Patent Application
20210268770
The present invention relates to a roughened nickel-plated sheet having a roughened nickel layer as an outermost surface layer.
Conventionally, as a member constituting the battery, or a member constituting the electronic-related equipment, nickel plated steel sheet is used. In such a nickel-plated steel sheet, when bonded with other members, in a view of improving adhesion, a method of controlling the surface structure of the nickel-plated steel sheet is known.
For example, Patent Document 1 discloses a surface-treated steel sheet formed by forming a nickel plating layer having a microstructure controlled to a particle density of 2 to 500 particles/μm2 and an average particle diameter of 0.05 to 0.7 μm on a steel sheet.
Patent Document 1: Japanese Patent No. 5885345
However, in the surface-treated steel sheet disclosed in Patent Document 1, depending on the type of the member to be bonded to the surface-treated steel sheet and the bonding method, the adhesiveness with other members may be insufficient, and further improvement of the adhesiveness has been demanded.
On the other hand, a method of forming a nickel plating layer by roughening plating is also conceivable in order to improve the adhesion with other members, but when the present inventors have investigated, it has been found that there is a problem that the adhesion of the roughened plating layer itself foamed by roughening plating to the base material is lowered, and thus the reliability is lowered in some cases.
It is an object of the present invention to provide a roughened nickel-plated sheet exhibiting excellent adhesion to other members while maintaining good adhesion of a plating layer to a base material.
As a result of intensive studies to achieve the above object, the present inventors have found that by controlling the lightness and the glossiness of 85° of the surface of the roughened nickel layer to a specific range, it is possible to obtain a roughened nickel-plated sheet exhibiting excellent adhesion to other members while maintaining good adhesiveness of the plating layer to the base material, thereby completing the present invention.
Specifically, according to the present invention, there is provided a roughened nickel-plated sheet having a roughened nickel layer as an outermost surface layer on at least one surface of a metal base material, wherein
In the roughened nickel-plated sheet according to the present invention, it is preferable that the metal base material is a metal sheet or a metal foil made of one kind of pure metal selected from Fe, Cu, Al, and Ni, or a metal sheet or a metal foil made of an alloy containing one kind selected from Fe, Cu, Al, and Ni.
In the roughened nickel-plated sheet according to the present invention, it is preferable that the metal base material is a steel sheet.
In the roughened nickel-plated sheet according to the present invention, it is preferable that the thickness of the metal base material is 0.01 to 2.0 mm.
In the roughened nickel-plated sheet according to the present invention, it is preferable that the deposition amount of nickel plating is 5.0 to 50.0 g/m2.
In the roughened nickel-plated sheet according to the present invention, it is preferable that the roughened nickel layer has an arithmetic mean roughness Ra of 0.1 to 3.0 μm by laser microscopy, and the roughened nickel layer has a ten-point mean roughness Rzjis of 2.0 to 20.0 μm by laser microscopy.
According to the present invention, there can be provided a roughened nickel-plated sheet which is excellent in adhesion to other members while maintaining good adhesiveness of the plating layer to the base material.
In the present embodiment, as shown in
The metal base material 11 as a substrate of the roughened nickel-plated sheet 1 of the present embodiment is not particularly limited, a metal sheet or a metal foil made of a kind of pure metal selected from Fe, Cu, Al and Ni, or a metal sheet or a metal foil made of an alloy containing one kind selected from Fe, Cu, Al, and Ni, specifically, steel sheet, iron sheet, stainless steel sheet, cupper sheet, aluminum sheet, or nickel sheet (these may be any of pure metal and alloys, may be foil.) Among them, since the plating is easily performed even with a relatively simple pretreatment of the plating process and it is easy to form a high adhesion roughened nickel layer to the metal base material, a steel sheet or a copper sheet is preferred, in particular, a low-carbon aluminum-killed steel (carbon content of 0.01 to 0.15% by weight), extra-low carbon steel having a carbon content of 0.01% by weight or less (preferably a carbon content of 0.003% by weight or less), or non-aging extra-low carbon steel made by adding Ti, Nb and the like to an extra-low carbon steel are preferably used.
In the present embodiment, steel sheet, cupper sheet, aluminum sheet, or a nickel sheet which is obtained by hot rolling any of these sheets, acid pickling the hot rolled sheet to remove scales (oxide film) on the surface, cold rolling the pickled sheet can be used as a substrate. Alternatively, a sheet to which annealing or tempering rolling is performed after electrolytic cleaning may be used. In this case, annealing may be any of continuous annealing or box annealing, not particularly limited. In addition, as the electrolytic foil produced by electroforming method, copper foil, nickel foil, iron foil or the like can also be used as a metal base material.
Incidentally, as the metal base material 11, when using a metal base material in which a passive film is foamed on the surface such as a stainless steel sheet and a nickel sheet, before roughened nickel plating or before plating process for forming the underlying metal plating, it is preferable to use those subjected to strike nickel plating. The conditions of the strike nickel plating are not particularly limited, and for example, the following conditions can be given. Under the following conditions, the deposition amount of nickel by strike nickel plating is usually 0.08 to 0.89 g/m2, but when forming an underlying nickel layer, the sum of the deposition amount of nickel by strike nickel plating and the deposition amount of nickel by nickel plating to form an underlying nickel layer is measured as the deposition amount of nickel by the underlying nickel layer.
Bath composition: Nickel sulfate hexahydrate 100 to 300 g/L, sulfuric acid 10 to 200 g/L
The thickness of the metal base material 11 is not particularly limited, but is preferably 0.01 to 2.0 mm, more preferably 0.025 to 1.6 mm, and still more preferably 0.025 to 0.3 mm. Further, the roughness of the metal base material 11 is not particularly limited, but the arithmetic mean roughness Ra in the stylus surface roughness meter is 0.05 to 2.0 μm, more preferably 0.05 to 0.9 μm, and still more preferably 0.05 to 0.5 μm.
The roughened nickel layer 12 formed on the outermost surface of the roughened nickel-plated sheet 1 of the present embodiment is one where the brightness L* of the surface is controlled to 30 to 50 and a glossiness of 85° of the surface is controlled to 3 to 50. According to the present embodiment, by controlling the brightness L* and the glossiness of 85° of the surfaces of the roughened nickel layer 12 within the above ranges, the roughened nickel-plated sheet 1 can be made one which exhibits excellent adhesion to other members while maintaining good adhesion of the roughened nickel layer 12 to the metal base material 11.
In particular, as a result of intensive investigation by the present inventors of the relation between the brightness L* and the glossiness of 85° of the surface of the roughened nickel layer 12 and the adhesiveness of the roughened nickel layer 12 to the metal base material 11 and the adhesiveness of the roughened nickel layer 12 to other members, the present inventors have found that by setting the brightness L* and the glossiness of 85° of the surface of the roughened nickel layer 12 to the above ranges, the roughened nickel-plated sheet 1 can exhibit excellent adhesiveness to other members while maintaining the adhesiveness of the roughened nickel layer 12 well, and the present invention has been completed.
Here, according to the present embodiment, in addition to exhibiting excellent adhesion to other members, attention is also paid to the adhesiveness of the roughened nickel layer 12 to the metal base material 11, which is for the following reason. That is, by forming the roughened nickel layer 12, even if it is possible to exhibit excellent adhesion to other members, when the roughened nickel layer 12 is easy to fall off from the metal base material 11, due to that the roughened nickel layer 12 falls off, the effect by forming the roughened nickel layer 12 becomes insufficient, i.e., the effect where it is possible to exhibit excellent adhesion to other members becomes insufficient. Therefore, from such a viewpoint, the present inventors have paid the attention to the adhesion of the roughened nickel layer 12 to the metal base material 11, and have improved this.
In addition, if the adhesion of the roughened nickel layer 12 to the metal base material 11 is insufficient, when producing the roughened nickel-plated sheet 1 of the present embodiment, the plating film scraps (Ni powder) due to the falling off of the roughened nickel layer 12 is mixed in the manufacturing line, in addition to that may cause contamination or failure of the production line, there is a case that causes product defects due to the plating film scraps remaining in the production line. Furthermore, using the roughened nickel-plated sheet 1 of the present embodiment, even when actually processed into products or parts, and there is it causes contamination or failure of the manufacturing line similarly, and there is a possibility that it causes defects in terms of the quality or function of the final product. Therefore, also from such viewpoint, the present inventors have paid attention to the importance of the adhesion of the roughened nickel layer 12 to the metal base material 11, and have improved this.
The brightness of the surface of the roughened nickel layer 12 is from 30 to 50, preferably from 30 to 48, more preferably from 30 to 45, and even more preferably from 35 to 45, by a value of L*. From the viewpoint of emphasizing production efficiency and production cost, it is preferable that the brightness of the surface of the roughened nickel layer 12 is 36 to 48. If the value of the brightness L* is too small, the adhesion of the roughened nickel layer 12 to the metal base material 11 becomes inferior, whereas, if the value of the brightness L* is too large, the adhesion to other members becomes inferior. Note that the brightness L* of the surface of the roughened nickel layer 12 can be measured using a spectrophotometer by the SCE-method (specular reflected light removing method) in accordance with JIS 28722.
The glossiness of 85° of the surface of the roughened nickel layer 12 is 1.5 to 50, preferably 1.5 to 35, and more preferably 2 to 30. From the viewpoint of emphasizing production efficiency and production cost, the glossiness of 85° of the surface of the roughened nickel layer 12 is preferably 15 to 50. If the glossiness of 85° is too small, the adhesion of the roughened nickel layer 12 to the metal base material 11 becomes inferior. If the glossiness is too large, the adhesion to other members becomes inferior. Note that, glossiness of 85° of the surface of the roughened nickel-layer 12 can be determined by measuring the specular gloss of 85° using a glossmeter in accordance with JIS 28741. Incidentally, the glossiness of 60° 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.
Although the chromaticity a*, b* of the surface of the roughened nickel layer 12 is not particularly limited, 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, from the viewpoint that the adhesion of the roughened nickel layer 12 to the metal base material 11 and the adhesion of the roughened nickel layer 12 to other members can be further improved.
The roughened nickel layer 12 may have the brightness L* of the surface and the glossiness of 85° of the surface within the above ranges, but the arithmetic mean roughness Ra is preferably 0.1 to 3 μm, from the viewpoint of 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, and from the viewpoint of improving the adhesion (plating adhesion) of the roughened nickel layer 12 to the metal base material 11, the arithmetic mean roughness Ra is more preferably 1.8 μm or less, still more preferably 1.6 μm or less, even more preferably 1.3 μm or less. In addition, from the viewpoint of emphasizing production efficiency and production cost, the arithmetic average roughness Ra is preferably 0.18 to 0.5 μm, more preferably 0.18 to 0.49 μm. The roughened nickel layer 12 preferably has a ten-point mean roughness Rzjis of 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 mean roughness Rzjis is more preferably 3 μm or more, still more preferably 4 μm or more, and even more preferably 5 μm or more, and from the viewpoint of further improving the adhesion (plating adhesion) of the roughened nickel layer 12 to the metal base material 11, the ten-point mean roughness Rzjis is more preferably 16 μm or less, still more preferably 14 μm or less, and even more preferably 12 μm or less. From the viewpoint of emphasizing production efficiencies and production costs, it is preferable that the ten-point mean roughness Rzjis is 3.0 to 7.0 μm. Note that, 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. The surface roughnesses Ra, Rzjis, and Rz are preferably measured by laser microscopy.
The deposition amount of the roughened nickel layer 12 in the roughened nickel-plated sheet 1 of the present embodiment is not particularly limited, but is preferably 1.34 to 45.0 g/m2, and 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/m2 or more, still more preferably 5 g/m2 or more, and 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/m2 or less, still more preferably 32.0 g/m2 or less, and even more preferably 31 g/m2 or less. The deposition amount of the roughened nickel layer 12 can be obtained by measuring the total nickel amount of the roughened nickel-plated sheet 1 using a fluorescent X-ray apparatus. Incidentally, when an underlying metal plating layer 13 made of nickel to be described later is formed, after measuring the total amount of nickel using a fluorescent X-ray apparatus for the roughened nickel-plated sheet 1, it can be determined by subtracting the amount of nickel corresponding to the underlying metal plating layer 13 from the total amount of nickel. The amount of nickel corresponding to the underlying metal plating layer 13 can be measured, for example, by a method of measuring the thickness of the underlying metal plating layer 13 by cutting the roughened nickel-plated sheet 1 and observing the cross-section by a scanning electron microscope (SEM), then determining the amount of nickel converted from the thickness of the underlying metal plating layer 13, a method of measuring the amount of nickel on the metal base material 11 at the time of forming the underlying metal plating layer 13 using a fluorescent X-ray apparatus, a method of determining the amount of electrodeposition calculated from the coulomb amount when forming the underlying metal plating layer 13 by plating to the metal base material 11 and the like.
In the present embodiment, the method of setting the brightness L* and the glossiness of 85° of the surface of the roughened nickel layer 12 in the above ranges is not particularly limited, but a method of forming the roughened nickel layer 12 by the method described below, or the like, is exemplified.
One example of a method of forming the roughened nickel layer 12 will be described below with reference to
The condition of the roughened nickel plating for precipitating the nickel granules 121 in an agglomerated state is not particularly limited, but from the viewpoint that the brightness L* and the glossiness of 85° of the surfaces of the roughened nickel layers 12 can be suitably controlled within the above ranges, a method by electrolytic plating using a plating bath containing nickel sulfate hexahydrate at a concentration of 10 to 100 g/L and containing ammonium sulfate at a concentration of 1 to 100 g/L is preferable. The concentration of nickel sulfate hexahydrate in the plating bath used is preferably from 10 to 70 g/L, more preferably from 10 to 50 g/L, and still more preferably from 15 to 25 g/L. Note that, as a nickel ion source, nickel chloride hexahydrate may be applied 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 set to 1 to 40 g/L. However, when the nickel ion concentration and the chlorine ion concentration increase, an appropriate roughened shape having a predetermined brightness and glossiness becomes difficult to obtain, and therefore, care should be taken in combination with nickel sulfate hexahydrate and ammonium chloride. In addition, when ammonium sulfate is used as a source of ammonia in the plating solution, the concentration of ammonium sulfate in the plating bath used is preferably 10 to 50 g/L, more preferably 10 to 45 g/L, and still more preferably 15 to 40 g/L. Note that, the addition of ammonia to the nickel plating bath may be performed by adding ammonia water or by adding a salt such as ammonium sulfate and ammonium chloride. The concentration of ammonia 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.
In addition, the pH of the nickel plating bath is preferably 4.0 to 8.0 when performing roughened nickel plating for precipitating the nickel granules 121 in an agglomerated state, from the viewpoint that the brightness L* and the glossiness of 85° of the surface of the roughened nickel layer 12 can be controlled more suitably. If the pH is too high, nickel ions in the bath tend to form a hydrate and cause plating failure, so that the upper limit thereof is more preferably 7.5 or less, and still more preferably 7.0 or less. When the pH is low, the bath resistance is low, and the nickel particles are less likely to precipitate in the state in which the secondary particles are formed, so that a normal precipitation form (flat plating) is likely to be formed and it is difficult to form a roughened nickel layer, it is more preferably 4.5 or more, still more preferably 4.8 or more, and particularly preferably 5.0 or more.
The current density when performing roughened nickel plating for precipitating the nickel granules 121 in an agglomerated state is preferably 5 to 40 A/dm2 from the viewpoint that the brightness L* and the glossiness of 85° of the surface of the roughened nickel layer 12 can be controlled more suitably. When the current density is high, the precipitation efficiency tends to be lowered, and plating unevenness and surface roughness control unevenness tend to occur in the range of plating treatment, so that 30 A/dm2 or less is more preferable, still more preferably 25 A/dm2 or less, and particularly preferably 20 A/dm2 or less, in order to secure a large plating area of 100 cm2 or more in particular. When the current density is low, the nickel particles are less likely to precipitate in the form of the secondary particles, and the nickel particles are more likely to be in the normal precipitation form, and therefore, the roughened nickel layers are less likely to be formed. Therefore, it is more preferable that the current density is 10 A/dm2 or more. In the present embodiment, from the viewpoint of controlling the brightness L* and the glossiness of 85° of the roughened nickel layer 12 more suitably, it is preferable to control the current density in accordance with 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 atomic concentration in the nickel plating bath, and the like.
The bath temperature of the nickel plating bath at the time of performing the roughened nickel plating is not particularly limited, but is preferably 25 to 60° C., more preferably 25 to 50° C., and still more preferably 30 to 50° C., from the viewpoint that the brightness L* and the glossiness of 85° of the surfaces of the roughened nickel layers 12 can be controlled more suitably.
In the present embodiment, when performing roughened nickel plating for precipitating the nickel granules 121 in a state of being agglomerated, it is preferable to perform plating while stirring the nickel plating. By stirring the nickel plating bath, the nickel granules 121 are easily precipitated uniformly on the metal base material 11 while being agglomerated, whereby the brightness L* and the glossiness of 85° of the surface of the roughened nickel layer 12 can be controlled more suitably. The method of performing stirring is not particularly limited, and examples thereof include a method such as bubbling and pump circulation. As a condition of bubbling, there is no particular limitation on the type of gas, but air is preferably used as a gas from the viewpoint of versatility, and as a timing for supplying a gas, continuous aeration is preferable for stably stirring. As the aeration amount, since the targeted roughened shape is hardly obtained when stirring is too strong, for example, the aeration amount is preferably 1 L/min or less with respect to the plating solution of the volume 2 L. As a condition of the pump circulation, continuous circulation is preferable in order to stably stir.
The precipitation amount at the time of precipitating the nickel granules 121 in an agglomerated state by roughened nickel plating is not particularly limited, but is preferably 0.89 to 4.45 g/m2 from the viewpoint of controlling the brightness L* and glossiness of 85° of the surfaces of the roughened nickel layer 12 to the above ranges, and from the viewpoint of further improving the adhesiveness of the nickel layer 12 to other members, the precipitation amount at the time of precipitating the nickel granules 121 in an agglomerated state is more preferably 1.34 g/m2 or more, still more preferably 1.60 g/m2 or more, and from the viewpoint of further improving the adhesiveness (plating adhesiveness) of the roughened nickel layer 12 to the metal base material 11, the precipitation amount at the time of precipitating the nickel granules 121 in an agglomerated state is more preferably 4.01 g/m2 or less, still more preferably 3.56 g/m2 or less, and particularly preferably 3.12 g/m2 or less. In addition, from the viewpoint of emphasizing production efficiencies and production costs, it is preferable that the precipitation amount is 1.34 to 2.23 g/m2 when the nickel granules 121 are precipitated in the agglomerated state.
Then, in the manufacturing method of the present embodiment, the nickel granules 121 are precipitated by roughened nickel plating in an agglomerated state, and then the nickel granules 121 are coated with the nickel film 122 by further performing a covering nickel plating. Covering nickel plating for coating the nickel particulate 121 with the nickel film 122 may be performed by any plating method of electrolytic plating or electroless plating, but it is preferably formed by electrolytic plating.
When the covering nickel plating is performed by the electrolytic plating method, for example, as the nickel plating bath, 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 may be used, and nickel plating may be performed under the conditions of pH of 3.0 to 5.0, bath temperature of 40 to 70° C., current density of 5 to 30 A/dm2 (preferably 10 to 20 A/dm2), followed by washing with water.
The deposition amount of nickel film 122 (coverage amount) to cover nickel granules 121 with nickel film 122 is not particularly limited. However, from the viewpoint that the brightness L* and the glossiness of 85° of the surfaces of the roughened nickel layers 12 can be suitably controlled within the above ranges, the brightness L* and the glossiness of 85° of the surfaces of the roughened nickel layers 12 can be suitably controlled within the above ranges is preferably 4.45 to 26.70 g/m2, and from the viewpoint of further improving the adhesiveness (plating adhesiveness) of the roughened nickel layer 12, the deposition amount nickel film 122 (coverage amount) to cover nickel granules 121 with nickel film 122 is more preferably 6.23 g/m2 or more, and from the viewpoint of further improving the adhesiveness of the roughened nickel layer 12 to other members, the deposition amount nickel film 122 (coverage amount) to cover nickel granules 121 with nickel film 122 is more preferably 19.58 g/m2 or less, and still more preferably 16.02 g/m2 or less. In addition, from the viewpoint of emphasizing production efficiencies and production costs, the deposition amount nickel film 122 to cover nickel granules 121 with nickel film 122 is more preferably is 4.45 to 8.90 g/m2. Further, the ratio between of the amount of deposition by the roughened nickel plating and the amount of deposition by the covering nickel plating is not particularly limited, but “the amount of deposition by the roughened nickel plating: the amount of deposition by the covering nickel plating” in the weight ratio, preferably 1:2 to 1:14, more preferably 2:4.5 to 2:15, still more preferably 2:5 to 2:15. Note that, in the case where the underlying nickel layer is formed as the underlying metal plating layer 13, when the covering nickel plating is performed, in addition to the covering of the nickel granules 121 with the nickel film 122, a part thereof contributes to the growth of the underlying nickel layer (thickening of a portion where the underlying layer is exposed without the nickel granules). Therefore, in this case, the above-mentioned amount of deposition is the sum of the amount of coating by the nickel film 122 by the covering nickel plating and the amount of forming the underlying nickel layer by the covering nickel plating.
Further, in the present embodiment, from the viewpoint of further improving the adhesion between the metal base material 11 and the roughened nickel layer 12, it is preferable to form an underlying metal plating layer 13 between the metal base material 11 and the roughened nickel layer 12, as the underlying metal plating layer 13, a nickel plating layer or copper plating layer is preferable, a nickel plating layer is more preferable. In particular, the nickel granules 121 formed by the roughened nickel plating described above are in a state in which the particulate precipitates are aggregated and precipitated in the form of protrusions and exist as aggregates, and it is preferable to have gaps between the aggregates from the viewpoint of adhesion to other members, and therefore, there are cases in which the entire surface of the metal base material 11 is not completely covered. Therefore, for example, in the case of using a steel sheet as the metal base material 11, in order to improve the effect of suppressing the occurrence of rust of the steel sheet, it is preferable to provide the underlying metal plating layer 13. Incidentally, for the purpose of such an effect of improving the corrosion resistance, it is preferable to select the metal base material 11 according to the application and to perform an underlying plating process corresponding thereto. When using a steel sheet or copper as the metal base material 11, as the underlying metal plating layer 13, it is preferable to form an underlying nickel plating layer or an underlying copper plating layer. Further, when applying the nickel layer by electrolytic nickel plating to the underlayer plating process, good compatibility with the subsequent coating plating process, it is possible to further enhance the plating adhesion of the roughened nickel layer 12. Although the effect of plating adhesion is obtained only by covering nickel plating process in a state where there is no underlying metal plating layer 13, since the covering nickel plating process tends to preferentially nickel precipitated on the nickel granules 121, from such a point of view, it is preferable to form the underlying metal plating layer 13 in order to improve corrosion resistance. When the metal base material 11 is a copper sheet, it is also possible to further enhance the plating adhesion of the roughened nickel layer 12 by performing an acid treatment or the like as the pre-treatment.
The underlying metal plating layer 13 can be formed by plating the metal base material 11 in advance before forming the roughened nickel layer 12 on the metal base material 11. In the case where the underlying metal plating layer 13 is the nickel plating layer, the nickel plating layer may be formed using any plating method of electrolytic plating or electroless plating, it is preferable to form by electrolytic plating.
In the case where the underlying metal plating layer 13 is the nickel plating layer, when an electrolytic plating method is used as a method for forming the base nickel plating layer, for example, as the nickel plating bath, 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 may be used, and nickel plating may be performed under the conditions of pH of 3.0 to 5.0, bath temperature of 40 to 70° C., current density of 5 to 30 A/dm2 (preferably 10 to 20 A/dm2), followed by washing with water.
When the underlying metal plating layer 13 is formed, the deposition amount of the roughened nickel layer 12 in the roughened nickel-plated sheet 1 of the present embodiment is preferably 26.70 g/m2 or less, more preferably 4.45 to 22.25 g/m2, still more preferably 4.45 to 17.80 g/m2, and particularly preferably 4.45 to 13.35 g/m2 from the viewpoint of further improving the adhesion between the metal base material 11 and the roughened nickel layer 12.
When forming the underlying metal plating layer 13, the total deposition amount of the roughened nickel layer 12 and the underlying metal plating layer 13 in the roughened nickel-plated sheet 1 of the present embodiment is not particularly limited, but is preferably 5.0 to 50.00 g/m2, more preferably 12.02 to 50.00 g/m2, still more preferably 12.28 to 40.94 g/m2, and particularly preferably 12.28 to 32.49 g/m2 from the viewpoint of improving the adhesion of the roughened nickel layer 12 to the metal base 11 and the adhesion of the roughened nickel layer 12 to other members. In addition, from the viewpoint of emphasizing production efficiencies and production costs, it is preferable that the total deposition amount of the roughened nickel layer 12 and the underlying metal plating layer 13 is 10.24 to 22.25 g/m2. Further, when high corrosion resistance is required, and particularly when high adhesion of the roughened nickel layer 12 to the metal base material 11 and adhesion of the roughened nickel layer 12 to other members are required, the total deposition amount of the roughened nickel layer 12 and the underlying metal plating layer 13 is preferably 32.50 to 57.85 g/m2. The total deposition amount of the roughened nickel layer 12 and the underlying metal plating layer 13 can be obtained by measuring the total amount of nickel of the roughened nickel-plated sheet 1 using a fluorescent X-ray apparatus.
As described above, according to the present embodiment, as shown in
In particular, when roughened nickel plating is performed, or when covering nickel plating is further performed after roughened nickel plating, as shown in
That is, in the above case, by adjusting the plating conditions, it is possible to control the size, shape and density of the protruding aggregate, thereby, it was found that it is possible to achieve both good plating adhesion to the metal base material 11 and good adhesion to other members appropriately. In addition, although there is Rzjis as a parameter representing the height difference in the surface, it has been found that the adhesion to other members and the adhesion of the roughened nickel layer 12 cannot be controlled by simply only adjusting Rzjis or other parameters representing roughness such as Ra and Rz. That is, as the tendency, while it is possible to ensure adhesion to other members by a certain degree of difference in height (Rzjis), if the difference in height (Rzjis) is too large, the adhesion of the roughened nickel layer 12 to the metal base material 11 tends to deteriorate. In particular, however, it has been found that the adhesion of the roughened nickel layer 12 to the metal base material 11 is not simply determined by Rzjis alone. In addition, it was found that the density of the protruding aggregate in the roughened nickel layer 12 was too high to allow resin or the like to enter between the protruding aggregate and to ensure the adhesiveness to other members such as a resin film or the like. On the other hand, it has been found that when the density of the protruding aggregate is too low, the individual protruding aggregates are liable to be finely broken, and the adhesiveness of the roughened nickel layer 12 to the metal base material 11 is likely to be lowered, or the protruding aggregates themselves are too small to obtain the anchor effect, and the adhesiveness to other members such as the resin film is not obtained. On the other hand, it has been difficult to measure the size, shape, and density of such a protruding aggregate and to specify a suitable range thereof.
In such a circumstance, the present inventors have further investigated that, as parameters for replacing such sizes, shapes, and densities, focusing on the two parameters of the brightness L* and the glossiness of 85° of the roughened nickel layer 12, both the brightness L* and the glossiness of 85° are found to be in specified ranges when the adhesiveness of the roughened nickel layer 12 to the base material and the adhesiveness to other members are good.
In particular, although it is generally known that the numerical value of the brightness L* fluctuates depending on the unevenness of the sheet surface, in the protruding aggregate formed of the secondary particles (nickel-particulate matter 121) as shown in
Furthermore, the present inventors have found a problem that the adhesion of the roughened nickel layer 12 to the metal base material 11 may be inferior even if the brightness L* is within a suitable range. In particular, in such cases, it is considered that the plating particles on the surfaces of the protruding aggregates are large and relatively smooth, so that the brightness L* is in a suitable range, while the plating particles are large and porous, so that the plating particles are easily detached from the metal base material 11. One of the reasons for this is considered to be that, when the plated particles are large, the protruding aggregates tend to break and fall off because Rzjis tends to be high. Measuring the plating particles are those very time consuming, in the case of such plating particles is large, the glossiness measured at a low angle of incidence light with respect to the plated sheet of glossiness of 85° is found together to be extremely low.
Based on such knowledge, the present inventors have conceived a roughened nickel-plated sheet 1 in which the brightness L* and the glossiness of 85° of the roughened nickel layers 12 fall within the above-mentioned specified ranges.
As described above, in the present embodiment, as the roughened nickel layer 12, aggregates having a protrusion-like shape (columnar shape) is provided on the surface, so that adhesion to other members such as a resin film can be ensured. Then, the present inventors have investigated that the plating layer having such protruding aggregate can be formed by performing plating under the situation of conducting current under the condition that the supply of nickel ions is insufficient with respect to the plating current. That is, it can be formed by insufficient supply of nickel ions with respect to the plating current to cause abnormal electrodeposition.
On the other hand, in such abnormality electrodeposition, since the embodiment of abnormal electrodeposition changes depending on the nickel concentration in the plating solution, the bath temperature of the plating solution, the pH of the plating solution, the current density at the time of plating, and the like, it was difficult to obtain a roughened nickel plated sheet that satisfies both the adhesiveness of the roughened nickel layer 12 to the metal base material 11 and the adhesiveness of the roughened nickel layer 12 to other members at the same time by simply performing plating under the condition that causes abnormal electrodeposition. In particular, according to the method of abnormal electrodeposition, since the unevenness is easily formed, while easy adhesion to other members can be obtained, easily precipitated plating particles fall off, there is a case that falls off during handling. On the other hand, the present inventors have found that, in order to solve the problem of simultaneously satisfying both the adhesiveness of the roughened nickel layer 12 to the metal base material 11 and the adhesiveness of the roughened nickel layer 12 to other members, the size of the primary particles, the size of the protruding aggregate, and the shape of the protruding aggregate constituting the roughened nickel layer 12 are important.
Here,
That is, according to the findings of the present invention inventors, as the roughened nickel layer 12, by the embodiment as shown in
Here, the term “not 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
Further, according to the embodiment as shown in
On the other hand, in the embodiment shown in
In addition, in the embodiment shown in
Further, the embodiment shown in
In addition, in the embodiment shown in
Further, in the embodiment shown in
Further, in the embodiment shown in
Then, the present inventors have been found that, in the above embodiments in
The method of forming the roughened nickel layer 12 as shown in
In the present embodiment, as a method for forming the roughened nickel layer as shown in
Note that, a cross-sectional SEM photograph of the roughened nickel layer according to the embodiment shown in
According to the roughened nickel-plated sheet 1 of the present embodiment as described above, since the adhesion of the roughened nickel layer 12 to the metal base material 11 is good and the adhesion to other members is excellent, it can be used as applications used by bonding with other members, for example, various containers where the adhesion to various members such as resin and active material, electronic device member (such as a substrate), the battery member (outer package, current collector, tab lead).
In particular, the roughened nickel-plated sheet 1 of the present embodiment, since the adhesion of the roughened nickel layer 12, i.e., the adhesion to the base material 11 is excellent, for example, even if the plated sheets overlap or contact, the roughened nickel layer 12 in the surface is difficult to peel off or fall off, and it can be suitably used as a roughened nickel-plated sheet 1 having a roughened nickel layer 12 on the outermost surface of both surfaces as shown in
On the other hand, if the adhesion to the other member is required only one side of the plated sheet, it is sufficient that the roughened nickel layer 12 is formed only on one side as in the roughened nickel-plated sheet 1 shown in
When producing the roughened nickel-plated sheet 1 as shown in
Hereinafter, the present invention will be described more specifically by way of Examples, but the present invention is not limited to these Examples.
Here, the evaluation method of each characteristic is as follows.
On the surface of the roughened nickel-plated sheet on which the roughened nickel layers were formed, a field of view of 97 μm×129 (length×width) (measurement field width of 129 μm, measurement area of about 12,500 μm2 (12,500±100)) was scanned using a laser microscope (manufactured by Olympus Co., Ltd., model number: OLS3500) in accordance with JIS B0601:2013, and then the field of view was analyzed using analysis software (software name: LEXT-OLS) under the condition of analysis mode: roughness analysis, whereby the arithmetic mean roughness Ra and the ten-point mean roughness Rzjis were measured. Note that, the cut-off value at the time of measurement by a laser microscope was a wavelength of about 43 μm (43.2 on the display), which is a length of ⅓ of the measurement field width (129 μm).
In the present example, the amount of nickel in the underlying nickel layer and the roughened nickel layer (nickel granules and nickel film) was determined by measurement using a fluorescent X-ray apparatus after the respective steps of forming the underlying nickel layer, nickel granules and nickel film. Specifically, the amount of nickel in the underlying nickel layer was once determined by using a fluorescent X-ray apparatus at the time of forming the underlying nickel layer. Thereafter, after the nickel granules were formed, the total amount of nickel was determined again by a fluorescent X-ray apparatus, and the difference between the obtained total amount of nickel and the amount of nickel in the underlying nickel layer was defined as the amount of nickel in the nickel granules. Further, after the nickel film was foiled, the total amount of nickel was determined again by a fluorescent X-ray apparatus, and the difference between the total amount of nickel before the formation of the nickel film and the total amount of nickel after the formation of the nickel film was obtained, thereby determining the nickel amount of the nickel film in the same manner. Then, the amount of nickel in the total of the nickel granules and the nickel film was determined as the deposition amount of the roughened nickel layer.
Here, in the case where a metal containing nickel such as a stainless steel sheet or a nickel sheet is used as a base material, the amount of nickel in each layer cannot be measured by the above-mentioned X-ray fluorescence device. Therefore, using a base material containing no nickel such as a steel sheet in advance, at a plating condition where a underlying nickel layer having the predetermined amount of nickel is obtained, a metal sheet containing nickel such as stainless steel sheet and nickel sheet is electrolyzed so that it is possible to make it one having the same deposition amount.
Note that, although the measurement of the amount of nickel is performed by the above method in the present examples and the comparative examples, the measurement method of the amount of nickel is not limited to such a method, and the following method may be used. In the present example, the following methods were also adopted in part. That is, first, the roughened nickel-plated sheet where the underlying nickel layer, the nickel granules, and the nickel film are formed is measured by a fluorescent X-ray apparatus to determine the total amount of nickel in the layers formed in the roughened nickel-plated sheet. Then, by cutting the roughened nickel-plated sheet and observing the cross-section by a scanning electron microscope (SEM) so as to measure the thickness of the underlying nickel layer, the amount of nickel converted from the thickness of the underlying nickel layer determined, which is the amount of nickel in the underlying nickel layer. Then, by subtracting the amount of nickel of the underlying nickel layer from the total amount of nickel, the total amount of nickel of the nickel granules and the nickel film is obtained, and this can be used as the deposition amount of the roughened nickel layer. In particular, when the covering nickel plating is performed, in addition that the nickel film 122 forms the roughened nickel layer 12 by covering the nickel particulate 121, the nickel film 122 fauns the underlying nickel layer in a part thereof. Therefore, according to such a method, the nickel amount of the underlying nickel layer in consideration of the growth (thickening) of the underlying nickel layer by the covering nickel plating can be obtained.
Here, when the cross-section was observed by a scanning electron microscope (SEM), the boundary between the metal base material and the underlying nickel layer, and the boundary between the underlying nickel layer and the roughened nickel layer were determined as shown in
The brightness L* of the surface of the roughened nickel layer was measured using a spectrophotometer (product name “CM-5”, manufactured by Konica Minolta, inc.) in accordance with the geometric condition C in JIS Z8722 using the SCE-method (specular reflected light removing method).
The glossiness of 85° of the surface of the roughened nickel layer was measured using a gloss meter (product name “VG 7000”, manufactured by Nippon Denshoku Industries Co., Ltd.) according to JIS 28741. When the glossiness of 60° was measured using the same measuring instrument, it was less than 1.5 in all Examples (Examples 1 to 32).
First, as a reference sample, an adhesive tape (product name “Cellotape (registered trademark)” manufactured by Nichiban Co., Ltd.) pasted on the backing paper was prepared, and the brightness L* and the chromaticity a*, b* were measured using a spectrophotometer (product name “CM-5”, manufactured by Konica Minolta, inc.). In the measurement, CIE1976L*a*b* color-difference models were used.
Then, an adhesive tape (product name “Cellotape (registered trademark)” manufactured by Nichiban Co., Ltd.) was attached to the surface of the roughened nickel-plated sheet obtained in Examples and Comparative Examples on which the roughened nickel layer was formed so as to have a width of 24 mm and a length of 50 mm, and then a peeling test using the attached adhesive tape was performed in accordance with the peeling test methods described in JIS H8504. Then, the adhesive tape after the peeling test was attached on the same backing paper as the above reference sample, and the brightness L* and the chromaticity a*, b* were measured in the same manner as described above using a spectrophotometer. Then, from the measured results of the brightness L* and the chromaticity a*, b* of the reference sample which was measured in advance and the measured results of the brightness L* and the chromaticity a*, b* of the adhesive tape after the peeling test, these differences ΔE*ab (ΔE*ab=[(ΔL*)2+(Δa*)2+(Δb*)2]1/2) were calculated, and the adhesion of the roughened nickel layer was evaluated based on the following criteria. Note that, the smaller the ΔE*ab, the smaller the peeling amount in the peeling test, that is, the higher the residual rate of the roughened nickel layer after the peeling test, and the better the adhesion of the roughened nickel layer to the metal base material can be judged.
The roughened nickel-plated sheets obtained in Examples and Comparative Examples were cut into two test master sheets each having a width of 15 mm and a length of 50 mm, which were used as T-peel test pieces. Then, for the two T-peel test pieces, respectively bent so that the bent angle becomes 90° at a position of length 20 mm. Then, surfaces having roughened nickel layer of each T-peel test piece were faced, and a polypropylene resin film having a width of 15 mm, a length of 15 mm, and a thickness of 60 μm (product name “Modic”, polypropylene resin bilayer film manufactured by Mitsubishi Chemical Corporation, a bonding surface used for evaluation is bonding surfaces between a polypropylene resin and a T-peel test piece, and product name “Modic” is an adhesive layer for stabilizing a test) was sandwiched therebetween, and heat sealing was performed under the conditions of temperature : 190° C., pressing time : 5 seconds, and heat sealing pressure: 2.0 kgf/cm2, and two T-peel test pieces were bonded via a polypropylene resin film. The position where the polypropylene resin film is sandwiched is an end portion in the length direction of a T-peel test body, and the entire polypropylene resin film becomes a bonding surface. The T-peel test body thus prepared is subjected to tensile test using a tensile tester (universal material testing instrument Tensilon RTC-1350A manufactured by ORIENTEC CORPORATION), and is subjected to measure the peel load (T-peel strength). Measurement conditions were 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.
As a substrate, a steel sheet obtained by annealing a cold rolled sheet of low carbon aluminum killed steel (thickness 0.25 mm) is prepared.
Then, the prepared steel sheet was subjected to alkali electrolytic degreasing and pickling by sulfuric acid immersion, followed by electrolytic plating under the following conditions using underlying nickel plating bath having the following bath composition to form underlying nickel layers on both surfaces of the steel sheet.
Next, the steel sheet on which the underlying nickel layer was formed was subjected to electrolytic plating (roughened nickel plating) under the following conditions using a roughened nickel plating bath having the following bath composition, whereby nickel granules were precipitated on the underlying nickel layer on both sides of the steel sheet.
Next, the steel sheet on which nickel granules were precipitated on the underlying nickel layer was subjected to electrolytic plating (covering nickel plating) under the following conditions by using a covering nickel plating bath having the following bath composition to cover the nickel granules precipitated on the underlying nickel layer with a nickel file, whereby a roughened nickel-plated sheet of Example 1 was obtained.
The obtained roughened nickel-plated sheet was subjected to measurements and evaluations of the amounts of nickel in the underlying nickel layer, nickel granules and nickel file, the brightness L* and glossiness of 85° of the roughened nickel layer surfaces, the adhesion of the roughened nickel layer, and the adhesion of the polypropylene resin (PP resin). The results are shown in Table 1.
The roughened nickel-plated sheets of Examples 2 to 15 were obtained and evaluated in the same manner as in Example 1, except that the plating bath and plating conditions of roughened nickel plating were changed to the conditions shown in Table 1, and the processing time of the covering nickel plating was changed so that the deposition amount of the nickel film to be formed became the amount shown in Table 1. The results are shown in Table 1.
The roughened nickel-plated sheets of Examples 16 to 31 were obtained and evaluated in the same manner as in Example 1, except that the plating conditions of roughened nickel plating were changed to the conditions shown in Table 2, and the processing time of the covering nickel plating was changed so that the deposition amount of the nickel film to be formed became the amount shown in Table 2. The results are shown in Table 2.
The roughened nickel-plated sheet of Example 32 was obtained and evaluated in the same manner as in Example 1, except that a copper sheet (electrolytic copper foil manufactured by Fukuda Metal Foil & Powder Co., Ltd. (Ra: 0.1 μm, Rzjis: 1.7 μm as measured values by laser microscopy) was used as the metal base material, the conditions of roughened nickel plating were changed to the conditions shown in Table 2, and the processing time of covering nickel plating was changed so that the deposition amount of the nickel film to be formed became the amount shown in Table 2. The results are shown in Table 2.
The roughened nickel-plated sheets of Examples 33 to 36 were obtained and evaluated in the same manner as in Example 1, except that the roughened nickel plating conditions were changed to the conditions shown in Table 2, and the processing time of the covering nickel plating was changed so that the deposition amount of the nickel film to be formed became the amount shown in Table 2. The results are shown in Table 2.
The roughened nickel-plated sheets of Examples 37 to 41 were obtained and evaluated in the same manner as in Example 1, except that SUS304 (Example 37), SUS316 (Example 38), SUS430 (Example 39), SUS444 (Example 40), and pure nickel sheet (Example 41) were used as the metal base materials, respectively, and the roughened nickel plating conditions were changed to the conditions shown in Table 2, and the processing time of the covering nickel plating was changed so that the deposition amount of the nickel film to be formed became the amount shown in Table 2. The results are shown in Table 2. Note that, in Examples 37 to 41, SUS304, SUS316, SUS430, SUS444 and pure nickel sheet were used, and after pickling in the sulfuric acid immersion, the underlying nickel layers were formed after electrolysis (strike nickel plating) under the following conditions by using a strike nickel plating bath having the following bath compositions.
The roughened nickel-plated sheets of Comparative Examples 1 to 10 were obtained and evaluated in the same manner as in Example 1, except that the conditions of roughened nickel plating and covering nickel plating were changed to the conditions shown in Table 3. The results are shown in Table 3.
The roughened nickel-plated sheets of Comparative Examples 11 to 22 were obtained and evaluated in the same manner as in Example 1, except that the roughened nickel plating conditions were changed to the conditions shown in Table 3 and the covering nickel plating was not performed. The results are shown in Table 3.
The roughened nickel-plated sheets of Comparative Examples 23 and 24 were obtained and evaluated in the same manner as in Example 1, except that a copper sheet was used as the metal base material, the roughened nickel plating conditions were changed to the conditions shown in Table 4, and the covering nickel plating was not performed. The results are shown in Table 4. In Comparative Example 23, an electrolytic copper foil manufactured by Fukuda Metal Foil & Powder Co., Ltd. (Ra: 0.1 μm, Rzjis: 1.7 μm as measured values by laser microscopy) was used as a copper sheet, and in Comparative Example 24, a copper foil whose surfaces were roughened by performing roughening copper plating on the same copper foil as in Comparative Example 23 was used as a copper sheet.
The roughened nickel-plated sheets of Comparative Examples 25 to 32 were obtained and evaluated in the same manner as in Example 1, except that the roughened nickel plating conditions were changed to the conditions shown in Table 4 and the covering nickel plating was not performed. The results are shown in Table 4.
The roughened nickel-plated sheets of Comparative Example 33 was obtained and evaluated in the same manner as in Example 1, except that neither roughened nickel plating nor covering nickel plating was performed. The results are shown in Table 4.
The roughened nickel-plated sheets of Comparative Examples 34 to 36 were obtained and evaluated in the same manner as in Example 1, except that the roughened nickel plating conditions were changed to the conditions shown in Table 4 and the covering nickel plating was not performed. The results are shown in Table 4.
The roughened nickel-plated sheets of Comparative Examples 37 to 39 were obtained and evaluated in the same manner as in Example 1, except that the conditions of roughened nickel plating and covering nickel plating were changed to the conditions shown in Table 4. The results are shown in Table 4.
As can be confirmed from Tables 1 to 4, when the brightness L* of the surface of the roughened nickel layer was 30 to 50 and the glossiness of 85° of the surface of the roughened nickel layer was 1.5 to 50, the adhesion of the roughened nickel layer to the metal base material was good and the adhesion to the polypropylene resin (PP resin) was excellent (Examples 1 to 36).
On the other hand, when the roughened nickel layer was not formed, or when the brightness L* or the glossiness of 85° of the surface of the roughened nickel layer was outside the specified ranges defined in the present invention, the adhesion of the roughened nickel layer to the metal base material and/or the adhesion to the polypropylene resin (PP resin) was inferior (Comparative Examples 1 to 39).
Incidentally,
Note that, in
Further, in Table 1 to Table 4, the deposition amount of nickel of the underlying nickel layer was calculated from the processing conditions in the underlying nickel plating, and the calculated amount was described as “underlying nickel layer”. Also, the deposition amount of nickel plating of the nickel film 122 was calculated from the processing conditions by the covering nickel plating, and the calculated amount was described as “nickel film”. Note that, when performing the covering nickel plating, the nickel film forms the roughened nickel layer 12 as a nickel film 122 covering the nickel granules 121, and also a portion thereof forms the underlying nickel layer. That is, it also contributes to the growth of the underlying nickel layer. Actually, the thickness of the formed underlying nickel layer was calculated by scanning electron microscopy (SEM), and the amount of nickel of the underlying nickel layer was calculated from the calculated thickness, and it was 11.6 g/m2 in Example 5, 11.6 g/m2 in Example 6, 12.5 g/m2 in Example 7, and 13.4 g/m2 in Example 8. By calculating the difference between these values and the calculated values from the plating processing conditions of Examples 5 to 8, it is possible to calculate the growth of the underlying nickel layer. Similarly, in Examples 1 to 36, the difference was calculated to be 1.8 to 4.5 g/m2 (shown in Table 1 and Table 2). Further, the averages thereof were also 2.8 g/m2. Note that, in Table 1 and Table 2, the nickel thickness (μm) of the underlying nickel layer measured from the scanning electron microscopy (SEM) cross-sectional image is shown in the third column from the right, and the amount of nickel (g/m2) of the underlying nickel layer calculated from the nickel thickness of the underlying nickel layer is shown in the second column from the right. In addition, in the rightmost columns of Table 1 and Table 2, the growth amount of the underlying nickel layer, that is, the amount of increase in the underlying nickel layer by performing covering nickel plating after performing plating for forming the underlying nickel layer, is shown.
In this manner, in the embodiment of the present application, when the deposition amounts of the underlying nickel layer and the roughened plating layer are obtained from the cross-sectional images of the scanning electron microscope, the deposition amounts (thicknesses) of the respective layers can be calculated by subtracting 2. 8 g/m2 (amount corresponding to 0.32 μm) from the underlying nickel layer and adding it to the roughened plating layer.
After the underlying nickel layer was formed 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 electroplating was performed on the opposite side of the masked side using the roughened nickel plating bath having the same bath composition as in Example 1 under the same conditions as in Example 1, whereby nickel granules were precipitated on the underlying nickel layer. Further, by performing electrolytic plating under the same condition as in Example 1 using the covering nickel plating bath having the same bath composition as in Example 1, covering nickel plating was performed, thereby obtaining a roughened nickel-plated sheet (a roughened nickel-plated sheet of the embodiment shown in
| Number | Date | Country | Kind |
|---|---|---|---|
| 2018-135582 | Jul 2018 | JP | national |
| 2019-015942 | Jan 2019 | JP | national |
| 2019-108779 | Jun 2019 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2019/028562 | 7/19/2019 | WO | 00 |
