Nickel-plated metal material

Abstract

Provided is a nickel-plated metal material having adhesion to another member while suppressing the height of a roughened nickel layer. The nickel-plated metal material is characterized in that the nickel-plated metal material comprises a substrate made of metal and a roughened nickel layer arranged on at least one surface of the substrate, the ten-point average roughness Rzjis of the outermost surface of the nickel-plated metal material on the roughened nickel layer side is 1.0 [mu] m or more and less than 4.8 [mu] m, and the roughened surface area of the outermost surface of the nickel-plated metal material on the roughened nickel layer side is 1.5 m < 2 > / 1 m < 2 > or more.

Description

Technical Field

[0001] The present disclosure relates to nickel-plated metal materials. Background Art

[0002] In recent years, in the technology of forming a coating on a substrate such as a metal plate or a metal foil, it is well known that not only the coating is formed smoothly, but also unevenness is formed by plating, or a so-called roughened coating is formed in which metal adheres to the substrate in a granular or needle-like shape.

[0003] For example, in Patent Document 1, in order to form a roughened nickel-plated plate that maintains the adhesion of the coating to the substrate and has excellent adhesion to other members, a roughened nickel-plated plate is disclosed in which the lightness and 85° glossiness of the surface of the roughened nickel layer are specified. Further, in Patent Document 2, a roughened nickel-plated plate is disclosed in which, in addition to the adhesion of the coating to the substrate and the adhesion to other members, the liquid penetration resistance when joined to other members is improved.

[0004] Prior Art Documents

[0005] Patent Documents

[0006] Patent Document 1: International Publication No. 2020 / 017655

[0007] Patent Document 2: International Publication No. 2021 / 149821 Summary of the Invention

[0008] Problems to be Solved by the Invention

[0009] Regarding products using roughened nickel-plated materials, it is desired to improve the characteristics in more diverse environments. As an example, there is a case of long-term use in a high-temperature environment and a highly corrosive liquid. However, it has been found that in conventional roughened nickel-plated materials, when the height of the roughened portion is increased in order to obtain a certain level of adhesion to other members, if continuously exposed in the above-mentioned harsh environment, the liquid penetration resistance (resistance to the intrusion and spread of liquid to the interface) tends to decrease. On the other hand, in the case of conventional roughened nickel-plated materials, if the height of the roughened portion is reduced, the adhesion to other members is insufficient.

[0010] The present disclosure has been completed in view of solving such problems, and provides a nickel-plated metal material that has adhesion to other members while suppressing the height of the roughened portion in the roughened nickel layer.

[0011] Means for Solving the Problems

[0012] In order to solve the above problems, the nickel-plated metal material of the present embodiment is characterized in that it includes a base material made of metal and a roughened nickel layer provided on at least one surface of the base material. The ten-point average roughness Rzjis of the outermost surface on the roughened nickel layer side of the nickel-plated metal material is 1.0 μm or more and less than 4.8 μm, and the roughened surface area of the outermost surface on the roughened nickel layer side is 1.5 m 2 / 1m 2 or more.

[0013] Effects of the Invention

[0014] According to the present disclosure, it is possible to provide a nickel-plated metal material that improves the liquid penetration resistance of the bonding interface with other components by suppressing the height of the roughened portions in the roughened nickel layer and has adhesiveness to other components by increasing the roughened surface area described later. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 FIG. is a schematic cross-sectional view showing the nickel-plated metal material according to the present embodiment.

[0016] Figure 2 FIG. is a schematic cross-sectional view showing the nickel-plated metal material according to another embodiment.

[0017] Figure 3 FIG. is a schematic cross-sectional view showing the nickel-plated metal material according to another embodiment.

[0018] Figure 4 FIG. is a schematic cross-sectional view showing the nickel-plated metal material according to another embodiment.

[0019] Figure 5 FIG. is a diagram showing an example of a method for obtaining the thickness of the diffusion alloy layer of iron and nickel.

[0020] Figure 6 FIG. is a schematic diagram showing the difference in roughened surface area caused by the difference in the shape of the roughened portions. DETAILED DESCRIPTION OF THE INVENTION

[0021] <<Nickel-Plated Metal Material>>

[0022] Hereinafter, embodiments of the nickel-plated metal material for implementing the present disclosure will be described. It should be noted that in the present disclosure, the "roughened portion" refers to the uneven portion of the surface formed by the roughened nickel layer formed by the roughening plating process on the substrate and the protrusions composed of nickel particles on the substrate 20. Hereinafter, the nickel-plated metal material of the present disclosure will be described as a plate-shaped material. Although not limited thereto, it may have a curved surface shape or a three-dimensional shape formed by shaping the plate, and may have a three-dimensional shape such as a cylindrical shape or a cubic shape. In addition, as long as the roughened nickel layer is formed in the region where the roughened portion is required, it is not necessarily formed comprehensively. That is, the nickel-plated metal material of the present disclosure may have the roughened nickel layer formed in at least a part of the entire shape area.

[0023] <First Embodiment>

[0024] Figure 1 The cross-sectional view schematically shows an embodiment of the nickel-plated metal material 100 of the present disclosure. It should be noted that for the nickel-plated metal material 100 of the present embodiment, for example, it is applied to the current collector of the positive electrode and / or negative electrode of a secondary battery, electronic equipment, electrical products, automobiles, building components, etc.

[0025] The nickel-plated metal material 100 of the present embodiment includes: a substrate 20 made of metal, and a roughened nickel layer 50 provided on the substrate 20. It should be noted that for the nickel-plated metal material 100 of the present embodiment, as Figure 1 shown, the roughened nickel layer 50 side is formed on at least the outermost surface of one of them.

[0026] <Substrate 20>

[0027] As the substrate 20 used in the nickel-plated metal material 100 of the present embodiment, for example, a metal plate or metal foil made of a pure metal selected from iron (Fe), copper (Cu), aluminum (Al), and nickel (Ni), or a metal plate made of an alloy containing one of iron (Fe), copper (Cu), aluminum (Al), and nickel (Ni), a product formed by shaping the plate, a casting material, a forging material, etc. can be cited. Preferably, a metal plate or metal foil made of these metals can be used. In addition, a nickel-plated steel sheet, a metal plate in which a diffusion alloy layer of iron and nickel is formed on the surface layer or near the surface layer by heat treatment of the nickel-plated steel sheet (hereinafter also referred to as "diffusion surface treatment steel sheet"), a galvanized steel sheet, etc. can also be used.

[0028] From the perspective of achieving good plating adhesion between the substrate 20, the roughened nickel layer 50, and the composite roughened plating layer 60 described in the following section, a steel plate, iron foil, or a diffusion-treated steel plate is preferably used as the substrate 20. Furthermore, from the perspective of improving the corrosion resistance of the entire metal plate, a nickel-plated steel plate, a diffusion-treated steel plate, or a galvanized steel plate is preferably used as the substrate 20. From the perspective of achieving both plating adhesion and corrosion resistance, a diffusion-treated steel plate is particularly preferred.

[0029] When the substrate 20 is a steel plate, the content of chromium (Cr) and other added metal elements is preferably less than 1.0% by weight. Specifically, it is preferable to use low-carbon steel (carbon content 0.01 to 0.15% by weight) such as low-carbon aluminum-killed steel, ultra-low carbon steel with a carbon content of less than 0.01% by weight, or non-aging ultra-low carbon steel obtained by adding titanium (Ti), niobium (Nb), etc. to ultra-low carbon steel.

[0030] It should be noted that when a nickel-plated steel plate, a diffusion-treated steel plate, or a galvanized steel plate is used as the substrate 20, it is preferred to use as its substrate a low-carbon steel (carbon content 0.01 to 0.15 wt%) represented by the same low-carbon aluminum-killed steel as mentioned above, an ultra-low carbon steel with a carbon content of less than 0.01 wt%, or a non-aging ultra-low carbon steel obtained by adding Ti, Nb, etc. to the ultra-low carbon steel.

[0031] When the substrate 20 is an iron foil, pure iron foil is preferred from the viewpoints of elongation, corrosion resistance, and the above-mentioned plating adhesion. In particular, from the viewpoint of thinning, the entire substrate 20 is preferably an electrolytic iron foil obtained by electroplating.

[0032] It should be noted that when a metal substrate having a passivation film formed on the surface, such as a stainless steel plate, a nickel plate, a nickel-plated steel plate, or a diffusion-treated steel plate, is used as the substrate 20, it is preferable to perform impact nickel plating before forming the roughened nickel layer 50 or the plating treatment of the metal layer 40 described in the following section. The conditions for impact nickel plating are not particularly limited, and for example, the following conditions can be cited. Under the following conditions, the amount of nickel deposited by impact nickel plating is generally 0.01 to 0.89 g / m 2 When a nickel layer is formed as the metal layer 40 (also called a base nickel layer), the total amount of nickel adhesion generated by impact nickel plating and the amount of nickel adhesion generated by nickel plating used to form the base nickel layer is measured as the nickel adhesion amount of the base nickel layer.

[0033] <Example of nickel impact plating conditions>

[0034] Bath composition: nickel sulfate hexahydrate 100-300g / L, sulfuric acid 10-200g / L

[0035] pH: below 1.0

[0036] Bath temperature: 40 - 70 °C

[0037] Current density: 5 - 100 A / dm 2

[0038] Plating time: 3 - 100 seconds

[0039] In addition, when the substrate 20 is a pure aluminum plate or pure aluminum foil, or an aluminum alloy plate or aluminum alloy foil, before the plating treatment for forming the roughened nickel layer 50 or the metal layer 40 described in the latter stage, it is preferable to perform a zinc immersion treatment for surface displacement galvanizing of aluminum. As the conditions for the zinc immersion treatment, there are no particular limitations, and for example, the following conditions can be cited. For a pure aluminum plate or pure aluminum foil, or an aluminum alloy plate or aluminum alloy foil, degreasing is performed with an alkaline solution, and then, etching treatment is performed in sulfuric acid. Next, after performing ash removal treatment in a solution obtained by mixing nitric acid and ferric chloride solution, it is immersed in the following zinc immersion treatment solution to perform the first zinc immersion treatment. Then, it is immersed in the same treatment solution used in the ash removal treatment to remove the zinc deposited by the first zinc immersion treatment, and then immersed in the same treatment solution used in the first zinc immersion treatment to perform the second zinc immersion treatment (hereinafter also referred to as double zinc immersion treatment). In this case, a water washing treatment is performed after the treatment of each process. It should be noted that the amount of zinc deposition can be adjusted by appropriately selecting the concentration of zinc ions in the treatment solution and the immersion time in the treatment solution during the second zinc immersion treatment. In addition, for zinc displacement plating, after degreasing treatment, pickling treatment, and ash removal treatment, it can be performed by performing a single zinc immersion treatment in which only the first zinc immersion treatment process is performed. At this time, the amount of zinc deposition can be adjusted by appropriately selecting the concentration of zinc ions in the treatment solution and the immersion time in the treatment solution during the first zinc immersion treatment. It should be noted that for the amount of zinc deposition formed by double zinc immersion treatment or single zinc immersion treatment, in order to make the adhesion of the subsequently formed metal layer 40 good, it is preferably in the range of 5 - 600 mg / m 2 and more preferably in the range of 30 - 400 mg / m 2 to be formed. Through this double zinc immersion treatment or single zinc immersion treatment, a zinc layer can be formed between the roughened nickel layer or the metal layer 40 and the substrate 20. It should be noted that the amount of zinc deposition of the zinc layer formed by double zinc immersion treatment or single zinc immersion treatment can be measured by fluorescence X-ray analysis (XRF) or the like.

[0040] <An example of zinc immersion treatment conditions>

[0041] <Degreasing conditions>

[0042] Bath composition: Sodium hydroxide 10 - 50 g / L, Sodium carbonate 2 - 20 g / L

[0043] pH: 12 or more

[0044] Bath temperature: 5 - 80 °C

[0045] Soaking time: 10 seconds to 3 minutes

[0046] Pickling Conditions

[0047] Bath composition: sulfuric acid 40-100g / L

[0048] pH: below 1.0

[0049] Bath temperature: 5~80℃

[0050] Soaking time: 10 seconds to 3 minutes

[0051] Ash Removal Conditions

[0052] Bath composition: 60% nitric acid 100-400 mL / L, ferric chloride solution 1-10 mL / L

[0053] pH: below 1.0

[0054] Bath temperature: 5~80℃

[0055] Soaking time: 10 seconds to 2 minutes

[0056] First zinc immersion conditions

[0057] Bath composition: sodium hydroxide 100-200g / L, Rochelle salt 20-80g / L, zinc oxide 10-50g / L, ferrous chloride 0.5-3.0g / L

[0058] pH: 12-14

[0059] Bath temperature: 5~50℃

[0060] Soaking time: 10 seconds to 2 minutes

[0061] De-zincification Conditions

[0062] Bath composition: 60% nitric acid 100-400 mL / L, ferric chloride solution 1-10 mL / L

[0063] pH: below 1.0

[0064] Bath temperature: 5~50℃

[0065] Soaking time: 10 seconds to 2 minutes

[0066] Second zinc immersion conditions

[0067] Bath composition: sodium hydroxide 100-200g / L, Rochelle salt 20-80g / L, zinc oxide 10-50g / L, ferrous chloride 0.5-3.0g / L

[0068] pH: 12-14

[0069] Bath temperature: 5 to 50 °C

[0070] Immersion time: 10 seconds to 2 minutes

[0071] Regarding the thickness of the base material 20 used in the nickel-plated metal material 100 of the present embodiment, a range of 0.004 to 5.0 mm is preferred. For example, when used as a current collector of a battery, an increase in volumetric and gravimetric energy density is required. Therefore, considering the balance of light weight, thin wall, and strength, it is preferably 0.004 to 0.5 mm, more preferably 0.01 to 0.3 mm, and further preferably 0.025 to 0.1 mm. In addition, for example, in applications such as electronic devices, electrical products, automobiles, and building components, from the viewpoints of rigidity, strength, and workability, it is preferably 0.025 to 5.0 mm, more preferably 0.1 to 4.0 mm, further preferably 0.2 to 3.0 mm, and even more preferably 0.5 to 1.0 mm.

[0072] Regarding the thickness of the base material 20, thickness measurement by cross-sectional observation using an optical microscope or a scanning electron microscope (SEM) is preferably used. In addition, as the thickness before roughening nickel plating, thickness measurement using a micrometer can be applied.

[0073] As a method for obtaining the thickness of the diffusion alloy layer of iron and nickel when using a diffusion surface-treated steel sheet as the base material 20, similar to International Publication No. 2022 / 231009, a method of reading from a coordinate diagram obtained by SEM-EDX (refer to Figure 5 ) can be applied. Specifically, in Figure 5 , the horizontal axis represents the distance (μm) in the depth direction from the surface layer side, and the vertical axis represents the X-ray intensity of Ni and Fe. In the coordinate diagram of Figure 5 , toward the thickness direction, the shallower part indicates a higher nickel content and a lower iron content. On the other hand, as it progresses in the thickness direction, the iron content increases. In the part before and after the curves of nickel and iron cross, in the present embodiment, the distance between 2 / 10 of the maximum values of nickel and iron respectively can be used as the diffusion alloy layer of iron and nickel, and its thickness can be read from the coordinate diagram.

[0074] Regarding the thickness of the diffusion alloy layer of iron and nickel in the diffusion surface-treated steel sheet, from the viewpoint of improving corrosion resistance, the thickness of at least one surface is preferably 0.4 μm or more, more preferably 0.6 μm or more, and further preferably 0.7 μm or more. There is no particular limitation on the upper limit. From the viewpoints of productivity and manufacturing cost, it is preferably 7.5 μm or less per single surface, more preferably 6.0 μm or less. In the diffusion surface-treated steel sheet, it is preferable to form a diffusion alloy layer of iron and nickel with a thickness of 0.4 μm or more and 7.5 μm or less on both sides thereof.

[0075] In addition, there are no particular limitations on the roughness of the base material 20. The arithmetic mean roughness Ra measured using a stylus surface roughness meter is 0.05 to 0.9 μm, more preferably 0.05 to 0.5 μm, further preferably 0.05 to 0.3 μm, and particularly preferably 0.08 to 0.2 μm. It should be noted that the arithmetic mean roughness Ra is in accordance with JIS B 0601:2013.

[0076] <Roughened nickel layer 50>

[0077] The roughened nickel layer 50 can be formed on the outermost surface of the single-sided side of the nickel-plated metal material 100 as shown in Figure 1 Although not shown, it can also be formed on the outermost surfaces of both sides. The roughened nickel layer 50 is formed of nickel.

[0078] The nickel-plated metal material of the present embodiment is characterized in that the ten-point mean roughness Rzjis of the outermost surface on the roughened nickel layer 50 side is 1.0 μm or more and less than 4.8 μm, and the roughened surface area of the outermost surface on the roughened nickel layer side is 1.5 m 2 / 1m 2 or more. For the nickel-plated metal material of the present embodiment, by defining the surface shape of the roughened nickel layer 50 as described above, the liquid penetration resistance of the bonding interface with other members is improved, and a nickel-plated metal material having good adhesion to other members can be formed.

[0079] It should be noted that examples of the resin herein include thermoplastic resins, thermosetting resins, rubbers, elastomers, etc. Further, in the present disclosure, the resin includes substances such as coatings, active substances, and products containing a part of the resin in a slurry-like substance that have fluidity when bonding to the roughened nickel layer.

[0080] Specifically, regarding the ten-point mean roughness Rzjis, in the nickel-plated metal material of the present embodiment, it is a value corresponding to the protrusion height of the roughened portion. In the present disclosure, the ten-point mean roughness Rzjis is defined within the above range as a characteristic of the shape of the roughened portion that can improve the liquid penetration resistance while obtaining preferable adhesion to other members. By setting the roughened surface area described below to a specified value together with this, a preferable effect can be exhibited.

[0081] In addition, the roughened surface area is the surface area per unit area in the nickel-plated metal material on which the roughened nickel layer 50 is formed. That is, in the nickel-plated metal material of the present disclosure, due to the protrusions composed of nickel particles formed in the roughening nickel plating process, the surface area increases with respect to the horizontal projection area. In other words, with respect to the roughened surface area, when the roughened nickel layer 50 side of the nickel-plated metal material 100 of the present disclosure is joined to other members, it is a numerical value representing the contact area between the resin and the roughened portion when, for example, resin that is melted or softened by heating flows in. In the present disclosure, by defining the range of the above-mentioned ten-point average roughness Rzjis and, at the same time, as a feature of the shape of the roughened portion for obtaining preferable adhesion between other members and the roughened portion, the roughened surface area is specified to be within the above range, whereby a preferable effect can be exhibited.

[0082] The present inventors considered the reasons for obtaining a preferable effect by controlling the ten-point average roughness Rzjis and the roughened surface area as follows. When the ten-point average roughness Rzjis is a large value (for example, 4.8 μm or more), the adhesion to the resin is likely to be improved. However, as described above, it is known that since the protrusion height of the roughened portion is high, the liquid permeability is likely to decrease after a long period in a high-temperature environment or a highly corrosive environment. The reason why the liquid permeability is likely to decrease when the protrusion height of the roughened portion is high is not clear, but the present inventors consider it as follows.

[0083] When liquid permeates between the resin and the roughened nickel-plated material, the liquid permeates along the surface of the protrusion of the roughened portion. Therefore, in the conventional roughened nickel-plated material, if there are groove portions and flat portions at the root, the liquid becomes easy to permeate. However, it is considered that if the root of the roughened portion is thickened to reduce the groove and flat portions, when the height of the roughened portion is high, the liquid permeation route becomes longer, which is advantageous.

[0084] Among them, generally, during electroplating, there is a tendency for current to concentrate on convex portions. In the case of plating with granular nickel used for forming the roughened nickel layer, compared with ordinary nickel plating, it is a plating in which nucleation occurs preferentially compared to particle growth. Therefore, it is considered that this tendency is particularly strong. That is, for protrusions with a large distance from the substrate surface to the tip of the protrusion, they grow preferentially to form higher protrusions (hereinafter also referred to as high protrusions). Such high protrusions, as the height of the roughened portion, are reflected in the ten-point average roughness Rzjis. At this time, in the conventional roughened nickel plating, for a roughened nickel-plated material with a large ten-point average roughness Rzjis, as described above, high protrusions are more likely to grow preferentially. Therefore, it is considered that protrusions with a small distance from the substrate surface to the tip of the protrusion (hereinafter also referred to as slightly lower protrusions) are difficult to form or grow.

[0085] From the test results maintained under severe environments over a long period, the present inventors focused on: studying the penetration path of the liquid on the surface of the roughened portion. As a result, it was considered that, compared with the path through the tip of the high protrusions, from any angle of the protrusions, the path at a lower position, that is, the path that penetrates around the protrusions near the substrate surface, is more likely to penetrate the liquid. That is to say, for the roughened nickel plating material with a high roughened portion as in the past, since many high protrusions are formed and few low protrusions are formed, it is speculated that the liquid penetration resistance is likely to decrease after a long period under the above-mentioned severe environments. However, it was found that: in order to improve the liquid penetration resistance, by simply reducing the adhesion amount and only by reducing the protrusion height of the roughened portion, the adhesion with other members is insufficient. Moreover, the present inventors considered that in order to maintain the adhesion with the resin while setting an upper limit on the ten-point average roughness Rzjis, it is necessary to increase the contact area (roughened surface area) between the roughened portion and the resin. As a result of trial and error to obtain the shape of the roughened portion that can increase the roughened surface area while suppressing the height, the present inventors obtained: by controlling the average current density of the plating for forming granular nickel, the bath temperature, the circulation of the plating solution, and the circulation of the plating solution during nickel growth plating, the ten-point average roughness Rzjis and the roughened surface area are in the above ranges, and a nickel-plated metal material that can achieve both an improvement in adhesion with other members and liquid penetration resistance is obtained.

[0086] That is, it is considered that: by making the protrusion height of the roughened portion low so that the ten-point average roughness Rzjis becomes 4.8 μm or less and forming the roughened surface area to be 1.5 m 2 / m 2 or more of the roughened nickel layer, low protrusions are formed, fine protrusions are formed near the root of the low protrusions, and a roughened portion with a sufficient surface area can be formed. As a result, it is considered that: the path length of liquid penetration near the substrate surface where the liquid is easily penetrated is significantly extended, the liquid penetration resistance is improved, and at the same time, since it has a surface area of a certain level or more, the adhesion with other members can be ensured. Furthermore, it was also found that: for the nickel-plated steel sheet on which such slightly low protrusions and fine protrusions are formed, when joining with the resin, according to the temperature, speed, etc. of flowing the resin into the roughened portion, the effect of suppressing the voids that may be formed near the root of the roughened portion can also be expected.

[0087] In addition, in the above-mentioned trial and error, the present inventors compared samples with the same level of the height (ten-point average roughness Rzjis), the number of protrusions (vertex density Spd), and the surface area from above (developed area ratio Sdr) of the roughened portion obtained by a laser microscope. As a result, the resin adhesion was sometimes different. Moreover, by exploring the reason, it was found that: in the measurement using a laser microscope, due to the presence or shape of the protrusions that are difficult to reflect, the roughened surface area may be different. <![CDATA[

[0088] ]] Specifically, as Figure 6As shown, even when the upper surface area of the roughened portion obtained by using a laser microscope is the same, it can be predicted that due to the differences in the protrusions near the root of the roughened portion, near the substrate surface, and their shapes, the roughened surface area may sometimes be different. Specifically, for example, Figure 6 (b) and Figure 6 (d) show the state where relatively many fine protrusions are formed near the root of the roughened portion, Figure 6 (a) and Figure 6 (c) show the state where fine protrusions are not formed relatively many. In addition, regarding the vertical arrow, it represents the laser irradiated on the specimen surface when measuring the surface properties with a laser microscope. In the case of using a laser microscope or a device that measures the surface roughness by a similar action from the vertical direction, it is considered that the laser is blocked by the surrounding high protrusions and it is difficult to reach the fine protrusions as shown in (b). In such a case, in the measurement result of the surface properties using a laser microscope, the presence or absence and shape of the fine protrusions are basically not reflected, Figure 6 (a) and Figure 6 (b) have the same degree of height (ten-point mean roughness Rzjis) of the roughened portion, number of protrusions (peak density Spd), and upper surface area (developed area ratio Sdr) of the roughened portion measured by the laser microscope.

[0089] On the other hand, compared with Figure 6 (a) and (c), Figure 6 (b) and (d) show that the total surface area of the high and low protrusions of the roughened portion is large. That is, it is known that the roughened surface area in the present disclosure is not necessarily a parameter related to surface property parameters such as the height (ten-point mean roughness Rzjis) of the roughened portion that can be measured by a laser microscope. It should be noted that Figure 6 For the schematic diagram to facilitate the understanding of the roughened surface area, the shape of the roughened portion of the present disclosure is not limited to Figure 6 . It should be noted that Figure 6 (a) and (b) show the form of forming the roughened nickel layer 50 on the outermost surface of the substrate, Figure 6 (c) and (d) are schematic diagrams showing the form of forming the coating layer 70 on the roughened nickel layer 50.

[0090] Regarding the nickel-plated metal material of the present embodiment, by controlling the ten-point mean roughness Rzjis and the roughened surface area, a nickel-plated metal material with high liquid impermeability can be formed. Therefore, even when the liquid content is sealed using the nickel-plated metal material of the present embodiment for a long time, the risk of leakage of the content can be reduced. In addition, the liquid impermeability at the bonding interface with other components can be improved, and thus it can be expected to maintain the adhesion between the resin and the roughened portion even after a longer period.

[0091] The upper limit of the ten-point average roughness Rzjis is less than 4.8 μm, preferably 3.5 μm or less, from the perspective of improving liquid penetration resistance. On the other hand, the lower limit of the ten-point average roughness Rzjis is 1.0 μm or greater, preferably 1.2 μm or greater, and more preferably 1.3 μm or greater, from the perspective of improving adhesion to resin.

[0092] The ten-point average roughness Rzjis can be measured using a known laser microscope or the like in accordance with JIS B0601:2013.

[0093] The upper limit of the roughened surface area is not particularly limited, but is considered to be 100 m³ / s from the viewpoint of the difficulty in breaking the protrusions composed of the aggregate of granular nickel and the adhesion of the roughened portion to the substrate. 2 / 1m 2 Below, more preferably 60m 2 / 1m 2 On the other hand, the lower limit of the roughened surface area is 1.5 m 2 / 1m 2 As for the lower limit of the roughened surface area, from the viewpoint of improving the adhesion with other members, it is more preferably 2.0 m 2 / 1m 2 More than 5.0m 2 / 1m 2 More than 5.3m is more preferred 2 / 1m 2 above.

[0094] The method for measuring the roughened surface area of the present embodiment is not to measure the surface area from the roughened portion using a laser microscope, but is preferably a method that can measure the surface area of the root of the roughened portion. As a method for measuring the roughened surface area, the BET multi-point method disclosed in Japanese Patent Application Laid-Open No. 2017-177654 can be used. As a method for measuring the roughened surface area, specifically, for example, a gas such as krypton is adsorbed on the surface of the roughened portion, and its adsorption amount is calculated, thereby obtaining the specific surface area. Then, based on the obtained specific surface area, the roughened surface area (unit: m 2 / 1m 2 ) is taken as the actual surface area per unit area. It should be noted that the detailed calculation method of the roughened surface area in this disclosure will be described later.

[0095] It is particularly preferred that the ten-point average roughness Rzjis of the outermost surface of the roughened nickel layer 50 side of the nickel-plated metal material 100 of this embodiment is 1.0 μm or more and 3.5 μm or less, and the roughened surface area is 5.3 m 2 / 1m2 The above.

[0096] Furthermore, regarding the nickel-plated metal material of the present embodiment, in order to define the shape of the surface formed by the protrusions composed of granular nickel in the roughened coating, it is also preferable to define the average length Rsm of the profile units (elements). Specifically, the average length Rsm of the profile units is preferably 3.0 μm to 15 μm. By satisfying this, a higher anchoring effect is obtained, and particularly high adhesion strength can be expected.

[0097] It should be noted that the average length Rsm of the profile units can be measured by a known laser microscope or the like in accordance with JIS B0601:2013.

[0098] In the nickel-plated metal material 100 of the present embodiment, considering the productivity and manufacturing cost, the adhesion amount of nickel per single side in the roughened nickel layer 50 is preferably 16 g / m 2 Hereinafter, it is more preferably 15 g / m 2 Hereinafter, it is further preferably 14 g / m 2 Hereinafter. In addition, considering the corrosion resistance and obtaining the target roughened shape, it is preferably 2 g / m 2 Hereinafter, it is more preferably 3 g / m 2 Hereinafter, it is further preferably 4 g / m 2 Hereinafter. It should be noted that the adhesion amount of nickel in the roughened nickel layer 50 can be measured by fluorescence X-ray analysis (XRF) or the like.

[0099] As the method for measuring the nickel adhesion amount in the present embodiment, for example, the methods described in International Publication No. 2020 / 017655 and International Publication No. 2021 / 020338 can be appropriately adopted. That is, for the nickel-plated metal material 100, the total nickel amount can be measured by using fluorescence X-ray analysis (XRF) or the like and obtained.

[0100] The thickness of the entire nickel-plated metal material 100 in the present embodiment will be described. It should be noted that the so-called "thickness of the nickel-plated metal material 100" in the present embodiment can also be applied to the thickness measurement by cross-sectional observation using a scanning electron microscope (SEM) or the thickness measurement using a micrometer.

[0101] The overall thickness of the nickel-plated metal material 100 in this embodiment is preferably in the range of 0.005 to 5.01 mm. For example, when used as a current collector of a battery, an increase in volumetric and gravimetric energy density is required. Therefore, considering the balance of light weight, thin wall, and strength, it is more preferably 0.005 to 0.51 mm, further preferably 0.01 to 0.31 mm, and even more preferably 0.035 mm to 0.11 mm. For example, as components for electronic devices, electrical products, automobiles, and buildings, from the viewpoints of rigidity, strength, and workability, it is preferably 0.035 mm to 5.01 mm, more preferably 0.11 to 4.01 mm, further preferably 0.21 to 3.01 mm, and even more preferably 0.51 to 1.01 mm. The overall thickness of the nickel-plated metal material 100 is applicable to thickness measurement by cross-sectional observation using a micrometer, an optical microscope, or a scanning electron microscope (SEM).

[0102] When the nickel-plated metal material 100 is used as a current collector of a battery, if it exceeds the upper limit of the above thickness range, for example, it is not preferable from the viewpoint of the volumetric and gravimetric energy density of the manufactured battery, especially when aiming for a thinner battery. On the other hand, if the thickness is less than the lower limit of the above thickness range, not only is it difficult to have sufficient strength against the effects associated with the charge and discharge of the battery, but also the possibility of breakage, fragmentation, or wrinkling during battery manufacturing, handling, etc. increases. When used for components of electronic devices, electrical products, automobiles, and buildings, if it exceeds the upper limit of the above thickness range, it is not preferable from the viewpoints of workability and light weight. On the other hand, if the thickness is less than the lower limit of the above thickness range, it is not preferable from the viewpoints of the rigidity and strength of the obtained components.

[0103] As described above, according to the nickel-plated metal material 100 in this embodiment, the liquid penetration resistance at the bonding interface with other components can be improved. Specifically, in order to improve the liquid penetration resistance, the ten-point average roughness Rzjis of the outermost surface on the roughened nickel layer side is set to a specified value. In addition, for the nickel-plated metal material 100 in this embodiment, since the roughened surface area of the roughened nickel layer has a specified value, it has adhesiveness to other components.

[0104] <First Modification of the First Embodiment>

[0105] Next, use Figure 2, a nickel-plated metal material 200, which is a modification of the first embodiment described above, will be described. The nickel-plated metal material 200 in this modification is different from the first embodiment described above in that a metal layer 40 is provided between the roughened nickel layer 50 and the substrate 20. Therefore, this difference will be mainly described, and the same reference numerals are used for other aspects, and their descriptions are omitted. It should be noted that in this modification, on the outermost surface on the side of the roughened nickel layer, the ten-point average roughness Rzjis is also 1.0 μm or more and less than 4.8 μm, and the roughened surface area is 1.5 m 2 / 1m 2 or more.

[0106] <Metal layer 40>

[0107] Regarding the metal layer 40, as described above, it is provided between the substrate 20 and the roughened nickel layer 50. As the metal material constituting the metal layer 40, for example, nickel and nickel alloys can be cited. It should be noted that the metal layer 40 is shown as one layer in Figure 2 but is not limited thereto and can be composed of multiple layers.

[0108] As an example of the metal layer 40, an iron-nickel alloy layer, a nickel-phosphorus alloy layer, and a nickel layer can be exemplified. When the metal layer 40 is an iron-nickel alloy layer, as the alloy state composed of iron and nickel, a solid solution, eutectoid-eutectic, and compound (intermetallic compound) are all possible, and these can also coexist. In addition, the metal layer 40 may contain metal elements and inevitable impurities other than iron and nickel, and may contain metal elements such as cobalt (Co) and molybdenum (Mo), and additive elements such as boron (B).

[0109] In the nickel-plated metal material 200, the preferred range of the nickel adhesion amount per single side of the roughened nickel layer 50 is the same as that of the nickel-plated metal material 100 described above.

[0110] Regarding the total nickel adhesion amount of the metal layer 40 and the roughened nickel layer 50 per single side in the nickel-plated metal material 200, as an upper limit, from the viewpoints of productivity and manufacturing cost, it is preferably 40 g / m 2 or less, more preferably 35 g / m 2 or less, and further preferably 32 g / m 2 or less. In addition, from the viewpoints of not obtaining corrosion resistance and the target roughened shape, as a lower limit, it is preferably 4 g / m 2 or more, more preferably 5 g / m 2 or more, and further preferably 6 g / m 2 or more.

[0111] In the nickel-plated metal material 200, as a method for measuring the nickel adhesion amount, a method described in, for example, International Publication No. 2020 / 017655 and International Publication No. 2021 / 020338 can be appropriately adopted. That is, for the nickel-plated metal material 200, using fluorescence X-ray analysis (XRF) or the like, the total nickel adhesion amount per single side of the metal layer 40 and the roughened nickel layer 50 can be measured. In addition, by confirming the boundary between the metal layer 40 and the roughened nickel layer 50 in a cross-sectional image or the like, the nickel amounts of the metal layer 40 and the roughened nickel layer 50 can be obtained. It should be noted that when the base material 20 is a nickel-plated steel sheet or a diffusion surface-treated steel sheet and the metal layer 40 is a nickel or nickel alloy layer, it is sometimes difficult to confirm the clear boundary between the base material 20 and the metal layer 40. In this case, the total nickel adhesion amount per single side of the base material 20, the metal layer 40, and the roughened nickel layer 50 can be within the above range.

[0112] In the nickel-plated metal material 200, as the effects of forming the metal layer 40 on the base material 20, the following aspects can be cited. That is, by forming the metal layer 40, it is possible to ensure the adhesion of the roughened nickel layer 50 to the base material 20 and improve the corrosion resistance of the entire nickel-plated metal material 200.

[0113] The overall thickness of the nickel-plated metal material 200 is preferably in the range of 0.005 mm to 5.01 mm. When used as, for example, a current collector of a battery, an increase in volume and weight energy density is required. Therefore, considering the balance of light weight, thin wall, and strength, it is more preferably 0.005 mm to 0.51 mm, further preferably 0.01 mm to 0.31 mm, and even more preferably 0.035 mm to 0.11 mm. For example, as components for electronic devices, electrical products, automobiles, and buildings, from the viewpoints of rigidity, strength, and workability, it is preferably 0.035 mm to 5.01 mm, more preferably 0.11 mm to 4.01 mm, further preferably 0.21 mm to 3.01 mm, and even more preferably 0.51 mm to 1.01 mm. Regarding the overall thickness of the nickel-plated metal material 200, thickness measurement by cross-sectional observation using a micrometer, an optical microscope, or a scanning electron microscope (SEM) is suitable.

[0114] <Second Embodiment>

[0115] Next, by Figure 3, the nickel-plated metal material 300 in the second embodiment will be described. The nickel-plated metal material 300 in the second embodiment is different from the above-described first embodiment in that it has a coating layer 70 on the roughened nickel layer 50. Therefore, mainly this difference will be described, and the same reference numerals are used for other aspects, and their descriptions are omitted. It should be noted that in the nickel-plated metal material 300, the roughened nickel layer 50 and the coating layer 70 are collectively referred to as "composite roughened coating 60". In the nickel-plated metal material 300, on the outermost surface on the side of the composite roughened coating 60, the ten-point average roughness Rzjis is 1.0 μm or more and less than 4.8 μm, and the roughened surface area is 1.5 m 2 / 1m 2 or more.

[0116] <Coating layer 70>

[0117] As described above, the coating layer 70 is provided on the roughened nickel layer 50. As the metal material constituting the coating layer 70, for example, nickel alloys such as iron-nickel alloy, zinc (Zn) and zinc alloys, tin (Sn) and tin alloys, and chromium (Cr) and chromium alloys can be cited. That is, in the present embodiment, on the outermost surface on the side of the roughened nickel layer 50, any one of a zinc layer, a zinc alloy layer, a tin layer, a tin alloy layer, a chromium layer, a chromium alloy layer, and an iron-nickel alloy layer is provided.

[0118] The coating layer 70 helps to improve the adhesion between the roughened nickel layer 50 and the base material 20. In addition, when the coating layer 70 contains zinc, it is advantageous in terms of imparting sacrificial corrosion protection to the nickel-plated metal material 300 as a whole. In addition, when the coating layer 70 contains tin, when the nickel-plated metal material 300 is used as a current collector of a battery, for example, the hydrogen overvoltage can be increased, and the generation of hydrogen can be suppressed, so it is advantageous. In addition, when the coating layer 70 contains chromium, the corrosion resistance of the nickel-plated metal material 300 as a whole can be further improved, and in addition, the adhesion between the resin and the roughened portion can be improved. It should be noted that in the present disclosure, when the metal material constituting the coating layer 70 is chromium or its alloy, it is set to include a chromate film. In addition, when the coating layer 70 is made of an iron-nickel alloy, the wear resistance of the outermost surface can be improved.

[0119] The preferred metal deposition amount in the coating layer 70 is as follows. When the coating layer 70 is zinc, regarding the zinc deposition amount, as an upper limit, from the viewpoints of productivity, manufacturing cost, and obtaining the target roughened shape, it is preferably 22.0 g / m 2 or less, more preferably 17.0 g / m 2 or less, and further preferably 15.0 g / m 2 or less. As a lower limit of the zinc deposition amount, from the viewpoints of improving corrosion resistance and the adhesion between the base material and the roughened nickel plating layer, it is preferably 0.5 g / m 2More preferably, it is 3.5 g / m or more 2 More preferably, it is 5.0 g / m or more 2 More. When the coating layer 70 is tin, in terms of the tin adhesion amount, as the upper limit, from the viewpoints of productivity, manufacturing cost, and obtaining the target roughened shape, it is preferably 22.0 g / m or less 2 More preferably, it is 17.0 g / m or less 2 More preferably, it is 15.0 g / m or less 2 More. As the lower limit of the tin adhesion amount, from the viewpoints of improving corrosion resistance and the adhesion between the base material and the roughened nickel plating layer, it is preferably 0.5 g / m or more 2 More preferably, it is 1.5 g / m or more 2 More preferably, it is 3.5 g / m or more 2 More. When the coating layer 70 is chromium, in terms of the chromium adhesion amount, as the upper limit, from the viewpoints of productivity, manufacturing cost, and obtaining the target roughened shape, it is preferably 22.0 g / m or less 2 More preferably, it is 17.0 g / m or less 2 More preferably, it is 15.0 g / m or less 2 More. As the lower limit of the chromium adhesion amount, from the viewpoints of improving corrosion resistance and the adhesion between the base material and the roughened nickel plating layer, it is preferably 0.1 g / m or more 2 More preferably, it is 0.3 g / m or more 2 More preferably, it is 0.5 g / m or more 2 More preferably, it is 0.8 g / m or more 2 More. The measurement of the preferred adhesion amount in the coating layer 70 can be carried out by using known methods such as fluorescence X-ray (XRF) measurement or ICP emission spectroscopic analysis

[0120] The coating layer 70 of the present embodiment can be formed on the roughened nickel layer 50 by electroplating method, sputtering method, evaporation method, chemical vapor deposition method, etc. of the respective corresponding metals. In particular, from the viewpoints of production cost and the ability to uniformly coat the roughened part, the electroplating method is preferred

[0121] <Modification of the Second Embodiment>

[0122] In Figure 4Shown is a nickel-plated metal material 400 as a modified example of the above-described second embodiment. The nickel-plated metal material 400 in this modified example is different from the above-described second embodiment in that a metal layer 40 is provided between the composite roughened coating 60 and the base material 20. In addition, the metal layer 40 can be applied to the metal layer 40 described in the modified example of the above-described first embodiment. Therefore, the same reference numerals are used and their descriptions are omitted. It should be noted that in this modified example, on the outermost surface on the side of the roughened nickel layer, the ten-point average roughness Rzjis is 1.0 μm or more and less than 4.8 μm, and the roughened surface area is 1.5 m 2 / 1m 2 or more.

[0123] "Manufacturing Method of Nickel-Plated Metal Material"

[0124] Hereinafter, the manufacturing method of the nickel-plated metal material will be described. The manufacturing method of the nickel-plated metal material of the present embodiment is characterized in that in the roughened nickel plating process for forming the roughened nickel layer 50, it includes: on at least one surface of a base material 20 made of metal, for an average current density of 20.0 A / dm 2 or more, a bath temperature of 50 °C or more, and for example, a 2 L plating solution in volume, a circulating bath is used to perform the granular nickel formation plating process for roughened nickel plating with a liquid circulation amount using a pump exceeding a flow rate of 1 L / min.

[0125] As the plating bath in the granular nickel formation plating process, the chloride ion concentration is preferably 3 to 90 g / L, more preferably 3 to 75 g / L, further preferably 3 to 50 g / L. The ratio of nickel ions to ammonium ions, expressed as the weight ratio of "nickel ions / ammonium ions", is preferably 0.05 to 0.75, more preferably 0.05 to 0.60, further preferably 0.05 to 0.50, and even more preferably 0.05 to 0.30. In addition, the bath conductivity at 50 °C is preferably 5.00 to 30.00 S / m, more preferably 5.00 to 20.00 S / m, and further preferably 7.00 to 20.00 S / m. It should be noted that when the chloride ion concentration is 10 g / L or more, even if the adhesion amount in the roughened nickel plating is small, it is easy to achieve a good roughened plating state. As a method for adjusting the chloride ion concentration, the ratio of nickel ions to ammonium ions, and the bath conductivity of the plating bath to the above ranges, there is no particular limitation. For example, a method of making the plating bath contain nickel sulfate hexahydrate, nickel chloride hexahydrate, and ammonium sulfate and appropriately adjusting the blending amounts thereof can be cited.

[0126] An example of the plating conditions is as follows.

[0127] [Granular Nickel Formation Plating Conditions]

[0128] Bath Composition

[0129] Nickel sulfate hexahydrate 10 - 100 g / L, nickel chloride hexahydrate 1 - 90 g / L, ammonium sulfate 10 - 130 g / L

[0130] pH 4.0 - 8.0

[0131] Bath temperature above 50°C and below 80°C

[0132] Average current density: 20 A / dm 2 Above and 60 A / dm 2 Below

[0133] Plating time: 5 seconds - 150 seconds

[0134] Electric charge: 100 - 1500 C / dm 2

[0135] Presence or absence of stirring, etc.: Circulating bath (for example, for a 2 L plating solution, the liquid circulation volume by a pump is more than 1 L / min)

[0136] Under the above conditions, by using a circulating bath so that the total electric charge becomes the above-mentioned manner, the plating treatment can be carried out once or multiple times.

[0137] It should be noted that regarding the addition of ammonia to the plating bath in the granular nickel formation plating process, ammonia water, ammonium chloride, etc. can be used instead of ammonium sulfate. The ammonium ion concentration in the plating bath is preferably 6 - 35 g / L, more preferably 10 - 35 g / L, further preferably 16 - 35 g / L, and even more preferably 20 - 35 g / L. In addition, in order to control the chloride ion concentration, hydrochloric acid, sodium chloride, potassium chloride, etc. can be used.

[0138] The stirring condition of the plating bath in the granular nickel formation plating process preferably adopts the circulating bath method of circulating the plating solution with a pump. Specifically, it is preferably to continuously circulate the plating solution in an amount exceeding 1 L / min with respect to a 2 L plating solution. When the bath temperature is high, it is preferred that the plating liquid circulation volume is high. When the average current density is high, it is preferred that the plating liquid circulation volume is high. When the nickel ion concentration is low, it is preferred that the plating liquid circulation volume is high. There is no particular limitation on the upper limit of the plating liquid circulation volume, and it is preferably 20 L / min or less. However, in order to control the shape to the target in the roughening part, it is necessary to control the bath temperature, average current density, and plating liquid circulation volume to appropriate conditions for plating.

[0139] In addition, in the above plating bath, by increasing the average current density to 20 A / dm 2The above and raising the bath temperature to 50°C or higher can promote the formation of more plating nuclei. As a result, the number of protrusions in the roughened portion increases, and even when the height of the roughened portion is less than the ten-point average roughness Rzjis of 4.8 μm, it is also possible to easily make the roughened surface area 1.5 m 2 / 1m 2 or more. In addition, in the granular nickel formation plating process, by generating more plating nuclei, plating nuclei can be formed at the root of the protrusion when it is roughened in the nickel growth plating process described later. Regarding the upper limit of the average current density, from the viewpoint of improving the adhesion between the substrate and the roughened nickel plating layer, it is preferably 50 A / dm 2 or less. Furthermore, by continuously circulating the plating solution at a rate exceeding 1 L / min for a plating solution with a volume of 2 L, for example, during the growth of the generated plating nuclei and further during the precipitation of new plating nuclei on them to grow as protrusions, the preferential growth of a part of the protrusions is suppressed, and the growth difference of each protrusion is reduced, thereby promoting the formation of a sufficient number of low protrusions. As a result, it is possible to easily make the ten-point average roughness Rzjis less than 4.8 μm and at the same time make the roughened surface area 1.5 m 2 / 1m 2 or more. In addition, for the average length Rsm of the profile units, it can also be easily formed to be 3.0 μm to 15 μm. In addition, it is considered that by performing the average current density, bath temperature, and circulation of the plating solution within the above ranges, the formation of plating nuclei that become fine protrusions near the further root of the low protrusions can be promoted. In this way, by controlling the bath temperature, average current density, and liquid circulation amount to appropriate conditions for plating, a roughened portion with a target shape can be formed.

[0140] Regarding the upper limit of the nickel adhesion amount in the granular nickel formation plating process, from the viewpoint of improving liquid permeability resistance, it is preferably 16 g / m 2 or less, more preferably 15 g / m 2 or less, and further preferably 14 g / m 2 or less. In addition, for the lower limit, from the viewpoint of adhesion with other components, it is preferably 1.8 g / m 2 or more, more preferably 2.8 g / m 2 or more, and further preferably 3.8 g / m 2 or more. By controlling the average current density, bath temperature, circulation of the plating solution, and further controlling the nickel adhesion amount to 1.8 to 16 g / m 2 as described above, the height of the roughened portion can be suppressed. As a result, in the nickel-plated metal plate after the nickel growth plating process or the coating plating process described later, Rzjis can be 1.0 μm or more and less than 4.8 μm.

[0141] [Nickel Growth Plating Conditions]

[0142] The bath composition contains 200 - 350 g / L of nickel sulfate hexahydrate, 20 - 60 g / L of nickel chloride hexahydrate, and 10 - 50 g / L of boric acid

[0143] pH is 3.0 - 5.0

[0144] The bath temperature is 40 - 70 °C

[0145] The current density is 5 - 30 A / dm 2

[0146] Presence or absence of stirring, etc.: Circulating bath (for example, for a 2 L plating solution, the liquid circulation volume using a pump is more than 1 L / min)

[0147] Regarding the stirring conditions of the plating bath in the nickel growth plating process, by using a circulating bath in which the plating solution is circulated by a pump, the roughened surface area of the obtained nickel-plated metal material can be controlled to a preferable value

[0148] Regarding nickel growth plating, it is a process mainly aimed at improving the adhesion between the roughened nickel layer and the substrate by further growing each nickel grain in the protrusions composed of aggregates of nickel grains formed in the above-mentioned granular nickel formation plating process. In the present disclosure, it is considered that, in addition to this purpose, in this nickel growth plating process, by performing stirring with a liquid circulation of a certain amount or more, the formation of the above-mentioned fine protrusions can be promoted. For example, by continuously circulating the plating solution at a rate of more than 1 L / min for a 2 L plating solution, the plating nuclei that become the nuclei of the fine protrusions formed by the above-mentioned granular nickel formation plating can grow in this growth plating to form fine protrusions, and as a result, the surface area can be increased

[0149] Regarding the upper limit of the nickel deposition amount in the nickel growth plating process, from the viewpoints of adhesion to other components, productivity, and manufacturing cost, it is preferably 7.0 g / m 2 Hereinafter, it is more preferably 6.0 g / m 2 Hereinafter, it is further preferably 5.0 g / m 2 Hereinafter. In addition, for the lower limit, from the viewpoint of adhesion of the plating layer to the substrate, it is preferably 0.2 g / m 2 Above, it is more preferably 0.4 g / m 2 Above. It should be noted that the above nickel growth plating process is not an essential process

[0150] By going through the above process, on the outermost surface of the roughened nickel layer side of the obtained nickel-plated metal material, the ten-point average roughness Rzjis is preferably 1.0 μm or more and less than 4.8 μm, and the roughened surface area of the outermost surface of the roughened nickel layer side becomes 1.5 m 2 / 1 m 2Above.

[0151] Furthermore, on the outermost surface of the roughened nickel layer side of the obtained nickel-plated metal material, it is preferable that the average length Rsm of the profile units be 3.0 μm to 15 μm.

[0152] In Figure 3 or Figure 4 In the method for manufacturing the nickel-plated metal material shown, a step of forming a coating layer 70 (coating layer forming step) may be further included. Specifically, the coating layer forming step is performed at least after the above-described granular nickel forming plating step. In addition, the coating layer forming step may be performed subsequent to the granular nickel forming plating step and the nickel growth plating step.

[0153] In the case where the coating layer forming step is performed by zinc plating, as an example of the bath composition and plating conditions for zinc plating, they are as follows.

[0154] Zinc sulfate heptahydrate: 100 to 400 g / L

[0155] Ammonium sulfate: 10 to 100 g / L

[0156] Bath temperature: 30 to 70 °C

[0157] pH: 1.0 to 5.0

[0158] Presence or absence of stirring, etc.: Circulating bath (for example, for 2 L of plating solution, the liquid circulation amount using a pump is more than 1 L / min)

[0159] Current density: 2.5 to 60 A / dm 2

[0160] As described above, as the plating bath for zinc plating, a bath that uses sulfate as a supply source of zinc ions and appropriately adds conductive auxiliary salts such as ammonium sulfate and sulfuric acid for improving the conductivity of the plating solution can be used. Additives such as known brighteners may be further added to the plating bath for bright zinc plating or semi-bright zinc plating.

[0161] In the case where the coating layer forming step is performed by zinc plating, the amount of zinc deposition formed by zinc plating is preferably 0.5 g / m 2 to 22.0 g / m 2 . The measurement of the amount of zinc deposition can be performed using known methods such as fluorescence X-ray (XRF) measurement or ICP emission spectroscopic analysis.

[0162] In the case where the coating layer forming step is performed by tin plating, as an example of the bath composition and plating conditions for tin plating, they are as follows.

[0163] Stannous sulfate: 30 to 80 g / L

[0164] Phenolsulfonic acid: 30 - 60 g / L

[0165] Ethoxylated - α - naphthol: 2 - 6 g / L

[0166] Ethoxylated - α - naphtholsulfonic acid: 4 - 12 g / L

[0167] pH: 0.1 - 2.0

[0168] Bath temperature: 20 - 55 °C

[0169] Presence or absence of stirring, etc.: Circulating bath (for example, for a 2 L plating solution, the liquid circulation volume using a pump is more than 1 L / min)

[0170] Current density: 2.5 - 10 A / dm 2

[0171] In the case of the coating formation process by tin plating, the tin adhesion amount formed by tin plating is preferably 0.5 g / m 2 - 22.0 g / m 2 . The measurement of the tin adhesion amount can be carried out by using well - known methods such as fluorescence X - ray (XRF) measurement or ICP emission spectrometry analysis.

[0172] In the case of the coating formation process by chromium plating, as an example of the bath composition and plating conditions for chromium plating, they are as follows.

[0173] Chromium(VI) oxide: 30 - 200 g / L

[0174] Sodium fluoride: 1 - 10 g / L

[0175] pH: 1.0 or less

[0176] Bath temperature: 35 - 65 °C

[0177] Presence or absence of stirring, etc.: Circulating bath (for example, for a 2 L plating solution, the liquid circulation volume using a pump exceeds 1 L / min)

[0178] Current density: 5 - 50 A / dm 2

[0179] In the case of the coating formation process by iron - nickel alloy plating, as an example of the bath composition and plating conditions for iron - nickel alloy plating, they are as follows. 2 - 22.0 g / m 2 . The measurement of the chromium adhesion amount can be carried out by using well - known methods such as fluorescence X - ray (XRF) measurement or ICP emission spectrometry analysis.

[0180] In the case of the coating formation process by iron - nickel alloy plating, as an example of the bath composition and plating conditions for iron - nickel alloy plating, they are as described below.

[0181] [An Example of Iron-Nickel Alloy Plating Bath and Plating Conditions]

[0182] ·Bath Composition

[0183] Nickel Sulfate Hexahydrate: 150 - 250 g / L

[0184] Ferric Sulfate Heptahydrate: 5 - 100 g / L

[0185] Nickel Chloride Hexahydrate: 20 - 50 g / L

[0186] Boric Acid: 20 - 50 g / L

[0187] Sodium Citrate (or Trisodium Citrate): 1 - 15 g / L

[0188] Sodium Saccharin: 1 - 10 g / L

[0189] ·Temperature: 25 - 70 °C

[0190] ·pH: 2 - 4

[0191] ·Presence or Absence of Stirring, etc.: Circulating Bath (for example, for a 2 L plating solution volume, the liquid circulation volume by a pump exceeds a flow rate of 1 L / min)

[0192] ·Current Density: 5 - 40 A / dm 2

[0193] In the case of forming a coating layer by iron-nickel alloy plating, the total adhesion amount of iron and nickel contained in the iron-nickel alloy layer is preferably 0.2 g / m 2 - 7.0 g / m 2 . The total adhesion amount of iron and nickel can be calculated by finding the weight difference before and after iron-nickel alloy plating. In addition, when the coating layer is an iron-nickel alloy layer, the total nickel adhesion amount per single side contained in the base material and the composite roughened layer in the nickel-plated metal material is preferably 5 g / m 2 - 40 g / m 2 . In addition, when there is a metal layer 40 and nickel is contained in the metal layer 40, the total nickel adhesion amount per single side contained in the base material, the metal layer 40, and the composite roughened layer can also be set within the above range.

[0194] The formation of the above coating layer 70 is a process mainly aimed at achieving the adhesion between the roughened nickel layer and the base material and imparting an additional effect generated by the metal constituting the coating layer. In the present disclosure, in addition to its purpose, in this coating plating process, by performing stirring under a certain amount of liquid circulation, it can be expected that the nuclei of the fine protrusions formed in the above granular nickel formation plating are also covered by the coating metal layer, increasing the surface area.

[0195] In Figure 2 orFigure 4 In the method for manufacturing the nickel-plated metal material shown, a step of forming a metal layer 40 (metal layer forming step) may be further included. Specifically, regarding the metal layer forming step, it is performed on the substrate 20 before the above-mentioned granular nickel forming plating step. As the metal layer 40 formed by the metal layer forming step, an iron-nickel alloy layer, a nickel-phosphorus alloy layer, and a nickel layer can be cited.

[0196] When forming an iron-nickel alloy layer by the metal layer forming step, it can be formed by performing alloy electroplating using an alloy plating bath containing iron ions and nickel ions on at least one side of the substrate 20. In this case, known alloy plating conditions can be appropriately applied.

[0197] When forming a nickel-phosphorus alloy layer by the metal layer forming step, the nickel-phosphorus alloy layer can be formed by performing alloy electroplating using an alloy plating bath containing nickel ions and phosphorus ions on at least one side of the substrate 20.

[0198] When forming a nickel layer by the metal layer forming step, a nickel layer can be formed on at least one side of the substrate 20, for example, by a known Watts bath.

[0199] The metal layer forming step is not necessarily a single step, and multiple steps can be appropriately combined and performed. For example, both a nickel-phosphorus alloy layer and a nickel layer can be formed by the metal layer forming step.

[0200] When using a diffusion surface-treated steel sheet as the substrate 20, after forming a nickel plating layer by electroplating, heat treatment is performed, and an iron-nickel alloy layer generated by thermal diffusion can be formed.

[0201] Specifically, continuous annealing or batch annealing (box annealing) can be performed. Regarding examples of the temperature and time during continuous annealing treatment, it can be performed in the range of 650 °C to 950 °C with a soaking time of 15 seconds to 150 seconds. Regarding examples of the temperature and time during batch annealing (box annealing) treatment, it can be performed in the range of 450 °C to 690 °C with a soaking time of 1.5 hours to 20 hours, and the total time of heating, soaking, and cooling is in the range of 4 hours to 80 hours. After the above heat treatment, rolling can be performed. Additionally, heat treatment can be performed again after rolling.

[0202] <<Examples>>

[0203] Hereinafter, examples are cited to illustrate the present invention more specifically. First, the measurement methods in the examples are described.

[0204] [Measurement Method of Surface Property Parameters]

[0205] Regarding the ten-point mean roughness Rzjis and the mean length Rsm of profile elements, which are surface property parameters of the surface of the roughened nickel layer 50, they are measured using a laser microscope (manufactured by Olympus Corporation, 3D measurement laser microscope LEXT OLS5000). In the measurement of the ten-point mean roughness Rzjis and the mean length Rsm of profile elements, in accordance with JIS B0601:2013, it is measured with an objective lens magnification of 50 times (lens name: MPLAPON50XLEXT) to obtain an analysis image with a field of view of 257 μm × 257 μm. Next, for the obtained analysis image, an analysis application program is used to perform noise removal and slope correction, which are automatic correction processes. Then, line roughness measurement is adopted to calculate the ten-point mean roughness Rzjis and the mean length Rsm of profile elements. It should be noted that the analysis is performed without setting the filter conditions (shape removal λf, low-pass filter λs, high-pass filter λc) during analysis, that is, under unconditional conditions. The average value is calculated when measured 15 times under the above conditions.

[0206] [Method for Measuring the Roughened Surface Area]

[0207] Regarding the roughened surface area of the surface of the roughened nickel layer 50, it is measured by the constant volume method using a fully automatic gas adsorption measurement device. As the fully automatic gas adsorption measurement device, the model AS1-MP manufactured by Quantachrome Corporation is used. In addition, krypton gas is used as the adsorbed gas. Arbitrary numbers of pieces with a size of 5 mm × 50 mm are cut out from the measurement sample, and the mass of the entire sample is weighed. The measurement sample is placed in the measurement cell, vacuum degassed at room temperature for more than 2 hours, and the specific surface area using the BET multi-point method is measured under liquid nitrogen at -195.8 °C. Based on the obtained specific surface area, the roughened surface area is calculated.

[0208] Specifically, when the measurement sample has roughened nickel layers on both sides, after multiplying the value of the specific surface area by the sample mass, it is divided by the number of measurement pieces. Furthermore, after setting this value to 1 / 2, it is divided by the horizontal projection area (5 mm × 50 mm) of each sample piece, thereby calculating the roughened surface area.

[0209] In addition, when measuring a sample with a roughened nickel layer on one side, first, multiply the specific surface area value by the sample mass, then divide by the number of measurement pieces to calculate the total surface area of each sample piece. Since the surface area of the non-treated side needs to be subtracted, a reference substrate is prepared. After calculating the specific surface area in the same way, multiply by the sample mass, then divide by the number of measurement pieces, and further calculate a value that is 1 / 2 of this value to obtain the surface area of each single side of the reference substrate. Then subtract the surface area of each single side of the reference substrate from the total surface area of each sample piece, and divide by the horizontal projection area (5 mm × 50 mm) of each sample piece to calculate the roughened surface area. It should be noted that as the reference substrate, the product obtained by subjecting the substrate to base nickel plating in Example 1 described below is used.

[0210] It should be noted that in the measurement of each sample, in order to improve the test accuracy, 20 to 60 test pieces are used for measurement, and 60 test pieces are used for measurement of the reference sample with a particularly small surface area. In addition, for the measurement samples in the following examples and comparative examples, since the thickness is thin enough, the influence of the end face can be ignored.

[0211] [Resin adhesion test (peel test) and evaluation]

[0212] As the adhesion evaluation with other components, the adhesion with resin is evaluated. Specifically, for the resin adhesion evaluation, a peel test is conducted to obtain the peel strength. The measurement method is described below. Prepare the nickel-plated metal materials (30 mm × 100 mm) obtained in the examples and comparative examples, which have a roughened nickel layer formed on at least one side. On the evaluation surface side (roughened nickel layer side), overlap the single ends of a polypropylene film with a thickness of 140 μm (25 mm × 100 mm), and heat-seal the 25 mm × 25 mm range of the overlapped part with a heat-sealing agent (manufactured by Tester Sangyo Co., Ltd., TP-701-B) to make a test piece. The temperature of the heat-sealing, that is, the set temperature of the heat-sealing agent, is set to 156°C, and the pressure during heat-sealing is set to 0.1 MPa. The time for pressing with the heat-sealing agent at the above set temperature and pressure (hereinafter also referred to as the pressing time) is set to 5 seconds. The produced test piece is fixed to a fixture with a tensile test device (manufactured by Orientec Co., Ltd., RTC-1210A) in a state where the resin film is folded relative to the nickel-plated metal material at 180° with the heat-sealed end as the starting point, and stretched at a speed of 50 mm / min to obtain the 180° peel strength.

[0213] ◎: The 180° peel strength is 13 N / 25 mm or more

[0214] ○: The 180° peel strength is 5 N / 25 mm or more and less than 13 N / 25 mm

[0215] ×: The 180° peel strength is less than 5 N / 25 mm

[0216] [Evaluation of Liquid Permeability When Bonded to Polypropylene Resin (PP Resin)]

[0217] The nickel-plated metal materials obtained in the examples and comparative examples were cut to produce test pieces for evaluating liquid permeability with a width of 90 mm and a length of 140 mm. Then, on the obtained test pieces for evaluating liquid permeability, a marking sheet for alkaline aqueous solution (manufactured by Macherey-nagel, pH test paper) with a width of 7 mm and a length of 7 mm was placed, and a polypropylene resin film (manufactured by Mitsubishi Chemical Corporation, trade name "Modic" / two-layer polypropylene resin film (the side with the trade name "Modic" was used as the adhesive layer for the bonding surface)) with a width of 110 mm, a length of 160 mm, and a thickness of 60 μm was placed thereon. While clamping the marking sheet for alkaline aqueous solution, a laminating roller was used under the conditions of temperature: 150 °C, pressure: 0.6 MPa (confirmed using pressure-sensitive paper), and roller passing speed: 70 mm / second. After full-surface heat sealing, a circle with a diameter of 30 mm was punched out with the marking as the center, and thus a measurement sample in which the marking sheet for alkaline aqueous solution was sealed was obtained. Then, the obtained measurement sample was immersed in an aqueous solution of Formula 618-TK-2 manufactured by Nippon Quaker Chemical Corporation, which is a 30 g / L alkaline aqueous solution, at a liquid temperature of 80 °C, and the degree of color change (color change caused by the intrusion of the alkaline aqueous solution into the interior of the measurement sample) that occurred over time in the marking sheet for alkaline aqueous solution in the measurement sample after immersion was confirmed, and evaluated according to the following criteria.

[0218] ◎: No color change was found in the marking sheet for alkaline aqueous solution after 240 hours.

[0219] ○: No color change was found in the marking sheet for alkaline aqueous solution after 48 hours, but color change was found after 240 hours.

[0220] △: No color change was found in the marking sheet for alkaline aqueous solution after 36 hours, but color change was found after 48 hours.

[0221] ×: Color change was found in the marking sheet for alkaline aqueous solution after 30 hours.

[0222] It should be noted that the liquid permeability evaluation in the present disclosure is a so-called accelerated test using conditions that have a stronger impact on the interface. That is, it is a test of immersion in a highly corrosive alkaline aqueous solution at high temperature for a long time, and does not directly reflect the conditions when applied to actual products.

[0223] <Example 1>

[0224] First, a cold-rolled steel sheet (thickness 60 μm) of low-carbon aluminum-killed steel having the chemical composition shown below was prepared.

[0225] C: 0.04 wt%, Mn: 0.32 wt%, Si: 0.01 wt%, P: 0.012 wt%, S: 0.014 wt%, balance: Fe and inevitable impurities

[0226] Next, the cold-rolled steel sheet was subjected to electrolytic degreasing and pickling by immersion in sulfuric acid, and then nickel-plated to form a 8.9 g / m 2 The nickel layer with a thickness of 2.2 μm was formed on both surfaces by continuous annealing, thermal diffusion treatment, and temper rolling. The obtained diffusion surface treated steel sheet was used as the substrate 20.

[0227] A diffusion surface treated steel sheet as the base material 20 is subjected to strike nickel plating under the strike nickel plating conditions described below, and then a base nickel layer is formed under the base nickel plating conditions.

[0228] <Impact nickel plating conditions>

[0229] Bath composition: nickel sulfate hexahydrate 250g / L, sulfuric acid 50g / L

[0230] pH less than 1.0

[0231] Bath temperature 60℃

[0232] Current density 30A / dm 2

[0233] Electrolysis time 5 seconds

[0234] <Base Nickel Plating Conditions>

[0235] Bath composition: nickel sulfate hexahydrate 250g / L, nickel chloride hexahydrate 45g / L, boric acid 30g / L

[0236] pH 4.0~5.0

[0237] Bath temperature 60℃

[0238] Current density 10A / dm 2

[0239] Electrolysis time: 15.1 seconds

[0240] Next, a roughened nickel layer was formed on the underlying nickel layer on one side under the following conditions. The roughened nickel layer was formed by performing the following granular nickel forming plating and nickel growth plating.

[0241] <Granular Nickel Formation Plating Conditions>

[0242] Nickel sulfate hexahydrate concentration in the plating bath: 10 g / L

[0243] Concentration of nickel chloride hexahydrate in the plating bath: 10 g / L

[0244] Concentration of chloride ions in the plating bath: 16.6 g / L

[0245] Ratio of nickel ions to ammonium ions in the plating bath: nickel ions / ammonium ions (weight ratio) = 0.2

[0246] pH: 6.0

[0247] Bath temperature: 52 °C

[0248] Average current density: 21.0 A / dm 2

[0249] Electrolysis time: 15.0 seconds

[0250] Stirring method: Circulating stirring (stirring flow rate: small)

[0251] Conductivity of the plating bath (bath conductivity): 13.8 S / m (in the case of bath temperature 50 °C, pH = 6.0)

[0252] It should be noted that in the examples and comparative examples, the description of the stirring flow rate in the circulating stirring is based on the following criteria.

[0253] Large stirring flow rate: For a 2 L plating solution, the liquid circulation rate using a pump is 3 L / min or more and less than 4 L / min

[0254] Medium stirring flow rate: For a 2 L plating solution, the liquid circulation rate using a pump is 2 L / min or more and less than 3 L / min

[0255] Small stirring flow rate: For a 2 L plating solution, the liquid circulation rate using a pump is 1 L / min or more and less than 2 / min

[0256] No stirring: For a 2 L plating solution, the liquid circulation rate using a pump is less than 1 L / min

[0257] <Nickel growth plating conditions>

[0258] Bath composition: 250 g / L of nickel sulfate hexahydrate, 45 g / L of nickel chloride hexahydrate, 30 g / L of boric acid

[0259] pH: 4.0 - 5.0

[0260] Bath temperature: 60 °C

[0261] Current density: 10 A / dm 2

[0262] Electrolysis time: 1.4 seconds

[0263] Stirring method: Circulating stirring (stirring flow rate: medium)

[0264] In the nickel-plated metal material thus obtained, the values of the ten-point average roughness Rzjis and the average length Rsm of the profile units on the outermost surface of the roughened nickel layer are shown in Table 5. It should be noted that these surface property parameters were measured using a laser microscope (manufactured by Olympus Corporation, 3D measurement laser microscope LEXT OLS5000). In the measurement of the ten-point average roughness Rzjis and the average length Rsm of the profile units, measurement was carried out at an objective lens magnification of 50 times, and no filter conditions were set during analysis, and analysis was carried out without conditions. Measurement of the roughened surface area, 180° peel strength test and evaluation, and liquid permeability evaluation were also carried out.

[0265] It should be noted that, regarding the nickel adhesion amount in the roughened nickel layer and the nickel-plated metal material, it was measured using a fluorescent X-ray device (ZSX100e manufactured by Rigaku Corporation), and the obtained numerical values are shown in Table 1. It should be noted that the specific measurement method is the same as the method described in International Publication No. 2020 / 017655, and therefore detailed description is omitted here. The nickel adhesion amounts shown in Tables 1 to 4 are all values per single side.

[0266] <Example 2>

[0267] The conditions for substrate nickel plating, granular nickel formation plating, and nickel growth plating are shown in Tables 1 and 2. Other than this, it was carried out in the same manner as in Example 1. The obtained results are shown in Tables 1, 2, and 5.

[0268] <Example 3>

[0269] As the base material 20, a steel plate without an iron-nickel alloy layer was used. Specifically, a product obtained by electrolytic degreasing and pickling in sulfuric acid of the cold-rolled steel plate described in Example 1 was used as the base material 20. Other than this, it was carried out in the same manner as in Example 1. The obtained results are shown in Tables 1, 2, and 5.

[0270] <Examples 4 to 17>

[0271] The conditions for the base material, substrate nickel plating, granular nickel formation plating, and nickel growth plating are shown in Tables 1 and 2. Other than this, it was carried out in the same manner as in Example 1. The obtained results are shown in Table 5.

[0272] <Example 18>

[0273] First, as the base material 20, a metal base material the same as that in Example 3 was prepared, and electrolytic degreasing and pickling in sulfuric acid the same as that in Example 3 were carried out. Then, a base nickel layer located between the base material and the roughened nickel layer was formed under the same conditions as in Example 1.

[0274] Next, a composite roughened coating is formed on the substrate nickel layer on one side under the following conditions. It should be noted that for the composite roughened coating, it is formed through the following plating process for forming granular nickel of the roughened nickel layer and the coating formation process for forming the coating layer. The coating treatment process is carried out by galvanizing.

[0275] <Granular nickel formation plating conditions>

[0276] Concentration of nickel sulfate hexahydrate in the plating bath: 10 g / L

[0277] Concentration of nickel chloride hexahydrate in the plating bath: 10 g / L

[0278] Chloride ion concentration of the plating bath: 16.6 g / L

[0279] Ratio of nickel ions to ammonium ions in the plating bath: nickel ions / ammonium ions (weight ratio) = 0.2

[0280] pH: 6.0

[0281] Bath temperature: 55 °C

[0282] Average current density: 23.3 A / dm 2

[0283] Electrolysis time: 20.0 seconds

[0284] Stirring method: Circulating stirring (stirring flow rate: medium)

[0285] Conductivity of the plating bath (bath conductivity): 13.8 S / m (where the bath temperature is 50 °C and pH = 6.0)

[0286] <Coating layer formation conditions>

[0287] Bath composition: 220 g / L of zinc sulfate heptahydrate, 30 g / L of ammonium sulfate

[0288] pH: 1.5 - 2.5 (adjustment was carried out using sulfuric acid.)

[0289] Bath temperature: 55 °C

[0290] Current density: 10 A / dm 2

[0291] Electrolysis time: 9.3 seconds

[0292] Stirring method: Circulating stirring (stirring flow rate: large)

[0293] Through the above, a zinc coating is obtained.

[0294] In the same manner as in Example 1, the values of the ten-point average roughness Rzjis and the mean length Rsm of the profile elements at the outermost surface on the side of the composite roughened coating of the nickel-plated metal material were measured and are shown in Table 5. It should be noted that these surface property parameters were measured using a laser microscope (manufactured by Olympus Corporation, 3D measurement laser microscope LEXT OLS5000). In the measurement of the ten-point average roughness Rzjis and the mean length Rsm of the profile elements, the measurement was carried out at an objective lens magnification of 50 times, and the analysis was performed without setting the filter conditions during analysis. The roughened surface area, 180° peel strength test, and liquid penetration resistance test were also carried out.

[0295] It should be noted that regarding the nickel adhesion amount in the composite roughened coating, it was measured using a fluorescent X-ray device (ZSX100e manufactured by Rigaku Corporation). It should be noted that for the specific measurement method, it is the same as the method described in International Publication No. 2020 / 017655, and thus the detailed description is omitted here. Regarding the zinc adhesion amount of the zinc coating, it was also measured using a fluorescent X-ray device. The values obtained are shown in Tables 3, 4, and 6.

[0296] <Example 19>

[0297] The conditions for substrate, base nickel plating, granular nickel formation plating, and zinc plating were as shown in Tables 3 and 4. Other than that, it was carried out in the same manner as in Example 18. The results obtained are shown in Table 6.

[0298] <Example 20>

[0299] As the substrate 20, a stainless steel plate (SUS430) with a thickness of 50 μm having the chemical composition shown below was prepared.

[0300] C: 0.12% by weight, Cr: 16 - 18% by weight, Si: 0.75% by weight, Mn: 1.00% by weight or less, P: 0.04% by weight or less, S: 0.03% by weight or less, balance: inevitable impurities

[0301] For the substrate, after performing shock nickel plating treatment under the shock nickel plating conditions shown in Example 1, base nickel plating, granular nickel formation plating, and nickel growth plating were carried out under the conditions shown in Tables 7 and 8. Other than that, it was carried out in the same manner as in Example 1. The results obtained are shown in Table 9.

[0302] <Example 21>

[0303] As the substrate 20, a rolled aluminum plate (hereinafter, also referred to as an aluminum plate) with a thickness of 40 μm of an aluminum alloy (A8079) having the chemical composition shown below was prepared.

[0304] Si: 0.05 to 0.30 wt%, Fe: 0.7 to 1.3 wt%, Cu: 0.05 wt% or less, Zn: 0.10 wt% or less, balance: inevitable impurities

[0305] Next, for the above aluminum plate, zinc plating was replaced on the surface of the aluminum plate under the zinc immersion treatment conditions shown below. Then, as shown in Tables 7 and 8, substrate nickel plating, granular nickel formation plating, and nickel growth plating were carried out. The obtained results are shown in Table 9.

[0306] <Zinc immersion treatment conditions>

[0307] 《Degreasing conditions》

[0308] Bath composition: 22.5 g / L of sodium hydroxide, 4.5 g / L of sodium carbonate

[0309] pH: 12 or more

[0310] Bath temperature: 25 °C

[0311] Immersion time: 2 minutes

[0312] 《Pickling conditions》

[0313] Bath composition: 70 g / L of sulfuric acid

[0314] pH: 1.0 or less

[0315] Bath temperature: 25 °C

[0316] Immersion time: 2 minutes

[0317] 《Ash removal conditions》

[0318] Bath composition: 250 mL / L of 60% nitric acid, 4 mL / L of ferric chloride solution

[0319] pH: 1.0 or less

[0320] Bath temperature: 25 °C

[0321] Immersion time: 30 seconds

[0322] 《First zinc immersion conditions》

[0323] Bath composition: 150 g / L of sodium hydroxide, 50 g / L of Rochelle salt, 25 g / L of zinc oxide, 1.5 g / L of ferrous chloride

[0324] pH: 12 to 14

[0325] Bath temperature: 25 °C

[0326] Immersion time: 50 seconds

[0327] 《Dezincification conditions》

[0328] Bath composition: 250 mL / L of 60% nitric acid, 4 mL / L of ferric chloride solution

[0329] pH: Below 1.0

[0330] Bath temperature: 25 °C

[0331] Immersion time: 30 seconds

[0332] 《Second zinc immersion conditions》

[0333] Bath composition: 150 g / L of sodium hydroxide, 50 g / L of Rochelle salt, 25 g / L of zinc oxide, 1.5 g / L of ferrous chloride

[0334] pH: 12 - 14

[0335] Bath temperature: 25 °C

[0336] Immersion time: 50 seconds

[0337] First, as the substrate 20, prepare the same metal substrate as in Example 3, and perform the same electrolytic degreasing and pickling immersion in sulfuric acid as in Example 3. Then, form a base nickel layer between the substrate and the roughened nickel layer under the same conditions as in Example 1.

[0338] Secondly, under the following conditions, form a composite roughened coating on the base nickel layer on one side. It should be noted that the composite roughened coating is formed by the following plating process for forming granular nickel of the roughened nickel layer and the coating formation process for forming the coating layer. The coating treatment process is carried out by tin plating.

[0339] <Plating conditions for forming granular nickel>

[0340] Concentration of nickel sulfate hexahydrate in the plating bath: 10 g / L

[0341] Concentration of nickel chloride hexahydrate in the plating bath: 10 g / L

[0342] Concentration of chloride ions in the plating bath: 16.6 g / L

[0343] Ratio of nickel ions to ammonium ions in the plating bath: nickel ions / ammonium ions (weight ratio) = 0.2

[0344] pH: 6.0

[0345] Bath temperature: 50 °C

[0346] Average current density: 20.0 A / dm 2

[0347] Electrolysis time: 15.0 seconds

[0348] Stirring method: Circulating stirring (stirring flow rate: medium)

[0349] Conductivity of the plating bath (bath conductivity): 13.8 S / m (bath temperature 50°C, pH = 6.0)

[0350] <Coating layer formation conditions>

[0351] Stannous sulfate: 80g / L

[0352] Phenolsulfonic acid: 60g / L

[0353] Ethoxylated α-naphthol: 3g / L

[0354] Ethoxylated-α-naphtholsulfonic acid: 3g / L

[0355] pH: 0.5 to 1.5 (Adjusted with sulfuric acid.)

[0356] Bath temperature: 40°C

[0357] Current density: 5.0A / dm 2

[0358] Electrolysis time: 1.2 seconds

[0359] Stirring method: Circulation stirring (stirring flow rate: small)

[0360] Through the above, a tin coating layer is obtained.

[0361] The ten-point average roughness Rzjis and the average length Rsm of the contour unit on the outermost surface of the composite roughened coating side of the nickel-plated metal material were measured in the same manner as in Example 1, and the values are shown in Table 12. It should be noted that these surface properties were measured using a laser microscope (LEXT OLS5000, a 3D measurement laser microscope manufactured by Olympus Corporation). The ten-point average roughness Rzjis and the average length Rsm of the contour unit were measured with a 50x objective lens, and the analysis was performed without setting the filter conditions during analysis. The roughened surface area, 180° peel strength test, and liquid penetration resistance test were also performed.

[0362] It is to be noted that the nickel adhesion amount in the composite roughening coating is measured using a fluorescent X-ray device (ZSX100e manufactured by Rigaku Corporation). It is to be noted that for a specific measurement method, since it is the same as the method described in International Publication No. 2020 / 017655, a detailed description is omitted here. The tin adhesion amount of the coated tin layer is also measured using a fluorescent X-ray device. The obtained values are shown in Tables 10, 11 and 12.

[0363] <Comparative Example 1>

[0364] The conditions for nickel plating on the substrate, forming the granular nickel plating, and growing the nickel plating are shown in Tables 1 and 2. Other than this, it was carried out in the same manner as in Example 1. The results obtained are shown in Table 5. It should be noted that since the 180° peel strength of Comparative Example 1 was 0, it was difficult to evaluate the liquid penetration resistance, and thus it was not carried out.

[0365] <Comparative Example 2>

[0366] The conditions for nickel plating on the substrate, forming the granular nickel plating, and growing the nickel plating are shown in Tables 1 and 2. Other than this, it was carried out in the same manner as in Example 1. The results obtained are shown in Table 5.

[0367] <Comparative Example 3>

[0368] The conditions for nickel plating on the substrate, forming the granular nickel plating, and growing the nickel plating are shown in Tables 1 and 2. Other than this, it was carried out in the same manner as in Example 2. The results obtained are shown in Table 5.

[0369] <Comparative Example 4>

[0370] The conditions for nickel plating on the substrate, forming the granular nickel plating, and growing the nickel plating are shown in Tables 1 and 2. Other than this, it was carried out in the same manner as in Example 1. The results obtained are shown in Table 5.

[0371] <Comparative Example 5>

[0372] The conditions for nickel plating on the substrate, forming the granular nickel plating, and zinc plating are shown in Tables 3 and 4. Other than this, it was carried out in the same manner as in Example 18. The results obtained are shown in Table 6. It should be noted that since the 180° peel strength of Comparative Example 5 was 0, it was difficult to evaluate the liquid penetration resistance, and thus it was not carried out.

[0373] <Comparative Example 6>

[0374] The conditions for nickel plating on the substrate, forming the granular nickel plating, and zinc plating are shown in Tables 3 and 4. Other than this, it was carried out in the same manner as in Example 18. The results obtained are shown in Table 6.

[0375] <Comparative Example 7>

[0376] The conditions for nickel plating on the substrate, forming the granular nickel plating, and growing the nickel plating are shown in Tables 7 and 8. Other than this, it was carried out in the same manner as in Example 20. The results obtained are shown in Table 9.

[0377] <Comparative Example 8>

[0378] The conditions for nickel plating on the substrate, forming the granular nickel plating, and growing the nickel plating are shown in Tables 7 and 8. Other than this, it was carried out in the same manner as in Example 20. The results obtained are shown in Table 9.

[0379] <Comparative Example 9>

[0380] The conditions for nickel plating on the substrate, forming the granular nickel plating, and nickel growth plating are shown in Tables 7 and 8. Other than this, it is carried out in the same manner as in Example 21. The obtained results are shown in Table 9.

[0381] <Comparative Example 10>

[0382] The conditions for nickel plating on the substrate, forming the granular nickel plating, and tin plating are shown in Tables 10 and 11. Other than this, it is carried out in the same manner as in Example 22. The obtained results are shown in Table 12.

[0383] [Table 1]

[0384]

[0385]

[0386] [Table 3]

[0387]

[0388]

[0389] [Table 5]

[0390]

[0391] [Table 6]

[0392]

[0393] [Table 7]

[0394]

[0395]

[0396] [Table 9]

[0397]

[0398] [Table 10]

[0399]

[0400]

[0401] [Table 12]

[0402]

[0403] It was confirmed that Examples 1 to 17 all had preferable characteristics in terms of resin adhesion strength and liquid penetration resistance. On the other hand, in Comparative Examples 1 to 3, the resin adhesion strength was 3.3 N / 25 mm or less, and the object was not achieved from the viewpoint of resin adhesion strength. In addition, in Comparative Examples 4 to 5, the object was not achieved from the viewpoint of liquid penetration resistance.

[0404] More specifically, when comparing Example 8 and Comparative Example 3, although the ten-point average roughness Rzjis was approximately the same value, it was found that there were differences between the Example and the Comparative Example in the value of the roughened surface area. Therefore, the target resin adhesion strength was not obtained in the Comparative Example. It should be noted that it is speculated that the difference in the values of these roughened surface areas is due to the different shapes of the individual protrusions including the shape of the root of the roughened portion, and the detailed situation is not yet clear.

[0405] Regarding Example 18 and Example 19, Comparative Example 5 and Comparative Example 6, they are embodiments in which zinc is formed as a coating layer. Regarding Example 18 and Example 19, on the surface of the composite roughened plating layer formed with a coating layer composed of zinc, the ten-point average roughness Rzjis is 1.0 μm or more and less than 4.8 μm, and the roughened surface area is 1.5 m 2 / 1 m 2 Above, it was confirmed that they have preferable characteristics in terms of resin adhesion strength and liquid penetration resistance. On the other hand, the value of the ten-point average roughness Rzjis of Comparative Example 5 was outside the above range. As a result, the object was not achieved from the viewpoints of resin adhesion strength and liquid penetration resistance. In addition, regarding Comparative Example 6, since the ten-point average roughness Rzjis became 4.9 μm, exceeding 4.8 μm, the target liquid penetration resistance was not obtained.

[0406] In addition, as shown in Examples 1 to 9, 18, and 19, the ten-point average roughness Rzjis on the outermost surface of the roughened nickel layer 50 side is 1.0 μm or more and 3.5 μm or less, and the roughened surface area is 5.3 m 2 / 1 m 2 In the above case, more preferable results were obtained from the viewpoints of both resin adhesion strength and liquid penetration resistance.

[0407] Examples 20, Comparative Example 7, and Comparative Example 8 are embodiments using a stainless steel plate as a substrate. In addition, Examples 21 and Comparative Example 9 are embodiments using an aluminum plate as a substrate. In Examples 20 and 21, it was confirmed that Rzjis was 1.0 μm or more and less than 4.8 μm and the roughened surface area was 1.5 m 2 / 1 m 2As described above, it has preferable characteristics in both resin adhesion strength and liquid penetration resistance. On the other hand, in Comparative Example 7, Rzjis is less than 1.0 μm and the roughened surface area is less than 1.5 m 2 / 1m 2 , resulting in a significant decrease in the adhesion to the resin. In addition, in Comparative Example 8 and Comparative Example 9, Rzjis exceeds 4.8 μm, and the object cannot be achieved from the viewpoint of liquid penetration resistance.

[0408] Examples 22 and Comparative Example 10 are embodiments in which tin is formed as a coating layer. In Example 22, on the surface of the composite roughened plating layer formed with a coating layer composed of tin, the ten-point average roughness Rzjis is 1.0 μm or more and less than 4.8 μm, and the roughened surface area is 1.5 m 2 / 1m 2 or more, and it has preferable characteristics in resin adhesion strength and liquid penetration resistance. On the other hand, the ten-point average roughness Rzjis of Comparative Example 10 becomes 5.5 μm, exceeding 4.8 μm, so the target liquid penetration resistance is not obtained.

[0409] From these results, it can be understood that in order to obtain preferable characteristics in both resin adhesion strength and liquid penetration resistance, it is necessary to control both the ten-point average roughness Rzjis and the roughened surface area.

[0410] It should be noted that the above-described embodiments and each example can be variously modified without departing from the gist of the present disclosure.

[0411] Industrial Applicability

[0412] As described above, the nickel-plated metal material of the present disclosure can be applied to various uses such as current collectors for positive electrodes and / or negative electrodes of secondary batteries, electronic devices, electrical products, automobiles, and building components.

[0413] Explanation of Reference Numerals

[0414] 100, 200, 300, 400: Nickel-plated metal material

[0415] 20: Substrate

[0416] 40: Metal layer

[0417] 50: Roughened nickel layer

[0418] 60: Composite roughened plating layer

[0419] 70: Coating layer

Claims

1. A nickel-plated metal material, characterized in that, Comprising: a substrate made of metal, and a roughened nickel layer provided on at least one surface of the substrate, the ten-point average roughness Rzjis of the outermost surface on the roughened nickel layer side of the nickel-plated metal material is 1.0 μm or more and less than 4.8 μm, and The roughened surface area of the outermost surface on the side of the roughened nickel layer is 1.5 m 2 / 1 m 2 or more.

2. The nickel-plated metal material according to claim 1, which is in the form of a plate with an overall thickness of 0.005 to 5.01 mm.

3. The nickel-plated metal material according to claim 1, wherein The ten-point average roughness Rzjis is 1.0 μm or more and 3.5 μm or less.

4. The nickel-plated metal material according to claim 1 or 2, wherein, The roughened surface area is 5.3 m 2 / 1 m 2 or more.

5. The nickel-plated metal material according to claim 1 or 2, wherein The roughened nickel layer is formed on the outermost surface.

6. The nickel-plated metal material according to claim 1 or 2, wherein, It is the outermost surface on the roughened nickel layer side, and any one of an iron-nickel alloy layer, a zinc layer, a zinc alloy layer, a tin layer, a tin alloy layer, a chromium layer, and a chromium alloy layer is provided on the roughened nickel layer.

7. The nickel-plated metal material according to claim 1 or 2, wherein The adhesion amount of nickel in the roughened nickel layer is 2.0 g / m 2 or more and 16 g / m 2 or less.

8. The nickel-plated metal material according to claim 1 or 2, wherein The thickness of the substrate is 0.004 mm to 5.0 mm.

9. The nickel-plated metal material according to claim 1 or 2, wherein, The substrate is any one of the following: a metal plate or metal foil made of a pure metal selected from iron, copper, aluminum, and nickel; a metal plate or metal foil made of an alloy containing one selected from iron, copper, aluminum, and nickel; a nickel-plated steel sheet, a diffusion surface-treated steel sheet in which a diffusion alloy layer of iron and nickel is formed on the surface layer or near the surface layer by heat-treating the nickel-plated steel sheet, and a galvanized steel sheet.

10. The nickel-plated metal material according to claim 1 or 2, wherein, There is a metal layer between the substrate and the roughened nickel layer, The metal layer is any one of an iron-nickel alloy layer, a nickel-phosphorus alloy layer, and a nickel layer.

11. The nickel-plated metal material according to claim 9, wherein, The total nickel adhesion amount of the metal layer and the roughened nickel layer on each single side of the roughened nickel layer side of the nickel-plated metal material is 4 g / m 2 or more and 40 g / m 2 or less.

12. The nickel-plated metal material according to claim 9, wherein, The total nickel adhesion amount per single side of the base material, the metal layer, and the roughened nickel layer is 4 g / m 2 or more and 40 g / m 2 or less.

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