer 10' or a release agent such as a remover (for example, Sansai Kako Co., Ltd. trade name: Neoliver S-701) is used to remove the plated steel sheet 1'. The colored resin layer 11' is removed. On the surface of the galvanized layer 10', five arbitrary rectangular areas of 1 mm x 1 mm are selected. EPMA analysis is performed on the selected rectangular area. By image analysis, a region in which Zn is not detected (Zn undetected region) in each rectangular region is specified. In the second embodiment, a region in which the detection intensity of Zn is 1/16 or less when a standard sample (pure Zn) is measured is recognized as a Zn undetected region. The ratio (area %) of the total area of the Zn undetected region among the five rectangular regions to the total area of the five rectangular regions is defined as the iron exposure rate (area %).

In addition, in the plated steel sheet 1' of the second embodiment, an inorganic film or an organic-inorganic composite film is formed between the colored resin layer 11' and the galvanized layer 10' for the purpose of improving corrosion resistance or adhesion. do. The inorganic film has light-transmitting properties. The inorganic film is, for example, an amorphous silica film, a zirconia film, or a phosphate film. The organic-inorganic composite film has light-transmitting properties. The organic-inorganic composite film contains, for example, a silane coupling agent and an organic resin. The organic-inorganic composite film has light-transmitting properties.

[Manufacturing method]

An example of the manufacturing method of the plated steel sheet 1' of 2nd Embodiment is demonstrated. The manufacturing method demonstrated later is an example for manufacturing the plated steel plate 1' of 2nd Embodiment. Accordingly, the plated steel sheet 1' having the above-described configuration may be manufactured by a manufacturing method other than the manufacturing method described later. However, the manufacturing method demonstrated later is a preferable example of the manufacturing method of the plated steel plate 1' of 2nd Embodiment.

The manufacturing method of the second embodiment includes a step of preparing the base steel sheet 100' (preparation step: S1'), and a step of forming the galvanized layer 10' on the base steel sheet 100' (galvanizing treatment). Step: S2'), a step of forming a texture on the surface of the galvanized layer 10' (texturing step: S3'), and a step of forming the colored resin layer 11' on the plated steel sheet (colored resin layer) forming step: S4'). Hereinafter, each process is demonstrated.

[Preparation process (S1')]

In the preparation step S1', the base steel sheet 100' is prepared. A steel plate may be sufficient as the base material steel plate 100', and another shape may be sufficient as it. When the base steel sheet 100 ′ is a steel sheet, the base steel sheet 100 ′ may be a hot rolled steel sheet or a cold rolled steel sheet.

[Galvanizing process (S2')]

In the galvanizing treatment step S2', zinc plating is performed on the prepared base steel sheet 100', and a zinc plating layer 10' is formed on the surface of the base steel sheet 100'.

What is necessary is just to implement a galvanizing process by a well-known method. For example, the zinc plating layer 10' is formed using a well-known electroplating method. In this case, it is sufficient to use a well-known bath for an electrogalvanizing bath and an electrozinc alloy plating bath. The electroplating bath is, for example, a sulfuric acid bath, a chloride bath, a zincate bath, a cyanide bath, a pyrophosphoric acid bath, a boric acid bath, a citric acid bath, other complex baths, and combinations thereof. The electro zinc alloy plating bath contains, for example, one or more monoions or complex ions selected from Co, Cr, Cu, Fe, Ni, P, Sn, Mn, Mo, V, W, and Zr in addition to Zn ions. do.

The chemical composition, temperature, flow rate, and conditions (current density, energization pattern, etc.) of an electrogalvanizing bath and an electrozinc alloy plating bath in an electrogalvanizing process can be adjusted suitably. The thickness of the galvanizing layer 10' in the electrogalvanizing process can be adjusted by adjusting the current value and time within the range of the current density in the electrogalvanizing process.

The galvanized layer 10' may be formed by hot-dip galvanizing or alloyed hot-dip galvanizing. Also in this case, a well-known galvanizing bath is prepared. The galvanizing bath may contain, for example, one or more elements selected from Mg, Al, and Si mainly from Zn. When the galvanized layer 10' is a hot-dip galvanized layer, the base steel sheet 100' is immersed in a galvanizing bath whose bath temperature and chemical composition of the bath are adjusted, and the galvanized layer ( 10') (a hot-dip galvanized layer) is formed. In addition, when the galvanized layer 10' is an alloyed hot-dip galvanized layer, the base steel sheet 100' on which the hot-dip galvanized layer is formed is subjected to a known heat treatment in a known alloying furnace to alloy the galvanized layer 10'. A hot-dip galvanized layer. The thickness of the galvanizing layer 10' in the hot-dip galvanizing process can be adjusted by adjusting the immersion time in the galvanizing bath and the amount of zinc plating removed by gas wiping. Note that, before the plating treatment, a known degreasing treatment such as electrolytic degreasing may be performed on the base steel sheet 100'.

Through the above manufacturing process, the base steel sheet 100' and the plated steel sheet 1' provided with the zinc plating layer 10' are manufactured.

[Texture processing process (S3')]

In the texturing process S3', a texture 10S' is formed on the surface of the galvanized layer 10' by performing a well-known texturing on the surface of the galvanized layer 10' of the plated steel sheet.

When the texture 10S' is a hairline, well-known hairline processing is performed. The hairline processing method is, for example, a method of forming a hairline by polishing the surface with a well-known abrasive belt, a method of forming a hairline by polishing the surface with a well-known abrasive brush, and rolling and transferring with a roll to which a hairline shape is given. There is a method of forming a hairline, and the like. The length, depth, and frequency of a hairline can be adjusted by adjusting the particle size of a well-known abrasive belt, the particle size of a well-known abrasive-grain brush, and the surface shape of a roll. That is, the arithmetic mean roughness Ra(MC)' and the iron exposure rate can be adjusted by adjusting the particle size of a well-known abrasive belt, the particle size of a well-known abrasive-grain brush, and the surface shape of a roll. Moreover, as a method of providing a hairline, it is preferable from a viewpoint of surface quality to polish the surface with an abrasive belt or an abrasive-grain brush to form a hairline. In addition, in this manufacturing method, the process of forming a texture on the base material surface is not included, and since it does not have a texture on the base material surface, the plating surface before the start of the texturing process S3' is comparatively flat. Therefore, the concave portion of the texture is formed by polishing or the like by the texturing step S3'. At this time, the recessed part is formed so that the three-dimensional average roughness Saave' may be more than 5 nm and 200 nm or less.

A plated steel sheet comprising a base steel sheet 100' and a galvanized layer 10' by the above manufacturing process, and a texture 10S' extending in one direction is formed on the surface of the galvanized layer 10' ( 1') is prepared.

[Colored resin layer forming step (S4')]

In the colored resin layer forming step S4', the colored resin layer 11' is formed on the galvanized layer 10' of the plated steel sheet with the texture 10S'. Hereinafter, a colored resin layer formation process (S4') is demonstrated in detail.

It is preferable that the paint used for formation of the colored resin layer 11' follows the surface shape of the steel material at the moment it is applied to the plated steel sheet, and the leveling after once reflecting the surface shape of the steel material is slow. That is, when the shear rate is fast, the viscosity is low, and when the shear rate is slow, it is preferable that the coating material has a high viscosity. Specifically, when the shear rate is 0.1 [1/sec], it has a viscosity of 10 [Pa·s] or more, and when the shear rate is 1000 [1/sec], it has a viscosity of 0.01 [Pa·s] or less. it is preferable

Adjustment of the shear viscosity of the paint can be performed by the following method. When the paint is a water-based emulsion paint, it can be adjusted by adding a known viscosity modifier having hydrogen bonding properties. Such hydrogen-bonding viscosity modifiers bind to each other by hydrogen bonding at a low shear rate. Therefore, the viscosity of a coating material can be raised. On the other hand, hydrogen bonds are cleaved at high shear rates. Therefore, the viscosity of a coating material falls.

By adjusting the shear viscosity of the coating material used for formation of the colored resin layer 11', the surface shape of the colored resin layer 11' mentioned above can be adjusted.

A well-known method may be sufficient as the method of forming the colored resin layer 11' on the galvanizing layer 10'. For example, a paint whose viscosity is adjusted is applied on the galvanized layer 10' by a spraying method, a roll coater method, a curtain coater method, or a immersion pulling method. Then, natural drying or baking drying is performed with respect to the coating material on the galvanizing layer 10', and the colored resin layer 11' is formed. Drying temperature, drying time, baking temperature, and baking time can be adjusted suitably. The three-dimensional average roughness Saave', the minimum thickness DKmin' of the colored resin layer 11', by adjusting the shear viscosity of the coating material used for formation of the colored resin layer 11', the application amount on the galvanizing layer 10', etc. , the maximum thickness DKmax' can be adjusted. Moreover, by adjusting content of the coloring agent in a coating material, coloring agent content CK' in colored resin layer 11' can be adjusted.

According to the above manufacturing process, the plated steel sheet 1' of 2nd Embodiment can be manufactured. In addition, the plated steel sheet 1' of the second embodiment is not limited to the above manufacturing method, and as long as the plated steel sheet 1' having the above-described configuration can be manufactured, it can be manufactured by a manufacturing method other than the above manufacturing method. You may manufacture the plated steel sheet 1' of 2nd Embodiment. However, the said manufacturing method is suitable for manufacture of the plated steel plate 1' of 2nd Embodiment.

As mentioned above, although each of 1st Embodiment and 2nd Embodiment of this invention was demonstrated, it is also possible to combine the structure of these 1st Embodiment, and the structure of 2nd Embodiment suitably. The specific aspect illustrated in the description of the first embodiment may be applied to the plated steel sheet of the second embodiment, and vice versa.

In the plated steel sheet 1 of 1st Embodiment of this invention, and the plated steel sheet 1' of 2nd Embodiment, it is good also considering a colored resin layer as a laminated resin layer. Thereby, the visibility of the surface of a galvanizing layer can be improved further and fluctuation|variation in color tone can be suppressed. This is because the dispersion|variation in the local thickness of a colored resin layer can be suppressed by making a colored resin layer into a laminated resin layer. The variation in thickness is correlated with variation in the concentration of the colorant (pigment). Therefore, by suppressing the fluctuation|variation in thickness, the fluctuation|variation of a coloring agent density|concentration is suppressed, and the fluctuation|variation of color tone can be suppressed.

In addition, the number of each colored may be the sum of the product of the content of the coloring CK _N and _N DK thickness of the resin layer to less than 15.0 area% and ㎛. That is, the content of CK _N and _N DK thickness of the coloring of the colored resin layer, it may meet the expression.

Σ[k=1→n] (CK _k × DK _k )≤15.0

Thereby, the laminated resin layer can be colored to such an extent that the surface of a galvanizing layer can be visually recognized. And the visibility of the surface of a galvanizing layer can be improved further, and color tone fluctuation|variation, such as color nonuniformity and color fluctuation|variation, can fully be suppressed. _{A preferable upper limit of the sum of the product of the content CK N} of the colorant in each colored resin layer and the thickness DK _N is 12.0 area%·탆, 10.0 area%·탆, or 8.0 area%·탆.

In addition, the colorant content (area %) of the _{deepest color resin layer is defined as "C 1ST} ", the thickness (㎛) of the deepest color resin layer _{is defined as "D 1ST} ", and the colorant of the second deep color colored resin layer When the content (area%) of "C _2ND " is defined and the thickness (㎛) of the second hyperchromic colored resin layer _{is defined as "D 2ND} ", the laminated resin layer may satisfy the following formula (4) .

1.00<(C _1ST ×D _1ST )/(C _2ND ×D _2ND )≤4.00 (4)

That is, the ratio of the color density index I _1ST (=C _1ST × D _1ST ) of the deepest color colored resin layer to the color density index I _2ND (=C _2ND × D _2ND ) of the second hyperchromic colored resin layer is 4.00 or less can be done with Hereinafter, (C _1ST × D _1ST )/(C _2ND × D _2ND ) is referred to as “color density ratio RF”.

When the color density ratio RF is 4.00 or less, the color density of the most hyperchromic colored resin layer and the color density of the second hyperchromic colored resin layer do not differ so much. Therefore, when the resin layer is colored to such a degree that the surface of the galvanized layer is visually recognizable, the surface of the galvanized layer is visually recognizable, and color variations such as color unevenness and color variation can be sufficiently suppressed.

The preferable upper limit of the color intensity ratio RF is 3.80, more preferably 3.50, still more preferably 3.00, still more preferably 2.50, still more preferably 2.00. The color intensity ratio RF is preferably closer to 1.00. Therefore, the lower limit of the color intensity ratio RF is more than 1.00. In addition, when each of several colored resin layer LK contains several types of coloring agents from which a hue differs, the said RF should just be 4.00 or less for every colorant of the same hue.

Although the thickness (total thickness) of a laminated resin layer is not specifically limited, It is good also as 10.0 micrometers or less, for example. If the thickness of the laminated resin layer is 10.0 µm or less, on the premise that the above requirements are satisfied, even if the laminated resin layer is colored to such a degree that the surface of the galvanized layer can be visually recognized, the surface of the galvanized layer can be visually recognized, and color unevenness It is possible to sufficiently suppress color tone fluctuations such as color fluctuations, and the metallic feeling is also sufficiently increased. The more preferable upper limit of the thickness of a laminated resin layer is 9.0 micrometers, More preferably, it is 8.0 micrometers.

In addition, the minimum of a preferable laminated resin layer is 0.5 micrometer. Corrosion resistance becomes still higher that a laminated resin layer is 0.5 micrometer or more. The minimum with more preferable laminated resin layer is 0.7 micrometer, More preferably, it is 1.0 micrometer, More preferably, it is 2.0 micrometer, More preferably, it is 3.0 micrometer.

As for the laminated resin layer 30, the one or several transparent resin layer which does not contain a coloring agent may be laminated|stacked between several colored resin layers. A "transparent resin layer" does not contain a coloring agent, but consists of resin which has translucency. The translucent resin is a design galvanized steel sheet comprising a colored resin layer containing a colorant and a resin, and a laminated resin layer containing a transparent resin layer in an environment equivalent to sunlight in the morning on a clear sky (illuminance about 65000 lux) When placed, it means that the surface of the base steel sheet can be visually recognized. The order of lamination|stacking of a colored resin layer and a transparent resin layer is not specifically limited. In the laminated resin layer, a plurality of transparent resin layers may be continuously laminated.

Example

(Example 1)

Hereinafter, the effect of one aspect of the present invention will be described in more detail by way of Examples. The conditions in the following examples are examples of conditions employed in order to confirm the feasibility and effect of the plated steel sheet 1 of the first embodiment of the present invention. Accordingly, the present invention is not limited to this one condition example. Various conditions can be employ|adopted for this invention, as long as the objective of this invention is achieved without deviating from the summary of this invention.

Galvanized steel sheets of the test numbers shown in Table 1 were prepared. The base steel sheet of each galvanized steel sheet was SPCC prescribed in JIS G 3141 (2017), and the thickness was 0.6 mm.

[Table 1]

The base material surface texture forming process was performed for each base steel sheet to form various types of base material textures (hairline or less) on the base material surface. In addition, in Test Nos. 1, 18, 23, and 28, no texture was formed on the surface of the base material. In the column "base material texture" of Table 1, the presence or absence and type of the base material surface texture formation process in each test number were shown.

For each base steel sheet, plating pretreatment was performed. Specifically, for each steel material, _{using a Na 4} SiO ₄ treatment solution having a concentration of 30 g/L, the treatment solution temperature was 60° C., the current density was 20 A/dm 2 , and the treatment time was 10 seconds, followed by electrolytic degreasing and washing with water. . _{The steel materials after electrolytic degreasing were immersed in H 2} SO ₄ aqueous solution having a concentration of 50 g/L at 60° C. for 10 seconds, followed by washing with water.

The following plating process was performed with respect to the steel plate of each test number after plating pretreatment, and the electrogalvanizing layer was formed. Specifically, in Test Nos. 1 to 17, the electrogalvanized layer was formed by electroplating. Specifically, a plating bath containing 1.0 mol/L of Zn sulfate heptahydrate and 50 g/L of anhydrous sodium sulfate and pH adjusted to 2.0 was prepared. In the electroplating, the bath temperature was 50° C. and the current density was 50 A/dm 2 . The plating time was adjusted so that the adhesion amount might be about 30.0 g/m<2>. According to the above process, the electrogalvanized layer was formed (indicated as "EG" in the column of "plating type" in Table 1).

In Test Nos. 18 to 22, the electrogalvanized layer containing Ni was formed as the galvanized layer. Specifically, a plating bath containing 1.2 mol/L of Zn sulfate heptahydrate and Ni sulfate hexahydrate in total, and 50 g/L of anhydrous sodium sulfate, and pH adjusted to 2.0 was prepared. In the electroplating, the bath temperature was 50° C. and the current density was 50 A/dm 2 . The plating time was adjusted so that the adhesion amount might be about 30.0 g/m<2>. By the above process, an electrogalvanized layer containing 12% Ni by mass % and the balance being Zn and impurities was formed (indicated as "Zn-12% Ni" in the "Plating type" column in Table 1).

In Test Nos. 23 to 27, the electrogalvanized layer containing Fe was formed as the galvanized layer. Specifically, a plating bath containing 1.2 mol/L of Zn sulfate heptahydrate and Fe(II) sulfate heptahydrate in total, and 50 g/L of anhydrous sodium sulfate, and pH adjusted to 2.0 was prepared. In the electroplating, the bath temperature was 50° C. and the current density was 50 A/dm 2 . The plating time was adjusted so that the adhesion amount might be about 30.0 g/m<2>. By the above process, an electrogalvanized layer containing 14% Fe by mass % and the balance consisting of Zn and impurities was formed (indicated as "Zn-14% Fe" in the "Plating species" column in Table 1).

In Test Nos. 28 to 32, the electrogalvanized layer containing Co was formed as the galvanized layer. Specifically, a plating bath containing 1.2 mol/L of Zn sulfate heptahydrate and Co sulfate hexahydrate in total, and 50 g/L of anhydrous sodium sulfate, and pH adjusted to 2.0 was prepared. In the electroplating, the bath temperature was 50° C. and the current density was 50 A/dm 2 . The plating time was adjusted so that the adhesion amount might be about 30.0 g/m<2>. By the above process, an electrogalvanized layer containing 2% Co by mass % and the balance consisting of Zn and impurities was formed (indicated as "Zn-2% Co" in the "Plating species" column in Table 1).

In the electroplating process of each test number, the plating liquid was made to flow so that a relative flow rate might be set to 1 m/sec. In addition, the composition of the obtained electrogalvanizing layer was measured by the following method. The steel sheet on which the electroplating layer was formed was immersed in 10 mass % hydrochloric acid containing an inhibitor (NO.700AS by Asahi Chemical), and the electrogalvanized layer was melt|dissolved and peeled. Then, ICP analysis was performed on the solution in which the electrogalvanized layer was dissolved, and the composition of the electrogalvanized layer was confirmed.

After forming the galvanized layer, in Test Nos. 2 to 4, 6 to 17, 19 to 22, 24 to 27, and 29 to 32, a galvanized surface texture forming step is performed, and a polishing step is further performed to obtain a galvanized layer Calculation of the convex part of the was ground and polished. In the galvanized surface texture forming step and the polishing step, abrasive belts of various grain sizes were pressed against the top of the convex portions of the galvanized layer, and grinding and polishing were performed by changing the reduction force and the number of polishings. In the galvanizing surface texture forming process, an abrasive belt having a coarser grain size than in the grinding process was used. In addition, in Test Nos. 1, 5, 18, 23, and 28, the galvanizing surface texture forming process and the grinding|polishing process were not implemented. In the column "Plating texture" of Table 1, the presence or absence and type of the zinc plating surface texture formation process in each test number were shown.

Note that even a plated steel sheet obtained without going through the galvanizing surface texture forming step has a plating texture as long as the base material texture is formed through the base material surface texture forming step. This is because, when a base steel sheet having a base material texture is galvanized to form a galvanized layer, a plating texture conforming to the base material texture is formed on the surface of the galvanized layer. For example, the plated steel sheet of Test No. 5 was manufactured without going through a galvanized surface texture forming process. Therefore, regarding Test No. 5, "None" was described in the column "Plating Texture" of Table 1. However, since the plated steel sheet of Test No. 5 was manufactured through a base material surface texture forming process, it had a plating texture.

For galvanized steel sheets with hairline (Test Nos. 2 to 17, 19 to 22, 24 to 17, 29 to 32) and without hairline (Test Nos. 1, 18, 23, 28), A colored resin layer was formed. Among the colored resin layers, paints having various concentrations and viscosities in which a urethane-based resin (manufactured by ADEKA, Ltd., HUX-232) were dispersed in water as an organic resin were prepared. Pigments (carbon black) of various concentrations were added to the paint. As the carbon black, trade name #850 manufactured by Mitsubishi Chemical Corporation was used.

The paint was scooped up with a roll and applied to the surface of the galvanized layer of the galvanized steel sheet of each test number. Baking-drying was performed with respect to the coating material after application|coating. Specifically, a galvanized steel sheet coated with a paint was charged into a furnace maintained at 250°C. The galvanized steel sheet was held in the furnace for 1 to 5 minutes until the reached temperature of the galvanized steel sheet reached 210°C. After holding, the galvanized steel sheet was taken out from the furnace and cooled.

The viscosity of the said coating material was adjusted using the viscosity modifier (made by Big Chemie, brand name: BYK-425). Specifically, at a shear rate of 0.1 (1/sec), the paint viscosity becomes 10 (Pa·s) or more, and at a shear rate of 1000 (1/sec), the paint viscosity becomes 0.01 (Pa·s) or less. The viscosity was adjusted. By the above process, the colored resin layer was formed on the galvanizing layer of each test number.

By the above manufacturing method, the galvanized steel sheet of each test number was manufactured. In Test No. 18, 0.5 µm of a pigment-free urethane-based resin (made by ADEKA, HUX-232) was applied between the colored resin layer and the galvanized layer. Then, the colored resin layer was formed.

[Evaluation Test]

[Measurement test of three-dimensional average roughness Sas at the bottom of the concave and normal three-dimensional roughness Sah at the convex part]

The maximum three-dimensional average roughness of the texture (hairline) of the surface of the galvanized layer of the galvanized steel sheet of each test number was measured by the following method. First, the colored resin layer of the galvanized steel sheet was removed using a solvent that does not invade the galvanized layer (trade name: Neoliver S-701 manufactured by Sansai Kaco Co., Ltd.). Among the surfaces of the galvanized layer, one arbitrary 1000 µm length range in the second direction orthogonal to the extending direction (first direction) of the texture (hairline) was selected. For the selected 1000 μm length range, the roughness profile of the texture was measured. The roughness profile was measured with a three-dimensional surface roughness measuring device (Surfcom 1500DX3 manufactured by Tokyo Seimitsu).

Attention was paid to each recess 10RE in the measured roughness profile. In each recessed part 10RE, the position with the lowest height was defined as the recessed part bottom point PRE. Among the plurality of recess bottom PREs in the roughness profile in the 1000 μm length range, from the lowest recess bottom PRE1, 10 recess bottom points PRE1, PRE2, ... , PRE10 was specified.

As shown in Fig. 6A, the surface of the galvanized layer was viewed in a plan view, and the bottom region of the minute recesses of 1 μm × 1 μm centered on the defined bottom points PREk of each recess (k is 1 to 10) was specified. . For each of the 10 specified micro-recess bottom regions, the three-dimensional average roughness Sa was measured. The three-dimensional average roughness Sa is an arithmetic mean roughness prescribed in ISO 25178, in which Ra (arithmetic mean roughness of a line) prescribed in JIS B 0601 (2013) is extended to a surface. The arithmetic mean value of the measured three-dimensional average roughness Sa was defined as the three-dimensional average roughness Sas (μm) of the bottom of the concave portion.

Similarly, attention was paid to each convex portion 10CO in the measured roughness profile. In each convex part 10CO, the position with the highest height was defined as the convex part apex PCO. Among the plurality of convex apex PCOs in the roughness profile in the 1000 µm length range, from the highest convex apex PCO1, 10 convex vertices PCO1, PCO2, ... , PCO10 was specified.

As shown in Fig. 6B, when the surface of the galvanized layer was viewed in a plan view, a 1 µm x 1 µm micro-convex apex region was specified centered on the defined convex apex PCok (k is 1 to 10). . Three-dimensional average roughness Sa was measured in each of the 10 specified micro-convex part normal regions. The three-dimensional average roughness Sa is an arithmetic mean roughness prescribed in ISO 25178, in which Ra (arithmetic mean roughness of a line) prescribed in JIS B 0601 (2013) is extended to a surface. The arithmetic mean value of the ten measured three-dimensional average roughness Sa was defined as the convex part normal three-dimensional average roughness Sah (micrometer).

[DKmin, DKmax measurement test]

The thickness (DKmin, DKmax) of the colored resin layer of the galvanized steel sheet of each test number was measured by the following method. In the galvanized steel sheet of each test number, the sample which has on the surface the cross section orthogonal to the 1st direction of a texture (hairline) was taken. Among the samples, an observation cross section with a length of 100 µm in a direction orthogonal to the extension direction of the texture (hairline) was observed with a reflection electron image (BSE) at a magnification of 2000 using a scanning electron microscope (SEM). In the observation cross section, the thickness of the colored resin layer was measured at a pitch of 0.5 µm in the direction WD. Among the measured thicknesses, the minimum thickness was defined as the minimum thickness DKmin (㎛). Among the measured thicknesses, the maximum thickness was defined as the maximum thickness DKmax (μm).

[Colorant content CK measurement test]

Colorant content (area %) in the colored resin layer of the galvanized steel sheet of each test number was calculated|required by the following method. A sample having a cross-section orthogonal to the first direction of the texture (hairline) on the surface was taken. The sample WHEREIN: The cross section orthogonal to the 1st direction of the texture (hairline) was made into the observation surface. From the sample, using FIB, a thin film sample in which the colored resin layer and the galvanized layer of the observation surface can be observed was produced. The film thickness of the thin film sample was 150 nm. Among the observation surfaces of the produced thin film sample, the length in the direction perpendicular to the thickness direction of the colored resin layer (ie, the second direction WD) is 3 µm, and the thickness direction of the colored resin layer (ie, the third direction TD) is WHEREIN: The visual field which has the length including the whole colored resin layer was observed using TEM. TEM observation WHEREIN: The resin and the pigment in the colored resin layer were distinguishable by contrast. ^{The total area A1 (micrometer 2} ) of several pigment in the colored resin layer in an observation cross section was calculated|required. ^{Moreover, the area (micrometer 2} ) of the colored resin layer in an observation cross section was calculated|required. Based on the calculated|required total area A1 and area A0, the coloring agent content (area %) in the colored resin layer 11 was calculated|required with the following formula.

CK=A1/A0×100

[Test for roughness Ra (CC) and Ra (CL) measurement of colored resin layer]

Roughness Ra (CC) and Ra (CL) in the colored resin layer of the galvanized steel sheet of each test number were calculated|required by the following method.

Surface roughness Ra (CL) was measured by the measuring method of the arithmetic mean roughness prescribed|regulated to JISB0601 (2013). The surface of the colored resin layer WHEREIN: 10 arbitrary places were made into the measurement location. In each measurement location, the arithmetic mean roughness Ra was measured in the evaluation length extended in the 1st direction of a texture (hairline). The evaluation length was set to 5 times the reference length (cut-off wavelength). The measurement of the arithmetic mean roughness Ra was performed using the three-dimensional surface roughness measuring machine (Surfcom 1500DX3 manufactured by Tokyo Seimitsu), and the measurement speed was 0.5 mm/sec. Among the 10 obtained arithmetic mean roughness Ra, 6 arithmetic mean roughness Ra, excluding the largest arithmetic mean roughness Ra, the second largest arithmetic mean roughness Ra, the smallest arithmetic mean roughness Ra, and the second smallest arithmetic mean roughness Ra, The arithmetic mean value was defined as surface roughness Ra(CL).

Similarly, surface roughness Ra (CC) was measured by the measuring method of the arithmetic mean roughness prescribed|regulated to JISB0601 (2013). The surface of the colored resin layer WHEREIN: 10 arbitrary places were made into the measurement location. In each measurement location, the arithmetic mean roughness Ra was measured in the evaluation length extended in the 2nd direction of a texture (hairline). The evaluation length was set to 5 times the reference length (cut-off wavelength). The measurement of the arithmetic mean roughness Ra was performed using the three-dimensional surface roughness measuring machine mentioned above, and the measurement speed was 0.5 mm/sec. Among the 10 obtained arithmetic mean roughness Ra, 6 arithmetic mean roughness Ra, excluding the largest arithmetic mean roughness Ra, the second largest arithmetic mean roughness Ra, the smallest arithmetic mean roughness Ra, and the second smallest arithmetic mean roughness Ra, The arithmetic mean value was defined as surface roughness Ra (CC).

[Surface roughness Ra (MC) measurement test of galvanized layer]

The surface roughness Ra (MC) of the galvanized layer of the galvanized steel sheet of each test number was calculated|required by the following method.

Surface roughness Ra (MC) was measured by the measuring method of the arithmetic mean roughness prescribed|regulated to JISB0601 (2013). The colored resin layer of the galvanized steel sheet was removed using the solvent which does not invade the zinc plating layer (Sansai Kaco Co., Ltd. product name: Neoliver S-701). The texture (hairline) of the galvanized layer after removing the colored resin layer WHEREIN: Ten arbitrary places were made into the measurement location. In each measurement location, the arithmetic mean roughness Ra was measured in the evaluation length extended in the 2nd direction. The evaluation length was set to 5 times the reference length (cut-off wavelength). The measurement of the arithmetic mean roughness Ra was performed using the three-dimensional surface roughness measuring machine mentioned above, and the measurement speed was 0.5 mm/sec. Among the 10 obtained arithmetic mean roughness Ra, 6 arithmetic mean roughness Ra, excluding the largest arithmetic mean roughness Ra, the second largest arithmetic mean roughness Ra, the smallest arithmetic mean roughness Ra, and the second smallest arithmetic mean roughness Ra, An arithmetic mean value was defined as surface roughness Ra(MC) (micrometer).

[Measurement test of iron exposure rate]

The iron exposure rate of the galvanized steel sheet of each test number was measured by the following method. A galvanized steel sheet from which the colored resin layer was removed was prepared. On the surface of the galvanized layer, five arbitrary rectangular areas of 1 mm x 1 mm were selected. EPMA analysis was performed on selected rectangular areas. By image analysis, a region in which Zn was not detected (Zn undetected region) in each rectangular region was specified. A region in which the detection intensity of Zn was 1/16 or less when a standard sample (pure Zn) was measured was recognized as a Zn undetected region. The ratio (area %) of the total area of the Zn undetected region among the five rectangular regions to the total area of the five rectangular regions was defined as the iron exposure rate (area %).

[Texture Visibility Test]

The galvanized steel sheet of each test number was put in the environment of sunlight equivalent (illuminance about 65000 lux) in the morning of a clear sky. Then, by changing the angle of the light source, the steel plate, and the line of sight in various ways, it was checked whether the texture could be visually recognized. If the texture could be visually recognized from all angles from 5° to 80° with respect to the vertical direction of the surface of the steel sheet, it was very good and evaluated as a pass (evaluation "A" in Table 1). In addition, if a texture could be visually recognized at some angles from 5 degrees to 80 degrees with respect to the vertical direction of the steel plate surface, it evaluated as pass (evaluation "B" in Table 1). On the other hand, when the texture could not be visually recognized at all, it was evaluated as disqualified (evaluation "C" in Table 1).

[Brightness measurement test]

With respect to the galvanized steel sheet of each test number, the brightness L* value was measured as a reference value by the following method. For the measurement, a colorimeter (trade name: CM-2600d) manufactured by Konica Minolta Corporation was used. In the measurement, the CIE standard light source D65 was used as the light source, and the L* value was calculated for the CIELAB display color by the SCI method as a viewing angle of 10°.

Here, the CIE standard light source D65 is prescribed in JIS Z 8720 (2000) "Illuminite for color measurement (standard light) and standard light source", and ISO 10526 (2007) also has the same rule. CIE is an abbreviation of Commission Internationale de I'Eclairage, which stands for International Commission on Illumination. The CIE standard light source D65 is used when displaying the color of an object illuminated by the main light. Regarding the viewing angle of 10°, JIS Z 8723 (2009) "visual comparison method of surface color" is prescribed, and ISO/DIS 3668 also has the same rule.

The SCI method is referred to as a method including specular light, and refers to a method of measuring color without removing specular light. The brightness measurement method according to the SCI method is prescribed in JIS Z 8722 (2009). In the SCI method, the actual object color is obtained because the measurement is performed without removing the specular reflected light.

The CIELAB display color is a uniform color space recommended in 1976 and stipulated in JIS Z 8781 (2013) in order to measure a color difference due to a difference between perception and a measurement value by an apparatus. The three coordinates of CIELAB are represented by L* value, a* value, and b* value. L* value represents lightness and is represented by 0-100. When the L* value is 0, it means black, and when the L* value is 100, it means the diffuse color of white.

[Corrosion resistance evaluation test]

The galvanized steel sheet of each test number was evaluated for corrosion resistance (long-term corrosion resistance) by the following method. A 75 mm x 100 mm test piece was taken from the galvanized steel sheet of each test number. The end face and the back face of the test piece were protected with a tape seal. Then, the salt spray test of 5% NaCl maintained at 35 degreeC was implemented based on JIS Z 2371 (2015). The test was performed for 240 hours, and the rust generation rate after the test was calculated|required. When the rust occurrence rate was 0%, it was determined as corrosion resistance evaluation A, and when the rust occurrence rate was more than 0% and 5% or less, it was determined as corrosion resistance evaluation B, and corrosion resistance was evaluated as good. In addition, when the rust occurrence rate was more than 5 %, it determined with corrosion-resistance evaluation C. However, the main subject of the present invention is to improve texture visibility. Therefore, even if corrosion resistance evaluation was C, the example of the test number which passed the texture visibility test was judged to be the example of this invention.

[Adhesiveness test]

The following method evaluated the adhesiveness of the colored resin layer about the galvanized steel sheet of each test number. A test piece having a width of 50 mm and a length of 50 mm was produced from the galvanized steel sheet of each test number. 180 degree bending was performed with respect to the obtained test piece. After bending, a tape peeling test was performed on the outside of the bent portion. The external appearance of the tape peeling part was observed with a magnifying glass having a magnification of 10 times. And the following evaluation criteria evaluated. Bending was performed in an atmosphere of 20°C with a 0.6 mm spacer interposed therebetween. The obtained results are shown in Table 1 below.

(Evaluation standard)

A: Peeling is not recognized by a coating film

B: Peeling is recognized by the coating film of a part of pole (peeling area ≤ 2%)

C: Peeling is recognized by some coating films (2% < peeling area ≤ 20%)

D: Peeling is recognized in the coating film (peeling area > 20%)

When evaluation was A-C, it was judged that it was excellent in adhesiveness. When evaluation was D, it was judged that adhesiveness was low. However, the main subject of the present invention is to improve texture visibility. Therefore, even if adhesiveness was determined as D, the example of the test number which passed the texture visibility test was judged to be the example of this invention.

[Metallic feeling evaluation test]

The metallic feeling of the galvanized steel sheet of each test number was measured by the following method. The plated steel sheet 1 of each test number is polished at any point, glossiness G60 (Gl) in the direction parallel to the texture (hairline) and glossiness G60 (Gc) in the direction perpendicular to the texture (hairline) It was measured with a gauge. As the gloss meter, a gloss meter (trade name: UGV-6P) manufactured by Suga Chemical Co., Ltd. was used. Based on the obtained glossiness Gl and glossiness Gc, Gc/Gl was calculated|required. Texture was visually recognizable, and it was judged that the outstanding metallic feeling was obtained as Gc/Gl ≤ 0.70 (evaluation "A" in Table 1). Texture was visually recognizable, and it was judged that the favorable metallic feeling was obtained if 0.70<Gc/Gl<=0.90 (evaluation "B" in Table 1). Even if the texture could not be visually recognized or the texture could be visually recognized, it was judged that the metallic feeling was not obtained when 0.90 < Gc/Gl (evaluation "C" in Table 1). However, the main subject of the present invention is to improve texture visibility. Therefore, even if the metallic feeling was C determination, the example of the test number which passed the texture visibility test was judged to be the example of this invention.

[Evaluation results]

Referring to Table 1, in Test Nos. 4, 5, 8 to 17, 20 to 22, 25 to 27, and 30 to 32, the concave bottom three-dimensional average roughness Sas was greater than 200 nm and less than or equal to 2000 nm. Moreover, in these test numbers, F1 was 15.0 or less, and F2 was larger than 1.0. Therefore, in these test numbers, even if the brightness was 50 or less, in the texture visibility test, the texture was visually recognizable (evaluation A or B). Moreover, in these test numbers, it was excellent also in adhesiveness. Test No. 2 was outside the range of 1st Embodiment, and although corrosion resistance was slightly low compared with other invention examples, it was in the range of 2nd Embodiment, a metallic feeling was high, and it had favorable aesthetics.

Moreover, in the test numbers except test number 5 among test numbers 4, 5, 8-17, 20-22, 25-27, 30-32, the convex part normal three-dimensional average roughness Sah was more than 5 nm and 200 nm or less . Therefore, in the test numbers 4, 10-17, 20-22, 25-27, 30-32, compared with the test number 5, even if the brightness was low, the texture was visually recognizable.

In addition, among test numbers 4, 5, 8-17, 20-22, 25-27, and 30-32, in the test numbers other than test numbers 4 and 10, the iron exposure rate was less than 5 %. Therefore, in the test numbers 5, 8, 9, 11-17, 20-22, 35-27, 30-32, in the corrosion resistance evaluation test, the rust occurrence rate was less than 5 %, and sufficient corrosion resistance was obtained (Evaluation A or B).

On the other hand, in Test No. 1, the plating texture was not formed. Therefore, the maximum thickness DKmax of the colored resin layer, the minimum thickness DKmin, and the coloring agent content CK did not satisfy Formula (2). In addition, the surface roughness Ra(CL) and the surface roughness Ra(CC) did not satisfy the formula (3). Therefore, in the texture visibility test, the texture could not be visually recognized (evaluation C).

In the test numbers 3 and 6, the minimum thickness DKmin of the colored resin layer and the coloring agent content CK in the colored resin layer did not satisfy Formula (1). Therefore, in the texture visibility test, the texture could not be visually recognized (evaluation C).

In the test number 7, the maximum thickness DKmax of the colored resin layer, the minimum thickness DKmin, and the coloring agent content CK did not satisfy Formula (2). Therefore, in the texture visibility test, the texture could not be visually recognized (evaluation C).

In Test No. 18, no plating texture was formed. Therefore, the maximum thickness DKmax of the colored resin layer, the minimum thickness DKmin, and the coloring agent content CK did not satisfy Formula (2). Therefore, in the texture visibility test, the texture could not be visually recognized (evaluation C).

In test number 19, the minimum thickness DKmin of the colored resin layer and the coloring agent content CK in the colored resin layer did not satisfy Formula (1). Therefore, in the texture visibility test, the texture could not be visually recognized (evaluation C).

In Test No. 23, no plating texture was formed. Therefore, the maximum thickness DKmax of the colored resin layer, the minimum thickness DKmin, and the coloring agent content CK did not satisfy Formula (2). Therefore, in the texture visibility test, the texture could not be visually recognized (evaluation C).

In test number 24, the minimum thickness DKmin of the colored resin layer and the coloring agent content CK in the colored resin layer did not satisfy Formula (1). Therefore, in the texture visibility test, the texture could not be visually recognized (evaluation C).

In Test No. 28, no plating texture was formed. Therefore, the maximum thickness DKmax of the colored resin layer, the minimum thickness DKmin, and the coloring agent content CK did not satisfy Formula (2). Therefore, in the texture visibility test, the texture could not be visually recognized (evaluation C).

In test number 29, the minimum thickness DKmin of the colored resin layer and the coloring agent content CK in the colored resin layer did not satisfy Formula (1). Therefore, in the texture visibility test, the texture could not be visually recognized (evaluation C).

In the above, the first embodiment of the present invention has been described. However, the above-mentioned embodiment is only an illustration for implementing this invention. Therefore, this invention is not limited to the above-mentioned embodiment, The above-mentioned embodiment can be suitably changed and implemented within the range which does not deviate from the meaning.

(Example 2)

Next, various examples manufactured in order to confirm the feasibility and effect of the plated steel sheet 1' of the second embodiment of the present invention will be described below.

Galvanized steel sheets of the test numbers shown in Table 2 were prepared. The steel material (steel sheet) of each galvanized steel sheet was SPCC prescribed|regulated to JIS G 3141 (2017), and the thickness was 0.6 mm.

[Table 2]

Plating pretreatment was performed on each steel material. Specifically, for each steel material, _{using a Na 4} SiO ₄ treatment solution having a concentration of 30 g/L, the treatment solution temperature was 60° C., the current density was 20 A/dm 2 , and the treatment time was 10 seconds, followed by electrolytic degreasing and washing with water. . _{The steel materials after electrolytic degreasing were immersed in H 2} SO ₄ aqueous solution having a concentration of 50 g/L at 60° C. for 10 seconds, followed by washing with water.

The following plating process was performed with respect to the steel of each test number after plating pre-processing, and the electrogalvanizing layer was formed. Specifically, in Test Nos. 1' to 16', the electrogalvanized layer was formed by electroplating. Specifically, a plating bath containing 1.0 mol/l of Zn sulfate heptahydrate and 50 g/L of anhydrous sodium sulfate and pH adjusted to 2.0 was prepared. In the electroplating, the bath temperature was 50° C. and the current density was 50 A/dm 2 . The plating time was adjusted so that the adhesion amount might be about 30.0 g/m<2>. According to the above process, the electrogalvanized layer was formed (indicated with "EG" in the column of "plating type" in Table 2).

In Test Nos. 17' to 20', an electrogalvanized layer containing Ni was formed as the galvanized layer. Specifically, a plating bath containing 1.2 mol/l of Zn sulfate heptahydrate and Ni sulfate hexahydrate in total, and 50 g/L of anhydrous sodium sulfate, and pH adjusted to 2.0 was prepared. In the electroplating, the bath temperature was 50° C. and the current density was 50 A/dm 2 . The plating time was adjusted so that the adhesion amount might be about 30.0 g/m<2>. Through the above steps, an electrogalvanized layer containing 12% Ni by mass% and the balance being Zn and impurities was formed (indicated as “Zn-12% Ni” in the “Plating type” column in Table 2).

In Test Nos. 21' to 24', the electrogalvanized layer containing Fe was formed as the galvanized layer. Specifically, a plating bath containing 1.2 mol/l of Zn sulfate heptahydrate and Fe(II) sulfate heptahydrate in total, and 50 g/L of anhydrous sodium sulfate, and pH adjusted to 2.0 was prepared. In the electroplating, the bath temperature was 50° C. and the current density was 50 A/dm 2 . The plating time was adjusted so that the adhesion amount might be about 30.0 g/m<2>. By the above steps, an electrogalvanized layer containing 14% Fe by mass% and the balance being Zn and impurities was formed (indicated as “Zn-14% Fe” in the “Plating species” column in Table 2).

In Test Nos. 25' to 28', as the galvanized layer, an electrogalvanized layer containing Co was formed. Specifically, a plating bath containing 1.2 mol/l of Zn sulfate heptahydrate and Co sulfate hexahydrate in total and 50 g/L of anhydrous sodium sulfate and pH adjusted to 2.0 was prepared. In the electroplating, the bath temperature was 50° C. and the current density was 50 A/dm 2 . The plating time was adjusted so that the adhesion amount might be about 30.0 g/m<2>. By the above process, an electrogalvanized layer containing 2% Co by mass % and the balance consisting of Zn and impurities was formed (indicated as "Zn-2% Co" in the "Plating type" column in Table 2).

In the electroplating process of each test number, the plating liquid was made to flow so that a relative flow rate might be set to 1 m/sec. In addition, the composition of the obtained electrogalvanizing layer was measured by the following method. The steel sheet on which the electroplating layer was formed was immersed in 10 mass % hydrochloric acid containing an inhibitor (NO.700AS manufactured by Asahi Chemical), and the electrogalvanized layer was dissolved and peeled off. Then, ICP analysis was performed on the solution in which the electrogalvanized layer was dissolved, and the composition of the electrogalvanized layer was confirmed.

After forming the galvanized layer, in Test Nos. 2' to 16', 18' to 20', 22' to 24', 26' to 28', texturing was performed with respect to the galvanized steel sheet along the rolling direction RD of the steel sheet. and a hairline was provided on the surface of the galvanized layer. Specifically, abrasive paper of various particle sizes was pressed against the surface of the galvanized layer, and the pressing force and number of polishing were changed to give various hairlines. In the column "texture" of Table 2, the presence or absence of texturing in each test number and the type were shown.

A galvanized steel sheet with a hairline formed (Test Nos. 2' to 16', 18' to 20', 22' to 24', 26' to 28') and a galvanized steel sheet without a hairline formed (Test No. 1', 17', 21' and 25'), a colored resin layer was formed. Among the colored resin layers, paints having various concentrations and viscosities in which a urethane-based resin (manufactured by ADEKA, Ltd., HUX-232) were dispersed in water as an organic resin were prepared. Colorants (carbon black) of various concentrations were added to the paint. As the carbon black, trade name #850 manufactured by Mitsubishi Chemical Corporation was used.

The paint was scooped up with a roll and applied to the surface of the galvanized layer of the galvanized steel sheet of each test number. Baking-drying was performed with respect to the coating material after application|coating. Specifically, a galvanized steel sheet coated with a paint was charged into a furnace maintained at 250°C. The galvanized steel sheet was held in the furnace for 1 to 5 minutes until the reached temperature of the galvanized steel sheet reached 210°C. After holding, the galvanized steel sheet was taken out from the furnace and cooled.

The viscosity of the said coating material was adjusted using the viscosity modifier (made by Big Chemie, brand name: BYK-425). Specifically, at a shear rate of 0.1 (1/sec), the paint viscosity becomes 10 (Pa·s) or more, and at a shear rate of 1000 (1/sec), the paint viscosity becomes 0.01 (Pa·s) or less. The viscosity was adjusted. By the above process, the colored resin layer was formed on the galvanizing layer of each test number.

By the above manufacturing method, the galvanized steel sheet of each test number was manufactured. In Test No. 16', 0.5 µm of a urethane-based resin (manufactured by ADEKA, Ltd., HUX-232) containing no colorant was applied between the colored resin layer and the galvanized layer. Then, the colored resin layer was formed.

[Evaluation Test]

[Three-dimensional average roughness Saave' measurement test]

The maximum three-dimensional average roughness of the texture (hairline) of the surface of the galvanized layer of the galvanized steel sheet of each test number was measured by the following method. First, the colored resin layer of the galvanized steel sheet was removed using a solvent that does not invade the galvanized layer (trade name: Neoliver S-701 manufactured by Sansai Kaco Co., Ltd.). Among the surfaces of the galvanized layer, one arbitrary 1000 µm length range in a direction orthogonal to the extension direction of the texture (hairline) was selected. For the selected 1000 μm length range, the roughness profile of the texture was measured. The roughness profile was measured with a three-dimensional surface roughness measuring device (Surfcom 1500DX3 manufactured by Tokyo Seimitsu). Among the positions on the measured roughness profile, 10 positions of the lowest height are specified in the order of the height, and the bottom points of the recesses PRE1', PRE2', ... , PRE10' was defined. Among the positions on the measured roughness profile, 10 positions of the highest height are specified in the order of height, and the convex vertices PCO1', PCO2', ... , PCO10' was defined.

As shown in Fig. 14A, when the surface of the galvanized layer was viewed in a plan view, a micro concave region of 1 μm × 1 μm centered on the defined bottom point PREk' (k is 1 to 10) of each recess was specified. . Similarly, as shown in Fig. 14B, when the surface of the galvanized layer is viewed in a plan view, a micro-convex region of 1 µm x 1 µm centered on each defined convex apex PCOk' (k is 1 to 10) is specified. did

The three-dimensional average roughness Sa' was measured in the 10 minute concave portion regions and the 10 minute convex portion regions specified by the above method. A laser microscope (trade name: VK-9710) manufactured by Keyence Corporation was used for the measurement of the three-dimensional average roughness Sa' of the minute concave portion region and the minute convex portion region. Further, in VK-9710, the display resolution in the height direction was 1 nm or more, and the display resolution in the width direction was 1 nm or more. The arithmetic mean value of the measured three-dimensional average roughness Sa' of 20 pieces (10 micro concave areas and 10 micro convex area areas) was defined as three-dimensional mean roughness Saave'.

[DKmin', DKmax' measurement test]

The thickness (DKmin', DKmax') of the colored resin layer of the galvanized steel sheet of each test number was measured by the following method. In the galvanized steel sheet of each test number, the sample which has on the surface the cross section orthogonal to the extending direction of a texture (hairline) was taken. Among the samples, an observation cross section with a length of 100 µm in a direction orthogonal to the extension direction of the texture (hairline) was observed with a reflection electron image (BSE) at a magnification of 2000 using a scanning electron microscope (SEM). In the observation cross section, the thickness of the colored resin layer was measured at a pitch of 0.5 µm in the direction WD'. Among the measured thicknesses, the minimum thickness was defined as the minimum thickness DKmin' (μm). Among the measured thicknesses, the maximum thickness was defined as the maximum thickness DKmax' (㎛).

[Colorant content CK' measurement test]

Colorant content (area %) in the colored resin layer of the galvanized steel sheet of each test number was calculated|required by the following method. A sample having a cross-section orthogonal to the extending direction of the texture (hairline) on the surface was taken. The sample WHEREIN: The cross section orthogonal to the extending direction of the texture (hairline) was made into the observation surface. From the sample, using FIB, a thin film sample in which the colored resin layer and the galvanized layer of the observation surface can be observed was produced. The film thickness of the thin film sample was 150 nm. Among the observation surfaces of the produced thin film sample, the length in the direction perpendicular to the thickness direction of the colored resin layer (ie, direction WD') is 3 µm, and in the thickness direction of the colored resin layer (ie, direction TD'), , a visual field having a length including the entire colored resin layer was observed using TEM. TEM observation WHEREIN: Resin in a colored resin layer and a coloring agent were distinguishable by contrast. ^{The total area A1' (micrometer 2} ) of several coloring agents in the colored resin layer in an observation cross section was calculated|required. ^{Moreover, area A0' (micrometer 2} ) of the colored resin layer in an observation cross section was calculated|required. Based on the calculated|required total area A1' and area A0', the coloring agent content (area %) in the colored resin layer 11 was calculated|required with the following formula.

CK'=A1'/A0'×100

[Roughness Ra(CC)' and Ra(CL)' measurement test of colored resin layer]

The roughness Ra(CC)' and Ra(CL)' in the colored resin layer of the galvanized steel sheet of each test number was calculated|required by the following method.

Surface roughness Ra(CL)' was measured by the measuring method of the arithmetic mean roughness prescribed|regulated to JISB0601 (2013). The surface of the colored resin layer WHEREIN: 10 arbitrary places were made into the measurement location. In each measurement location, the arithmetic mean roughness Ra was measured by the evaluation length extended in the extension direction of a texture (hairline). The evaluation length was set to 5 times the reference length (cut-off wavelength). The measurement of the arithmetic mean roughness Ra was performed using the three-dimensional surface roughness measuring machine (Surfcom 1500DX3 manufactured by Tokyo Seimitsu), and the measurement speed was 0.5 mm/sec. Among the 10 obtained arithmetic mean roughness Ra, 6 arithmetic mean roughness Ra, excluding the largest arithmetic mean roughness Ra, the second largest arithmetic mean roughness Ra, the smallest arithmetic mean roughness Ra, and the second smallest arithmetic mean roughness Ra, The arithmetic mean value was defined as surface roughness Ra(CL)'.

Similarly, surface roughness Ra(CC)' was measured by the measuring method of the arithmetic mean roughness prescribed|regulated to JISB0601 (2013). The surface of the colored resin layer WHEREIN: 10 arbitrary places were made into the measurement location. In each measurement location, the arithmetic mean roughness Ra was measured by the evaluation length extended in the direction orthogonal to the extension direction of the texture (hairline). The evaluation length was set to 5 times the reference length (cut-off wavelength). The measurement of the arithmetic mean roughness Ra was performed using the three-dimensional surface roughness measuring machine mentioned above, and the measurement speed was 0.5 mm/sec. Among the 10 obtained arithmetic mean roughness Ra, 6 arithmetic mean roughness Ra, excluding the largest arithmetic mean roughness Ra, the second largest arithmetic mean roughness Ra, the smallest arithmetic mean roughness Ra, and the second smallest arithmetic mean roughness Ra, The arithmetic mean value was defined as surface roughness Ra(CC)'.

[Surface roughness Ra(MC)' measurement test of galvanized layer]

The surface roughness Ra(MC)' of the galvanized layer of the galvanized steel sheet of each test number was calculated|required by the following method.

Surface roughness Ra(MC)' was measured by the measuring method of the arithmetic mean roughness prescribed|regulated to JISB0601 (2013). The colored resin layer of the galvanized steel sheet was removed using the solvent which does not invade the zinc plating layer (Sansai Kaco Co., Ltd. product name: Neoliver S-701). The texture (hairline) of the galvanized layer after removing the colored resin layer WHEREIN: Ten arbitrary places were made into the measurement location. In each measurement location, the arithmetic mean roughness Ra was measured by the evaluation length extended in the direction orthogonal to the extension direction of the texture (hairline). The evaluation length was set to 5 times the reference length (cut-off wavelength). The measurement of the arithmetic mean roughness Ra was performed using the three-dimensional surface roughness measuring machine mentioned above, and the measurement speed was 0.5 mm/sec. Among the 10 obtained arithmetic mean roughness Ra, 6 arithmetic mean roughness Ra, excluding the largest arithmetic mean roughness Ra, the second largest arithmetic mean roughness Ra, the smallest arithmetic mean roughness Ra, and the second smallest arithmetic mean roughness Ra, An arithmetic mean value was defined as surface roughness Ra(MC)' (micrometer).

[Measurement test of iron exposure rate]

The iron exposure rate of the galvanized steel sheet of each test number was measured by the following method. A galvanized steel sheet from which the colored resin layer was removed was prepared. On the surface of the galvanized layer, five arbitrary rectangular areas of 1 mm x 1 mm were selected. EPMA analysis was performed on selected rectangular areas. By image analysis, a region in which Zn was not detected (Zn undetected region) in each rectangular region was specified. A region in which the detection intensity of Zn was 1/16 or less when a standard sample (pure Zn) was measured was recognized as a Zn undetected region. The ratio (area %) of the total area of the Zn undetected region among the five rectangular regions to the total area of the five rectangular regions was defined as the iron exposure rate (area %).

[Texture Visibility Test]

The galvanized steel sheet of each test number was put in the environment of sunlight equivalent (illuminance about 65000 lux) in the morning of a clear sky. Then, by changing the angle of the light source, the steel plate, and the line of sight in various ways, it was checked whether the texture could be visually recognized. If the texture could be visually recognized from all angles from 5° to 80° with respect to the vertical direction of the surface of the steel sheet, it was very good and evaluated as a pass (evaluation "A" in Table 1). In addition, if a texture could be visually recognized at some angles from 5 degrees to 80 degrees with respect to the vertical direction of the steel plate surface, it evaluated as pass (evaluation "B" in Table 1). On the other hand, when the texture could not be visually recognized at all, it was evaluated as disqualified (evaluation "C" in Table 1).

[Brightness measurement test]

With respect to the galvanized steel sheet of each test number, the brightness L* value was measured as a reference value by the following method. For the measurement, a colorimeter (trade name: CM-2600d) manufactured by Konica Minolta Corporation was used. In the measurement, the CIE standard light source D65 was used as the light source, and the L* value was calculated for the CIELAB display color by the SCI method as a viewing angle of 10°.

Here, the CIE standard light source D65 is prescribed in JIS Z 8720 (2000) "Illuminite for color measurement (standard light) and standard light source", and ISO 10526 (2007) also has the same rule. CIE is an abbreviation of Commission Internationale de I'Eclairage, which stands for International Commission on Illumination. The CIE standard light source D65 is used when displaying the color of an object illuminated by the main light. Regarding the viewing angle of 10°, JIS Z 8723 (2009) "visual comparison method of surface color" is prescribed, and ISO/DIS 3668 also has the same rule.

The SCI method is referred to as a method including specular light, and refers to a method of measuring color without removing specular light. The brightness measurement method according to the SCI method is prescribed in JIS Z 8722 (2009). In the SCI method, the actual object color is obtained because the measurement is performed without removing the specular reflected light.

The CIELAB display color is a uniform color space recommended in 1976 and stipulated in JIS Z 8781 (2013) in order to measure a color difference due to a difference between perception and a measurement value by an apparatus. The three coordinates of CIELAB are represented by L* value, a* value, and b* value. L* value represents lightness and is represented by 0-100. When the L* value is 0, it means black, and when the L* value is 100, it means the diffuse color of white.

[Corrosion resistance evaluation test]

The galvanized steel sheet of each test number was evaluated for corrosion resistance (long-term corrosion resistance) by the following method. A 75 mm x 100 mm test piece was taken from the galvanized steel sheet of each test number. The end face and the back face of the test piece were protected with a tape seal. Then, the salt spray test of 5% NaCl maintained at 35 degreeC was implemented based on JIS Z 2371 (2015). The test was performed for 240 hours, and the rust generation rate after the test was calculated|required. When the rust occurrence rate was 0%, it was determined as corrosion resistance evaluation A, and when the rust occurrence rate was more than 0% and 5% or less, it was determined as corrosion resistance evaluation B, and corrosion resistance was evaluated as good. Moreover, when the rust occurrence rate was more than 5 %, it determined with corrosion-resistance evaluation C. However, the main subject of the present invention is to improve aesthetics such as texture visibility. Therefore, even if corrosion resistance evaluation was C, the example of the test number which passed the texture visibility test was judged to be the example of this invention.

[Metallic feeling evaluation test]

The metallic feeling of the galvanized steel sheet of each test number was measured by the following method. Glossiness G60 (Gl) in the direction parallel to the texture (hairline) and glossiness G60 (Gc) in the direction perpendicular to the texture (hairline) is polished at any point on the plated steel sheet 1 of each test number. It was measured with a gauge. As the gloss meter, a gloss meter (trade name: UGV-6P) manufactured by Suga Chemical Co., Ltd. was used. Based on the obtained glossiness Gl and glossiness Gc, Gc/Gl was calculated|required. Texture was visually recognizable, and it was judged that the outstanding metallic feeling was obtained as Gc/Gl ≤ 0.70 (evaluation "A" in Table 1). Texture was visually recognizable, and it was judged that the favorable metallic feeling was obtained if 0.70<Gc/Gl<=0.90 (evaluation "B" in Table 1). Even if the texture could not be visually recognized or the texture could be visually recognized, it was judged that the metallic feeling was not obtained when 0.90 < Gc/Gl (evaluation "C" in Table 1). However, the main subject of the present invention is to improve texture visibility. Therefore, even if the metallic feeling was C determination, the example of the test number which passed the texture visibility test was judged to be the example of this invention.

[Evaluation results]

Referring to Table 1, in Test Nos. 3', 6' to 16', 19', 20', 23', 24', 27' and 28', the three-dimensional average roughness Saave' is greater than 5 nm and less than or equal to 200 nm, The minimum thickness DKmin' of the colored resin layer and the coloring agent content CK' in the colored resin layer satisfied the formula (1'). Moreover, the maximum thickness DKmax' of the colored resin layer, the minimum thickness DKmin', and the coloring agent content CK' satisfied Formula (2'). Therefore, in the texture visibility test, the texture was visually recognizable (evaluation A or B).

In addition, among test numbers 3', 6' to 16', 19', 20', 23', 24', 27' and 28', in test numbers other than test number 3', the iron exposure rate was less than 5%. . Therefore, in the corrosion resistance evaluation test, the rust occurrence rate was less than 5 %, and sufficient corrosion resistance was obtained (evaluation A).

On the other hand, in the test number 1', the three-dimensional average roughness Saave' was too large. Moreover, the maximum thickness DKmax' of the colored resin layer, the minimum thickness DKmin', and the coloring agent content CK' did not satisfy Formula (2'). Therefore, in the texture visibility test, the texture could not be visually recognized (evaluation C).

In test number 2', the minimum thickness DKmin' of the colored resin layer and the coloring agent content CK' in the colored resin layer did not satisfy Formula (1'). Therefore, in the texture visibility test, the texture could not be visually recognized (evaluation C).

In test number 4', the minimum thickness DKmin' of the colored resin layer and the coloring agent content CK' in the colored resin layer did not satisfy Formula (1'). Therefore, in the texture visibility test, the texture could not be visually recognized (evaluation C).

In test number 5', the maximum thickness DKmax' of the colored resin layer, the minimum thickness DKmin', and the coloring agent content CK' did not satisfy Formula (2'). Therefore, in the texture visibility test, the texture could not be visually recognized (evaluation C).

In test number 17', the maximum thickness DKmax' of the colored resin layer, the minimum thickness DKmin', and the coloring agent content CK' did not satisfy Formula (2'). Therefore, in the texture visibility test, the texture could not be visually recognized (evaluation C).

In test number 18', the minimum thickness DKmin' of the colored resin layer and the coloring agent content CK' in the colored resin layer did not satisfy Formula (1'). Therefore, in the texture visibility test, the texture could not be visually recognized (evaluation C).

In test number 21', the maximum thickness DKmax' of the colored resin layer, the minimum thickness DKmin', and the coloring agent content CK' did not satisfy Formula (2'). Therefore, in the texture visibility test, the texture could not be visually recognized (evaluation C).

In test number 22', the minimum thickness DKmin' of the colored resin layer and the coloring agent content CK' in the colored resin layer did not satisfy Formula (1'). Therefore, in the texture visibility test, the texture could not be visually recognized (evaluation C).

In test number 25', the maximum thickness DKmax' of the colored resin layer, the minimum thickness DKmin', and the coloring agent content CK' did not satisfy Formula (2'). Therefore, in the texture visibility test, the texture could not be visually recognized (evaluation C).

In Test No. 26', the minimum thickness DKmin' of the colored resin layer and the coloring agent content CK' in the colored resin layer did not satisfy Formula (1'). Therefore, in the texture visibility test, the texture could not be visually recognized (evaluation C).

(Example 3)

In Examples 1 and 2, Test Nos. 12, 14 to 16, 20 to 21, 25 to 26, 30 to 31, 13' to 16', 19' to 20', 23' to 24', 27' to For 28', the same coating material was used, respectively, and it was divided into multiple times so that the total film thickness of the colored resin layer might become equal, and it was applied and it was set as the laminated resin layer. Those coated with the laminated resin were shown in Tables 3A and 3B by adding # to the original test number. In the laminated resin layer formation process, the manufacturing line containing the resin layer manufacturing apparatus which combined the colored resin application apparatus and the baking furnace was used. When laminating|stacking resin, manufacture of the resin layer using the resin layer manufacturing apparatus was performed multiple times. In Test Nos. 15# and 15'#, a clear resin layer not containing a colored pigment was laminated as the third layer, and the number of laminated resin layers was set to 3 (in the "Number of laminated layers" column of the "Lamination resin layer" column, " 3”). In Test Nos. 16# and 16'#, a clear resin layer not containing a colored pigment was laminated as the first layer, and the number of laminated resin layers was set to 3 (in the "Number of Laminations" column of the "Lamination Resin Layer" column, " 3”). In the other test numbers made into laminated resin, the number of colored resin layers in the laminated resin layer was set to 2 (referred to as "2" in the "number of laminated layers" column of the "laminated resin layer" column).

[Table 3A]

[Table 3B]

[Evaluation Test]

[Measurement of pigment content CK and thickness DK in each colored resin layer LK]

Pigment content CK and thickness DK of each colored resin layer of the laminated resin layer of each test number were measured by the following method. With reference to FIG. 15A, the design galvanized steel sheet was cut in the normal direction ND, and the cut surface CS containing the normal direction ND and the plate width direction TD was produced. Referring to FIG. 15B , in the cross section CS, the direction perpendicular to the normal direction ND (the plate width direction TD in this embodiment) was defined as the cross section width direction CD. The cross-section CS was divided into thirds by the cross-section CD in the cross-section. In each of the sections X1 to X3 divided into three equal parts, the sample SA which is the central position of the cross section CD in the cross section and contains the laminated resin layer 30 was sampled. Each of the three samples SA contained at least the laminated resin layer 30 and the galvanized layer 10 . The length of the cross-section width direction CD was 10 mm, and the length in the direction perpendicular to the normal direction ND and the cross-section width direction CD was 10 mm. With respect to the cut out sample SA, using a converging ion beam apparatus (FIB), a sample in which the laminated resin layer 30 and the galvanized layer 10 can be observed with a transmission electron microscope was produced.

A surface (observation surface) including the normal direction ND and the cross-sectional direction CD of the sample SA was observed with a reflection electron image (BSE) at a magnification of 2000 using a scanning electron microscope (SEM). In observation with a reflected electron image (BSE) of a scanning electron microscope (SEM), the base steel sheet, the galvanized layer, and the laminated resin layer were easily discriminable by contrast. In addition, since each colored resin layer used the resin layer from which a composition differs among the laminated resin layers, it was distinguishable by the contrast.

After each colored resin layer was identified, the pigment content CK (vol%) in each colored resin layer and the average thickness DK of each colored resin layer were calculated|required by the following method.

Transmission electron microscope observation WHEREIN: Total area A1 (micrometer ² ) of several pigment in the colored resin layer in an observation surface was calculated|required. ^{And the area A0 (micrometer 2} ) of the colored resin layer in the observation surface was calculated|required. Based on the calculated|required total area A1 and area A0, the pigment area ratio (area %) in the colored resin layer was calculated|required with the following formula.

Area ratio = A1/A0×100

In three samples, the area ratio of the pigment mentioned above was calculated|required, and the average of the three calculated|required area ratios was defined as pigment content CK (volume %) of the colored resin layer.

In addition, in each sample SA, thickness (micrometer) was measured at arbitrary 1 point of each colored resin layer. The average of the three thicknesses obtained in three samples SA was defined as thickness DK (micrometer) of the colored resin layer. The pigment content CK (area %) of each identified colored resin layer and thickness DK (micrometer) were calculated|required by the above method.

Based on the pigment content CK and thickness DK of each colored resin layer, the color density parameter|index IK used as the parameter|index of the color density of each colored resin layer was calculated|required with the following formula.

Color depth index IK=CK×DK

Moreover, the total value of the color density index of each colored resin layer was calculated|required. The calculated total value is shown in the "Total color density index" column in the "Laminated resin layer" column in Tables 3A and 3B.

[Measurement of thickness of laminated resin layer]

The thickness of the laminated resin layer 30 was measured by the following method. 15A and 15B , in the cut plane CS, the direction perpendicular to the normal direction ND was defined as the cut plane width direction CD (corresponding to the plate width direction TD in this embodiment). The cross-section CS was divided into thirds by the cross-section CD in the cross-section. In each of the sections X1 to X3 divided into three equal parts, the sample SA which is the central position of the cross section CD in the cross section and contains the laminated resin layer 30 was sampled. Each of the three samples SA contains at least the laminated resin layer 30 and the galvanized layer 10 . The length of the cross-section width direction CD was 10 mm. In the sample SA, the length in the direction perpendicular to the normal direction ND and the cross-section width direction CD was 10 mm. Gold deposition was performed on the cut surface CS of the cut sample SA. Thereafter, the sample SA was sandwiched between the backing plates and embedded in the resin, and polished to prepare an observation sample having the cut surface CS as the observation surface. The observation surface of the sample for observation was observed with the reflection electron image (BSE) of 2000 times using the scanning electron microscope (SEM). In observation with a reflection electron image (BSE) of a scanning electron microscope (SEM), the base steel sheet 100, the galvanized layer 10, and the laminated resin layer 30 were easily discriminable by contrast. In each sample SA, the thickness of the laminated resin layer 30 was measured at 100 micrometers pitch in the cross-section width direction CD at 10 points|pieces. The average value of the thickness (30 points|pieces in total) measured with three samples SA was defined as the thickness (micrometer) of the laminated resin layer 30. The measured thickness (micrometer) of the laminated resin layer is shown in "total film thickness" in the column of "laminated resin layer" in Table 1.

[Selection of the deepest color colored resin layer L _1ST and the second deep color colored resin layer L _2ND]

Among the colored resin layers, the colored resin layer having the largest color density index IK is _{defined as “the deepest color colored resin layer L 1ST} ”, and the colored resin layer having the highest color density index IK after the _{deepest color colored resin layer L 1ST;} That is, the color resin layer with the second highest color density index IK was defined as " _{2nd hyperchromic colored resin layer L 2ND".} In addition, it defines the maximum hyperchromic colored resin layer L _1ST of the pigment content (% by area) as the number of the definitions, the outermost hyperchromic colored "C _1ST" The thickness of the resin layer L _1ST (㎛) as "D _1ST". The second colored resin layer defined a hyperchromic L _2ND of the pigment content (% by area) of, and defined as "C _2ND" second hyperchromic be colored resin layer thickness of L _2ND (㎛) to "D _2ND". Choi deep color indicates the colored resin layer of the pigment content of C L _{1ST 1ST,} the thickness D _1ST, second pigment content of the colored resin layer can hyperchromic L _2ND C _2ND, thickness (㎛) D _2ND in Table 3A and Table 3B. In addition, in Table 3A and Table 3B, the "stacking position" in the column of "the most _{deep color colored resin layer L 1ST} " shows the number of layers of the most dark _{colored colored resin layer L 1ST.} For example, in test number 12#, _{it shows that the deepest color colored resin layer L1ST} was a 1st layer. Similarly, Table 3A and Table "stacking position" of the "second number of the colored resin layer hyperchromic _2ND L" in column 3B, the deep color and a second colored resin layer L can _2ND denotes yieotneunjireul claim place.Which floor. For example, in test number 12#, _{it shows that 2nd hyperchromic colored resin layer L2ND} was a 2nd layer.

In addition, the pigment content of the innermost deep color resin layer L _1ST colored C _1ST, the thickness D _1ST, second by using the deep color pigment content of the colored resin layer L _2ND C _2ND, thickness (㎛) D _2ND,, color concentration ratio by the following formula: RF was obtained.

Color intensity ratio RF=(C _1ST ×D _1ST )/(C _2ND ×D _2ND )

The obtained color density ratio RF is shown in the "Color density ratio RF" column of the "Laminated resin layer" column in Tables 3A and 3B.

[Galvanized layer surface visibility test]

Each sample was placed in an environment equivalent to sunlight in the morning of a clear sky (illuminance about 65000 lux), and it was determined whether or not the surface of the base steel sheet 100 could be visually recognized.

[Color unevenness evaluation test]

The following method evaluated the color nonuniformity of the designable galvanized steel sheet of each test number. Referring to Fig. 16, in an arbitrary measurement line segment OD1 of 1200 mm orthogonal to the extension direction HD of the hairline 23 of the design galvanized steel sheet 1 of each test number, 81 measurement points at a pitch of 15 mm (P1 to P81) were specified. At each of the measurement points P1 to P81, the L* value, a* value, and b* value in the L*a*b* color space were calculated. And the ΔL* value, Δa* value, and Δb* value at two adjacent measurement points Pi and Pi+1 (i is a natural number from 1 to 80) were calculated|required by the following formula.

ΔL*=L*i-L*i+1

Δa*=a*i-a*i+1

Δb*=b*i-b*i+1

Then, based on the obtained ΔL*, Δa*, and Δb*, the color difference ΔE* at two adjacent measurement points was calculated by the following equation.

ΔE*=((ΔL*) ² +(Δa*) ² +(Δb*) ² )

Based on the obtained 80 pieces of ?E*, color unevenness was evaluated as follows.

Rating G: More than 90% of the color difference ΔE* between two adjacent points is 2.0 or less

Rating P: 11% or more of the color difference ΔE* between two adjacent points exceeds 2.0

The obtained result is shown in the "color nonuniformity" column of the "evaluation test" column in Table 3A and Table 3B.

[Color variation evaluation test]

The color variation of the designable galvanized steel sheet of each test number was evaluated by the following method. With reference to FIG. 17, in the designable galvanized steel sheet 1 of each test number, each measurement position S1 - S20 of 20 points|pieces was specified with 50000 mm pitch (50 m pitch) in rolling direction RD. Then, at each of the measurement positions S1 to S20, the color difference ΔE* of the measurement points Q1 and Q2 at an interval of 1000 mm in the direction perpendicular to the extension direction HD of the hairline (direction OD) was calculated.

Based on the obtained 20 color differences ?E*, color variations were evaluated as follows.

G: All of 20 points are ΔE*≤3.0

ΔE*>3.0 out of 20 points of P: 1 or more

The obtained result is shown in the "color fluctuation" column of the "evaluation test" column in Table 1.

In addition, in the color non-uniformity evaluation test and color fluctuation evaluation test, the L* values, a* values and b* values of each of the measurement points P1 to P81, Q1 and Q2 were measured using a Konica Minolta Co., Ltd. colorimeter (trade name: CM). -2600d) was used. In the measurement, the L* value, a* value, and b* value were calculated|required with the CIELAB display color by the SCE method using the CIE standard light source D65 as a light source, making the viewing angle 10 degrees.

Here, the CIE standard light source D65 is prescribed in JIS Z 8720 (2000) "Illuminite for color measurement (standard light) and standard light source", and ISO 10526 (2007) also has the same rule. CIE is an abbreviation of Commission Internationale de I'Eclairage, which stands for International Commission on Illumination. The CIE standard light source D65 is used when displaying the color of an object illuminated by the main light. Regarding the viewing angle of 10°, JIS Z 8723 (2009) "visual comparison method of surface color" is prescribed, and ISO/DIS 3668 also has the same rule.

The SCE method is called a specular light removal method, and refers to a method of measuring color by removing specular light. The definition of the SCE system is prescribed|regulated by JIS Z 8722 (2009). In the SCE method, since specular light is removed and measured, it becomes a color close to the color seen by the human eye (so-called luminous color).

The CIELAB display color is a uniform color space recommended in 1976 and stipulated in JIS Z 8781 (2013) in order to measure the color difference due to the difference between perception and apparatus. The three coordinates of CIELAB are represented by L* value, a* value, and b* value. L* value represents lightness and is represented by 0-100. When the L* value is 0, it means black, and when the L* value is 100, it means the diffuse color of white. The a* value represents a color between red and green. A negative value of a* means a color close to green, and a positive value means a color close to red. The b* value means a color between yellow and blue. If b* is negative, it means a color close to blue, and when b* is positive, it means a color close to yellow.

[Evaluation results]

With reference to Tables 3A and 3B, the test number that is not laminated resinized (the one not marked with #) was evaluated as "P" in either or both of "color unevenness" and "color fluctuation". , both of "color unevenness" and "color fluctuation" were evaluated as "G" in the test numbers (things appended with #) which were laminated and resinized.

1, 1': plated steel plate
10, 10': galvanized layer
10S, 10S': texture
11, 11': colored resin layer
30: laminated resin layer
31, 31': resin
32, 32': colorant
100, 100': base steel plate

Claims (16)

It is a plated steel plate,
A base steel sheet having a base material texture on the surface, and
a galvanized layer formed on the surface of the base steel sheet having the base material texture;
and a colored resin layer formed on the galvanized layer;
The zinc plating layer has a plating texture on its surface,
The colored resin layer contains a colorant,
The plating texture is
a plurality of convex portions;
comprising a plurality of recesses;
When the rolling direction of the base steel sheet is defined as the first direction, and the direction orthogonal to the first direction on the surface of the plated steel sheet is defined as the second direction, the plated steel sheet has the following (A) to ( c) to be met;
plated steel plate.
(A) When the roughness profile in the range of the length of 1000 µm in the second direction of the plating texture is measured, and the lowest position in each of the recesses in the measured roughness profile is defined as the bottom point of the recess , three-dimensionality of a micro-region of 1 μm×1 μm centered on the specified bottom points of the recesses, and specifying 10 bottom points of the recesses in the lowest order among the bottom points of the plurality of recesses of the roughness profile. When the average roughness Sa is measured and the arithmetic mean of the ten measured three-dimensional average roughness Sa is defined as the three-dimensional average roughness Sas at the bottom of the recess, the three-dimensional average roughness Sas at the bottom of the recess is greater than 200 nm and less than or equal to 2000 nm.
(B) In the range of 100 μm length in the second direction, the minimum thickness (μm) of the colored resin layer is defined as DKmin, and the content (area%) of the coloring agent in the colored resin layer is defined as CK, , when F1 is defined by Formula (1), F1 is 15.0 or less.
F1=DKmin×CK (1)
(C) In the range of the length of 100 µm in the second direction, when the maximum thickness (µm) of the colored resin layer is defined as DKmax and F2 is defined by the formula (2), the F2 is greater than 1.0.
F2=(DKmax-DKmin)×CK (2) According to claim 1,
Further, a plated steel sheet that satisfies the following (D).
(D) When the roughness profile in the range of the length of 1000 µm in the second direction of the plating texture is measured, and the highest position in each of the convex portions in the measured roughness profile is defined as the convex portion apex , 10 of the convex vertices of the roughness profile are specified in the highest order, and three-dimensionality of a minute region of 1 μm×1 μm centered on the specified convex vertex. When the average roughness Sa is measured and the arithmetic mean value of the ten measured three-dimensional average roughness Sa is defined as the convex part normal three-dimensional average roughness Sas, the convex part normal three-dimensional average roughness Sah is more than 5 nm and 200 nm or less. 3. The method of claim 2,
The plurality of convex portions and the plurality of concave portions extend in the first direction,
The plurality of the convex portions and the plurality of the concave portions are arranged in the second direction. 4. The method of claim 3,
The base material texture is a hairline,
The plating texture is a hairline,
The plated steel sheet is also
A plated steel sheet satisfying the following (E) and (F).
(E) The surface roughness Ra of the colored resin layer in the first direction is defined as Ra(CL), the surface roughness Ra of the colored resin layer in the second direction is defined as Ra(CC), and F3 is defined as the formula When defined by (3), the F3 is 1.10 or more.
F3=Ra(CC)/Ra(CL) (3)
(F) When the surface roughness of the galvanized layer in the second direction is defined as Ra(MC), Ra(MC) is 0.30 µm or more. 5. The method according to any one of claims 1 to 4,
The plated steel sheet having a brightness L*(SCI) of 45 or less when the plated steel sheet is viewed from the colored resin layer side. 6. The method according to any one of claims 1 to 5,
F1 is 13.5 or less, plated steel sheet. 7. The method according to any one of claims 1 to 6,
F2 is greater than 2.0, plated steel. 8. The method according to any one of claims 4 to 7,
The F3 is 1.15 or more, a plated steel sheet. 9. The method according to any one of claims 1 to 8,
The galvanized steel sheet, wherein the iron exposure rate of the galvanized layer is less than 5%. 3. The method of claim 2,
The plurality of the convex portions are formed by polishing the surface of the galvanized layer,
A plated steel sheet in which the plurality of concave portions are not polished. It is a plated steel plate,
base steel plate,
a galvanized layer formed on the surface of the base steel sheet;
and a colored resin layer formed on the galvanized layer;
The galvanized layer has a texture extending in one direction on its surface,
The colored resin layer contains a colorant,
Satisfying all of the following (A') to (C'),
plated steel plate.
(A') Measure the roughness profile in the range of a length of 1000 μm in the direction perpendicular to the extension direction of the texture, and among the measured locations on the roughness profile, 10 specific positions in the order of height are selected as the bottom point of the recess Among the positions on the measured roughness profile, 10 specific positions in the order of height are defined as convex vertices, and 1 μm × 1 μm centered at the bottom of each concave portion and each convex vertex is defined as When the three-dimensional average roughness Sa' of the microregion is measured and the arithmetic mean value of the measured three-dimensional average roughness Sa' is defined as the three-dimensional average roughness Saave', the three-dimensional average roughness Saave' is greater than 5 nm and less than or equal to 200 nm.
(B') In the range of a length of 100 µm in a direction orthogonal to the extending direction of the texture, the minimum thickness (µm) of the colored resin layer is defined as DKmin', and the content (area) of the colorant in the colored resin layer %) is defined as CK', Equation (1') is satisfied.
DKmin'×CK'≤15.0 (1')
(C') Expression (2') is satisfied when the maximum thickness (µm) of the colored resin layer is defined as DKmax' in a 100 µm length range in a direction perpendicular to the extension direction of the texture.
(DKmax'-DKmin')×CK'>1.0 (2') 12. The method of claim 11,
The texture is a hairline,
A plated steel sheet satisfying the following (D') and (E').
(D') The surface roughness Ra of the colored resin layer in the extending direction of the texture is defined as Ra(CL)', and the surface roughness Ra of the colored resin layer in the direction perpendicular to the extending direction of the texture is Ra(CC). )', Equation (3') is satisfied.
Ra(CC)'≥Ra(CL)'×1.10 (3')
(E') When the surface roughness of the galvanized layer in the direction orthogonal to the extending direction of the texture is defined as Ra(MC)', Ra(MC)' is 0.30 µm or more. 13. The method of claim 11 or 12,
The galvanized steel sheet, wherein the iron exposure rate of the galvanized layer is less than 5%. 14. The method according to any one of claims 1 to 13,
The colored resin layer is a laminated resin layer,
The laminated resin layer,
A plurality of colored resin layers laminated in a direction normal to the surface of the base steel sheet,
In the plurality of colored resin layers, the sum of the product of the content (area%) of the coloring agent in the colored resin layer and the thickness (μm) of the colored resin layer is 15.0 area%·μm or less,
Among the plurality of colored resin layers, the colored resin layer in which the product of the content (area %) of the coloring agent in the colored resin layer and the thickness (μm) of the colored resin layer is the maximum is defined as the deepest colored colored resin layer, When the product of the content of the coloring agent in the colored resin layer and the thickness of the colored resin layer is defined as the second largest colored resin layer as the second hyperchromic colored resin layer,
_{Content C 1ST} (area %) of the colorant in the deepest color resin layer, thickness D _{1ST (μm) of the deepest color resin layer, and content C 2ND} (area%) of the colorant in the second deep color color resin layer _{and a thickness D 2ND} (μm) of the second hyperchromic colored resin layer satisfies Formula (4).
1.00<(C _1ST ×D _1ST )/(C _2ND ×D _2ND )≤4.00 (4) 15. The method of claim 14,
The thickness of the said laminated resin layer is 10.0 micrometers or less, The plated steel plate. 16. The method of claim 14 or 15,
The laminated resin layer,
Further comprising one or a plurality of transparent resin layers that do not contain the colorant,
The laminated resin layer,
A plated steel sheet formed by laminating the plurality of colored resin layers and the one or more transparent resin layers.

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