Roughened nickel plating plate

Abstract

To provide a surface roughened nickel plated plate having excellent adhesion to other materials while maintaining good adhesion of a plating layer to a substrate.SOLUTION: A roughened nickel plated plate comprises a roughened nickel layer as an outermost layer on at least one side of the metal substrate, in which an amount of surface roughened nickel plating deposited on the roughened nickel plated plate is 5.0 to 50.0 g / m2, lightness L* of a surface of the roughened nickel layer is 30 to 50, and the 85° glossiness of the surface of the roughened nickel layer is 1.5 to 50.SELECTED DRAWING: Figure 4

Description

[Technical field]

[0001] The present invention relates to a roughened nickel-plated sheet having a roughened nickel layer as an outermost layer. [Background technology]

[0002] Conventionally, nickel-plated steel sheets have been used as components for batteries and electronic devices. In such nickel-plated steel sheets, a method of controlling the surface structure of the nickel-plated steel sheet is known from the viewpoint of improving adhesion when the nickel-plated steel sheet is joined to another member.

[0003] For example, in Patent Document 1, a particle density of 2 to 500 particles / μm is applied to a steel sheet. 2 The document discloses a surface-treated steel sheet having a nickel plating layer formed thereon, the nickel plating layer having a microstructure in which the average grain size is controlled to 0.05 to 0.7 μm. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 5885345 Summary of the Invention [Problem to be solved by the invention]

[0005] However, the surface-treated steel sheet disclosed in Patent Document 1 may have insufficient adhesion to other members depending on the type of member to be joined to the surface-treated steel sheet and the joining method, and further improvement in adhesion is required. In response to this, a method of forming a nickel plating layer by roughening plating may be considered in order to improve adhesion to other members. However, the inventors of the present invention conducted an investigation and found that there is a problem in that the adhesion of the roughening plating layer itself formed by roughening plating to the base material is reduced, which may result in reduced reliability.

[0006] An object of the present invention is to provide a roughened nickel plating plate that exhibits excellent adhesion to other members while maintaining good adhesion of the plating layer to a base material.

Means for Solving the Problems

[0007] As a result of intensive studies to achieve the above object, the inventors of the present invention have found that by controlling the lightness and 85° glossiness of the surface of the roughened nickel layer within a specific range, it is possible to obtain a roughened nickel plating plate that exhibits excellent adhesion to other members while maintaining good adhesion of the plating layer to a base material, and thus have completed the present invention.

[0008] That is, according to the present invention, there is provided a roughened nickel plating plate having a roughened nickel layer as the outermost layer on at least one surface of a metal base material, wherein the lightness L of the surface of the roughened nickel layer * is 30 to 50, and the 85° glossiness of the surface of the roughened nickel layer is 1.5 to 50.

[0009] In the roughened nickel plating plate of the present invention, it is preferable that the metal base material is a metal plate or metal foil made of a pure metal selected from Fe, Cu, Al, and Ni, or a metal plate or metal foil made of an alloy containing one selected from Fe, Cu, Al, and Ni. In the roughened nickel plating plate of the present invention, the adhesion amount of the nickel plating is preferably 5.0 to 50.0 g / m 2 . In the roughened nickel plating plate of the present invention, the arithmetic mean roughness Ra of the roughened nickel layer measured by laser microscopy is 0.1 to 3.0 μm, and the ten-point mean roughness Rz of the roughened nickel layer measured by laser microscopy jis is preferably 2.0 to 20.0 μm.

Effects of the Invention

[0010] According to the present invention, it is possible to provide a roughened nickel plating plate that exhibits excellent adhesion to other members while maintaining good adhesion of the plating layer to the base material.

Brief Description of the Drawings

[0011]

Figure 1A

Figure 1B

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Figure 15

Mode for Carrying Out the Invention

[0012] Figure 1A is a diagram showing the configuration of the roughened nickel plating plate 1 of the present embodiment. As shown in Figure 1A, the roughened nickel plating plate 1 of the present embodiment is formed with a roughened nickel layer 12 as the outermost layer on a metal substrate 11. In the roughened nickel plating plate 1 according to the present embodiment, the roughened nickel layer 12 has a brightness L on its surface * that is controlled to be 30 to 50 and a glossiness at 85° of 3 to 50. In addition, in the present embodiment, as shown in Figure 1A, as the roughened nickel plating plate 1, an example is shown in which the roughened nickel layer 12 is formed on both sides of the metal substrate 11, but it is not particularly limited to such an aspect. For example, as in the roughened nickel plating plate 1a shown in Figure 1B, the roughened nickel layer 12 may be formed on one surface of the metal substrate 11.

[0013] <Metal Substrate 11> The metal substrate 11 that serves as the substrate of the roughened nickel-plated sheet 1 of the present embodiment is not particularly limited, and examples thereof include a metal plate or metal foil made of a single pure metal selected from Fe, Cu, Al, and Ni, or a metal plate or metal foil made of an alloy containing one selected from Fe, Cu, Al, and Ni. Specifically, there are a steel plate, an iron plate, a stainless steel plate, a copper plate, an aluminum plate, or a nickel plate (these may be either a pure metal or an alloy, and may also be in the form of a foil). Among these, a steel plate or a copper plate is preferred because the pretreatment for plating is relatively simple and it is easy to perform plating, and it is also easy to favorably form a roughened nickel layer with high adhesion to the metal substrate. In particular, low-carbon aluminum-killed steel (carbon content: 0.01 to 0.15% by weight), ultra-low-carbon steel with a carbon content of 0.01% by weight or less (preferably a carbon content of 0.003% by weight or less), or non-ageing ultra-low-carbon steel obtained by adding Ti, Nb, etc. to ultra-low-carbon steel is preferably used.

[0014] In the present embodiment, after pickling the hot-rolled sheet of the metal substrate to remove the scale (oxide film) on the surface, cold rolling is performed, and then a steel plate, a stainless steel plate, a copper plate, an aluminum plate, or a nickel plate obtained by electrolytically cleaning the rolling oil can be used as the substrate. Further, after electrolytic cleaning, those subjected to annealing or temper rolling may be used. In this case, the annealing may be either continuous annealing or box annealing, and is not particularly limited. In addition, as electrolytic foils produced by electroforming or the like, copper foil, nickel foil, iron foil, etc. can also be used as the metal substrate.

[0015] When using a metal substrate such as a stainless steel plate or a nickel plate on which a passive film is formed on the surface as the metal substrate 11, it is preferable to use one that has been subjected to strike nickel plating before the plating treatment for forming roughened nickel plating or undercoat metal plating. The conditions for strike nickel plating are not particularly limited, and examples thereof include the following conditions. Under the following conditions, the adhesion amount of nickel by strike nickel plating is usually 0.08 to 0.89 g / m 2However, when forming the underlying nickel layer, the total amount of nickel deposition by strike nickel plating and the amount of nickel deposition by nickel plating for forming the underlying nickel layer is measured as the amount of nickel deposition of the underlying nickel layer. Bath composition: 100 - 300 g / L of nickel sulfate hexahydrate, 10 - 200 g / L of sulfuric acid pH: 1.0 or less Bath temperature: 40 - 70 °C Current density: 5 - 100 A / dm 2 Plating time: 3 - 100 seconds

[0016] The thickness of the metal substrate 11 is not particularly limited, but is preferably 0.01 - 2.0 mm, more preferably 0.025 - 1.6 mm, and even more preferably 0.025 - 0.3 mm. Also, the roughness of the metal substrate 11 is not particularly limited, but the arithmetic mean roughness Ra measured with a stylus surface roughness meter is 0.05 - 2.0 μm, more preferably 0.05 - 0.9 μm, and even more preferably 0.05 - 0.5 μm.

[0017] <Roughened nickel layer 12> The roughened nickel layer 12 formed on the outermost surface of the roughened nickel plated sheet 1 of the present embodiment has a brightness L of its surface * controlled to be 30 - 50 and a glossiness at 85° of 3 - 50. According to the present embodiment, by controlling the brightness L * and the glossiness at 85° of the surface of the roughened nickel layer 12 within the above ranges, while maintaining good adhesion of the roughened nickel layer 12 to the metal substrate 11, the roughened nickel plated sheet 1 can be made to exhibit excellent adhesion to other members.

[0018] In particular, the inventors have intensively studied the relationship between the brightness L * and the glossiness at 85° of the surface of the roughened nickel layer 12, the adhesion of the roughened nickel layer 12 to the metal substrate 11, and the adhesion to other members. As a result, the brightness L of the surface of the roughened nickel layer 12 *By setting the glossiness at 85° within the above range, it has been found that the roughened nickel plating sheet 1 can exhibit excellent adhesion to other members while maintaining good adhesion of the roughened nickel layer 12, leading to the completion of the present invention.

[0019] Here, according to the present embodiment, in addition to showing excellent adhesion to other members, attention is also paid to the adhesion of the roughened nickel layer 12 to the metal substrate 11, which is for the following reasons. That is, even if excellent adhesion to other members can be achieved by forming the roughened nickel layer 12, if the roughened nickel layer 12 is likely to peel off from the metal substrate 11, the effect of forming the roughened nickel layer 12, that is, the effect of being able to show excellent adhesion to other members, will become insufficient due to the peeling off of the roughened nickel layer 12. Therefore, according to the present inventors, from such a perspective, attention has also been paid to the adhesion of the roughened nickel layer 12 to the metal substrate 11 and efforts have been made to improve it.

[0020] In addition, when the adhesion of the roughened nickel layer 12 to the metal substrate 11 is insufficient, when manufacturing the roughened nickel plating sheet 1 of the present embodiment, plating film debris (Ni powder) caused by the peeling off of the roughened nickel layer 12 may mix into the production line, which may cause contamination and failure of the production line. In addition, it may cause product defects due to the plating film debris remaining in the production line. Furthermore, when actually processing products or parts using the roughened nickel plating sheet 1 of the present embodiment, it may similarly cause contamination and failure of the production line or cause defects in the quality and function of the final product. Therefore, according to the present inventors, from such a perspective as well, attention has been paid to the importance of the adhesion of the roughened nickel layer 12 to the metal substrate 11 and efforts have been made to improve it.

[0021] The lightness of the surface of the roughened nickel layer 12 is L *The value is 30 to 50, preferably 30 to 48, more preferably 30 to 45, and even more preferably 35 to 45. Further, from the viewpoint of emphasizing production efficiency and production cost, the lightness of the surface of the roughened nickel layer 12 is preferably 36 to 48. Lightness L * If the value of is too small, the adhesion of the roughened nickel layer 12 to the metal substrate 11 will be poor. On the other hand, if the value of lightness L * is too large, the adhesion to other members will be poor. The lightness L of the surface of the roughened nickel layer 12 * can be measured using a spectrocolorimeter by the SCE method (regular reflection light removal method) in accordance with JIS Z8722.

[0022] Also, the 85° gloss of the surface of the roughened nickel layer 12 is 1.5 to 50, preferably 1.5 to 35, and even more preferably 2 to 30. Further, from the viewpoint of emphasizing production efficiency and production cost, the 85° gloss of the surface of the roughened nickel layer 12 is preferably 15 to 50. If the 85° gloss is too small, the adhesion of the roughened nickel layer 12 to the metal substrate 11 will be poor. Also, if the gloss is too large, the adhesion to other members will be poor. The 85° gloss of the surface of the roughened nickel layer 12 can be obtained by measuring the 85° specular gloss using a gloss meter in accordance with JIS Z8741. The 60° gloss of the roughened nickel layer 12 formed on the outermost surface of the roughened nickel-plated sheet 1 of the present embodiment is usually 10 or less.

[0023] The chromaticity a of the surface of the roughened nickel layer 12 * , b * is not particularly limited, but from the viewpoint of being able to further improve the adhesion of the roughened nickel layer 12 to the metal substrate 11 and the adhesion to other members, the chromaticity a * is preferably 0.1 to 3.0, more preferably 0.3 to 1.5, and the chromaticity b * is preferably 1.0 to 8.0, more preferably 2.0 to 7.0.

[0024] Further, for the roughened nickel layer 12, it is sufficient that the lightness L of its surface * and the glossiness at 85° are within the above ranges, but the arithmetic mean roughness Ra is preferably 0.1 to 3 μm. From the viewpoint of further improving the adhesion of the roughened nickel layer 12 to other members, the arithmetic mean roughness Ra is more preferably 0.18 μm or more, still more preferably 0.3 μm or more. From the viewpoint of further improving the adhesion (plating adhesion) of the roughened nickel layer 12 to the metal substrate 11, the arithmetic mean roughness Ra is more preferably 1.8 μm or less, still more preferably 1.6 μm or less, and even more preferably 1.3 μm or less. Also, from the viewpoint of emphasizing production efficiency and production cost, the arithmetic mean roughness Ra is preferably 0.18 to 0.5 μm, more preferably 0.18 to 0.49 μm. Further, for the roughened nickel layer 12, the ten-point height roughness Rz jis is preferably 2.0 to 20.0 μm. From the viewpoint of further improving the adhesion of the roughened nickel layer 12 to other members, the ten-point height roughness Rz jis is more preferably 3 μm or more, still more preferably 4 μm or more, and even more preferably 5 μm or more. From the viewpoint of further improving the adhesion (plating adhesion) of the roughened nickel layer 12 to the metal substrate 11, the ten-point height roughness Rz jis is more preferably 16 μm or less, still more preferably 14 μm or less, and even more preferably 12 μm or less. Also, from the viewpoint of emphasizing production efficiency and production cost, the ten-point height roughness Rz jis is preferably 3.0 to 7.0 μm. The maximum height roughness Rz of the roughened nickel layer 12 is not particularly limited, but is preferably 2.5 to 25.0 μm, more preferably 2.5 to 20.0 μm, and still more preferably 3.5 to 18.0 μm. Note that the surface roughness Ra, Rzjis, and Rz are preferably measured by a laser microscope.

[0025] In the roughened nickel-plated sheet 1 of the present embodiment, the adhesion amount of the roughened nickel layer 12 is not particularly limited, but is preferably 1.34 to 45.0 g / m 2and from the viewpoint of further improving the adhesion (plating adhesion) of the roughened nickel layer 12, the deposition amount of the roughened nickel layer 12 is more preferably 2.67 g / m 2 or more, and still more preferably 5 g / m 2 or more. From the viewpoint of further improving the adhesion of the roughened nickel layer 12 to other members, the deposition amount of the roughened nickel layer 12 is more preferably 38.0 g / m 2 or less, and still more preferably 32.0 g / m 2 or less, and even more preferably 31 g / m 2 or less. The deposition amount of the roughened nickel layer 12 can be determined by measuring the total nickel amount of the roughened nickel plating plate 1 using a fluorescent X-ray apparatus. When the underlying metal plating layer 13 made of nickel described later is formed, after measuring the total nickel amount of the roughened nickel plating plate 1 using a fluorescent X-ray apparatus, the amount corresponding to the underlying metal plating layer 13 is subtracted from this total nickel amount to obtain it. The nickel amount corresponding to the underlying metal plating layer 13 can be obtained, for example, by cutting the roughened nickel plating plate 1 and observing the cross-section with a scanning electron microscope (SEM) to measure the thickness of the underlying metal plating layer 13 and obtaining the nickel amount converted from the thickness of the underlying metal plating layer 13, or by measuring the nickel amount on the metal substrate 11 when the underlying metal plating layer 13 is formed on the metal substrate 11 using a fluorescent X-ray apparatus, or by calculating the amount of electrolysis calculated from the amount of electricity during the formation of the underlying metal plating layer 13 by plating on the metal substrate 11.

[0026] In this embodiment, the lightness L on the surface of the roughened nickel layer 12 * and the glossiness at 85° are in the above ranges. The method is not particularly limited, but examples include the method of forming the roughened nickel layer 12 by the method described below.

[0027] An example of the method for forming the roughened nickel layer 12 will be described below with reference to FIGS. 2 to 4. First, as shown in FIG. 2, from the viewpoint of further improving the adhesion between the metal substrate 11 and the roughened nickel layer 12 and from the viewpoint of imparting corrosion resistance according to the application, an undercoat metal plating layer 13 is formed on the metal substrate 11 as required. Note that the roughened nickel layer 12 may be directly formed on the metal substrate 11 without forming the undercoat metal plating layer 13. Next, by performing roughened nickel plating, nickel particles 121 are deposited in an aggregated state on the metal substrate 11 as shown in FIG. 3. Next, as shown in FIG. 4, by further performing covering nickel plating, the nickel particles 121 are covered with a nickel film 122, and the roughened nickel layer 12 is formed on the metal substrate 11 with the undercoat metal plating layer 13 formed as required interposed therebetween.

[0028] The conditions for the roughened nickel plating for depositing the nickel particles 121 in an aggregated state are not particularly limited, but the brightness L of the surface of the roughened nickel layer 12 *From the viewpoint that the 85° gloss can be suitably controlled within the above range, an electrolytic plating method using a plating bath containing nickel sulfate hexahydrate at a concentration of 10 to 100 g / L and ammonium sulfate at a concentration of 1 to 100 g / L is preferred. The concentration of nickel sulfate hexahydrate in the plating bath to be used is preferably 10 to 70 g / L, more preferably 10 to 50 g / L, and still more preferably 15 to 25 g / L. In addition, nickel chloride hexahydrate may be applied as the nickel ion supply source, or nickel chloride hexahydrate and nickel sulfate hexahydrate may be used in combination. When nickel chloride hexahydrate is used, the concentration of nickel chloride hexahydrate is preferably 1 to 40 g / L. However, when the nickel ion concentration and the chlorine ion concentration increase, it becomes difficult to obtain an appropriate roughened shape that provides a predetermined lightness and gloss, so care is required when used in combination with nickel sulfate hexahydrate or ammonium chloride. Also, when ammonium sulfate is used as the ammonia supply source in the plating solution, the concentration of ammonium sulfate in the plating bath to be used is preferably 10 to 50 g / L, more preferably 10 to 45 g / L, and still more preferably 15 to 40 g / L. In addition, ammonia may be added to the nickel plating bath by adding aqueous ammonia or by adding salts such as ammonium sulfate and ammonium chloride. The ammonia concentration in the plating bath is preferably 0.3 to 30 g / L, more preferably 1 to 20 g / L, still more preferably 3 to 15 g / L, and particularly preferably 3 to 12 g / L or less.

[0029] Also, when performing roughened nickel plating for depositing the nickel particulate matter 121 in an aggregated state, the pH of the nickel plating bath is the lightness L of the surface of the roughened nickel layer 12 *From the viewpoint of more suitably controlling the 85° glossiness, it is preferably 4.0 to 8.0. If the pH is too high, nickel ions in the bath tend to form hydrates, which is likely to cause poor plating. Therefore, the upper limit is more preferably 7.5 or less, still more preferably 7.0 or less. If the pH is low, the bath resistance becomes low, and it becomes difficult for nickel particles to deposit in a state where secondary particles are formed, and it is likely to become a normal deposition form (flat plating). Therefore, it becomes difficult to form a roughened nickel layer. Therefore, it is more preferably 4.5 or more, still more preferably 4.8 or more, and particularly preferably 5.0 or more.

[0030] When performing roughened nickel plating for depositing the nickel particulate matter 121 in an aggregated state, the current density is the lightness L on the surface of the roughened nickel layer 12 * From the viewpoint of more suitably controlling the 85° glossiness, it is preferably 5 to 40 A / dm 2 is. When the current density is high, the deposition efficiency tends to decrease, and plating unevenness and surface roughness control unevenness are likely to occur in the plating treatment range. Therefore, especially for an area of 100 cm 2 or more, it is more preferably 30 A / dm 2 or less, still more preferably 25 A / dm 2 or less, and particularly preferably 20 A / dm 2 or less. When the current density is low, it becomes difficult for nickel particles to deposit in a state where secondary particles are formed, and it is likely to become a normal deposition form. Therefore, it becomes difficult to form a roughened nickel layer. Therefore, the current density is more preferably 10 A / dm 2 or more. In this embodiment, from the viewpoint of more suitably controlling the lightness L on the surface of the roughened nickel layer 12 * and the 85° glossiness, the current density is preferably controlled according to the nickel ion concentration in the nickel plating bath (controlled by nickel sulfate hexahydrate (g / L) in the plating bath in the examples described later), the temperature of the nickel plating bath, the pH of the nickel plating bath, the ammonia concentration in the nickel plating bath, the halogen atom concentration in the nickel plating bath, and the like.

[0031] In addition, the bath temperature of the nickel plating bath when performing roughened nickel plating is not particularly limited, but the brightness L of the surface of the roughened nickel layer 12 * From the viewpoint of more suitably controlling the 85° gloss, it is preferably 25 to 60°C, more preferably 25 to 50°C, and still more preferably 30 to 50°C.

[0032] In the present embodiment, when performing roughened nickel plating for depositing the nickel particles 121 in an aggregated state, it is preferable to perform plating while stirring the nickel plating bath. By stirring the nickel plating bath, it becomes easier to uniformly deposit the nickel particles 121 on the metal substrate 11 while aggregating them, and thereby, the brightness L of the surface of the roughened nickel layer 12 * And the 85° gloss can be more suitably controlled. The method of stirring is not particularly limited, but examples include methods such as bubbling and pump circulation. As the conditions for bubbling, the type of gas is not particularly limited, but it is preferable to use air as the gas from the viewpoint of versatility. Also, as the timing of supplying the gas, continuous aeration is preferable for stable stirring. As the aeration amount, if the stirring is too strong, it is difficult to obtain the desired roughened shape. For example, for a plating solution with a volume of 2 L, it is preferably 1 L / min or less. As the conditions for pump circulation, continuous circulation is preferable for stable stirring.

[0033] The deposition amount when depositing the nickel particles 121 in an aggregated state by roughened nickel plating is not particularly limited, but from the viewpoint of controlling the brightness L of the surface of the roughened nickel layer 12 * And the 85° gloss within the above range, it is preferably 0.89 to 4.45 g / m 2 From the viewpoint of further improving the adhesion of the roughened nickel layer 12 to other members, the deposition amount when depositing the nickel particles 121 in an aggregated state is more preferably 1.34 g / m 2 Or more, and still more preferably 1.60 g / m 2The above is the case. From the viewpoint of further improving the adhesion (plating adhesion) of the roughened nickel layer 12 to the metal substrate 11, the deposition amount when depositing the nickel particles 121 in an aggregated state is more preferably 4.01 g / m 2 or less, more preferably 3.56 g / m 2 or less, and particularly preferably 3.12 g / m 2 or less. Further, from the viewpoint of emphasizing production efficiency and production cost, the deposition amount when depositing the nickel particles 121 in an aggregated state is preferably 1.34 to 2.23 g / m 2 .

[0034] And in the manufacturing method of the present embodiment, after depositing the nickel particles 121 in an aggregated state by roughened nickel plating, further nickel plating is performed to coat the nickel particles 121 with a nickel film 122. The nickel plating for coating the nickel particles 121 with the nickel film 122 may be performed by either electrolytic plating or electroless plating, but it is preferably formed by electrolytic plating.

[0035] When performing the nickel plating for coating by the electrolytic plating method, for example, as a nickel plating bath, a Watts bath having a bath composition of 200 to 350 g / L of nickel sulfate hexahydrate, 20 to 60 g / L of nickel chloride hexahydrate, and 10 to 50 g / L of boric acid is used, with a pH of 3.0 to 5.0, a bath temperature of 40 to 70°C, and a current density of 5 to 30 A / dm 2 (preferably 10 to 20 A / dm 2 ) to perform nickel plating, and then a method of washing with water can be used.

[0036] When coating the nickel particles 121 with the nickel film 122 by nickel plating for coating, the deposition amount (coating amount) is not particularly limited, but from the viewpoint of controlling the lightness L * and the 85° gloss of the surface of the roughened nickel layer 12 within the above range, it is preferably 4.45 to 26.70 g / m 2and from the viewpoint of further improving the adhesion (plating adhesion) of the roughened nickel layer 12, the deposition amount (coating amount) when coating the nickel particles 121 with the nickel coating 122 is more preferably 6.23 g / m 2 or more. From the viewpoint of further improving the adhesion of the roughened nickel layer 12 to other members, the deposition amount (coating amount) when coating the nickel particles 121 with the nickel coating 122 is more preferably 19.58 g / m 2 or less, and more preferably 16.02 g / m 2 or less. Also, from the viewpoint of emphasizing production efficiency and production cost, the deposition amount when coating the nickel particles 121 with the nickel coating 122 is preferably 4.45 to 8.90 g / m 2 . Further, the ratio of the deposition amount by the roughened nickel plating to the deposition amount by the coating nickel plating is not particularly limited, but is preferably 1:2 to 1:14, more preferably 2:4.5 to 2:15, and still more preferably 2:5 to 2:15 in terms of the weight ratio of "deposition amount by roughened nickel plating: deposition amount by coating nickel plating". When a base nickel layer is formed as the base metal plating layer 13, when the coating nickel plating is performed, in addition to the coating of the nickel particles 121 with the nickel coating 122, a part thereof also contributes to the growth of the base nickel layer (thickening of the portion where the base is exposed without nickel particles). Therefore, in this case, the above deposition amount is the sum of the coating amount by the coating nickel plating with the nickel coating 122 and the formation amount of the base nickel layer by the coating nickel plating.

[0037] Further, in the present embodiment, from the viewpoint of further improving the adhesion between the metal substrate 11 and the roughened nickel layer 12, it is preferable to form an undercoat metal plating layer 13 between the metal substrate 11 and the roughened nickel layer 12. As the undercoat metal plating layer 13, a nickel plating layer or a copper plating layer is preferable, and a nickel plating layer is more preferable. In particular, the nickel particles 121 formed by the above-described roughened nickel plating are in a state where the particulate precipitates aggregate and protrude to form aggregates, and it is preferable that there are gaps between the aggregates from the viewpoint of adhesion to other members. Therefore, the entire surface of the metal substrate 11 may not be completely covered. Therefore, for example, when a steel plate is used as the metal substrate 11, it is preferable to provide the undercoat metal plating layer 13 in order to improve the effect of suppressing the generation of rust on the steel plate. In addition, for the purpose of such an effect of improving corrosion resistance, it is preferable to select a metal substrate 11 according to the application and perform an undercoat plating treatment accordingly. When a steel plate or copper is used for the metal substrate 11, it is preferable to provide an undercoat nickel plating layer or an undercoat copper plating layer as the undercoat metal plating layer 13. Further, when a nickel layer formed by electrolytic nickel plating is applied to the undercoat plating treatment, the compatibility with the subsequent coating plating treatment is good, and the plating adhesion of the roughened nickel layer 12 can be further enhanced. Although the effect of plating adhesion can be obtained only by the coating nickel plating treatment without the undercoat metal plating layer 13, in the coating nickel plating treatment, nickel tends to preferentially precipitate on the nickel particles 121. Therefore, from such a viewpoint, it is preferable to form the undercoat metal plating layer 13 for improving corrosion resistance. When the metal substrate 11 is a copper plate, it is also possible to further enhance the plating adhesion of the roughened nickel layer 12 by performing an acid treatment or the like in the pretreatment.

[0038] The undercoat metal plating layer 13 can be formed by previously plating the metal substrate 11 before forming the roughened nickel layer 12 on the metal substrate 11. When the undercoat metal plating layer 13 is a nickel plating layer, either an electrolytic plating method or an electroless plating method may be used for forming, but it is preferably formed by electrolytic plating.

[0039] When the underlying metal plating layer 13 is a nickel plating layer and the electrolytic plating method is used as a method for forming the underlying nickel plating layer, for example, as a nickel plating bath, a Watts bath having a bath composition of 200 to 350 g / L of nickel sulfate hexahydrate, 20 to 60 g / L of nickel chloride hexahydrate, and 10 to 50 g / L of boric acid is used, with a pH of 3.0 to 5.0, a bath temperature of 40 to 70 °C, and a current density of 5 to 30 A / dm 2 (preferably 10 to 20 A / dm 2 ), nickel plating is performed under these conditions, and then a method of washing with water can be used.

[0040] In the case of forming the underlying metal plating layer 13, in the roughened nickel plating plate 1 of the present embodiment, the adhesion amount of the roughened nickel layer 12 is preferably 26.70 g / m 2 or less, more preferably 4.45 to 22.25 g / m 2 , even more preferably 4.45 to 17.80 g / m 2 , particularly preferably 4.45 to 13.35 g / m 2 from the viewpoint of further improving the adhesion between the metal base material 11 and the roughened nickel layer 12.

[0041] Also, in the case of forming the underlying metal plating layer 13, in the roughened nickel plating plate 1 of the present embodiment, the total adhesion amount of the roughened nickel layer 12 and the underlying metal plating layer 13 is not particularly limited, but from the viewpoint of being able to further improve the adhesion of the roughened nickel layer 12 to the metal base material 11 and the adhesion to other members, it is preferably 5.0 to 50.00 g / m 2 , more preferably 12.02 to 50.00 g / m 2 , even more preferably 12.28 to 40.94 g / m 2 , particularly preferably 12.28 to 32.49 g / m 2 . Also, from the viewpoint of emphasizing production efficiency and production cost, the total adhesion amount of the roughened nickel layer 12 and the underlying metal plating layer 13 is 10.24 to 22.25 g / m 2is preferable. Further, when high corrosion resistance is required, and particularly when high adhesion of the roughened nickel layer 12 to the metal substrate 11 and adhesion to other members are required, the total adhesion amount of the roughened nickel layer 12 and the underlying metal plating layer 13 is 32.50 to 57.85 g / m 2 is preferable. The total adhesion amount of the roughened nickel layer 12 and the underlying metal plating layer 13 can be determined by measuring the total nickel amount of the roughened nickel plating sheet 1 using a fluorescent X-ray apparatus.

[0042] As described above, according to the present embodiment, as shown in FIG. 3, by roughened nickel plating, nickel particles 121 are deposited on the metal substrate 11 in an aggregated state, and then, as shown in FIG. 4, by further performing coating nickel plating, a method of coating the nickel particles 121 with a nickel film 122 is adopted. By controlling these formation conditions, the lightness L on the surface of the roughened nickel layer 12 * and the 85° gloss can be within the above ranges.

[0043] Particularly, when roughened nickel plating is performed or when coating nickel plating is further performed after roughened nickel plating, as shown in FIG. 3, a protruding (columnar) aggregate composed of secondary particles (nickel particles 121) in which primary particles are aggregated is formed. On the other hand, as a result of investigations by the present inventors, the following findings were obtained. That is, in the above case, by adjusting the plating conditions, the size, shape, and density of the protruding aggregate can be controlled, and thereby it has been found that both good plating adhesion to the metal substrate 11 and good adhesion to appropriate other members can be achieved. Further, as a parameter representing the surface height difference, there is Rz jis However, it has been found that simply using parameters such as Rz jis or other roughness parameters such as Ra and Rz cannot control the adhesion to other members and the adhesion of the roughened nickel layer 12. That is, as a tendency, there is a certain degree of height difference (Rz jis) can ensure adhesion with other members, while if the height difference (Rz jis ) is too large, the adhesion of the roughened nickel layer 12 to the metal substrate 11 tends to deteriorate. However, it has been found that the adhesion of the roughened nickel layer 12 to the metal substrate 11, in particular, is not simply determined by Rz jis alone. Also, regarding the density of the protrusion aggregates in the roughened nickel layer 12, it has been found that if the density of the protrusion aggregates is too high, resin or the like cannot enter between the protrusions, and adhesion to other members such as a resin film cannot be ensured. On the other hand, when the density of the protrusion aggregates is too low, each protrusion aggregate becomes thin and is easily broken, and there is a risk that the adhesion of the roughened nickel layer 12 to the metal substrate 11 may decrease, or there are too few protrusion aggregates themselves to obtain an anchor effect, and adhesion to other members such as a resin film cannot be obtained. On the other hand, it has been difficult to measure the size, shape, and density of such protrusion aggregates and to specify their suitable ranges. In contrast, when the inventors of the present application conducted further studies, as parameters to replace such size, shape, and density, they focused on two parameters, the lightness L * of the roughened nickel layer 12 and the 85° glossiness, and found that when the adhesion of the roughened nickel layer 12 to the substrate and the adhesion to other members are good, both the lightness L * and the 85° glossiness fall within specific ranges.

[0044] In particular, although it is generally known that the numerical value of the lightness L * varies depending on the unevenness of the plate surface, in the protrusion aggregates composed of secondary particles (nickel particulate matter 121) as shown in FIG. 3, the inventors have found that not only the size of the protrusions (Rz jis ) but also the influence of the particle size of the primary particles of the plating particles at the tip of the protrusions is large. That is, it has been found that the lightness L * varies due to the change in the surface shape of the tip of the protrusion aggregate depending on the size of the primary particle size. Furthermore, the lightness L* Even when it is within a suitable range, there is a problem that the adhesion of the roughened nickel layer 12 to the metal substrate 11 may be poor. In particular, in such a case, since the plating particles on the surface of the protruding aggregate are large and relatively smooth, the lightness L * is within a suitable range. On the other hand, it is considered that the plating particles are large and porous, so that the plating particles are likely to peel off from the metal substrate 11. As one of the causes, when the plating particles are large, Rz jis tends to be high, so that the protruding aggregate is likely to break and fall off. Measuring the plating particles is very time-consuming. In such a case where the plating particles are large, it has also been found that the glossiness measured with low-angle incident light on the plating sheet, i.e., the 85° glossiness, becomes extremely low. Based on such findings, the inventors have conceived of a roughened nickel-plated sheet 1 in which the lightness L * and the 85° glossiness of the roughened nickel layer 12 are within the above specific ranges.

[0045] As described above, in the present embodiment, as the roughened nickel layer 12, by having a protruding (columnar) aggregate on the surface, the adhesion to other members such as a resin film can be ensured. Then, as a result of the study by the inventors, such a plating layer having a protruding aggregate can be formed by performing plating under conditions where the supply of nickel ions is insufficient with respect to the plating current. That is, it can be formed by causing abnormal electrodeposition by reducing the supply of nickel ions with respect to the plating current.

[0046] On the other hand, as a result of further investigations by the present inventors, in such abnormal electroplating, the mode of abnormal electroplating changes depending on the nickel concentration in the plating solution, the bath temperature of the plating solution, the pH of the plating solution, and further the current density during plating. Therefore, it has been difficult to obtain a roughened nickel-plated sheet that simultaneously satisfies both the adhesion of the roughened nickel layer 12 to the metal substrate 11 and the adhesion to other members by simply performing plating under conditions that cause abnormal electroplating. In particular, according to the method of causing abnormal electroplating, since unevenness is likely to be formed, while adhesion to other members is easily obtained, the deposited plating particles are likely to fall off and may fall off during handling. In contrast, the present inventors have found that in order to solve the problem of simultaneously satisfying both the adhesion of the roughened nickel layer 12 to the metal substrate 11 and the adhesion to other members, the size of the primary particles, the size of the protrusion-like aggregates, and the shape of the protrusion-like aggregates that constitute the roughened nickel layer 12 are important.

[0047] Here, FIG. 7(B) is a diagram showing a specific mode of the roughened nickel layer 12 according to the present embodiment, and is a schematic diagram based on the SEM photographs of the roughened nickel layer 12 shown in FIGS. 5(D) and 14(A). Further, FIG. 7(A) is a diagram showing the mode of the plating layer obtained by roughened nickel plating, and is a schematic diagram based on the SEM photograph shown in FIG. 14(B). The mode shown in FIG. 7(B) is obtained by forming a plating layer of the mode shown in FIG. 7(A) by roughened nickel plating and then applying covering nickel plating thereto. In FIGS. 7(A) and 7(B), the case where the underlying nickel plating layer is formed is illustrated, but the mode of forming the underlying nickel plating layer is not particularly limited (the same applies to FIGS. 8(A) to 8(C), FIGS. 9(A) to 9(D), and FIGS. 10(A) to 10(D)).

[0048] That is, according to the findings of the present inventors, as the roughened nickel layer 12, in the form shown in FIG. 7(B), specifically, (1) the primary particles forming the aggregated body of protrusions should not be too small and should have an appropriate size (the average particle diameter of the primary particles is preferably 0.3 to 3.0 μm, more preferably 0.5 to 2.0 μm), (2) the shape of the aggregated body composed of secondary particles in which such primary particles are aggregated should be protrusion-shaped or columnar, (3) the height of the aggregated body should not be too low or too high (the height is preferably 1 to 20 μm, more preferably 2 to 15 μm, and particularly preferably 2.0 to 10.0 μm from the viewpoint of emphasizing production efficiency and production cost), (4) the density of the aggregated body should not be too sparse (protrusion-shaped aggregated bodies are formed at a certain distance (a distance that is not too close and not too far)), and it has been found that by satisfying the conditions (1) to (4) above, the above problems can be solved. If the primary particles are too small, the adhesion (bonding) between the primary particles becomes poor, and the plating adhesion decreases. If the primary particles are too large, they cannot take on a protrusion-shaped or columnar form, or local protrusions grow excessively, making the protrusions prone to breakage by external forces or the like. As a result, the plating adhesion becomes poor. Here, not being too small and having an appropriate size means, more specifically, as confirmed by the cross-sectional SEM images of the roughened nickel layer 12 shown in FIGS. 5(C) and 5(D), among the primary particles constituting the protrusion-shaped or columnar secondary particles, a state where 70% or more of the whole is composed of primary particles with a particle diameter of 0.3 to 3.0 μm, more preferably a state composed of primary particles with a particle diameter of 0.5 to 2.0 μm. Note that the above 70% of the whole means that the area of 70% or more of the total cross-sectional area of all the primary particles is the area of the particles within the above particle diameter range. Also, although it is difficult to derive each particle diameter from the cross-sectional SEM image, when the particle diameter of the primary particles constituting the secondary particles is too small, since 70% or more of the particles have a particle diameter clearly less than 0.3 μm, clear identification is possible.

[0049] Furthermore, according to the embodiment shown in FIG. 7(B) like this, it has been found that the lightness L* and the glossiness at 85° are within the predetermined ranges of the present invention, and both the adhesion of the roughened nickel layer 12 to the metal substrate 11 and the adhesion to other members are satisfied simultaneously.

[0050] On the other hand, in the embodiment shown in FIG. 7(A) where no coated nickel plating is performed, since the primary particles are very fine or the height of the protruding aggregates is low, the lightness L* is outside the predetermined range of the present invention, and the adhesion of the roughened nickel layer 12 to the metal substrate 11 or the adhesion to other members becomes inferior. Note that the embodiment shown in FIG. 7(A) corresponds to Comparative Examples 11 to 16 and 34 described later.

[0051] Also, in the embodiment shown in FIG. 8(A), the embodiment shown in FIG. 8(B) obtained by applying coated nickel plating thereto, and the embodiment shown in FIG. 8(C) where no roughened nickel layer is formed, the height of the protruding aggregates is low or the protruding aggregates themselves are not formed, the lightness L* is outside the predetermined range of the present invention, and the adhesion of the roughened nickel layer 12 to the metal substrate 11 or the adhesion to other members becomes inferior. Note that the embodiment shown in FIG. 8(A) corresponds to Comparative Examples 17 to 20 described later, and the embodiments shown in FIGS. 8(B) and 8(C) correspond to Comparative Examples 1 to 4, 33, and 37 to 39 described later.

[0052] Also, in the aspect shown in Fig. 9(A) and the aspect shown in Fig. 9(B) obtained by applying a coating nickel plating thereto, the influence of the unevenness on the surface of the underlying nickel plating layer or the influence of the coarsening of the secondary particles of the roughened nickel layer is great. In the aspect shown in Fig. 9(A), the 85° glossiness is outside the predetermined range of the present invention, and the adhesion of the roughened nickel layer 12 to the metal substrate 11 is poor. In the aspect shown in Fig. 9(B), the lightness L* is outside the predetermined range of the present invention, and the adhesion to other members is poor. The aspect shown in Fig. 9(A) corresponds to Comparative Example 24 described later, and the aspect shown in Fig. 9(B) corresponds to Comparative Example 10 described later.

[0053] Furthermore, in the aspect shown in Fig. 9(C) and the aspect shown in Fig. 9(D) obtained by applying a coating nickel plating thereto, an aggregate having voids or a porous aggregate is formed, and the 85° glossiness is outside the predetermined range of the present invention, and the adhesion of the roughened nickel layer 12 to the metal substrate 11 is poor. The aspect shown in Fig. 9(C) corresponds to Comparative Examples 30 and 31 described later, and the aspect shown in Fig. 9(D) corresponds to Comparative Examples 8 and 9 described later.

[0054] Also, in the aspect shown in Fig. 10(A) and the aspect shown in Fig. 10(B) obtained by applying a coating nickel plating thereto, the height of the protrusion-like aggregate is too high, and furthermore, the formation density of the protrusion-like aggregate is low, the lightness L* is outside the predetermined range of the present invention, and the adhesion of the roughened nickel layer 12 to the metal substrate 11 is poor. The aspect shown in Fig. 10(A) corresponds to Comparative Examples 21 to 23, 25 to 29, 35, and 36 described later, and the aspect shown in Fig. 10(B) corresponds to Comparative Example 5 described later.

[0055] Also, in the aspect shown in Fig. 10(C) and the aspect shown in Fig. 10(D) obtained by applying nickel plating to this, the height of the protruding aggregate is too high, the lightness L* and the 85° glossiness are outside the specified range of the present invention, and the adhesion of the roughened nickel layer 12 to the metal substrate 11 is poor. The aspect shown in Fig. 10(C) corresponds to Comparative Example 32 described later, and the aspect shown in Fig. 10(D) corresponds to Comparative Examples 6 and 7 described later.

[0056] According to the present inventors, in the aspects shown in Figs. 7(A), 8(A) to 8(C), 9(A) to 9(D), and 10(A) to 10(D), either the lightness L* or the 85° glossiness is outside the specified range of the present invention, and either the adhesion of the roughened nickel layer 12 to the metal substrate 11 or the adhesion to other members is poor. On the other hand, according to the aspect as shown in Fig. 7(B), the lightness L* and the 85° glossiness are within the specified range of the present invention, and it has been found that both the adhesion of the roughened nickel layer 12 to the metal substrate 11 and the adhesion to other members can be satisfied simultaneously.

[0057] As a method for forming the roughened nickel layer 12 as shown in FIG. 7(B), the methods described above can be mentioned. At this time, for example, it is presumed that the roughened nickel layer 12 as shown in FIG. 7(B) is formed through the precipitation step and the growth step described below. That is, first, as described above, as roughened nickel plating, by passing an appropriate current (applying a voltage) that excites precipitation in a dilute nickel aqueous solution, metallic nickel can be precipitated simultaneously from a large number of nuclei, and furthermore, the growth of the precipitated particles in the plane direction can be suppressed to some extent. Also at this time, since the nuclei of the primary particles are likely to preferentially precipitate on the convex portions formed by the precipitated particles, as a result, the primary particles of the plated granular material are laminated in the height direction, and the shape of the secondary particles formed by the aggregation of the primary particles can be made into a protrusion shape. However, even when such an aggregate is formed, if the primary particles are too small as shown in FIG. 7(A), the contact surface between the primary particles is too small, so the primary particles are likely to peel off. Therefore, as described above, after the roughened nickel plating, covering nickel plating is performed. Here, although it is expressed as "covering", according to the study by the present inventors, according to such covering nickel plating, in addition to the precipitation that covers the primary particles formed by the roughened nickel plating, in fact, it has been confirmed that grain growth in which the primary particles grow also occurs. In particular, such growth of the primary particles due to the covering nickel plating is considered to occur not only on the top surface of the protrusion-shaped aggregate but also in the particles on the side surface and the internal particles of the aggregate. As a result, the primary particles have an appropriate size, thereby improving the adhesion between the primary particles, and furthermore, it is considered that the thickness of the protrusion-shaped aggregate also increases and becomes less likely to break. Therefore, the roughened nickel layer 12, which is the aspect shown in FIG. 7(B), has good adhesion of the roughened nickel layer 12 to the metal base material 11. In addition to this, since it has a protrusion-shaped aggregate with an appropriate height, it also has excellent adhesion to other members. In this embodiment, as a method for forming the roughened nickel layer as shown in Fig. 7(B), a method of applying a coating nickel plating after the roughened nickel plating is given. However, if the above-mentioned conditions (1) to (4) are satisfied after the roughened nickel plating, the lightness L* and the glossiness at 85° will naturally fall within the predetermined range of the present invention, and a roughened nickel plated sheet excellent in the adhesion of the roughened nickel layer 12 to the metal substrate 11 and the adhesion to other members can be obtained. Therefore, the coating nickel plating process may be omitted.

[0058] The cross-sectional SEM photographs of the roughened nickel layer according to the embodiment shown in Fig. 8(A) are shown in Fig. 11(A), those according to the embodiment shown in Fig. 8(B) are shown in Fig. 11(B), those according to the embodiment shown in Fig. 8(C) are shown in Fig. 11(C), those according to the embodiment shown in Fig. 9(A) are shown in Fig. 12(A), those according to the embodiment shown in Fig. 9(B) are shown in Fig. 12(B), those according to the embodiment shown in Fig. 9(D) are shown in Fig. 12(C), those according to the embodiment shown in Fig. 10(A) are shown in Fig. 13(A), and those according to the embodiment shown in Fig. 10(C) are shown in Fig. 13(B), respectively.

[0059] According to the roughened nickel plated sheet 1 of the present embodiment as described above, the adhesion of the roughened nickel layer 12 to the metal substrate 11 is good, and the adhesion to other members is excellent. Therefore, it can be suitably used for applications where it is joined to other members, such as various containers, electronic device members (such as substrates), and battery members (outer tanks, current collectors, tab leads) that require adhesion to various members such as resins and active materials.

[0060] In particular, the roughened nickel-plated sheet 1 of the present embodiment is excellent in the adhesion of the roughened nickel layer 12, that is, the adhesion to the base material 11. Therefore, even if the plated sheets overlap or come into contact with each other, the roughened nickel layer 12 on the surface is less likely to peel off or fall off. As shown in FIG. 1A, it can be preferably used as the roughened nickel-plated sheet 1 having the roughened nickel layer 12 on the outermost surfaces of both sides.

[0061] On the other hand, when adhesion to other members is required only for one side of the plated sheet, as in the roughened nickel-plated sheet 1 shown in FIG. 1B, it is sufficient that the roughened nickel layer 12 is formed only on one side. On the surface where the roughened nickel layer 12 is not formed, the base material 11 will be located on the outermost surface. For example, when the base material 11 is a steel sheet, it may remain as an untreated steel sheet, or a surface treatment according to the required characteristics such as nickel plating, zinc plating, or chemical conversion treatment may be performed. Particularly when resistance to an alkaline solution is required, a roughened nickel-plated steel sheet having a normal nickel plating layer (for example, a nickel plating layer formed under the conditions for forming the above-described underlayer nickel plating layer) formed on the surface where the roughened nickel layer 12 is not formed can be preferably applied because the both surfaces of the base material 11 will be covered with the nickel layer. When manufacturing the roughened nickel-plated sheet 1 as shown in FIG. 1B, for example, in the process of performing roughened nickel plating, a roughened nickel-plated steel sheet having the roughened nickel layer 12 only on one side can be obtained by a method of performing plating treatment without applying current to the surface where the roughened nickel layer 12 is not formed or by a masking method.

Examples

[0062] Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. The evaluation methods for each characteristic are as follows.

[0063] <Surface roughness> For the surface of the roughened nickel plating plate on which the roughened nickel layer is formed, in accordance with JIS B0601:2013, using a laser microscope (manufactured by Olympus, model number: OLS3500), a field of view of 97 μm × 129 μm (vertical × horizontal) (measurement field width 129 μm, measurement area approximately 12,500 μm 2 (12,500 ± 100)) was scanned, and then, using analysis software (software name: LEXT - OLS), by analyzing under the conditions of the analysis mode: roughness analysis, the arithmetic mean roughness Ra and the ten - point mean roughness Rz jis were measured. In addition, the cut - off value when measuring with the laser microscope was set to a wavelength of about 43 μm (displayed as 43.2), which is 1 / 3 of the length of the measurement field width (129 μm).

[0064] <Nickel amount> In this example, after each process of forming the underlying nickel layer, nickel particles, and nickel coating, by measuring with a fluorescent X - ray device, the nickel amounts in the underlying nickel layer and the roughened nickel layer (nickel particles and nickel coating) were respectively determined. Specifically, when the underlying nickel layer was formed, the nickel amount of the underlying nickel layer was determined once using a fluorescent X - ray device. Then, after forming the nickel particles, the total nickel amount was determined again with the fluorescent X - ray device, and the difference between the obtained total nickel amount and the nickel amount of the underlying nickel layer was taken as the nickel amount of the nickel particles. Furthermore, after forming the nickel coating, the total nickel amount was determined again with the fluorescent X - ray device, and the nickel amount of the nickel coating was obtained in the same way by finding the difference between the total nickel amount before nickel coating formation and after formation. And the total nickel amount of the nickel particles and the nickel coating was determined as the adhesion amount of the roughened nickel layer. Here, when using metals containing nickel such as stainless steel plates and nickel plates as the substrate, the nickel amounts of each layer cannot be measured by the above - mentioned fluorescent X - ray device. Therefore, by using a substrate that does not contain nickel such as a steel plate in advance, under the plating conditions where the nickel amount of a predetermined underlying nickel layer is obtained, electrolyzing the substrate into a metal plate containing nickel such as a stainless steel plate and a nickel plate, the same adhesion amount can be obtained. In the present example and the comparative examples, the nickel amount was measured by the above method. However, the measurement of the nickel amount is not limited to such a method, and the following method may also be used. In the present example, the following method was also partly adopted. That is, first, for the roughened nickel plating plate on which the underlying nickel layer, nickel particulate matter, and nickel coating were formed, measurement was performed with a fluorescent X-ray apparatus to obtain the total nickel amount of the layer formed on the roughened nickel plating plate. Next, the roughened nickel plating plate was cut, and the thickness of the underlying nickel layer was measured by observing the cross section with a scanning electron microscope (SEM), and the nickel amount converted from the thickness of the underlying nickel layer was obtained, and this was taken as the nickel amount of the underlying nickel layer. Then, by subtracting the nickel amount of the underlying nickel layer from the total nickel amount, the total nickel amount of the nickel particulate matter and the nickel coating can be obtained, and this can be taken as the adhesion amount of the roughened nickel layer. In particular, when performing coated nickel plating, as the nickel coating 122 that coats the nickel particulate matter 121, in addition to forming the roughened nickel layer 12, in part, the underlying nickel layer is formed. According to such a method, it is possible to obtain the nickel amount of the underlying nickel layer taking into account the growth (thickening) of the underlying nickel layer due to the coated nickel plating. Here, regarding the boundary between the metal substrate and the underlying nickel layer and the boundary between the underlying nickel layer and the roughened nickel layer when observing the cross section with a scanning electron microscope (SEM), the determination was made as shown in FIG. 15. That is, as shown in FIG. 15, since the boundary between the metal substrate and the underlying nickel layer can be clearly observed as shown in FIG. 15, the position shown in FIG. 15 (the lower broken line position) was taken. On the other hand, regarding the boundary between the underlying nickel layer and the roughened nickel layer, as shown in FIG. 15, the position with the lowest height among the bases of the protrusions by the secondary particles (the upper broken line position) was taken. Note that FIG. 15 is a diagram for explaining the method of determining the boundary between the metal substrate and the underlying nickel layer and the boundary between the underlying nickel layer and the roughened nickel layer in the example and the comparative example. FIG. 15(A) and FIG. 15(B) are diagrams showing the same scanning electron microscope (SEM) photographs side by side. In FIG. 15, in FIG. 15(B), each boundary position is indicated by a broken line.

[0065] <Lightness L * > The lightness L of the roughened nickel layer surface * was measured by the SCE method (regular reflection light removal method) in accordance with the geometric condition C in JIS Z8722 using a spectrocolorimeter (product name "CM-5", manufactured by Konica Minolta).

[0066] <85° Glossiness> The 85° glossiness of the roughened nickel layer surface was measured in accordance with JIS Z8741 using a gloss meter (product name "VG 7000", manufactured by Nippon Denshoku Industries Co., Ltd.). When the 60° glossiness was measured using the same measuring instrument, it was less than 1.5 in any of the examples (Examples 1 to 32).

[0067] <Adhesion of the roughened nickel layer> First, as a reference sample, a pressure-sensitive adhesive tape (manufactured by Nichiban Co., Ltd., product name "Cellotape (registered trademark)") attached to a backing paper was prepared, and the lightness L * , chromaticity a * , b * were measured using a spectrocolorimeter (product name "CM-5", manufactured by Konica Minolta). When measuring, the CIE1976L * a * b * color difference model was used. Then, a pressure-sensitive adhesive tape (manufactured by Nichiban Co., Ltd., product name "Cellotape (registered trademark)") was attached to the surface of the roughened nickel layer formed on the roughened nickel plating plates obtained in the examples and comparative examples so as to have a width of 24 mm and a length of 50 mm. After that, a peeling test using the attached pressure-sensitive adhesive tape was conducted according to the procedure of the peeling test method described in JIS H 8504. Then, the pressure-sensitive adhesive tape after the peeling test was attached to the same backing paper as the reference sample, and in the same manner as above, the lightness L * , chromaticity a * , b * were measured using a spectrocolorimeter. Then, the previously measured lightness L * , chromaticity a * , b * measurement results of the reference sample, and the lightness L * , chromaticity a* , b * From the measurement results of these, the difference ΔE * ab (ΔE * ab = 〔(ΔL * ) 2 + (Δa * ) 2 + (Δb * ) 2 〕 1 / 2 ) was calculated, and based on the following criteria, the adhesion of the roughened nickel layer was evaluated. Note that the smaller ΔE * ab is, the less the amount of peeling in the peel test, that is, it can be judged that the residual rate of the roughened nickel layer after the peel test is high and the adhesion to the base material is excellent. 5 points: ΔE * ab < 1 4 points: ΔE * ab ≥ 1 and < 10 3 points: ΔE * ab ≥ 10 and < 30 2 points: ΔE * ab ≥ 30 and < 40 1 point: ΔE * ab ≥ 40

[0068] <Adhesion of polypropylene resin (PP resin) (T-peel strength)> The roughened nickel-plated plates obtained in the examples and comparative examples were cut to produce two test blanks with dimensions of 15 mm in width and 50 mm in length, which were used as T-peel test pieces. Then, the two T-peel test pieces were each bent at a 90° angle at a position 20 mm in length. Next, the surfaces of each T-peel test piece having the roughened nickel layer were faced each other, and a polypropylene resin film (manufactured by Mitsubishi Chemical Corporation, trade name "Modic" / polypropylene resin two-layer film, the bonding surface to be evaluated is the bonding surface between the polypropylene resin and the T-peel test piece, and the trade name "Modic" is an adhesive layer for stabilizing the test) with a width of 15 mm, a length of 15 mm, and a thickness of 60 μm was sandwiched, temperature: 190 °C, pressing time: 5 seconds, heat seal pressure: 2.0 kgf / cm 2Heat sealing was performed under the specified conditions, and two T-peel test pieces were joined through a polypropylene resin film. The position where the polypropylene resin film was sandwiched was the end in the length direction of the T-peel test body, and the entire polypropylene resin film became the bonding surface. For the T-peel test body thus prepared, a tensile test was conducted using a tensile testing machine (Universal Material Testing Machine Tensilon RTC-1350A manufactured by ORIENTEC), and the peel load (T-peel strength) was measured. The measurement conditions were a tensile speed of 10 mm / min at room temperature. It can be judged that the higher the T-peel strength, the better the adhesion to the resin.

[0069] 《Example 1》 As the substrate, a steel sheet obtained by annealing a cold-rolled sheet of low-carbon aluminum-killed steel (thickness 0.25 mm) was prepared.

[0070] Then, for the prepared steel sheet, after performing alkaline electrolytic degreasing and pickling in sulfuric acid immersion, electrolytic plating was carried out under the following conditions using an undercoat nickel plating bath with the following bath composition to form undercoat nickel layers on both sides of the steel sheet. <Undercoat Nickel Plating Conditions> Bath composition: Nickel sulfate hexahydrate 250 g / L, Nickel chloride hexahydrate 45 g / L, Boric acid 30 g / L pH: 4.2 Bath temperature: 60 °C Current density: 10 A / dm 2 Plating time: 30 seconds

[0071] Next, for the steel sheet with the undercoat nickel layer formed, electrolytic plating (roughened nickel plating) was carried out under the following conditions using a roughened nickel plating bath with the following bath composition to deposit nickel granular substances on the undercoat nickel layers on both sides of the steel sheet. <Roughened Nickel Plating Conditions> Bath composition: Nickel sulfate hexahydrate 20 g / L, Ammonium sulfate 20 g / L pH: 6.2 Bath temperature: 30 °C Current density: 20 A / dm 2 Plating time: 11 seconds

[0072] Next, on the steel sheet with nickel particles deposited on the underlying nickel layer, electrolytic plating (coating nickel plating) is performed under the following conditions using a coating nickel plating bath with the following bath composition to coat the nickel particles deposited on the underlying nickel layer with a nickel film, thereby obtaining the roughened nickel plated sheet of Example 1. <Coating Nickel Plating Conditions> Bath composition: 250 g / L of nickel sulfate hexahydrate, 45 g / L of nickel chloride hexahydrate, 30 g / L of boric acid pH: 4.2 Bath temperature: 60 °C Current density: 10 A / dm 2 Plating time: 30 seconds

[0073] Then, for the obtained roughened nickel plated sheet, the nickel amounts of the underlying nickel layer, nickel particles, and nickel film, the lightness L of the surface of the roughened nickel layer * and the 85° gloss, the adhesion of the roughened nickel layer, and the adhesion of polypropylene resin (PP resin) were each measured and evaluated. The results are shown in Table 1.

[0074] 《Examples 2 - 15》 The plating bath and plating conditions of the roughened nickel plating were changed to the conditions shown in Table 1, and except that the treatment time of the coating nickel plating was changed so that the deposition amount of the formed nickel film became the amount shown in Table 1, in the same manner as in Example 1, roughened nickel plated sheets of Examples 2 - 15 were obtained and evaluated in the same manner. The results are shown in Table 1.

[0075] 《Examples 16 - 31》 The conditions of the roughened nickel plating were changed to the conditions shown in Table 2, and except that the treatment time of the coating nickel plating was changed so that the deposition amount of the formed nickel film became the amount shown in Table 2, in the same manner as in Example 1, roughened nickel plated sheets of Examples 16 - 31 were obtained and evaluated in the same manner. The results are shown in Table 2.

[0076] 《Example 32》 As the metal substrate, a copper plate (electrolytic copper foil manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., Ra: 0.1 μm and Rz jis : 1.7 μm as measured by a laser microscope) was used. In addition, the conditions for roughened nickel plating were changed to the conditions shown in Table 2, and the treatment time for coated nickel plating was changed so that the deposition amount of the formed nickel film became the amount shown in Table 2. Except for this, in the same manner as in Example 1, a roughened nickel plating plate of Example 32 was obtained and evaluated in the same manner. The results are shown in Table 2.

[0077] 《Examples 33 to 36》 The conditions for roughened nickel plating were changed to the conditions shown in Table 2, and the treatment time for coated nickel plating was changed so that the deposition amount of the formed nickel film became the amount shown in Table 2. Except for this, in the same manner as in Example 1, roughened nickel plating plates of Examples 33 to 36 were obtained and evaluated in the same manner. The results are shown in Table 2.

[0078] 《Examples 37 to 41》 As the metal substrate, SUS304 (Example 37), SUS316 (Example 38), SUS430 (Example 39), SUS444 (Example 40), and pure nickel plate (Example 41) were used respectively. In addition, the conditions for roughened nickel plating were changed to the conditions shown in Table 2, and the treatment time for coated nickel plating was changed so that the deposition amount of the formed nickel film became the amount shown in Table 2. Except for this, in the same manner as in Example 1, roughened nickel plating plates of Examples 37 to 41 were obtained and evaluated in the same manner. The results are shown in Table 2. In Examples 37 to 41, after pickling with sulfuric acid immersion using SUS304, SUS316, SUS430, SUS444, and pure nickel plate, electrolysis (strike nickel plating) was performed under the following conditions using a strike nickel plating bath with the following bath composition to form an underlying nickel layer. <Strike nickel plating conditions> Bath composition: Nickel sulfate hexahydrate 250 g / L, sulfuric acid 50 g / L pH: 1.0 or less Bath temperature: 60 °C Current density: 30 A / dm2 Plating time: 5 seconds

[0079] 《Comparative Examples 1 - 10》 Except that the conditions of the roughened nickel plating and the coated nickel plating were changed to the conditions shown in Table 3, the roughened nickel plating plates of Comparative Examples 1 - 10 were obtained and evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0080] 《Comparative Examples 11 - 22》 Except that the conditions of the roughened nickel plating were changed to the conditions shown in Table 3 and the coated nickel plating was not performed, the roughened nickel plating plates of Comparative Examples 11 - 22 were obtained and evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0081] 《Comparative Examples 23, 24》 Except that a copper plate was used as the metal substrate, the conditions of the roughened nickel plating were changed to the conditions shown in Table 4, and the coated nickel plating was not performed, the roughened nickel plating plates of Comparative Examples 23, 24 were obtained and evaluated in the same manner as in Example 1. The results are shown in Table 4. In Comparative Example 23, an electrolytic copper foil manufactured by Fukuda Metal Foil Powder Industry Co., Ltd. (as measured by a laser microscope, Ra: 0.1 μm, Rz jis : 1.7 μm) was used. In Comparative Example 24, a copper foil whose surface was roughened by performing roughened copper plating on the same copper foil as in Comparative Example 23 was used as the copper plate.

[0082] 《Comparative Examples 25 - 32》 Except that the conditions of the roughened nickel plating were changed to the conditions shown in Table 4 and the coated nickel plating was not performed, the roughened nickel plating plates of Comparative Examples 25 - 32 were obtained and evaluated in the same manner as in Example 1. The results are shown in Table 4.

[0083] 《Comparative Example 33》 Except that neither the roughened nickel plating nor the coated nickel plating was performed, the roughened nickel plating plate of Comparative Example 33 was obtained and evaluated in the same manner as in Example 1. The results are shown in Table 4.

[0084] 《Comparative Examples 34 - 36》 The conditions for the roughened nickel plating were changed to those shown in Table 4, and roughened nickel plated sheets for Comparative Examples 34 - 36 were obtained and evaluated in the same manner as in Example 1, except that the coated nickel plating was not performed. The results are shown in Table 4.

[0085] 《Comparative Examples 37 - 39》 Roughened nickel plated sheets for Comparative Examples 37 - 39 were obtained and evaluated in the same manner as in Example 1, except that the conditions for the roughened nickel plating and the coated nickel plating were changed to those shown in Table 4. The results are shown in Table 4.

[0086]

Table 1

[0087]

Table 2

[0088]

Table 3

[0089]

Table 4

[0090] As can be confirmed from Tables 1 - 4, when the lightness L of the surface of the roughened nickel layer is 30 - 50 and the 85° glossiness of the surface of the roughened nickel layer is 1.5 - 50, in all cases, the adhesion of the roughened nickel layer to the metal substrate is good, and moreover, the adhesion to the polypropylene resin (PP resin) is excellent (Examples 1 - 36). * On the other hand, when the roughened nickel layer is not formed, or when the lightness L of the surface of the roughened nickel layer * ​When the glossiness is 85° or outside the specified range of the present invention, the adhesion of the roughened nickel layer to the metal substrate and / or the adhesion to the polypropylene resin (PP resin) deteriorates (Comparative Examples 1 to 39). Note that FIGS. 5(A) and 5(B) are images obtained by observing the surface of the roughened nickel-plated plate of Example 28 with a scanning electron microscope (SEM), and FIGS. 5(C) and 5(D) are images obtained by observing the cross-section of the roughened nickel-plated plate of Example 28 with a scanning electron microscope (SEM). Also, FIGS. 6(A) and 6(B) are images obtained by observing the surface of the roughened nickel-plated plate of Comparative Example 5 with a scanning electron microscope (SEM), and FIGS. 6(C) and 6(D) are images obtained by observing the cross-section of the roughened nickel-plated plate of Comparative Example 5 with a scanning electron microscope (SEM). In FIGS. 5(A) to 5(D) and FIGS. 6(A) to 6(D), the scale bars (white lines) in the measurement condition description part at the lower left of the images all indicate a length of 1 μm.

[0091] In Tables 1 to 4, the nickel amount of the underlying nickel layer was calculated from the treatment conditions of the underlying nickel plating and described as the "underlying nickel layer", and the nickel plating amount of the nickel coating 122 was calculated from the treatment conditions of the coating nickel plating and described as the "nickel coating". However, when the coating nickel plating was performed, in addition to forming the roughened nickel layer 12 as the nickel coating 122 covering the nickel particles 121, a part of it also formed the underlying nickel layer. That is, it also contributes to the growth of the underlying nickel layer. Actually, when the thickness of the formed underlying nickel layer was calculated by a scanning electron microscope (SEM) and the nickel amount of the underlying nickel layer was calculated from the calculated thickness, in Example 5, it was 11.6 g / m 2 and in Example 6, it was 11.6 g / m 2 and in Example 7, it was 12.5 g / m 2 and in Example 8, it was 13.4 g / m 2It was. From the difference between these numerical values and the calculated values from the plating treatment conditions of Examples 5 to 8, the growth of the underlying nickel layer can be calculated. Similarly, in Examples 1 to 36, when the difference was calculated, it was 1.8 to 4.5 g / m 2 resulted. (Shown in Tables 1 and 2.) Also, as these averages, it was 2.8 g / m 2 resulted. In Tables 1 and 2, in the third column from the right, the nickel thickness (μm) of the underlying nickel layer measured from the cross-sectional image of the scanning electron microscope (SEM) is shown, and in the second column from the right, the nickel amount (g / m 2 ) of the underlying nickel layer calculated from the nickel thickness of the underlying nickel layer is shown respectively. Also, in Tables 1 and 2, in the rightmost column, the underlying nickel growth amount, that is, the increase amount of the underlying nickel layer by performing the coating nickel plating after performing the plating for forming the underlying nickel layer, is shown. In this way, in the embodiment of the present application, when obtaining the adhesion amount of the underlying nickel layer and the roughened plating layer from the cross-sectional image of the scanning electron microscope, by subtracting 2.8 g / m 2 (corresponding to 0.32 μm) from the underlying nickel layer and adding it to the roughened plating layer, the adhesion amount (thickness) of each layer can be calculated.

[0092] 《Example 42》 After forming the underlying nickel layer on both sides of the steel sheet under the same conditions as in Example 1, one side of the steel sheet on which the underlying nickel layer was formed was masked, and on the side opposite to the masked side, using a roughened nickel plating bath having the same bath composition as in Example 1, electrolytic plating was performed under the same conditions as in Example 1 to deposit nickel particles on the underlying nickel layer. Further, using a coating nickel plating bath having the same bath composition as in Example 1, electrolytic plating was performed under the same conditions as in Example 1 to perform the coating nickel plating, whereby a roughened nickel plated sheet (roughened nickel plated sheet in the form shown in Fig. 1B) having the roughened nickel layer formed only on one side was obtained. Then, when the obtained roughened nickel plated sheet was evaluated in the same manner as in Example 1, it was confirmed that the same shape and effects were obtained.

Explanation of Signs

[0093] 1, 1a… Roughened nickel plating sheet 11… Metal substrate 12… Roughened nickel layer 121… Nickel particles 122… Nickel coating 13… Underlying nickel layer

Claims

1. A roughened nickel-plated sheet having a roughened nickel layer as the outermost layer on at least one surface of a metal substrate, In the roughened nickel plating plate, the adhesion amount of nickel plating is 5.0 to 50.0 g / m ２ and wherein the metal substrate is a metal plate or metal foil made of a pure metal selected from Cu and Al, or a metal plate or metal foil made of an alloy containing one selected from Cu and Al, The lightness L of the surface of the roughened nickel layer ＊ is 30 to 50, and the 85° glossiness of the surface of the roughened nickel layer is 1.5 to 50. The roughened nickel-plated sheet.

2. The roughened nickel-plated sheet according to claim 1, wherein the thickness of the metal substrate is 0.01 to 2.0 mm.

3. The arithmetic mean roughness Ra of the roughened nickel layer measured by laser microscopy is 0.1 to 3.0 µm, and the ten-point mean roughness Rz of the roughened nickel layer measured by laser microscopy ｊｉｓ is 2.0 to 20.0 µm. The roughened nickel plating sheet according to claim 1 or 2

Images