Roughened nickel-plated material and method for producing same

Abstract

The invention relates to a roughening nickel plating material and a manufacturing method thereof. Provided is a roughening nickel plating material in which unevenness of a roughening nickel plating layer and unevenness such as the generation of grooves are suppressed in the roughening nickel plating material. The roughened nickel plating material is characterized by comprising a base material as a rolled material and a roughened nickel plating layer formed on at least one surface of the base material, the surface SRzjis of the roughened nickel plating layer being 2 [mu] m or more, and the maximum height of the roughened nickel plating layer being SRz, 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 (RD) of the base material is less than 40 [mu] m in terms of linear distance.

Description

[0001] This application is a divisional application of the Chinese patent application with application number 202080044964.X, application date July 27, 2020, and invention name “Roughened nickel-plated material and manufacturing method thereof”. Technical Field

[0002] The present invention relates to a plating material having a roughened nickel plating layer and a method for producing the same. Background Art

[0003] In recent years, the technology of forming a plating layer on a substrate such as a metal plate or metal foil has not stopped at forming the plating layer smoothly. There are known technologies for forming a roughened plating layer by forming an uneven surface on the plating surface or by attaching the metal to the substrate in a granular or needle-like shape.

[0004] Among them, the roughened nickel-plated material having a roughened nickel-plated layer formed thereon is used as a material for food cans, beverage cans, battery cans, etc., for example, in order to have functions suitable for respective uses or to further improve the functions.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent No. 5885345

[0008] Patent Document 2: Japanese Patent Application Publication No. 2019-104948

[0009] Patent Document 3: Japanese Patent Application Publication No. 2019-104949 Summary of the invention

[0010] Problems to be solved by the invention

[0011] On the other hand, depending on the above-mentioned use, a layer of resin or the like may be further formed on the roughened nickel plating layer of these roughened nickel plating materials.

[0012] On the other hand, the inventors have conducted in-depth research and found that depending on the manufacturing conditions of the roughened nickel-plated material, the growth in the height direction of the roughened nickel-plated layer sometimes becomes uneven. In particular, it was found that although the roughened nickel-plated layer is continuously precipitated in a specific direction of the roughened nickel-plated material, sometimes a portion that is difficult to grow is generated, and sometimes the portion is formed in a groove shape (hereinafter, the groove-shaped area formed by the above-mentioned difficult-to-grow portion, that is, the area that is slightly lower than the surrounding roughened portion when the height of each aggregate of nickel particles in the roughened portion is compared is also referred to as a "groove").

[0013] Due to the non-uniformity of the roughened nickel plating layer and the presence of grooves, there is a possibility that the original intended function cannot be fully exhibited, especially when another layer is coated on the roughened nickel plating layer as disclosed in the patent document.

[0014] The present inventors have further conducted intensive studies and found that the above-mentioned non-uniformity of the roughened nickel plating layer and the generation of grooves can be suppressed by adopting a specific method in the formation of the roughened nickel plating layer.

[0015] That is, with respect to the present invention, in view of the fact that the above-mentioned problem is solved as an example, the purpose is to provide a method for manufacturing a roughened nickel-plated material and a roughened nickel-plated material thereof that can suppress the unevenness of the roughened nickel-plated layer and the generation of grooves (hereinafter also referred to as "uneven formation").

[0016] Means for solving problems

[0017] The roughened nickel-plated material in the present embodiment is characterized in that (1) it comprises: a metal substrate, and a roughened nickel-plated layer formed on at least one surface of the substrate, wherein SRzjis of the surface of the roughened nickel-plated layer is greater than 2 μm, and the maximum height in the roughened nickel-plated layer is set to SRz, and the valley region B in any imaginary plane region A observed at a height position of SRz×0.25 satisfies the following (i).

[0018] (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 terms of linear distance.

[0019] In the above (1), it is preferred that (2) the maximum value of the peripheral length CL of the valley region B is less than 500 μm.

[0020] In addition, with regard to the roughened nickel-plated material in the present embodiment, (3) it is also characterized in that it comprises: a metal substrate, and a roughened nickel-plated layer formed on at least one surface of the above-mentioned substrate, wherein Str among the three-dimensional surface property parameters of the surface of the above-mentioned roughened nickel-plated layer is greater than 0.1.

[0021] In the roughened nickel plating material of the present embodiment, in the above (3), preferably (4) Sk among the three-dimensional surface texture parameters of the surface of the roughened nickel plating layer is 1.0 μm to 4.0 μm.

[0022] In addition, in the roughened nickel plating material of the present embodiment, in the above (3), it is preferred that (5) Vvc of the three-dimensional surface property parameters of the surface of the roughened nickel plating layer is 0.6 μm. 3 / μm 2 ~3.0μm 3 / μm 2 .

[0023] Furthermore, in the roughened nickel plating material of the present embodiment, in the above (3), it is preferred that (6) Vmc of the three-dimensional surface property parameters of the surface of the roughened nickel plating layer is 0.45 μm. 3 / μm 2 ~2.0μm 3 / μm 2 .

[0024] In the roughening nickel plating material of the present embodiment, in any one of the above (1) to (6), preferably (7) the substrate is a steel plate.

[0025] In the roughened nickel plating material of the present embodiment, in any one of the above (1) to (7), preferably (8) the brightness of the surface of the roughened nickel plating layer of the substrate is L ＊ The value is 30 to 50.

[0026] In the roughened nickel plating material of the present embodiment, in any one of the above (1) to (7), preferably (9) the surface glossiness of the roughened nickel plating layer of the substrate is 1.5 to 50 as measured by an 85° gloss meter.

[0027] The roughened nickel plating material in the present embodiment, in any one of (1) to (9) above, preferably has (10) a base nickel layer between the substrate and the roughened nickel plating layer.

[0028] In addition, the method for manufacturing the roughened nickel-plated material in this embodiment comprises: (11) a substrate surface treatment step for making the SRzjis at the surface of the substrate greater than 0.5 μm and less than 1.7 μm, and a roughened nickel-plating step for forming a roughened nickel-plated layer on the substrate.

[0029] In addition, the method for manufacturing the roughened nickel-plated material in this embodiment comprises: (12) a step of providing a base nickel-plated layer having a surface Sku of 4.0 or more on a metal substrate, and a roughening nickel-plating step of forming a roughened nickel-plated layer on the base nickel-plated layer.

[0030] In the above (12), the method for producing a roughened nickel-plated material in the present embodiment is further preferably (13) that the Vvc of the surface of the above-mentioned base nickel-plated layer is 0.45 μm 3 / μm 2 the following.

[0031] In the above (11), it is preferred that (14) the surface treatment step is a cold rolling step or a temper rolling step.

[0032] In addition, in the above (14), preferably (15) the surface roughness of the final rolling roll after the cold rolling process with a reduction ratio of 5% or more is 0.01 μm to 0.5 μm. Alternatively, in the above (14), preferably (16) the surface roughness of the final rolling roll after the temper rolling process with a reduction ratio of 0.1% to less than 5% is 0.01 μm to 0.5 μm.

[0033] Furthermore, in any one of the above (11) to (16), preferably (17) the substrate is a steel plate.

[0034] Effects of the Invention

[0035] According to the manufacturing method of the roughened nickel-plated material of the present invention, a roughened nickel-plated material in which the above-mentioned uneven formation is suppressed can be provided. As for the roughened nickel-plated material of the present invention, by utilizing its excellent properties, it can be used in packaging containers such as beverage cans and bags with liquid as the content, battery components, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] FIG. 1( a ) is a schematic diagram showing a cross section of a roughened nickel plating material 1 in the present embodiment.

[0037] FIG1( b ) is a schematic diagram showing a cross section of a roughened nickel plating material 1 in the present embodiment.

[0038] FIG. 2( a ) is a schematic diagram showing a virtual plane region A of the roughened nickel plating layer 12 in the present embodiment.

[0039] FIG. 2( b ) is a schematic diagram showing a virtual plane region A of the roughened nickel plating layer 12 in the present embodiment.

[0040] FIG. 3( a ) is a view showing a photograph of the appearance of a roughened nickel-plated material obtained in the present embodiment.

[0041] FIG. 3( b ) is a diagram showing a cross-sectional curve at an arbitrary cross section of the roughened nickel-plated material obtained in the present embodiment.

[0042] FIG. 3( c ) is a diagram showing a brightness image of the roughened nickel-plated material obtained in this embodiment.

[0043] FIG. 3( d ) is a diagram showing a binary image of the roughened nickel-plated material obtained in this embodiment.

[0044] FIG. 3( e ) is a diagram showing a three-dimensional surface texture photograph of the roughened nickel-plated material obtained in the present embodiment when measuring Str.

[0045] FIG. 4( a ) is a view showing a photograph of the appearance of a roughened nickel-plated material obtained in the present embodiment.

[0046] FIG. 4( b ) is a diagram showing a cross-sectional curve at an arbitrary cross section of the roughened nickel-plated material obtained in the present embodiment.

[0047] FIG. 4( c ) is a diagram showing a brightness image of the roughened nickel-plated material obtained in this embodiment.

[0048] FIG. 4( d ) is a diagram showing a binary image of the roughened nickel-plated material obtained in this embodiment.

[0049] FIG. 5( a ) is a view showing a photograph of the appearance of a roughened nickel-plated material obtained in the present embodiment.

[0050] FIG. 5( b ) is a diagram showing a cross-sectional curve at an arbitrary cross section of the roughened nickel-plated material obtained in the present embodiment.

[0051] FIG. 5( c ) is a diagram showing a brightness image of the roughened nickel-plated material obtained in this embodiment.

[0052] FIG. 5( d ) is a diagram showing a binary image of the roughened nickel-plated material obtained in this embodiment.

[0053] FIG. 5( e ) is a diagram showing a photograph of the appearance of the roughened nickel-plated material obtained in this embodiment.

[0054] FIG5(f) is a diagram showing a cross-sectional curve at an arbitrary cross section of the roughened nickel-plated material obtained in the present embodiment.

[0055] FIG5(g) is a diagram showing a brightness image of the roughened nickel-plated material obtained in this embodiment.

[0056] FIG5(h) is a diagram showing a binary image of the roughened nickel-plated material obtained in this embodiment.

[0057] FIG. 6( a ) is a diagram showing a three-dimensional surface texture photograph of the roughened nickel-plated material obtained in the comparative example of the present embodiment when Str was measured.

[0058] FIG6(b) is a diagram showing a three-dimensional surface texture photograph of the roughened nickel-plated material obtained in the comparative example of the present embodiment when Str was measured.

[0059] FIG6(c) is a diagram showing a photograph of the appearance of a roughened nickel-plated material obtained in a comparative example of the present embodiment.

[0060] FIG6(d) is a diagram showing a cross-sectional curve at an arbitrary cross section of the roughened nickel-plated material obtained in a comparative example of the present embodiment.

[0061] FIG6(e) is a diagram showing a brightness image of a roughened nickel-plated material obtained in a comparative example of the present embodiment.

[0062] FIG6(f) is a diagram showing a binary image of a roughened nickel-plated material obtained in a comparative example of the present embodiment.

[0063] FIG6(g) is a diagram showing a three-dimensional surface texture photograph of the roughened nickel-plated material obtained in the comparative example of the present embodiment when Str was measured.

[0064] Figure 7 It is a figure which shows the surface etc. of the roughened nickel-plated material obtained in the Example, the Comparative Example, and the Reference Example of this embodiment. DETAILED DESCRIPTION

[0065] Hereinafter, an embodiment as an example for implementing the present invention will be described with reference to the drawings.

[0066] Fig. 1 is a diagram schematically showing a roughened nickel-plated material 1 according to the present embodiment. As shown in Fig. 1(a), the roughened nickel-plated material 1 according to the present embodiment comprises: a substrate 11 and a roughened nickel-plated layer 12 formed on at least one surface of the substrate 11.

[0067] In this embodiment, an example is shown in which roughened nickel plating layer 12 is formed on one surface of substrate 11 , but the present invention is not limited to this embodiment, and roughened nickel plating layer 12 may be formed on both surfaces of substrate 11 .

[0068] <Base material 11>

[0069] As the base material 11 in the present embodiment, a known metal plate or metal foil used as a plating base material can be applied.

[0070] Examples of the material of the substrate 11 include a metal plate or metal foil made of a pure metal selected from Fe, Cu, Al, and Ni, or a metal plate or metal foil made of an alloy containing one selected from Fe, Cu, Al, and Ni.

[0071] Specifically, a steel plate, an iron plate, a stainless steel plate, a copper plate, an aluminum plate, or a nickel plate (these may be any of pure metals or alloys and may be in the form of foil) and the like are mentioned.

[0072] In particular, as steel plates, it is preferred to use low-carbon aluminum-killed steel (carbon content 0.01 to 0.15 wt %), ultra-low carbon steel with a carbon content of less than 0.01 wt % (preferably a carbon content of less than 0.003 wt %), or non-aging ultra-low carbon steel with Ti, Nb, etc. added to the ultra-low carbon steel.

[0073] As the metal plate or metal foil as the substrate 11, rolled materials and electrolytic foils can be applied. In particular, from the perspective of productivity and cost in mass production, rolled materials are preferred, and materials that have undergone known cold rolling, annealing, temper rolling and other processes can be used.

[0074] In addition, the metal plate or metal foil used as the substrate 11 may be a product subjected to a known surface treatment. As known surface treatments, for example, impact nickel plating applied immediately before roughening nickel plating on stainless steel plates and nickel plates, various platings such as nickel plating or nickel alloy plating, zinc plating or zinc alloy plating applied to steel plates, and heat treatments applied after the above various platings can be cited. As the substrate 11 in this embodiment, a metal layer resulting from the above various platings or heat treatments can be formed by such known surface treatments.

[0075] The thickness of the substrate 11 is preferably 0.01 to 2.0 mm, more preferably 0.025 to 1.6 mm, and even more preferably 0.025 to 0.3 mm.

[0076] It should be noted that the "thickness of the substrate 11" in this embodiment refers to the average value of the values ​​obtained by measuring the thickness of the substrate 11 at any 10 points in the optical microscope photograph of the cross section of the substrate 11. Simply, thickness measurement using a microscope can also be applied.

[0077] In the present embodiment, when the surface state of the substrate 11 is in a specific state, the roughened nickel plating material obtained becomes extremely suitable.

[0078] In this embodiment, a roughened nickel plating layer can be formed on the surface of the substrate 11 by using electroplating or other means. In this case, according to the research of the present inventors, it is derived that the roughened nickel plating layer grows by precipitation of nickel ions in the plating bath on the surface of the substrate 11, and the growth degree (growth rate) of the roughened nickel plating layer is locally different depending on the surface state of the substrate 11, especially the surface shape.

[0079] In this embodiment, a rolled plate or rolled foil of a metal can be used as the substrate 11. Generally, these rolled plates or rolled foils (hereinafter, rolled plates and rolled foils are sometimes collectively referred to as "rolled materials") can be obtained by rolling a metal plate with a rolling roller. It is known that the shape (concavity and convexity) of the roller surface of the rolling roller contributes greatly to the surface shape of the metal plate, and generally, it is said that the shape of the roller surface is transferred.

[0080] At this time, it is known that the surface shape formed in the rolled plate and rolled foil varies not only due to the roll surface shape (roller roughness) of the rolling roll, but also due to the reduction rate, rolling speed, hardness of the metal (rolling object material), viscosity of the rolling oil, etc. The main surface shapes in the continuous metal strip include concave parts such as depressions and stripe-like concave and convex parts along the plate passing direction. In particular, it is known that in the rolled material, the concave and convex parts of the rolling roll do not become the shape of the rolled material surface as they are, and sometimes stretching is performed during rolling, thereby forming stripe-like concave parts in the rolled material through the convex parts of the rolling roll, etc., which are called rolling holes, rolling stripes, transfer stripes, etc.

[0081] The inventors of the present invention have found that the surface state of the substrate 11, in particular, the shape of the rolling stripes (size of the concave and convex, height difference, width, angle, etc.) of the above-mentioned rolling stripes, has different local growth rates in the roughened nickel plating layer 12 formed on the substrate 11; and the unevenness and grooves of the roughened nickel plating layer 12 are generated. That is, in the striped part, the roughened nickel plating layer is also precipitated, and each particle also grows to a certain size, so there is no problem as to the characteristics of the entire surface (for example, the adhesion with the resin and other components). On the other hand, it is believed that: in the case of using an extremely small area for example as an electrode of a battery to bond the active material, sometimes the adhesion cannot be ensured in the extremely small area containing the part with a slow growth rate. In addition, it is believed that: in the case of forming unevenness into a large groove shape, sometimes a difference is generated in the adhesion in the rolling direction and the adhesion in the direction perpendicular to the rolling direction, etc. to form unevenness.

[0082] In order to solve such a problem, the present invention has been completed by controlling the surface state of the substrate 11 described above to suppress the unevenness of the roughened nickel plating layer 12 and the generation of grooves.

[0083] In this embodiment, the surface state of the substrate 11 is defined based on parameters in non-contact and three-dimensional surface property measurement as follows.

[0084] Specifically, in this specification, SRa, SRz, and SRzjis are measured and calculated as follows.

[0085] First, based on JIS B 0601 (2013), two-dimensional Ra, Rz, and Rzjis were measured.

[0086] In the present embodiment, the measurement is performed in the rolling direction or in a direction perpendicular to the sheet passing direction. In addition, the measurement range is preferably 100 μm or more, and preferably in the range of 100 μm to 150 μm.

[0087] In addition, the measurement of Ra, Rz, and Rzjis is repeated multiple times while moving the measurement starting point in the rolling direction or the plate passing direction RD, preferably 100 times or more, more preferably 300 times or more. It should be noted that in the examples of the present application described later, 768 measurements were performed.

[0088] From the obtained measurement results, various parameters can be obtained as follows.

[0089] SRa=(R a-1 +R a-2 +···+R a-n ) / n

[0090] SRz=(R z-1 +R z-2 +···+R z-n ) / n

[0091] SRzjis=(Rzjis -1 +Rzjis -2 +···+Rzjis -n ) / n

[0092] It should be noted that n is the number of measurements.

[0093] In the present embodiment, the three-dimensional arithmetic mean height SRa of the surface of the substrate 11 is preferably SRa=0.02 μm to 0.17 μm, and preferably 0.03 μm to 0.15 μm from the viewpoint of suppressing the above-mentioned formation unevenness, and preferably 0.08 μm to 0.15 μm from the viewpoint of cost.

[0094] When the SRa of the surface of the substrate 11 is less than 0.02 μm, not only is excessive cost incurred in the process of adjusting the surface of the substrate 11 to this value, but there is a possibility that the roughened nickel plating layer may not be formed on the substrate 11, or the surface of the roughened nickel plating layer 12 formed on the substrate 11 may become excessively smooth, and the originally required properties and functions of the roughened nickel plating cannot be maximized, so it is not preferred.

[0095] On the other hand, when the SRa of the surface of substrate 11 exceeds 0.17 μm, the growth of roughened nickel plating layer 12 may become non-uniform or grooves may be generated in the obtained roughened nickel plating layer 12 , which is not preferable.

[0096] The surface of the substrate 11 in the present embodiment preferably has a three-dimensional ten-point average roughness SRzjis of SRzjis=0.3 μm or more and less than 1.7 μm. Furthermore, from the viewpoint of suppressing the above-mentioned uneven formation, it is preferably 0.4 μm to 1.6 μm, and from the viewpoint of cost, it is preferably 0.8 μm to 1.5 μm.

[0097] This is due to the following reasons. As described later, the inventors have discovered the following problem: rolling streaks and other concave portions with a length and area of ​​tens of micrometers rather than point depressions are located on the substrate, and when the concave portions are deep, numerous, or wide to a certain depth, poor growth of the roughened plating layer is likely to occur.

[0098] It is difficult to distinguish such concave parts with a length and area of ​​tens of micrometers using the usual two-dimensional roughness parameters. Therefore, attention is paid to the three-dimensional ten-point average roughness SRzjis calculated based on the two-dimensional ten-point average roughness measured in the direction perpendicular to the rolling direction or the plate passing direction RD. As for the three-dimensional ten-point average roughness SRzjis, since it is calculated as the average value of the entire surface based on Rzjis measured in the direction perpendicular to RD, when the concave parts with a length and area of ​​tens of micrometers are located on the surface of the substrate, it becomes a parameter that easily reflects their total number and length.

[0099] In particular, in a rolled material whose mountainous portion is flattened by rolling as described later, the contribution of the SRzjis of the concave portion becomes greater. Therefore, the larger the SRzjis in the 100 μm×100-150 μm region, the more depressions of a size that cause uneven formation of roughened plating on the substrate or the larger the depression area.

[0100] The inventors have further found that by making the SRzjis of the substrate 11 less than 1.7 μm, the valley region in the roughened plating layer 12 after the roughening plating described later can be significantly suppressed. It should be noted that there is no restriction on the lower limit for the purpose of reducing the concave portion of the substrate 11, but in a mirror surface without any unevenness, plating particles for forming the roughened plating layer under the roughening plating conditions are difficult to precipitate, so it is preferably 0.3 μm or more.

[0101] <Base nickel plating>

[0102] In this embodiment, while forming the base nickel plating layer 13 as shown in Figure 1(b) on the substrate 11, the surface state of the base nickel plating layer 13 can also be specified by the three-dimensional surface property parameters specified in ISO-25178-2:2012 (corresponding to JIS B 0681-2:2018).

[0103] It should be noted that as the base nickel plating layer 13, 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, so the detailed description is omitted here.

[0104] In the present embodiment, on the surface of the base nickel plating layer 13, among the three-dimensional surface property parameters described above, it is preferred that Sku (kurtosis), which is a parameter that quantifies the statistic of the height, be 4.0 or more.

[0105] The reason for making the Sku of the base nickel plating layer 13 4.0 or more is as follows. That is, when the base nickel plating layer 13 is formed on the substrate 11, the macroscopic unevenness of the substrate 11 is slightly alleviated by the base nickel plating layer 13, and microscopic fine unevenness caused by the plated particles of the base nickel plating layer 13 is formed. However, for example, when the rolling stripes of the substrate 11 are large, the stripe-like valleys and hills may not be sufficiently alleviated even after the base nickel plating layer 13 is formed.

[0106] Here, the inventors found that after nickel plating (after formation of the base nickel plating layer 13), when there are many constant depths in one direction like rolling stripes with respect to the plane of the plate, Sku, which indicates the sharpness of the height distribution of the three-dimensional surface roughness, reflects its shape well and becomes less than 4.0. That is, it was found that since a large groove portion that causes anisotropy is not formed after roughening nickel plating, it is preferable to control Sku to 4.0 or more.

[0107] It should be noted that Sku is a numerical value indicating the sharpness of the height distribution. When Sku is 3.0, the height distribution is normally distributed. Generally, when Sku exceeds 3.0, it means that there are many sharp mountains and valleys on the surface, and when Sku is less than 3.0, it means that the surface is flat. However, it is known that it does not represent a simple concave and convex shape.

[0108] Based on the above findings, the present inventors have determined through trial and error that the Sku of the surface of the base nickel plating layer 13 is set to be 4.0 or more.

[0109] Furthermore, it was found that it is preferable to set the volume parameter Vvc of the surface of the base nickel plating layer 13 to 0.45 μm. 3 / μm 2 The following describes the case where Vvc is 0.45 μm. 3 / μm 2 The following reasons are as follows.

[0110] That is, Vvc is the volume of the space of the core portion when the load area ratio separating the core portion and the protruding mountain portion is set to 10% and the load area ratio separating the core portion and the protruding valley portion is set to 80%.

[0111] That is, by reducing the space volume in the core portion, which is the center portion of the unevenness on the surface of the base nickel plating layer 13, the groove portion that causes the anisotropy after the roughened nickel plating layer 12 is formed can be reduced.

[0112] The inventors found that by making the Vvc of the surface of the base nickel plating layer 13 0.45 μm 3 / μm 2 As a result, the anisotropy of the surface of the roughened nickel-plated material after the roughening plating can be suppressed.

[0113] <Roughening nickel plating layer>

[0114] Next, roughened nickel plating layer 12 in the present embodiment will be described.

[0115] As for the roughened nickel plating layer 12 in this embodiment, as shown in FIG1, in the cross section, it has a shape in which nickel particles and their aggregates are precipitated on the substrate 11. It is to be noted that the shape of the roughened nickel plating layer 12 is the same as 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 part of the present invention, that is, the difference from the above-mentioned Patent Document 2 or Patent Document 3 is mainly described, and the description of the common points is omitted.

[0116] In addition, for the roughened nickel plating layer 12 in the present embodiment, the roughened nickel plating layer described in Japanese Patent Application No. 2019-108779 can be appropriately referred to.

[0117] 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 that the adhesion with other components such as resin is improved. There is no particular restriction on the upper limit, but it is 20 μm from the viewpoints of plating adhesion, production efficiency, production cost, etc.

[0118] The more preferred range of SRzjis is as follows: That is, from the viewpoint of further improving the adhesion of roughened nickel plating layer 12 to other members, SRzjis is more preferably 3 μm or more, more preferably 4 μm or more, and even more preferably 5 μm or more.

[0119] From the viewpoint of further improving the adhesion of roughened nickel plating layer 12 to substrate 11 (plating adhesion), SRzjis is more preferably 16 μm or less, further preferably 14 μm or less, and still further preferably 12 μm or less.

[0120] In addition, from the viewpoint of emphasizing production efficiency and production cost, SRzjis is preferably 3.0 μm to 7.0 μm.

[0121] In the present embodiment, SRa of roughened nickel plating layer 12 is preferably SRa = 0.1 μm to 3 μm. Furthermore, from the viewpoint of further improving the adhesion of roughened nickel plating layer 12 to other members, SRa is more preferably 0.18 μm or more, and even more preferably 0.3 μm or more.

[0122] From the viewpoint of further improving the adhesion of roughened nickel plating layer 12 to substrate 11 (plating adhesion), SRa is more preferably 1.8 μm or less, further preferably 1.6 μm or less, and still further preferably 1.3 μm or less.

[0123] In addition, from the viewpoint of emphasizing production efficiency and production cost, SRa is preferably 0.18 μm to 0.5 μm, and more preferably 0.18 μm to 0.49 μm.

[0124] From the perspective of plating adhesion, production efficiency, production cost, etc., it is preferred to roughen the brightness of the surface of the nickel plating layer 12 by L ＊ The value is 30 to 50. ＊ When the value of is less than 30, it is not preferable from the viewpoint of plating adhesion. ＊ When the value of exceeds 50, it is not preferable from the viewpoint of adhesion with other members (resin layer, etc.) that may be formed on roughened nickel plating layer 12 .

[0125] In addition, regarding the brightness L of the roughened nickel plating layer 12, ＊ The measurement can be performed using a spectrophotometer using an SCE method (specular reflection elimination method) in accordance with JIS Z8722.

[0126] The glossiness of the roughened nickel plating layer 12 is described below. In the present embodiment, from the viewpoints of plating adhesion, production efficiency, production cost, etc., the glossiness of the roughened nickel plating layer 12 is preferably 1.5 to 50 in terms of 85° glossiness. When the 85° glossiness is less than 1.5, it is not preferred from the viewpoint of plating adhesion. On the other hand, when the 85° glossiness exceeds 50, it 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.

[0127] The 85° glossiness of the surface of the roughened nickel plating layer 12 can be determined by measuring the 85° specular glossiness using a gloss meter in accordance with JIS Z8741.

[0128] On the other hand, the 60° glossiness of roughened nickel plating layer 12 of the present embodiment is usually 10 or less.

[0129] In this embodiment, the chromaticity a of the surface of the roughened nickel plating layer 12 is＊ , b ＊ There is no particular limitation, but from the viewpoint of plating adhesion and adhesion with a resin layer that may be formed on the roughened nickel plating layer 12, the chromaticity a ＊ Preferably 0.1 to 3.0, chromaticity b ＊ It is preferably 1.0 to 8.0.

[0130] In the present embodiment, the arithmetic mean height SRa at the surface of the roughened nickel plating layer 12 is preferably 0.1 μm to 3 μm. This is based on the adhesion with a resin layer that may be formed on the roughened nickel plating layer 12, the adhesion between the roughened nickel plating layer 12 and the substrate 11 (plating adhesion), production efficiency, production cost, and the like.

[0131] In the present 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.

[0132] In addition, the three-dimensional surface roughness SRa, SRzjis, and SRz are preferably measured by a laser microscope.

[0133] In this embodiment, the nickel deposition amount of the roughened nickel plating layer 12 is not particularly limited, but is 1.34 g / m 2 ~57.85g / m 2 Among them, the adhesion amount of the roughened nickel plating layer excluding the base nickel is preferably 1.34 to 45.0 g / m 2 In addition, from the viewpoint of further improving the adhesion (plating adhesion) of the roughened nickel plating layer 12, the adhesion amount of the roughened nickel plating layer 12 is more preferably 2.67 g / m 2 More than 5g / m 2 From the viewpoint of further improving the adhesion of the roughened nickel plating layer 12 to other members, the adhesion amount of the roughened nickel plating layer 12 is more preferably 38.0 g / m 2 Below, more preferably 32.0 g / m 2 Below, more preferably 31g / m 2 the following.

[0134] In addition, the adhesion amount when including the base nickel is 5.0 to 50.00 g / m 2 . Furthermore, it is more preferably 12.02m 2 ~50.00g / m 2 , and more preferably 12.28m 2 ~40.94g / m 2 , especially preferably 12.28m 2 ~32.49g / m 2 .

[0135] In addition, from the viewpoint of focusing on production efficiency and production cost, the total deposition amount of the roughened nickel plating layer 12 and the base metal plating layer 13 is preferably 10.24 m 2 ~22.25g / m 2 Furthermore, in the case where high corrosion resistance is required and particularly high adhesion of the roughened nickel plating layer 12 to the metal substrate 11 and adhesion to other components is required, the total adhesion amount of the roughened nickel plating layer 12 and the base metal plating layer 13 is preferably 32.50 g / m 2 ~57.85g / m 2 .

[0136] The total deposition amount of roughened nickel plating layer 12 and base metal plating layer 13 can be determined by measuring the total nickel amount of roughened nickel plating plate 1 using a fluorescent X-ray device.

[0137] The adhesion amount of roughened nickel plating layer 12 can be determined by measuring the total nickel amount of roughened nickel plating plate 1 using a fluorescent X-ray device, but the method is not limited to this method and other known measuring methods may be used.

[0138] In the present embodiment, preferably, when the maximum height roughness of the roughened nickel plating layer is SRz, valley region B in any virtual plane region A observed at a height position of SRz×0.25 satisfies the following (i).

[0139] (i) The length of the valley region B in the rolling direction (sheet passing direction) RD of the substrate is less than 50 μm in terms of linear distance.

[0140] In addition, it is more preferable that the valley region B satisfies the following (ii).

[0141] (ii) In any straight line length of 80 μm, the total length of the portion of the valley region B that is 10 μm or more in the rolling direction RD of the substrate is less than 50 μm.

[0142] The following description will be given using the accompanying drawings.

[0143] Fig. 2 is a diagram for describing the above-mentioned imaginary plane for explaining the present embodiment and the features of the present embodiment obtained based thereon. Fig. 2(a) is a diagram schematically showing the maximum height roughness SRz of the roughened nickel plating layer 12 and the imaginary plane region A in the present embodiment. Fig. 2(b) is a schematic diagram when the valley region B and the rest thereof are binarized when the roughened nickel plating layer 12 is cut by the imaginary plane region A.

[0144] As shown in Fig. 2(a), when the surface of the roughened nickel plating layer is observed three-dimensionally, a plurality of hills and valleys are observed. The height of the highest hill and the depth of the deepest valley in the observation area are added together to form SRz, and a schematic diagram obtained when a plane is obtained from a position 1 / 4 (0.25) away in the height direction (Z direction in Fig. 2(a)) can be referred to as the virtual plane area A shown in Fig. 2(b).

[0145] As shown in FIG2(b), the valley region B and other parts (mountains and valleys whose depth is less than the plane) exist in the virtual plane region A. In other words, the valley region B indicated by the oblique lines can be said to be a region of a concave portion that is recessed below the reference plane when a reference plane parallel to the main surface is obtained at a height of 1 / 4 of SRz.

[0146] Furthermore, in the present embodiment, the valley region B preferably satisfies the above-mentioned condition (i).

[0147] That is, as shown in FIG. 2( b ), as condition (i), it is preferable that the length L of the plurality of valley regions B existing in the imaginary plane region A in the rolling direction RD is B1 , L B2 , L B3 ,...In terms of straight-line distance, the distances are all less than 40μm.

[0148] Secondly, as condition (ii), when there are multiple valley regions B in an arbitrary straight line L of 80 μm in length parallel to the rolling direction RD, it is preferred that the total length (D1+D2+···) of the parts where the straight line L intersects the valley region B, that is, the parts D1, D2··· whose length is greater than 10 μm, is less than 50 μm.

[0149] Furthermore, the surface state of roughened nickel plating layer 12 in the present embodiment may also be specified by three-dimensional surface texture parameters specified in ISO-25178-2:2012 (corresponding JIS B 0681-2:2018).

[0150] For example, by specifying Str, a parameter representing the aspect ratio (i.e., anisotropy) of the texture, the non-uniformity of the roughened nickel-plated layer 12 and the generation of grooves (uneven formation) can be suppressed. That is, by making Str greater than 0.1, a material with controlled anisotropy can be formed for the obtained roughened nickel-plated material 1. Preferably, Str is greater than 0.15, more preferably greater than 0.2, further preferably greater than 0.3, and particularly preferably greater than 0.4. The upper limit of Str is 1, and in the present embodiment, it is also set to less than 1.0.

[0151] Thus, by controlling the anisotropy of the roughened nickel-plated material 1, the following advantages are obtained. First, when the anisotropy is significant, the bonding strength and corrosion resistance with the resin to be bonded may be fragile in one direction. In contrast, the roughened nickel-plated material of the present embodiment reduces the anisotropy, so it can also be used in applications that hate the anisotropy of extreme properties. In addition, secondly, for example, when the roughened nickel-plated material 1 is cut into a specified size and used as a cutting material for food cans, beverage cans, battery cans, etc., even if the roughened nickel-plated material 1 is visually uniform, in the case of having anisotropy in the microscopic range, in order to exert the material properties, it is necessary to be manufactured under the direction constraints of the cutting material, and the manufacturability may be reduced.

[0152] In the present embodiment, since anisotropy can be controlled even in the cut material, for example, during manufacturing, the product can be manufactured without being restricted by the direction of the cut material, and the manufacturability is significantly improved.

[0153] It should be noted that for the surface state of the roughened nickel plating layer 12 of the present embodiment, the parameters other than the above-mentioned Str are preferably specified as follows. It should be noted that the parameters are disclosed in ISO-25178-2:2012 (corresponding JIS B 0681-2:2018), so the detailed description is omitted here.

[0154] Sku: 3.0 or above

[0155] Sa(μm): 0.2~1.3

[0156] Sk(μm):1.0~4.0

[0157] Vvc(μm 3 / μm 2 ): 0.6~3.0

[0158] Vmc(μm 3 / μm 2 ): 0.45~2.0

[0159] By defining the parameters as described above, uneven formation can be further suppressed in the roughened nickel plating material, which is preferred. In addition, from the viewpoints of suppressing anisotropy, improving adhesion with other components, plating adhesion, etc., it is more preferred to control within the following ranges.

[0160] Sku: 3.32 or above

[0161] Sa(μm): 0.36~1.2

[0162] Sk(μm):1.3~4.0

[0163] Vvc(μm 3 / μm 2 ): 0.7~2.5

[0164] Vmc(μm 3 / μm 2 ): 0.5~1.5

[0165] It should be noted that the above-mentioned three-dimensional surface texture parameters Str, Sku, Sa, Sk, Vvc, Vmc and the like are preferably measured using a laser microscope.

[0166] In the present embodiment, the reason why the unevenness of the roughened nickel plating layer and the generation of grooves (hereinafter also referred to as “uneven formation”) can be suppressed by the above-mentioned limitation is as follows.

[0167] That is, as a characteristic of the roughened nickel plating layer when grown by electroplating, as also described in the above-mentioned Patent Document 2 and / or Patent Document 3, it is confirmed that the cores of the primary particles of nickel tend to precipitate preferentially on the protrusions (including the protrusions formed by the precipitated nickel particles).

[0168] Therefore, in the case of forming a roughened nickel plating layer with a higher roughness, it is preferred that the concavity and convexity of the substrate 11 is large. However, if the concavity and convexity of the substrate is too large, it is possible to form roughening locally. Therefore, in order to form a uniform high coating over a wide range, as a method of flattening while making the roughness of a certain degree of convex portion (mountain) remain in the substrate, the inventor pays attention to the control of the surface shape in the rolled material. However, it is known that: in the usual nickel plating, the substrate appearance is flat, even if the roughness range is not fluctuated in the plating formation, there is also a new topic in the nickel roughening coating.

[0169] That is, when the roughened plated material is viewed over a wide range, Figure 7 The low-magnification image (×150) shows that the roughened nickel plating layer is formed on the entire surface. Therefore, there is no problem in the required properties in a wide range (for example, in the case of close adhesion with resin etc. in a wide range). Figure 7 In the observation of a very small range at a high magnification such as (×10000), it can be confirmed that a roughened nickel particle aggregate is formed on the entire surface of the substrate 11. However, when the height is fully confirmed from the surface side at a medium magnification as shown in Figures 4 to 6, it is found that a groove-like region (concave portion) of the order of tens of micrometers is sometimes formed, which is different from the height difference of each aggregate.

[0170] For such a groove with an area of ​​tens of micrometers, Figure 7It is difficult to know from the cross-sectional image of the high-magnification image of the part. According to the research of the present inventors, as the reason for the formation of such a groove in the region of tens of microns, it is speculated that even if it is flattened by rolling, it is difficult for the particles and aggregates that form the roughened nickel plating to grow in the concave parts with a certain area such as the rolling stripes of the substrate 11. Furthermore, around the concave parts, it is easy to grow to a normal height or to grow higher, so it is speculated that the unevenness after the roughened nickel plating appears more significantly than the unevenness of the rolling stripes before the roughened nickel plating, and becomes a larger groove shape.

[0171] As a result, it is inferred that the height of the roughened nickel plating layer formed on the concave portion caused by the rolling streaks of the substrate 11 is lower than the height of the roughened nickel plating layer formed on the convex portion caused by the rolling streaks. Furthermore, when observing such a portion with reduced height and its surroundings, it was confirmed from the actual surface observation image that the portion with reduced height was observed as a groove shape.

[0172] The inventors of the present invention have repeatedly conducted experiments and have confirmed that by setting the surface state of the substrate 11 (the state of the unevenness caused by the rolling streaks, surface roughness, etc.) to a specific state, the groove portion of the roughened nickel plating layer formed on the concave portion of the rolling streak can disappear.

[0173] Furthermore, the present inventors have conducted intensive studies on a method of expressing the surface state of the roughened nickel plating layer 12 and have found that the objective problem can be solved and the effect can be achieved by expressing the surface state as in the above conditions (i) and (ii).

[0174] It should be noted that in this embodiment, there are multiple valley regions B (B1, B2, B3...) in the virtual plane region A as described above. Moreover, the maximum value CLmax of the perimeter CL (CL1, CL2, CL3...) of each valley region B is preferably less than 500 μm. In other words, the perimeter of the valley region B in the virtual plane region A is preferably shorter than the specified length.

[0175] That is, when circumference CL is longer than a predetermined length, it is not preferable because it is considered that a groove shape is formed in roughened nickel plating layer 12 as described above. More preferably, CLmax is less than 100 μm.

[0176] In addition, in the present embodiment, the maximum value of the maximum diameter of each valley region B is preferably 25 μm or less. That is, the maximum value MDmax of the maximum diameter MD (MD1, MD2, MD3, etc.) of each valley region B is preferably 25 μm or less. It should be noted that the maximum diameter of the valley region B can be measured by a known measuring device.

[0177] It is noted that in the present embodiment, the roughened nickel plating layer 12 may include a base nickel layer or a coating nickel layer therein. It is noted that for the base nickel layer and the coating nickel layer, since the contents disclosed in the above-mentioned patent documents 2 and 3, and further in Japanese patent application 2019-108779, can be appropriately applied, detailed descriptions are omitted in the present application.

[0178] <Method for producing roughened nickel-plated material>

[0179] Next, a method for producing the roughened nickel plating material 1 in the present embodiment will be described.

[0180] As for the manufacturing method of the roughened nickel-plated material 1 in this embodiment, it is roughly the same as the method described in the above-mentioned Patent Document 2 and Patent Document 3 and Japanese Patent Application No. 2019-108779, and has a characteristic in that the surface state of the substrate 11 or the base nickel-plated layer 13 is made to be a specified state, so this characteristic part is mainly described.

[0181] The method for producing the roughened nickel plated material 1 of the present embodiment is characterized by comprising: a substrate surface treatment step of making the SRzjis of the surface of the substrate 11 be 0.5 μm or more and less than 1.7 μm; and a roughened nickel plating step of forming the roughened nickel plated layer 12 on the substrate 11 .

[0182] The substrate surface treatment step is preferably a rolling step of the substrate 11, more preferably a cold rolling step or a temper rolling step. The rolling reduction rate and the surface roughness of the rolling roll surface used in the rolling step can be appropriately adjusted within a known range.

[0183] On the other hand, it is preferable that the SRzjis of the surface of the substrate 11 be set to 0.5 μm or more and less than 1.7 μm by the substrate surface treatment step.

[0184] By setting the SRzjis of the surface of the substrate 11 to this value, the above-mentioned unevenness of the roughened nickel plating layer 12 and the occurrence of grooves and the like can be suppressed.

[0185] It should be noted that since the SRzjis of the surface of the substrate 11 is made to be greater than 0.5 μm and less than 1.7 μm, when final finishing is performed in the cold rolling process or the temper rolling process, the roughness of the roller (final roller) used for final finishing of the surface of the substrate 11, that is, the surface roughness is important. The preferred range of the roller roughness is Ra = 0.01 μm to 0.5 μm.

[0186] In particular, when the substrate 11 is finally finished in the cold rolling process (when the cold rolling process is the final finishing of the substrate surface), the surface roughness of the roll for rolling with a reduction ratio of 5% or more is important, and the surface roughness of the roll is preferably within the above range.

[0187] 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.

[0188] When the final finishing of the substrate 11 is completed in the temper rolling step, the final rolling roll before the temper rolling step is preferably within the above range. Incidentally, the reduction ratio in the temper rolling step is generally 0.1% or more and less than 5%.

[0189] Alternatively, the manufacturing method of the roughened nickel-plated material 1 of the present embodiment is characterized in that it comprises: a process of providing a base nickel-plated layer 13 having a surface Sku of 4.0 or more on a metal substrate 11, and a roughening nickel-plating process of forming a roughened nickel-plated layer 12 on the base nickel-plated layer 13.

[0190] Furthermore, it is preferred that the Vvc of the surface of the above-mentioned base nickel plating layer is 0.45 μm 3 / μm 2 the following.

[0191] It is to be noted that as a method for controlling the above-mentioned parameter Sku or parameter Vvc on the surface of the base nickel plating layer 13 to the above-mentioned numerical range, there can be listed a method of controlling the roughness of the substrate 11, a method of controlling the roughness by grinding and tempering the base nickel plating layer 13, a method of controlling by the plating conditions when the base nickel plating layer 13 is formed, etc. Among them, as a method of controlling by the plating conditions when the base nickel plating layer 13 is formed, there can be listed a method of thickening the base nickel plating and controlling the particle size of the base nickel plating.

[0192] In order to make the SRzjis of the surface of the substrate 11 not less than 0.5 μm and less than 1.7 μm, the surface may be finally finished by polishing, for example, mechanical polishing (buffing polishing) or chemical polishing.

[0193] It should be noted that in the present embodiment, the roughening nickel plating process for forming a roughened nickel plating layer 12 on the substrate 11 or on the base nickel plating layer 13 is substantially the same as the method described in the above-mentioned Patent Documents 2 and 3 and Japanese Patent Application No. 2019-108779, and therefore the details thereof are omitted.

[0194] In this embodiment, nickel particles can be precipitated by a roughening nickel plating bath on the substrate 11 or the base nickel plating layer 13. In addition, a covering nickel plating layer can be appropriately precipitated on the roughening nickel plating layer 12.

[0195] Example

[0196] The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these Examples.

[0197] <Example 1>

[0198] First, a cold-rolled sheet (thickness 0.1 mm) of low-carbon aluminum-killed steel was prepared as a substrate. The cold-rolled sheet was finally rolled at room temperature using the rolling conditions (reduction rate, rolling rolls) shown in Table 1 in such a manner as to have the surface shape (SRa, SRzjis) shown in Table 1. Next, alkaline electrolytic degreasing and pickling by sulfuric acid immersion were performed to obtain a substrate 11. Then, electroplating was performed on the substrate 11 using a base nickel plating bath having the following bath composition under the following conditions to form a base nickel layer.

[0199] <<Base Nickel Plating Conditions>>

[0200] Bath composition: Nickel sulfate hexahydrate 250g / L, nickel chloride hexahydrate 45g / L, boric acid 30g / L

[0201] pH 4.2

[0202] Bath temperature 60℃

[0203] Current density 10A / dm 2

[0204] Plating time 30 seconds

[0205] In addition, the parameters of the obtained base nickel layer are shown in Table 3.

[0206] Next, the steel sheet having the above-mentioned base nickel layer formed thereon was subjected to electroplating (roughening nickel plating) under the following conditions using a roughening nickel plating bath having the following bath composition, thereby precipitating nickel particles on the base nickel layer.

[0207] 《Roughening Nickel Plating Conditions》

[0208] Bath composition: Nickel sulfate hexahydrate 20g / L, nickel chloride hexahydrate 20g / L, ammonium sulfate 20g / L

[0209] pH 6

[0210] Bath temperature 30℃

[0211] Current density 15A / dm 2

[0212] Plating time: 26 seconds

[0213] Next, the steel sheet having the roughened nickel plating layer formed thereon was electroplated (nickel coating) using the following bath composition and conditions to form a roughened nickel plating layer 12 on the substrate 11, thereby obtaining a roughened nickel material 1 in Example 1.

[0214] << Nickel coating conditions 》

[0215] Bath composition: Nickel sulfate hexahydrate 250g / L, nickel chloride hexahydrate 45g / L, boric acid 30g / L

[0216] pH 4.2

[0217] Bath temperature 60℃

[0218] Current density 10A / dm 2

[0219] Plating time 30 seconds

[0220] The roughened nickel-plated material was subjected to various measurements and evaluations. The details of the measurements and evaluations are described below. The results are shown in Table 2.

[0221] <<Three-dimensional roughness measurement (1)》

[0222] For the substrate 11 before the roughened nickel plating layer is formed, the surface of the substrate 11 on which the base nickel plating layer 13 is formed, and the surface of the roughened nickel plating plate 1 on which the roughened nickel plating layer 12 is formed, a laser microscope (manufactured by Olympus Corporation, model: OLS3500) was used in accordance with JIS B0601:2013, with the measurement direction being perpendicular to the rolling direction, and a 97 μm×129 μm (vertical×horizontal) (measurement field width 129 μm, measurement area approximately 12500 μm 2 After scanning the field of view (12500±100)), the analysis software (software name: LEXT-OLS) was used to analyze the roughness analysis mode, and the various values ​​of SRp, SRv, SRz, SRc, SRa, SRq, and SRzjis were measured. It should be noted that the cutoff value when measuring with a laser microscope is set to a wavelength of about 43 μm (43.2 in the display), which is 1 / 3 of the length of the measurement field width (129 μm).

[0223] The obtained parameters are shown in Tables 2 to 4.

[0224] 《3D Roughness Measurement (2)》>>

[0225] For the surface of the substrate 11 on which the base nickel plating layer 13 is formed before the roughened nickel plating layer is formed and the surface of the roughened nickel plating plate 1 on which the roughened nickel plating layer 12 is formed, the three-dimensional surface property parameters (arithmetic mean height Sa, kurtosis Sku, aspect ratio Str of the texture, level difference Sk of the core, core spatial volume Vvc, core solid volume Vmc) were measured in accordance with ISO25178-2:2012 using a laser microscope (manufactured by Olympus Corporation, 3D measurement laser microscope LEXT OLS5000).

[0226] Specifically, first, a pasted 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 100 times objective lens (lens name: MPLAPON100XLEXT) to obtain an image for analysis. Next, the obtained image for analysis was subjected to noise removal and slope correction as automatic correction processing using an analysis application.

[0227] Then, click the icon for surface roughness measurement and perform analysis to obtain the three-dimensional surface property parameters (arithmetic mean height Sa, kurtosis Sku, aspect ratio of texture Str, level difference of core Sk, core space volume Vvc, core solid volume Vmc).

[0228] Note that, in the analysis, all filter conditions (F calculation, S filter, L filter) were not set, and the analysis was performed without conditions.

[0229] The obtained parameters are shown in Tables 3 and 4.

[0230] <<Measurement of Nickel Adhesion Amount>>

[0231] The nickel adhesion amount was measured using a fluorescent X-ray device, and the obtained values ​​are shown in Table 2. The amount of nickel in the roughened nickel plating layer (base nickel layer, nickel granules, and nickel film) was determined by measuring with a fluorescent X-ray device after each process in which a base nickel layer, nickel granules, and a nickel film were formed. It should be noted that the specific measurement method is the same as the method described in Japanese Patent Application No. 2019-108779, so a detailed description is omitted here.

[0232] <<Glossiness>

[0233] The 60° glossiness and 85° glossiness of the surface of the roughened nickel plating layer were measured using a gloss meter (product name "VG 7000", manufactured by Nippon Denshoku Industries, Ltd.) in accordance with JIS Z8741. The results are shown in Table 1.

[0234] 《Measurement of the length, circumference and maximum diameter of valley area B》

[0235] The length, circumference and maximum diameter of the valley region B were measured in the same manner as the three-dimensional roughness measurement described above, using a laser microscope (manufactured by Olympus Corporation, model: OLS3500) with the measurement range of 97×129 μm scanned and then performed using the analytical software by the above method.

[0236] It should be noted that with regard to the presence or absence of uneven formation of more than 40 μm in the rolling direction or the plate passing direction RD, the above-mentioned measurement range (97×129 μm) is taken as one field of view, and observation is performed in any total of 10 fields of view. The situation where no uneven formation of more than 40 μm in length is observed in more than 7 fields of view is recorded as less than 40 μm.

[0237] Tensile strength test

[0238] <Adhesion of resin (T peel strength)>

[0239] The roughened nickel-plated plates obtained in the examples and comparative examples were cut to produce two original test plates with a width of 15 mm and a length of 50 mm, which were used as T peel test pieces. The two T peel test pieces were then bent at a length of 20 mm at an angle of 90°.

[0240] Next, the surfaces of the T peel test pieces with the roughened nickel plating layer were made to face each other, and a polypropylene resin film (manufactured by Mitsubishi Chemical Corporation, trade name "Modek" / 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, and the trade name "Modek" is an adhesive layer for stabilizing the test) with a width of 15 mm, a length of 15 mm, and a thickness of 60 μm was sandwiched and the test pieces were placed at a temperature of 190°C, a pressing time of 5 seconds, and a heat sealing pressure of 2.0 kgf / cm 2 The two T peel test pieces were heat-sealed under the conditions of , and the two T peel test pieces were joined via the polypropylene resin film. The positions where the polypropylene resin films were sandwiched were the ends in the longitudinal direction of the T peel test body, and the entire polypropylene resin film became the joining surface.

[0241] For the T peel test body thus prepared, a tensile test was performed using a tensile testing machine (TENSILON RTC-1350A, a universal material testing machine manufactured by ORIENTEC) to measure the peel load (T peel strength). The measurement conditions were set to a tensile speed of 10 mm / min at room temperature. It can be judged that the higher the T peel strength, the better the adhesion with the resin. The Examples and Comparative Examples were all 8N / 15mm wide or more.

[0242] <Consistency of strength>

[0243] The above-mentioned T peel strength test was performed on the roughened nickel-plated layer 12 of the roughened nickel-plated plate 1 in both directions parallel to the rolling direction and the straight direction. The consistency rate (%) of the T peel strength in both directions is shown in Table 5. It should be noted that the consistency rate (%) is obtained by the following formula.

[0244] Coincidence rate (%) = "Strength in direction 1" / "Strength in direction 2" × 100

[0245] Here, the above-mentioned directions 1 and 2 are defined as "strength in direction 1 <strength in direction 2". That is, the T-peel strength test is performed in the above-mentioned two directions, and the direction with the larger T-peel strength is defined as direction 2, and the direction with the smaller T-peel strength is defined as direction 1.

[0246] The results shown in Table 5 show that the present embodiment achieves a strength consistency of 80% or more, whereas the comparative example has a large difference in strength in both directions. This result shows that the present embodiment can suppress anisotropy in both directions.

[0247] <Examples 2 to 5>

[0248] The same method as in Example 1 was used except that the substrates shown in Tables 1 and 2 were used. The results are shown in Table 2. In addition, the appearance photograph of the roughened nickel-plated material obtained in Example 3, the cross-sectional curve at any cross section, the brightness image, and the binary image are shown in FIG. 3 (a), and the three-dimensional surface property photograph during Str measurement is shown in FIG. 3 (b). Furthermore, the appearance photograph of the roughened nickel-plated material obtained in Example 5, the cross-sectional curve at any cross section, the brightness image, and the binary image are shown in FIG.

[0249] <Example 6>

[0250] The cold rolled sheet used in Example 1 was tempered using a temper rolling roll having the final rolling roll surface roughness shown in Table 1. The reduction ratio during the temper rolling is shown in Table 1. Other than this, the same procedure as in Example 1 was followed. The results are shown in Table 2. In addition, an appearance photograph of the obtained roughened nickel-plated material, a cross-sectional curve at an arbitrary cross section, a brightness image, and a binary image are shown in FIG5 .

[0251] <Comparative Examples 1 to 3>

[0252] The same method as in Example 1 was used except that the substrates shown in Tables 1 and 2 were used. The results are shown in Table 2. In addition, a three-dimensional surface property photograph when Str was measured in Comparative Example 1 is shown in FIG6(a). A three-dimensional surface property photograph when Str was measured in Comparative Example 2 is shown in FIG6(b). An appearance photograph 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 FIG6(c), and a three-dimensional surface property photograph when Str was measured is shown in FIG6(d).

[0253] <Reference example>

[0254] The same procedure as in Example 1 was performed except that the thickness of the base nickel plating layer was changed to 5 μm. The results are shown in Figure 7 middle.

[0255] [Table 1]

[0256]

[0257] [Table 2

[0258]

[0259] [Table 3]

[0260]

[0261] [Table 4

[0262]

[0263] [Table 5]

[0264]

[0265] According to the above-described embodiments and examples of the present invention, a roughened nickel-plated material that can suppress the unevenness of the roughened nickel-plated layer and the generation of grooves (forming unevenness) can be provided, and can be applied to, for example, beautiful food cans, beverage cans, battery cans, etc., and uses for joining with other components, for example, it can be suitable for use as a material for various containers, electronic equipment components (substrates, etc.), and battery components (outer tanks, collectors, lead tabs) that require adhesion to various components such as resins and active materials. In addition, since a roughened nickel-plated material that suppresses anisotropy can be provided, it will not be constrained by the rolling direction of the substrate, and can be applied to the manufacture of the above-mentioned purposes, and the manufacturability is improved.

[0266] It should be noted that the above-described embodiments and examples may be subject to additional deformation, cutting, and modification without departing from the spirit and scope of the present invention.

[0267] Industrial Applicability

[0268] The roughened nickel-plated material of the present invention can exhibit excellent functionality by being used in applications such as materials for containers such as food cans, beverage cans, and battery cans, electronic device components (substrates, etc.), and battery components (outer tanks, collectors, and lead tabs), which are used in conjunction with other components such as resins and active materials.

[0269] Description of Reference Numerals

[0270] 1 Roughening nickel plating material

[0271] 11 Base material

[0272] 12 Roughening of nickel plating layer

[0273] 13Base nickel plating

Claims

1. A roughened nickel-plated material, characterized in that: Include: As a metal substrate, and a roughened nickel plating layer formed on at least one surface of the substrate, The SRzjis of the surface of the roughened nickel plating layer is 2 μm or more, and The maximum height in the roughened nickel plating layer is defined as SRz, and the valley region B in an arbitrary virtual 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 terms of linear distance.

2. The roughened nickel-plated material according to claim 1, wherein: The maximum value CLmax of the peripheral length CL of the valley region B is less than 500 μm.

3. A roughened nickel-plated material, characterized in that: Include: As a metal substrate, and a roughened nickel plating layer formed on at least one surface of the substrate, The Str among the three-dimensional surface texture parameters of the surface of the roughened nickel plating layer is greater than or equal to 0.

1.

4. The roughened nickel-plated material according to claim 3, wherein: Furthermore, the three-dimensional surface property parameter Sk of the surface of the roughened nickel plating layer is 1.0 μm to 4.0 μm.

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

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

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

8. The roughened nickel-plated material according to any one of claims 1 to 7, wherein The brightness of the surface of the roughened nickel-plated layer is expressed by L ＊ The value is 30 to 50.

9. The roughened nickel-plated material according to any one of claims 1 to 7, wherein The glossiness of the surface of the roughened nickel plating layer is 1.5-50, expressed as 85° glossiness.

10. The roughened nickel-plated material according to any one of claims 1 to 9, wherein A base nickel layer is provided between the substrate and the roughened nickel plated layer.

11. A method for manufacturing a roughened nickel-plated material, comprising: A substrate surface treatment step of making the SRzjis at the surface of the substrate 0.5 μm or more and less than 1.7 μm, and A roughening nickel plating step is performed to form a roughening nickel plating layer on the substrate.

12. A method for manufacturing a roughened nickel-plated material, comprising: A step of providing a base nickel plating layer having a surface Sku of 4.0 or more on a metal substrate, and A roughening nickel plating step is to form a roughening nickel plating layer on the base nickel plating layer.

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

14. The method for producing a roughened nickel-plated material according to claim 11, wherein: The substrate surface treatment process is a cold rolling process or a tempering rolling process.

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

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

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

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