Nickel-plated metal material

Abstract

[Object]Disclosed is a nickel-plated metal material, which has adhesion with another member while suppressing the height of a roughened nickel layer.[Solving Means]The nickel-plated metal material includes a base material made of metal and a roughened nickel layer formed on at least one side on the base material. A ten-point mean roughness Rzjis on an outermost surface on a side of the roughened nickel layer of the nickel-plated metal material is 1.0 μm or greater and smaller than 4.8 μm, and a roughened surface area on the outermost surface on the side of the roughened nickel layer is 1.5 m2 / 1 m2 or greater.

Description

TECHNICAL FIELD

[0001] The present disclosure relates to a nickel-plated metal material.BACKGROUND ART

[0002] In recent years, in a technology that forms a plating layer on a base material such as a metal sheet or a metal foil, techniques are not limited to smoothly forming the plating layer, and are known to form roughness by plating or to deposit metal in a granular or acicular form on the base material, that is, to form what is called a roughened plating layer.

[0003] For example, PTL 1 discloses a roughened nickel-plated sheet, the lightness and 85° gloss of a surface of a roughened nickel layer of which are specified to provide the roughened nickel-plated sheet with excellent adhesion with another member while allowing the plating layer to hold adhesion with a base material. Further, PTL 2 discloses a roughened nickel-plated sheet improved in liquid penetration resistance when joined with another member, in addition to the adhesion of a plating layer to a base material and adhesion with another member.CITATION LISTPatent Literature[PTL 1]

[0004] PCT Patent Publication No. WO2020 / 017655[PTL 2]

[0005] PCT Patent Publication No. WO2021 / 149821SUMMARYTechnical Problem

[0006] Appliances that use a roughened nickel-plated material are desired to have improved characteristics under a higher diversity of environments. As an example of these environments, a case can be mentioned in which such an appliance is used for a long period of time under a high-temperature environment or in a highly corrosive liquid. However, it came to knowledge that, if the height of a roughened portion was made high to obtain a certain level of adhesion or higher with another member in a conventional roughened nickel-plated material, liquid penetration resistance (resistance to penetration and spreading of a liquid to and in an interface) tended to decrease when continued to be exposed to such a severe environment as described above. If the height of the roughened portion was made low, on the other hand, the adhesion with another member was insufficient with such a conventional roughened nickel-plated material.

[0007] The present disclosure has been made with a view to solving such a problem, and has, as an object thereof, the provision of a nickel-plated metal material, which has adhesion with another member while suppressing the height of a roughened portion in a roughened nickel layer.Solution to Problem

[0008] To solve the above-described problem, a nickel-plated metal material of the present embodiment is a nickel-plated metal material including a base material made of metal and a roughened nickel layer formed on at least one side on the base material. A ten-point mean roughness Rzjis on an outermost surface on a side of the roughened nickel layer of the nickel-plated metal material is 1.0 μm or greater and smaller than 4.8 μm, and a roughened surface area on the outermost surface on the side of the roughened nickel layer is 1.5 m2 / 1 m2 or greater.Advantageous Effect of Invention

[0009] According to the present disclosure, it is possible to provide a nickel-plated metal material, which has improved liquid penetration resistance at an adhesion interface with another member by suppressing the height of a roughened portion in a roughened nickel layer and also has adhesion with another member by increasing a roughened surface area to be mentioned below.BRIEF DESCRIPTION OF DRAWINGS

[0010] FIG. 1 is a cross-sectional view schematically depicting a nickel-plated metal material of the present embodiment.

[0011] FIG. 2 is a cross-sectional view schematically depicting a nickel-plated metal material according to another embodiment.

[0012] FIG. 3 is a cross-sectional view schematically depicting a nickel-plated metal material according to still another embodiment.

[0013] FIG. 4 is a cross-sectional view schematically depicting a nickel-plated metal material according to yet another embodiment.

[0014] FIG. 5 is a graph presenting a method example for determining the thickness of an iron-nickel diffusion alloy layer.

[0015] FIG. 6 depicts schematic diagrams illustrating differences in roughened surface area due to differences in the shapes of roughened portions.DESCRIPTION OF EMBODIMENTS<<Nickel-Plated Metal Material>>

[0016] A description will hereinafter be made regarding embodiments for implementing the nickel-plated metal material of the present disclosure. It is to be noted that a “roughened portion” in the present disclosure is a rough surface portion including a roughened nickel layer formed on a base material by a roughened plating step and formed by protrusions made from nickel granules on the base material 20. The nickel-plated metal material of the present disclosure will hereinafter be described as a plate-shaped one, but without being limited to it, may have a curved surface shape or three-dimensional shape formed by pressing a plate-shape material with a mold, or may have a three-dimensional shape such as a cylinder shape or a cube. Moreover, the roughened nickel-plating layer is not needed to be formed on the entire surface if the roughened nickel layer is formed in an area where a roughened portion is required. In other words, the nickel-plated metal material of the present disclosure may be one with a roughened nickel layer formed in at least a part of area on a whole shape.First Embodiment

[0017] FIG. 1 is a cross-sectional view schematically depicting an embodiment of a nickel-plated metal material 100 of the present disclosure. It is to be noted that the nickel-plated metal material 100 of the present embodiment is used, for example, as current collectors of positive electrodes and / or negative electrodes of secondary batteries and the like, members for electronic devices, electric appliances, automobiles, and constructions, and so on.

[0018] The nickel-plated metal material 100 of the present embodiment includes the base material 20 made of metal, and a roughened nickel layer 50 formed on the base material 20. It is to be noted that, in the nickel-plated metal material 100 of the present embodiment, the roughened nickel layer 50 is formed on at least one outermost surface as depicted in FIG. 1.<Base Material 20>

[0019] As the base material 20 for use in the nickel-plated metal material 100 of the present embodiment, a metal sheet or metal foil made of a pure metal selected from iron (Fe), copper (Cu), aluminum (Al), or nickel (Ni), a metal sheet made of an alloy containing one type selected from iron (Fe), copper (Cu), aluminum (Al), or nickel (Ni), one obtained by forming such a sheet, a cast material, a forged material, or the like can be mentioned, for example. Preferably, a metal sheet or metal foil made of such a metal can be used. It is also possible to use a nickel-plated steel sheet, a metal sheet (hereinafter also called a “surface diffusion-treated steel sheet”) with a diffusion alloy layer of iron and nickel formed on a surface layer or in a vicinity of the surface layer by subjecting a nickel-plated steel sheet to heat treatment, a zinc-plated steel sheet, or the like.

[0020] In the viewpoint of improving the plating adhesion between the base material 20 and the roughened nickel layer 50 and a composite roughened plating layer 60 to be described in a latter part, a steel sheet, iron foil, or a surface diffusion-treated steel sheet is preferred as the base material 20. In the viewpoint of improving the corrosion resistance of the whole metal sheet, on the other hand, a nickel-plated steel sheet, a surface diffusion-treated steel sheet, or a zinc-plated steel sheet is preferred as the base material 20. In the viewpoint of satisfying these plating adhesion and corrosion resistance together, a surface diffusion-treated steel sheet is particularly preferred.

[0021] If the base material 20 is a steel sheet, chromium (Cr) and other additive metal elements are preferably lower than 1.0 wt %. Specifically, low-carbon steel (carbon content: 0.01 to 0.15 wt %) represented by low-carbon aluminum-killed steel, ultralow-carbon steel having a carbon content of lower than 0.01 wt %, or non-aging ultralow-carbon steel prepared by adding titanium (Ti), niobium (Nb), and / or the like to ultralow-carbon steel is suitably used.

[0022] It is to be noted that, if a nickel-plated steel sheet, a surface diffusion-treated steel sheet, or a zinc-plated steel sheet is used as the base material 20, low-carbon steel (carbon content: 0.01 to 0.15 wt %) represented by low-carbon aluminum-killed steel, ultralow-carbon steel having a carbon content of lower than 0.01 wt %, or non-aging ultralow-carbon steel prepared by adding Ti, Nb, and / or the like to ultralow-carbon steel, which are / is similar to those / that described above, is suitably used as the base material.

[0023] If the base material 20 is an iron foil, a pure iron foil is preferred from the viewpoints of elongation, corrosion resistance, and the above-described plating adhesion, and from the viewpoint of thinning in particular, the whole base material 20 is preferably an electrolytic iron foil that is obtained by electrolytic plating.

[0024] It is to be noted that, if a metal base material with a passive film formed on a surface thereof, such as a stainless steel sheet, a nickel sheet, a nickel-plated steel sheet, or a surface diffusion-treated steel sheet, is used as the base material 20, strike nickel plating is preferably applied before plating treatment that forms the roughened nickel layer 50 or a metal layer 40 to be described in a latter part. Conditions for the strike nickel plating are not particularly limited, but may include, for example, the following conditions or the like. Under the below-described conditions, the deposition amount of nickel by strike nickel plating is generally 0.01 to 0.89 g / m2. If a nickel layer (also called an “undercoat nickel layer”) is formed as the metal layer 40, the total amount of a deposition amount of nickel by strike nickel plating and a nickel deposition amount by nickel plating to form the undercoat nickel layer is measured as the nickel deposition amount of the undercoat nickel layer.<Examples of Strike Nickel-Plating Conditions>Bath composition:

[0026] Nickel sulfate hexahydrate 100 to 300 g / L, sulfuric acid: 10 to 200 g / L

[0027] pH: 1.0 or lower

[0028] Bath temperature: 40° C. to 70° C.

[0029] Current density: 5 to 100 A / dm2

[0030] Plating time: 3 to 100 seconds

[0031] If the base material 20 is a pure aluminum sheet, a pure aluminum foil, an aluminum alloy sheet, or an aluminum alloy foil, on the other hand, zincate treatment that conducts substitution plating of zinc on a surface of aluminum is preferably applied before plating treatment that forms the roughened nickel layer 50 or the metal layer 40 to be described in the latter part. Zincate treatment conditions are not particularly limited, but may include, for example, the following conditions or the like. To the pure aluminum sheet or the pure aluminum foil, or the aluminum alloy sheet or the aluminum alloy foil, degreasing is conducted with an alkaline solution, etching treatment is next applied in sulfuric acid, and desmut treatment is then applied in a solution with nitric acid and a ferric chloride solution mixed therein. After that, the resulting pure aluminum sheet or pure aluminum foil, or the resulting aluminum alloy sheet or aluminum alloy foil is dipped in the below-described zincate treatment solution to conduct first zincate treatment. Subsequently, the resulting pure aluminum sheet or pure aluminum foil, or aluminum alloy sheet or aluminum alloy foil is dipped in the same treatment solution as that used in the desmut treatment, thereby removing zinc substitution-precipitated by the first zincate treatment, and is then dipped in the same treatment solution as that used in the first zincate treatment, to conduct a second zincate treatment (hereinafter also called “double zincate treatment”). In this case, water rinsing treatment is conducted after the treatment in each step. It is to be noted that the deposition amount of zinc can be adjusted by appropriately choosing the concentration of zinc ions in the treatment solution and the time during which the dipping in the treatment solution is conducted in the second zincate treatment. As an alternative, the substitution plating of zinc may also be conducted by conducting only the step of the first zincate treatment after the degreasing treatment, pickling treatment, and desmut treatment, that is, by applying single zincate treatment. Here, the deposition amount of zinc can be adjusted by appropriately choosing the concentration of zinc ions in the treatment solution and the time during which the dipping in the treatment solution is conducted in the first zincate treatment. It is to be noted that the deposition amount of zinc formed by the double zincate treatment or single zincate treatment is desirably formed to fall preferably in a range of 5 to 600 mg / m2, more preferably in a range of 30 to 400 mg / m2, to improve the adhesion of the metal layer 40 to be formed subsequently. By this double zincate treatment or single zincate treatment, a zinc layer may be formed between the roughened nickel layer or metal layer 40 and the base material 20. It is to be noted that the deposition amount of the zinc layer formed by the double zincate treatment or single zincate treatment can be measured by X-ray fluorescence (XRF) analysis or the like.<Examples of Zincate Treatment Conditions><<Degreasing Conditions>>Bath composition:

[0033] Sodium hydroxide 10 to 50 g / L, sodium carbonate 2 to 20 g / L

[0034] pH: 12 or higher

[0035] Bath temperature: 5° C. to 80° C.

[0036] Dipping time: 10 seconds to 3 minutes<<Pickling Conditions>>Bath composition:

[0038] Sulfuric acid 40 to 100 g / L

[0039] pH: 1.0 or lower

[0040] Bath temperature: 5° C. to 80° C.

[0041] Dipping time: 10 seconds to 3 minutes<<Desmut Conditions>>Bath composition:

[0043] 60% nitric acid 100 to 400 mL / L, ferric chloride solution 1 to 10 mL / L

[0044] pH: 1.0 or lower

[0045] Bath temperature: 5° C. to 80° C.

[0046] Dipping time: 10 seconds to 2 minutes<<First Zincate Conditions>>Bath composition:

[0048] Sodium hydroxide 100 to 200 g / L, Rochelle salt 20 to 80 g / L, zinc oxide 10 to 50 g / L, ferrous chloride 0.5 to 3.0 g / L

[0049] pH: 12 to 14

[0050] Bath temperature: 5° C. to 50° C.

[0051] Dipping time: 10 seconds to 2 minutes<<Dezincate Conditions>>Bath composition:

[0053] 60% nitric acid 100 to 400 mL / L, ferric chloride solution 1 to 10 mL / L

[0054] pH: 1.0 or lower

[0055] Bath temperature: 5° C. to 50° C.

[0056] Dipping time: 10 seconds to 2 minutes<<Second Zincate Conditions>>Bath composition:

[0058] Sodium hydroxide 100 to 200 g / L, Rochelle salt 20 to 80 g / L, zinc oxide 10 to 50 g / L, ferrous chloride 0.5 to 3.0 g / L

[0059] pH: 12 to 14

[0060] Bath temperature: 5° C. to 50° C.

[0061] Dipping time: 10 seconds to 2 minutes

[0062] As the thickness of the base material 20 for use in the nickel-plated metal material 100 of the present embodiment, a range of 0.004 to 5.0 mm is suited. If used as a current collector in a battery, for example, improvement in volumetric and gravimetric energy densities is required. Taking into consideration balancing of lightweighting and thinning with strength, the thickness of the base material 20 is hence preferably 0.004 to 0.5 mm, more preferably 0.01 to 0.3 mm, and still more preferably 0.025 to 0.1 mm. Further, in applications, for example, such as members for electronic devices, electric appliances, automobiles, and constructions, and so on, the thickness of the base material 20 is preferably 0.025 to 5.0 mm, more preferably 0.1 to 4.0 mm, still more preferably 0.2 to 3.0 mm, and even still more preferably 0.5 to 1.0 mm from the viewpoints of rigidity, strength, and workability.

[0063] For the thickness of the base material 20, thickness measurement by cross-sectional observation under an optical microscope or a scanning electron microscope (SEM) is suitably applied. Further, for the thickness before the roughened nickel plating, thickness measurement by a micrometer or the like can be applied.

[0064] As a method for determining the thickness of a diffusion alloy layer of iron and nickel when a surface diffusion-treated steel sheet is used as the base material 20, a method that reads it from a graph (see FIG. 5) obtained by scanning electron microscope-energy dispersive X-ray spectrometry (SEM-EDX) as in PCT Patent Publication No. WO2022 / 231009 can be applied. Specifically, in FIG. 5, the abscissas represent distances (μm) in a depth direction from a side of a surface layer, and the ordinates represent X-ray strengths of Ni and Fe. In the graph of FIG. 5, it is indicated that a portion, which is shallow toward a thickness direction, is high in nickel content and low in iron content. As the distance increases in the thickness direction, on the other hand, the content of iron progressively increases. Assuming that, in a portion before and after the curve of nickel and the curve of iron cross, the distance between 2 / 10 of the maximum value of nickel and 2 / 10 of the maximum value of iron corresponds to the diffusion alloy layer of iron and nickel in the present embodiment, its thickness can be read from the graph.

[0065] As the thickness of the diffusion alloy layer of iron and nickel in the surface diffusion-treated steel sheet, its thickness on at least one side is preferably 0.4 μm or greater, more preferably 0.6 μm or greater, and still more preferably 0.7 μm or greater from the viewpoint of improvement in corrosion resistance. Although there is no upper limit in particular, the thickness per side of the diffusion alloy layer of iron and nickel is preferably 7.5 μm or smaller, more preferably 6.0 μm or smaller, from the viewpoints of productivity and manufacturing cost. In the surface diffusion-treated steel sheet, it is preferred that, on its both sides, a diffusion alloy layer of iron and nickel be formed with a thickness of 0.4 μm or greater and 7.5 μm or smaller.

[0066] Further, the roughness of the base material 20 is not particularly limited, but the arithmetical mean roughness Ra by a contact probe surface roughness meter is 0.05 to 0.9 μm, more preferably 0.05 to 0.5 μm, still more preferably 0.05 to 0.3 μm, and particularly preferably 0.08 to 0.2 μm. It is to be noted that the arithmetical mean roughness Ra conforms to Japanese Industrial Standard (JIS) B 0601:2013.<Roughened Nickel Layer 50>

[0067] The roughened nickel layer 50 may be formed on an outermost surface on one side of the nickel-plated metal material 100 as depicted in FIG. 1, or may be formed on outermost surfaces on both sides although not depicted in any of the figures. The roughened nickel layer 50 is formed with nickel.

[0068] The nickel-plated metal material of the present embodiment is characterized in that a ten-point mean roughness Rzjis on the outermost surface on a side of the roughened nickel layer 50 is 1.0 μm or greater and smaller than 4.8 μm and a roughened surface area on the outermost surface on the side of the roughened nickel layer is 1.5 m2 / 1 m2 or greater. By specifying the surface shape of the roughened nickel layer 50 as described above, the nickel-plated metal material of the present embodiment can be provided as a nickel-plated metal material improved in liquid penetration resistance at an adhesion interface thereof with another member and having adhesion with another member.

[0069] It is to be noted that the term “resin” as used herein includes a thermoplastic resin, a thermosetting resin, a rubber, an elastomer, or the like. In the present disclosure, the resin also includes a material having fluidity when joined with the roughened nickel layer, such as one partly containing resin in a slurry material, such as a coating material or an active material.

[0070] Specifically, the ten-point mean roughness Rzjis is a value corresponding to the heights of protrusions on the roughened portion in the nickel-plated metal material of the present embodiment. In the present disclosure, the ten-point mean roughness Rzjis is specified in the above-described range as characteristics of the shape of the roughened portion which makes it possible to obtain preferred adhesion with another member while improving the liquid penetration resistance. By also specifying the roughened surface area to a prescribed value, preferred effects can be exhibited.

[0071] On the other hand, the roughened surface area is a surface area per unit area on the nickel-plated metal material on which the roughened nickel layer 50 is formed. Specifically, the nickel-plated metal material of the present disclosure has a surface aera increased relative to its horizontal projection area owing to the protrusions made from nickel granules formed in the roughened nickel-plating step. In other words, the roughened surface area is a value representing an area of contact between the resin and the roughened portion when another member is joined to the side of the roughened nickel layer 50 of the nickel-plated metal material 100 of the present disclosure, for example, when the resin that has been heated and melted or softened is allowed to flow. In the present disclosure, as characteristics of the shape of the roughened portion in which preferred adhesion is obtained between another member and the roughened portion while limiting the range of the above-described ten-point mean roughness Rzjis, preferred effects can be exhibited by specifying the roughened surface area to the above-described range.

[0072] Regarding reasons that the preferred effects are obtained by controlling the ten-point mean roughness Rzjis and the roughened surface area, the present inventors consider as follows. If the ten-point mean roughness Rzjis has a great value (for example, 4.8 μm or greater), the adhesion with the resin tends to be high. However, it was found that, as the height of the protrusions in the roughened portion was tall as mentioned above, the liquid penetration resistance tended to decrease when a long period of time elapsed under a high-temperature environment or a highly corrosive environment. No elucidation had been made regarding a cause for the tendency of a decrease of the liquid penetration resistance when the height of protrusions in the roughened portion was tall, the present inventors considered as follows.

[0073] When liquid penetration takes place between resin and a roughened nickel-plated material, the liquid progressively penetrates along the surfaces of protrusions in a roughened portion, so that the liquid more easily penetrates if there are groove portions and flat portions at roots in a conventional roughened nickel-plated material. It has however been considered that, if such grooves and flat portions are decreased by thickening the roots of roughening, a taller height of the roughened portion leads to longer penetration routes for the liquid and is thus advantageous.

[0074] Here, an electrical current generally tends to concentrate on protruding portions during electroplating, and this tendency is considered to be strong especially in granular nickel-forming plating for forming a roughened nickel layer because granular nickel-forming plating is plating that preferentially induces nuclei precipitation than grain growth compared with ordinary nickel plating. Accordingly, protrusions that are large in the distances from the surface of the base material to tip portions of the protrusions grow preferentially, still taller protrusions (hereinafter also referred to as “somewhat tall protrusions”) are formed, and such somewhat tall protrusions are reflected as the height of the roughened portion to the ten-point mean roughness Rzjis. It is hence considered that, in conventional roughened nickel plating, a roughened nickel-plated material of a great ten-point mean roughness Rzjis is prone to allow somewhat taller protrusions to grow more preferentially as described above, and therefore is difficult to form protrusions which are small in the distances from the surface of the base material to their tip portions (hereinafter also referred to as “somewhat short protrusions”) or is difficult to allow them to grow.

[0075] From the results of a long-term holding test under a severe environment, the present inventors scrutinized a penetration route of the liquid in the surface of the roughened portion, and appreciated that the liquid is considered to more easily penetrate along such routes that the liquid penetrates around protrusions at rather low positions thereof, in other words, in a vicinity of the surface of a base material than along routes passing through the tip portions of tall protrusions. The present inventors therefore assumed that a roughened nickel-plated material with a tall roughened portion as before was formed with many somewhat tall protrusions and included fewer somewhat short protrusions and therefore was decreased in liquid penetration resistance when a long period of time elapsed under such a severe environment as described above. It was however found that the adhesion with another member was insufficient if the height of the protrusions in the roughened portion was merely made short by simply decreasing the deposition amount for improvements in liquid penetration resistance. The present inventors then considered that, in order to maintain the adhesion with the resin despite the imposition of an upper limit on ten-point mean roughness Rzjis, there was a need to increase an area (roughened surface area) over which the roughened portion and the resin were in contact with each other. The present inventors repeated trials and errors with a view to determining a shape of a roughened portion, which made it possible to increase the roughened surface area while suppressing the height, and, as a result, have obtained a nickel-plated metal material, which assures both the adhesion with another member and improvements in liquid penetration resistance by controlling the ten-point mean roughness Rzjis and roughened surface area to the above-described ranges through control of the average current density, bath temperature, circulation of a plating solution of granular nickel-forming plating, and the circulation of the plating solution in nickel-growing plating.

[0076] Specifically, it is considered possible to form somewhat short protrusions and also microprotrusions around the roots of the microprotrusions and also to form a roughened portion having a sufficient surface area by controlling the protrusion height of the roughened portion somewhat low so as to control the ten-point mean roughness Rzjis to 4.8 μm or smaller and forming a roughened nickel layer such that its roughened surface area is 1.5 m2 / m2 or greater. It is considered that, as a result, the liquid penetration resistance can be improved by making longer the route lengths for liquid penetration significantly in the vicinity of the surface of the base material, where the liquid is easy to penetrate, and the adhesion with another member can be ensured by having a prescribed surface area or greater. It has also been found that a nickel-plated steel sheet with such somewhat short protrusions and microprotrusions formed thereon can be expected to be effective for suppressing intervals which may be formed around roots in a roughened portion depending on the temperature, rate, and the like at which the resin is allowed to flow into the roughened portion when joined with the resin.

[0077] When, in the course of the above-described trials and errors, the present inventors also compared specimens which were comparable in all of the height of a roughened portion (ten-point mean roughness Rzjis), the number of protrusions (Density Of Peaks Spd), and the surface area of the roughened portion from above by a laser microscope (Developed Interfacial Area Ratio Sdr), there were cases with different resin adhesions. The present inventors delved into those cases. As a result, a possibility was found that the roughened surface area might differ by the existence or shape of protrusions which are difficult to be reflected to the measurement by the laser microscope.

[0078] Specifically, it is possible to predict that, due to protrusions around the roots in the roughened portion and in the vicinity of the surface of the base material and differences in their shapes as illustrated in FIG. 6, there are cases of different surface areas even if the surface areas of the roughened portions from above by the laser microscope are equivalent to one another. Specifically, for example, FIG. 6(b) and FIG. 6(d) illustrate states in each of which relatively many microprotrusions are formed around the roots of the roughened portion, while FIG. 6(a) and FIG. 6(c) illustrate states in each of which relatively few microprotrusions are formed. Further, arrows in a vertical direction indicate laser applied to the surface of each specimen upon measurement of its surface texture by the laser microscope. If a laser microscope or a similar instrument, which measures the roughness of a surface by an action from a vertical direction, is used, the laser is blocked by surrounding tall protrusions and is therefore considered to be difficult to reach such microprotrusions as in FIG. 6(b). In such a case, the occurrence or non-occurrence of formation of microprotrusions or their shapes are substantially not reflected to the measurement results of the surface texture by the laser microscope, so that the height of the roughened portion (ten-point mean roughness Rzjis), the number of protrusions (Density Of Peaks Spd), and the surface area of the roughened portion from above by the laser microscope (Developed Interfacial Area Ratio Sdr) are comparable in FIG. 6(a) and FIG. 6(b).

[0079] Compared with FIGS. 6(a) and 6(c), on the other hand, FIGS. 6(b) and 6(d) indicate that the roughened portion is great in the total surface area of tall protrusions and short protrusions. It is hence understood that each roughened surface area in the present disclosure is not necessarily a parameter having a correlation with a surface texture parameter, such as the height (ten-point mean roughness Rzjis) of a roughened portion, measurable by the laser microscope. FIG. 6 depicts schematic diagrams for facilitating understanding of the roughened surface area, and the shapes of roughened portions in the present disclosure should not be limited to FIG. 6. It is to be noted that FIGS. 6(a) and 6(b) are schematic diagrams illustrating forms in which the roughened nickel layer 50 is formed on the outermost surface of the base material, and FIGS. 6(c) and 6(d) are schematic diagrams illustrating forms in which the coating layer 70 is formed on the roughened nickel layer 50.

[0080] By controlling the ten-point mean roughness Rzjis and the roughened surface area, the nickel-plated metal material of the present embodiment can be manufactured as a nickel-plated metal material having high liquid penetration resistance. The use of the nickel-plated metal material of the present embodiment can therefore reduce the risk of a liquid leakage of liquid contents even if a long period of time has elapsed with the contents sealed. In addition, the adhesion between the resin and the roughened portion can be expected to remain even after elapse of a longer period of time because the liquid penetration resistance at the adhesion interface with another member can be improved.

[0081] It is to be noted that, from the viewpoint of improving the liquid leakage resistance, the upper limit of the ten-point mean roughness Rzjis is characterized to be smaller than 4.8 μm, with 3.5 μm or smaller being preferred. On the other hand, the lower limit of the ten-point mean roughness Rzjis is 1.0 μm or greater, preferably 1.2 μm or greater, and more preferably 1.3 μm or greater from the viewpoint of increasing the adhesion with the resin.

[0082] It is to be noted that, by a known laser microscope or the like, the ten-point mean roughness Rzjis can be measured in accordance with JIS B0601:2013.

[0083] Further, no particular limitation is imposed on the upper limit of the roughened surface area, but, from the viewpoints of the resistance to breakage of protrusions formed of aggregates of granular nickel and the adhesion of the roughened portion with the base material, the upper limit of the roughened surface area is considered to be, for example, 100 m2 / 1 m2 or smaller, with 60 m2 / 1 m2 being more preferred. On the other hand, the lower limit of the roughened surface area is characterized to be 1.5 m2 / 1 m2 or greater from the viewpoint of the adhesion with the resin. From the viewpoint of increasing the adhesion with another member, the lower limit of the roughened surface area is more preferably 2.0 m2 / 1 m2 or greater, and still more preferably 5.0 m2 / 1 m2 or greater, with 5.3 m2 / 1 m2 or greater being even still more preferred.

[0084] A measuring method of the roughened surface area in the present embodiment is not a surface area measurement from above the roughened portion by a laser microscope, but is preferably a method that can measure a surface area also including the roots of the roughened portion. As the measuring method of the roughened surface area, the Brunauer-Emmett-Teller (BET) multipoint method disclosed in Japanese Patent Laid-open No. 2017-177654, etc. can be used. As the method for measuring the roughened surface area, a specific surface area can be obtained specifically, for example, by allowing a gas such as krypton to be adsorbed on the surface of the roughened portion, and determining its adsorption amount. A roughened surface area (unit: m2 / 1 m2) can then be calculated as a real surface area per unit area based on the specific surface area so obtained. It is to be noted that a detailed calculation method of the roughened surface area in the present disclosure will be mentioned subsequently herein.

[0085] It is particularly preferred for the nickel-plated metal material 100 of the present embodiment that, on the outermost surface on the side of the roughened nickel layer 50, the ten-point mean roughness Rzjis be 1.0 μm or greater and 3.5 μm or smaller and the roughened surface area is 5.3 m2 / 1 m2 or greater.

[0086] Furthermore, it is also preferred for the nickel-plated metal material of the present embodiment to specify a Mean Width Of The Profile Elements Rsm of elements in order to specify the shape of the surface formed by the protrusions formed of the granular nickel in the roughened plating layer. Specifically, the Mean Width Of The Profile Elements Rsm of elements is preferably 3.0 to 15 μm. By satisfying this, higher anchoring effect can be obtained, and a particularly high adhesion strength can be expected.

[0087] It is to be noted that, by a known laser microscope or the like, the Mean Width Of The Profile Elements Rsm of elements can be measured in accordance with JIS B0601:2013.

[0088] In the nickel-plated metal material 100 of the present embodiment, the deposition amount per side of nickel in the roughened nickel layer 50 is preferably 16 g / m2 or less, more preferably 15 g / m2 or less, and still more preferably 14 g / m2 or less from the viewpoints of productivity and manufacturing cost. From the viewpoints of corrosion resistance and obtaining the intended roughened shape, on the other hand, the deposition amount per side of nickel in the roughened nickel layer 50 is preferably 2 g / m2 or more, more preferably 3 g / m2 or more, and still more preferably 4 g / m2 or more. It is to be noted that the deposition amount of nickel in the roughened nickel layer 50 can be measured by X-ray fluorescence (XRF) analysis or the like.

[0089] As a measuring method of the nickel deposition amount in the present embodiment, the method described in PCT Patent Publication No. WO2020 / 017655 or PCT Patent Publication No. WO2021 / 020338, or the like can be appropriately adopted, for example. Specifically, the nickel deposition amount can be determined by measuring the total nickel amount with respect to the nickel-plated metal material 100 using X-ray fluorescence (XRF) analysis or the like.

[0090] A description will be made regarding the thickness of the whole nickel-plated metal material 100 in the present embodiment. Here, for the “thickness of the nickel-plated metal material 100” in the present embodiment, thickness measurement by cross-sectional observation under an SEM or thickness measurement by a micrometer can be also applied.

[0091] As the thickness of the whole nickel-plated metal material 100 in the present embodiment, a range of 0.005 to 5.01 mm is suited. If used as a current collector in a battery, for example, improvement in volumetric and gravimetric energy densities is required. Taking into consideration balancing of lightweighting and thinning with strength, the thickness of the whole nickel-plated metal material 100 is hence more preferably 0.005 to 0.51 mm, still more preferably 0.01 to 0.31 mm, and even still more preferably 0.035 to 0.11 mm. In applications as members or the like for electronic devices, electric appliances, automobiles, and constructions, for example, the thickness of the whole nickel-plated metal material 100 is preferably 0.035 to 5.01 mm, more preferably 0.11 to 4.01 mm, still more preferably 0.21 to 3.01 mm, and even still more preferably 0.51 to 1.01 mm from the viewpoints of rigidity, strength, and workability. For the thickness of the whole nickel-plated metal material 100, thickness measurement by a micrometer or cross-sectional observation under an optical microscope or a scanning electron microscope (SEM) is suitably used.

[0092] If the nickel-plated metal material 100 is used as a current collector in a battery, a case in which the thickness is greater than the upper limit of the above-described thickness range is not preferred from the viewpoints of the volumetric and gravimetric energy densities of the battery to be manufactured, especially if the aim is to thin the battery. With a thickness smaller than the lower limit of the above-described thickness range, on the other hand, it is not only difficult to have sufficient strength against effects associated with charging and discharging of the battery, but also highly possible to induce ripping, tearing, wrinkling, and / or the like during manufacture, handling, and the like of the battery. If used as members for electronic devices, electric appliances, automobiles, and constructions, a case in which the thickness is greater than the upper limit of the above-described thickness range is not preferred from the viewpoints of workability and lightweighting. On the other hand, a thickness smaller than the lower limit of the above-described thickness range is not preferred from the viewpoints of the rigidity and strength of the members so obtained.

[0093] According to the nickel-plated metal material 100 in the present embodiment, the liquid penetration resistance at the adhesion interface with another member can be improved as described above. Specifically, the ten-point mean roughness Rzjis on the outermost surface on the side of the roughened nickel layer has been specified to the prescribed value to improve the liquid penetration resistance. In addition, the nickel-plated metal material 100 in the present embodiment has the prescribed value as the roughened surface area of the roughened nickel layer, and therefore has adhesion with another member.<<Modification of First Embodiment>>

[0094] Using FIG. 2, a description will next be made regarding a nickel-plated metal material 200 as a modification of the above-mentioned first embodiment. The nickel-plated metal material 200 in the present modification is different from the above-mentioned first embodiment in that the metal layer 40 is included between the roughened nickel layer 50 and the base material 20. Accordingly, this different point will be primarily described, the other points will be identified by the same reference signs, and their description is omitted. It is to be noted that, in the present modification, the ten-point mean roughness Rzjis and roughened surface area on the outermost surface on the side of the roughened nickel layer are also 1.0 μm or greater and smaller than 4.8 μm and 1.5 m2 / 1 m2 or greater, respectively.<Metal Layer 40>

[0095] The metal layer 40 is disposed between the base material 20 and the roughened nickel layer 50 as mentioned above. As a metallic material that forms the metal layer 40, nickel or a nickel alloy is mentioned, for example. It is to be noted that the metal layer 40 is presented as a single layer in FIG. 2, but, without being limited to this configuration, may be formed of a plurality of layers.

[0096] As an example of the metal layer 40, an iron-nickel alloy layer, a nickel-phosphorus alloy layer, or a nickel layer can be exemplified. If the metal layer 40 is an iron-nickel alloy layer, the alloy phase formed of iron and nickel may be any one of a solid solution, an eutectoid / eutectic, or a compound (intermetallic compound), or two or more of these phases may coexist. Further, the metal layer 40 may contain one or more metal elements other than iron and nickel, and inevitable impurities, and may also contain metal elements such as cobalt (Co) and molybdenum (Mo) and an additive element such as boron (B).

[0097] In the nickel-plated metal material 200, the preferred range of the nickel deposition amount per side in the roughened nickel layer 50 is the same as that in the nickel-plated metal material 100.

[0098] The total nickel deposition amount per side in the metal layer 40 and the roughened nickel layer 50 in the nickel-plated metal material 200 is, as an upper limit, preferably 40 g / m2 or less, more preferably 35 g / m2 or less, and still more preferably 32 g / m2 or less from the viewpoints of productivity and manufacturing cost. In view of unavailability of corrosion resistance and the intended roughened shape, on the other hand, the lower limit is preferably 4 g / m2 or more, more preferably 5 g / m2 or more, and still more preferably 6 g / m2.

[0099] As a measuring method of the nickel deposition amount in the nickel-plated metal material 200, the method described in PCT Patent Publication No. WO2020 / 017655 or PCT Patent Publication No. WO2021 / 020338, or the like can be appropriately adopted, for example. Specifically, the total nickel deposition amount per side in the metal layer 40 and the roughened nickel layer 50 can be measured by using X-ray fluorescence (XRF) analysis or the like with respect to the nickel-plated metal material 200. As an alternative, the respective nickel amounts in the metal layer 40 and the roughened nickel layer 50 can be determined by ascertaining a boundary between the metal layer 40 and the roughened nickel layer 50 on a cross-sectional image or the like. It is to be noted that, if the base material 20 is a nickel-plated steel sheet or a surface diffusion-treated steel sheet and the metal layer 40 is nickel or a nickel alloy layer, there is a case where ascertainment of the clear boundary between the base material 20 and the metal layer 40 is difficult, and if this is the case, the total nickel deposition amount per side in the base material 20, the metal layer 40, and the roughened nickel layer50 may be controlled to the above-described range.

[0100] As an effect of the formation of the metal layer 40 on the base material 20 in the nickel-plated metal material 200, the following points can be mentioned. Specifically, the formation of the metal layer 40 allows to ensure the adhesion of the roughened nickel layer 50 with the base material 20 and to move forward with improvements in the corrosion resistance of the whole nickel-plated metal material 200.

[0101] As the thickness of the whole nickel-plated metal material 200, a range of 0.005 to 5.01 mm is suited. If used as a current collector in a battery, for example, improvements in volumetric and gravimetric energy densities are required. Taking into consideration balancing of lightweighting and thinning with strength, the thickness of the whole nickel-plated metal material 200 is hence more preferably 0.005 to 0.51 mm, still more preferably 0.01 to 0.31 mm, and even still more preferably 0.035 to 0.11 mm. In applications as members or the like for electronic devices, electric appliances, automobiles, and constructions, for example, the thickness of the whole nickel-plated metal material 200 is preferably 0.035 to 5.01 mm, more preferably 0.11 to 4.01 mm, still more preferably 0.21 to 3.01 mm, and even still more preferably 0.51 to 1.01 mm from the viewpoints of rigidity, strength, and workability. For the thickness of the whole nickel-plated metal material 200, thickness measurement by a micrometer or a cross-sectional observation under an optical microscope or scanning electron microscope (SEM) is suitably used.Second Embodiment

[0102] On the basis of FIG. 3, a nickel-plated metal material 300 in a second embodiment will next be described. The nickel-plated metal material 300 in the second embodiment is different from the above-mentioned first embodiment in that a coating layer 70 is included on the roughened nickel layer 50. Accordingly, this different point will be primarily described, the other points will be identified by the same reference signs, and their description is omitted. It is to be noted that, in the nickel-plated metal material 300, the roughened nickel layer 50 and the coating layer 70 will be collectively called a “composite roughened plating layer 60.” In the nickel-plated metal material 300, the ten-point mean roughness Rzjis and roughened surface area on the outermost surface on the side of the composite roughened plating layer 60 are 1.0 μm or greater and smaller than 4.8 μm and 1.5 m2 / 1 mm2 or greater, respectively.<Coating Layer 70>

[0103] As mentioned above, the coating layer 70 is disposed on the roughened nickel layer 50. An example of a metal material forming the coating layer 70 includes nickel alloys such as iron-nickel alloy, zinc (Zn) and zinc alloys, tin (Sn) and tin alloys, and chromium (Cr) and chromium alloys. In the present embodiment, 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 therefore included on the outermost surface on the side of the roughened nickel layer 50.

[0104] The coating layer 70 contributes to improvements in the adhesion between the roughened nickel layer 50 and the base material 20. Further, if the coating layer 70 contains zinc, this is advantageous in that a sacrificial corrosion protection property is imparted to the whole nickel-plated metal material 300. Furthermore, if the coating layer 70 contains tin, this is advantageous because if the nickel-plated metal material 300 is used, for example, as a current collector in a battery, the hydrogen overpotential can be set high, leading to suppression of hydrogen generation. In addition, if the coating layer 70 contains chromium, the corrosion resistance of the whole nickel-plated metal material 300 can be further improved, and the adhesion between the resin and the roughened portion can be improved. It is to be noted that, if the metal material, which makes up the coating layer 70, is chromium or an alloy thereof in the present disclosure, a chromate film should be included. Further, if the coating layer 70 is made of an iron-nickel alloy, the abrasion resistance of the outermost surface can be improved.

[0105] A preferred metal deposition amount in the coating layer 70 is as follows. If the coating layer 70 is zinc, the zinc deposition amount is, as an upper limit, preferably 22.0 g / m2 or less, more preferably 17.0 g / m2 or less, and still more preferably 15.0 g / m2 or less from the viewpoints of productivity and manufacturing cost and obtaining the intended roughened shape. The lower limit of the zinc deposition amount is preferably 0.5 g / m2 or more, more preferably 3.5 g / m2 or more, and still more preferably 5.0 g / m2 or more, from the viewpoints of corrosion resistance and increasing the adhesion between the base material and the roughened nickel-plating layer. If the coating layer 70 is tin, the tin deposition amount is, as an upper limit, preferably 22.0 g / m2 or less, more preferably 17.0 g / m2 or less, and still more preferably 15.0 g / m2 or less from the viewpoints of productivity and manufacturing cost and obtaining the intended roughened shape. The lower limit of the tin deposition amount is preferably 0.5 g / m2 or more, more preferably 1.5 g / m2 or more, and still more preferably 3.5 g / m2 or more, from the viewpoints of corrosion resistance and increasing the adhesion between the base material and the roughened nickel-plating layer. If the coating layer 70 is chromium, the chromium deposition amount is, as an upper limit, preferably 22.0 g / m2 or less, more preferably 17.0 g / m2 or less, and still more preferably 15.0 g / m2 or less from the viewpoints of productivity and manufacturing cost and obtaining the intended roughened shape. The lower limit of the chromium deposition amount is preferably 0.1 g / m2 or more, more preferably 0.3 g / m2 or more, still more preferably 0.5 g / m2 or more, and even still more preferably 0.8 g / m2 or more, from the viewpoints of corrosion resistance and increasing the adhesion between the base material and the roughened nickel-plating layer. The measurement of a preferred deposition amount in the coating layer 70 can be conducted by using a known method such as X-ray fluorescence (XRF) analysis or inductively coupled plasma (ICP) emission spectroscopy.

[0106] The coating layer 70 in tis embodiment can be formed on the roughened nickel layer 50 by electroplating, sputtering, vapor deposition, chemical vapor deposition, or the like of the corresponding metal. Electroplating is particularly preferred from the viewpoints of manufacturing cost and capability of uniform coating to the roughened portion.<Modification of Second Embodiment>

[0107] In FIG. 4, a nickel-plated metal material 400 is illustrated as a modification of the above-mentioned second embodiment. The nickel-plated metal material 400 in the present modification is different from the above-mentioned second embodiment in that a metal layer 40 is included between the composite roughened plating layer 60 and the base material 20. As the metal layer 40, the metal layer 40 described in the above-mentioned modification of the first embodiment can be applied. Accordingly, the metal layer in the present modification is identified by the same reference sign, and its description is omitted. It is to be noted that, in the present modification, the ten-point mean roughness Rzjis and roughened surface area on the outermost surface on the side of the roughened nickel layer are also 1.0 μm or greater and smaller than 4.8 μm and 1.5 m2 / 1 m2 or greater, respectively.<<Manufacturing Process of Nickel-Plated Metal Material>>

[0108] A description will hereinafter be made regarding a manufacturing process of a nickel-plated metal material. The manufacturing process of the present embodiment for the nickel-plated metal material is characterized by including, in a roughened nickel plating step of forming the roughened nickel layer 50, a granular nickel-forming plating step of applying roughened nickel plating using a circulating bath at an average current density of 20.0 A / dm2 or higher, a bath temperature of 50° C. or higher, and a rate that the solution circulation rate by a pump for a plating solution of, for example, 2 L volume exceeds a flow rate of 1 L / min.

[0109] As a plating bath in the granular nickel-forming plating step, the chloride ion concentration is preferably 3 to 90 g / L, more preferably 3 to 75 g / L, and still more preferably 3 to 50 g / L, the ratio of nickel ions to ammonium ions is preferably 0.05 to 0.75, more preferably 0.05 to 0.60, still more preferably 0.05 to 0.50, and even still more preferably 0.05 to 0.30 in terms of the weight ratio of “nickel ions / ammonium ions,” and the bath electrical conductivity at 50° C. is preferably 5.00 to 30.00 S / m, more preferably 5.00 to 20.00 S / m, and still more preferably 7.00 to 20.00 S / m. It is to be noted that, if the chloride ion concentration is 10 g / L or higher, a good roughened plating state is easily obtained even if the deposition amount in the roughened nickel-plating is somewhat small. Examples of a method that adjusts the chloride ion concentration, the ratio of nickel ions to ammonium ions, and the bath electrical conductivity in the plating bath to the above-described ranges include, but are not particularly limited to, a method that uses, as the plating bath, one containing nickel sulfate hexahydrate, nickel chloride hexahydrate, and ammonium sulfate, and appropriately adjusts their blending amounts.

[0110] Examples of plating conditions are as follows.[Granular Nickel-Forming Plating Conditions]Bath composition

[0112] Nickel sulfate hexahydrate: 10 to 100 g / L, nickel chloride hexahydrate: 1 to 90 g / L, ammonium sulfate: 10 to 130 g / L

[0113] pH: 4.0 to 8.0

[0114] Bath temperature: 50° C. or higher and 80° C. or lower

[0115] Average current density: 20 A / dm2 or higher and 60 A / dm2 or lower

[0116] Plating time: 5 to 150 seconds

[0117] Electricity quantity: 100 to 1500 C / dm2

[0118] Agitated / not agitated, etc.: circulating bath (a rate that the solution circulation rate by a pump for the plating solution of, for example, 2 L volume exceeds a flow rate of 1 L / min)

[0119] Under the above-described conditions, plating treatment can be conducted once or a plurality of times in the circulating bath such that the total electricity quantity is controlled as described above.

[0120] It is to be noted that the addition of ammonia to the plating bath in the granular nickel-forming plating step may be conducted by using ammonia solution, ammonium chloride, or the like in place of ammonium sulfate. The ammonium ion concentration in the plating bath is preferably 6 to 35 g / L, more preferably 10 to 35 g / L, still more preferably 16 to 35 g / L, and even still more preferably 20 to 35 g / L. Further, hydrochloric acid, sodium chloride, potassium chloride, or the like may be used to control the chloride ion concentration.

[0121] As agitation conditions for the plating bath in the granular nickel-forming plating step, a circulating bath system that circulates the plating solution by a pump is desired. Specifically, it is preferred to continuously circulate, through the plating solution of 2 L volume, the plating solution at a rate higher than 1 L / min. A higher circulation rate of the plating solution is preferred if the bath temperature is high, a higher circulation rate of the plating solution is preferred if the average current density is high, and a higher circulation rate of the plating solution is preferred if the nickel ion concentration is low. Although no particular limitation is imposed on the upper limit of the circulation rate of the plating solution, 20 L / min or lower is preferred. To control the roughened portion to an intended shape, however, there is a need to conduct plating by controlling the bath temperature, the average current density, and the circulation rate of the plating solution under adequate conditions.

[0122] Further, by increasing the average current density and bath temperature to 20 A / dm2 or higher and 50° C. or higher in the above-described plating solution, formation of more plating nuclei can be promoted. As a result, the number of protrusions in the roughened portion can be increased, thereby making it easy to control the roughened surface area to 1.5 m2 / 1 m2 or greater even if the height of the roughened portion is controlled to smaller than 4.8 μm. Furthermore, by conducting the formation of more plating nuclei in the granular nickel-forming plating step, the plating nuclei can be used as plating nuclei when roughening is effected to the roots of the protrusions in the nickel-growing plating step to be mentioned below. The upper limit of the average current density is preferably 50 A / dm2 or lower from the viewpoint of increasing the adhesion between the base material and the roughened nickel-plating layer. Moreover, the continuous circulation of the plating solution at a rate higher than 1 L / min through the plating solution of, for example, 2 L volume can promote the formation of a sufficient number of short protrusions by suppressing preferential growth of some of the protrusions and decreasing differences in growth among the individual protrusions when allowing the formed plating nuclei to grow and also allowing new plating nuclei to precipitate over the plating nuclei so formed and to grow as protrusions. As a result, it is made possible to easily control the roughened surface area to 1.5 mm2 / 1 m2 or greater while controlling the ten-point mean roughness Rzjis to smaller than 4.8 μm. Still moreover, it is also made possible to easily control the Mean Width Of The Profile Elements Rsm of elements to 3.0 to 15 μm. Even moreover, it is also considered possible to promote the formation of plating nuclei as nuclei for microprotrusions around the roots of somewhat short protrusions by conducting the circulation of the plating solution in the above-described ranges of the average current density and bath temperature. A roughened portion of an intended shape can be formed by conducting plating while controlling the bath temperature, average current density, and circulation rate under adequate conditions as described above.

[0123] The upper limit of the nickel deposition amount in the granular nickel-forming plating step is preferably 16 g / m2 or less, more preferably 15 g / m2 or less, and still more preferably 14 g / m2 or less from the viewpoints of improvements in liquid penetration resistance. On the other hand, the lower limit is preferably 1.8 g / m2 or more, more preferably 2.8 g / m2 or more, and still more preferably 3.8 g / m2 or more from the viewpoint of the adhesion with another member. The height of the roughened portion can be controlled by controlling the average current density, the bath temperature, and the circulation of the plating solution, and further controlling the nickel deposition amount to 1.8 to 16 g / m2, as described above in the granular nickel-forming plating. As a result, Rzjis can be controlled to 1.0 μm or greater and smaller than 4.8 μm in the nickel-plated metal sheet after going through the below-mentioned nickel-growing plating step or coating plating step.[Nickel-Growing Plating Conditions]Bath composition:

[0125] Nickel sulfate hexahydrate 200 to 350 g / L, nickel chloride hexahydrate 20 to 60 g / L, boric acid 10 to 50 g / L

[0126] pH: 3.0 to 5.0

[0127] Bath temperature: 40° C. to 70° C.

[0128] Current density: 5 to 30 A / dm2

[0129] Agitated / not agitated, etc.: circulating bath (a rate that the solution circulation rate by a pump for the plating solution of, for example, 2 L volume exceeds a flow rate of 1 L / min)

[0130] The agitation conditions of the plating bath in the nickel-growing plating step can control the roughened surface area of the nickel-plated metal material so obtained to a preferred value by using the plating solution as the circulating bath that the plating solution is circulated by the pump.

[0131] The nickel-growing plating is a step, a primary objective of which is to ensure the adhesion between the roughened nickel layer and the base material by allowing individual nickel granules to grow further in the protrusions formed of aggregates of nickel granules which have been formed in the above-described granular nickel-forming plating step. In the present disclosure, it is considered possible, in addition to the primary objective, to promote the formation of the microprotrusions by conducting the agitation at a prescribed liquid circulation or higher in this nickel-growing plating step. By continuously conducting the circulation of the plating solution at a rate higher than 1 L / min through the plating solution of, for example, 2 L volume, the plating nuclei as the nuclei for the microprotrusions formed by the above-describe granular nickel-forming plating are allowed to grow and to form microprotrusions by this growing plating, and, as a result, the surface area can be increased.

[0132] The upper limit of the nickel deposition amount in the nickel-growing plating step is preferably 7.0 g / m2 or less, more preferably 6.0 g / m2 or less, and still more preferably 5.0 g / m2 or less from the viewpoints of the adhesion to another member, productivity, and manufacturing cost. On the other hand, the lower limit is preferably 0.2 g / m2 or more, more preferably 0.4 g / m2 or more, from the viewpoint of the adhesion of the plating layer with the base material. It is to be noted that the above-described nickel-growing plating step is not an essential step.

[0133] It is preferred that, by going through the above-described steps, the ten-point mean roughness Rzjis fall to 1.0 μm or greater and smaller than 4.8 μm on the outermost surface on the side of the roughened nickel layer of the nickel-plated metal material so obtained and the roughened surface area on the outermost surface on the side of the above-described roughened nickel layer fall to 1.5 m2 / 1 m2 or greater.

[0134] It is also preferred that, on the outermost surface on the side of the roughened nickel layer of the nickel-plated metal material so obtained, the Mean Width Of The Profile Elements Rsm of elements be 3.0 to 15 μm.

[0135] The manufacturing process of the nickel-plated metal material depicted in FIG. 3 or 4 may further include a step of forming the coating layer 70 (coating-layer forming step). Specifically, the coating-layer forming step is conducted at least after the above-mentioned granular nickel-forming plating step. As an alternative, the coating-layer forming step may also be conducted by following the granular nickel-forming plating step and the nickel-growing plating step.

[0136] If the coating-layer forming step is conducted by zinc plating, examples of bath composition and plating conditions for the zinc plating are as follows.

[0137] Zinc sulfate heptahydrate: 100 to 400 g / L

[0138] Ammonium sulfate: 10 to 100 g / L

[0139] Bath temperature: 30° C. to 70° C.

[0140] pH: 1.0 to 5.0

[0141] Agitated / not agitated, etc.: circulating bath (a rate that the solution circulation rate by a pump for the plating solution of, for example, 2 L volume exceeds a flow rate of 1 L / min)

[0142] Current density: 2.5 to 60 A / dm2

[0143] As described above, it is possible to use, as a plating bath for use in zinc plating, a bath that uses a sulfate salt as a supply source for zinc ions and is appropriately added with a conductive adjuvant salt such as ammonium sulfate or sulfuric acid to increase the electrical conductivity of the plating solution. In addition, an additive such as a known gloss agent may be added to the plating bath to form gloss zinc plating or semi-gloss zinc plating.

[0144] If the coating-layer forming step is conducted by zinc plating, the zinc deposition amount to be formed by the zinc plating is preferably 0.5 to 22.0 g / m2. The measurement of the zinc deposition amount can be conducted by using a known method such as X-ray fluorescence (XRF) analysis or ICP emission spectroscopy.

[0145] If the coating-layer forming step is conducted by tin plating, examples of bath composition and plating conditions for the tin plating are as follows.

[0146] Stannous sulfate: 30 to 80 g / L

[0147] Phenolsulfonic acid: 30 to 60 g / L

[0148] Ethoxylated a-naphthol: 2 to 6 g / L

[0149] Ethoxylated a-naphtholsulfonic acid: 4 to 12 g / L

[0150] pH: 0.1 to 2.0

[0151] Bath temperature: 20° C. to 55° C.

[0152] Agitated / not agitated, etc.: circulating bath (a rate that the solution circulation rate by a pump for the plating solution of, for example, 2 L volume exceeds a flow rate of 1 L / min)

[0153] Current density: 2.5 to 10 A / dm2

[0154] If the coating-layer forming step is conducted by tin plating, the tin deposition amount to be formed by the tin plating is preferably 0.5 to 22.0 g / m2. The measurement of the tin deposition amount can be conducted by using a known method such as X-ray fluorescence (XRF) analysis or ICP emission spectroscopy.

[0155] If the coating-layer forming step is conducted by chromium plating, examples of bath composition and plating conditions for the chromium plating are as follows.

[0156] Chromium(VI) oxide: 30 to 200 g / L

[0157] Sodium fluoride: 1 to 10 g / L

[0158] pH: 1.0 or lower

[0159] Bath temperature: 35° C. to 65° C.

[0160] Agitated / not agitated, etc.: circulating bath (a rate that the solution circulation rate by a pump for the plating solution of, for example, 2 L volume exceeds a flow rate of 1 L / min)

[0161] Current density: 5 to 50 A / dm2

[0162] If the coating-layer forming step is conducted by chromium plating, the chromium deposition amount to be formed by the chromium plating is preferably 0.1 to 22.0 g / m2. The measurement of the chromium deposition amount can be conducted by using a known method such as X-ray fluorescence (XRF) analysis or ICP emission spectroscopy.

[0163] If the coating-layer forming step is conducted by iron-nickel alloy plating, examples of a bath composition and plating conditions for the iron-nickel alloy plating are as follows.[Examples of Iron-Nickel Alloy Plating Bath and Plating Conditions]Bath composition:

[0165] Nickel sulfate hexahydrate: 150 to 250 g / L

[0166] Iron sulfate heptahydrate: 5 to 100 g / L

[0167] Nickel chloride hexahydrate: 20 to 50 g / L

[0168] Boric acid: 20 to 50 g / L

[0169] Sodium citrate (or trisodium citrate): 1 to 15 g / L Saccharin sodium: 1 to 10 g / L

[0170] Temperature: 25° C. to 70° C.

[0171] pH: 2 to 4

[0172] Agitated / not agitated, etc.: circulating bath (a rate that the solution circulation rate by a pump for the plating solution of, for example, 2 L volume exceeds a flow rate of 1 L / min)

[0173] Current density: 5 to 40 A / dm2

[0174] If the coating-layer forming step is conducted by iron-nickel alloy plating, the total deposition amount of iron and nickel contained in the iron-nickel alloy layer is preferably 0.2 to 7.0 g / m2. The total deposition amount of iron and nickel can be calculated by determining a weight difference before and after the iron-nickel alloy plating. Further, if the coating layer is the iron-nickel alloy layer, the total nickel deposition amount contained per side in the base material and composite roughened layer in the nickel-plated metal material is preferably 5 to 40 g / m2. Furthermore, if the metal layer 40 is included and nickel is contained in the metal layer 40, the total nickel deposition amount contained per side in the base material, the metal layer 40, and the composite roughened layer may also be controlled to the above-described range.

[0175] The above-described formation of the coating layer 70 is a step, a primary objective of which is to ensure the adhesion between the roughened nickel layer and the base material and to impart additional effects by the pieces of metal forming the coating layer. In the present disclosure, it is possible, in addition to the primary objective, to also cover the nuclei of the microprotrusions, which have been formed by the above-described granular nickel-forming plating, with the coating metal layer and to increase the surface area by conducting the agitation at a prescribed liquid circulation or higher in this coating plating step.

[0176] The manufacturing process of the nickel-plated metal material depicted in FIG. 2 or FIG. 4 may further include a step of forming the metal layer 40 (metal-layer forming step). Specifically, the metal-layer forming step is conducted on the base material 20 before the above-described 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, or a nickel layer is mentioned.

[0177] If the iron-nickel alloy layer is formed by the metal-layer forming step, it may be formed by applying alloy electrolytic plating to at least one side of the base material 20 using an alloy plating bath containing iron ions and nickel ions. In this case too, known alloy plating conditions can be appropriately applied.

[0178] If the nickel-phosphorus alloy layer is formed by the metal-layer forming step, a nickel-phosphorus alloy layer may be formed by applying alloy electrolytic plating to at least one side of the base material 20 using an alloy plating bath containing nickel ions and phosphorus ions.

[0179] If the nickel layer is formed by the metal-layer forming step, the nickel layer can be formed on at least one side of the base material 20, for example, in a known Watts bath or the like.

[0180] The metal-layer forming step is not needed to be a single step, and may be conducted by appropriately combining a plurality of steps. For example, the nickel-phosphorus alloy layer and the nickel layer may be both formed by the metal-layer forming step.

[0181] If a surface diffusion-treated steel sheet is used as the base material 20, an iron-nickel alloy layer can be formed through thermal diffusion by applying heat treatment after forming a nickel-plating layer by electroplating.

[0182] Specifically, continuous annealing or batch annealing (box annealing) can be conducted. As examples of a temperature and time in a case of continuous annealing treatment, the continuous annealing treatment can be conducted at 650° C. to 950° C. for a soaking time in a range of 15 to 150 seconds. As examples of a temperature and time in a case of batch annealing (box annealing) treatment, the batch annealing (box annealing) treatment can be conducted at 450° C. to 690° C., for a soaking time in a range of 1.5 to 20 hours, and for a total time of heatup, soaking, and cooling time in a range of 4 to 80 hours. Rolling may be applied after the above-described heat treatment. Further, heat treatment may be conducted again after the rolling.EXAMPLES

[0183] The present invention will hereinafter be described more specifically by giving examples. A description will first be made regarding measuring methods in the examples.[Measuring Methods of Surface Texture Parameters]

[0184] Surface texture parameters on the surface of the roughened nickel layer 50, such as the ten-point mean roughness Rzjis and the Mean Width Of The Profile Elements Rsm of elements were measured by using a laser microscope (manufactured by Olympus Corporation, 3D measuring laser microscope “LEXT OLS5000”). In the measurements of the ten-point mean roughness Rzjis and the Mean Width Of The Profile Elements Rsm of elements, the surface of the roughened nickel layer 50 was measured with a 50× objective lens (lens name: “MPLAPON50XLEXT”) following JIS B0601:2013, whereby an analysis image of 257 μm×257 μm visual field was acquired. Using an analysis application, denoising and an inclination correction as automated correction processing were then conducted on the analysis image so acquired. Subsequently, the ten-point mean roughness Rzjis and the Mean Width Of The Profile Elements Rsm of elements were calculated by line roughness measurement. It is to be noted that the analysis was conducted under no conditions without setting filter criteria (tilt correction λf, low-pass filter λs, high-pass filter λc) at the time of the analysis. Mean values upon 15 measurements under the above-described conditions were calculated.[Measuring Method of Roughened Surface Area]

[0185] The roughened surface area at the surface of the roughened nickel layer 50 was measured by a constant volume method that used a fully automatic gas adsorption amount measuring instrument. As the fully automatic gas adsorption amount measuring instrument, a model “AS1-MP” manufactured by Quantachrome Instruments, Inc. was used. Further, as an adsorbate gas, krypton gas was used. A desired number of measurement specimens were cut in a size of 5 mm×50 mm, and the overall specimen mass was measured. The measurement specimens were placed in a measurement cell, and were vacuum-deaerated at room temperature for 2 hours or longer. The specific surface area was measured by the BET multipoint method under liquid nitrogen of −195.8° C., and on the basis of the specific surface area so obtained, the roughened surface area was calculated.

[0186] Specifically, if measurement specimens included a roughened nickel layer on both sides thereof, the value of the specific surface area was multiplied with the specimen mass, followed by a division with the number of the measured specimens. The resulting value was then halved, followed by a division with a horizontal projection area (5 mm×50 mm) per specimen to determine the roughened surface area.

[0187] If measurement specimens included a roughened nickel layer on one side thereof, the value of the specific surface area was first multiplied with the specimen mass, followed by a division with the number of the measured specimens to determine the overall surface area per specimen. Here, because of a need to subtract the surface area of untreated surfaces, a reference base material was provided. After its specific surface area was calculated in a similar manner, the specific surface area was multiplied with the specimen mass, followed by a division with the number of the measured specimens. The value of ½ of the quotient was then calculated to determine the surface area per side of the reference base material. From the overall surface area per specimen, the surface area per side of the reference base material was then subtracted, followed by a division with the horizontal projection area (5 mm×50 mm) per specimen to determine the roughened surface area. It is to be noted that, as the reference base material, one prepared by applying undercoat nickel plating to the base material in Example 1 to be mentioned later was used.

[0188] It is to be noted that, in the measurement of individual specimens, the measurement was made using 20 to 60 specimens to improve the accuracy of the test, and, especially with reference specimens of a small surface area, 60 of them were measured. In addition, the measurement specimens in the following examples and comparative examples were sufficiently small in thickness, so that effects of their end surfaces should be negligible.[Resin Adhesion Test (Peel Test) and Evaluation]

[0189] As an evaluation of the adhesion with another member, the adhesion with resin was evaluated. Specifically, for the evaluation of the resin adhesion, a peel test was conducted to obtain a peel strength. A description will hereinafter be made regarding its measuring method.

[0190] A nickel-plated metal material (30 mm×100 mm), which was obtained in each example or comparative example and had a roughened nickel layer formed on at least one side thereof, was provided. A polypropylene film of 140 μm thickness (25 mm×100 mm) was overlaid on the side of a surface to be evaluated (the side of the roughened nickel layer) with their one end portions trued up, and was heat-sealed in a range of 25 mm×25 mm at an overlayed portion thereof by a heat sealer (manufactured by TESTER SANGYO CO., LTD., “TP-701-B”), whereby a specimen was obtained. The heat-sealing temperature, in other words, the setting temperature of the heat sealer was set to 156° C., and the pressure at the time of the heat sealing was set to 0.1 MPa. Under a condition that the time (hereinafter also referred to as “press time”), for which pressing was conducted at the above-described setting temperature under the above-described pressure, was 5 seconds, a specimen was prepared by the heat sealer. By a tensile testing machine (manufactured by Orientec Co., Ltd., “RTC-121OA”), each specimen so prepared was fixed on a jig with the resin film folded back at the heat-sealed end as a starting point in 180° direction relative to the nickel-plated metal material, and was pulled at a rate of 50 mm / min, whereby its 180° peel strength was obtained.

[0191] EXCELLENT: the value of 180° peel strength was 13N / 25 mm or higher

[0192] GOOD: the value of 180° peel strength was 5N / 25 mm or higher and lower than 13N / 25 mm

[0193] POOR: the value of 180° peel strength was lower than 5N / 25 mm[Liquid Penetrability Evaluation when Joined with Polypropylene (PP) Resin]

[0194] The nickel-plated metal materials obtained in the examples and comparative examples were cut to prepare specimens for the liquid penetrability evaluation, which had dimensions of 90 mm wide and 140 mm long. On each specimen for liquid penetrability evaluation so obtained, a marker sheet for an aqueous alkali solution (manufactured by Macherey-nagel GmbH & Co., KG, “pH TEST PAPER”), which had dimensions of 7 mm wide and 7 mm long, was then placed, and a polypropylene resin film (manufactured by Mitsubishi Chemical Corporation, “MODIC” (trade name) / polypropylene resin two-layer film (a side of “MODIC” (trade name) was used as an adhesive layer, that is, as a joining surface) of 110 mm wide, 160 mm long, and 60 μm thick was placed over the marker sheet. With the marker sheet for the aqueous alkali solution sandwiched, heat sealing was conducted over the entire width and length using laminating rolls under conditions of a temperature: 150° C., a pressure: 0.6 MPa (checked with a pressure-sensitive paper), and a roll passing rate: 70 mm / second. Thereafter, the resulting laminate was cut into a circle centering around the marker and having a diameter of 30 mm, whereby a measurement specimen with the marker sheet for the aqueous alkali solution sealed therein was obtained. The measurement specimen so obtained was dipped in a 30 g / L aqueous solution of “Formula 618-TK-2” (manufactured by Nippon Quaker Chemical Ltd.) as an aqueous alkali solution with the solution temperature maintained at 80° C., and observation was made for the extent of any discoloration of the marker sheet for the aqueous alkali solution in the measurement specimen over the time elapsed after the dipping (discoloration by penetration of the aqueous alkali solution into the measurement specimen), and the extent of discoloration was evaluated on the following criteria.

[0195] EXCELLENT: discoloration was not observed on the marker sheet for the aqueous alkali solution even after 240 hours.

[0196] GOOD: discoloration was not observed on the marker sheet for the aqueous alkali solution 48 hours later, but was observed 240 hours later.

[0197] MODERATE: discoloration was not observed on the marker sheet for the aqueous alkali solution 36 hours later, but was observed 48 hours later.

[0198] POOR: discoloration was observed on the marker sheet for the aqueous alkali solution 30 hours later.

[0199] It is to be noted that the liquid penetrability evaluation in the present disclosure is what is called an accelerated test using conditions with stronger effects on an interface. Therefore, it is a test to dip each specimen in the strongly corrosive aqueous alkali solution at a high temperature for a long time, and is not one directly reflecting conditions when applied to real products.Example 1

[0200] A cold-rolled steel sheet (60 μm thickness) of low-carbon aluminum-killed steel having a chemical composition presented below was first provided.

[0201] 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

[0202] After electrolytic degreasing and pickling by dipping in sulfuric acid were next carried out on the above-described cold-rolled steel sheet, a nickel layer was formed to a deposition amount of 8.9 g / m2 by known nickel plating. Subsequently, thermal diffusion treatment was conducted by a continuous annealing step, and quality control rolling was applied, whereby an iron-nickel alloy layer of 2.2 μm thickness was formed on both sides. The resulting surface diffusion-treated steel sheet was provided as a base material 20.

[0203] On the surface diffusion-treated steel sheet as the base material 20, strike nickel-plating treatment was conducted under the strike nickel-plating conditions presented below, followed by formation of an undercoat nickel layer under undercoat nickel-plating conditions.<Strike Nickel-Plating Conditions>Bath composition:

[0205] Nickel sulfate hexahydrate 250 g / L, sulfuric acid 50 g / L

[0206] pH: lower than 1.0

[0207] Bath temperature: 60° C.

[0208] Current density: 30 A / dm2

[0209] Electrolysis time: 5 seconds<Undercoat Nickel-Plating Conditions>Bath composition:

[0211] Nickel sulfate hexahydrate 250 g / L, nickel chloride hexahydrate 45 g / L, boric acid: 30 g / L

[0212] pH: 4.0 to 5.0

[0213] Bath temperature: 60° C.

[0214] Current density: 10 A / dm2

[0215] Electrolysis time: 15.1 seconds

[0216] On the undercoat nickel layer on one side, a roughened nickel layer was next formed under the following conditions. It is to be noted that the roughened nickel layer was formed by applying the following granular nickel-forming plating and nickel-growing plating.<Granular Nickel-Forming Plating Conditions>Concentration of nickel sulfate hexahydrate in plating bath: 10 g / L

[0218] Concentration of nickel chloride hexahydrate in plating bath: 10 g / L

[0219] Concentration of chloride ions in plating bath: 16.6 g / L

[0220] Ratio of nickel ions to ammonium ions in plating bath: nickel ions / ammonium ions (weight ratio)=0.2

[0221] pH: 6.0

[0222] Bath temperature: 52° C.

[0223] Average current density: 21.0 A / dm2

[0224] Electrolysis time: 15.0 seconds

[0225] Agitation method: circulation agitation (agitation flow rate: low)

[0226] Electrical conductivity of the plating bath (bath electrical conductivity): 13.8 S / m (with a proviso in the case of bath temperature 50° C. and pH=6.0)

[0227] It is to be noted that, in the examples and comparative examples, agitation flow rates in circulation agitation were described according to the following criteria.

[0228] High agitation flow rate: the solution circulation rate by a pump for the plating solution of 2 L volume was 3 L / min or higher and lower than 4 L / min

[0229] Medium agitation flow rate: the solution circulation rate by the pump for the plating solution of 2 L volume was 2 L / min or higher and lower than 3 L / min

[0230] Low agitation flow rate: the solution circulation rate by the pump for the plating solution of 2 L volume was 1 L / min or higher and lower than 2 L / min

[0231] No agitation: the solution circulation rate by the pump for the plating solution of 2 L volume was lower than 1 L / min<Nickel-Growing Plating Conditions>Bath composition:

[0233] Nickel sulfate hexahydrate 250 g / L, nickel chloride hexahydrate 45 g / L, boric acid: 30 g / L

[0234] pH: 4.0 to 5.0

[0235] Bath temperature: 60° C.

[0236] Current density: 10 A / dm2

[0237] Electrolysis time: 1.4 seconds

[0238] Agitation method: circulation agitation (agitation flow rate: medium)

[0239] In the nickel-plated metal material thus obtained, values of the ten-point mean roughness Rzjis and the Mean Width Of The Profile Elements Rsm of elements on the outermost surface of the above-described roughened nickel layer are presented in Table 5. It is to be noted that these surface texture parameters were measured by using the laser microscope (manufactured by Olympus Corporation, 3D measuring laser microscope “LEXT OLS5000”). In the measurements of the ten-point mean roughness Rzjis and the Mean Width Of The Profile Elements Rsm of elements, the outermost surface of the roughened nickel layer was measured with the 50× objective lens, and the analysis was conducted under no conditions without setting any of filter criteria at the time of the analysis. Measurement of the roughened surface area, a 180° peel strength test and the evaluation, and the liquid penetrability evaluation were also conducted.

[0240] It is to be noted that the nickel deposition amount in the roughened nickel layer and the nickel-plated metal material was measured by using the X-ray fluorescence spectrometer (manufactured by Rigaku Corporation, “ZSX100e”), and the value so obtained is presented in Table 1. It is also to be noted that the specific measuring method is similar to the method described in PCT Patent Publication No. WO2020 / 017655, and therefore, its detailed description is omitted herein. All the nickel deposition amounts presented in Tables 1 to 4 are values per side.Example 2

[0241] The conditions for undercoat nickel plating, granular nickel-forming plating, and nickel-growing plating were set as presented in Table 1 and Table 2. Otherwise, the procedures of Example 1 were followed. The results so obtained are presented in Table 1, Table 2, and Table 5.Example 3

[0242] As a base material 20, a steel sheet having no iron-nickel alloy layer was used. Specifically, one obtained by carrying out electrolytic degreasing and pickling by dipping in sulfuric acid on the cold-rolled steel sheet described in Example 1 was used as a base material 20. Otherwise, the procedures of Example 1 were followed. The results so obtained are presented in Table 1, Table 2, and Table 5.Examples 4 to 17

[0243] Conditions for a base material, undercoat nickel plating, granular nickel-forming plating, and nickel-growing plating were set as in Table 1 and Table 2. Otherwise, the procedures of Example 1 were followed. The results so obtained are presented in Table 5.Example 18

[0244] As a base material 20, a similar metal base material to that in Example 3 was first provided, and similar electrolytic degreasing and pickling by dipping in sulfuric acid to that in Example 3 were then carried out. Subsequently, an undercoat nickel-plating layer to be located between the base material and a roughened nickel layer was formed under similar conditions to those in Example 1.

[0245] Under the following conditions, a composite roughened plating layer was next formed on the undercoat nickel layer on one side. It is to be noted that the composite roughened plating layer was formed by the following granular nickel-forming plating step of forming a roughened nickel layer and coating layer forming step of forming a coating layer. The coating treatment step was conducted by zinc plating.<Granular Nickel-Forming Plating Conditions>Concentration of nickel sulfate hexahydrate in plating bath: 10 g / L

[0247] Concentration of nickel chloride hexahydrate in plating bath: 10 g / L

[0248] Concentration of chloride ions in plating bath: 16.6 g / L

[0249] Ratio of nickel ions to ammonium ions in plating bath: nickel ions / ammonium ions (weight ratio)=0.2

[0250] pH: 6.0

[0251] Bath temperature: 55° C.

[0252] Average current density: 23.3 A / dm2

[0253] Electrolysis time: 20.0 seconds

[0254] Agitation method: circulation agitation (agitation flow rate: medium)

[0255] Electrical conductivity of the plating bath (bath electrical conductivity): 13.8 S / m (with a proviso in the case of bath temperature 50° C. and pH=6.0)<Coating Layer Forming Conditions>Bath composition:

[0257] Zinc sulfate heptahydrate: 220 g / L, ammonium sulfate 30 g / L

[0258] pH: 1.5 to 2.5 (An adjustment with sulfuric acid was conducted.)

[0259] Bath temperature: 55° C.

[0260] Current density: 10 A / dm2

[0261] Electrolysis time: 9.3 seconds

[0262] Under the above conditions, a coating zinc layer was obtained.

[0263] Agitation method: circulation agitation (agitation flow rate: high)

[0264] Values of the ten-point mean roughness Rzjis and the Mean Width Of The Profile Elements Rsm of elements on the outermost surface on the side of the composite roughened plating layer of the nickel-plated metal material were measured as in Example 1, and are presented in Table 5. It is to be noted that these surface texture parameters were measured by using the laser microscope (manufactured by Olympus Corporation, 3D measuring laser microscope “LEXT OLS5000”). In the measurements of the ten-point mean roughness Rzjis and the Mean Width Of The Profile Elements Rsm of elements, the outermost surface on the side of the composite roughened plating layer was measured with the 50× objective lens, and the analysis was conducted without setting any of filter criteria at the time of the analysis. The roughened surface area, the 180° peel strength test, and the liquid penetrability evaluation were also conducted.

[0265] It is to be noted that, concerning the nickel deposition amount in the composite roughened plating layer, its measurement was conducted by using the X-ray fluorescence spectrometer (manufactured by Rigaku Corporation, “ZSX100e”). It is to be noted that the specific measuring method is similar to the method described in PCT Patent Publication No. WO2020 / 017655, and therefore, its detailed description is omitted herein. Also concerning the zinc deposition amount of the coating zinc layer, its measurement was conducted by using the X-ray fluorescence spectrometer. Their values so obtained are presented in Table 3, Table 4, and Table 6.Example 19

[0266] Conditions for a base material, undercoat nickel plating, granular nickel-forming plating, and zinc plating were set as in Table 3 and Table 4. Otherwise, the procedures of Example 18 were followed. The results so obtained are presented in Table 6.Example 20

[0267] A stainless steel sheet (SUS430) of 50 μm thickness having a chemical composition presented below was provided as a base material 20.

[0268] C: 0.12 wt %, Cr: 16 to 18 wt %, Si: 0.75 wt %, Mn: 1.00 wt % or lower, P: 0.04 wt % or lower, S: 0.03 wt % or lower, Balance: inevitable impurities

[0269] On the base material, strike nickel-plating treatment was conducted under the strike nickel-plating conditions presented in Example 1, followed by undercoat nickel plating, granular nickel-forming plating, and nickel-growing plating under the conditions of Table 7 and Table 8. Otherwise, the procedures of Example 1 were followed. The results so obtained are presented in Table 9.Example 21

[0270] A 40 μm-thick, rolled aluminum sheet (hereinafter also called an “aluminum sheet”) of an aluminum alloy (A8079) having a chemical composition presented below was provided as a base material 20.

[0271] Si: 0.05 to 0.30 wt %, Fe: 0.7 to 1.3 wt %, Cu: 0.05 wt % or lower, Zn: 0.10 wt % or lower, Balance: inevitable impurities

[0272] With respect to the above-described aluminum sheet, substitution plating of zinc was next conducted on a surface of the aluminum sheet under zincate treatment conditions presented below. Subsequently, undercoat nickel plating, granular nickel-forming plating, and nickel-growing plating were conducted by setting their conditions as presented in Table 7 and Table 8. The results so obtained are presented in Table 9.<Zincate Treatment Conditions><<Degreasing Conditions>>Bath composition:

[0274] Sodium hydroxide 22.5 g / L, sodium carbonate 4.5 g / L

[0275] pH: 12 or higher

[0276] Bath temperature: 25° C.

[0277] Dipping time: 2 minutes<<Pickling Conditions>>Bath composition:

[0279] Sulfuric acid 70 g / L

[0280] pH: 1.0 or lower

[0281] Bath temperature: 25° C.

[0282] Dipping time: 2 minutes<<Desmut Conditions>>Bath composition:

[0284] 60% nitric acid 250 mL / L, ferric chloride solution 4 mL / L

[0285] pH: 1.0 or lower

[0286] Bath temperature: 25° C.

[0287] Dipping time: 30 seconds<<First Zincate Conditions>>Bath composition:

[0289] Sodium hydroxide 150 g / L, Rochelle salt 50 g / L, zinc oxide 25 g / L, ferrous chloride 1.5 g / L

[0290] pH: 12 to 14

[0291] Bath temperature: 25° C.

[0292] Dipping time: 50 seconds<<Dezincate Conditions>>Bath composition:

[0294] 60% nitric acid 250 mL / L, ferric chloride solution 4 mL / L

[0295] pH: 1.0 or lower

[0296] Bath temperature: 25° C.

[0297] Dipping time: 30 seconds<<Second Zincate Conditions>>Bath composition:

[0299] Sodium hydroxide 150 g / L, Rochelle salt 50 g / L, zinc oxide 25 g / L, ferrous chloride 1.5 g / L

[0300] pH: 12 to 14

[0301] Bath temperature: 25° C.

[0302] Dipping time: 50 seconds

[0303] As a base material 20, a similar metal base material to that in Example 3 was first provided, and electrolytic degreasing and pickling by dipping in sulfuric acid were carried out as in Example 3. Subsequently, an undercoat nickel layer to be located between the base material and a roughened nickel layer was formed under similar conditions to those in Example 1.

[0304] Under the following conditions, a composite roughened plating layer was next formed on the undercoat nickel layer on one side. It is to be noted that the composite roughened plating layer was formed by the following granular nickel-forming plating step of forming a roughened nickel layer and coating layer forming step of forming a coating layer. The coating treatment step was conducted by tin plating.<Granular Nickel-Forming Plating Conditions>Concentration of nickel sulfate hexahydrate in plating bath: 10 g / L

[0306] Concentration of nickel chloride hexahydrate in plating bath: 10 g / L

[0307] Concentration of chloride ions in plating bath: 16.6 g / L

[0308] Ratio of nickel ions to ammonium ions in plating bath: nickel ions / ammonium ions (weight ratio)=0.2

[0309] pH: 6.0

[0310] Bath temperature: 50° C.

[0311] Average current density: 20.0 A / dm2

[0312] Electrolysis time: 15.0 seconds

[0313] Agitation method: circulation agitation (agitation flow rate: medium)

[0314] Electrical conductivity of the plating bath (bath electrical conductivity): 13.8 S / m (with a proviso in the case of bath temperature 50° C. and pH=6.0)<Coating Layer Forming Conditions>Stannous sulfate: 80 g / L

[0316] Phenolsulfonic acid: 60 g / L

[0317] Ethoxylated a-naphthol: 3 g / L

[0318] Ethoxylated a-naphtholsulfonic acid: 3 g / L

[0319] pH: 0.5 to 1.5 (An adjustment with sulfuric acid was conducted.)

[0320] Bath temperature: 40° C.

[0321] Current density: 5.0 A / dm2

[0322] Electrolysis time: 1.2 seconds

[0323] Agitation method: circulation agitation (agitation flow rate: low)

[0324] Under the above conditions, a coating tin layer was obtained.

[0325] Values of the ten-point mean roughness Rzjis and the Mean Width Of The Profile Elements Rsm of elements on the outermost surface on the side of the composite roughened plating layer of the nickel-plated metal material were measured as in Example 1, and are presented in Table 12. It is to be noted that these surface texture parameters were measured by using the laser microscope (manufactured by Olympus Corporation, 3D measuring laser microscope “LEXT OLS5000”). In the measurements of the ten-point mean roughness Rzjis and the Mean Width Of The Profile Elements Rsm of elements, the outermost surface on the side of the composite roughened plating layer was measured with the 50× objective lens, and the analysis was conducted without setting any of filter criteria at the time of the analysis. The roughened surface area, the 180° peel strength test, and the liquid penetrability evaluation were also conducted.

[0326] It is to be noted that, concerning the nickel deposition amount in the composite roughened plating layer, its measurement was conducted by using the X-ray fluorescence spectrometer (manufactured by Rigaku Corporation, “ZSX100e”). It is to be noted that the specific measuring method is similar to the method described in PCT Patent Publication No. WO2020 / 017655, and therefore, its detailed description is omitted herein. Also concerning the tin deposition amount of the coating tin layer, its measurement was conducted by using the X-ray fluorescence spectrometer. Their values so obtained are presented in Table 10, Table 11, and Table 12.Comparative Example 1

[0327] The conditions for undercoat nickel plating, granular nickel-forming plating, and nickel-growing plating were set as presented in Table 1 and Table 2. Otherwise, the procedures of Example 1 were followed. The results so obtained are presented in Table 5. It is to be noted that, in Comparative Example 1, the 180° peel strength was 0, and therefore, the evaluation of liquid penetration resistance was difficult and was not conducted.Comparative Example 2

[0328] The conditions for undercoat nickel plating, granular nickel-forming plating, and nickel-growing plating were set as presented in Table 1 and Table 2. Otherwise, the procedures of Example 1 were followed. The results so obtained are presented in Table 5.Comparative Example 3

[0329] The conditions for undercoat nickel plating, granular nickel-forming plating, and nickel-growing plating were set as presented in Table 1 and Table 2. Otherwise, the procedures of Example 2 were followed. The results so obtained are presented in Table 5.Comparative Example 4

[0330] The conditions for undercoat nickel plating, granular nickel-forming plating, and nickel-growing plating were set as presented in Table 1 and Table 2. Otherwise, the procedures of Example 1 were followed. The results so obtained are presented in Table 5.Comparative Example 5

[0331] The conditions for undercoat nickel plating, granular nickel-forming plating, and zinc plating were set as presented in Table 3 and Table 4. Otherwise, the procedures of Example 18 were followed. The results so obtained are presented in Table 6. It is to be noted that, in Comparative Example 5, the 180° peel strength was 0, and therefore, the evaluation of liquid penetration resistance was difficult and was not conducted.Comparative Example 6

[0332] The conditions for undercoat nickel plating, granular nickel-forming plating, and zinc plating were set as presented in Table 3 and Table 4. Otherwise, the procedures of Example 18 were followed. The results so obtained are presented in Table 6.Comparative Example 7

[0333] The conditions for undercoat nickel plating, granular nickel-forming plating, and nickel-growing plating were set as presented in Table 7 and Table 8. Otherwise, the procedures of Example 20 were followed. The results so obtained are presented in Table 9.Comparative Example 8

[0334] The conditions for undercoat nickel plating, granular nickel-forming plating, and nickel-growing plating were set as presented in Table 7 and Table 8. Otherwise, the procedures of Example 20 were followed. The results so obtained are presented in Table 9.Comparative Example 9

[0335] The conditions for undercoat nickel plating, granular nickel-forming plating, and nickel-growing plating were set as presented in Table 7 and Table 8. Otherwise, the procedures of Example 21 were followed. The results so obtained are presented in Table 9.Comparative Example 10

[0336] The conditions for undercoat nickel plating, granular nickel-forming plating, and tin plating were set as presented in Table 10 and Table 11. Otherwise, the procedures of Example 22 were followed. The results so obtained are presented in Table 12.TABLE 1UNDERCOAT NICKEL-PLATING CONDITIONSELEC-NICKELTEMPER-CURRENTTROLYSISDEPOSITIONATUREDENSITYTIMEBATHAMOUNTBASE MATERIALpH(° C.)(A / dm2)(sec.)CONDITIONS(g / m2)Example 1SURFACE DIFFUSION-4.0~5.0601015.1WATTS BATH4.5TREATED STEEL SHEETExample 2SURFACE DIFFUSION-4.0~5.0601015.1WATTS BATH4.5TREATED STEEL SHEETExample 3STEEL SHEET4.0~5.0601015.1WATTS BATH4.5Example 4SURFACE DIFFUSION-4.0~5.0601010.5WATTS BATH3.1TREATED STEEL SHEETExample 5STEEL SHEET4.0~5.0601015.1WATTS BATH4.5Example 6STEEL SHEET4.0~5.0601010.5WATTS BATH3.1Example 7SURFACE DIFFUSION-4.0~5.0601010.5WATTS BATH3.1TREATED STEEL SHEETExample 8SURFACE DIFFUSION-4.0~5.0601015.1WATTS BATH4.5TREATED STEEL SHEETExample 9STEEL SHEET4.0~5.0601015.1WATTS BATH4.5Example 10SURFACE DIFFUSION-4.0~5.0601010.5WATTS BATH3.1TREATED STEEL SHEETExample 11SURFACE DIFFUSION-4.0~5.0601015.1WATTS BATH4.5TREATED STEEL SHEETExample 12SURFACE DIFFUSION-4.0~5.0601015.1WATTS BATH4.5TREATED STEEL SHEETExample 13STEEL SHEET4.0~5.0601010.5WATTS BATH3.1Example 14STEEL SHEET4.0~5.0601015.1WATTS BATH4.5Example 15SURFACE DIFFUSION-4.0~5.0601010.5WATTS BATH3.1TREATED STEEL SHEETExample 16STEEL SHEET4.0~5.0601010.5WATTS BATH3.1Example 17SURFACE DIFFUSION-4.0~5.0601015.1WATTS BATH4.5TREATED STEEL SHEETComparativeSTEEL SHEET4.0~5.0601015.1WATTS BATH4.5Example 1ComparativeSURFACE DIFFUSION-4.0~5.0601010.5WATTS BATH3.1Example 2TREATED STEEL SHEETComparativeSTEEL SHEET4.0~5.0601015.1WATTS BATH4.5Example 3ComparativeSURFACE DIFFUSION-4.0~5.0601010.5WATTS BATH3.1Example 4TREATED STEEL SHEETTABLE 2GRANULAR NICKEL-FORMING PLATING CONDITIONSNICKELAGITATIONCURRENTELECTROLYSISDEPOSITIONFLOWTEMPERATUREDENSITYTIMEAMOUNTAGITATIONRATEpH(° C.)(A / dm2)(sec.)(g / m2)METHOD(L / min.)mple 16.05221.015.04.2CIRCULATEDLOWmple 26.05723.519.26.2CIRCULATEDMEDIUMmple 36.05423.220.56.4CIRCULATEDMEDIUMmple 46.06023.318.26.0CIRCULATEDHIGHmple 56.05227.017.55.4CIRCULATEDMEDIUMmple 66.05235.413.35.0CIRCULATEDLOWmple 76.05021.028.07.6CIRCULATEDHIGHmple 86.05221.035.010.3CIRCULATEDHIGHmple 96.05520.037.510.8CIRCULATEDMEDIUMnple 106.05420.016.25.3CIRCULATEDLOWnple 116.05420.519.36.2CIRCULATEDMEDIUMmple 126.05020.023.07.0CIRCULATEDHIGHmple 136.05121.626.88.2CIRCULATEDMEDIUMmple 146.05522.236.511.4CIRCULATEDMEDIUMmple 156.05022.035.510.5CIRCULATEDHIGHnple 166.05723.435.110.7CIRCULATEDMEDIUMnple 176.05123.338.012.5CIRCULATEDHIGHComparative6.0453.082.94.1NOT—*Example 1AGITATEDComparative6.05016.035.78.3NOT—Example 2AGITATEDComparative6.04520.051.212.8CIRCULATEDLOWExample 3Comparative6.04215.082.016.0NOT—Example 4AGITATEDNICKEL-GROWING PLATING CONDITIONSNICKELAGITATIONCURRENTELECTROLYSISDEPOSITIONFLOWTEMPERATUREDENSITYTIMEAMOUNTAGITATIONRATEpH(° C.)(A / dm2)(sec.)(g / m2)METHOD(L / min.)mple 14.0~5.060101.40.5CIRCULATEDMEDIUMmple 24.0~5.060102.50.8CIRCULATEDHIGHmple 34.0~5.060101.20.4CIRCULATEDMEDIUMmple 44.0~5.060101.40.5CIRCULATEDHIGHmple 54.0~5.060109.12.5CIRCULATEDMEDIUMmple 64.0~5.060109.52.9CIRCULATEDLOWmple 74.0~5.060109.12.5CIRCULATEDMEDIUMmple 84.0~5.0601010.43.2CIRCULATEDHIGHmple 94.0~5.0601010.43.2CIRCULATEDHIGHnple 104.0~5.060109.12.5CIRCULATEDLOWnple 114.0~5.060108.02.2CIRCULATEDLOWmple 124.0~5.0602.736.03.2CIRCULATEDMEDIUMmple 134.0~5.060109.52.9CIRCULATEDLOWmple 144.0~5.0601013.54.2CIRCULATEDMEDIUMmple 154.0~5.060109.52.7CIRCULATEDLOWnple 164.0~5.0601012.83.8CIRCULATEDHIGHnple 174.0~5.060109.52.7CIRCULATEDMEDIUMComparative4.0~5.060109.12.5NOT—Example 1AGITATEDComparative4.0~5.0601028.58.5NOT—Example 2AGITATEDComparative4.0~5.0601018.05.3NOT—Example 3AGITATEDComparative4.0~5.0601022.06.5NOT—Example 4AGITATED*If not agitated, the flow rate is less than 1 L / min.TABLE 3UNDERCOAT NICKEL-PLATING CONDITIONSNICKELTEMPER-CURRENTELEC-DEPOSITIONBASE ATUREDENSITYTROLYSISBATHAMOUNTMATERIALpH(° C.)(A / dm2)TIMECONDITIONS(g / m2)Example 18STEEL SHEET4.0~5.0601015.1WATTS BATH4.5Example 19STEEL SHEET4.0~5.0601015.1WATTS BATH4.5ComparativeSTEEL SHEET4.0~5.0601015.1WATTS BATH4.5Example 5ComparativeSTEEL SHEET4.0~5.0601015.1WATTS BATH4.5Example 6TABLE 4GRANULAR NICKEL-FORMING PLATING CONDITIONSNICKELAGITATIONCURRENTELECTROLYSISDEPOSITIONFLOWTEMPERATUREDENSITYTIMEAMOUNTAGITATIONRATEpH(° C.)(A / dm2)(sec.)(g / m2)METHOD(L / min.)Example 186.05523.320.04.0CIRCULATEDMEDIUMExample 195.05230.010.52.0CIRCULATEDHIGHComparative5.04515.05.00.7NOT —*Example 5AGITATEDComparative5.04515.048.66.8NOT —Example 6AGITATEDCOATING ZINC PLAT ING CONDITIONSNICKELAGITATIONCURRENTELECTROLYSISDEPOSITIONFLOWTEMPERATUREDENSITYTIMEAMOUNTAGITATIONRATEpH(° C.)(A / dm2)(sec.)(g / m2)METHOD(L / min.)Example 181.5~2.555109.32.1CIRCULATEDHIGHExample 191.5~2.5551026.37.5CIRCULATEDMEDIUMComparative1.5~2.5551026.37.5NOT —Example 5AGITATEDComparative1.5~2.5551026.37.5NOT —Example 6AGITATEDTABLE 5ROUGHENED180º PEEL STRENGTHLIQUIDExample / SURFACE(=RESIN ADHESIONPENETRATIONComparativeRzjisRsmAREASTRENGTH)RESISTANCEExampleμmμmm2 / 1 m2N / 25 mmEVALUATIONEVALUATIONExample 11.36.07.015.2EXCELLENTEXCELLENTExample 21.65.08.616.5EXCELLENTEXCELLENTExample 31.96.28.016.0EXCELLENTEXCELLENTExample 42.25.38.726.9EXCELLENTEXCELLENTExample 52.45.88.126.5EXCELLENTEXCELLENTExample 62.54.96.425.6EXCELLENTEXCELLENTExample 72.65.16.923.0EXCELLENTEXCELLENTExample 82.85.88.820.6EXCELLENTEXCELLENTExample 93.46.09.830.5EXCELLENTEXCELLENTExample 101.111.13.96.7GOODEXCELLENTExample 111.57.72.65.8GOODEXCELLENTExample 121.65.35.212.2GOODEXCELLENTExample 132.37.02.410.2GOODEXCELLENTExample 143.95.85.131.1EXCELLENTGOODExample 154.06.621.327.9EXCELLENTGOODExample 164.26.012.748.5EXCELLENTGOODExample 174.66.828.830.8EXCELLENTGOODComparative0.98.20.20.0POORNOTExample 1EVALUATEDComparative2.99.11.43.3POOREXCELLENTExample 2Comparative4.86.44.034.1EXCELLENTMODERATEExample 3Comparative6.57.18.543.3EXCELLENTPOORExample 4TABLE 6ROUGHENED180° PEEL STRENGTHLIQUIDExample / SURFACE(=RESIN ADHESIONPENETRATIONComparativeRzjisRsmAREASTRENGTH)RESISTANCEExampleμmμmm2 / 1 m2N / 25 mmEVALUATIONEVALUATIONExample 182.35.39.536.2EXCELLENTEXCELLENTExample 193.26.310.642.5EXCELLENTEXCELLENTComparative0.827.62.80.0POORNOTExample 5EVALUATEDComparative4.97.812.246.7EXCELLENTMODERATEExample 6TABLE 7UNDERCOAT NICKEL-PLATING CONDITIONSELEC-NICKEL TEMPER-CURRENTTROLYSISDEPOSITIONATUREDENSITYTIMEBATHAMOUNTBASE MATERIALpH(° C.)(A / dm2)(sec.)CONDITIONS(g / m2)Example 20STEEL SHEET4.0~5.0601015.1WATTS BATH4.5Example 21ALUMINUM 4.0~5.0601015.1WATTS BATH4.5SHEETComparativeSTEEL SHEET4.0~5.0601015.1WATTS BATH4.5Example 7ComparativeSTEEL SHEET4.0~5.0601015.1WATTS BATH4.5Example 8ComparativeALUMINUM 4.0~5.0601015.1WATTS BATH4.5Example 9SHEETTABLE 8GRANULAR NICKEL-FORMING PLATING CONDITIONSNICKELAGITATIONCURRENTELECTROLYSISDEPOSITIONFLOWTEMPERATUREDENSITYTIMEAMOUNTAGITATIONRATEpH(° C.)(A / dm2)(sec.)(g / m2)METHOD(L / min.)Example 206.05625.016.05.5CIRCULATEDMEDIUMExample 216.05622.014.75.3CIRCULATEDHIGHComparative6.05010.09.01.2NOT—Example 7AGITATEDComparative6.04223.048.09.6CIRCULATEDLOWExample 8Comparative6.05015.037.08.9NOTLOWExample 9AGITATEDNICKEL-GROWING PLATING CONDITIONSNICKELAGITATIONCURRENTELECTROLYSISDEPOSITIONFLOWTEMPERATUREDENSITYTIMEAMOUNTAGITATIONRATEpH(° C.)(A / dm2)(sec.)(g / m2)METHOD(L / min.)Example 204.0~ 5.050103.00.8CIRCULATEDMEDIUMExample 214.0~ 5.050102.00.3CIRCULATEDLOWComparative4.0~ 5.060105.01.4NOT—Example 7AGITATEDComparative4.0~ 5.0601032.010.6NOT—Example 8AGITATEDComparative4.0~ 5.0601011.03.2NOT—Example 9AGITATEDTABLE 9ROUGHENED180º PEEL STRENGTHLIQUIDExample / SURFACE (=RESIN ADHESIONPENETRATIONComparativeRzjisRsmAREASTRENGTH)RESISTANCEExampleμmμmm2 / 1 m2N / 25 mmEVALUATIONEVALUATIONExample 202.04.410.142.0EXCELLENTEXCELLENTExample 213.38.77.517.4EXCELLENTEXCELLENTComparative0.64.11.00.0POORNOT Example 7EVALUATEDComparative7.98.215.643.9EXCELLENTPOORExample 8Comparative5.88.77.821.1EXCELLENTPOORExample 9TABLE 10UNDERCOAT NICKEL-PLATING CONDITIONSELEC-NICKELTEMPER-CURRENTTROLYSISBATHDEPOSITIONBASE ATUREDENSITYTIMECONDITIONSAMOUNTMATERIALpH(° C.)(A / dm2)(sec.)CONDITIONS(g / m2)Example 22STEEL SHEET4.0~5.0601015.1WATTS BATH4.5ComparativeSTEEL SHEET4.0~5.0601015.1WATTS BATH4.5Example 10TABLE 11GRANULAR NICKEL-FORMING PLATING CONDITIONSNICKELAGITATIONCURRENTELECTROLYSISDEPOSITIONFLOWTEMPERATUREDENSITYTIMEAMOUNTAGITATIONRATEpH(° C.)(A / dm2)(sec.)(g / m2)METHOD(L / min.)Example 226.05020.015.04.4CIRCULATEDMEDIUMComparative6.05020.037.54.5NOT—Example 10AGITATEDCOATING TIN PLATING CONDITIONSNICKELAGITATIONCURRENTELECTROLYSISDEPOSITIONFLOWTEMPERATUREDENSITYTIMEAMOUNTAGITATIONRATEpH(° C.)(A / dm2)(sec.)(g / m2)METHOD(L / min.)Example 220.5~1.5405.01.21.1CIRCULATEDLOWComparative0.5~1.5405.047.67.3NOT —Example 10AGITATED*If not agitated, the flow rate is less than 1 L / min.TABLE 12ROUGHENED180° PEEL STRENGTHLIQUIDExample / SURFACE(=RESIN ADHESIONPENETRATIONComparativeRzjisRsmAREASTRENGTH)RESISTANCEExampleμmμmm2 / 1 m2N / 25 mmEVALUATIONEVALUATIONExample 222.09.66.550.2EXCELLENTEXCELLENTComparative5.57.13.720.6EXCELLENTPOORExample 10Examples 1 to 17 have been confirmed to have preferred characteristics in both resin adhesion strength and liquid penetration resistance. In Comparative Examples 1 to 3, on the other hand, the resin adhesion strength was 3.3N / 25 mm or lower, thereby failing to achieve the object in the viewpoint of resin adhesion strength. Further, in Comparative Examples 4 and 5, it failed to achieve the object in the viewpoint of liquid penetration resistance.In more detail, it was found that, when Example 8 and Comparative Example 3 are compared with each other, their values of the ten-point mean roughness Rzjis were substantially the same, but the intended resin adhesion strength was not obtained in the comparative example because there was a difference in value of the roughened surface area between the example and the comparative example. It is to be noted that the difference in value of the roughened surface area between them could be attributed to differences in shape among the individual protrusions including the shapes of roots of the roughened portion, but details were not clear.Example 18, Example 19, Comparative Example 5, and Comparative Example 6 are embodiments in which zinc was formed as a coating layer. In Example 18 and Example 19, the ten-point mean roughness Rzjis was 1.0 μm or greater and smaller than 4.8 μm, and the roughened surface area was 1.5 mm2 / 1 m2 or greater, on the surface of the composite roughened plating layer with the coating layer made of zinc and formed thereon, and Example 18 and Example 19 have been confirmed to have preferred characteristics in resin adhesion strength and liquid penetration resistance. In Comparative Example 5, on the other hand, the value of the ten-point mean roughness Rzjis was out of the above-described range, and, as a result, it failed to achieve the object in the viewpoint of adhesion strength. Further, in Comparative Example 6, the ten-point mean roughness Rzjis was 4.9 μm, that is, greater than 4.8 μm, so that the intended liquid penetration resistance was not obtained.Further, the preferred results were obtained from the viewpoints of both resin adhesion strength and liquid penetration resistance when, on the uppermost surface on the side of the roughened nickel layer 50, the ten-point mean roughness Rzjis was 1.0 μm or greater and 3.5 μm or smaller and the roughened surface area was 5.3 m2 / 1 m2 or greater, as presented in Examples 1 to 9, 18, and 19.Example 20, Comparative Example 7, and Comparative Example 8 are embodiments in which a stainless steel sheet was used as a base material. On the other hand, Example 21 and Comparative Example 9 are embodiments in which an aluminum sheet was used as a base material. In Example 20 and Example 21, Rzjis was 1.0 μm or greater and smaller than 4.8 μm, and the roughened surface area was 1.5 mm2 / 1 m2 or greater, so that Example 20 and Example 21 have been confirmed to have preferred characteristics in both resin adhesion strength and liquid penetration resistance. In Comparative Example 7, on the other hand, Rzjis was smaller 1.0 μm, and the roughened surface area was smaller than 1.5 mm2 / 1 m2, resulting in a significant reduction in the adhesion with the resin. Further, in Comparative Example 8 and Comparative Example 9, Rzjis was greater than 4.8 μm, thereby failing to achieve the object in the viewpoint of liquid penetration resistance.Example 22 and Comparative Example 10 are embodiments in which tin was formed as a coating layer. In Example 22, the ten-point mean roughness Rzjis was 1.0 μm or greater and smaller than 4.8 μm, and the roughened surface area was 1.5 mm2 / 1 m2 or greater, on the surface of the composite roughened plating layer with the coating layer made of tin and formed thereon, and Example 22 has been confirmed to have preferred characteristics in resin adhesion strength and liquid penetration resistance. In Comparative Example 10, on the other hand, the ten-point mean roughness Rzjis was 5.5 μm, that is, greater than 4.8 μm, so that the intended liquid penetration resistance was not obtained.From these results, it is understood necessary to control both the ten-point mean roughness Rzjis and the roughened surface area for obtaining preferred characteristics in both the resin adhesion strength and the liquid penetration resistance.Various modifications can be made to the above-described embodiments and the individual examples within a scope not departing from the spirit of the present disclosure.INDUSTRIAL APPLICABILITYAs described above, the nickel-plated metal material of the present disclosure can be used for various applications such as current collectors of positive electrodes and / or negative electrodes of secondary batteries and the like, members for electronic devices, electric appliances, automobiles, and constructions, and so on.REFERENCE SIGNS LIST100, 200, 300, 400: Nickel-plated metal material20: Base material40: Metal layer50: Roughened nickel layer

[0350] 60: Composite roughened plating layer

[0351] 70: Coating layer

Examples

first embodiment

[0017]FIG. 1 is a cross-sectional view schematically depicting an embodiment of a nickel-plated metal material 100 of the present disclosure. It is to be noted that the nickel-plated metal material 100 of the present embodiment is used, for example, as current collectors of positive electrodes and / or negative electrodes of secondary batteries and the like, members for electronic devices, electric appliances, automobiles, and constructions, and so on.

[0018]The nickel-plated metal material 100 of the present embodiment includes the base material 20 made of metal, and a roughened nickel layer 50 formed on the base material 20. It is to be noted that, in the nickel-plated metal material 100 of the present embodiment, the roughened nickel layer 50 is formed on at least one outermost surface as depicted in FIG. 1.

20>

[0019]As the base material 20 for use in the nickel-plated metal material 100 of the present embodiment, a metal sheet or metal foil made of a pure metal selected from iron (F...

second embodiment

[0102]On the basis of FIG. 3, a nickel-plated metal material 300 in a second embodiment will next be described. The nickel-plated metal material 300 in the second embodiment is different from the above-mentioned first embodiment in that a coating layer 70 is included on the roughened nickel layer 50. Accordingly, this different point will be primarily described, the other points will be identified by the same reference signs, and their description is omitted. It is to be noted that, in the nickel-plated metal material 300, the roughened nickel layer 50 and the coating layer 70 will be collectively called a “composite roughened plating layer 60.” In the nickel-plated metal material 300, the ten-point mean roughness Rzjis and roughened surface area on the outermost surface on the side of the composite roughened plating layer 60 are 1.0 μm or greater and smaller than 4.8 μm and 1.5 m2 / 1 mm2 or greater, respectively.

70>

[0103]As mentioned above, the coating layer 70 is disposed on the ro...

example 1

[0200]A cold-rolled steel sheet (60 μm thickness) of low-carbon aluminum-killed steel having a chemical composition presented below was first provided.[0201]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

[0202]After electrolytic degreasing and pickling by dipping in sulfuric acid were next carried out on the above-described cold-rolled steel sheet, a nickel layer was formed to a deposition amount of 8.9 g / m2 by known nickel plating. Subsequently, thermal diffusion treatment was conducted by a continuous annealing step, and quality control rolling was applied, whereby an iron-nickel alloy layer of 2.2 μm thickness was formed on both sides. The resulting surface diffusion-treated steel sheet was provided as a base material 20.

[0203]On the surface diffusion-treated steel sheet as the base material 20, strike nickel-plating treatment was conducted under the strike nickel-plating conditions presented below, followed by forma...

TECHNICAL FIELD

[0001] The present disclosure relates to a nickel-plated metal material.BACKGROUND ART

[0002] In recent years, in a technology that forms a plating layer on a base material such as a metal sheet or a metal foil, techniques are not limited to smoothly forming the plating layer, and are known to form roughness by plating or to deposit metal in a granular or acicular form on the base material, that is, to form what is called a roughened plating layer.

[0003] For example, PTL 1 discloses a roughened nickel-plated sheet, the lightness and 85° gloss of a surface of a roughened nickel layer of which are specified to provide the roughened nickel-plated sheet with excellent adhesion with another member while allowing the plating layer to hold adhesion with a base material. Further, PTL 2 discloses a roughened nickel-plated sheet improved in liquid penetration resistance when joined with another member, in addition to the adhesion of a plating layer to a base material and adhesion with another member.CITATION LISTPatent Literature[PTL 1]

[0004] PCT Patent Publication No. WO2020 / 017655[PTL 2]

[0005] PCT Patent Publication No. WO2021 / 149821SUMMARYTechnical Problem

[0006] Appliances that use a roughened nickel-plated material are desired to have improved characteristics under a higher diversity of environments. As an example of these environments, a case can be mentioned in which such an appliance is used for a long period of time under a high-temperature environment or in a highly corrosive liquid. However, it came to knowledge that, if the height of a roughened portion was made high to obtain a certain level of adhesion or higher with another member in a conventional roughened nickel-plated material, liquid penetration resistance (resistance to penetration and spreading of a liquid to and in an interface) tended to decrease when continued to be exposed to such a severe environment as described above. If the height of the roughened portion was made low, on the other hand, the adhesion with another member was insufficient with such a conventional roughened nickel-plated material.

[0007] The present disclosure has been made with a view to solving such a problem, and has, as an object thereof, the provision of a nickel-plated metal material, which has adhesion with another member while suppressing the height of a roughened portion in a roughened nickel layer.Solution to Problem

[0008] To solve the above-described problem, a nickel-plated metal material of the present embodiment is a nickel-plated metal material including a base material made of metal and a roughened nickel layer formed on at least one side on the base material. A ten-point mean roughness Rzjis on an outermost surface on a side of the roughened nickel layer of the nickel-plated metal material is 1.0 μm or greater and smaller than 4.8 μm, and a roughened surface area on the outermost surface on the side of the roughened nickel layer is 1.5 m2 / 1 m2 or greater.Advantageous Effect of Invention

[0009] According to the present disclosure, it is possible to provide a nickel-plated metal material, which has improved liquid penetration resistance at an adhesion interface with another member by suppressing the height of a roughened portion in a roughened nickel layer and also has adhesion with another member by increasing a roughened surface area to be mentioned below.BRIEF DESCRIPTION OF DRAWINGS

[0010] FIG. 1 is a cross-sectional view schematically depicting a nickel-plated metal material of the present embodiment.

[0011] FIG. 2 is a cross-sectional view schematically depicting a nickel-plated metal material according to another embodiment.

[0012] FIG. 3 is a cross-sectional view schematically depicting a nickel-plated metal material according to still another embodiment.

[0013] FIG. 4 is a cross-sectional view schematically depicting a nickel-plated metal material according to yet another embodiment.

[0014] FIG. 5 is a graph presenting a method example for determining the thickness of an iron-nickel diffusion alloy layer.

[0015] FIG. 6 depicts schematic diagrams illustrating differences in roughened surface area due to differences in the shapes of roughened portions.DESCRIPTION OF EMBODIMENTS<<Nickel-Plated Metal Material>>

[0016] A description will hereinafter be made regarding embodiments for implementing the nickel-plated metal material of the present disclosure. It is to be noted that a “roughened portion” in the present disclosure is a rough surface portion including a roughened nickel layer formed on a base material by a roughened plating step and formed by protrusions made from nickel granules on the base material 20. The nickel-plated metal material of the present disclosure will hereinafter be described as a plate-shaped one, but without being limited to it, may have a curved surface shape or three-dimensional shape formed by pressing a plate-shape material with a mold, or may have a three-dimensional shape such as a cylinder shape or a cube. Moreover, the roughened nickel-plating layer is not needed to be formed on the entire surface if the roughened nickel layer is formed in an area where a roughened portion is required. In other words, the nickel-plated metal material of the present disclosure may be one with a roughened nickel layer formed in at least a part of area on a whole shape.First Embodiment

[0017] FIG. 1 is a cross-sectional view schematically depicting an embodiment of a nickel-plated metal material 100 of the present disclosure. It is to be noted that the nickel-plated metal material 100 of the present embodiment is used, for example, as current collectors of positive electrodes and / or negative electrodes of secondary batteries and the like, members for electronic devices, electric appliances, automobiles, and constructions, and so on.

[0018] The nickel-plated metal material 100 of the present embodiment includes the base material 20 made of metal, and a roughened nickel layer 50 formed on the base material 20. It is to be noted that, in the nickel-plated metal material 100 of the present embodiment, the roughened nickel layer 50 is formed on at least one outermost surface as depicted in FIG. 1.<Base Material 20>

[0019] As the base material 20 for use in the nickel-plated metal material 100 of the present embodiment, a metal sheet or metal foil made of a pure metal selected from iron (Fe), copper (Cu), aluminum (Al), or nickel (Ni), a metal sheet made of an alloy containing one type selected from iron (Fe), copper (Cu), aluminum (Al), or nickel (Ni), one obtained by forming such a sheet, a cast material, a forged material, or the like can be mentioned, for example. Preferably, a metal sheet or metal foil made of such a metal can be used. It is also possible to use a nickel-plated steel sheet, a metal sheet (hereinafter also called a “surface diffusion-treated steel sheet”) with a diffusion alloy layer of iron and nickel formed on a surface layer or in a vicinity of the surface layer by subjecting a nickel-plated steel sheet to heat treatment, a zinc-plated steel sheet, or the like.

[0020] In the viewpoint of improving the plating adhesion between the base material 20 and the roughened nickel layer 50 and a composite roughened plating layer 60 to be described in a latter part, a steel sheet, iron foil, or a surface diffusion-treated steel sheet is preferred as the base material 20. In the viewpoint of improving the corrosion resistance of the whole metal sheet, on the other hand, a nickel-plated steel sheet, a surface diffusion-treated steel sheet, or a zinc-plated steel sheet is preferred as the base material 20. In the viewpoint of satisfying these plating adhesion and corrosion resistance together, a surface diffusion-treated steel sheet is particularly preferred.

[0021] If the base material 20 is a steel sheet, chromium (Cr) and other additive metal elements are preferably lower than 1.0 wt %. Specifically, low-carbon steel (carbon content: 0.01 to 0.15 wt %) represented by low-carbon aluminum-killed steel, ultralow-carbon steel having a carbon content of lower than 0.01 wt %, or non-aging ultralow-carbon steel prepared by adding titanium (Ti), niobium (Nb), and / or the like to ultralow-carbon steel is suitably used.

[0022] It is to be noted that, if a nickel-plated steel sheet, a surface diffusion-treated steel sheet, or a zinc-plated steel sheet is used as the base material 20, low-carbon steel (carbon content: 0.01 to 0.15 wt %) represented by low-carbon aluminum-killed steel, ultralow-carbon steel having a carbon content of lower than 0.01 wt %, or non-aging ultralow-carbon steel prepared by adding Ti, Nb, and / or the like to ultralow-carbon steel, which are / is similar to those / that described above, is suitably used as the base material.

[0023] If the base material 20 is an iron foil, a pure iron foil is preferred from the viewpoints of elongation, corrosion resistance, and the above-described plating adhesion, and from the viewpoint of thinning in particular, the whole base material 20 is preferably an electrolytic iron foil that is obtained by electrolytic plating.

[0024] It is to be noted that, if a metal base material with a passive film formed on a surface thereof, such as a stainless steel sheet, a nickel sheet, a nickel-plated steel sheet, or a surface diffusion-treated steel sheet, is used as the base material 20, strike nickel plating is preferably applied before plating treatment that forms the roughened nickel layer 50 or a metal layer 40 to be described in a latter part. Conditions for the strike nickel plating are not particularly limited, but may include, for example, the following conditions or the like. Under the below-described conditions, the deposition amount of nickel by strike nickel plating is generally 0.01 to 0.89 g / m2. If a nickel layer (also called an “undercoat nickel layer”) is formed as the metal layer 40, the total amount of a deposition amount of nickel by strike nickel plating and a nickel deposition amount by nickel plating to form the undercoat nickel layer is measured as the nickel deposition amount of the undercoat nickel layer.<Examples of Strike Nickel-Plating Conditions>Bath composition:

[0026] Nickel sulfate hexahydrate 100 to 300 g / L, sulfuric acid: 10 to 200 g / L

[0027] pH: 1.0 or lower

[0028] Bath temperature: 40° C. to 70° C.

[0029] Current density: 5 to 100 A / dm2

[0030] Plating time: 3 to 100 seconds

[0031] If the base material 20 is a pure aluminum sheet, a pure aluminum foil, an aluminum alloy sheet, or an aluminum alloy foil, on the other hand, zincate treatment that conducts substitution plating of zinc on a surface of aluminum is preferably applied before plating treatment that forms the roughened nickel layer 50 or the metal layer 40 to be described in the latter part. Zincate treatment conditions are not particularly limited, but may include, for example, the following conditions or the like. To the pure aluminum sheet or the pure aluminum foil, or the aluminum alloy sheet or the aluminum alloy foil, degreasing is conducted with an alkaline solution, etching treatment is next applied in sulfuric acid, and desmut treatment is then applied in a solution with nitric acid and a ferric chloride solution mixed therein. After that, the resulting pure aluminum sheet or pure aluminum foil, or the resulting aluminum alloy sheet or aluminum alloy foil is dipped in the below-described zincate treatment solution to conduct first zincate treatment. Subsequently, the resulting pure aluminum sheet or pure aluminum foil, or aluminum alloy sheet or aluminum alloy foil is dipped in the same treatment solution as that used in the desmut treatment, thereby removing zinc substitution-precipitated by the first zincate treatment, and is then dipped in the same treatment solution as that used in the first zincate treatment, to conduct a second zincate treatment (hereinafter also called “double zincate treatment”). In this case, water rinsing treatment is conducted after the treatment in each step. It is to be noted that the deposition amount of zinc can be adjusted by appropriately choosing the concentration of zinc ions in the treatment solution and the time during which the dipping in the treatment solution is conducted in the second zincate treatment. As an alternative, the substitution plating of zinc may also be conducted by conducting only the step of the first zincate treatment after the degreasing treatment, pickling treatment, and desmut treatment, that is, by applying single zincate treatment. Here, the deposition amount of zinc can be adjusted by appropriately choosing the concentration of zinc ions in the treatment solution and the time during which the dipping in the treatment solution is conducted in the first zincate treatment. It is to be noted that the deposition amount of zinc formed by the double zincate treatment or single zincate treatment is desirably formed to fall preferably in a range of 5 to 600 mg / m2, more preferably in a range of 30 to 400 mg / m2, to improve the adhesion of the metal layer 40 to be formed subsequently. By this double zincate treatment or single zincate treatment, a zinc layer may be formed between the roughened nickel layer or metal layer 40 and the base material 20. It is to be noted that the deposition amount of the zinc layer formed by the double zincate treatment or single zincate treatment can be measured by X-ray fluorescence (XRF) analysis or the like.<Examples of Zincate Treatment Conditions><<Degreasing Conditions>>Bath composition:

[0033] Sodium hydroxide 10 to 50 g / L, sodium carbonate 2 to 20 g / L

[0034] pH: 12 or higher

[0035] Bath temperature: 5° C. to 80° C.

[0036] Dipping time: 10 seconds to 3 minutes<<Pickling Conditions>>Bath composition:

[0038] Sulfuric acid 40 to 100 g / L

[0039] pH: 1.0 or lower

[0040] Bath temperature: 5° C. to 80° C.

[0041] Dipping time: 10 seconds to 3 minutes<<Desmut Conditions>>Bath composition:

[0043] 60% nitric acid 100 to 400 mL / L, ferric chloride solution 1 to 10 mL / L

[0044] pH: 1.0 or lower

[0045] Bath temperature: 5° C. to 80° C.

[0046] Dipping time: 10 seconds to 2 minutes<<First Zincate Conditions>>Bath composition:

[0048] Sodium hydroxide 100 to 200 g / L, Rochelle salt 20 to 80 g / L, zinc oxide 10 to 50 g / L, ferrous chloride 0.5 to 3.0 g / L

[0049] pH: 12 to 14

[0050] Bath temperature: 5° C. to 50° C.

[0051] Dipping time: 10 seconds to 2 minutes<<Dezincate Conditions>>Bath composition:

[0053] 60% nitric acid 100 to 400 mL / L, ferric chloride solution 1 to 10 mL / L

[0054] pH: 1.0 or lower

[0055] Bath temperature: 5° C. to 50° C.

[0056] Dipping time: 10 seconds to 2 minutes<<Second Zincate Conditions>>Bath composition:

[0058] Sodium hydroxide 100 to 200 g / L, Rochelle salt 20 to 80 g / L, zinc oxide 10 to 50 g / L, ferrous chloride 0.5 to 3.0 g / L

[0059] pH: 12 to 14

[0060] Bath temperature: 5° C. to 50° C.

[0061] Dipping time: 10 seconds to 2 minutes

[0062] As the thickness of the base material 20 for use in the nickel-plated metal material 100 of the present embodiment, a range of 0.004 to 5.0 mm is suited. If used as a current collector in a battery, for example, improvement in volumetric and gravimetric energy densities is required. Taking into consideration balancing of lightweighting and thinning with strength, the thickness of the base material 20 is hence preferably 0.004 to 0.5 mm, more preferably 0.01 to 0.3 mm, and still more preferably 0.025 to 0.1 mm. Further, in applications, for example, such as members for electronic devices, electric appliances, automobiles, and constructions, and so on, the thickness of the base material 20 is preferably 0.025 to 5.0 mm, more preferably 0.1 to 4.0 mm, still more preferably 0.2 to 3.0 mm, and even still more preferably 0.5 to 1.0 mm from the viewpoints of rigidity, strength, and workability.

[0063] For the thickness of the base material 20, thickness measurement by cross-sectional observation under an optical microscope or a scanning electron microscope (SEM) is suitably applied. Further, for the thickness before the roughened nickel plating, thickness measurement by a micrometer or the like can be applied.

[0064] As a method for determining the thickness of a diffusion alloy layer of iron and nickel when a surface diffusion-treated steel sheet is used as the base material 20, a method that reads it from a graph (see FIG. 5) obtained by scanning electron microscope-energy dispersive X-ray spectrometry (SEM-EDX) as in PCT Patent Publication No. WO2022 / 231009 can be applied. Specifically, in FIG. 5, the abscissas represent distances (μm) in a depth direction from a side of a surface layer, and the ordinates represent X-ray strengths of Ni and Fe. In the graph of FIG. 5, it is indicated that a portion, which is shallow toward a thickness direction, is high in nickel content and low in iron content. As the distance increases in the thickness direction, on the other hand, the content of iron progressively increases. Assuming that, in a portion before and after the curve of nickel and the curve of iron cross, the distance between 2 / 10 of the maximum value of nickel and 2 / 10 of the maximum value of iron corresponds to the diffusion alloy layer of iron and nickel in the present embodiment, its thickness can be read from the graph.

[0065] As the thickness of the diffusion alloy layer of iron and nickel in the surface diffusion-treated steel sheet, its thickness on at least one side is preferably 0.4 μm or greater, more preferably 0.6 μm or greater, and still more preferably 0.7 μm or greater from the viewpoint of improvement in corrosion resistance. Although there is no upper limit in particular, the thickness per side of the diffusion alloy layer of iron and nickel is preferably 7.5 μm or smaller, more preferably 6.0 μm or smaller, from the viewpoints of productivity and manufacturing cost. In the surface diffusion-treated steel sheet, it is preferred that, on its both sides, a diffusion alloy layer of iron and nickel be formed with a thickness of 0.4 μm or greater and 7.5 μm or smaller.

[0066] Further, the roughness of the base material 20 is not particularly limited, but the arithmetical mean roughness Ra by a contact probe surface roughness meter is 0.05 to 0.9 μm, more preferably 0.05 to 0.5 μm, still more preferably 0.05 to 0.3 μm, and particularly preferably 0.08 to 0.2 μm. It is to be noted that the arithmetical mean roughness Ra conforms to Japanese Industrial Standard (JIS) B 0601:2013.<Roughened Nickel Layer 50>

[0067] The roughened nickel layer 50 may be formed on an outermost surface on one side of the nickel-plated metal material 100 as depicted in FIG. 1, or may be formed on outermost surfaces on both sides although not depicted in any of the figures. The roughened nickel layer 50 is formed with nickel.

[0068] The nickel-plated metal material of the present embodiment is characterized in that a ten-point mean roughness Rzjis on the outermost surface on a side of the roughened nickel layer 50 is 1.0 μm or greater and smaller than 4.8 μm and a roughened surface area on the outermost surface on the side of the roughened nickel layer is 1.5 m2 / 1 m2 or greater. By specifying the surface shape of the roughened nickel layer 50 as described above, the nickel-plated metal material of the present embodiment can be provided as a nickel-plated metal material improved in liquid penetration resistance at an adhesion interface thereof with another member and having adhesion with another member.

[0069] It is to be noted that the term “resin” as used herein includes a thermoplastic resin, a thermosetting resin, a rubber, an elastomer, or the like. In the present disclosure, the resin also includes a material having fluidity when joined with the roughened nickel layer, such as one partly containing resin in a slurry material, such as a coating material or an active material.

[0070] Specifically, the ten-point mean roughness Rzjis is a value corresponding to the heights of protrusions on the roughened portion in the nickel-plated metal material of the present embodiment. In the present disclosure, the ten-point mean roughness Rzjis is specified in the above-described range as characteristics of the shape of the roughened portion which makes it possible to obtain preferred adhesion with another member while improving the liquid penetration resistance. By also specifying the roughened surface area to a prescribed value, preferred effects can be exhibited.

[0071] On the other hand, the roughened surface area is a surface area per unit area on the nickel-plated metal material on which the roughened nickel layer 50 is formed. Specifically, the nickel-plated metal material of the present disclosure has a surface aera increased relative to its horizontal projection area owing to the protrusions made from nickel granules formed in the roughened nickel-plating step. In other words, the roughened surface area is a value representing an area of contact between the resin and the roughened portion when another member is joined to the side of the roughened nickel layer 50 of the nickel-plated metal material 100 of the present disclosure, for example, when the resin that has been heated and melted or softened is allowed to flow. In the present disclosure, as characteristics of the shape of the roughened portion in which preferred adhesion is obtained between another member and the roughened portion while limiting the range of the above-described ten-point mean roughness Rzjis, preferred effects can be exhibited by specifying the roughened surface area to the above-described range.

[0072] Regarding reasons that the preferred effects are obtained by controlling the ten-point mean roughness Rzjis and the roughened surface area, the present inventors consider as follows. If the ten-point mean roughness Rzjis has a great value (for example, 4.8 μm or greater), the adhesion with the resin tends to be high. However, it was found that, as the height of the protrusions in the roughened portion was tall as mentioned above, the liquid penetration resistance tended to decrease when a long period of time elapsed under a high-temperature environment or a highly corrosive environment. No elucidation had been made regarding a cause for the tendency of a decrease of the liquid penetration resistance when the height of protrusions in the roughened portion was tall, the present inventors considered as follows.

[0073] When liquid penetration takes place between resin and a roughened nickel-plated material, the liquid progressively penetrates along the surfaces of protrusions in a roughened portion, so that the liquid more easily penetrates if there are groove portions and flat portions at roots in a conventional roughened nickel-plated material. It has however been considered that, if such grooves and flat portions are decreased by thickening the roots of roughening, a taller height of the roughened portion leads to longer penetration routes for the liquid and is thus advantageous.

[0074] Here, an electrical current generally tends to concentrate on protruding portions during electroplating, and this tendency is considered to be strong especially in granular nickel-forming plating for forming a roughened nickel layer because granular nickel-forming plating is plating that preferentially induces nuclei precipitation than grain growth compared with ordinary nickel plating. Accordingly, protrusions that are large in the distances from the surface of the base material to tip portions of the protrusions grow preferentially, still taller protrusions (hereinafter also referred to as “somewhat tall protrusions”) are formed, and such somewhat tall protrusions are reflected as the height of the roughened portion to the ten-point mean roughness Rzjis. It is hence considered that, in conventional roughened nickel plating, a roughened nickel-plated material of a great ten-point mean roughness Rzjis is prone to allow somewhat taller protrusions to grow more preferentially as described above, and therefore is difficult to form protrusions which are small in the distances from the surface of the base material to their tip portions (hereinafter also referred to as “somewhat short protrusions”) or is difficult to allow them to grow.

[0075] From the results of a long-term holding test under a severe environment, the present inventors scrutinized a penetration route of the liquid in the surface of the roughened portion, and appreciated that the liquid is considered to more easily penetrate along such routes that the liquid penetrates around protrusions at rather low positions thereof, in other words, in a vicinity of the surface of a base material than along routes passing through the tip portions of tall protrusions. The present inventors therefore assumed that a roughened nickel-plated material with a tall roughened portion as before was formed with many somewhat tall protrusions and included fewer somewhat short protrusions and therefore was decreased in liquid penetration resistance when a long period of time elapsed under such a severe environment as described above. It was however found that the adhesion with another member was insufficient if the height of the protrusions in the roughened portion was merely made short by simply decreasing the deposition amount for improvements in liquid penetration resistance. The present inventors then considered that, in order to maintain the adhesion with the resin despite the imposition of an upper limit on ten-point mean roughness Rzjis, there was a need to increase an area (roughened surface area) over which the roughened portion and the resin were in contact with each other. The present inventors repeated trials and errors with a view to determining a shape of a roughened portion, which made it possible to increase the roughened surface area while suppressing the height, and, as a result, have obtained a nickel-plated metal material, which assures both the adhesion with another member and improvements in liquid penetration resistance by controlling the ten-point mean roughness Rzjis and roughened surface area to the above-described ranges through control of the average current density, bath temperature, circulation of a plating solution of granular nickel-forming plating, and the circulation of the plating solution in nickel-growing plating.

[0076] Specifically, it is considered possible to form somewhat short protrusions and also microprotrusions around the roots of the microprotrusions and also to form a roughened portion having a sufficient surface area by controlling the protrusion height of the roughened portion somewhat low so as to control the ten-point mean roughness Rzjis to 4.8 μm or smaller and forming a roughened nickel layer such that its roughened surface area is 1.5 m2 / m2 or greater. It is considered that, as a result, the liquid penetration resistance can be improved by making longer the route lengths for liquid penetration significantly in the vicinity of the surface of the base material, where the liquid is easy to penetrate, and the adhesion with another member can be ensured by having a prescribed surface area or greater. It has also been found that a nickel-plated steel sheet with such somewhat short protrusions and microprotrusions formed thereon can be expected to be effective for suppressing intervals which may be formed around roots in a roughened portion depending on the temperature, rate, and the like at which the resin is allowed to flow into the roughened portion when joined with the resin.

[0077] When, in the course of the above-described trials and errors, the present inventors also compared specimens which were comparable in all of the height of a roughened portion (ten-point mean roughness Rzjis), the number of protrusions (Density Of Peaks Spd), and the surface area of the roughened portion from above by a laser microscope (Developed Interfacial Area Ratio Sdr), there were cases with different resin adhesions. The present inventors delved into those cases. As a result, a possibility was found that the roughened surface area might differ by the existence or shape of protrusions which are difficult to be reflected to the measurement by the laser microscope.

[0078] Specifically, it is possible to predict that, due to protrusions around the roots in the roughened portion and in the vicinity of the surface of the base material and differences in their shapes as illustrated in FIG. 6, there are cases of different surface areas even if the surface areas of the roughened portions from above by the laser microscope are equivalent to one another. Specifically, for example, FIG. 6(b) and FIG. 6(d) illustrate states in each of which relatively many microprotrusions are formed around the roots of the roughened portion, while FIG. 6(a) and FIG. 6(c) illustrate states in each of which relatively few microprotrusions are formed. Further, arrows in a vertical direction indicate laser applied to the surface of each specimen upon measurement of its surface texture by the laser microscope. If a laser microscope or a similar instrument, which measures the roughness of a surface by an action from a vertical direction, is used, the laser is blocked by surrounding tall protrusions and is therefore considered to be difficult to reach such microprotrusions as in FIG. 6(b). In such a case, the occurrence or non-occurrence of formation of microprotrusions or their shapes are substantially not reflected to the measurement results of the surface texture by the laser microscope, so that the height of the roughened portion (ten-point mean roughness Rzjis), the number of protrusions (Density Of Peaks Spd), and the surface area of the roughened portion from above by the laser microscope (Developed Interfacial Area Ratio Sdr) are comparable in FIG. 6(a) and FIG. 6(b).

[0079] Compared with FIGS. 6(a) and 6(c), on the other hand, FIGS. 6(b) and 6(d) indicate that the roughened portion is great in the total surface area of tall protrusions and short protrusions. It is hence understood that each roughened surface area in the present disclosure is not necessarily a parameter having a correlation with a surface texture parameter, such as the height (ten-point mean roughness Rzjis) of a roughened portion, measurable by the laser microscope. FIG. 6 depicts schematic diagrams for facilitating understanding of the roughened surface area, and the shapes of roughened portions in the present disclosure should not be limited to FIG. 6. It is to be noted that FIGS. 6(a) and 6(b) are schematic diagrams illustrating forms in which the roughened nickel layer 50 is formed on the outermost surface of the base material, and FIGS. 6(c) and 6(d) are schematic diagrams illustrating forms in which the coating layer 70 is formed on the roughened nickel layer 50.

[0080] By controlling the ten-point mean roughness Rzjis and the roughened surface area, the nickel-plated metal material of the present embodiment can be manufactured as a nickel-plated metal material having high liquid penetration resistance. The use of the nickel-plated metal material of the present embodiment can therefore reduce the risk of a liquid leakage of liquid contents even if a long period of time has elapsed with the contents sealed. In addition, the adhesion between the resin and the roughened portion can be expected to remain even after elapse of a longer period of time because the liquid penetration resistance at the adhesion interface with another member can be improved.

[0081] It is to be noted that, from the viewpoint of improving the liquid leakage resistance, the upper limit of the ten-point mean roughness Rzjis is characterized to be smaller than 4.8 μm, with 3.5 μm or smaller being preferred. On the other hand, the lower limit of the ten-point mean roughness Rzjis is 1.0 μm or greater, preferably 1.2 μm or greater, and more preferably 1.3 μm or greater from the viewpoint of increasing the adhesion with the resin.

[0082] It is to be noted that, by a known laser microscope or the like, the ten-point mean roughness Rzjis can be measured in accordance with JIS B0601:2013.

[0083] Further, no particular limitation is imposed on the upper limit of the roughened surface area, but, from the viewpoints of the resistance to breakage of protrusions formed of aggregates of granular nickel and the adhesion of the roughened portion with the base material, the upper limit of the roughened surface area is considered to be, for example, 100 m2 / 1 m2 or smaller, with 60 m2 / 1 m2 being more preferred. On the other hand, the lower limit of the roughened surface area is characterized to be 1.5 m2 / 1 m2 or greater from the viewpoint of the adhesion with the resin. From the viewpoint of increasing the adhesion with another member, the lower limit of the roughened surface area is more preferably 2.0 m2 / 1 m2 or greater, and still more preferably 5.0 m2 / 1 m2 or greater, with 5.3 m2 / 1 m2 or greater being even still more preferred.

[0084] A measuring method of the roughened surface area in the present embodiment is not a surface area measurement from above the roughened portion by a laser microscope, but is preferably a method that can measure a surface area also including the roots of the roughened portion. As the measuring method of the roughened surface area, the Brunauer-Emmett-Teller (BET) multipoint method disclosed in Japanese Patent Laid-open No. 2017-177654, etc. can be used. As the method for measuring the roughened surface area, a specific surface area can be obtained specifically, for example, by allowing a gas such as krypton to be adsorbed on the surface of the roughened portion, and determining its adsorption amount. A roughened surface area (unit: m2 / 1 m2) can then be calculated as a real surface area per unit area based on the specific surface area so obtained. It is to be noted that a detailed calculation method of the roughened surface area in the present disclosure will be mentioned subsequently herein.

[0085] It is particularly preferred for the nickel-plated metal material 100 of the present embodiment that, on the outermost surface on the side of the roughened nickel layer 50, the ten-point mean roughness Rzjis be 1.0 μm or greater and 3.5 μm or smaller and the roughened surface area is 5.3 m2 / 1 m2 or greater.

[0086] Furthermore, it is also preferred for the nickel-plated metal material of the present embodiment to specify a Mean Width Of The Profile Elements Rsm of elements in order to specify the shape of the surface formed by the protrusions formed of the granular nickel in the roughened plating layer. Specifically, the Mean Width Of The Profile Elements Rsm of elements is preferably 3.0 to 15 μm. By satisfying this, higher anchoring effect can be obtained, and a particularly high adhesion strength can be expected.

[0087] It is to be noted that, by a known laser microscope or the like, the Mean Width Of The Profile Elements Rsm of elements can be measured in accordance with JIS B0601:2013.

[0088] In the nickel-plated metal material 100 of the present embodiment, the deposition amount per side of nickel in the roughened nickel layer 50 is preferably 16 g / m2 or less, more preferably 15 g / m2 or less, and still more preferably 14 g / m2 or less from the viewpoints of productivity and manufacturing cost. From the viewpoints of corrosion resistance and obtaining the intended roughened shape, on the other hand, the deposition amount per side of nickel in the roughened nickel layer 50 is preferably 2 g / m2 or more, more preferably 3 g / m2 or more, and still more preferably 4 g / m2 or more. It is to be noted that the deposition amount of nickel in the roughened nickel layer 50 can be measured by X-ray fluorescence (XRF) analysis or the like.

[0089] As a measuring method of the nickel deposition amount in the present embodiment, the method described in PCT Patent Publication No. WO2020 / 017655 or PCT Patent Publication No. WO2021 / 020338, or the like can be appropriately adopted, for example. Specifically, the nickel deposition amount can be determined by measuring the total nickel amount with respect to the nickel-plated metal material 100 using X-ray fluorescence (XRF) analysis or the like.

[0090] A description will be made regarding the thickness of the whole nickel-plated metal material 100 in the present embodiment. Here, for the “thickness of the nickel-plated metal material 100” in the present embodiment, thickness measurement by cross-sectional observation under an SEM or thickness measurement by a micrometer can be also applied.

[0091] As the thickness of the whole nickel-plated metal material 100 in the present embodiment, a range of 0.005 to 5.01 mm is suited. If used as a current collector in a battery, for example, improvement in volumetric and gravimetric energy densities is required. Taking into consideration balancing of lightweighting and thinning with strength, the thickness of the whole nickel-plated metal material 100 is hence more preferably 0.005 to 0.51 mm, still more preferably 0.01 to 0.31 mm, and even still more preferably 0.035 to 0.11 mm. In applications as members or the like for electronic devices, electric appliances, automobiles, and constructions, for example, the thickness of the whole nickel-plated metal material 100 is preferably 0.035 to 5.01 mm, more preferably 0.11 to 4.01 mm, still more preferably 0.21 to 3.01 mm, and even still more preferably 0.51 to 1.01 mm from the viewpoints of rigidity, strength, and workability. For the thickness of the whole nickel-plated metal material 100, thickness measurement by a micrometer or cross-sectional observation under an optical microscope or a scanning electron microscope (SEM) is suitably used.

[0092] If the nickel-plated metal material 100 is used as a current collector in a battery, a case in which the thickness is greater than the upper limit of the above-described thickness range is not preferred from the viewpoints of the volumetric and gravimetric energy densities of the battery to be manufactured, especially if the aim is to thin the battery. With a thickness smaller than the lower limit of the above-described thickness range, on the other hand, it is not only difficult to have sufficient strength against effects associated with charging and discharging of the battery, but also highly possible to induce ripping, tearing, wrinkling, and / or the like during manufacture, handling, and the like of the battery. If used as members for electronic devices, electric appliances, automobiles, and constructions, a case in which the thickness is greater than the upper limit of the above-described thickness range is not preferred from the viewpoints of workability and lightweighting. On the other hand, a thickness smaller than the lower limit of the above-described thickness range is not preferred from the viewpoints of the rigidity and strength of the members so obtained.

[0093] According to the nickel-plated metal material 100 in the present embodiment, the liquid penetration resistance at the adhesion interface with another member can be improved as described above. Specifically, the ten-point mean roughness Rzjis on the outermost surface on the side of the roughened nickel layer has been specified to the prescribed value to improve the liquid penetration resistance. In addition, the nickel-plated metal material 100 in the present embodiment has the prescribed value as the roughened surface area of the roughened nickel layer, and therefore has adhesion with another member.<<Modification of First Embodiment>>

[0094] Using FIG. 2, a description will next be made regarding a nickel-plated metal material 200 as a modification of the above-mentioned first embodiment. The nickel-plated metal material 200 in the present modification is different from the above-mentioned first embodiment in that the metal layer 40 is included between the roughened nickel layer 50 and the base material 20. Accordingly, this different point will be primarily described, the other points will be identified by the same reference signs, and their description is omitted. It is to be noted that, in the present modification, the ten-point mean roughness Rzjis and roughened surface area on the outermost surface on the side of the roughened nickel layer are also 1.0 μm or greater and smaller than 4.8 μm and 1.5 m2 / 1 m2 or greater, respectively.<Metal Layer 40>

[0095] The metal layer 40 is disposed between the base material 20 and the roughened nickel layer 50 as mentioned above. As a metallic material that forms the metal layer 40, nickel or a nickel alloy is mentioned, for example. It is to be noted that the metal layer 40 is presented as a single layer in FIG. 2, but, without being limited to this configuration, may be formed of a plurality of layers.

[0096] As an example of the metal layer 40, an iron-nickel alloy layer, a nickel-phosphorus alloy layer, or a nickel layer can be exemplified. If the metal layer 40 is an iron-nickel alloy layer, the alloy phase formed of iron and nickel may be any one of a solid solution, an eutectoid / eutectic, or a compound (intermetallic compound), or two or more of these phases may coexist. Further, the metal layer 40 may contain one or more metal elements other than iron and nickel, and inevitable impurities, and may also contain metal elements such as cobalt (Co) and molybdenum (Mo) and an additive element such as boron (B).

[0097] In the nickel-plated metal material 200, the preferred range of the nickel deposition amount per side in the roughened nickel layer 50 is the same as that in the nickel-plated metal material 100.

[0098] The total nickel deposition amount per side in the metal layer 40 and the roughened nickel layer 50 in the nickel-plated metal material 200 is, as an upper limit, preferably 40 g / m2 or less, more preferably 35 g / m2 or less, and still more preferably 32 g / m2 or less from the viewpoints of productivity and manufacturing cost. In view of unavailability of corrosion resistance and the intended roughened shape, on the other hand, the lower limit is preferably 4 g / m2 or more, more preferably 5 g / m2 or more, and still more preferably 6 g / m2.

[0099] As a measuring method of the nickel deposition amount in the nickel-plated metal material 200, the method described in PCT Patent Publication No. WO2020 / 017655 or PCT Patent Publication No. WO2021 / 020338, or the like can be appropriately adopted, for example. Specifically, the total nickel deposition amount per side in the metal layer 40 and the roughened nickel layer 50 can be measured by using X-ray fluorescence (XRF) analysis or the like with respect to the nickel-plated metal material 200. As an alternative, the respective nickel amounts in the metal layer 40 and the roughened nickel layer 50 can be determined by ascertaining a boundary between the metal layer 40 and the roughened nickel layer 50 on a cross-sectional image or the like. It is to be noted that, if the base material 20 is a nickel-plated steel sheet or a surface diffusion-treated steel sheet and the metal layer 40 is nickel or a nickel alloy layer, there is a case where ascertainment of the clear boundary between the base material 20 and the metal layer 40 is difficult, and if this is the case, the total nickel deposition amount per side in the base material 20, the metal layer 40, and the roughened nickel layer50 may be controlled to the above-described range.

[0100] As an effect of the formation of the metal layer 40 on the base material 20 in the nickel-plated metal material 200, the following points can be mentioned. Specifically, the formation of the metal layer 40 allows to ensure the adhesion of the roughened nickel layer 50 with the base material 20 and to move forward with improvements in the corrosion resistance of the whole nickel-plated metal material 200.

[0101] As the thickness of the whole nickel-plated metal material 200, a range of 0.005 to 5.01 mm is suited. If used as a current collector in a battery, for example, improvements in volumetric and gravimetric energy densities are required. Taking into consideration balancing of lightweighting and thinning with strength, the thickness of the whole nickel-plated metal material 200 is hence more preferably 0.005 to 0.51 mm, still more preferably 0.01 to 0.31 mm, and even still more preferably 0.035 to 0.11 mm. In applications as members or the like for electronic devices, electric appliances, automobiles, and constructions, for example, the thickness of the whole nickel-plated metal material 200 is preferably 0.035 to 5.01 mm, more preferably 0.11 to 4.01 mm, still more preferably 0.21 to 3.01 mm, and even still more preferably 0.51 to 1.01 mm from the viewpoints of rigidity, strength, and workability. For the thickness of the whole nickel-plated metal material 200, thickness measurement by a micrometer or a cross-sectional observation under an optical microscope or scanning electron microscope (SEM) is suitably used.Second Embodiment

[0102] On the basis of FIG. 3, a nickel-plated metal material 300 in a second embodiment will next be described. The nickel-plated metal material 300 in the second embodiment is different from the above-mentioned first embodiment in that a coating layer 70 is included on the roughened nickel layer 50. Accordingly, this different point will be primarily described, the other points will be identified by the same reference signs, and their description is omitted. It is to be noted that, in the nickel-plated metal material 300, the roughened nickel layer 50 and the coating layer 70 will be collectively called a “composite roughened plating layer 60.” In the nickel-plated metal material 300, the ten-point mean roughness Rzjis and roughened surface area on the outermost surface on the side of the composite roughened plating layer 60 are 1.0 μm or greater and smaller than 4.8 μm and 1.5 m2 / 1 mm2 or greater, respectively.<Coating Layer 70>

[0103] As mentioned above, the coating layer 70 is disposed on the roughened nickel layer 50. An example of a metal material forming the coating layer 70 includes nickel alloys such as iron-nickel alloy, zinc (Zn) and zinc alloys, tin (Sn) and tin alloys, and chromium (Cr) and chromium alloys. In the present embodiment, 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 therefore included on the outermost surface on the side of the roughened nickel layer 50.

[0104] The coating layer 70 contributes to improvements in the adhesion between the roughened nickel layer 50 and the base material 20. Further, if the coating layer 70 contains zinc, this is advantageous in that a sacrificial corrosion protection property is imparted to the whole nickel-plated metal material 300. Furthermore, if the coating layer 70 contains tin, this is advantageous because if the nickel-plated metal material 300 is used, for example, as a current collector in a battery, the hydrogen overpotential can be set high, leading to suppression of hydrogen generation. In addition, if the coating layer 70 contains chromium, the corrosion resistance of the whole nickel-plated metal material 300 can be further improved, and the adhesion between the resin and the roughened portion can be improved. It is to be noted that, if the metal material, which makes up the coating layer 70, is chromium or an alloy thereof in the present disclosure, a chromate film should be included. Further, if the coating layer 70 is made of an iron-nickel alloy, the abrasion resistance of the outermost surface can be improved.

[0105] A preferred metal deposition amount in the coating layer 70 is as follows. If the coating layer 70 is zinc, the zinc deposition amount is, as an upper limit, preferably 22.0 g / m2 or less, more preferably 17.0 g / m2 or less, and still more preferably 15.0 g / m2 or less from the viewpoints of productivity and manufacturing cost and obtaining the intended roughened shape. The lower limit of the zinc deposition amount is preferably 0.5 g / m2 or more, more preferably 3.5 g / m2 or more, and still more preferably 5.0 g / m2 or more, from the viewpoints of corrosion resistance and increasing the adhesion between the base material and the roughened nickel-plating layer. If the coating layer 70 is tin, the tin deposition amount is, as an upper limit, preferably 22.0 g / m2 or less, more preferably 17.0 g / m2 or less, and still more preferably 15.0 g / m2 or less from the viewpoints of productivity and manufacturing cost and obtaining the intended roughened shape. The lower limit of the tin deposition amount is preferably 0.5 g / m2 or more, more preferably 1.5 g / m2 or more, and still more preferably 3.5 g / m2 or more, from the viewpoints of corrosion resistance and increasing the adhesion between the base material and the roughened nickel-plating layer. If the coating layer 70 is chromium, the chromium deposition amount is, as an upper limit, preferably 22.0 g / m2 or less, more preferably 17.0 g / m2 or less, and still more preferably 15.0 g / m2 or less from the viewpoints of productivity and manufacturing cost and obtaining the intended roughened shape. The lower limit of the chromium deposition amount is preferably 0.1 g / m2 or more, more preferably 0.3 g / m2 or more, still more preferably 0.5 g / m2 or more, and even still more preferably 0.8 g / m2 or more, from the viewpoints of corrosion resistance and increasing the adhesion between the base material and the roughened nickel-plating layer. The measurement of a preferred deposition amount in the coating layer 70 can be conducted by using a known method such as X-ray fluorescence (XRF) analysis or inductively coupled plasma (ICP) emission spectroscopy.

[0106] The coating layer 70 in tis embodiment can be formed on the roughened nickel layer 50 by electroplating, sputtering, vapor deposition, chemical vapor deposition, or the like of the corresponding metal. Electroplating is particularly preferred from the viewpoints of manufacturing cost and capability of uniform coating to the roughened portion.<Modification of Second Embodiment>

[0107] In FIG. 4, a nickel-plated metal material 400 is illustrated as a modification of the above-mentioned second embodiment. The nickel-plated metal material 400 in the present modification is different from the above-mentioned second embodiment in that a metal layer 40 is included between the composite roughened plating layer 60 and the base material 20. As the metal layer 40, the metal layer 40 described in the above-mentioned modification of the first embodiment can be applied. Accordingly, the metal layer in the present modification is identified by the same reference sign, and its description is omitted. It is to be noted that, in the present modification, the ten-point mean roughness Rzjis and roughened surface area on the outermost surface on the side of the roughened nickel layer are also 1.0 μm or greater and smaller than 4.8 μm and 1.5 m2 / 1 m2 or greater, respectively.<<Manufacturing Process of Nickel-Plated Metal Material>>

[0108] A description will hereinafter be made regarding a manufacturing process of a nickel-plated metal material. The manufacturing process of the present embodiment for the nickel-plated metal material is characterized by including, in a roughened nickel plating step of forming the roughened nickel layer 50, a granular nickel-forming plating step of applying roughened nickel plating using a circulating bath at an average current density of 20.0 A / dm2 or higher, a bath temperature of 50° C. or higher, and a rate that the solution circulation rate by a pump for a plating solution of, for example, 2 L volume exceeds a flow rate of 1 L / min.

[0109] As a plating bath in the granular nickel-forming plating step, the chloride ion concentration is preferably 3 to 90 g / L, more preferably 3 to 75 g / L, and still more preferably 3 to 50 g / L, the ratio of nickel ions to ammonium ions is preferably 0.05 to 0.75, more preferably 0.05 to 0.60, still more preferably 0.05 to 0.50, and even still more preferably 0.05 to 0.30 in terms of the weight ratio of “nickel ions / ammonium ions,” and the bath electrical conductivity at 50° C. is preferably 5.00 to 30.00 S / m, more preferably 5.00 to 20.00 S / m, and still more preferably 7.00 to 20.00 S / m. It is to be noted that, if the chloride ion concentration is 10 g / L or higher, a good roughened plating state is easily obtained even if the deposition amount in the roughened nickel-plating is somewhat small. Examples of a method that adjusts the chloride ion concentration, the ratio of nickel ions to ammonium ions, and the bath electrical conductivity in the plating bath to the above-described ranges include, but are not particularly limited to, a method that uses, as the plating bath, one containing nickel sulfate hexahydrate, nickel chloride hexahydrate, and ammonium sulfate, and appropriately adjusts their blending amounts.

[0110] Examples of plating conditions are as follows.[Granular Nickel-Forming Plating Conditions]Bath composition

[0112] Nickel sulfate hexahydrate: 10 to 100 g / L, nickel chloride hexahydrate: 1 to 90 g / L, ammonium sulfate: 10 to 130 g / L

[0113] pH: 4.0 to 8.0

[0114] Bath temperature: 50° C. or higher and 80° C. or lower

[0115] Average current density: 20 A / dm2 or higher and 60 A / dm2 or lower

[0116] Plating time: 5 to 150 seconds

[0117] Electricity quantity: 100 to 1500 C / dm2

[0118] Agitated / not agitated, etc.: circulating bath (a rate that the solution circulation rate by a pump for the plating solution of, for example, 2 L volume exceeds a flow rate of 1 L / min)

[0119] Under the above-described conditions, plating treatment can be conducted once or a plurality of times in the circulating bath such that the total electricity quantity is controlled as described above.

[0120] It is to be noted that the addition of ammonia to the plating bath in the granular nickel-forming plating step may be conducted by using ammonia solution, ammonium chloride, or the like in place of ammonium sulfate. The ammonium ion concentration in the plating bath is preferably 6 to 35 g / L, more preferably 10 to 35 g / L, still more preferably 16 to 35 g / L, and even still more preferably 20 to 35 g / L. Further, hydrochloric acid, sodium chloride, potassium chloride, or the like may be used to control the chloride ion concentration.

[0121] As agitation conditions for the plating bath in the granular nickel-forming plating step, a circulating bath system that circulates the plating solution by a pump is desired. Specifically, it is preferred to continuously circulate, through the plating solution of 2 L volume, the plating solution at a rate higher than 1 L / min. A higher circulation rate of the plating solution is preferred if the bath temperature is high, a higher circulation rate of the plating solution is preferred if the average current density is high, and a higher circulation rate of the plating solution is preferred if the nickel ion concentration is low. Although no particular limitation is imposed on the upper limit of the circulation rate of the plating solution, 20 L / min or lower is preferred. To control the roughened portion to an intended shape, however, there is a need to conduct plating by controlling the bath temperature, the average current density, and the circulation rate of the plating solution under adequate conditions.

[0122] Further, by increasing the average current density and bath temperature to 20 A / dm2 or higher and 50° C. or higher in the above-described plating solution, formation of more plating nuclei can be promoted. As a result, the number of protrusions in the roughened portion can be increased, thereby making it easy to control the roughened surface area to 1.5 m2 / 1 m2 or greater even if the height of the roughened portion is controlled to smaller than 4.8 μm. Furthermore, by conducting the formation of more plating nuclei in the granular nickel-forming plating step, the plating nuclei can be used as plating nuclei when roughening is effected to the roots of the protrusions in the nickel-growing plating step to be mentioned below. The upper limit of the average current density is preferably 50 A / dm2 or lower from the viewpoint of increasing the adhesion between the base material and the roughened nickel-plating layer. Moreover, the continuous circulation of the plating solution at a rate higher than 1 L / min through the plating solution of, for example, 2 L volume can promote the formation of a sufficient number of short protrusions by suppressing preferential growth of some of the protrusions and decreasing differences in growth among the individual protrusions when allowing the formed plating nuclei to grow and also allowing new plating nuclei to precipitate over the plating nuclei so formed and to grow as protrusions. As a result, it is made possible to easily control the roughened surface area to 1.5 mm2 / 1 m2 or greater while controlling the ten-point mean roughness Rzjis to smaller than 4.8 μm. Still moreover, it is also made possible to easily control the Mean Width Of The Profile Elements Rsm of elements to 3.0 to 15 μm. Even moreover, it is also considered possible to promote the formation of plating nuclei as nuclei for microprotrusions around the roots of somewhat short protrusions by conducting the circulation of the plating solution in the above-described ranges of the average current density and bath temperature. A roughened portion of an intended shape can be formed by conducting plating while controlling the bath temperature, average current density, and circulation rate under adequate conditions as described above.

[0123] The upper limit of the nickel deposition amount in the granular nickel-forming plating step is preferably 16 g / m2 or less, more preferably 15 g / m2 or less, and still more preferably 14 g / m2 or less from the viewpoints of improvements in liquid penetration resistance. On the other hand, the lower limit is preferably 1.8 g / m2 or more, more preferably 2.8 g / m2 or more, and still more preferably 3.8 g / m2 or more from the viewpoint of the adhesion with another member. The height of the roughened portion can be controlled by controlling the average current density, the bath temperature, and the circulation of the plating solution, and further controlling the nickel deposition amount to 1.8 to 16 g / m2, as described above in the granular nickel-forming plating. As a result, Rzjis can be controlled to 1.0 μm or greater and smaller than 4.8 μm in the nickel-plated metal sheet after going through the below-mentioned nickel-growing plating step or coating plating step.[Nickel-Growing Plating Conditions]Bath composition:

[0125] Nickel sulfate hexahydrate 200 to 350 g / L, nickel chloride hexahydrate 20 to 60 g / L, boric acid 10 to 50 g / L

[0126] pH: 3.0 to 5.0

[0127] Bath temperature: 40° C. to 70° C.

[0128] Current density: 5 to 30 A / dm2

[0129] Agitated / not agitated, etc.: circulating bath (a rate that the solution circulation rate by a pump for the plating solution of, for example, 2 L volume exceeds a flow rate of 1 L / min)

[0130] The agitation conditions of the plating bath in the nickel-growing plating step can control the roughened surface area of the nickel-plated metal material so obtained to a preferred value by using the plating solution as the circulating bath that the plating solution is circulated by the pump.

[0131] The nickel-growing plating is a step, a primary objective of which is to ensure the adhesion between the roughened nickel layer and the base material by allowing individual nickel granules to grow further in the protrusions formed of aggregates of nickel granules which have been formed in the above-described granular nickel-forming plating step. In the present disclosure, it is considered possible, in addition to the primary objective, to promote the formation of the microprotrusions by conducting the agitation at a prescribed liquid circulation or higher in this nickel-growing plating step. By continuously conducting the circulation of the plating solution at a rate higher than 1 L / min through the plating solution of, for example, 2 L volume, the plating nuclei as the nuclei for the microprotrusions formed by the above-describe granular nickel-forming plating are allowed to grow and to form microprotrusions by this growing plating, and, as a result, the surface area can be increased.

[0132] The upper limit of the nickel deposition amount in the nickel-growing plating step is preferably 7.0 g / m2 or less, more preferably 6.0 g / m2 or less, and still more preferably 5.0 g / m2 or less from the viewpoints of the adhesion to another member, productivity, and manufacturing cost. On the other hand, the lower limit is preferably 0.2 g / m2 or more, more preferably 0.4 g / m2 or more, from the viewpoint of the adhesion of the plating layer with the base material. It is to be noted that the above-described nickel-growing plating step is not an essential step.

[0133] It is preferred that, by going through the above-described steps, the ten-point mean roughness Rzjis fall to 1.0 μm or greater and smaller than 4.8 μm on the outermost surface on the side of the roughened nickel layer of the nickel-plated metal material so obtained and the roughened surface area on the outermost surface on the side of the above-described roughened nickel layer fall to 1.5 m2 / 1 m2 or greater.

[0134] It is also preferred that, on the outermost surface on the side of the roughened nickel layer of the nickel-plated metal material so obtained, the Mean Width Of The Profile Elements Rsm of elements be 3.0 to 15 μm.

[0135] The manufacturing process of the nickel-plated metal material depicted in FIG. 3 or 4 may further include a step of forming the coating layer 70 (coating-layer forming step). Specifically, the coating-layer forming step is conducted at least after the above-mentioned granular nickel-forming plating step. As an alternative, the coating-layer forming step may also be conducted by following the granular nickel-forming plating step and the nickel-growing plating step.

[0136] If the coating-layer forming step is conducted by zinc plating, examples of bath composition and plating conditions for the zinc plating are as follows.

[0137] Zinc sulfate heptahydrate: 100 to 400 g / L

[0138] Ammonium sulfate: 10 to 100 g / L

[0139] Bath temperature: 30° C. to 70° C.

[0140] pH: 1.0 to 5.0

[0141] Agitated / not agitated, etc.: circulating bath (a rate that the solution circulation rate by a pump for the plating solution of, for example, 2 L volume exceeds a flow rate of 1 L / min)

[0142] Current density: 2.5 to 60 A / dm2

[0143] As described above, it is possible to use, as a plating bath for use in zinc plating, a bath that uses a sulfate salt as a supply source for zinc ions and is appropriately added with a conductive adjuvant salt such as ammonium sulfate or sulfuric acid to increase the electrical conductivity of the plating solution. In addition, an additive such as a known gloss agent may be added to the plating bath to form gloss zinc plating or semi-gloss zinc plating.

[0144] If the coating-layer forming step is conducted by zinc plating, the zinc deposition amount to be formed by the zinc plating is preferably 0.5 to 22.0 g / m2. The measurement of the zinc deposition amount can be conducted by using a known method such as X-ray fluorescence (XRF) analysis or ICP emission spectroscopy.

[0145] If the coating-layer forming step is conducted by tin plating, examples of bath composition and plating conditions for the tin plating are as follows.

[0146] Stannous sulfate: 30 to 80 g / L

[0147] Phenolsulfonic acid: 30 to 60 g / L

[0148] Ethoxylated a-naphthol: 2 to 6 g / L

[0149] Ethoxylated a-naphtholsulfonic acid: 4 to 12 g / L

[0150] pH: 0.1 to 2.0

[0151] Bath temperature: 20° C. to 55° C.

[0152] Agitated / not agitated, etc.: circulating bath (a rate that the solution circulation rate by a pump for the plating solution of, for example, 2 L volume exceeds a flow rate of 1 L / min)

[0153] Current density: 2.5 to 10 A / dm2

[0154] If the coating-layer forming step is conducted by tin plating, the tin deposition amount to be formed by the tin plating is preferably 0.5 to 22.0 g / m2. The measurement of the tin deposition amount can be conducted by using a known method such as X-ray fluorescence (XRF) analysis or ICP emission spectroscopy.

[0155] If the coating-layer forming step is conducted by chromium plating, examples of bath composition and plating conditions for the chromium plating are as follows.

[0156] Chromium(VI) oxide: 30 to 200 g / L

[0157] Sodium fluoride: 1 to 10 g / L

[0158] pH: 1.0 or lower

[0159] Bath temperature: 35° C. to 65° C.

[0160] Agitated / not agitated, etc.: circulating bath (a rate that the solution circulation rate by a pump for the plating solution of, for example, 2 L volume exceeds a flow rate of 1 L / min)

[0161] Current density: 5 to 50 A / dm2

[0162] If the coating-layer forming step is conducted by chromium plating, the chromium deposition amount to be formed by the chromium plating is preferably 0.1 to 22.0 g / m2. The measurement of the chromium deposition amount can be conducted by using a known method such as X-ray fluorescence (XRF) analysis or ICP emission spectroscopy.

[0163] If the coating-layer forming step is conducted by iron-nickel alloy plating, examples of a bath composition and plating conditions for the iron-nickel alloy plating are as follows.[Examples of Iron-Nickel Alloy Plating Bath and Plating Conditions]Bath composition:

[0165] Nickel sulfate hexahydrate: 150 to 250 g / L

[0166] Iron sulfate heptahydrate: 5 to 100 g / L

[0167] Nickel chloride hexahydrate: 20 to 50 g / L

[0168] Boric acid: 20 to 50 g / L

[0169] Sodium citrate (or trisodium citrate): 1 to 15 g / L Saccharin sodium: 1 to 10 g / L

[0170] Temperature: 25° C. to 70° C.

[0171] pH: 2 to 4

[0172] Agitated / not agitated, etc.: circulating bath (a rate that the solution circulation rate by a pump for the plating solution of, for example, 2 L volume exceeds a flow rate of 1 L / min)

[0173] Current density: 5 to 40 A / dm2

[0174] If the coating-layer forming step is conducted by iron-nickel alloy plating, the total deposition amount of iron and nickel contained in the iron-nickel alloy layer is preferably 0.2 to 7.0 g / m2. The total deposition amount of iron and nickel can be calculated by determining a weight difference before and after the iron-nickel alloy plating. Further, if the coating layer is the iron-nickel alloy layer, the total nickel deposition amount contained per side in the base material and composite roughened layer in the nickel-plated metal material is preferably 5 to 40 g / m2. Furthermore, if the metal layer 40 is included and nickel is contained in the metal layer 40, the total nickel deposition amount contained per side in the base material, the metal layer 40, and the composite roughened layer may also be controlled to the above-described range.

[0175] The above-described formation of the coating layer 70 is a step, a primary objective of which is to ensure the adhesion between the roughened nickel layer and the base material and to impart additional effects by the pieces of metal forming the coating layer. In the present disclosure, it is possible, in addition to the primary objective, to also cover the nuclei of the microprotrusions, which have been formed by the above-described granular nickel-forming plating, with the coating metal layer and to increase the surface area by conducting the agitation at a prescribed liquid circulation or higher in this coating plating step.

[0176] The manufacturing process of the nickel-plated metal material depicted in FIG. 2 or FIG. 4 may further include a step of forming the metal layer 40 (metal-layer forming step). Specifically, the metal-layer forming step is conducted on the base material 20 before the above-described 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, or a nickel layer is mentioned.

[0177] If the iron-nickel alloy layer is formed by the metal-layer forming step, it may be formed by applying alloy electrolytic plating to at least one side of the base material 20 using an alloy plating bath containing iron ions and nickel ions. In this case too, known alloy plating conditions can be appropriately applied.

[0178] If the nickel-phosphorus alloy layer is formed by the metal-layer forming step, a nickel-phosphorus alloy layer may be formed by applying alloy electrolytic plating to at least one side of the base material 20 using an alloy plating bath containing nickel ions and phosphorus ions.

[0179] If the nickel layer is formed by the metal-layer forming step, the nickel layer can be formed on at least one side of the base material 20, for example, in a known Watts bath or the like.

[0180] The metal-layer forming step is not needed to be a single step, and may be conducted by appropriately combining a plurality of steps. For example, the nickel-phosphorus alloy layer and the nickel layer may be both formed by the metal-layer forming step.

[0181] If a surface diffusion-treated steel sheet is used as the base material 20, an iron-nickel alloy layer can be formed through thermal diffusion by applying heat treatment after forming a nickel-plating layer by electroplating.

[0182] Specifically, continuous annealing or batch annealing (box annealing) can be conducted. As examples of a temperature and time in a case of continuous annealing treatment, the continuous annealing treatment can be conducted at 650° C. to 950° C. for a soaking time in a range of 15 to 150 seconds. As examples of a temperature and time in a case of batch annealing (box annealing) treatment, the batch annealing (box annealing) treatment can be conducted at 450° C. to 690° C., for a soaking time in a range of 1.5 to 20 hours, and for a total time of heatup, soaking, and cooling time in a range of 4 to 80 hours. Rolling may be applied after the above-described heat treatment. Further, heat treatment may be conducted again after the rolling.EXAMPLES

[0183] The present invention will hereinafter be described more specifically by giving examples. A description will first be made regarding measuring methods in the examples.[Measuring Methods of Surface Texture Parameters]

[0184] Surface texture parameters on the surface of the roughened nickel layer 50, such as the ten-point mean roughness Rzjis and the Mean Width Of The Profile Elements Rsm of elements were measured by using a laser microscope (manufactured by Olympus Corporation, 3D measuring laser microscope “LEXT OLS5000”). In the measurements of the ten-point mean roughness Rzjis and the Mean Width Of The Profile Elements Rsm of elements, the surface of the roughened nickel layer 50 was measured with a 50× objective lens (lens name: “MPLAPON50XLEXT”) following JIS B0601:2013, whereby an analysis image of 257 μm×257 μm visual field was acquired. Using an analysis application, denoising and an inclination correction as automated correction processing were then conducted on the analysis image so acquired. Subsequently, the ten-point mean roughness Rzjis and the Mean Width Of The Profile Elements Rsm of elements were calculated by line roughness measurement. It is to be noted that the analysis was conducted under no conditions without setting filter criteria (tilt correction λf, low-pass filter λs, high-pass filter λc) at the time of the analysis. Mean values upon 15 measurements under the above-described conditions were calculated.[Measuring Method of Roughened Surface Area]

[0185] The roughened surface area at the surface of the roughened nickel layer 50 was measured by a constant volume method that used a fully automatic gas adsorption amount measuring instrument. As the fully automatic gas adsorption amount measuring instrument, a model “AS1-MP” manufactured by Quantachrome Instruments, Inc. was used. Further, as an adsorbate gas, krypton gas was used. A desired number of measurement specimens were cut in a size of 5 mm×50 mm, and the overall specimen mass was measured. The measurement specimens were placed in a measurement cell, and were vacuum-deaerated at room temperature for 2 hours or longer. The specific surface area was measured by the BET multipoint method under liquid nitrogen of −195.8° C., and on the basis of the specific surface area so obtained, the roughened surface area was calculated.

[0186] Specifically, if measurement specimens included a roughened nickel layer on both sides thereof, the value of the specific surface area was multiplied with the specimen mass, followed by a division with the number of the measured specimens. The resulting value was then halved, followed by a division with a horizontal projection area (5 mm×50 mm) per specimen to determine the roughened surface area.

[0187] If measurement specimens included a roughened nickel layer on one side thereof, the value of the specific surface area was first multiplied with the specimen mass, followed by a division with the number of the measured specimens to determine the overall surface area per specimen. Here, because of a need to subtract the surface area of untreated surfaces, a reference base material was provided. After its specific surface area was calculated in a similar manner, the specific surface area was multiplied with the specimen mass, followed by a division with the number of the measured specimens. The value of ½ of the quotient was then calculated to determine the surface area per side of the reference base material. From the overall surface area per specimen, the surface area per side of the reference base material was then subtracted, followed by a division with the horizontal projection area (5 mm×50 mm) per specimen to determine the roughened surface area. It is to be noted that, as the reference base material, one prepared by applying undercoat nickel plating to the base material in Example 1 to be mentioned later was used.

[0188] It is to be noted that, in the measurement of individual specimens, the measurement was made using 20 to 60 specimens to improve the accuracy of the test, and, especially with reference specimens of a small surface area, 60 of them were measured. In addition, the measurement specimens in the following examples and comparative examples were sufficiently small in thickness, so that effects of their end surfaces should be negligible.[Resin Adhesion Test (Peel Test) and Evaluation]

[0189] As an evaluation of the adhesion with another member, the adhesion with resin was evaluated. Specifically, for the evaluation of the resin adhesion, a peel test was conducted to obtain a peel strength. A description will hereinafter be made regarding its measuring method.

[0190] A nickel-plated metal material (30 mm×100 mm), which was obtained in each example or comparative example and had a roughened nickel layer formed on at least one side thereof, was provided. A polypropylene film of 140 μm thickness (25 mm×100 mm) was overlaid on the side of a surface to be evaluated (the side of the roughened nickel layer) with their one end portions trued up, and was heat-sealed in a range of 25 mm×25 mm at an overlayed portion thereof by a heat sealer (manufactured by TESTER SANGYO CO., LTD., “TP-701-B”), whereby a specimen was obtained. The heat-sealing temperature, in other words, the setting temperature of the heat sealer was set to 156° C., and the pressure at the time of the heat sealing was set to 0.1 MPa. Under a condition that the time (hereinafter also referred to as “press time”), for which pressing was conducted at the above-described setting temperature under the above-described pressure, was 5 seconds, a specimen was prepared by the heat sealer. By a tensile testing machine (manufactured by Orientec Co., Ltd., “RTC-121OA”), each specimen so prepared was fixed on a jig with the resin film folded back at the heat-sealed end as a starting point in 180° direction relative to the nickel-plated metal material, and was pulled at a rate of 50 mm / min, whereby its 180° peel strength was obtained.

[0191] EXCELLENT: the value of 180° peel strength was 13N / 25 mm or higher

[0192] GOOD: the value of 180° peel strength was 5N / 25 mm or higher and lower than 13N / 25 mm

[0193] POOR: the value of 180° peel strength was lower than 5N / 25 mm[Liquid Penetrability Evaluation when Joined with Polypropylene (PP) Resin]

[0194] The nickel-plated metal materials obtained in the examples and comparative examples were cut to prepare specimens for the liquid penetrability evaluation, which had dimensions of 90 mm wide and 140 mm long. On each specimen for liquid penetrability evaluation so obtained, a marker sheet for an aqueous alkali solution (manufactured by Macherey-nagel GmbH & Co., KG, “pH TEST PAPER”), which had dimensions of 7 mm wide and 7 mm long, was then placed, and a polypropylene resin film (manufactured by Mitsubishi Chemical Corporation, “MODIC” (trade name) / polypropylene resin two-layer film (a side of “MODIC” (trade name) was used as an adhesive layer, that is, as a joining surface) of 110 mm wide, 160 mm long, and 60 μm thick was placed over the marker sheet. With the marker sheet for the aqueous alkali solution sandwiched, heat sealing was conducted over the entire width and length using laminating rolls under conditions of a temperature: 150° C., a pressure: 0.6 MPa (checked with a pressure-sensitive paper), and a roll passing rate: 70 mm / second. Thereafter, the resulting laminate was cut into a circle centering around the marker and having a diameter of 30 mm, whereby a measurement specimen with the marker sheet for the aqueous alkali solution sealed therein was obtained. The measurement specimen so obtained was dipped in a 30 g / L aqueous solution of “Formula 618-TK-2” (manufactured by Nippon Quaker Chemical Ltd.) as an aqueous alkali solution with the solution temperature maintained at 80° C., and observation was made for the extent of any discoloration of the marker sheet for the aqueous alkali solution in the measurement specimen over the time elapsed after the dipping (discoloration by penetration of the aqueous alkali solution into the measurement specimen), and the extent of discoloration was evaluated on the following criteria.

[0195] EXCELLENT: discoloration was not observed on the marker sheet for the aqueous alkali solution even after 240 hours.

[0196] GOOD: discoloration was not observed on the marker sheet for the aqueous alkali solution 48 hours later, but was observed 240 hours later.

[0197] MODERATE: discoloration was not observed on the marker sheet for the aqueous alkali solution 36 hours later, but was observed 48 hours later.

[0198] POOR: discoloration was observed on the marker sheet for the aqueous alkali solution 30 hours later.

[0199] It is to be noted that the liquid penetrability evaluation in the present disclosure is what is called an accelerated test using conditions with stronger effects on an interface. Therefore, it is a test to dip each specimen in the strongly corrosive aqueous alkali solution at a high temperature for a long time, and is not one directly reflecting conditions when applied to real products.Example 1

[0200] A cold-rolled steel sheet (60 μm thickness) of low-carbon aluminum-killed steel having a chemical composition presented below was first provided.

[0201] 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

[0202] After electrolytic degreasing and pickling by dipping in sulfuric acid were next carried out on the above-described cold-rolled steel sheet, a nickel layer was formed to a deposition amount of 8.9 g / m2 by known nickel plating. Subsequently, thermal diffusion treatment was conducted by a continuous annealing step, and quality control rolling was applied, whereby an iron-nickel alloy layer of 2.2 μm thickness was formed on both sides. The resulting surface diffusion-treated steel sheet was provided as a base material 20.

[0203] On the surface diffusion-treated steel sheet as the base material 20, strike nickel-plating treatment was conducted under the strike nickel-plating conditions presented below, followed by formation of an undercoat nickel layer under undercoat nickel-plating conditions.<Strike Nickel-Plating Conditions>Bath composition:

[0205] Nickel sulfate hexahydrate 250 g / L, sulfuric acid 50 g / L

[0206] pH: lower than 1.0

[0207] Bath temperature: 60° C.

[0208] Current density: 30 A / dm2

[0209] Electrolysis time: 5 seconds<Undercoat Nickel-Plating Conditions>Bath composition:

[0211] Nickel sulfate hexahydrate 250 g / L, nickel chloride hexahydrate 45 g / L, boric acid: 30 g / L

[0212] pH: 4.0 to 5.0

[0213] Bath temperature: 60° C.

[0214] Current density: 10 A / dm2

[0215] Electrolysis time: 15.1 seconds

[0216] On the undercoat nickel layer on one side, a roughened nickel layer was next formed under the following conditions. It is to be noted that the roughened nickel layer was formed by applying the following granular nickel-forming plating and nickel-growing plating.<Granular Nickel-Forming Plating Conditions>Concentration of nickel sulfate hexahydrate in plating bath: 10 g / L

[0218] Concentration of nickel chloride hexahydrate in plating bath: 10 g / L

[0219] Concentration of chloride ions in plating bath: 16.6 g / L

[0220] Ratio of nickel ions to ammonium ions in plating bath: nickel ions / ammonium ions (weight ratio)=0.2

[0221] pH: 6.0

[0222] Bath temperature: 52° C.

[0223] Average current density: 21.0 A / dm2

[0224] Electrolysis time: 15.0 seconds

[0225] Agitation method: circulation agitation (agitation flow rate: low)

[0226] Electrical conductivity of the plating bath (bath electrical conductivity): 13.8 S / m (with a proviso in the case of bath temperature 50° C. and pH=6.0)

[0227] It is to be noted that, in the examples and comparative examples, agitation flow rates in circulation agitation were described according to the following criteria.

[0228] High agitation flow rate: the solution circulation rate by a pump for the plating solution of 2 L volume was 3 L / min or higher and lower than 4 L / min

[0229] Medium agitation flow rate: the solution circulation rate by the pump for the plating solution of 2 L volume was 2 L / min or higher and lower than 3 L / min

[0230] Low agitation flow rate: the solution circulation rate by the pump for the plating solution of 2 L volume was 1 L / min or higher and lower than 2 L / min

[0231] No agitation: the solution circulation rate by the pump for the plating solution of 2 L volume was lower than 1 L / min<Nickel-Growing Plating Conditions>Bath composition:

[0233] Nickel sulfate hexahydrate 250 g / L, nickel chloride hexahydrate 45 g / L, boric acid: 30 g / L

[0234] pH: 4.0 to 5.0

[0235] Bath temperature: 60° C.

[0236] Current density: 10 A / dm2

[0237] Electrolysis time: 1.4 seconds

[0238] Agitation method: circulation agitation (agitation flow rate: medium)

[0239] In the nickel-plated metal material thus obtained, values of the ten-point mean roughness Rzjis and the Mean Width Of The Profile Elements Rsm of elements on the outermost surface of the above-described roughened nickel layer are presented in Table 5. It is to be noted that these surface texture parameters were measured by using the laser microscope (manufactured by Olympus Corporation, 3D measuring laser microscope “LEXT OLS5000”). In the measurements of the ten-point mean roughness Rzjis and the Mean Width Of The Profile Elements Rsm of elements, the outermost surface of the roughened nickel layer was measured with the 50× objective lens, and the analysis was conducted under no conditions without setting any of filter criteria at the time of the analysis. Measurement of the roughened surface area, a 180° peel strength test and the evaluation, and the liquid penetrability evaluation were also conducted.

[0240] It is to be noted that the nickel deposition amount in the roughened nickel layer and the nickel-plated metal material was measured by using the X-ray fluorescence spectrometer (manufactured by Rigaku Corporation, “ZSX100e”), and the value so obtained is presented in Table 1. It is also to be noted that the specific measuring method is similar to the method described in PCT Patent Publication No. WO2020 / 017655, and therefore, its detailed description is omitted herein. All the nickel deposition amounts presented in Tables 1 to 4 are values per side.Example 2

[0241] The conditions for undercoat nickel plating, granular nickel-forming plating, and nickel-growing plating were set as presented in Table 1 and Table 2. Otherwise, the procedures of Example 1 were followed. The results so obtained are presented in Table 1, Table 2, and Table 5.Example 3

[0242] As a base material 20, a steel sheet having no iron-nickel alloy layer was used. Specifically, one obtained by carrying out electrolytic degreasing and pickling by dipping in sulfuric acid on the cold-rolled steel sheet described in Example 1 was used as a base material 20. Otherwise, the procedures of Example 1 were followed. The results so obtained are presented in Table 1, Table 2, and Table 5.Examples 4 to 17

[0243] Conditions for a base material, undercoat nickel plating, granular nickel-forming plating, and nickel-growing plating were set as in Table 1 and Table 2. Otherwise, the procedures of Example 1 were followed. The results so obtained are presented in Table 5.Example 18

[0244] As a base material 20, a similar metal base material to that in Example 3 was first provided, and similar electrolytic degreasing and pickling by dipping in sulfuric acid to that in Example 3 were then carried out. Subsequently, an undercoat nickel-plating layer to be located between the base material and a roughened nickel layer was formed under similar conditions to those in Example 1.

[0245] Under the following conditions, a composite roughened plating layer was next formed on the undercoat nickel layer on one side. It is to be noted that the composite roughened plating layer was formed by the following granular nickel-forming plating step of forming a roughened nickel layer and coating layer forming step of forming a coating layer. The coating treatment step was conducted by zinc plating.<Granular Nickel-Forming Plating Conditions>Concentration of nickel sulfate hexahydrate in plating bath: 10 g / L

[0247] Concentration of nickel chloride hexahydrate in plating bath: 10 g / L

[0248] Concentration of chloride ions in plating bath: 16.6 g / L

[0249] Ratio of nickel ions to ammonium ions in plating bath: nickel ions / ammonium ions (weight ratio)=0.2

[0250] pH: 6.0

[0251] Bath temperature: 55° C.

[0252] Average current density: 23.3 A / dm2

[0253] Electrolysis time: 20.0 seconds

[0254] Agitation method: circulation agitation (agitation flow rate: medium)

[0255] Electrical conductivity of the plating bath (bath electrical conductivity): 13.8 S / m (with a proviso in the case of bath temperature 50° C. and pH=6.0)<Coating Layer Forming Conditions>Bath composition:

[0257] Zinc sulfate heptahydrate: 220 g / L, ammonium sulfate 30 g / L

[0258] pH: 1.5 to 2.5 (An adjustment with sulfuric acid was conducted.)

[0259] Bath temperature: 55° C.

[0260] Current density: 10 A / dm2

[0261] Electrolysis time: 9.3 seconds

[0262] Under the above conditions, a coating zinc layer was obtained.

[0263] Agitation method: circulation agitation (agitation flow rate: high)

[0264] Values of the ten-point mean roughness Rzjis and the Mean Width Of The Profile Elements Rsm of elements on the outermost surface on the side of the composite roughened plating layer of the nickel-plated metal material were measured as in Example 1, and are presented in Table 5. It is to be noted that these surface texture parameters were measured by using the laser microscope (manufactured by Olympus Corporation, 3D measuring laser microscope “LEXT OLS5000”). In the measurements of the ten-point mean roughness Rzjis and the Mean Width Of The Profile Elements Rsm of elements, the outermost surface on the side of the composite roughened plating layer was measured with the 50× objective lens, and the analysis was conducted without setting any of filter criteria at the time of the analysis. The roughened surface area, the 180° peel strength test, and the liquid penetrability evaluation were also conducted.

[0265] It is to be noted that, concerning the nickel deposition amount in the composite roughened plating layer, its measurement was conducted by using the X-ray fluorescence spectrometer (manufactured by Rigaku Corporation, “ZSX100e”). It is to be noted that the specific measuring method is similar to the method described in PCT Patent Publication No. WO2020 / 017655, and therefore, its detailed description is omitted herein. Also concerning the zinc deposition amount of the coating zinc layer, its measurement was conducted by using the X-ray fluorescence spectrometer. Their values so obtained are presented in Table 3, Table 4, and Table 6.Example 19

[0266] Conditions for a base material, undercoat nickel plating, granular nickel-forming plating, and zinc plating were set as in Table 3 and Table 4. Otherwise, the procedures of Example 18 were followed. The results so obtained are presented in Table 6.Example 20

[0267] A stainless steel sheet (SUS430) of 50 μm thickness having a chemical composition presented below was provided as a base material 20.

[0268] C: 0.12 wt %, Cr: 16 to 18 wt %, Si: 0.75 wt %, Mn: 1.00 wt % or lower, P: 0.04 wt % or lower, S: 0.03 wt % or lower, Balance: inevitable impurities

[0269] On the base material, strike nickel-plating treatment was conducted under the strike nickel-plating conditions presented in Example 1, followed by undercoat nickel plating, granular nickel-forming plating, and nickel-growing plating under the conditions of Table 7 and Table 8. Otherwise, the procedures of Example 1 were followed. The results so obtained are presented in Table 9.Example 21

[0270] A 40 μm-thick, rolled aluminum sheet (hereinafter also called an “aluminum sheet”) of an aluminum alloy (A8079) having a chemical composition presented below was provided as a base material 20.

[0271] Si: 0.05 to 0.30 wt %, Fe: 0.7 to 1.3 wt %, Cu: 0.05 wt % or lower, Zn: 0.10 wt % or lower, Balance: inevitable impurities

[0272] With respect to the above-described aluminum sheet, substitution plating of zinc was next conducted on a surface of the aluminum sheet under zincate treatment conditions presented below. Subsequently, undercoat nickel plating, granular nickel-forming plating, and nickel-growing plating were conducted by setting their conditions as presented in Table 7 and Table 8. The results so obtained are presented in Table 9.<Zincate Treatment Conditions><<Degreasing Conditions>>Bath composition:

[0274] Sodium hydroxide 22.5 g / L, sodium carbonate 4.5 g / L

[0275] pH: 12 or higher

[0276] Bath temperature: 25° C.

[0277] Dipping time: 2 minutes<<Pickling Conditions>>Bath composition:

[0279] Sulfuric acid 70 g / L

[0280] pH: 1.0 or lower

[0281] Bath temperature: 25° C.

[0282] Dipping time: 2 minutes<<Desmut Conditions>>Bath composition:

[0284] 60% nitric acid 250 mL / L, ferric chloride solution 4 mL / L

[0285] pH: 1.0 or lower

[0286] Bath temperature: 25° C.

[0287] Dipping time: 30 seconds<<First Zincate Conditions>>Bath composition:

[0289] Sodium hydroxide 150 g / L, Rochelle salt 50 g / L, zinc oxide 25 g / L, ferrous chloride 1.5 g / L

[0290] pH: 12 to 14

[0291] Bath temperature: 25° C.

[0292] Dipping time: 50 seconds<<Dezincate Conditions>>Bath composition:

[0294] 60% nitric acid 250 mL / L, ferric chloride solution 4 mL / L

[0295] pH: 1.0 or lower

[0296] Bath temperature: 25° C.

[0297] Dipping time: 30 seconds<<Second Zincate Conditions>>Bath composition:

[0299] Sodium hydroxide 150 g / L, Rochelle salt 50 g / L, zinc oxide 25 g / L, ferrous chloride 1.5 g / L

[0300] pH: 12 to 14

[0301] Bath temperature: 25° C.

[0302] Dipping time: 50 seconds

[0303] As a base material 20, a similar metal base material to that in Example 3 was first provided, and electrolytic degreasing and pickling by dipping in sulfuric acid were carried out as in Example 3. Subsequently, an undercoat nickel layer to be located between the base material and a roughened nickel layer was formed under similar conditions to those in Example 1.

[0304] Under the following conditions, a composite roughened plating layer was next formed on the undercoat nickel layer on one side. It is to be noted that the composite roughened plating layer was formed by the following granular nickel-forming plating step of forming a roughened nickel layer and coating layer forming step of forming a coating layer. The coating treatment step was conducted by tin plating.<Granular Nickel-Forming Plating Conditions>Concentration of nickel sulfate hexahydrate in plating bath: 10 g / L

[0306] Concentration of nickel chloride hexahydrate in plating bath: 10 g / L

[0307] Concentration of chloride ions in plating bath: 16.6 g / L

[0308] Ratio of nickel ions to ammonium ions in plating bath: nickel ions / ammonium ions (weight ratio)=0.2

[0309] pH: 6.0

[0310] Bath temperature: 50° C.

[0311] Average current density: 20.0 A / dm2

[0312] Electrolysis time: 15.0 seconds

[0313] Agitation method: circulation agitation (agitation flow rate: medium)

[0314] Electrical conductivity of the plating bath (bath electrical conductivity): 13.8 S / m (with a proviso in the case of bath temperature 50° C. and pH=6.0)<Coating Layer Forming Conditions>Stannous sulfate: 80 g / L

[0316] Phenolsulfonic acid: 60 g / L

[0317] Ethoxylated a-naphthol: 3 g / L

[0318] Ethoxylated a-naphtholsulfonic acid: 3 g / L

[0319] pH: 0.5 to 1.5 (An adjustment with sulfuric acid was conducted.)

[0320] Bath temperature: 40° C.

[0321] Current density: 5.0 A / dm2

[0322] Electrolysis time: 1.2 seconds

[0323] Agitation method: circulation agitation (agitation flow rate: low)

[0324] Under the above conditions, a coating tin layer was obtained.

[0325] Values of the ten-point mean roughness Rzjis and the Mean Width Of The Profile Elements Rsm of elements on the outermost surface on the side of the composite roughened plating layer of the nickel-plated metal material were measured as in Example 1, and are presented in Table 12. It is to be noted that these surface texture parameters were measured by using the laser microscope (manufactured by Olympus Corporation, 3D measuring laser microscope “LEXT OLS5000”). In the measurements of the ten-point mean roughness Rzjis and the Mean Width Of The Profile Elements Rsm of elements, the outermost surface on the side of the composite roughened plating layer was measured with the 50× objective lens, and the analysis was conducted without setting any of filter criteria at the time of the analysis. The roughened surface area, the 180° peel strength test, and the liquid penetrability evaluation were also conducted.

[0326] It is to be noted that, concerning the nickel deposition amount in the composite roughened plating layer, its measurement was conducted by using the X-ray fluorescence spectrometer (manufactured by Rigaku Corporation, “ZSX100e”). It is to be noted that the specific measuring method is similar to the method described in PCT Patent Publication No. WO2020 / 017655, and therefore, its detailed description is omitted herein. Also concerning the tin deposition amount of the coating tin layer, its measurement was conducted by using the X-ray fluorescence spectrometer. Their values so obtained are presented in Table 10, Table 11, and Table 12.Comparative Example 1

[0327] The conditions for undercoat nickel plating, granular nickel-forming plating, and nickel-growing plating were set as presented in Table 1 and Table 2. Otherwise, the procedures of Example 1 were followed. The results so obtained are presented in Table 5. It is to be noted that, in Comparative Example 1, the 180° peel strength was 0, and therefore, the evaluation of liquid penetration resistance was difficult and was not conducted.Comparative Example 2

[0328] The conditions for undercoat nickel plating, granular nickel-forming plating, and nickel-growing plating were set as presented in Table 1 and Table 2. Otherwise, the procedures of Example 1 were followed. The results so obtained are presented in Table 5.Comparative Example 3

[0329] The conditions for undercoat nickel plating, granular nickel-forming plating, and nickel-growing plating were set as presented in Table 1 and Table 2. Otherwise, the procedures of Example 2 were followed. The results so obtained are presented in Table 5.Comparative Example 4

[0330] The conditions for undercoat nickel plating, granular nickel-forming plating, and nickel-growing plating were set as presented in Table 1 and Table 2. Otherwise, the procedures of Example 1 were followed. The results so obtained are presented in Table 5.Comparative Example 5

[0331] The conditions for undercoat nickel plating, granular nickel-forming plating, and zinc plating were set as presented in Table 3 and Table 4. Otherwise, the procedures of Example 18 were followed. The results so obtained are presented in Table 6. It is to be noted that, in Comparative Example 5, the 180° peel strength was 0, and therefore, the evaluation of liquid penetration resistance was difficult and was not conducted.Comparative Example 6

[0332] The conditions for undercoat nickel plating, granular nickel-forming plating, and zinc plating were set as presented in Table 3 and Table 4. Otherwise, the procedures of Example 18 were followed. The results so obtained are presented in Table 6.Comparative Example 7

[0333] The conditions for undercoat nickel plating, granular nickel-forming plating, and nickel-growing plating were set as presented in Table 7 and Table 8. Otherwise, the procedures of Example 20 were followed. The results so obtained are presented in Table 9.Comparative Example 8

[0334] The conditions for undercoat nickel plating, granular nickel-forming plating, and nickel-growing plating were set as presented in Table 7 and Table 8. Otherwise, the procedures of Example 20 were followed. The results so obtained are presented in Table 9.Comparative Example 9

[0335] The conditions for undercoat nickel plating, granular nickel-forming plating, and nickel-growing plating were set as presented in Table 7 and Table 8. Otherwise, the procedures of Example 21 were followed. The results so obtained are presented in Table 9.Comparative Example 10

[0336] The conditions for undercoat nickel plating, granular nickel-forming plating, and tin plating were set as presented in Table 10 and Table 11. Otherwise, the procedures of Example 22 were followed. The results so obtained are presented in Table 12.TABLE 1UNDERCOAT NICKEL-PLATING CONDITIONSELEC-NICKELTEMPER-CURRENTTROLYSISDEPOSITIONATUREDENSITYTIMEBATHAMOUNTBASE MATERIALpH(° C.)(A / dm2)(sec.)CONDITIONS(g / m2)Example 1SURFACE DIFFUSION-4.0~5.0601015.1WATTS BATH4.5TREATED STEEL SHEETExample 2SURFACE DIFFUSION-4.0~5.0601015.1WATTS BATH4.5TREATED STEEL SHEETExample 3STEEL SHEET4.0~5.0601015.1WATTS BATH4.5Example 4SURFACE DIFFUSION-4.0~5.0601010.5WATTS BATH3.1TREATED STEEL SHEETExample 5STEEL SHEET4.0~5.0601015.1WATTS BATH4.5Example 6STEEL SHEET4.0~5.0601010.5WATTS BATH3.1Example 7SURFACE DIFFUSION-4.0~5.0601010.5WATTS BATH3.1TREATED STEEL SHEETExample 8SURFACE DIFFUSION-4.0~5.0601015.1WATTS BATH4.5TREATED STEEL SHEETExample 9STEEL SHEET4.0~5.0601015.1WATTS BATH4.5Example 10SURFACE DIFFUSION-4.0~5.0601010.5WATTS BATH3.1TREATED STEEL SHEETExample 11SURFACE DIFFUSION-4.0~5.0601015.1WATTS BATH4.5TREATED STEEL SHEETExample 12SURFACE DIFFUSION-4.0~5.0601015.1WATTS BATH4.5TREATED STEEL SHEETExample 13STEEL SHEET4.0~5.0601010.5WATTS BATH3.1Example 14STEEL SHEET4.0~5.0601015.1WATTS BATH4.5Example 15SURFACE DIFFUSION-4.0~5.0601010.5WATTS BATH3.1TREATED STEEL SHEETExample 16STEEL SHEET4.0~5.0601010.5WATTS BATH3.1Example 17SURFACE DIFFUSION-4.0~5.0601015.1WATTS BATH4.5TREATED STEEL SHEETComparativeSTEEL SHEET4.0~5.0601015.1WATTS BATH4.5Example 1ComparativeSURFACE DIFFUSION-4.0~5.0601010.5WATTS BATH3.1Example 2TREATED STEEL SHEETComparativeSTEEL SHEET4.0~5.0601015.1WATTS BATH4.5Example 3ComparativeSURFACE DIFFUSION-4.0~5.0601010.5WATTS BATH3.1Example 4TREATED STEEL SHEETTABLE 2GRANULAR NICKEL-FORMING PLATING CONDITIONSNICKELAGITATIONCURRENTELECTROLYSISDEPOSITIONFLOWTEMPERATUREDENSITYTIMEAMOUNTAGITATIONRATEpH(° C.)(A / dm2)(sec.)(g / m2)METHOD(L / min.)mple 16.05221.015.04.2CIRCULATEDLOWmple 26.05723.519.26.2CIRCULATEDMEDIUMmple 36.05423.220.56.4CIRCULATEDMEDIUMmple 46.06023.318.26.0CIRCULATEDHIGHmple 56.05227.017.55.4CIRCULATEDMEDIUMmple 66.05235.413.35.0CIRCULATEDLOWmple 76.05021.028.07.6CIRCULATEDHIGHmple 86.05221.035.010.3CIRCULATEDHIGHmple 96.05520.037.510.8CIRCULATEDMEDIUMnple 106.05420.016.25.3CIRCULATEDLOWnple 116.05420.519.36.2CIRCULATEDMEDIUMmple 126.05020.023.07.0CIRCULATEDHIGHmple 136.05121.626.88.2CIRCULATEDMEDIUMmple 146.05522.236.511.4CIRCULATEDMEDIUMmple 156.05022.035.510.5CIRCULATEDHIGHnple 166.05723.435.110.7CIRCULATEDMEDIUMnple 176.05123.338.012.5CIRCULATEDHIGHComparative6.0453.082.94.1NOT—*Example 1AGITATEDComparative6.05016.035.78.3NOT—Example 2AGITATEDComparative6.04520.051.212.8CIRCULATEDLOWExample 3Comparative6.04215.082.016.0NOT—Example 4AGITATEDNICKEL-GROWING PLATING CONDITIONSNICKELAGITATIONCURRENTELECTROLYSISDEPOSITIONFLOWTEMPERATUREDENSITYTIMEAMOUNTAGITATIONRATEpH(° C.)(A / dm2)(sec.)(g / m2)METHOD(L / min.)mple 14.0~5.060101.40.5CIRCULATEDMEDIUMmple 24.0~5.060102.50.8CIRCULATEDHIGHmple 34.0~5.060101.20.4CIRCULATEDMEDIUMmple 44.0~5.060101.40.5CIRCULATEDHIGHmple 54.0~5.060109.12.5CIRCULATEDMEDIUMmple 64.0~5.060109.52.9CIRCULATEDLOWmple 74.0~5.060109.12.5CIRCULATEDMEDIUMmple 84.0~5.0601010.43.2CIRCULATEDHIGHmple 94.0~5.0601010.43.2CIRCULATEDHIGHnple 104.0~5.060109.12.5CIRCULATEDLOWnple 114.0~5.060108.02.2CIRCULATEDLOWmple 124.0~5.0602.736.03.2CIRCULATEDMEDIUMmple 134.0~5.060109.52.9CIRCULATEDLOWmple 144.0~5.0601013.54.2CIRCULATEDMEDIUMmple 154.0~5.060109.52.7CIRCULATEDLOWnple 164.0~5.0601012.83.8CIRCULATEDHIGHnple 174.0~5.060109.52.7CIRCULATEDMEDIUMComparative4.0~5.060109.12.5NOT—Example 1AGITATEDComparative4.0~5.0601028.58.5NOT—Example 2AGITATEDComparative4.0~5.0601018.05.3NOT—Example 3AGITATEDComparative4.0~5.0601022.06.5NOT—Example 4AGITATED*If not agitated, the flow rate is less than 1 L / min.TABLE 3UNDERCOAT NICKEL-PLATING CONDITIONSNICKELTEMPER-CURRENTELEC-DEPOSITIONBASE ATUREDENSITYTROLYSISBATHAMOUNTMATERIALpH(° C.)(A / dm2)TIMECONDITIONS(g / m2)Example 18STEEL SHEET4.0~5.0601015.1WATTS BATH4.5Example 19STEEL SHEET4.0~5.0601015.1WATTS BATH4.5ComparativeSTEEL SHEET4.0~5.0601015.1WATTS BATH4.5Example 5ComparativeSTEEL SHEET4.0~5.0601015.1WATTS BATH4.5Example 6TABLE 4GRANULAR NICKEL-FORMING PLATING CONDITIONSNICKELAGITATIONCURRENTELECTROLYSISDEPOSITIONFLOWTEMPERATUREDENSITYTIMEAMOUNTAGITATIONRATEpH(° C.)(A / dm2)(sec.)(g / m2)METHOD(L / min.)Example 186.05523.320.04.0CIRCULATEDMEDIUMExample 195.05230.010.52.0CIRCULATEDHIGHComparative5.04515.05.00.7NOT —*Example 5AGITATEDComparative5.04515.048.66.8NOT —Example 6AGITATEDCOATING ZINC PLAT ING CONDITIONSNICKELAGITATIONCURRENTELECTROLYSISDEPOSITIONFLOWTEMPERATUREDENSITYTIMEAMOUNTAGITATIONRATEpH(° C.)(A / dm2)(sec.)(g / m2)METHOD(L / min.)Example 181.5~2.555109.32.1CIRCULATEDHIGHExample 191.5~2.5551026.37.5CIRCULATEDMEDIUMComparative1.5~2.5551026.37.5NOT —Example 5AGITATEDComparative1.5~2.5551026.37.5NOT —Example 6AGITATEDTABLE 5ROUGHENED180º PEEL STRENGTHLIQUIDExample / SURFACE(=RESIN ADHESIONPENETRATIONComparativeRzjisRsmAREASTRENGTH)RESISTANCEExampleμmμmm2 / 1 m2N / 25 mmEVALUATIONEVALUATIONExample 11.36.07.015.2EXCELLENTEXCELLENTExample 21.65.08.616.5EXCELLENTEXCELLENTExample 31.96.28.016.0EXCELLENTEXCELLENTExample 42.25.38.726.9EXCELLENTEXCELLENTExample 52.45.88.126.5EXCELLENTEXCELLENTExample 62.54.96.425.6EXCELLENTEXCELLENTExample 72.65.16.923.0EXCELLENTEXCELLENTExample 82.85.88.820.6EXCELLENTEXCELLENTExample 93.46.09.830.5EXCELLENTEXCELLENTExample 101.111.13.96.7GOODEXCELLENTExample 111.57.72.65.8GOODEXCELLENTExample 121.65.35.212.2GOODEXCELLENTExample 132.37.02.410.2GOODEXCELLENTExample 143.95.85.131.1EXCELLENTGOODExample 154.06.621.327.9EXCELLENTGOODExample 164.26.012.748.5EXCELLENTGOODExample 174.66.828.830.8EXCELLENTGOODComparative0.98.20.20.0POORNOTExample 1EVALUATEDComparative2.99.11.43.3POOREXCELLENTExample 2Comparative4.86.44.034.1EXCELLENTMODERATEExample 3Comparative6.57.18.543.3EXCELLENTPOORExample 4TABLE 6ROUGHENED180° PEEL STRENGTHLIQUIDExample / SURFACE(=RESIN ADHESIONPENETRATIONComparativeRzjisRsmAREASTRENGTH)RESISTANCEExampleμmμmm2 / 1 m2N / 25 mmEVALUATIONEVALUATIONExample 182.35.39.536.2EXCELLENTEXCELLENTExample 193.26.310.642.5EXCELLENTEXCELLENTComparative0.827.62.80.0POORNOTExample 5EVALUATEDComparative4.97.812.246.7EXCELLENTMODERATEExample 6TABLE 7UNDERCOAT NICKEL-PLATING CONDITIONSELEC-NICKEL TEMPER-CURRENTTROLYSISDEPOSITIONATUREDENSITYTIMEBATHAMOUNTBASE MATERIALpH(° C.)(A / dm2)(sec.)CONDITIONS(g / m2)Example 20STEEL SHEET4.0~5.0601015.1WATTS BATH4.5Example 21ALUMINUM 4.0~5.0601015.1WATTS BATH4.5SHEETComparativeSTEEL SHEET4.0~5.0601015.1WATTS BATH4.5Example 7ComparativeSTEEL SHEET4.0~5.0601015.1WATTS BATH4.5Example 8ComparativeALUMINUM 4.0~5.0601015.1WATTS BATH4.5Example 9SHEETTABLE 8GRANULAR NICKEL-FORMING PLATING CONDITIONSNICKELAGITATIONCURRENTELECTROLYSISDEPOSITIONFLOWTEMPERATUREDENSITYTIMEAMOUNTAGITATIONRATEpH(° C.)(A / dm2)(sec.)(g / m2)METHOD(L / min.)Example 206.05625.016.05.5CIRCULATEDMEDIUMExample 216.05622.014.75.3CIRCULATEDHIGHComparative6.05010.09.01.2NOT—Example 7AGITATEDComparative6.04223.048.09.6CIRCULATEDLOWExample 8Comparative6.05015.037.08.9NOTLOWExample 9AGITATEDNICKEL-GROWING PLATING CONDITIONSNICKELAGITATIONCURRENTELECTROLYSISDEPOSITIONFLOWTEMPERATUREDENSITYTIMEAMOUNTAGITATIONRATEpH(° C.)(A / dm2)(sec.)(g / m2)METHOD(L / min.)Example 204.0~ 5.050103.00.8CIRCULATEDMEDIUMExample 214.0~ 5.050102.00.3CIRCULATEDLOWComparative4.0~ 5.060105.01.4NOT—Example 7AGITATEDComparative4.0~ 5.0601032.010.6NOT—Example 8AGITATEDComparative4.0~ 5.0601011.03.2NOT—Example 9AGITATEDTABLE 9ROUGHENED180º PEEL STRENGTHLIQUIDExample / SURFACE (=RESIN ADHESIONPENETRATIONComparativeRzjisRsmAREASTRENGTH)RESISTANCEExampleμmμmm2 / 1 m2N / 25 mmEVALUATIONEVALUATIONExample 202.04.410.142.0EXCELLENTEXCELLENTExample 213.38.77.517.4EXCELLENTEXCELLENTComparative0.64.11.00.0POORNOT Example 7EVALUATEDComparative7.98.215.643.9EXCELLENTPOORExample 8Comparative5.88.77.821.1EXCELLENTPOORExample 9TABLE 10UNDERCOAT NICKEL-PLATING CONDITIONSELEC-NICKELTEMPER-CURRENTTROLYSISBATHDEPOSITIONBASE ATUREDENSITYTIMECONDITIONSAMOUNTMATERIALpH(° C.)(A / dm2)(sec.)CONDITIONS(g / m2)Example 22STEEL SHEET4.0~5.0601015.1WATTS BATH4.5ComparativeSTEEL SHEET4.0~5.0601015.1WATTS BATH4.5Example 10TABLE 11GRANULAR NICKEL-FORMING PLATING CONDITIONSNICKELAGITATIONCURRENTELECTROLYSISDEPOSITIONFLOWTEMPERATUREDENSITYTIMEAMOUNTAGITATIONRATEpH(° C.)(A / dm2)(sec.)(g / m2)METHOD(L / min.)Example 226.05020.015.04.4CIRCULATEDMEDIUMComparative6.05020.037.54.5NOT—Example 10AGITATEDCOATING TIN PLATING CONDITIONSNICKELAGITATIONCURRENTELECTROLYSISDEPOSITIONFLOWTEMPERATUREDENSITYTIMEAMOUNTAGITATIONRATEpH(° C.)(A / dm2)(sec.)(g / m2)METHOD(L / min.)Example 220.5~1.5405.01.21.1CIRCULATEDLOWComparative0.5~1.5405.047.67.3NOT —Example 10AGITATED*If not agitated, the flow rate is less than 1 L / min.TABLE 12ROUGHENED180° PEEL STRENGTHLIQUIDExample / SURFACE(=RESIN ADHESIONPENETRATIONComparativeRzjisRsmAREASTRENGTH)RESISTANCEExampleμmμmm2 / 1 m2N / 25 mmEVALUATIONEVALUATIONExample 222.09.66.550.2EXCELLENTEXCELLENTComparative5.57.13.720.6EXCELLENTPOORExample 10Examples 1 to 17 have been confirmed to have preferred characteristics in both resin adhesion strength and liquid penetration resistance. In Comparative Examples 1 to 3, on the other hand, the resin adhesion strength was 3.3N / 25 mm or lower, thereby failing to achieve the object in the viewpoint of resin adhesion strength. Further, in Comparative Examples 4 and 5, it failed to achieve the object in the viewpoint of liquid penetration resistance.In more detail, it was found that, when Example 8 and Comparative Example 3 are compared with each other, their values of the ten-point mean roughness Rzjis were substantially the same, but the intended resin adhesion strength was not obtained in the comparative example because there was a difference in value of the roughened surface area between the example and the comparative example. It is to be noted that the difference in value of the roughened surface area between them could be attributed to differences in shape among the individual protrusions including the shapes of roots of the roughened portion, but details were not clear.Example 18, Example 19, Comparative Example 5, and Comparative Example 6 are embodiments in which zinc was formed as a coating layer. In Example 18 and Example 19, the ten-point mean roughness Rzjis was 1.0 μm or greater and smaller than 4.8 μm, and the roughened surface area was 1.5 mm2 / 1 m2 or greater, on the surface of the composite roughened plating layer with the coating layer made of zinc and formed thereon, and Example 18 and Example 19 have been confirmed to have preferred characteristics in resin adhesion strength and liquid penetration resistance. In Comparative Example 5, on the other hand, the value of the ten-point mean roughness Rzjis was out of the above-described range, and, as a result, it failed to achieve the object in the viewpoint of adhesion strength. Further, in Comparative Example 6, the ten-point mean roughness Rzjis was 4.9 μm, that is, greater than 4.8 μm, so that the intended liquid penetration resistance was not obtained.Further, the preferred results were obtained from the viewpoints of both resin adhesion strength and liquid penetration resistance when, on the uppermost surface on the side of the roughened nickel layer 50, the ten-point mean roughness Rzjis was 1.0 μm or greater and 3.5 μm or smaller and the roughened surface area was 5.3 m2 / 1 m2 or greater, as presented in Examples 1 to 9, 18, and 19.Example 20, Comparative Example 7, and Comparative Example 8 are embodiments in which a stainless steel sheet was used as a base material. On the other hand, Example 21 and Comparative Example 9 are embodiments in which an aluminum sheet was used as a base material. In Example 20 and Example 21, Rzjis was 1.0 μm or greater and smaller than 4.8 μm, and the roughened surface area was 1.5 mm2 / 1 m2 or greater, so that Example 20 and Example 21 have been confirmed to have preferred characteristics in both resin adhesion strength and liquid penetration resistance. In Comparative Example 7, on the other hand, Rzjis was smaller 1.0 μm, and the roughened surface area was smaller than 1.5 mm2 / 1 m2, resulting in a significant reduction in the adhesion with the resin. Further, in Comparative Example 8 and Comparative Example 9, Rzjis was greater than 4.8 μm, thereby failing to achieve the object in the viewpoint of liquid penetration resistance.Example 22 and Comparative Example 10 are embodiments in which tin was formed as a coating layer. In Example 22, the ten-point mean roughness Rzjis was 1.0 μm or greater and smaller than 4.8 μm, and the roughened surface area was 1.5 mm2 / 1 m2 or greater, on the surface of the composite roughened plating layer with the coating layer made of tin and formed thereon, and Example 22 has been confirmed to have preferred characteristics in resin adhesion strength and liquid penetration resistance. In Comparative Example 10, on the other hand, the ten-point mean roughness Rzjis was 5.5 μm, that is, greater than 4.8 μm, so that the intended liquid penetration resistance was not obtained.From these results, it is understood necessary to control both the ten-point mean roughness Rzjis and the roughened surface area for obtaining preferred characteristics in both the resin adhesion strength and the liquid penetration resistance.Various modifications can be made to the above-described embodiments and the individual examples within a scope not departing from the spirit of the present disclosure.INDUSTRIAL APPLICABILITYAs described above, the nickel-plated metal material of the present disclosure can be used for various applications such as current collectors of positive electrodes and / or negative electrodes of secondary batteries and the like, members for electronic devices, electric appliances, automobiles, and constructions, and so on.REFERENCE SIGNS LIST100, 200, 300, 400: Nickel-plated metal material20: Base material40: Metal layer50: Roughened nickel layer

[0350] 60: Composite roughened plating layer

[0351] 70: Coating layer

Examples

first embodiment

[0017]FIG. 1 is a cross-sectional view schematically depicting an embodiment of a nickel-plated metal material 100 of the present disclosure. It is to be noted that the nickel-plated metal material 100 of the present embodiment is used, for example, as current collectors of positive electrodes and / or negative electrodes of secondary batteries and the like, members for electronic devices, electric appliances, automobiles, and constructions, and so on.

[0018]The nickel-plated metal material 100 of the present embodiment includes the base material 20 made of metal, and a roughened nickel layer 50 formed on the base material 20. It is to be noted that, in the nickel-plated metal material 100 of the present embodiment, the roughened nickel layer 50 is formed on at least one outermost surface as depicted in FIG. 1.

20>

[0019]As the base material 20 for use in the nickel-plated metal material 100 of the present embodiment, a metal sheet or metal foil made of a pure metal selected from iron (F...

second embodiment

[0102]On the basis of FIG. 3, a nickel-plated metal material 300 in a second embodiment will next be described. The nickel-plated metal material 300 in the second embodiment is different from the above-mentioned first embodiment in that a coating layer 70 is included on the roughened nickel layer 50. Accordingly, this different point will be primarily described, the other points will be identified by the same reference signs, and their description is omitted. It is to be noted that, in the nickel-plated metal material 300, the roughened nickel layer 50 and the coating layer 70 will be collectively called a “composite roughened plating layer 60.” In the nickel-plated metal material 300, the ten-point mean roughness Rzjis and roughened surface area on the outermost surface on the side of the composite roughened plating layer 60 are 1.0 μm or greater and smaller than 4.8 μm and 1.5 m2 / 1 mm2 or greater, respectively.

70>

[0103]As mentioned above, the coating layer 70 is disposed on the ro...

example 1

[0200]A cold-rolled steel sheet (60 μm thickness) of low-carbon aluminum-killed steel having a chemical composition presented below was first provided.[0201]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

[0202]After electrolytic degreasing and pickling by dipping in sulfuric acid were next carried out on the above-described cold-rolled steel sheet, a nickel layer was formed to a deposition amount of 8.9 g / m2 by known nickel plating. Subsequently, thermal diffusion treatment was conducted by a continuous annealing step, and quality control rolling was applied, whereby an iron-nickel alloy layer of 2.2 μm thickness was formed on both sides. The resulting surface diffusion-treated steel sheet was provided as a base material 20.

[0203]On the surface diffusion-treated steel sheet as the base material 20, strike nickel-plating treatment was conducted under the strike nickel-plating conditions presented below, followed by forma...

Claims

1. A nickel-plated metal material comprising:a base material made of metal; anda roughened nickel layer formed on at least one side on the base material, whereina ten-point mean roughness Rzjis on an outermost surface on a side of the roughened nickel layer of the nickel-plated metal material is 1.0 μm or greater and smaller than 4.8 μm, anda roughened surface area on the outermost surface on the side of the roughened nickel layer is 1.5 m2 / 1 m2 or greater.

2. The nickel-plated metal material according to claim 1, wherein an overall thickness is 0.005 to 5.01 mm in a sheet shape.

3. The nickel-plated metal material according to claim 1, wherein the ten-point mean roughness Rzjis is 1.0 μm or greater and 3.5 μm or smaller.

4. The nickel-plated metal material according to claim 1, wherein the roughened surface area is 5.3 m2 / 1 m2 or greater.

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

6. The nickel-plated metal material according to claim 1, comprising:on the outermost surface on the side of the roughened nickel layer and the roughened nickel layer, 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, or a chromium alloy layer.

7. The nickel-plated metal material according to claim 1, wherein a deposition amount of nickel in the roughened nickel layer is 2.0 g / m2 or more and 16 g / m2 or less.

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

9. The nickel-plated metal material according to claim 1, whereinthe base material is any one ofa metal sheet or metal foil made of one type of pure metal selected from iron, copper, aluminum, or nickel,a metal sheet or metal foil made of an alloy containing one type selected from iron, copper, aluminum, or nickel, ora nickel-plated steel sheet, a surface diffusion-treated steel sheet with a diffusion alloy layer of iron and nickel formed on a surface layer thereof or in a vicinity of the surface layer by subjecting a nickel-plated steel sheet to heat treatment, or a zinc-plated steel sheet.

10. The nickel-plated metal material according to claim 1, whereina metal layer is included between the base material and the roughened nickel layer, andthe metal layer is any one of an iron-nickel alloy layer, a nickel-phosphorus alloy layer, or a nickel layer.

11. The nickel-plated metal material according to claim 9, wherein a total nickel deposition amount per side in the metal layer and the roughened nickel layer, the side being on a side of the roughened nickel layer, of the nickel-plated metal material is 4 g / m2 or more and 40 g / m2 or less.

12. The nickel-plated metal material according to claim 9, wherein a total nickel deposition amount per side of the base material, the metal layer, and the roughened nickel layer is 4 g / m2 or more and 40 g / m2 or less.

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