Roughened nickel plating material and manufacturing method thereof

Abstract

To provide a roughened nickel plating material that suppresses formation unevenness such as the unevenness of a roughened nickel plating layer and the occurrence of grooves in a roughened nickel plating material.SOLUTION: A roughened nickel plating material includes a base material that is a rolled material and a roughened nickel plating layer formed on at least one surface of the base material, in which the surface roughness (SRzjis) of the roughened nickel plating layer is 2 μm or more, the maximum height of the roughened nickel plating layer is SRz, and the valley region B in an arbitrary virtual plane region A observed at the height position of SRz×0.25 satisfies the following (i). (i) The length of the valley region B in a rolling direction RD of the base material is less than 40 μm in straight-line distance.SELECTED DRAWING: Figure 3(b)

Description

[Technical field]

[0001] The present invention relates to a plated product having a roughened nickel plating layer and a method for producing the same. [Background technology]

[0002] In recent years, in the technology for forming a plating layer on a substrate such as a metal plate or metal foil, a technology has become known that does not only form a smooth plating layer, but also forms irregularities on the plated surface or deposits metal in granular or needle-like form on the substrate, forming a so-called roughened plating layer.

[0003] Among these, roughened nickel-plated materials having a roughened nickel plating layer formed thereon are used, for example, as materials for food cans, beverage cans, battery cans, etc., to provide functions suitable for each application or to further improve the functions. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 5885345 [Patent Document 2] JP 2019-104948 A [Patent Document 3] JP 2019-104949 A Summary of the Invention [Problem to be solved by the invention]

[0005] On the other hand, depending on the above-mentioned applications, a layer of resin or the like may be further formed on the roughened nickel plating layer of these roughened nickel plated products.

[0006] On the other hand, as a result of intensive research by the present inventors, it was found that depending on the manufacturing conditions of the roughened nickel plated material, the growth in the height direction in the roughened nickel plating layer may be non-uniform. In particular, it was found that when the roughened nickel plating is continuously deposited in a specific direction of the roughened nickel plated material but a portion where growth is difficult occurs, the portion may be formed in a groove shape (the groove-shaped region formed by the portion where growth is difficult, i.e., a region where the height of each of the aggregates of nickel particles in the roughened portion is slightly lower than the surrounding roughened portion when comparing the heights of the individual particles, is hereinafter also referred to as "groove").

[0007] Due to the non-uniformity and the presence of grooves in the roughened nickel plating layer, as shown in the patent documents, particularly when another layer is coated on the roughened nickel plating layer, the originally intended function may not be fully exhibited.

[0008] As a result of further intensive research, the inventors have found that by adopting a specific method in forming a roughened nickel plating layer, it is possible to suppress the occurrence of unevenness and grooves in the roughened nickel plating layer as described above.

[0009] That is, the present invention has been made in consideration of solving the above-mentioned problems, as an example, and aims to provide a method for producing a roughened nickel-plated product that can suppress the occurrence of non-uniformity and grooves in the roughened nickel plating layer (hereinafter also referred to as "formation unevenness"), and the roughened nickel-plated product. [Means for solving the problem]

[0010] The roughened nickel-plated material in this embodiment includes (1) a metal substrate and a roughened nickel plating layer formed on at least one surface of the substrate, and is characterized in that SRzjis of a surface of the roughened nickel plating layer is 2 μm or more, and a valley region B in any imaginary plane region A observed at a height position of SRz × 0.25, where SRz is the maximum height of the roughened nickel plating layer, satisfies the following (i): (i) The length of the valley region B in the rolling direction or the sheet passing direction of the substrate is less than 40 μm in linear distance. In the above (1), (2) it is preferable that the maximum value of the perimeter CL of the valley region B is less than 500 μm. The roughened nickel-plated material in this embodiment is also characterized in that it includes (3) a metal substrate and a roughened nickel plating layer formed on at least one side of the substrate, and that the surface of the roughened nickel plating layer has a three-dimensional surface property parameter Str of 0.1 or more. In the roughened nickel-plated product of this embodiment, in the above (3), (4) it is preferable that the surface of the roughened nickel plating layer has a three-dimensional surface texture parameter Sk of 1.0 μm to 4.0 μm. In the present embodiment, the roughened nickel-plated material has the above-mentioned (3), and (5) the Vvc of the three-dimensional surface property parameter of the surface of the roughened nickel plating layer is 0.6 μm 3 / μm 2 ~3.0μm 3 / μm 2 It is preferable that: Further, in the roughened nickel-plated material of this embodiment, in the above (3), (6) the Vmc of the three-dimensional surface property parameter of the surface of the roughened nickel plating layer is 0.45 μm 3 / μm 2 ~2.0μm 3 / μm 2 It is preferable that: In the roughened nickel-plated product of the present embodiment, in any one of the above items (1) to (6), (7) the substrate is preferably a steel plate. The roughened nickel-plated material of the present embodiment is any one of the above items (1) to (7), further comprising: (8) the surface brightness of the substrate roughened nickel plating layer is L * The value is preferably 30 to 50. In the roughened nickel-plated product of the present embodiment, in any one of the above items (1) to (7), (9) it is preferable that the surface gloss of the base material roughened nickel plating layer is 1.5 to 50 at 85° gloss. In the roughened nickel-plated product of the present embodiment, in any one of the above items (1) to (9), (10) it is preferable that the roughened nickel-plated product has an undercoat nickel layer between the substrate and the roughened nickel-plated layer.

[0011] Moreover, the method for producing a roughened nickel-plated product in this embodiment includes: (11) a substrate surface treatment step of setting SRzjis on the surface of the substrate to 0.5 μm or more and less than 1.7 μm; and a roughened nickel plating step of forming a roughened nickel plating layer on the substrate. Furthermore, the method for producing a roughened nickel-plated material in this embodiment includes (12) a step of providing a base nickel plating layer having a surface Sku of 4.0 or more on a metal substrate, and a roughened nickel plating step of forming a roughened nickel plating layer on the base nickel plating layer. In the above (12), the method for producing a roughened nickel-plated product in this embodiment further comprises (13) providing that Vvc of the surface of the undercoat nickel plating layer is 0.45 μm 3 / μm 2 It is preferable that: In the above (11), (14) the surface treatment step is preferably a cold rolling step or a temper rolling step. In the above (14), (15) it is preferable that the surface roughness of the final roll used in the cold rolling step at a rolling reduction of 5% or more is 0.01 μm or more and 0.5 μm or less. Alternatively, in the above (14), (16) it is preferable that the surface roughness of the final roll used in the temper rolling step at a rolling reduction of 0.1% or more and less than 5% is 0.01 μm or more and 0.5 μm or less. Furthermore, in any one of the above items (11) to (16), (17) it is preferable that the substrate is a steel plate. Effect of the Invention

[0012] According to the method for producing a roughened nickel-plated product of the present invention, it is possible to provide a roughened nickel-plated product in which the above-mentioned formation unevenness is suppressed. Taking advantage of its excellent properties, the roughened nickel-plated product of the present invention can be suitably used for, for example, packaging containers such as beverage cans and pouches containing liquids, battery components, etc. [Brief description of the drawings]

[0013] [Figure 1(a)] 1 is a schematic diagram showing a cross section of a roughened nickel-plated product 1 in the present embodiment. [Figure 1(b)] 1 is a schematic diagram showing a cross section of a roughened nickel-plated product 1 in the present embodiment. [Figure 2(a)] 2 is a schematic diagram showing an imaginary plane region A of a roughened nickel plating layer 12 in the present embodiment. FIG. [Figure 2(b)] 2 is a schematic diagram showing an imaginary plane region A of a roughened nickel plating layer 12 in the present embodiment. FIG. [Figure 3(a)] FIG. 2 is a diagram showing the surface, etc., of a roughened nickel-plated product obtained in this embodiment. [Figure 3(b)] FIG. 2 is a diagram showing the surface, etc., of a roughened nickel-plated product obtained in this embodiment. [Figure 4] FIG. 2 is a diagram showing the surface, etc., of a roughened nickel-plated product obtained in this embodiment. [Diagram 5] FIG. 2 is a diagram showing the surface, etc., of a roughened nickel-plated product obtained in this embodiment. [Figure 6(a)] FIG. 2 is a diagram showing the surface, etc., of a roughened nickel-plated product obtained in a comparative example of this embodiment. [Figure 6(b)] FIG. 2 is a diagram showing the surface, etc., of a roughened nickel-plated product obtained in a comparative example of this embodiment. [Figure 6(c)] FIG. 2 is a diagram showing the surface, etc., of a roughened nickel-plated product obtained in a comparative example of this embodiment. [Figure 6(d)] FIG. 2 is a diagram showing the surface, etc., of a roughened nickel-plated product obtained in a comparative example of this embodiment. [Figure 7]FIG. 2 is a diagram showing the surface, etc., of roughened nickel-plated materials obtained in the examples, comparative examples, and reference examples of this embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] Hereinafter, an embodiment of the present invention will be described with reference to the drawings. Fig. 1 is a schematic diagram showing a roughened nickel-plated material 1 of the present embodiment. As shown in Fig. 1(a), the roughened nickel-plated material 1 of the present embodiment is characterized by including a base material 11 and a roughened nickel plating layer 12 formed on at least one surface of the base material 11. In this embodiment, an example is shown in which a roughened nickel plating layer 12 is formed on one side of the base material 11, but this is not limited to this form, and the roughened nickel plating layer 12 may be formed on both sides of the base material 11.

[0015] <Base material 11> As the substrate 11 in this embodiment, a known metal plate or metal foil used as a plating substrate can be used. Examples of materials for the substrate 11 include a metal plate or foil made of a pure metal selected from Fe, Cu, Al, and Ni, or a metal plate or foil made of an alloy containing one selected from Fe, Cu, Al, and Ni. Specific examples include steel plates, iron plates, stainless steel plates, copper plates, aluminum plates, and nickel plates (which may be either pure metals or alloys, and may be in the form of foil).

[0016] In particular, as the steel plate, low carbon aluminum killed steel (carbon content: 0.01 to 0.15% by weight), ultra-low carbon steel with a carbon content of 0.01% by weight or less (preferably a carbon content of 0.003% by weight or less), or non-aging ultra-low carbon steel obtained by adding Ti, Nb, etc. to ultra-low carbon steel, etc. are preferably used.

[0017] A rolled material or an electrolytic foil can be applied as the metal plate or metal foil as the above-mentioned substrate 11. In particular, a rolled material is preferable from the viewpoints of productivity and cost in mass production, and may be a material that has been subjected to known processes such as cold rolling, annealing, and temper rolling. The metal plate or metal foil as the substrate 11 may be subjected to a known surface treatment. Examples of known surface treatments include strike nickel plating applied to a stainless steel plate or a nickel plate immediately before roughening nickel plating, various platings such as nickel or nickel alloy plating, zinc or zinc alloy plating, etc. applied to a steel plate, and heat treatments applied after the various platings. The substrate 11 in this embodiment may have a metal layer formed thereon resulting from the various platings or heat treatments by such known surface treatments.

[0018] The thickness of the substrate 11 is preferably 0.01 to 2.0 mm, more preferably 0.025 to 1.6 mm, and further preferably 0.025 to 0.3 mm. In this embodiment, the "thickness of the substrate 11" refers to an average value of values ​​obtained by taking an optical microscope photograph of a cross section of the substrate 11 and measuring the thickness of the substrate 11 at any ten points in the optical microscope photograph. For simplicity, thickness measurement with a micrometer is also applicable.

[0019] In this embodiment, when the surface condition of the substrate 11 is in a specific state, the obtained roughened nickel-plated product is extremely suitable. This will be described in detail below.

[0020] In this embodiment, a roughened nickel plating layer can be formed on the surface of the substrate 11 by means of electrolytic plating or the like. In this case, the roughened nickel plating layer grows by the precipitation of nickel ions in a plating bath on the surface of the substrate 11, but the inventors have found through their studies that the degree of growth (growth rate) of the roughened nickel plating layer varies partially depending on the surface condition of the substrate 11, particularly the surface shape.

[0021] In this embodiment, a metal rolled plate or rolled foil can be used as the substrate 11. Generally, these rolled plates and rolled foils (hereinafter, the rolled plates and rolled foils may be collectively referred to as "rolled materials") can be obtained by rolling a metal plate with a rolling roll, and it is known that the shape (unevenness) of the roll surface of the rolling roll greatly contributes to the surface shape of the metal plate, and it is generally said that the shape of the roll surface is transferred.

[0022] In this case, it is known that the surface shape formed on the rolled plate or rolled foil varies not only with the roll surface shape (roll roughness) of the rolling rolls, but also with the reduction ratio, rolling speed, hardness of the metal (material being rolled), viscosity of the rolling oil, etc. Major surface shapes of a continuous metal strip include depressions such as dents and streak-like irregularities along the sheet passing direction. In particular, in rolled materials, the irregularities of the rolling rolls do not directly form the shape of the surface of the rolled material, and streak-like irregularities may be formed in the rolled material by the protrusions of the rolling rolls when the material is stretched by rolling, and these are known as rolling marks, rolling streaks, transferred streaks, etc.

[0023] The present inventors have found that the surface condition of the substrate 11, particularly the shape of the rolling streaks (size of unevenness, height difference, width, angle, etc.) as described above, causes the roughened nickel plating layer 12 formed on the substrate 11 to have different partial growth rates and to have unevenness and grooves in the roughened nickel plating layer 12. That is, the roughened nickel plating layer is deposited even on the streaky parts, and each fine particle also grows to a certain size, so there is no problem with the characteristics of the surface as a whole (for example, adhesion to resin and other members). On the other hand, in applications where a very small area is used, or in cases where an active material is bonded as an electrode for a battery, it is considered that there are cases where adhesion cannot be guaranteed in very microscopic regions including parts with a slow growth rate. In addition, when the formation unevenness is in the form of a large groove, it is considered that there are cases where formation unevenness occurs, such as a difference in adhesion between the rolling direction and the direction perpendicular to the rolling direction.

[0024] In response to these problems, the surface condition of the substrate 11 is controlled as described above, thereby suppressing the occurrence of unevenness and grooves in the roughened nickel plating layer 12, and thus the present invention has been completed.

[0025] In this embodiment, the surface state of the substrate 11 is defined based on parameters in non-contact and three-dimensional surface texture measurement as follows. Specifically, in this specification, SRa, SRz, and SRzjis are measured and calculated as follows. First, measure two-dimensional Ra, Rz, and Rzjis based on JIS B 0601 (2013). In this embodiment, the measurement is performed in a direction perpendicular to the rolling direction or the sheet passing direction. The measurement range is preferably 100 μm or more, and more preferably in the range of 100 μm to 150 μm. In addition, in measuring Ra, Rz, and Rzjis, the measurement start point is moved in the rolling direction or the sheet passing direction RD, and the measurement is repeated multiple times, preferably 100 times or more, more preferably 300 times or more. In the examples of the present application described later, 768 measurements were performed. From the measurement results, the following parameters can be obtained:

[0026] SRa = (R a-1 +R a-2 +···+R a-n ) / n SRz=(R z-1 +R z-2 +···+R z-n ) / n SRzjis=(Rzjis -1 + Rzjis -2 +···+Rzjis -n ) / n Here, n is the number of measurements.

[0027] In this embodiment, the surface of the base material 11 preferably has a three-dimensional arithmetic mean height SRa of 0.02 μm to 0.17 μm. From the viewpoint of suppressing uneven formation as described above, the height is preferably 0.03 μm to 0.15 μm, and from the viewpoint of cost, the height is preferably 0.08 μm to 0.15 μm.

[0028] If the SRa on the surface of the substrate 11 is less than 0.02 μm, not only will the process of adjusting the surface of the substrate 11 to that value be too costly, but it is also undesirable because there is a possibility that a roughened nickel plating layer will not be formed on the substrate 11, or that the surface of the roughened nickel plating layer 12 formed on the substrate 11 will be too smooth, making it impossible to maximize the characteristics and functions of the roughened nickel plating that are originally required.

[0029] On the other hand, if the SRa on the surface of the substrate 11 exceeds 0.17 μm, the growth of the roughened nickel plating layer 12 may become non-uniform and grooves may occur in the obtained roughened nickel plating layer 12, which is undesirable.

[0030] In the present embodiment, the surface of the base material 11 preferably has a three-dimensional ten-point average roughness SRzjis in the range of SRzjis=0.3 μm or more and less than 1.7 μm. From the viewpoint of suppressing uneven formation as described above, the surface roughness is preferably 0.4 μm to 1.6 μm, and from the viewpoint of cost, the surface roughness is preferably 0.8 μm to 1.5 μm.

[0031] This is due to the following reason: As will be described later, the present inventors have discovered a problem that poor growth of the roughened plating is likely to occur when a substrate has depressions, such as rolling streaks, that are not point depressions but have lengths and areas on the order of several tens of microns, and when these depressions are deep or numerous, or when they are wide and deep to a certain extent.

[0032] Such depressions, which have lengths and areas on the order of tens of microns, are difficult to distinguish using ordinary two-dimensional roughness parameters. Therefore, we focused on the three-dimensional ten-point average roughness SRzjis, which is calculated based on the two-dimensional ten-point average roughness measured in a direction perpendicular to the rolling direction or the sheet-threading direction RD. Since the three-dimensional ten-point average roughness SRzjis is calculated as the average value for the entire surface based on Rzjis measured in a direction perpendicular to RD, when depressions with lengths and areas on the order of tens of microns are present on the substrate surface, it is a parameter that easily reflects their total number and length.

[0033] In particular, in rolled materials in which the peaks have been flattened by rolling as described below, the contribution of SRzjis in the recessed portions is greater. Therefore, the larger the SRzjis in the region of 100 μm × 100 to 150 μm, the more recesses there are on the base material that are large enough to cause uneven formation of a roughened plating, or the larger the recessed area is.

[0034] The present inventors further found that by making the SRzjis of the substrate 11 less than 1.7 μm, it is possible to significantly suppress valley regions in the roughened plating layer 12 after the roughened plating described below. There is no lower limit for the purpose of reducing recesses in the substrate 11, but a lower limit of 0.3 μm or more is preferable because plating particles for forming a roughened plating layer are unlikely to precipitate on a mirror surface with no irregularities under the roughened plating conditions.

[0035] <Nickel undercoat layer> In this embodiment, a base nickel plating layer 13 as shown in FIG. 1(b) is formed on the substrate 11, and the surface condition of this base nickel plating layer 13 can also be defined by three-dimensional surface property parameters defined in ISO-25178-2:2012 (corresponding to JIS B 0681-2:2018). As the underlying nickel plating layer 13 can be appropriately applied to the contents disclosed in the above-mentioned Patent Documents 2 and 3, as well as Patent Application No. 2019-108779, detailed explanations will be omitted here.

[0036] In this embodiment, it is preferable that the surface of the primary nickel plating layer 13 has, among the above-mentioned three-dimensional surface quality parameters, Sku (kurtosis), which is a parameter that quantifies height statistics, of 4.0 or more.

[0037] The reason for setting the Sku of the primary nickel plating layer 13 to 4.0 or more is as follows: When the primary nickel plating layer 13 is formed on the substrate 11, the macroscopic unevenness of the substrate 11 is somewhat alleviated by the primary nickel plating layer 13, while microscopic fine unevenness is formed by the plating grains of the primary nickel plating layer 13. However, for example, if the substrate 11 has large rolling streaks, the streaky valleys and peaks may not be sufficiently alleviated even after the primary nickel plating layer 13 is formed.

[0038] Here, the inventors have found that after nickel plating (after formation of the base nickel plating layer 13), when there are many constant depths in one direction, such as rolling streaks in the plane of the sheet, Sku, which represents the sharpness of the height distribution of the three-dimensional surface roughness, reflects the shape well and is less than 4.0. In other words, they have found that it is preferable to control Sku to 4.0 or more in order to avoid the formation of large grooves that may cause anisotropy after roughened nickel plating.

[0039] Sku is a value that indicates the sharpness of the height distribution, and when Sku is 3.0, the height distribution is normal, whereas when Sku exceeds 3.0, it usually indicates that the surface has many sharp peaks and valleys, and when Sku is less than 3.0, it indicates that the surface is flat. However, it was found that it does not indicate a simple uneven shape.

[0040] Based on the above findings, the present inventors, through trial and error, decided that the Sku of the surface of the underlying nickel plating layer 13 should be 4.0 or more.

[0041] Furthermore, the volume parameter Vvc on the surface of the undercoat nickel plating layer 13 is set to 0.45 μm 3 / μm 2It has been found that it is preferable to set Vvc to 0.45 μm or less. 3 / μm 2 The reasons for the following are as follows:

[0042] That is, Vvc is the volume of the space in the core portion when the areal load ratio separating the core portion and the protruding peaks is 10% and the areal load ratio separating the core portion and the protruding valleys is 80%. In other words, by reducing the spatial volume in the core portion, which is the center of the unevenness on the surface of the base nickel plating layer 13, it is possible to reduce and control the groove portions that cause anisotropy after the formation of the roughened nickel plating layer 12.

[0043] The present inventors set the Vvc of the surface of the undercoat nickel plating layer 13 to 0.45 μm. 3 / μm 2 It has been found that the anisotropy of the surface of a roughened nickel-plated material after roughening plating can be suppressed by the following.

[0044] <Roughened nickel plating layer> Next, the roughened nickel plating layer 12 in this embodiment will be described. 1, the roughened nickel plating layer 12 in this embodiment has a cross-sectional shape in which nickel particles or aggregates thereof are precipitated on the substrate 11. The shape of this roughened nickel plating layer 12 is similar to that of the roughened nickel plating layer disclosed in the above-mentioned Patent Document 2 or Patent Document 3. Therefore, in this application, the characteristic parts of the present invention, i.e., the differences from the above-mentioned Patent Document 2 or Patent Document 3, will be mainly described, and a description of the common points will be omitted.

[0045] For the roughened nickel plating layer 12 in this embodiment, the roughened nickel plating layer described in Japanese Patent Application No. 2019-108779 can be appropriately referred to.

[0046] In the present embodiment, the roughened nickel plating layer 12 preferably has a three-dimensional ten-point average roughness SRzjis of 2 μm or more on its surface. The reason for this is to improve adhesion to other members such as resins. There is no particular upper limit, but it is 20 μm from the viewpoints of plating adhesion, production efficiency, production cost, etc. A more preferred range for SRzjis is as follows: From the viewpoint of further improving the adhesion of the roughened nickel plating layer 12 to other members, SRzjis is more preferably 3 μm or more, even more preferably 4 μm or more, and even more preferably 5 μm or more. From the viewpoint of further improving the adhesion (plating adhesion) of the roughened nickel plating layer 12 to the substrate 11, SRzjis is more preferably 16 μm or less, even more preferably 14 μm or less, and even more preferably 12 μm or less. From the viewpoint of emphasizing production efficiency and production costs, SRzjis is preferably 3.0 μm to 7.0 μm.

[0047] In the present embodiment, the SRa of the roughened nickel plating layer 12 is preferably 0.1 μm to 3 μm. From the viewpoint of further improving the adhesion of the roughened nickel plating layer 12 to other members, the SRa is more preferably 0.18 μm or more, and even more preferably 0.3 μm or more. From the viewpoint of further improving the adhesion (plating adhesion) of the roughened nickel plating layer 12 to the substrate 11, SRa is more preferably 1.8 μm or less, even more preferably 1.6 μm or less, and even more preferably 1.3 μm or less. From the viewpoint of emphasizing production efficiency and production costs, the SRa is preferably 0.18 μm to 0.5 μm, and more preferably 0.18 μm to 0.49 μm.

[0048] The brightness of the surface of the roughened nickel plating layer 12 is L *It is preferable that the lightness value is 30 to 50 from the viewpoints of plating adhesion, production efficiency, production costs, etc. * If the value is less than 30, it is not preferable from the viewpoint of plating adhesion. * If the value exceeds 50, this is not preferable from the viewpoint of adhesion to other members (such as a resin layer) that may be formed on the roughened nickel plating layer 12. The lightness L of the roughened nickel plating layer 12 is * The measurement can be performed using a spectrophotometer in accordance with JIS Z8722 using the SCE method (specular reflection elimination method).

[0049] The gloss of the roughened nickel plating layer 12 will now be described. In this embodiment, the gloss of the roughened nickel plating layer 12 is preferably 1.5 to 50 at 85° gloss from the viewpoints of plating adhesion, production efficiency, production cost, and the like. If the 85° gloss is less than 1.5, this is not preferred from the viewpoint of plating adhesion. On the other hand, if the 85° gloss is more than 50, this is not preferred from the viewpoint of adhesion with a resin layer or the like that may be formed on the roughened nickel plating layer 12. The 85° gloss of the surface of the roughened nickel plating layer 12 can be determined by measuring the 85° specular gloss using a glossmeter in accordance with JIS Z8741. On the other hand, the 60° gloss of the roughened nickel plating layer 12 of this embodiment is usually 10 or less.

[0050] In this embodiment, the chromaticity a of the surface of the roughened nickel plating layer 12 * , b * However, from the viewpoint of plating adhesion and adhesion to a resin layer or the like that may be formed on the roughened nickel plating layer 12, the chromaticity a * is preferably 0.1 to 3.0, and the chromaticity b * is preferably 1.0 to 8.0.

[0051] In this embodiment, the arithmetic mean height SRa of the surface of the roughened nickel plating layer 12 is preferably 0.1 μm to 3 μm. This is from the viewpoints of adhesion to a resin layer or the like that may be formed on the roughened nickel plating layer 12, adhesion between the roughened nickel plating layer 12 and the substrate 11 (plating adhesion), production efficiency, production costs, etc.

[0052] In this embodiment, the maximum height roughness SRz of the roughened nickel plating layer 12 is not particularly limited, but is preferably, for example, 2.5 μm to 25.0 μm. The three-dimensional surface roughnesses SRa, SRzjis, and SRz are preferably measured by a laser microscope.

[0053] In this embodiment, the nickel coating amount of the roughened nickel plating layer 12 is not particularly limited, but from the viewpoint of plating adhesion, etc., it is preferably 1.34 g / m 2 ~57.85g / m 2 Of these, the coating weight of the roughened nickel plating layer, not including the underlying nickel, is preferably 1.34 to 45.0 g / m 2 From the viewpoint of further improving the adhesion (plating adhesion) of the roughened nickel plating layer 12, the coating weight of the roughened nickel layer 12 is more preferably 2.67 g / m 2 More preferably, it is 5 g / m 2 From the viewpoint of further improving the adhesion of the roughened nickel layer 12 to other members, the coating weight of the roughened nickel layer 12 is more preferably 38.0 g / m 2 or less, and more preferably 32.0 g / m 2 and even more preferably 31 g / m 2 The following is the result.

[0054] In addition, when the base layer contains nickel, the coating weight is 5.0 to 50.00 g / m 2 Furthermore, it is more preferable that the length is 12.02m. 2 ~50.00g / m 2 , and more preferably 12.28 m 2 ~40.94g / m2 , particularly preferably 12.28 m 2 ~32.49g / m 2 It is. From the viewpoint of prioritizing production efficiency and production costs, the total coating weight of the roughened nickel layer 12 and the base metal plating layer 13 is 10.24 m 2 ~22.25g / m 2 Furthermore, when high corrosion resistance is required, and when particularly high adhesion of the roughened nickel plating layer 12 to the metal substrate 11 and to other members is required, the total coating weight of the roughened nickel layer 12 and the base metal plating layer 13 is preferably 32.50 g / m 2 ~57.85g / m 2 It is preferable that: The total coating weight of the roughened nickel layer 12 and the base metal plating layer 13 can be determined by measuring the total amount of nickel on the roughened nickel-plated sheet 1 using an X-ray fluorescence device.

[0055] The amount of the roughened nickel plating layer 12 deposited can be determined by measuring the total amount of nickel in the roughened nickel-plated sheet 1 using an X-ray fluorescence device, but this is not limited to this method and other known measurement methods can also be used.

[0056] In the present embodiment, the roughened nickel plating layer 12 preferably has a maximum height roughness SRz in the roughened nickel plating layer, and a valley region B in any imaginary plane region A observed at a height position of SRz × 0.25 satisfies the following (i). (i) The length of the valley region B in the rolling direction (sheet running direction) RD of the substrate is less than 50 μm in linear distance. It is more preferable that the valley region B satisfies the following (ii). (ii) Within any linear length of 80 μm, the total length of the portions in which the valley regions B exist for 10 μm or more in the rolling direction RD of the substrate is less than 50 μm. The following explains this using the figures.

[0057] Fig. 2 is a diagram for describing the above-mentioned imaginary plane for explaining this embodiment and the features of this embodiment obtained based on it. Fig. 2(a) is a diagram showing the maximum height roughness SRz of the roughened nickel plating layer 12 in this embodiment and the imaginary plane region A. Fig. 2(b) is a diagram showing the case where the roughened nickel plating layer 12 is cut at the imaginary plane region A and binarized into the valley region B and the rest.

[0058] As shown in Figure 2(a), when the surface of the roughened nickel plating layer is observed three-dimensionally, a shape with multiple peaks and valleys is observed. The sum of the height of the highest peak and the depth of the deepest valley in the observation area is taken as SRz, and the schematic diagram of a plane obtained at a position 1 / 4 (0.25) from the bottom in the height direction (Z direction in Figure 2(a)) can be said to be the imaginary plane area A shown in Figure 2(b). 2(b), there are valley region B and other parts (mountains and valleys whose depth does not reach the plane) in the imaginary plane region A. In other words, the valley region B indicated by the diagonal lines can be said to be a recessed region recessed below a reference plane parallel to the main surface at a height of 1 / 4 of SRz.

[0059] In this embodiment, it is preferable that the valley region B satisfies the above-mentioned condition (i). That is, as shown in FIG. 2(b), the condition (i) is that a plurality of valley regions B existing in the imaginary plane region A has a length L B1 , L B2 , L B3 It is preferable that each of the linear distances between the adjacent lines is less than 40 μm. Next, as condition (ii), when a plurality of valley regions B are present in any straight line L of 80 μm length parallel to the rolling direction RD, it is preferable that the total length (D1+D2+···) of the portions D1, D2,··· where the straight line L intersects with the valley regions B and which are 10 μm or longer is less than 50 μm.

[0060] Furthermore, the surface state of the roughened nickel plating layer 12 in this embodiment can also be defined by three-dimensional surface texture parameters defined in ISO-25178-2:2012 (corresponding to JIS B 0681-2:2018). For example, by specifying Str, which is a parameter representing the aspect ratio of the texture (i.e., anisotropy), it is possible to suppress the occurrence of non-uniformity and grooves (uneven formation) in the roughened nickel plating layer 12. That is, by making Str 0.1 or more, it is possible to form the obtained roughened nickel-plated material 1 with controlled anisotropy. Str is preferably 0.15 or more, more preferably 0.2 or more, even more preferably 0.3 or more, and particularly preferably 0.4 or more. The upper limit of Str is 1, and in this embodiment, it is 1.0 or less.

[0061] In this way, the following advantages can be obtained by controlling the anisotropy of the roughened nickel-plated material 1. First, when the anisotropy is significant, there is a risk of vulnerability in one direction in terms of adhesion strength and corrosion resistance with the resin to be joined, etc., whereas the roughened nickel-plated material of the present embodiment has reduced anisotropy, and can be suitably used in applications where extreme anisotropy of characteristics is undesirable. Second, for example, when the roughened nickel-plated material 1 is cut to a predetermined size and used as a cut material for food cans, beverage cans, battery cans, etc., if the roughened nickel-plated material 1 is visually uniform but has anisotropy in the microscopic range, it becomes necessary to perform production while being restricted in the direction of the cut material in order to exhibit the material performance, which may reduce manufacturability. In this embodiment, since the anisotropy can be controlled even in the cut material, for example, production can be performed without being restricted by the direction of the cut material during production, and manufacturability is significantly improved.

[0062] Regarding the surface state of the roughened nickel plating layer 12 of this embodiment, the parameters other than the above-mentioned Str are preferably defined as follows, and their numerical ranges are as follows: Note that all of the parameters are disclosed in ISO-25178-2:2012 (corresponding to JIS B 0681-2:2018), so detailed explanations are omitted here. Sku: 3.0 or higher Sa(μm):0.2~1.3 Sk(μm):1.0~4.0 Vvc(μm 3 / μm 2 ): 0.6~3.0 Vmc(μm 3 / μm 2 ): 0.45~2.0 By defining each parameter as above, it is possible to further suppress uneven formation in the roughened nickel plated material, which is preferable. From the viewpoints of suppressing anisotropy, improving adhesion to other members, plating adhesion, etc., it is more preferable to control the parameters within the following ranges. Sku: 3.32 or higher Sa(μm):0.36~1.2 Sk(μm):1.3~4.0 Vvc(μm 3 / μm 2 ): 0.7~2.5 Vmc(μm 3 / μm 2 ): 0.5~1.5 It is preferable that the above-mentioned three-dimensional surface texture parameters Str, Sku, Sa, Sk, Vvc, Vmc, etc. are measured by a laser microscope.

[0063] In this embodiment, the reason why the above-mentioned non-uniformity and the occurrence of grooves in the roughened nickel plating layer (hereinafter also referred to as "uneven formation") can be suppressed by the above-mentioned specifications is as follows. That is, as a characteristic of the roughened nickel plating layer grown by electrolytic plating, as described in the above-mentioned Patent Document 2 and / or Patent Document 3, it has been confirmed that the nuclei of the primary nickel particles tend to precipitate preferentially on the convex portions (including the convex portions formed by nickel particles that have already been precipitated).

[0064] Therefore, when forming a roughened nickel plating layer with a higher roughness, it is desirable that the unevenness of the substrate 11 is large. However, if the unevenness of the substrate is too large, there is a possibility that roughening will be formed partially. Therefore, in order to form plating with a uniform height over a wide area, the present inventors focused on controlling the surface shape of rolled material as a method of flattening the substrate while leaving some roughness of the convex parts (mountains) on the substrate. However, it was found that there are new issues with roughened nickel plating, even if the substrate is finished to be flat and there is no variation in the roughness range of the plating formation in normal nickel plating.

[0065] That is, when the entire roughened plated material is viewed over a wide range, a roughened nickel layer is formed over the entire surface, as shown in the low-magnification image (×150) of FIG. 7. Therefore, there is no problem with the characteristics required over a wide range (for example, when adhering to a resin or the like over a wide range). Moreover, even when observing a very small range, as shown in the high-magnification image (×10,000) of FIG. 7, it can be confirmed that roughened nickel particle aggregates are formed over the entire surface of the substrate 11. However, when the height is confirmed over the entire surface from the surface side at medium magnification as shown in FIGS. 4 to 6, it was found that groove-like regions (recesses) on the order of several tens of microns may be formed in addition to the height difference of each aggregate.

[0066] Such grooves in an area on the order of several tens of microns are difficult to see in a partial cross-sectional image such as the high-magnification image of Fig. 7. According to the study by the present inventors, it is presumed that the reason why such grooves in an area on the order of several tens of microns are formed is that particles and aggregates that form the roughened nickel plating are difficult to grow in recesses having a certain area such as rolled streaks of the base material 11, even if the surface is flattened by rolling. Furthermore, since the particles and aggregates tend to grow to a normal height or grow higher around the recesses, it is presumed that the unevenness difference after the roughened nickel plating is more noticeable than the unevenness difference of the rolled streaks before the roughened nickel plating, resulting in a larger groove shape.

[0067] As a result, it is presumed that the height of the roughened nickel plating layer formed on the recesses caused by the rolling streaks of the substrate 11 is lower than the height of the roughened nickel plating layer formed on the protrusions caused by the rolling streaks. When observing such a reduced-height portion and its surroundings, it was confirmed from the actual surface observation image that the reduced-height portion was observed to have a groove-like shape.

[0068] As a result of repeated experiments conducted by the inventors, it was confirmed that by controlling the surface condition of the substrate 11 (such as the state of unevenness due to rolling stripes, surface roughness, etc.) to a specific state, the groove portions of the roughened nickel plating layer formed on the recesses of the rolling stripes as described above can be eliminated. Furthermore, as a result of thorough investigation into methods for expressing the surface state of the roughened nickel plating layer 12, the inventors have found that by expressing it as in the above conditions (i) and (ii), it is possible to achieve the objectives and effects that they aim to achieve.

[0069] In this embodiment, as described above, there are multiple valley regions B (B1, B2, B3,...) in the imaginary plane region A. The maximum perimeter CLmax of each valley region B (CL1, CL2, CL3,...) is preferably less than 500 μm. In other words, the perimeter of the valley region B in the imaginary plane region A is preferably shorter than a predetermined length. That is, if the perimeter CL is longer than a predetermined length, it is undesirable because, as described above, a groove shape is formed in the roughened nickel plating layer 12. More preferably, CLmax is less than 100 μm. In this embodiment, the maximum diameter of each valley region B is preferably 25 μm or less. That is, the maximum value MDmax of the maximum diameters MD (MD1, MD2, MD3, ...) of each valley region B is preferably 25 μm or less. The maximum diameter of the valley region B can be measured by a known measuring device.

[0070] In this embodiment, the roughened nickel plating layer 12 may include an undercoat nickel layer or a coating nickel layer therein. Since the contents disclosed in the above-mentioned Patent Documents 2 and 3, and further in Japanese Patent Application No. 2019-108779 can be appropriately applied to the undercoat nickel layer and the coating nickel layer, detailed description thereof will be omitted in this application.

[0071] <Method of manufacturing roughened nickel plated material> Next, a method for producing the roughened nickel-plated product 1 in this embodiment will be described. The manufacturing method of the roughened nickel-plated material 1 in this embodiment is generally the same as the methods described in the above-mentioned Patent Documents 2 and 3, and Japanese Patent Application No. 2019-108779, but is characterized in that the surface state of the substrate 11 or the underlying nickel plating layer 13 is made to be in a predetermined state, so this characteristic part will be mainly described.

[0072] The manufacturing method of the roughened nickel-plated material 1 of the present embodiment is characterized by comprising a substrate surface treatment step of setting SRzjis on the surface of the substrate 11 to 0.5 μm or more and less than 1.7 μm, and a roughened nickel plating step of forming a roughened nickel plating layer 12 on the substrate 11.

[0073] Specifically, the above-mentioned substrate surface treatment step is preferably a rolling step, more preferably a cold rolling step or a temper rolling step, of the substrate 11. The reduction ratio used in this rolling step, the surface roughness of the rolling roll surface, and the like can be appropriately adjusted within known ranges.

[0074] On the other hand, it is preferable that SRzjis on the surface of the substrate 11 is set to 0.5 μm or more and less than 1.7 μm by this substrate surface treatment step. By setting SRzjis on the surface of the substrate 11 to this value, it is possible to suppress the occurrence of non-uniformity, grooves, and the like in the roughened nickel plating layer 12 as described above.

[0075] In addition, when final finishing is performed in a cold rolling process or a temper rolling process in order to set SRzjis on the surface of the substrate 11 to 0.5 μm or more and less than 1.7 μm, the surface roughness of the roll (final roll) for final finishing the surface of the substrate 11 is important. The preferred range of the roll roughness is Ra=0.01 μm to 0.5 μm.

[0076] In particular, when the final finish of the substrate 11 is performed in a cold rolling process (when the cold rolling process is the final finish of the substrate surface), the surface roughness of the roll that performs rolling at a reduction rate of 5% or more is important, and it is preferable that the surface roughness of this roll is in the above range. The reduction ratio in the cold rolling step (reduction ratio=(sheet thickness before rolling−sheet thickness after rolling) / sheet thickness before rolling×100) is preferably 10% or more.

[0077] In addition, when the final finish of the base material 11 is completed by a temper rolling process, it is preferable that the final rolling roll before the temper rolling process has the above range. Incidentally, the rolling reduction in the temper rolling process is generally 0.1% or more and less than 5%.

[0078] Alternatively, the manufacturing method of the roughened nickel-plated material 1 of this embodiment is characterized by having a step of providing an undercoat nickel plating layer 13 having a surface Sku of 4.0 or more on a metal substrate 11, and a roughened nickel plating step of forming a roughened nickel plating layer 12 on the undercoat nickel plating layer 13.

[0079] Furthermore, the Vvc of the surface of the undercoat nickel plating layer is 0.45 μm 3 / μm 2 It is preferable that:

[0080] Methods for controlling the above-mentioned parameter Sku or parameter Vvc on the surface of the base nickel plating layer 13 within the above-mentioned numerical range include a method for controlling the roughness of the substrate 11, a method for controlling the roughness by polishing or temper rolling the base nickel plating layer 13, and a method for controlling by the plating conditions when forming the base nickel plating layer 13. Among these, examples of the method for controlling by the plating conditions when forming the base nickel plating layer 13 include a method for increasing the thickness of the base nickel plating and a method for controlling the grain size of the base nickel plating.

[0081] Furthermore, in order to make the SRzjis of the surface of the base material 11 to be 0.5 μm or more and less than 1.7 μm, the surface may be subjected to final finishing by polishing, for example, mechanical polishing (buffing) or chemical polishing.

[0082] In this embodiment, the roughened nickel plating process for forming the roughened nickel plating layer 12 on the substrate 11 or the base nickel plating layer 13 is generally the same as the methods described in the above-mentioned Patent Documents 2 and 3, and Japanese Patent Application No. 2019-108779, and therefore detailed description thereof will be omitted. In this embodiment, nickel granules may be precipitated on the substrate 11 or on the undercoat nickel plating layer 13 using a roughening nickel plating bath. Also, a coating nickel plating layer may be appropriately precipitated on the roughening nickel plating layer 12. EXAMPLES

[0083] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[0084] <Example 1> First, a cold-rolled sheet (thickness 0.1 mm) of low carbon aluminum-killed steel was prepared as a substrate. This cold-rolled sheet was obtained by final rolling at room temperature under the rolling conditions (reduction ratio, rolling roll) shown in Table 1 so as to have the surface shape (SRa, SRzjis) shown in Table 1. Next, alkaline electrolytic degreasing and pickling by immersion in sulfuric acid were performed to obtain substrate 11. Then, electrolytic plating was performed on substrate 11 under the following conditions using a nickel undercoat plating bath having the following bath composition to form a nickel undercoat layer.

[0085] <Conditions for nickel plating base> Bath composition: Nickel sulfate hexahydrate 250g / L, Nickel chloride hexahydrate 45g / L, Boric acid 30g / L pH 4.2 Bath temperature 60℃ Current density 10A / dm 2 Plating time: 30 seconds The parameters of the obtained nickel underlayer were as shown in Table 3.

[0086] Next, the steel sheet on which the above-mentioned base nickel layer was formed was subjected to electrolytic plating (roughened nickel plating) under the following conditions using a roughened nickel plating bath having the following bath composition, thereby precipitating nickel granules on the base nickel layer.

[0087] <Roughened Nickel Plating Conditions> Bath composition: Nickel sulfate hexahydrate 20g / L, nickel chloride hexahydrate 20g / L, ammonium sulfate 20g / L pH 6 Bath temperature 30℃ Current density 15A / dm 2 Plating time: 26 seconds

[0088] Next, the steel sheet on which the roughened nickel plating layer was formed was subjected to electrolytic plating (coated nickel plating) using the bath composition below under the conditions below to form a roughened nickel plating layer 12 on the substrate 11, thereby obtaining a roughened nickel material 1 in Example 1.

[0089] <Conditions for nickel plating> Bath composition: Nickel sulfate hexahydrate 250g / L, Nickel chloride hexahydrate 45g / L, Boric acid 30g / L pH 4.2 Bath temperature 60℃ Current density 10A / dm 2 Plating time: 30 seconds

[0090] The roughened nickel-plated material thus obtained was subjected to various measurements and evaluations. The details of the measurements and evaluations are described below. The results are shown in Table 2.

[0091] <3D roughness measurement (1)> The substrate 11 before the formation of the roughened nickel plating layer, the surface of the substrate 11 on which the undercoat nickel plating layer 13 has been formed, and the surface of the roughened nickel-plated sheet 1 on which the roughened nickel plating layer 12 has been formed were measured in accordance with JIS B0601:2013 using a laser microscope (manufactured by Olympus Corporation, model number: OLS3500) to obtain a measurement field of 97 μm × 129 μm (length × width) (measurement field width 129 μm, measurement area approximately 12,500 μm 2 After scanning the field of view of (12,500±100) with the measurement direction perpendicular to the rolling direction, various values ​​of SRp, SRv, SRz, SRc, SRa, SRq, and SRzjis were measured by analyzing with analysis software (software name: LEXT-OLS) under the condition of analysis mode: roughness analysis. Note that the cutoff value when measuring with a laser microscope was set to a wavelength of about 43 μm (43.2 on the display), which is 1 / 3 of the length of the measurement field width (129 μm). The obtained parameters are shown in Tables 2 to 4.

[0092] <3D roughness measurement (2)> For the surface on which the base nickel plating layer 13 on the substrate 11 before the formation of the roughened nickel plating layer was formed, and the surface on which the roughened nickel plating layer 12 of the roughened nickel-plated sheet 1 was formed, each three-dimensional surface property parameter (arithmetic mean height Sa, kurtosis Sku, texture aspect ratio Str, core level difference Sk, core spatial volume Vvc, and core solid volume Vmc) was measured using a laser microscope (Olympus Corporation, 3D measuring laser microscope LEXT OLS5000) in accordance with ISO25178-2:2012. Specifically, first, a composite image with a field of view of 591 μm × 591 μm was obtained by scanning 25 images (5 images × 5 images) under the condition of a 100x objective lens (lens name: MPLAPON100XLEXT), and the image for analysis was obtained. Next, the obtained image for analysis was automatically corrected by noise removal and tilt correction using an analysis application. After that, the surface roughness measurement icon was clicked to perform the analysis and obtain each three-dimensional surface property parameter (arithmetic mean height Sa, kurtosis Sku, texture aspect ratio Str, core level difference Sk, core spatial volume Vvc, and core solid volume Vmc). In addition, the analysis was performed without setting all of the filter conditions (F calculation, S filter, L filter). The obtained parameters are shown in Tables 3 and 4.

[0093] <Nickel adhesion measurement> The amount of nickel attached was measured using an X-ray fluorescence device, and the obtained values ​​are shown in Table 2. The amount of nickel in the roughened nickel plating layer (the nickel base layer, the nickel granules, and the nickel coating) was determined by measuring with an X-ray fluorescence device after each process of forming the nickel base layer, the nickel granules, and the nickel coating. Note that the specific measurement method is the same as the method described in Japanese Patent Application No. 2019-108779, so a detailed explanation is omitted here.

[0094] <Glossiness> The 60° gloss and 85° gloss of the roughened nickel plating layer surface were measured in accordance with JIS Z8741 using a gloss meter (product name "VG 7000", manufactured by Nippon Denshoku Industries Co., Ltd.) The results are shown in Table 1.

[0095] <Measurement of length, circumference and maximum diameter of valley area B> The length, circumference and maximum diameter of valley region B were measured using a laser microscope (Olympus Corporation, model number: OLS3500) to scan a measurement range of 97 × 129 μm, as in the three-dimensional roughness measurement described above, and then the measurements were performed using analysis software according to the method described above. Regarding the presence or absence of formation unevenness having a length of 40 μm or more in the rolling direction or the sheet passing direction RD, the above measurement range (97 × 129 μm) was counted as one field of view, and observation was performed in a total of 10 arbitrary fields of view. If formation unevenness having a length of 40 μm or more was not observed in 7 or more fields of view, it was deemed to be less than 40 μm.

[0096] <Tensile strength test> <Resin adhesion (T-peel strength)> The roughened nickel-plated sheets obtained in the Examples and Comparative Examples were cut to prepare two test original sheets with dimensions of 15 mm in width and 50 mm in length, which were used as T-peel test pieces. Each of the two T-peel test pieces was then bent at a 90° angle at a position 20 mm in length. Next, the surfaces of the T-peel test pieces with the roughened nickel layer were placed face to face, and a polypropylene resin film 15 mm wide, 15 mm long, and 60 μm thick (manufactured by Mitsubishi Chemical Corporation, product name "Modic" / polypropylene resin two-layer film; the bonding surface to be evaluated is the bonding surface between the polypropylene resin and the T-peel test piece, the product name "Modic" is the adhesive layer to stabilize the test) was sandwiched between them, and the temperature was 190°C, pressing time was 5 seconds, and heat sealing pressure was 2.0 kgf / cm 2 The two T-peel test pieces were heat-sealed under the above conditions to bond the two pieces together via the polypropylene resin film. The polypropylene resin film was sandwiched at the end of the T-peel test piece in the longitudinal direction, and the entire polypropylene resin film became the bonding surface. A tensile test was carried out on the T-peel specimens thus prepared using a tensile tester (ORIENTEC universal material testing machine Tensilon RTC-1350A) to measure the peel load (T-peel strength). The measurement conditions were room temperature and a tensile speed of 10 mm / min. The higher the T-peel strength, the better the adhesion to the resin. In both the examples and comparative examples, the strength was 8 N / 15 mm width or more.

[0097] <Intensity match rate> The above-mentioned T-peel strength test was carried out in two directions, parallel and perpendicular to the rolling direction, for the roughened nickel plating layer 12 of the roughened nickel plating sheet 1. The agreement rate (%) of the T-peel strength in the two directions is shown in Table 5. The agreement rate (%) was obtained by the following formula. Match rate (%) = "Strength of direction 1" / "Strength of direction 2" x 100 Here, the above directions 1 and 2 are defined as "strength in direction 1 < strength in direction 2." In other words, as a result of the T-peel strength test in the above two directions, the direction with the greater T-peel strength was designated as direction 2, and the direction with the smaller T-peel strength was designated as direction 1.

[0098] The results shown in Table 5 indicate that the present embodiment achieved a match rate of 80% or more in intensity, whereas the comparative example showed a large difference in intensity between the two directions. This result indicates that the present embodiment can suppress anisotropy in two directions.

[0099] <Examples 2 to 5> The same procedure as in Example 1 was carried out except that the substrates shown in Tables 1 and 2 were used. The results are shown in Table 2. A photograph of the appearance of the roughened nickel-plated material obtained in Example 3, a cross-sectional curve at an arbitrary cross section, a brightness image, and a binarized image are shown in FIG. 3(a), and a photograph of the three-dimensional surface properties at the time of Str measurement is shown in FIG. 3(b). A photograph of the appearance of the roughened nickel-plated material obtained in Example 5, a cross-sectional curve at an arbitrary cross section, a brightness image, and a binarized image are shown in FIG. 4.

[0100] <Example 6> The cold-rolled sheet used in Example 1 was subjected to temper rolling using temper rolling rolls having the final rolling roll surface roughness shown in Table 1. The rolling reduction during temper rolling was as shown in Table 1. The rest was the same as in Example 1. The results are shown in Table 2. Also, a photograph of the appearance of the obtained roughened nickel-plated material, a cross-sectional curve at an arbitrary cross section, a brightness image and a binarized image are shown in FIG.

[0101] <Comparative Examples 1 to 3> The same procedure as in Example 1 was carried out except that the substrates shown in Tables 1 and 2 were used. The results are shown in Table 2. A photograph of the three-dimensional surface texture when Str was measured in Comparative Example 1 is shown in FIG. 6(a). A photograph of the three-dimensional surface texture when Str was measured in Comparative Example 2 is shown in FIG. 6(b). A photograph of the appearance of the roughened nickel-plated material obtained in Comparative Example 3, a cross-sectional curve at an arbitrary cross section, a brightness image, and a binarized image are shown in FIG. 6(c), and a photograph of the three-dimensional surface texture when Str was measured is shown in FIG. 6(d).

[0102] <Reference example> Except for changing the thickness of the undercoat nickel plating to 5 μm, the same procedure as in Example 1 was carried out. The results are shown in FIG.

[0103] [Table 1]

[0104] [Table 2]

[0105] [Table 3]

[0106] [Table 4]

[0107] [Table 5]

[0108] According to the above-described embodiments and examples of the present invention, a roughened nickel-plated material capable of suppressing the occurrence of non-uniformity and grooves in the roughened nickel plating layer (uneven formation) can be provided, and the material can be suitably applied to applications in which the material is used in conjunction with other members, such as beautiful food cans, beverage cans, battery cans, etc., for example, as a material for various containers requiring adhesion to various members such as resins and active materials, electronic device members (substrates, etc.), and battery members (outer tanks, current collectors, tab leads). In addition, since it is possible to provide a roughened nickel-plated material with suppressed anisotropy, the material can be applied to products for the above-mentioned applications without being restricted by the rolling direction of the substrate, improving manufacturability. The above-described embodiment and examples may be modified, cut, or decorated without departing from the spirit and scope of the present invention. [Industrial Applicability]

[0109] The roughened nickel-plated material of the present invention can exhibit excellent functionality when used in applications in which it is joined to other components such as resins and active materials, such as materials for containers such as food cans, beverage cans, and battery cans, electronic device components (substrates, etc.), and battery components (outer tanks, current collectors, tab leads). [Explanation of symbols]

[0110] 1. Roughened nickel plating material 11 Base material 12 Roughened nickel plating layer 13 Nickel plating layer

Claims

1. A substrate that is a metal; A roughened nickel plating layer formed on at least one surface of the substrate, The surface roughened nickel plating layer has an SRzjis of 2 μm or more, and A roughened nickel-plated material, characterized in that a maximum height in the roughened nickel plating layer is SRz, and a valley region B in an arbitrary imaginary plane region A observed at a height position of SRz × 0.25 satisfies the following (i). (i) The length of the valley region B in the rolling direction or the sheet passing direction of the substrate is less than 40 μm in linear distance.

2. The roughened nickel-plated product according to claim 1 , wherein a maximum value CLmax of a perimeter CL of the valley region B is less than 500 μm.

3. A substrate that is a metal; A roughened nickel plating layer formed on at least one surface of the substrate, A roughened nickel-plated material, characterized in that Str in three-dimensional surface property parameters of the surface of the roughened nickel plating layer is 0.1 or more.

4. The roughened nickel-plated material according to claim 3, further comprising a three-dimensional surface property parameter Sk of the surface of the roughened nickel plating layer of 1.0 μm to 4.0 μm.

5. Furthermore, the three-dimensional surface property parameter Vvc of the surface of the roughened nickel plating layer is 0.6 μm ３ / μm ２ ~3.0μm ３ / μm ２ The roughened nickel-plated product according to claim 3 .

6. Furthermore, the three-dimensional surface property parameter Vmc of the surface of the roughened nickel plating layer is 0.45 μm ３ / μm ２ ~2.0μm ３ / μm ２ The roughened nickel-plated product according to claim 3 .

7. The roughened nickel-plated product according to any one of claims 1 to 6, wherein the substrate is a steel plate.

8. The surface brightness of the roughened nickel plating layer is L ＊ The roughened nickel-plated product according to any one of claims 1 to 7, wherein the Roughened Nickel Plated Product has a value of 30 to 50.

9. The roughened nickel-plated product according to any one of claims 1 to 7, wherein the surface gloss of the roughened nickel plating layer is 1.5 to 50 at 85 ° gloss.

10. The roughened nickel-plated material according to any one of claims 1 to 9, further comprising an undercoat nickel layer between the substrate and the roughened nickel plating layer.

11. a substrate surface treatment step for setting SRzjis on the surface of the substrate to 0.5 μm or more and less than 1.7 μm; a roughened nickel plating step of forming a roughened nickel plating layer on the base material; The method for producing a roughened nickel-plated product comprising the steps of:

12. providing a base nickel plating layer having a surface Sku of 4.0 or more on a metal substrate; a roughening nickel plating step of forming a roughening nickel plating layer on the base nickel plating layer; The method for producing a roughened nickel-plated product comprising the steps of:

13. Furthermore, the Vvc of the surface of the undercoat nickel plating layer is 0.45 μm ３ / μm ２ The method for producing a roughened nickel-plated product according to claim 12, wherein:

14. The method for producing a roughened nickel-plated product according to claim 11, wherein the substrate surface treatment step is a cold rolling step or a temper rolling step.

15. The method for producing a roughened nickel-plated product according to claim 14, wherein a final rolling roll used for rolling at a rolling reduction rate of 5% or more in the cold rolling step has a surface roughness of 0.01 μm or more and 0.5 μm or less.

16. The method for producing a roughened nickel-plated product according to claim 14, wherein a final roll performing rolling at a rolling reduction rate of 0.1% or more and less than 5% in the temper rolling step has a surface roughness of 0.01 μm or more and 0.5 μm or less.

17. The method for producing a roughened nickel-plated product according to any one of claims 11 to 16, wherein the substrate is a steel plate.

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