Roughened plated sheet

Abstract

To provide a roughened plated sheet that has excellent corrosion resistance, and exhibits excellent adhesion to other components.SOLUTION: A provided roughened plated sheet comprises, on at least one side of a metal base material, a roughened nickel plated layer and a zinc plated layer in this order from the metal base material side, and ten-point average roughness Rzjis of a surface as measured by a laser microscope is 3 μm or more.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a roughened plated sheet having excellent corrosion resistance and excellent adhesion to other members.

Background Art

[0002] Conventionally, copper-plated steel sheets, nickel-plated steel sheets, copper sheets, and nickel sheets have been used as members constituting batteries and members constituting electronic-related devices. Among these, from the viewpoint of corrosion resistance, nickel-plated steel sheets and nickel sheets are widely used, and from the cost aspect, nickel-plated steel sheets are preferably used. In such materials, a method of controlling the surface structure is known from the viewpoint of improving adhesion when joining with other members.

[0003] 2 For example, in Patent Document 1, a surface-treated steel sheet is disclosed in which a nickel plating layer having a fine structure controlled to a particle density of 2 to ˈ500 particles / μm² and an average particle diameter of 0.05 to 0.7 μm is formed on a steel sheet.

[0004] Also, in Patent Document 2, a surface-treated copper foil is disclosed as a surface-treated copper foil for forming a copper-clad laminate by laminating with a resin film, in which an underlying nickel plating layer, a roughened copper plating layer composed of copper crystal roughened grains, and a zinc plating layer are formed on a copper raw foil. Further, in Patent Document 3, a joined body of a zinc-based plated steel sheet having ultrafine irregularities and an adherend made of a resin molded product of a thermoplastic resin composition containing at least one selected from polybutylene terephthalate, polyphenylene sulfide, and aromatic polyamide as a main component is disclosed.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

[0006] However, with the surface-treated steel sheet disclosed in Patent Document 1, depending on the type of member to which the surface-treated steel sheet is joined and the joining method, the adhesion with other members may be insufficient, and further improvement in adhesion was required. The surface-treated steel sheet disclosed in Patent Document 1 has a problem in that its outermost surface is formed of nickel, resulting in insufficient corrosion resistance (especially resistance to salt damage and pitting corrosion). Furthermore, the surface-treated copper foil disclosed in Patent Document 2 above has the problem that, because it forms a zinc plating layer on a copper plating layer which is electrochemically nobler than nickel, zinc easily dissolves from the zinc plating layer, resulting in insufficient corrosion resistance. Furthermore, the technology disclosed in Patent Document 3 requires etching after zinc plating, resulting in a complicated manufacturing process and, moreover, a long etching time, which leads to poor production efficiency.

[0007] The object of the present invention is to provide a roughened plated sheet that has excellent corrosion resistance and exhibits excellent adhesion to other components. [Means for solving the problem]

[0008] The inventors conducted diligent studies to achieve the above objective and have found a way to form a roughened plating layer on a metal substrate, comprising a roughened nickel plating layer and a zinc plating layer in that order, and to form such a roughened plating layer with a surface roughness of Rz jis We discovered that the above objective can be achieved by controlling the value within a predetermined range, and thus completed the present invention.

[0009] In other words, according to the present invention, a roughened plated sheet is provided having a roughened plated layer on at least one surface of a metal substrate, in which a roughened nickel plating layer and a zinc plating layer are formed in this order from the metal substrate side, wherein the surface roughness Rz is measured at 10 points by laser microscopy. jis A roughened plated sheet is provided, having a thickness of 3 μm or more.

[0010] The roughened plated sheet of the present invention has a lightness L of the surface of the roughened plated layer. * It is preferable that the value is 83 or less. The roughened plated sheet of the present invention has a ten-point average roughness Rz of the surface of the roughened plated layer. jis It is preferable that the particle size is 3 to 30 μm. The roughened plated sheet of the present invention has a lightness L of the surface of the roughened plated layer. * It is preferable that the value is between 45 and 83. The roughened plated sheet of the present invention preferably further comprises another plating layer between the metal substrate and the roughened nickel plating layer. In the roughened plated sheet of the present invention, it is preferable that the other plating layer is a nickel plating layer or a zinc plating layer. In the roughened plated sheet of the present invention, the amount of zinc plating layer adhering to the roughened plated layer is 3 g / m². 2 It is preferable that the above conditions are met. In the roughened plated sheet of the present invention, it is preferable that the metal substrate is a metal sheet or metal foil made of a pure metal selected from Fe, Cu, Al, and Ni, or a metal sheet or metal foil made of an alloy containing one selected from Fe, Cu, Al, and Ni. [Effects of the Invention]

[0011] According to the present invention, it is possible to provide a roughened plated sheet that has excellent corrosion resistance and exhibits excellent adhesion to other components. [Brief explanation of the drawing]

[0012] [Figure 1] Figure 1 is a diagram showing the configuration of a roughened plated sheet according to this embodiment. [Figure 2] Figure 2 is a schematic diagram showing the detailed structure of the roughened nickel plating layer and the zinc plating layer constituting the roughened plated sheet according to one embodiment of the present invention. [Figure 3] Figure 3 is a schematic diagram illustrating an example of a method for manufacturing a roughened plated sheet according to one embodiment of the present invention. [Figure 4] Figure 4 is a diagram showing the configuration of a roughened plated sheet according to another embodiment. [Figure 5] Figure 5(A) is an image obtained by observing the surface of the roughened plated sheet of Example 1 with a scanning electron microscope (SEM), Figure 5(B) is an image obtained by observing the cross-section of the roughened plated sheet of Example 1 with a scanning electron microscope (SEM), and Figure 5(C) is an image showing the distribution of zinc atoms as measured by an energy-dispersive X-ray spectrometer (EDS) when the cross-section shown in Figure 5(B) was observed with a scanning electron microscope (SEM). [Figure 6] Figure 6 shows a schematic diagram of a 180° peel test specimen. [Modes for carrying out the invention]

[0013] Figure 1 shows the configuration of the roughened plated sheet 1 of this embodiment. As shown in Figure 1, the roughened plated sheet 1 of this embodiment has a roughened plated layer 12 formed on a metal substrate 11, in which a roughened nickel plating layer 121 and a zinc plating layer 122 are formed in that order. In this embodiment, the roughened plated sheet 1 is exemplified as having a roughened plated layer 12 formed from a roughened nickel plating layer 121 and a zinc plating layer 122 on one side of a metal substrate 11. However, the embodiment is not particularly limited to this configuration, and the roughened plated layer 12 formed from the roughened nickel plating layer 121 and the zinc plating layer 122 may be formed on both sides of the metal substrate 11.

[0014] <Metal base material 11> The metal substrate 11 that serves as the base for the plated plate 1 in this embodiment is not particularly limited, but examples include a metal plate or metal foil made of a pure metal selected from Fe, Cu, Al, and Ni, or a metal plate or metal foil made of an alloy containing one selected from Fe, Cu, Al, and Ni. Specifically, examples include steel plates, stainless steel plates, copper plates, aluminum plates, or nickel plates (these may be pure metals or alloys, and may be in foil form). Among these, steel plates are preferred because they are easy to plate even with relatively simple pretreatment before plating, and the effect of improving adhesion to the metal substrate by forming a roughened nickel plating layer 121 and a zinc plating layer 122 can be further enhanced. In particular, low-carbon aluminum-killed steel (carbon content 0.01 to 0.15 wt%), ultra-low carbon steel with a carbon content of 0.01 wt% or less (preferably 0.003 wt% or less), or non-aging ultra-low carbon steel obtained by adding Ti or Nb to ultra-low carbon steel are preferably used.

[0015] In this embodiment, a hot-rolled metal substrate sheet can be pickled to remove surface scale (oxide film), then cold-rolled, and subsequently electrolytically cleaned with rolling oil to produce a steel sheet, stainless steel sheet, copper sheet, aluminum sheet, or nickel sheet, which can then be used as the substrate. Alternatively, a sheet that has been annealed or temper-rolled after electrolytic cleaning may be used. In this case, the annealing can be continuous annealing or box annealing, and is not particularly limited. In addition, electrolytic foils or metal sheets made by electroforming, such as copper foil or nickel foil, can also be used as the metal substrate.

[0016] In addition, when using a metal substrate 11 on which a passive film is formed, such as a stainless steel plate or a nickel plate, strike nickel plating may be applied before performing the roughening nickel plating for forming the roughening nickel plating layer 121 or before the plating treatment for forming an optionally formed underlayer metal plating layer. The conditions for the strike nickel plating are not particularly limited, and examples include the following conditions. In the following conditions, the adhesion amount of nickel by the strike nickel plating is usually 0.08 to 0.89 g / m 2 However, when forming an underlayer nickel layer as the underlayer metal plating layer, the total amount of the adhesion amount of nickel by the strike nickel plating and the adhesion amount of nickel by the nickel plating for forming the underlayer nickel layer is measured as the adhesion amount of nickel of the underlayer nickel layer. Bath composition: Nickel sulfate hexahydrate 100 - 300 g / L, sulfuric acid 10 - 200 g / L pH: 1.0 or less Bath temperature: 40 - 70 °C Current density: 5 - 100 A / dm[[ID=eleven]] 2 Plating time: 3 - 100 seconds

[0017] 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 type 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.

[0018] [[ID=二十一]]<Roughened plating layer 12 (roughening nickel plating layer 121 and zinc plating layer 122)> As shown in FIG. 1, the roughened plating plate 1 of the present embodiment includes a roughened plating layer 12 formed of a roughening nickel plating layer 121 and a zinc plating layer

[0019] In this embodiment, the ten-point average roughness Rz of the surface of the roughened plating layer 12, which is formed from a roughened nickel plating layer 121 and a zinc plating layer 122, is measured by laser microscopy. jis The roughness is controlled to be 3 μm or more. According to this embodiment, by forming a zinc plating layer 122 on a roughened nickel plating layer 121, the zinc plating layer 122 can provide excellent corrosion resistance (especially salt damage resistance and pitting corrosion resistance), thereby making the roughened plated sheet 1 highly corrosion resistant, and furthermore, the ten-point average roughness Rz on the surface of the roughened plated layer 12 measured by laser microscopy can be controlled. jis By setting the thickness to a range of 3 μm or more, the roughened plated sheet 1 can be made to have excellent adhesion to other components. In particular, according to this embodiment, by combining the roughened nickel plating layer 121 and the zinc plating layer 122, nickel has a standard electrode potential closer to that of zinc than copper, etc., so the zinc plating layer 122 is less likely to dissolve, and therefore the corrosion resistance-improving effect of zinc can be fully exerted, thereby achieving excellent corrosion resistance.

[0020] Here, when the roughened nickel plating layer 121 and the zinc plating layer (either as the underlying zinc plating layer as the underlying metal layer 13 described later, or as the zinc plating layer 121 constituting the roughened plating layer 12) coexist on the surface of the roughened plated sheet 1, under the usage environment of the roughened plated sheet 1 (for example, a corrosive environment), the potential difference between nickel and zinc causes the zinc surface to undergo an oxidation reaction, resulting in a black coloration and the formation of black zinc oxide. According to the inventors' findings, this black zinc oxide has been confirmed to have superior corrosion resistance compared to the white rust (white zinc hydroxide and zinc oxide) that is generated when zinc plating is used as a single layer. The mechanism by which the black zinc oxide improves corrosion resistance is not entirely clear, but for example, when a steel plate is used as the metal substrate 11, it is thought that the formation of black oxide on the zinc surface slows down the dissolution of zinc and allows the sacrificial corrosion protection effect of zinc to proceed slowly, thereby improving corrosion resistance, such as slowing down the occurrence of red rust.

[0021] In this embodiment, the ten-point average roughness Rz of the surface of the roughened plating layer 12 jis There are no particular limitations on the method for making the thickness 3 μm or more, but for example, a method in which the roughened plating layer 12 has a detailed structure as shown in Figure 2 is preferred. Here, Figure 2 is a schematic diagram showing the detailed structure of a roughened plating layer 12 composed of a roughened nickel plating layer 121 and a zinc plating layer 122 according to one embodiment of the present invention. As shown in Figure 2, the roughened plating layer 12 according to one embodiment of the present invention is a roughened nickel plating layer 121 consisting of a layer composed of a plurality of nickel granules 1210, and a zinc plating film 1220 (i.e., a zinc plating layer 122) is formed on the roughened nickel plating layer 121 consisting of such plurality of nickel granules 1210 so as to cover the plurality of nickel granules 1210.

[0022] The ten-point average roughness Rz on the surface of the roughened plating layer 12, measured by laser microscopy. jis The range of 3 μm or more is acceptable, but the ten-point average roughness Rz jisThe surface thickness is preferably 3 to 30 μm, more preferably 4 to 15 μm, and even more preferably 5 to 10 μm. Ten-point average roughness Rz jis If the roughness is less than 3 μm, the roughening will be insufficient, and adhesion to other components cannot be ensured. On the other hand, the ten-point average roughness Rz jis If the thickness exceeds 30 μm, the adhesion of the roughened plating layer to the metal substrate tends to deteriorate.

[0023] The roughened plating layer 12 has a ten-point average roughness Rz jis While it is acceptable for the above to be within the specified range, the arithmetic mean roughness Ra on the surface of the roughened plating layer 12, as measured by laser microscopy, is preferably 0.2 to 3.5 μm, more preferably 0.4 to 2.0 μm, and even more preferably 0.4 to 1.1 μm. If the arithmetic mean roughness Ra is less than 0.2 μm, the roughening may be insufficient, and adhesion to other components may not be ensured. On the other hand, if the arithmetic mean roughness Ra is greater than 3.5 μm, the adhesion of the roughened plating layer to the metal substrate may deteriorate.

[0024] Furthermore, the roughened plating layer 12 has a surface brightness of L * The value is preferably 83 or less, more preferably 45 to 83, even more preferably 53 to 70, and particularly preferably 58 to 70. Brightness L * By setting the range to the above-mentioned extent, the roughened plated sheet 1 can be made to have superior adhesion to other components.

[0025] Furthermore, the 85° gloss of the roughened plating layer 12 surface is preferably 0.3 to 83, more preferably 1 to 60, even more preferably 1 to 35, and particularly preferably 4 to 35.

[0026] In this embodiment, the ten-point average roughness Rz jis In addition, brightness L * The reasons for focusing on the 85° gloss level are as follows: For example, if the roughened plating layer 12 has a detailed structure as shown in Figure 2, then protruding (columnar) aggregates will be formed consisting of secondary particles (nickel granules 1210) formed from aggregated primary particles and zinc plating film 1220 (i.e., zinc plating layer 122). In such a structure, according to the inventors' findings, if the density of the roughened plating layer 12 is too high, resin and the like cannot penetrate between the protrusions, and adhesion may not be ensured. If the density is too low, each aggregate becomes thin and easily broken, which may reduce the adhesion of the roughened plating layer 12 to the metal substrate 11. Furthermore, if there are too few aggregates, the anchoring effect may not be sufficient, and the effect of improving adhesion with other components may not be sufficient. In this situation, the inventors conducted further investigations and found that the ten-point average roughness Rz is a parameter related to the size, shape, and density of the roughened plating layer 12. jis In addition, the brightness L of the roughened plating layer 12 * Furthermore, by focusing on the 85° glossiness, we found that by setting these values ​​within a specific range, it is possible to further improve adhesion to other components and the adhesion of the roughened plating layer 12 itself.

[0027] In this embodiment, the brightness L * It is preferable to set the brightness L to the above range. * If the gloss level is too high, the density of the roughened plating layer will be high, preventing other materials such as resin from penetrating between the protrusions, which may result in poor adhesion to other materials. Also, if the 85° gloss level is less than 0.3, the density of the roughened plating layer will be low, causing each aggregate to be thin and easily broken, which may reduce the adhesion of the roughened plating layer to the metal substrate. On the other hand, if the 85° gloss level exceeds 83, the density of the roughened plating layer will be high, preventing other materials such as resin from penetrating between the protrusions, which may result in poor adhesion to other materials.

[0028] Furthermore, from the viewpoint of further improving the adhesion of the roughened plating layer 12 itself (the adhesion of the roughened plating layer 12 to the metal substrate 11), the arithmetic mean roughness Ra of the surface of the roughened plating layer 12 is 1.1 μm or less, and the brightness of the surface of the roughened plating layer 12 is L * The value is preferably 58 or higher. This improves the adhesion of the roughened plating layer 12 itself (the adhesion of the roughened plating layer 12 to the metal substrate 11), thereby increasing reliability and stability when used in conjunction with other components.

[0029] The amount of roughened nickel plating layer 121 constituting the roughened plating layer 12 is not particularly limited, but is preferably 0.4 to 14.0 g / m². 2 More preferably 0.8 to 9.0 g / m 2 More preferably 0.8 to 6.0 g / m² 2 By setting the amount of roughened nickel plating layer 121 within the above range, the roughened plated sheet 1 can be made to have better adhesion to other components.

[0030] The amount of roughened nickel plating layer 121 can be determined by measuring the total amount of nickel in the obtained roughened plated sheet 1 using an X-ray fluorescence spectrometer if the underlying nickel plating layer 13, which will be described later, is not formed. On the other hand, if the underlying nickel plating layer 13, which will be described later, is formed, the amount of roughened nickel can be determined by measuring the total amount of nickel in the roughened plated sheet 1 using an X-ray fluorescence spectrometer, and then subtracting the amount of nickel corresponding to the underlying nickel plating layer 13 from this total amount of nickel. The amount of nickel corresponding to the underlying nickel plating layer as the underlying metal plating layer 13 can be determined by, for example, cutting the obtained roughened plated sheet 1 and observing the cross-section with a scanning electron microscope (SEM) to measure the thickness of the underlying nickel plating layer as the underlying metal plating layer 13 and calculating the amount of nickel converted from the thickness of the underlying nickel plating layer as the underlying metal plating layer 13; measuring the amount of nickel on the steel sheet at the time the underlying nickel plating layer as the underlying metal plating layer 13 is formed on the steel sheet using an X-ray fluorescence apparatus; or determining the amount of nickel from the amount of electrodeposition calculated from the amount of Coulomb when the underlying nickel plating layer as the underlying metal plating layer 13 is formed on the steel sheet by plating.

[0031] Furthermore, the amount of zinc plating layer 122 constituting the roughened plating layer 12 is not particularly limited, but from the viewpoint of corrosion resistance, it is preferably 3 g / m². 2 The above is more preferable to 6 g / m². 2 The above is preferable, and more preferably 6-30 g / m 2 Particularly preferred is 6-21 g / m² 2 By setting the amount of zinc plating layer 122 within the above range, the roughened plated sheet 1 can be made to have better adhesion to other components.

[0032] The amount of zinc plating layer 122 can be measured using an X-ray fluorescence apparatus, similar to the amount of roughened nickel plating layer 121, and can be determined depending on the presence or absence of the underlying zinc plating layer as the underlying metal plating layer 13, similar to the amount of roughened nickel plating layer 121. In other words, the amount of zinc plating layer 122 can be determined by measuring the total amount of zinc on the obtained roughened plated sheet 1 using an X-ray fluorescence device if the underlying zinc plating layer 13, which will be described later, has not been formed. On the other hand, if the underlying zinc plating layer 13, which will be described later, has been formed, the amount of zinc can be determined by measuring the total amount of zinc on the roughened plated sheet 1 using an X-ray fluorescence device, and then subtracting the amount of zinc corresponding to the underlying zinc plating layer 13 from this total amount of zinc. The amount of zinc corresponding to the underlying zinc plating layer 13 can also be determined in the same way as determining the amount of nickel corresponding to the underlying nickel plating layer, such as by measuring the thickness of the underlying zinc plating layer from cross-sectional observation and converting it, by measuring the amount of zinc at the time the underlying zinc plating layer was formed, or by calculating it from the amount of Coulomb when the underlying zinc plating layer was formed.

[0033] The ratio of the amount of roughened nickel plating layer 121 to the amount of zinc plating layer 122 is not particularly limited, but from the viewpoint of further improving adhesion with other components, the ratio of "amount of zinc plating layer 122 / (amount of roughened nickel plating layer 121 + amount of zinc plating layer 122)" (i.e., "Zn / (Ni + Zn)") is preferably 0.4 to 0.87, more preferably 0.55 to 0.87, and even more preferably 0.65 to 0.87.

[0034] As mentioned above, the ten-point average roughness Rz of the roughened plating layer 12 surface jisA suitable method for achieving a thickness of 3 μm or more is to make the roughened plating layer 12 have a detailed structure as shown in Figure 2. A roughened plating layer 12 having such a configuration can be manufactured, for example, by the following method. First, a roughened nickel plating is applied to a metal substrate 11, causing nickel granules 1210 to be deposited on the metal substrate 11 in an aggregated state, as shown in Figure 3, thereby forming a roughened nickel plating layer 121 composed of multiple nickel granules 1210. Next, zinc plating is applied to the metal substrate 11 on which the nickel granules 1210 have been deposited in an aggregated state, thereby covering the nickel granules 1210 with a zinc plating film 1220. This forms a zinc plating layer 122 as a zinc plating film 1220 on the roughened nickel plating layer 121 composed of multiple nickel granules 1210, thereby forming a roughened plating layer 12 having a detailed structure as shown in Figure 2.

[0035] When forming the roughened nickel plating layer 121, the conditions for roughened nickel plating to precipitate nickel granular material 1210 in an aggregated state are not particularly limited, but the ten-point average roughness Rz of the surface of the roughened plating layer 12 is important. jis From the viewpoint of being able to suitably control 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 used is preferably 10 to 60 g / L, more preferably 10 to 50 g / L, and even more preferably 10 to 40 g / L. In addition, nickel chloride hexahydrate may be used as the nickel ion source instead of nickel sulfate hexahydrate, 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 10 to 60 g / L, more preferably 10 to 50 g / L, and even more preferably 10 to 40 g / L. Note that as the nickel ion concentration and chloride ion concentration increase, the ten-point average roughness Rz jisCaution is required when using nickel chloride hexahydrate in combination with nickel sulfate hexahydrate or ammonium chloride, as it may become difficult to obtain an appropriate roughened shape that falls within a predetermined range. Furthermore, when using ammonium sulfate as a source of ammonia in the plating solution, the concentration of ammonium sulfate in the plating bath is preferably 10 to 50 g / L, more preferably 10 to 45 g / L, and even more preferably 15 to 40 g / L. Ammonia may be added to the nickel plating bath by adding ammonia water, or by adding salts such as ammonium sulfate or ammonium chloride, and the ammonia concentration in the plating bath is preferably 0.3 to 30 g / L, more preferably 1 to 20 g / L, even more preferably 3 to 15 g / L, and particularly preferably 3 to 12 g / L or less.

[0036] Furthermore, when performing roughening nickel plating to form the roughened nickel plating layer 121, in order to precipitate nickel granular material 1210 in an aggregated state, the pH of the nickel plating bath is the ten-point average roughness Rz of the surface of the roughened plating layer 12. jis From the viewpoint of being able to control it more effectively, the pH is preferably 4.0 to 8.0. If the pH is too high, nickel ions in the bath tend to form hydrates, which can easily cause plating defects, so the upper limit is more preferably 7.5 or less, and even more preferably 7.0 or less. If the pH is too low, the bath resistance becomes low, making it difficult for nickel particles to precipitate in a state where they form secondary particles, and it tends to result in a normal deposition form that is not roughened (flat plating), and therefore it becomes difficult to form a roughened nickel plating layer, so the pH is more preferably 4.5 or higher, even more preferably 4.8 or higher, and particularly preferably 5.0 or higher.

[0037] The current density when performing roughened nickel plating to precipitate nickel granules 1210 in an aggregated state is equal to the ten-point average roughness Rz of the surface of the roughened plating layer 12. jis From the viewpoint of being able to control it more effectively, preferably 5 to 40 A / dm 2 This is because high current densities tend to reduce deposition efficiency, and uneven plating and uneven surface roughness control are more likely to occur within the plating treatment area, especially at 100 cm². 2To secure such a large area, 30A / dm 2 The following are more preferable, and even more preferably, 25 A / dm 2 The following, and particularly preferably 20 A / dm 2 The following applies: When the current density is low, it becomes difficult for nickel particles to precipitate in a state where they form secondary particles, and the deposition tends to be in a normal, non-roughened state. Therefore, it becomes difficult to form a roughened nickel plating layer. For this reason, the current density should be 10 A / dm 2 The above is more preferable. In this embodiment, the ten-point average roughness Rz of the surface of the roughened plating layer 12 is jis From the viewpoint of more effectively controlling the current density, it is preferable to control it according to the nickel ion concentration in the nickel plating bath (controlled by nickel sulfate hexahydrate (g / L) in the plating bath in the embodiments 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 so on.

[0038] Furthermore, the temperature of the nickel plating bath when performing roughened nickel plating is not particularly limited, but the ten-point average roughness Rz of the roughened plating layer 12 surface jis From the viewpoint of being able to control it more effectively, the temperature is preferably 25-60°C, more preferably 25-50°C, and even more preferably 30-50°C.

[0039] In this embodiment, when performing roughened nickel plating to precipitate nickel granules 1210 in an aggregated state, it is preferable to perform the plating while stirring the nickel plating bath. By stirring the nickel plating bath, the nickel granules 1210 are more easily aggregated and uniformly deposited on the metal substrate 11, thereby improving the ten-point average roughness Rz of the roughened plating layer 12 surface. jis This allows for more favorable control. The method of stirring is not particularly limited, but examples include bubbling and pump circulation. As for the conditions of bubbling, the type of gas is not particularly limited, but for versatility, it is preferable to use air as the gas, and as for the timing of gas supply, continuous aeration is preferable in order to ensure stable stirring.

[0040] In the manufacturing method of this embodiment, nickel granules 1210 are deposited in an aggregated state by roughening nickel plating, thereby forming a roughening nickel plating layer 121 consisting of a plurality of nickel granules 1210. After that, zinc plating is applied to coat the nickel granules 1210 with a zinc plating film 1220, thereby forming a zinc plating layer 122 as a zinc plating film 1220 on the roughening nickel plating layer 121 composed of a plurality of nickel granules 1210. The zinc plating for coating the nickel granules 1210 with a zinc plating film 1220 may be performed by either electrolytic plating or electroless plating, but it is preferable to form it by electrolytic plating.

[0041] When zinc plating is performed by electroplating, the method is not particularly limited, but the ten-point average roughness Rz of the roughened plating layer 12 surface jis From the viewpoint of being able to suitably control the above range, a method of electroplating using a plating bath containing zinc sulfate heptahydrate at a concentration of 10 to 400 g / L and ammonium sulfate at a concentration of 10 to 100 g / L is preferred. The concentration of zinc sulfate heptahydrate in the plating bath used is preferably 50 to 300 g / L, more preferably 100 to 300 g / L, and even more preferably 200 to 300 g / L. 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 even more preferably 15 to 40 g / L. The addition of ammonia to the nickel plating bath may be done by adding ammonia water, or by adding salts such as ammonium sulfate or ammonium chloride.

[0042] When zinc plating is performed by electroplating, the current density is determined by the ten-point average roughness Rz of the roughened plating layer 12 surface. jis From the viewpoint of being able to control it more effectively, preferably 1 to 60 A / dm 2 A more preferable 5-30 A / dm 2 More preferably 10-20 A / dm 2Furthermore, when zinc plating is performed by electroplating, the temperature of the zinc plating bath is preferably 25 to 70°C, more preferably 30 to 60°C, and even more preferably 40 to 60°C, and the pH of the zinc plating bath is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2.

[0043] Furthermore, in this embodiment, from the viewpoint of further improving the adhesion between the metal substrate 11 and the roughened plating layer 12, it is preferable to form an underlay metal plating layer 13 between the metal substrate 11 and the roughened plating layer 12, more specifically, between the metal substrate 11 and the roughened nickel plating layer 121 constituting the roughened plating layer 12, as shown in Figure 4. Here, Figure 4 is a diagram showing the configuration of a roughened plated sheet 1a according to another embodiment, in which the roughened plated sheet 1a has an underlay metal plating layer 13 on the metal substrate 11, and a roughened plating layer 12 formed on the underlay metal plating layer 13 in the order of a roughened nickel plating layer 121 and a zinc plating layer 122. As such an underlay metal plating layer 13, a nickel plating layer or a zinc plating layer is preferred, and a nickel plating layer is more preferred. In particular, the multiple nickel granules 1210 constituting the roughened nickel plating layer 121 exist as aggregates formed by the aggregation and deposition of particulate precipitates in a protruding manner. From the viewpoint of adhesion with other components, it is preferable that there are gaps between each aggregate, and therefore, the entire surface of the metal substrate 11 may not be completely covered. For this reason, for example, when a steel plate is used as the metal substrate 11, it is preferable to provide an undercoat metal plating layer 13 in order to improve the effect of suppressing the occurrence of rust on the steel plate. In order to achieve this effect of improving corrosion resistance, it is preferable to select a metal substrate 11 according to the application and to apply an undercoat plating treatment accordingly. When a steel plate or copper is used as 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. In the case of a copper plate as the metal substrate 11, it is also possible to further improve the plating adhesion of the roughened plating layer 12 by applying an acid treatment or the like as a pretreatment.

[0044] The base metal plating layer 13 can be formed by pre-plating the metal substrate 11 before performing roughened nickel plating to deposit nickel granules 1210 in an aggregated state on the metal substrate 11, that is, before forming the roughened nickel plating layer 121 consisting of multiple nickel granules 1210. When the base metal plating layer 13 is a nickel plating layer, it may be formed using either electrolytic plating or electroless plating, but it is preferable to form it by electrolytic plating.

[0045] When the underlying metal plating layer 13 is a nickel plating layer, and electroplating is used as the method for forming the underlying nickel plating layer, for example, a Watt bath with a bath composition of 200-350 g / L nickel sulfate hexahydrate, 20-60 g / L nickel chloride hexahydrate, and 10-50 g / L boric acid is used as the nickel plating bath, with a pH of 3.0-5.0, a bath temperature of 40-70°C, and a current density of 5-30 A / dm². 2 (Preferably 10-20 A / dm 2 A method can be used in which nickel plating is applied under the conditions described above, followed by washing with water. In addition, when the underlying metal plating layer 13 is a zinc plating layer, if electroplating is used as the method for forming the underlying zinc plating layer, a method can be used in which electroplating is performed under the same conditions as described above for the zinc plating film 1220 (zinc plating layer 122).

[0046] As described above, according to one embodiment of the present invention, as shown in Figure 3, a roughened nickel plating layer 121 is formed by depositing nickel granules 1210 in an aggregated state on a metal substrate 11 by roughened nickel plating, and then a zinc plating layer 122 as a zinc plating film 1220 is formed by applying zinc plating to this, thereby forming a roughened plating layer 12 having a detailed structure as shown in Figure 2, and by controlling these formation conditions, the ten-point average roughness Rz of the surface of the roughened plating layer 12 can be controlled. jis The above range can be defined as follows.

[0047] As described above, the roughened plated sheet 1 of this embodiment has excellent corrosion resistance (especially salt damage resistance and pitting corrosion resistance) and exhibits excellent adhesion to other materials. Therefore, it can be suitably used in applications where it is joined to other materials, such as resins (for example, various resins such as nylon 6, nylon 66, nylon 610, nylon 12, polypropylene, ABS resin, polymethyl methacrylate resin, thermoplastic polyurethane resin, epoxy resin, etc., and resin composites containing fillers or reinforcing fibers in these resins), various containers, building materials, electronic equipment materials (housing, shielding materials, reinforcing materials), and battery materials (outer tank, current collector, tab lead). [Examples]

[0048] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The evaluation methods for each characteristic are as follows.

[0049] <Surface roughness> For the surface of the roughened plated sheet on which the roughened plating layer (roughened nickel plating layer and zinc plating layer) is formed, a laser microscope (Olympus, model number: OLS3500) was used in accordance with JIS B0601:2013, measuring an area of ​​97 μm × 129 μm (length × width) (measurement field width 129 μm, measurement area approximately 12,500 μm). 2 (12,500 μm 2 ±100 μm 2 After scanning the field of view, the analysis is performed using analysis software (software name: LEXT-OLS) under the condition of analysis mode: roughness analysis, thereby obtaining the arithmetic mean roughness Ra and the ten-point mean roughness Rz. jis The following measurements were taken. The cutoff value for measurements using a laser microscope was set to a wavelength of approximately 43 μm (displayed as 43.2 μm), which is one-third the length of the measurement field width (129 μm).

[0050] <Amount of roughened nickel plating layer, amount of zinc plating layer> After forming a zinc plating layer on a roughened nickel plating layer, the amount of roughened nickel plating and the amount of zinc plating constituting the roughened nickel plating layer were determined using an X-ray fluorescence spectrometer. In Examples 7, 8, 27, 28, 36, and 37, in which an undercoat nickel plating layer or undercoat zinc plating layer was formed, the amount of the undercoat nickel plating layer or undercoat zinc plating layer was determined by measuring with an X-ray fluorescence apparatus after the process of forming the undercoat nickel plating layer or undercoat zinc plating layer. By subtracting these amounts, the amount of roughened nickel plating constituting the roughened plating layer and the amount of zinc plating constituting the roughened plating layer were determined.

[0051] <Lightness L * > Brightness L of the roughened plating layer surface * The values ​​were measured using a spectrophotometer (product name "CM-5", manufactured by Konica Minolta Corporation) in accordance with geometric condition C of JIS Z8722, using the SCE method (specular reflection rejection method).

[0052] <85° gloss> The 85° gloss of the roughened plating layer surface was measured using a gloss meter (product name "VG 7000", manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS Z8741. When the 60° gloss was measured using the same instrument, the 60° gloss was less than 1.5 in all examples (Examples 1 to 32).

[0053] <Resin adhesion (180° peel strength)> A mold of a predetermined size (made of stainless steel) was prepared, and roughened plated plates and resin plates were stacked and placed inside the mold so that the volume of material was 105-110% of the volume inside the mold. Next, the mold into which the material was placed was sandwiched between stainless steel plates coated with a release agent, and then set between the upper and lower plates of a hot press (G-12 type foot pump type small press (manufactured by Techno Supply Co., Ltd.)). Then, a laminate made of metal and resin was fabricated by heating and pressurizing under the following lamination conditions. <Lamination conditions> 1) Preheating ⇒ Temperature: 180~310℃, Surface pressure: 0.5MPa, Holding time: 3 minutes 2) Pressing ⇒ Temperature: 180~310℃, Surface pressure: 5MPa, Holding time: 7 minutes 3) Cooling / Demolding ⇒ Temperature: 70℃ or less, surface pressure: 5MPa Next, the fabricated laminate was cut to dimensions of 20 mm in width and 100 mm in length, and a 180° peel specimen was obtained by peeling the metal from the end in the longitudinal direction up to a position of 40 mm. Then, a tensile test was performed on the obtained 180° peel specimen using a tensile testing machine, and the peel load (180° peel strength) was measured. The peel strength was calculated by averaging the load over a stroke of 25 mm to 75 mm and dividing it by the width of the specimen. Figure 6 shows a schematic of the 180° peel specimen. The higher the 180° peel strength, the better the adhesion to the resin can be considered to be. The 180° peel strength values ​​were expressed using an index where Comparative Example 2 was set to 1.0 for Examples 1-8 and Comparative Examples 1 and 12, and using an index where Comparative Example 4 was set to 1.0 for Examples 9-28 and Comparative Examples 3 and 13. Similarly, Example 29 was expressed using an index where Comparative Example 5 was set to 1.0, Example 30 using an index where Comparative Example 6 was set to 1.0, Example 31 using an index where Comparative Example 7 was set to 1.0, Examples 32, 36, 37 and Comparative Example 14 using an index where Comparative Example 8 was set to 1.0, Example 33 using an index where Comparative Example 9 was set to 1.0, Example 34 using an index where Comparative Example 10 was set to 1.0, and Example 35 using an index where Comparative Example 11 was set to 1.0.

[0054] <Corrosion resistance> Roughened plated sheets were cut into 50 mm x 130 mm strips, and the cut surfaces were covered with sealant to obtain strip-shaped evaluation samples. These strip-shaped evaluation samples were then subjected to a salt spray test using 5 wt% NaCl at 35°C and 98% humidity for 72 hours. After 27 hours, the evaluation samples were visually observed to assess their corrosion resistance according to the following criteria. The corrosion resistance evaluation was performed for Examples 1, 7, and 8, Comparative Examples 1 and 2, Examples 23, 27, and 28, Comparative Examples 3 and 4, Examples 32, 36, and 37, Comparative Example 8, and Comparative Examples 12 to 14. ◎: No visible red rust (spot rust) present. ○: Slight visible red rust (spot rust) has occurred (less than 10 points). △: Visible red rust (spot rust) is present throughout (tens of spots). ×: Red rust or extremely large, spotty red rust has occurred across the entire surface.

[0055] Example 1 As the base material, a steel plate obtained by annealing a cold-rolled low-carbon aluminum-killed steel sheet (0.1 mm thick) was prepared.

[0056] Then, after alkaline electrolytic degreasing and sulfuric acid pickling of the prepared steel plates, electrolytic plating (roughened nickel plating) was performed using a roughened nickel plating bath with the following bath composition and under the following conditions, thereby depositing nickel granules on one side of the steel plates and forming a roughened nickel plating layer. <Conditions for roughened nickel plating> Bath composition: Nickel sulfate hexahydrate 10g / L, nickel chloride hexahydrate 10g / L, ammonium sulfate 20g / L pH: 6.0 Bath temperature: 35℃ Current density: 15A / dm 2 Plating time: 20.8 seconds

[0057] Next, electroplating (zinc plating) was performed on the steel plate on which nickel granules had been deposited using a zinc plating bath with the following bath composition and under the following conditions, thereby coating the nickel granules deposited on the steel plate with a zinc plating film, and thus obtaining the roughened plated sheet of Example 1. <Zinc Plating Conditions> Bath composition: Zinc sulfate heptahydrate 220 g / L, Ammonium sulfate 30 g / L pH: 2.0 Bath temperature: 55℃ Current density: 10A / dm 2 Plating time: 47.0 seconds

[0058] Then, for the obtained roughened plated sheet, the amount of roughened nickel plating layer, the amount of zinc plating layer, the ten-point average roughness Rzjis and arithmetic mean roughness Ra of the roughened plated layer surface, and the brightness L of the roughened plated layer surface were determined. * Measurements of glossiness at 85° were also performed. The results are shown in Table 1.

[0059] Furthermore, 180° peel test specimens were prepared from the obtained roughened plated sheets using a nylon 6 (PA6, 1 mm thick) resin plate, and the resin adhesion (180° peel strength) was evaluated using the obtained 180° peel test specimens. Specifically, the obtained roughened plated sheet and resin sheet (nylon 6) were first cut to dimensions of 100 mm in length and 100 mm in width. The two materials were then stacked so that the roughened plated layer side of the roughened plated sheet was joined to the resin sheet, and a laminate was fabricated by heating and pressurizing it using a hot press. <Lamination conditions> 1) Preheating ⇒ Temperature: 270℃, Surface pressure: 0.5MPa, Holding time: 3 minutes 2) Pressing ⇒ Temperature: 270℃, Surface pressure: 5MPa, Holding time: 7 minutes 3) Cooling / Demolding ⇒ Temperature: 70℃ or less, surface pressure: 5MPa Then, 180° peel test specimens were prepared from the obtained laminates, and the resin adhesion (180° peel strength) was evaluated using the method described above. The results are shown in Table 1.

[0060] Examples 2-6, Comparative Example 1 Except for changing the plating time (processing time) for roughened nickel plating and zinc plating (processing time) to the conditions shown in Table 1, roughened plated sheets and 180° peel test specimens for Examples 2-6 and Comparative Example 1 were obtained in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1.

[0061] Example 7 After alkaline electrolytic degreasing and sulfuric acid pickling of the steel sheet, electroplating was performed using a nickel undercoat plating bath with the following bath composition and under the following conditions to form a 1 μm thick nickel undercoat on both sides of the steel sheet. Then, a roughened nickel plating layer was formed on this nickel undercoat layer in the same manner as in Example 1, and a zinc plating film was applied to obtain the roughened plate sheet of Example 7. A 180° peel test specimen was also obtained in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1. <Conditions for underlying nickel plating> Bath composition: Nickel sulfate hexahydrate 250g / L, Nickel chloride hexahydrate 45g / L, Boric acid 30g / L pH: 4.2 Bath temperature: 60℃ Current density: 10A / dm 2

[0062] Example 8 After alkaline electrolytic degreasing and sulfuric acid pickling of the steel sheet, electroplating was performed using a base zinc plating bath with the following bath composition and under the following conditions to form a 1 μm thick base zinc plating on both sides of the steel sheet. Then, a roughened nickel plating layer was formed on this base zinc plating layer in the same manner as in Example 1, and a zinc plating film was applied to obtain the roughened plate sheet of Example 8. A 180° peel test specimen was also obtained in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1. <Conditions for undercoat zinc plating> Bath composition: Zinc sulfate heptahydrate 220 g / L, Ammonium sulfate 30 g / L pH: 2.0 Bath temperature: 55℃ Current density: 10A / dm 2

[0063] Comparative Example 2 Except for directly zinc plating onto the steel plate without forming a roughened nickel plating, plated plates and 180° peel test specimens were obtained in the same manner as in Example 1 and evaluated in the same way. The results are shown in Table 1.

[0064] Example 9 Except for changing the plating time (processing time) for roughened nickel plating and zinc plating (processing time) to the conditions shown in Table 2, a roughened plated sheet of Example 9 was obtained in the same manner as in Example 1 and evaluated in the same manner. Then, except for using the obtained roughened plated sheet, using epoxy resin (EP, 1 mm thick) instead of nylon 6 as the resin sheet, and changing the heating temperature in the hot press to 180°C, a 180° peel test specimen was obtained in the same manner as in Example 1, and the resin adhesion (180° peel strength) was evaluated using the method described above. The results are shown in Table 2.

[0065] Examples 10-26, Comparative Example 3 Except for changing the plating time (processing time) for roughened nickel plating, the plating time (processing time) for zinc plating, the plating bath, current density, pH, and bath temperature to the conditions shown in Table 2, roughened plated plates and 180° peel test specimens for Examples 10-26 and Comparative Example 3 were obtained in the same manner as in Example 9 and evaluated in the same manner. The results are shown in Table 2.

[0066] Example 27 In the same manner as in Example 7, a 1 μm thick undercoat nickel plating was formed on both sides of the steel plate. Then, in the same manner as in Example 23, a roughened nickel plating layer was formed on this undercoat nickel plating layer, and a zinc plating film was applied to obtain the roughened plated sheet of Example 27. In the same manner as in Example 9, a 180° peel test specimen was obtained and evaluated in the same manner. The results are shown in Table 2.

[0067] Example 28 In the same manner as in Example 8, a 1 μm thick undercoat of zinc was formed on both sides of the steel plate. Then, in the same manner as in Example 23, a roughened nickel plating layer was formed on this undercoat of zinc, and the plate was coated with a zinc plating film to obtain the roughened plated sheet of Example 28. In the same manner as in Example 9, a 180° peel test specimen was obtained and evaluated in the same manner. The results are shown in Table 2.

[0068] Comparative Example 4 Except for directly zinc plating onto the steel plate without forming a roughened nickel plating, plated plates and 180° peel test specimens were obtained in the same manner as in Example 18 and evaluated in the same manner. The results are shown in Table 1.

[0069] Example 29 Except for using nylon 66 (PA66, 1 mm thick) instead of nylon 6 as the resin plate when obtaining the 180° peel test specimen, and changing the heating temperature in the hot press to 280°C, the procedure was the same as in Example 1. The resin adhesion (180° peel strength) was then evaluated using the method described above. The results are shown in Table 3.

[0070] Example 30 Except for using nylon 610 (PA610, 1 mm thick) instead of nylon 6 as the resin plate when obtaining the 180° peel test specimen, the procedure was the same as in Example 1, and the resin adhesion (180° peel strength) was evaluated using the method described above. The results are shown in Table 3.

[0071] Example 31 Except for using nylon 12 (PA12, 1 mm thick) instead of nylon 6 as the resin plate when obtaining the 180° peel test specimen, and changing the heating temperature in the hot press to 240°C, the procedure was the same as in Example 1. The resin adhesion (180° peel strength) was then evaluated using the method described above. The results are shown in Table 3.

[0072] Example 32 Except for using polypropylene resin (PP, 1 mm thick) instead of nylon 6 as the resin plate when obtaining the 180° peel test specimen, and changing the heating temperature in the hot press to 200°C, the procedure was the same as in Example 1. The resin adhesion (180° peel strength) was then evaluated using the method described above. The results are shown in Table 3.

[0073] Example 33 Except for using ABS resin (ABS, 1 mm thick) instead of nylon 6 as the resin plate when obtaining the 180° peel test specimen, and changing the heating temperature in the hot press to 240°C, the procedure was the same as in Example 1. The resin adhesion (180° peel strength) was then evaluated using the method described above. The results are shown in Table 3.

[0074] Example 34 Except for using polymethyl methacrylate resin (PMMA, 1 mm thick) instead of nylon 6 as the resin plate when obtaining 180° peel test specimens, and changing the heating temperature in the hot press to 250°C, the procedure was the same as in Example 1. Resin adhesion (180° peel strength) was evaluated using the method described above. The results are shown in Table 3.

[0075] Example 35 Except for using a thermoplastic polyurethane resin (TPU, 1 mm thick) instead of nylon 6 as the resin plate when obtaining the 180° peel test specimen, and changing the heating temperature in the hot press to 220°C, a roughened plated sheet was obtained in the same manner as in Example 1, and a 180° peel test specimen was obtained in the same manner as in Example 1. The resin adhesion (180° peel strength) was evaluated using the method described above. The results are shown in Table 3.

[0076] Example 36 Except for using polypropylene resin (PP, 1 mm thick) instead of nylon 6 as the resin plate when obtaining the 180° peel test specimen, and changing the heating temperature in the hot press to 200°C, the procedure was the same as in Example 7. The resin adhesion (180° peel strength) was then evaluated using the method described above. The results are shown in Table 3.

[0077] Example 37 Except for using polypropylene resin (PP, 1 mm thick) instead of nylon 6 as the resin plate when obtaining the 180° peel test specimen, and changing the heating temperature in the hot press to 200°C, the procedure was the same as in Example 8. The resin adhesion (180° peel strength) was then evaluated using the method described above. The results are shown in Table 3.

[0078] 《Comparative Examples 5-11》 In obtaining 180° peel test specimens, the following resin plates were used: nylon 66 plate (Comparative Example 5), nylon 610 plate (Comparative Example 6), nylon 12 plate (Comparative Example 7), polypropylene resin plate (Comparative Example 8), ABS resin plate (Comparative Example 9), polymethyl methacrylate resin plate (Comparative Example 10), and thermoplastic polyurethane resin plate (Comparative Example 11), as used in Examples 29 to 35, respectively. The plated plates obtained in the same manner as in Comparative Example 2 were used, and 180° peel test specimens were obtained in the same manner as in Comparative Example 2. The resin adhesion (180° peel strength) was evaluated using the method described above. The results are shown in Table 3.

[0079] Comparative Example 12 After alkaline electrolytic degreasing and sulfuric acid pickling of the steel sheet, electroplating was performed using a nickel plating bath with the following bath composition under the following conditions to form a 1 μm thick nickel plating on both sides of the steel sheet, thereby obtaining a nickel-plated sheet. The obtained nickel-plated sheet was evaluated in the same manner as in Example 1, and a 180° peel test specimen was obtained using the obtained nickel-plated sheet in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 4. <Nickel Plating Conditions> Bath composition: Nickel sulfate hexahydrate 250g / L, Nickel chloride hexahydrate 45g / L, Boric acid 30g / L pH: 4.2 Bath temperature: 60℃ Current density: 10A / dm 2 Plating time: 31.2 seconds

[0080] Comparative Example 13 Except for using epoxy resin (EP, 1 mm thick) instead of nylon 6 as the resin plate when obtaining 180° peel test specimens, and changing the heating temperature in the hot press to 180°C, the procedure was the same as in Comparative Example 12. Resin adhesion (180° peel strength) was evaluated using the method described above. The results are shown in Table 4.

[0081] Comparative Example 14 Except for using polypropylene resin (PP, 1 mm thick) instead of nylon 6 as the resin plate when obtaining 180° peel test specimens, and changing the heating temperature in the hot press to 200°C, the procedure was the same as in Comparative Example 12. Resin adhesion (180° peel strength) was evaluated using the method described above. The results are shown in Table 4.

[0082] [Table 1]

[0083] [Table 2]

[0084] [Table 3]

[0085] [Table 4]

[0086] As can be seen from Tables 1-4, the roughened plating layer is formed by creating a roughened nickel plating layer and a zinc plating layer in that order, and the ten-point average roughness Rz of the roughened plating layer surface jis The roughened plated sheets with a roughness of 3 μm or more all exhibited excellent adhesion to various resins (Examples 1-37). On the other hand, the ten-point average roughness Rz of the roughened plating layer surface jis However, when the thickness was less than 3 μm, or when no roughened plating layer was formed (i.e., when the zinc plating layer was formed directly without forming a roughened nickel plating layer), the adhesion to various resins was poor (Comparative Examples 1-11). Furthermore, even when the roughened plating layer was not formed, the adhesion to various resins was poor (Comparative Examples 12-14).

[0087] Furthermore, when an undercoat nickel plating layer was formed beneath the roughened plating layer, the resin adhesion was superior, and the corrosion resistance was extremely excellent (Examples 7, 27, 36). Furthermore, when an undercoat zinc plating layer was formed beneath the roughened plating layer, the corrosion resistance was extremely excellent (Examples 8, 28, 37). Furthermore, regardless of the presence or absence of the undercoat plating layer, no extreme difference was observed in surface roughness and appearance. Moreover, based on the results of Examples 1, 23, and 32, it can be considered that excellent corrosion resistance can be achieved in other examples as well.

[0088] Figure 5(A) is an image obtained by observing the surface of the roughened plated sheet of Example 1 with a scanning electron microscope (SEM), Figure 5(B) is an image obtained by observing the cross-section of the roughened plated sheet of Example 1 with a scanning electron microscope (SEM), and Figure 5(C) is an image showing the distribution of zinc atoms as observed by an energy-dispersive X-ray spectrometer (EDS) when the cross-section shown in Figure 5(B) was observed with a scanning electron microscope (SEM). As is clear from the comparison of Figures 5(B) and 5(C), the roughened plated layer of Example 1 is formed by a zinc plating film (zinc plating layer) formed on the surface of multiple nickel granules that form the roughened nickel plating layer, and therefore it can be said that the excellent corrosion resistance of the zinc plating film (zinc plating layer) can be fully exhibited. This was also the case for all of Examples 1 to 31, including Example 1. Furthermore, in Figures 5(B) and 5(C), regarding the protruding roughened plating layer formed by a zinc plating film (zinc plating layer) on the surface of nickel granules, the interface position between the substrate and the roughened plating layer was determined based on the position of the base of the protrusions. It was confirmed that the roughened plating layer was well formed at such an interface.

[0089] Furthermore, the arithmetic mean roughness Ra of the roughened plating layer 12 surface is 1.1 μm or less, and the brightness of the roughened plating layer 12 surface is L * For Examples 1, 4, 6-8, 10, 11, 13, 14, 18-24, 27-37, which have a value of 58.5 or higher, the adhesion of the roughened plating layer (the adhesion of the roughened plating layer itself to the metal substrate) was evaluated using the evaluation method described below, and in all cases, ΔE * The result was excellent, with ab = less than 5, and the adhesion of the roughened plating layer was also excellent. The following describes a method for evaluating the adhesion of the roughened plating layer.

[0090] <Adhesion of roughened plating layer> First, as a reference sample, we prepared adhesive tape (manufactured by Nichiban, product name "Sellotape (registered trademark)") attached to a backing sheet, and used a spectrophotometer (product name "CM-5", manufactured by Konica Minolta) to measure the lightness L * , chromaticity a * , b * The following was measured. Note that the CIE1976L was used for the measurement. * a * b * A color difference model was used. Then, adhesive tape (manufactured by Nichiban Co., Ltd., product name "Sellotape") was applied to the surface of the roughened plated sheet obtained in Examples 1, 4, 6-8, 10, 11, 13, 14, 18-24, 27-37, covering an area of ​​24 mm in width and 50 mm in length. A peel test was then performed using the applied adhesive tape in accordance with the peel test method described in JIS H 8504. After the peel test, the adhesive tape was attached to the same mounting board as the above reference sample, and the lightness L was measured using a spectrophotometer in the same manner as above. * , chromaticity a *, b * was measured. Then, the previously measured lightness L * , chromaticity a * , b * measurement results of the reference sample, and the lightness L * , chromaticity a * , b * measurement results of the adhesive tape after the peel test, from these differences ΔE * ab (ΔE * ab = [(ΔL * ) 2 +(Δa * ) 2 +(Δb * ) 2 1 / 2 ), the adhesion of the roughened plating layer was evaluated based on the following criteria. Note that the smaller ΔE * ab, the less the amount peeled off in the peel test, that is, the higher the remaining rate of the roughened nickel layer after the peel test, and it can be judged that the adhesion to the base material is excellent.

Explanation of Symbols

[0091] 1... Roughened plating plate 11... Metal base material 12... Roughened plating layer 121... Roughened nickel plating layer 1210... Nickel particles 122... Zinc plating layer 1220... Zinc plating film

Claims

1. A roughened plated sheet comprising a roughened plated layer formed on at least one surface of a metal substrate, in which a roughened nickel plating layer and a zinc plating layer are formed in this order from the metal substrate side, The ten-point average roughness Rz of the roughened plating layer surface, measured by laser microscopy. ｊｉｓ The size is 3 μm or larger. The arithmetic mean roughness Ra of the roughened plating layer surface, as measured by laser microscopy, is 0.3 μm or greater. The 85° gloss of the surface of the roughened plating layer is 35.5 or less. The amount of the roughened nickel plating layer is 0.8 to 14.0 g / m². ２ And, The amount of zinc plating layer deposited is 5.3 g / m². ２ That concludes the description of the roughened plated sheet.

2. The roughened nickel plated sheet according to claim 1, wherein the ratio of the amount of roughened nickel plating layer to the amount of zinc plating layer is 0.4 to 0.87, expressed as "amount of zinc plating layer / (amount of roughened nickel plating layer + amount of zinc plating layer)".

3. Brightness L of the surface of the roughened plating layer ＊ A roughened plated sheet according to claim 1 or 2, wherein the ratio is 83 or less.

4. The ten-point average roughness Rz of the roughened plating layer surface ｊｉｓ The roughened plated sheet according to claim 1 or 2, wherein the thickness is 3 to 30 μm.

5. Brightness L of the surface of the roughened plating layer ＊ A roughened plated sheet according to claim 1 or 2, wherein the ratio is 45 to 83.

6. The roughened plated sheet according to claim 1 or 2, further comprising another plating layer between the metal substrate and the roughened nickel plating layer.

7. The roughened plated sheet according to claim 6, wherein the other plating layer is a nickel plating layer or a zinc plating layer.

8. The roughened plated sheet according to claim 1 or 2, wherein the metal substrate 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.

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