WO2020250946A1 - 粗化めっき板 - Google Patents
粗化めっき板 Download PDFInfo
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- WO2020250946A1 WO2020250946A1 PCT/JP2020/022910 JP2020022910W WO2020250946A1 WO 2020250946 A1 WO2020250946 A1 WO 2020250946A1 JP 2020022910 W JP2020022910 W JP 2020022910W WO 2020250946 A1 WO2020250946 A1 WO 2020250946A1
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- roughened
- plating layer
- nickel
- plating
- plate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/017—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of aluminium or an aluminium alloy, another layer being formed of an alloy based on a non ferrous metal other than aluminium
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/16—Electroplating with layers of varying thickness
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/10—Agitating of electrolytes; Moving of racks
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/22—Electroplating: Baths therefor from solutions of zinc
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
- C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/538—Roughness
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/38—Pretreatment of metallic surfaces to be electroplated of refractory metals or nickel
- C25D5/40—Nickel; Chromium
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/42—Pretreatment of metallic surfaces to be electroplated of light metals
- C25D5/44—Aluminium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a roughened plated plate having excellent corrosion resistance and excellent adhesion to other members.
- nickel-plated steel sheets, nickel-plated steel sheets, copper plates, and nickel plates have been used as members that make up batteries and electronic-related devices.
- nickel-plated steel sheets and nickel plates are widely used from the viewpoint of corrosion resistance
- nickel-plated steel sheets are preferably used from the viewpoint of cost.
- a method of controlling the surface structure is known from the viewpoint of improving the adhesion when joining with another member.
- Patent Document 1 a surface formed on a steel sheet by forming a nickel plating layer having a fine structure controlled to have a particle density of 2 to 500 particles / ⁇ m 2 and an average particle size of 0.05 to 0.7 ⁇ m. Treated steel sheets are disclosed.
- Patent Document 2 as a surface-treated copper foil for forming a copper-clad laminate by bonding with a resin film, roughened copper composed of a base nickel plating layer and copper crystal roughened grains on a copper raw foil.
- a surface-treated copper foil in which a plating layer and a zinc plating layer are formed is disclosed.
- Patent Document 3 a resin molded product of a zinc-based plated steel sheet having ultrafine irregularities and a thermoplastic resin composition containing at least one selected from polybutylene terephthalate, polyphenylene sulfide, and aromatic polyamide as main components.
- a bonded body made of an adherend is disclosed.
- the surface-treated steel sheet disclosed in Patent Document 1 may have insufficient adhesion to other members depending on the type of member to be joined to the surface-treated steel sheet and the joining method. Was required to be further improved. Since the outermost surface of the surface-treated steel sheet disclosed in Patent Document 1 is formed of nickel, there is also a problem that corrosion resistance (particularly salt damage resistance and pitting corrosion resistance) is not sufficient. Further, since the surface-treated copper foil disclosed in Patent Document 2 forms a galvanized layer on a copper plating layer which is electrochemically noble as compared with nickel, the galvanized layer is formed. Therefore, there is a problem that zinc is easily dissolved and the corrosion resistance is not sufficient. Further, the technique disclosed in Patent Document 3 requires etching after galvanizing, the manufacturing process is complicated, and the time required for etching is long, so that the production efficiency is inferior. There is.
- An object of the present invention is to provide a roughened plated plate having excellent corrosion resistance and exhibiting excellent adhesion to other members.
- the present inventors have formed a roughened nickel plating layer and a roughened plating layer in which a galvanized plating layer is formed in this order on a metal substrate. Moreover , it has been found that the above object can be achieved by setting such a roughened plating layer to have the ten-point average roughness Rz jis of the surface controlled within a predetermined range, and the present invention has been completed. It was.
- a roughened plating layer is provided on at least one surface of the metal base material, wherein the roughened nickel plating layer and the zinc plating layer are formed in this order from the metal base material side.
- a galvanized plate having a surface ten-point average roughness Rz jis of 3 ⁇ m or more as measured by a laser microscope.
- the roughened plating plate of the present invention preferably has a brightness L * on the surface of the roughened plating layer of 83 or less.
- the roughened plating plate of the present invention preferably has a ten-point average roughness Rz jis of 3 to 30 ⁇ m on the surface of the roughened plating layer.
- the roughened plating plate of the present invention preferably has a lightness L * on the surface of the roughened plating layer of 45 to 83.
- the roughened plating plate of the present invention preferably further includes another plating layer between the metal base material and the roughened nickel plating layer. In the roughened plating plate of the present invention, it is preferable that the other plating layer is a nickel plating layer or a zinc plating layer.
- the amount of adhesion of the zinc plating layer constituting the roughened plating layer is preferably 3 g / m 2 or more.
- the metal base material is selected from a metal plate or metal foil made of a kind of pure metal selected from Fe, Cu, Al and Ni, or Fe, Cu, Al and Ni. It is preferable that the metal plate or metal foil is made of an alloy containing one of the above.
- FIG. 1 is a block diagram of a roughened plating plate according to the present embodiment.
- FIG. 2 is a schematic view showing a detailed structure of a roughened nickel plating layer and a zinc plating layer constituting the roughened plating plate according to the embodiment of the present invention.
- FIG. 3 is a schematic view for explaining an example of a method for manufacturing a roughened plating plate according to an embodiment of the present invention.
- FIG. 4 is a block diagram of a roughened plating plate according to another embodiment.
- FIG. 5A is an image obtained by observing the surface of the roughened plating plate of Example 1 with a scanning electron microscope (SEM), and
- FIG. 5B is a roughened plating plate of Example 1.
- FIG. 5 (C) shows the cross section shown in FIG. 5 (B) when observed with a scanning electron microscope (SEM).
- EDS energy dispersive X-ray microscope
- FIG. 6 is a diagram showing an outline of a 180 ° peel test piece.
- FIG. 1 is a diagram showing the configuration of the roughened plating plate 1 of the present embodiment.
- the roughened plating plate 1 of the present embodiment is a roughened plating layer in which a roughened nickel plating layer 121 and a zinc plating layer 122 are formed in this order on a metal base material 11. It has 12.
- a roughened plating layer 12 formed of a roughened nickel plating layer 121 and a zinc plating layer 122 is formed on one surface of the metal base material 11.
- the present invention is not particularly limited to such an embodiment, and the roughened plating layer 12 formed from the roughened nickel plating layer 121 and the zinc plating layer 122 is formed on both surfaces of the metal base material 11. May be done.
- the metal base material 11 to be the substrate of the plating plate 1 of the present embodiment is not particularly limited, but is a metal plate or metal foil made of a kind of pure metal selected from Fe, Cu, Al and Ni, or Fe, Examples thereof include metal plates or metal foils made of alloys containing one selected from Cu, Al and Ni, and specifically, steel plates, stainless steel plates, copper plates, aluminum plates, or nickel plates (these are pure metals, It may be any of alloys and may be in the form of foil.) Among these, even a pretreatment in which the pretreatment of the plating treatment is relatively simple is easy to perform plating and roughening.
- a steel plate is preferable from the viewpoint that the effect of improving the adhesion to the metal substrate can be further enhanced by forming the nickel plating layer 121 and the zinc plating layer 122, and in particular, a low carbon aluminum killed steel (carbon content 0.01). ⁇ 0.15% by weight), ultra-low carbon steel with a carbon content of 0.01% by weight or less (preferably 0.003% by weight or less), or ultra-low carbon steel with Ti, Nb, etc. added.
- Non-aging ultra-low carbon steel is preferably used.
- the hot-rolled plate of the metal base material is pickled to remove the scale (oxide film) on the surface, then cold-rolled, and then the rolling oil is electrolytically cleaned to form a steel plate or a stainless steel plate.
- Copper plate, aluminum plate, or nickel plate can be used as the substrate.
- those which have been annealed or tempered and rolled after electrolytic cleaning may be used.
- the annealing may be either continuous annealing or box-type annealing, and is not particularly limited.
- copper foil, nickel foil, or the like can be used as the metal base material as the electrolytic foil or the metal plate produced by the electroforming method or the like.
- the metal base material 11 When a metal base material on which an inert film is formed on a stainless steel plate, a nickel plate, or the like is used as the metal base material 11, before roughening nickel plating for forming the roughened nickel plating layer 121 is performed, Alternatively, those subjected to strike nickel plating may be used before the plating treatment for forming the arbitrarily formed base metal plating layer.
- the conditions for strike nickel plating are not particularly limited, and examples thereof include the following conditions. Under the following conditions, the amount of nickel adhered by strike nickel plating is usually 0.08 to 0.89 g / m 2 , but when a base nickel layer is formed as the base metal plating layer, strike nickel plating is used.
- the total amount of the amount of nickel attached and the amount of nickel attached by nickel plating for forming the underlying nickel layer is measured as the amount of nickel attached to the underlying nickel layer.
- Bath composition Nickel sulfate hexahydrate 100-300 g / L, sulfuric acid 10-200 g / L pH: 1.0 or less
- 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 further preferably 0.025 to 0.3 mm.
- the roughness of the metal base material 11 is not particularly limited, but the arithmetic average roughness Ra of the stylus type surface roughness meter is 0.05 to 2.0 ⁇ m, more preferably 0.05 to 0. It is 9 ⁇ m, more preferably 0.05 to 0.5 ⁇ m.
- the roughened plating plate 1 of the present embodiment includes a roughened plating layer 12 formed of a roughened nickel plating layer 121 and a zinc plating layer 122 on a metal base material 11. is there.
- the ten-point average roughness Rz j is measured by a laser microscope on the surface of the roughened plating layer 12 formed from the roughened nickel plating layer 121 and the galvanized layer 122 is controlled to 3 ⁇ m or more.
- the roughened plating layer 12 has a galvanized layer 122 formed on the roughened nickel plated layer 121, so that the galvanized layer 122 has excellent corrosion resistance (particularly salt damage resistance). Properties and pore corrosion resistance) can be imparted, whereby the roughened plating plate 1 can be made excellent in corrosion resistance, and further, by laser microscope measurement on the surface of the roughened plating layer 12.
- the roughened plating plate 1 can be made to have excellent adhesion to other members.
- nickel has a standard electrode potential closer to that of zinc as compared with copper or the like.
- the galvanized layer 122 is less likely to elute, so that the effect of improving the corrosion resistance of zinc can be sufficiently exhibited, and thus excellent corrosion resistance can be realized.
- the roughened nickel plating layer 121 and the zinc plating layer are roughened plating.
- the zinc surface changes black due to the oxidation reaction due to the potential difference between nickel and zinc in the use environment of the roughened plating plate 1 (for example, in a corrosive environment), and black zinc oxide is produced.
- this black zinc oxide has corrosion resistance as compared with white rust (white zinc hydroxide and zinc oxide) formed in the case of a layer structure of zinc plating alone. It has been confirmed that it is excellent.
- the mechanism for improving the corrosion resistance of black zinc oxide is not always clear, but for example, when a steel plate or the like is used as the metal base material 11, the effect of slowing the dissolution of zinc due to the formation of black oxide on the zinc surface is achieved. In addition, it is considered that the sacrificial anticorrosion action of zinc can be gradually promoted, and this has an effect of improving corrosion resistance such as slowing the occurrence of red rust.
- the method of setting the ten-point average roughness Rz cis on the surface of the roughened plating layer 12 to 3 ⁇ m or more is not particularly limited, but for example, the roughened plating layer 12 is as shown in FIG. A method having a detailed structure is preferable.
- FIG. 2 is a schematic view showing a detailed structure of the roughened plating layer 12 composed of the roughened nickel plating layer 121 and the zinc plating layer 122 according to the embodiment of the present invention.
- the roughened plating layer 12 according to the embodiment of the present invention comprises a layer composed of a plurality of nickel granules 1210 and a plurality of such nickel granules as the roughened nickel plating layer 121.
- a galvanized film 1220 (that is, a galvanized layer 122) is formed on the roughened nickel-plated layer 121 made of the material 1210 so as to cover the plurality of nickel granules 1210.
- the ten-point average roughness Rz jis on the surface of the roughened plating layer 12 as measured by a laser microscope may be in the range of 3 ⁇ m or more, but the ten-point average roughness Rz jis is preferably 3 to 30 ⁇ m, more preferably. It is 4 to 15 ⁇ m, more preferably 5 to 10 ⁇ m. If the ten-point average roughness Rz jis is less than 3 ⁇ m, the roughness becomes insufficient and the adhesion to other members cannot be ensured. On the other hand, if the ten-point average roughness Rz jis is more than 30 ⁇ m, the adhesion of the roughened plating layer to the metal substrate tends to deteriorate.
- the roughened plating layer 12 may have a ten-point average roughness Rz jis within the above range, but the arithmetic mean roughness Ra on the surface of the roughened plating layer 12 as measured by a laser microscope is 0.2 to 3.5 ⁇ m. It is preferably 0.4 to 2.0 ⁇ m, and even more preferably 0.4 to 1.1 ⁇ m. If the arithmetic average roughness Ra is less than 0.2 ⁇ m, the roughness may be insufficient and the adhesion to other members may not be ensured. On the other hand, if the arithmetic average roughness Ra is more than 3.5 ⁇ m, the adhesion of the roughened plating layer to the metal substrate may deteriorate.
- the brightness of the surface of the roughened plating layer 12 is preferably 83 or less in terms of L * value, more preferably 45 to 83, still more preferably 53 to 70, and particularly preferably 58. ⁇ 70.
- L * value more preferably 45 to 83
- the roughened plating plate 1 can be made more excellent in adhesion to other members.
- the 85 ° glossiness of the surface of the roughened plating layer 12 is preferably 0.3 to 83, more preferably 1 to 60, further preferably 1 to 35, and particularly preferably 4 to 35.
- the reasons for paying attention to the brightness L * and the 85 ° glossiness in addition to the ten-point average roughness Rz jis in this embodiment are as follows.
- the secondary particles nickel granules 1210 in which the primary particles are aggregated and the galvanized film 1220 (that is, zinc).
- a protruding (columnar) aggregate composed of the plating layer 122) will be formed.
- the density of the roughened plating layer 12 is too high, resin or the like cannot enter between the protrusions, and adhesion cannot be ensured.
- each aggregate may be thin and easily broken, and the adhesion of the roughened plating layer 12 to the metal substrate 11 may be lowered, and further. It has been found that the amount of the aggregate itself is too small and the anchor effect is not always sufficient, and the effect of improving the adhesion to other members may not be sufficient. In such a situation, as a result of further studies by the present inventors, rough plating is performed in addition to the ten-point average roughness Rz jis as parameters related to the size, shape, and density of the rough plating layer 12. Focusing on the brightness L * of the layer 12 and the glossiness of 85 °, by setting these in a specific range, the adhesion to other members and the adhesion of the roughened plating layer 12 itself can be further improved. We have found that it is possible.
- the lightness L * is preferably in the above range, and if the lightness L * is too high, the density of the roughened plating layer is high, and other members such as resin can enter between the protrusions. However, it may not be possible to secure adhesion with other members. Further, when the 85 ° glossiness is less than 0.3, the density of the roughened plating layer is low, each aggregate is thin and easily broken, and the adhesion of the roughened plating layer to the metal substrate is lowered. In some cases. On the other hand, if the 85 ° glossiness exceeds 83, the density of the roughened plating layer is high, and other members such as resin cannot enter between the protrusions, so that adhesion with other members may not be ensured. ..
- the adhesion of the roughened plating layer 12 itself (adhesion of the roughened plating layer 12 to the metal substrate 11) can be further improved
- the arithmetic average roughness Ra of the surface of the roughened plating layer 12 is determined. , 1.1 ⁇ m or less, and the brightness of the surface of the roughened plating layer 12 is preferably 58 or more in terms of L * value.
- the adhesion of the roughened plating layer 12 itself is further enhanced, so that reliability and stability when used by adhering to other members can be improved. Can be enhanced.
- the amount of adhesion of the roughened nickel plating layer 121 constituting the roughened plating layer 12 is not particularly limited, but is preferably 0.4 to 14.0 g / m 2 , and more preferably 0.8 to 9.0 g / m 2. It is m 2 , more preferably 0.8 to 6.0 g / m 2 .
- the roughened plating plate 1 can be made more excellent in adhesion to other members.
- the amount of adhesion of the roughened nickel plating layer 121 when the base nickel plating layer as the base metal plating layer 13 described later is not formed, a fluorescent X-ray apparatus is used for the obtained roughened plating plate 1. On the other hand, when the base nickel plating layer as the base metal plating layer 13 described later is formed, a fluorescent X-ray apparatus is used for the roughened plating plate 1. After measuring the total amount of nickel, it can be obtained by subtracting the amount of nickel corresponding to the base nickel plating layer as the base metal plating layer 13 from this total nickel amount.
- the amount of nickel corresponding to the base nickel plating layer as the base metal plating layer 13 can be obtained by, for example, cutting the obtained roughened plating plate 1 and observing the cross section with a scanning electron microscope (SEM).
- SEM scanning electron microscope
- a method of measuring the thickness of the base metal plating layer as the base metal 13 to obtain the amount of nickel converted from the thickness of the base metal plating layer 13 or the base metal plating layer 13 on the steel plate From the method of measuring the amount of nickel on the steel plate at the time of forming the plating layer using a fluorescent X-ray device, and the amount of Coulomb when forming the base nickel plating layer as the base metal plating layer 13 by plating on the steel plate. Examples thereof include a method of obtaining from the calculated amount of electrodeposition.
- the amount of adhesion of the galvanized layer 122 constituting the roughened plating layer 12 is not particularly limited, but is preferably 3 g / m 2 or more, more preferably 6 g / m 2 or more, from the viewpoint of corrosion resistance. It is more preferably 6 to 30 g / m 2 , and particularly preferably 6 to 21 g / m 2 .
- the amount of adhesion of the galvanized layer 122 can be measured using a fluorescent X-ray apparatus in the same manner as the amount of adhesion of the roughened nickel plating layer 121, and the amount of adhesion of the roughened nickel plating layer 121 can be measured. Similarly, it can be obtained depending on the presence or absence of the base zinc plating layer as the base metal plating layer 13. That is, the amount of adhesion of the galvanized layer 122 is the total amount of the obtained roughened galvanized plate 1 using a fluorescent X-ray apparatus when the base galvanized layer 13 as the base metal plating layer 13 described later is not formed. It can be obtained by measuring the amount of zinc.
- the roughened plating plate 1 is totaled using a fluorescent X-ray apparatus. After measuring the amount of zinc, it can be obtained by subtracting the amount of zinc corresponding to the base galvanized layer as the base metal plating layer 13 from this total amount of zinc.
- the amount of zinc corresponding to the base galvanized layer as the base metal plating layer 13 is also converted by measuring the thickness of the base galvanized layer from the cross-sectional observation in the same manner as when determining the amount of nickel corresponding to the base nickel plating layer. , It can be obtained by a method of measuring the amount of zinc at the time of forming the base galvanized layer, a method of calculating from the amount of Coulomb when forming the base galvanized layer, or the like.
- the ratio of the amount of adhesion of the roughened nickel plating layer 121 to the amount of adhesion of the zinc plating layer 122 is not particularly limited, but from the viewpoint of further improving the adhesion with other members, "the zinc plating layer 122 Adhesion amount / (adhesion amount of roughened nickel plating layer 121 + adhesion amount of zinc plating layer 122) "(that is,” Zn / (Ni + Zn) "), preferably 0.4 to 0.87, more preferably. Is 0.55 to 0.87, more preferably 0.65 to 0.87.
- the roughened plating layer 12 has a detailed structure as shown in FIG.
- the roughened plating layer 12 having such an aspect can be produced, for example, by the following method. That is, first, by subjecting the metal base material 11 to roughened nickel plating, as shown in FIG. 3, nickel granules 1210 are precipitated on the metal base material 11 in an aggregated state, whereby a plurality of nickel granules 1210 are precipitated.
- the roughened nickel plating layer 121 composed of the nickel granules 1210 of the above is formed.
- the metal base material 11 in which the nickel granules 1210 were precipitated in an aggregated state was subjected to galvanization, and the nickel granules 1210 were coated with the galvanized coating 1220 to form a plurality of nickel granules 1210.
- the galvanized layer 122 as the galvanized film 1220 on the roughened nickel plating layer 121 composed of the above, the roughened plating layer 12 having a detailed structure as shown in FIG. 2 can be formed. ..
- the conditions for roughened nickel plating for precipitating the nickel granules 1210 in an aggregated state are not particularly limited, but the ten-point average of the surfaces of the roughened plating layer 12 From the viewpoint that the roughness Rz jis can be suitably controlled in the above range, 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.
- the method by electrolytic plating using the above is preferable.
- 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.
- nickel chloride hexahydrate may be used instead of nickel sulfate hexahydrate, or nickel chloride hexahydrate and nickel sulfate hexahydrate may be used in combination. ..
- the concentration of nickel chloride hexahydrate is preferably 10 to 60 g / L, more preferably 10 to 50 g / L, still more preferably 10 to 40 g / L. is there.
- nickel chloride hexahydrate is used. Care should be taken when using with nickel sulfate hexahydrate or ammonium chloride.
- concentration of ammonium sulfate in the plating bath used is preferably 10 to 50 g / L, more preferably 10 to 45 g / L, and further preferably 15 to 40 g. / L.
- Ammonia may be added to the nickel plating bath by adding aqueous ammonia or by using a salt such as ammonium sulfate or ammonium chloride, and the ammonia concentration in the plating bath is preferably 0.3 to. It is 30 g / L, more preferably 1 to 20 g / L, further preferably 3 to 15 g / L, and particularly preferably 3 to 12 g / L or less.
- the pH of the nickel plating bath when performing roughened nickel plating for precipitating the nickel granules 1210 in an aggregated state is the surface of the roughened plating layer 12.
- the ten-point average roughness Rz jis can be controlled more preferably, it is preferably 4.0 to 8.0. If the pH is too high, nickel ions in the bath form hydrates and easily cause plating defects. Therefore, the upper limit is more preferably 7.5 or less, still more preferably 7.0 or less.
- the bath resistance becomes low, and it becomes difficult for nickel particles to precipitate in the state of forming secondary particles, and it tends to be in a normal precipitation form (flat plating) that is not roughened. Therefore, it is roughened. Since it becomes difficult to form the nickel plating layer, it is more preferably 4.5 or more, further preferably 4.8 or more, and particularly preferably 5.0 or more.
- the current density at the time of performing roughened nickel plating for precipitating the nickel granules 1210 in an aggregated state is from the viewpoint that the ten-point average roughness Rz jis on the surface of the roughened plating layer 12 can be more preferably controlled. It is preferably 5 to 40 A / dm 2 . If the current density is high, the precipitation efficiency tends to decrease, and plating unevenness and surface roughness control unevenness easily occur in the plating processing range. Therefore, in order to secure a wide area of 100 cm 2 or more, 30 A / dm 2 or less is particularly likely to occur. Is more preferably 25 A / dm 2 or less, and particularly preferably 20 A / dm 2 or less.
- the density is more preferably 10 A / dm 2 or more.
- the current density is the nickel ion concentration in the nickel plating bath (in the examples described later, from the viewpoint of more preferably controlling the ten-point average roughness Rz jis on the surface of the roughened plating layer 12).
- the bath temperature of the nickel plating bath when performing roughened nickel plating is not particularly limited, but is preferably 25 from the viewpoint that the ten-point average roughness Rz jis on the surface of the roughened plating layer 12 can be more preferably controlled. It is -60 ° C, more preferably 25-50 ° C, still more preferably 30-50 ° C.
- the method of stirring is not particularly limited, and examples thereof include bubbling, pump circulation, and the like.
- the type of gas is not particularly limited as the bubbling condition, but it is preferable to use air as the gas from the viewpoint of versatility, and the timing of supplying the gas is preferably continuous ventilation for stable stirring. ..
- the nickel granules 1210 were precipitated in an aggregated state by roughened nickel plating, thereby forming a roughened nickel plating layer 121 composed of a plurality of nickel granules 1210. Later, by further galvanizing, the nickel granules 1210 are coated with the zinc plating film 1220, whereby the roughened nickel plating layer 121 composed of the plurality of nickel granules 1210 is formed as the zinc plating film 1220.
- the galvanized layer 122 of the above is formed.
- the galvanizing for coating the nickel granules 1210 with the galvanizing film 1220 may be performed by either electrolytic plating or electroless plating, but it is preferably formed by electrolytic plating.
- the method is not particularly limited, but from the viewpoint that the ten-point average roughness Rz jis of the surface of the roughened plating layer 12 can be suitably controlled within the above range, zinc sulfate seven waters are used.
- a method by electroplating using a plating bath containing a Japanese product at a concentration of 10 to 400 g / L and ammonium sulfate at a concentration of 10 to 100 g / L is preferable.
- 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.
- Ammonia may be added to the nickel plating bath by adding aqueous ammonia or a salt such as ammonium sulfate or ammonium chloride.
- the current density when galvanizing is performed by the electrolytic plating method is preferably 1 to 60 A / dm 2 from the viewpoint that the ten-point average roughness Rz jis on the surface of the roughened plating layer 12 can be more preferably controlled. It is preferably 5 to 30 A / dm 2 , and more preferably 10 to 20 A / dm 2 .
- the bath temperature of the galvanizing bath when galvanizing is performed by the electrolytic plating method is preferably 25 to 70 ° C, more preferably 30 to 60 ° C, still more preferably 40 to 60 ° C, and the pH of the galvanizing bath. Is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2.
- FIG. 4 is a diagram showing the configuration of the roughened plating plate 1a according to another embodiment.
- the roughened plating plate 1a includes a base metal plating layer 13 on a metal base material 11, and is a base metal.
- the roughened nickel plating layer 121 and the zinc plating layer 122 are formed on the plating layer 13 in this order, and the roughened plating layer 12 is provided.
- a nickel plating layer or a zinc plating layer is preferable, and a nickel plating layer is more preferable.
- the plurality of nickel granules 1210 constituting the roughened nickel plating layer 121 are in a state in which particulate precipitates aggregate and precipitate in the form of protrusions and exist as an aggregate, and have good adhesion to other members. From the viewpoint, it is preferable to have a gap between the aggregates, and therefore, the entire surface of the metal base material 11 may not be completely covered. Therefore, for example, when a steel plate is used as the metal base material 11, it is preferable to provide the base metal plating layer 13 in order to improve the effect of suppressing the occurrence of rust on the steel plate.
- the metal base material 11 For the purpose of improving the corrosion resistance, it is preferable to select the metal base material 11 according to the application and perform the base plating treatment accordingly.
- the metal base material 11 is made of steel plate or copper, it is preferable.
- the base metal plating layer 13 it is preferable to provide a base nickel plating layer or a base copper plating layer.
- the metal base material 11 is a copper plate, it is possible to further improve the plating adhesion of the roughened plating layer 12 by subjecting the pretreatment to an acid treatment or the like.
- the base metal plating layer 13 is made of roughened nickel composed of a plurality of nickel granules 1210 before performing roughened nickel plating for precipitating nickel granules 1210 in an aggregated state on the metal base material 11. Before forming the plating layer 121, it can be formed by pre-plating the metal base material 11. When the base metal plating layer 13 is a nickel plating layer, it may be formed by either electrolytic plating or electroless plating, but it is preferably formed by electrolytic plating.
- the base metal plating layer 13 is a nickel plating layer and the electrolytic plating method is used as a method for forming the base nickel plating layer, for example, as a nickel plating bath, nickel sulfate hexahydrate 200 to 350 g / Using a watt bath with a bath composition of L, nickel chloride hexahydrate 20-60 g / L, and boric acid 10-50 g / L, pH 3.0-5.0, bath temperature 40-70 ° C, current density 5-30 A / A method can be used in which nickel plating is performed under the condition of dm 2 (preferably 10 to 20 A / dm 2 ) and then washed with water.
- dm 2 preferably 10 to 20 A / dm 2
- the base metal plating layer 13 is a galvanized layer and the electrolytic plating method is used as the method for forming the base zinc plating layer, it is the same as the above-mentioned galvanizing film 1220 (galvanizing layer 122). Examples thereof include a method of performing electrolytic plating under conditions.
- the nickel granules 1210 are precipitated on the metal base material 11 in an aggregated state.
- a roughened plating having a detailed structure as shown in FIG. 2 is formed by forming a galvanized nickel-plated layer 121 and then subjecting it to galvanizing to form a galvanized layer 122 as a galvanized film 1220.
- the layer 12 can be formed, and by controlling these formation conditions, the ten-point average roughness Rz jis of the surface of the roughened plating layer 12 can be within the above range.
- the roughened plating plate 1 of the present embodiment has excellent corrosion resistance (particularly salt damage resistance and pore corrosion resistance) and exhibits excellent adhesion to other members. Therefore, applications used in combination with other members, such as resins (eg, nylon 6, nylon 66, nylon 610, nylon 12, polypropylene, ABS resin, polymethylmethacrylate resin, thermoplastic polyurethane resin, epoxy) Various resins such as resins, resin composites containing fillers, reinforcing fibers, etc.
- resins eg, nylon 6, nylon 66, nylon 610, nylon 12, polypropylene, ABS resin, polymethylmethacrylate resin, thermoplastic polyurethane resin, epoxy
- various containers that require adhesion to various members, building members, electronic device members (housing) It can be suitably used as a body, a shield member, a reinforcing member), and a battery member (outer tank, current collector, tab lead).
- the amount of roughened nickel plating that constitutes the roughened plating layer and the amount of zinc plating that constitutes the roughened plating layer can be determined by using a fluorescent X-ray device. Obtained using. In Examples 7, 8, 27, 28, 36, and 37 in which the base nickel plating layer or the base zinc plating layer was formed, a fluorescent X-ray apparatus was used after the step of forming the base nickel plating layer or the base zinc plating layer.
- the amount of adhesion of the base nickel plating layer or the base zinc plating layer is obtained, and by subtracting these amounts, the amount of adhesion of the roughened nickel plating that constitutes the roughened plating layer and the roughened plating layer are constructed. The amount of galvanized adhesion was determined.
- the brightness L * of the surface of the roughened plating layer is measured by the SCE method (specular reflection) in accordance with the geometric condition C in JIS Z8722 using a spectrocolorimeter (product name "CM-5", manufactured by Konica Minolta). It was measured by the light removal method).
- the 85 ° glossiness of the surface of the roughened plating layer was measured using a gloss meter (product name "VG 7000", manufactured by Nippon Denshoku Kogyo Co., Ltd.) in accordance with JIS Z8741.
- VG 7000 manufactured by Nippon Denshoku Kogyo Co., Ltd.
- JIS Z8741 JIS Z8741
- the obtained 180 ° peel test piece was subjected to a tensile test with a tensile tester, and the peeling load (180 ° peel strength) was measured.
- the peel strength was defined as a value obtained by averaging a load having a stroke of 25 mm to 75 mm and dividing it by the width of the test piece.
- FIG. 6 shows an outline of a 180 ° peel test piece. It can be judged that the higher the 180 ° peel strength, the better the adhesion with the resin.
- the 180 ° peel strength values are expressed as an index with Comparative Example 2 as 1.0 for Examples 1 to 8 and Comparative Examples 1 and 12, and for Examples 9 to 28 and Comparative Examples 3 and 13.
- Comparative Example 4 was represented by an index of 1.0.
- Example 29 is an index with Comparative Example 5 as 1.0
- Example 30 is an index with Comparative Example 6 as 1.0
- Example 31 is an index with Comparative Example 7 as 1.0
- Examples 32, 36, 37 and Comparative Example 14 are indexes with Comparative Example 8 as 1.0
- Example 33 is an index with Comparative Example 9 as 1.0
- Example 34 is Comparative Example 10 with 1. The index was set to 0.0
- Example 35 was represented by an index set to 1.0 for Comparative Example 11.
- Corrosion resistance was evaluated according to the following criteria by visual observation. The evaluation of corrosion resistance was carried out in Examples 1, 7, 8, Comparative Examples 1, 2, 23, 27, 28, Comparative Examples 3, 4, Examples 32, 36, 37, Comparative Example 8, and Comparative Example 12. I went about 14 ⁇ 14.
- Example 1 As a substrate, a steel plate obtained by annealing a cold-rolled plate (thickness 0.1 mm) of low-carbon aluminum killed steel was prepared.
- a 180 ° peel test piece was prepared using a nylon 6 (PA6, thickness 1 mm) resin plate, and the obtained 180 ° peel test piece was used to adhere to the resin.
- the property (180 ° peel strength) was evaluated. Specifically, first, the obtained roughened plating plate and the resin plate (nylon 6) are cut into dimensions of 100 mm in length and 100 mm in width so that the roughened plating layer side of the roughened plating plate is joined to the resin plate.
- a laminated board was produced by superimposing two materials and heating and pressurizing them with a hot press.
- Examples 2 to 6 and Comparative Example 1 are the same as in Example 1 except that the plating time (treatment time) for roughened nickel plating and the plating time (treatment time) for zinc plating are changed to the conditions shown in Table 1. A roughened plated plate and a 180 ° peel test piece were obtained and evaluated in the same manner. The results are shown in Table 1.
- Example 7 The steel sheet is subjected to alkaline electrolytic degreasing and pickling by immersion in sulfuric acid, and then electrolytic plating is performed under the following conditions using a base nickel plating bath having the following bath composition, whereby both sides of the steel sheet have a thickness of 1 ⁇ m.
- a base nickel plating bath having the following bath composition, whereby both sides of the steel sheet have a thickness of 1 ⁇ m.
- a roughened nickel plating layer and a coating with a zinc plating film were formed on the base nickel plating layer in the same manner as in Example 1, and the roughened plating of Example 7 was performed.
- a plate was obtained, and a 180 ° peel test piece was obtained in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1.
- Example 8 After performing alkaline electrolytic degreasing and pickling by soaking in sulfuric acid, the steel sheet is electroplated under the following conditions using a base galvanized bath with the following bath composition, and the thickness is 1 ⁇ m on both sides of the steel sheet. After the base galvanization of Example 8 is formed, a roughened nickel plating layer is formed and a coating with a zinc plating film is formed on the base zinc plating layer in the same manner as in Example 1, and the roughening plating of Example 8 is performed. A plate was obtained, and a 180 ° peel test piece was obtained in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1.
- Comparative Example 2 >> A plated plate and a 180 ° peel test piece were obtained and evaluated in the same manner as in Example 1 except that zinc plating was performed directly on the steel sheet without forming roughened nickel plating. .. The results are shown in Table 1.
- Example 9 The roughened plating plate of Example 9 was prepared in the same manner as in Example 1 except that the plating time (treatment time) for roughened nickel plating and the plating time (treatment time) for zinc plating were changed to the conditions shown in Table 2. Obtained and evaluated in the same manner. Then, the obtained roughened plating plate was used, an epoxy resin (EP, thickness 1 mm) was used instead of nylon 6 as the resin plate, and the heating temperature in the hot press was changed to 180 ° C. Except for the above, a 180 ° peel test piece was obtained in the same manner as in Example 1, and the resin adhesion (180 ° peel strength) was evaluated by the above method. The results are shown in Table 2.
- Examples 10 to 26, Comparative Example 3 >> The same as in Example 9 except that the plating time (treatment time) for roughened nickel plating, the plating time (treatment time) for galvanization, the plating bath, the current density, the pH and the bath temperature were changed to the conditions shown in Table 2. Then, the roughened plated plates of Examples 10 to 26 and Comparative Example 3 and the 180 ° peel test piece were obtained and evaluated in the same manner. The results are shown in Table 2.
- Example 27 After forming a 1 ⁇ m-thick base nickel plating on both sides of the steel sheet in the same manner as in Example 7, a roughened nickel plating layer is formed on the base nickel plating layer in the same manner as in Example 23. , A roughened plated plate of Example 27 was obtained by coating with a zinc plating film, and a 180 ° peel test piece was obtained in the same manner as in Example 9 and evaluated in the same manner. The results are shown in Table 2.
- Example 28 After forming a 1 ⁇ m-thick base galvanized plate on both sides of the steel plate in the same manner as in Example 8, a roughened nickel plating layer is formed on the base galvanized layer in the same manner as in Example 23. , A galvanized film was applied to obtain a roughened plated plate of Example 28, and a 180 ° peel test piece was obtained in the same manner as in Example 9 and evaluated in the same manner. The results are shown in Table 2.
- Comparative Example 4 >> A plated plate and a 180 ° peel test piece were obtained and evaluated in the same manner as in Example 18 except that zinc plating was directly performed on the steel sheet without forming roughened nickel plating. .. The results are shown in Table 1.
- Example 29 Except for the fact that nylon 66 (PA66, thickness 1 mm) was used instead of nylon 6 as the resin plate when obtaining the 180 ° peel test piece, and that the heating temperature in the hot press was changed to 280 ° C. , A 180 ° peel test piece was obtained in the same manner as in Example 1, and the resin adhesion (180 ° peel strength) was evaluated by the above method. The results are shown in Table 3.
- Example 30 When the 180 ° peel test piece was obtained, the 180 ° peel test piece was prepared in the same manner as in Example 1 except that nylon 610 (PA610, thickness 1 mm) was used instead of nylon 6 as the resin plate. Then, the resin adhesion (180 ° peel strength) was evaluated by the above method. The results are shown in Table 3.
- Example 31 When obtaining the 180 ° peel test piece, nylon 12 (PA12, thickness 1 mm) was used instead of nylon 6 as the resin plate, and the heating temperature in the hot press was changed to 240 ° C. , A 180 ° peel test piece was obtained in the same manner as in Example 1, and the resin adhesion (180 ° peel strength) was evaluated by the above method. The results are shown in Table 3.
- Example 32 When obtaining the 180 ° peel test piece, polypropylene resin (PP, thickness 1 mm) was used instead of nylon 6 as the resin plate, and the heating temperature in the hot press was changed to 200 ° C. , A 180 ° peel test piece was obtained in the same manner as in Example 1, and the resin adhesion (180 ° peel strength) was evaluated by the above method. The results are shown in Table 3.
- Example 33 Except for the fact that ABS resin (ABS, thickness 1 mm) was used instead of nylon 6 as the resin plate when obtaining the 180 ° peel test piece, and that the heating temperature in the hot press was changed to 240 ° C. , A 180 ° peel test piece was obtained in the same manner as in Example 1, and the resin adhesion (180 ° peel strength) was evaluated by the above method. The results are shown in Table 3.
- Example 34 When obtaining the 180 ° peel test piece, polymethylmethacrylate resin (PMMA, thickness 1 mm) was used as the resin plate instead of nylon 6, and the heating temperature in the hot press was changed to 250 ° C. Except for the above, a 180 ° peel test piece was obtained in the same manner as in Example 1, and the resin adhesion (180 ° peel strength) was evaluated by the above method. The results are shown in Table 3.
- PMMA polymethylmethacrylate resin
- Example 35 When obtaining the 180 ° peel test piece, a thermoplastic polyurethane resin (TPU, thickness 1 mm) was used as the resin plate instead of nylon 6, and the heating temperature in the hot press was changed to 220 ° C. A 180 ° peel test piece was obtained in the same manner as in Example 1 using the roughened plating plate obtained in the same manner as in Example 1 except for the resin adhesion (180 ° peel) by the above method. Strength) was evaluated. The results are shown in Table 3.
- TPU thermoplastic polyurethane resin
- Example 36 When obtaining the 180 ° peel test piece, polypropylene resin (PP, thickness 1 mm) was used instead of nylon 6 as the resin plate, and the heating temperature in the hot press was changed to 200 ° C. , A 180 ° peel test piece was obtained in the same manner as in Example 7, and the resin adhesion (180 ° peel strength) was evaluated by the above method. The results are shown in Table 3.
- Example 37 When obtaining the 180 ° peel test piece, polypropylene resin (PP, thickness 1 mm) was used instead of nylon 6 as the resin plate, and the heating temperature in the hot press was changed to 200 ° C. , A 180 ° peel test piece was obtained in the same manner as in Example 8, and the resin adhesion (180 ° peel strength) was evaluated by the above method. The results are shown in Table 3.
- Comparative Examples 5 to 11 A nylon 66 plate (Comparative Example 5), a nylon 610 plate (Comparative Example 6), and a nylon 12 plate (comparative) used in Examples 29 to 35 as resin plates when obtaining a 180 ° peel test piece.
- Example 7 polypropylene resin plate (Comparative Example 8), ABS resin plate (Comparative Example 9), polymethylmethacrylate resin plate (Comparative Example 10), thermoplastic polyurethane resin plate (Comparative Example 11) are used.
- a 180 ° peel test piece was obtained in the same manner as in Comparative Example 2 using the plating plate obtained in the same manner as in Comparative Example 2 except that the heating temperature in the hot press was set to the temperature corresponding to each resin plate. Then, the resin adhesion (180 ° peel strength) was evaluated by the above method. The results are shown in Table 3.
- Comparative Example 12 After performing alkaline electrolytic degreasing and pickling by soaking in sulfuric acid, the steel sheet is electrolytically plated under the following conditions using a nickel plating bath with the following bath composition, so that both sides of the steel sheet have a thickness of 1 ⁇ m. By forming nickel plating, a nickel plated plate was obtained. Then, the obtained nickel-plated plate is evaluated in the same manner as in Example 1, and a 180 ° peel test piece is obtained in the same manner as in Example 1 using the obtained nickel-plated plate. Was evaluated. The results are shown in Table 4.
- Comparative Example 13 Except for the fact that an epoxy resin (EP, thickness 1 mm) was used instead of nylon 6 as the resin plate when the 180 ° peel test piece was obtained, and that the heating temperature in the hot press was changed to 180 ° C. , A 180 ° peel test piece was obtained in the same manner as in Comparative Example 12, and the resin adhesion (180 ° peel strength) was evaluated by the above method. The results are shown in Table 4.
- EP thickness 1 mm
- Comparative Example 14 When obtaining the 180 ° peel test piece, polypropylene resin (PP, thickness 1 mm) was used instead of nylon 6 as the resin plate, and the heating temperature in the hot press was changed to 200 ° C. , A 180 ° peel test piece was obtained in the same manner as in Comparative Example 12, and the resin adhesion (180 ° peel strength) was evaluated by the above method. The results are shown in Table 4.
- the roughened nickel plating layer and the roughened plating layer formed by forming the zinc plating layer in this order are provided, and the ten-point average roughness Rz jis of the surface of the roughened plating layer is provided.
- the roughened plated plate having a size of 3 ⁇ m or more all of them had excellent adhesion to various resins (Examples 1 to 37).
- the ten-point average roughness Rz jis on the surface of the roughened plating layer is less than 3 ⁇ m, or when the roughened plating layer is not formed (that is, the roughened nickel plating layer is not formed and the zinc plating layer is directly formed. In the case of forming), the result was that the adhesion to various resins was inferior (Comparative Examples 1 to 11). Further, even when the roughened plating layer was not formed, the adhesion to various resins was inferior (Comparative Examples 12 to 14).
- FIG. 5 (A) is an image obtained by observing the surface of the roughened plating plate of Example 1 with a scanning electron microscope (SEM), and FIG. 5 (B) is the roughening of Example 1. It is an image obtained by observing the cross section of the plating plate with a scanning electron microscope (SEM), and FIG. 5 (C) shows the cross section shown in FIG. 5 (B) observed with a scanning electron microscope (SEM). It is an image showing the distribution of zinc atoms by an energy dispersive X-ray microscope (EDS). As is clear from the comparison of FIGS.
- SEM scanning electron microscope
- the roughened plating layer of Example 1 has a galvanized coating on the surface of a plurality of nickel granules forming the roughened nickel plating layer. Since the (galvanized layer) is formed, it can be said that the excellent corrosion resistance of the galvanized film (galvanized layer) can be sufficiently exhibited. This was the same in all of Examples 1 to 31 including Example 1. Further, in FIGS. 5 (B) and 5 (C), the positions of the roots of the protrusions of the protrusion-shaped roughened plating layer formed by forming a galvanizing film (galvanizing layer) on the surface of the nickel granules are determined. When the position of the interface between the base material and the roughened plating layer was determined as the base, it was confirmed that the roughened plating layer was well formed at such an interface.
- the method for evaluating the adhesion of the roughened plating layer is shown below.
- ⁇ Adhesion of roughened plating layer> First, as a reference sample, prepare an adhesive tape (manufactured by Nichiban Co., Ltd., product name "Cellotape (registered trademark)") attached to a mount, and prepare a spectrophotometer (product name "CM-5", Konica Minolta). The brightness L * , chromaticity a * , and b * were measured using (manufactured by the company). A CIE1976L * a * b * color difference model was used for the measurement.
- an adhesive tape (adhesive tape) is applied to the surface of the roughened plating plate obtained in Examples 1, 4, 6 to 8, 10, 11, 13, 14, 18 to 24, 27 to 37 on which the roughened plating layer is formed.
- Nichiban Co., Ltd., trade name "Scotch tape” is attached so that it has a width of 24 mm and a length of 50 mm, and then a peeling test using the attached adhesive tape is performed, and the procedure of the peeling test method described in JIS H 8504. I went there.
- the adhesive tape after the peeling test was attached to the same mount as the reference sample, and the brightness L * , chromaticity a * , and b * were measured using a spectrophotometer in the same manner as described above.
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Abstract
Description
上記特許文献1に開示されている表面処理鋼板は、最表面がニッケルにより形成されているため、耐食性(特に、耐塩害性や、耐孔食性)が十分でないという課題もあった。
また、上記特許文献2に開示されている表面処理銅箔は、ニッケルと比較して、電気化学的に貴である銅めっき層上に、亜鉛めっき層を形成するものであるため、亜鉛めっき層から亜鉛が溶解しやすく、耐食性が十分でないという課題がある。
さらに、上記特許文献3に開示された技術は、亜鉛めっきを行った後に、エッチングを行う必要あり、製造工程が煩雑であり、さらには、エッチングに要する時間が長いため、生産効率に劣るという課題がある。
本発明の粗化めっき板は、前記粗化めっき層表面の十点平均粗さRzjisが3~30μmであることが好ましい。
本発明の粗化めっき板は、前記粗化めっき層表面の明度L*が45~83であることが好ましい。
本発明の粗化めっき板は、前記金属基材と、前記粗化ニッケルめっき層との間に、別のめっき層をさらに備えるものであることが好ましい。
本発明の粗化めっき板において、前記別のめっき層がニッケルめっき層、又は亜鉛めっき層であることが好ましい。
本発明の粗化めっき板において、前記粗化めっき層を構成する前記亜鉛めっき層の付着量が、3g/m2以上であることが好ましい。
本発明の粗化めっき板において、前記金属基材が、Fe,Cu,AlおよびNiから選択される一種の純金属からなる金属板もしくは金属箔、または、Fe,Cu,AlおよびNiから選択される一種を含む合金からなる金属板もしくは金属箔であることが好ましい。
なお、本実施形態においては、粗化めっき板1として、金属基材11の一方の面に、粗化ニッケルめっき層121と亜鉛めっき層122とから形成される粗化めっき層12が形成されてなるものを例示したが、このような態様に特に限定されず、粗化ニッケルめっき層121と亜鉛めっき層122とから形成される粗化めっき層12は、金属基材11の両方の面に形成されていてもよい。
本実施形態のめっき板1の基板となる金属基材11としては、特に限定されないが、Fe,Cu,AlおよびNiから選択される一種の純金属からなる金属板もしくは金属箔、または、Fe,Cu,AlおよびNiから選択される一種を含む合金からなる金属板もしくは金属箔などが挙げられ、具体的には、鋼板、ステンレス鋼板、銅板、アルミニウム板、またはニッケル板(これらは、純金属、合金のいずれであってもよく、箔状であってもよい。)などが挙げられ、これらのなかでも、めっき処理の前処理が比較的簡便な前処理でもめっきを施しやすく、また、粗化ニッケルめっき層121および亜鉛めっき層122を形成することによる、金属基材に対する密着性の向上効果をより高めることができるという観点から、鋼板が好ましく、特に、低炭素アルミキルド鋼(炭素量0.01~0.15重量%)、炭素量が0.01重量%以下(好ましくは炭素量が0.003重量%以下)の極低炭素鋼、または極低炭素鋼にTiやNbなどを添加してなる非時効性極低炭素鋼が好適に用いられる。
浴組成:硫酸ニッケル六水和物100~300g/L、硫酸10~200g/L
pH:1.0以下
浴温:40~70℃
電流密度:5~100A/dm2
めっき時間:3~100秒間
本実施形態の粗化めっき板1は、図1に示すように、金属基材11上に、粗化ニッケルめっき層121と亜鉛めっき層122とから形成される粗化めっき層12を備えるものである。
たとえば、粗化めっき層12が、図2に示すような詳細構造を有するものである場合には、一次粒子が集合した二次粒子(ニッケル粒状物1210)、および亜鉛めっき被膜1220(すなわち、亜鉛めっき層122)からなる突起状(柱状)の集合体が形成されることとなる。そして、このような構造においては、本発明者等の知見によると、粗化めっき層12の密度については、密度が高すぎると突起状間に樹脂などが入り込めず、密着性が確保できない場合があることや、密度が低すぎる場合には、一つ一つの集合体が細く折れやすくなり、金属基材11に対する、粗化めっき層12の密着性が低下するおそれがあること、さらには、集合体そのものが少なすぎてアンカー効果が必ずしも十分でなく、他の部材との密着性の向上効果が十分とならない場合があること等が見出された。
このような状況において、本発明者等がさらなる検討を行ったところ、粗化めっき層12の大きさや、形状、密度に関連するパラメータとして、十点平均粗さRzjisに加えて、粗化めっき層12の明度L*、さらには、85°光沢度に着目したところ、これらを特定の範囲とすることにより、他の部材に対する密着性や、粗化めっき層12自体の密着性のさらなる改善が可能となることを見出したものである。
すなわち、亜鉛めっき層122の付着量は、後述する下地金属めっき層13としての下地亜鉛めっき層が形成されていない場合には、得られた粗化めっき板1について蛍光X線装置を用いて総亜鉛量を測定することで求めることができ、一方、後述する下地金属めっき層13としての下地亜鉛めっき層が形成されている場合には、粗化めっき板1について蛍光X線装置を用いて総亜鉛量を測定した後、この総亜鉛量から、下地金属めっき層13としての下地亜鉛めっき層に相当する亜鉛量の分を差し引くことで求めることができる。下地金属めっき層13としての下地亜鉛めっき層に相当する亜鉛量も、下地ニッケルめっき層に相当するニッケル量を求める場合と同様に、断面観察から下地亜鉛めっき層の厚みを計測して換算する方法、下地亜鉛めっき層を形成した時点の亜鉛量を測定する方法、下地亜鉛めっき層を形成する際のクーロン量から算出する方法等により求めることができる。
なお、各特性の評価方法は、以下のとおりである。
粗化めっき板の粗化めっき層(粗化ニッケルめっき層および亜鉛めっき層)が形成された面について、JIS B0601:2013に準拠して、レーザー顕微鏡(オリンパス社製、型番:OLS3500)を用いて、97μm×129μm(縦×横)(測定視野幅129μm、測定面積約12,500μm2(12,500μm2±100μm2))の視野をスキャンした後、解析ソフト(ソフト名:LEXT-OLS)を用いて解析モード:粗さ解析の条件にて解析することにより、算術平均粗さRa、十点平均粗さRzjisを測定した。なお、レーザー顕微鏡により測定する際におけるカットオフ値は、測定視野幅(129μm)の1/3の長さである43μm程度(表示上は43.2μm)の波長とした。
粗化ニッケルめっき層の上に亜鉛めっき層を形成した後に、粗化めっき層を構成する粗化ニッケルめっきの付着量および粗化めっき層を構成する亜鉛めっきの付着量を、蛍光X線装置を用いて求めた。
なお、下地ニッケルめっき層または下地亜鉛めっき層を形成した実施例7,8,27,28,36,37においては、下地ニッケルめっき層または下地亜鉛めっき層を形成した工程後において蛍光X線装置による測定を行うことで、下地ニッケルめっき層または下地亜鉛めっき層の付着量を求め、これらの量を差し引くことで、粗化めっき層を構成する粗化ニッケルめっきの付着量および粗化めっき層を構成する亜鉛めっきの付着量を求めた。
粗化めっき層表面の明度L*を、分光測色計(製品名「CM-5」、コニカミノルタ社製)を使用して、JIS Z8722における幾何条件Cに準拠して、SCE方式(正反射光除去方式)にて測定した。
粗化めっき層表面の85°光沢度を、光沢計(製品名「VG 7000」、日本電色工業社製)を使用して、JIS Z8741に準拠して、測定した。なお、同じ測定器を用いて、60°光沢度を測定したところ、いずれの実施例(実施例1~32)においても、60°光沢度は、1.5未満であった。
所定サイズの型枠(SUS製)を用意し、この枠内体積に対し、材料体積が105~110%となるように粗化めっき板と樹脂板を重ねて枠内に配置した。次いで、材料が投入された型枠を離型剤を塗布したSUS板で挟んだ後、ホットプレス(G-12型フットポンプ式小型プレス(テクノサプライ社製)の上盤と下盤の間にセットした。
そして、以下の積層条件にて加熱と加圧を行い、金属と樹脂からなる積層板を作製した。
<積層条件>
1)予備加熱 ⇒ 温度:180~310℃、面圧:0.5MPa、保持時間:3分
2)プレス ⇒ 温度:180~310℃、面圧:5MPa、保持時間:7分
3)冷却/脱型 ⇒ 温度:70℃以下、面圧:5MPa
次に、作製した積層板を、幅20mm、長さ100mmの寸法に切断し、長さ方向の端部から40mmの位置まで金属を剥離させることで、180°ピール試験体を得た。次いで、得られた180°ピール試験体に対して、引張試験機にて引張試験を行い、剥離荷重(180°ピール強度)を測定した。尚、剥離強度は、ストローク25mm~75mmの荷重を平均し、それを試験体幅で除した値とした。図6に、180°ピール試験体の概略を示す。
180°ピール強度が高いほど、樹脂との密着性に優れると判断できる。
なお、180°ピール強度の値は、実施例1~8、比較例1,12については、比較例2を1.0とした指数で表し、実施例9~28、比較例3,13については、比較例4を1.0とした指数で表した。同様に、実施例29は比較例5を1.0とした指数で、実施例30は比較例6を1.0とした指数で、実施例31は比較例7を1.0とした指数で、実施例32,36,37、比較例14は比較例8を1.0とした指数で、実施例33は比較例9を1.0とした指数で、実施例34は比較例10を1.0とした指数で、実施例35は比較例11を1.0とした指数で、それぞれ表した。
粗化めっき板を、50mm×130mmに切断し、切断面をシールにより被覆することで、短冊状の評価サンプルを得た。そして、短冊状の評価サンプルについて、35℃、98%の湿度条件にて、5重量%NaClを用いた塩水噴霧試験を72時間の条件にて行い、27時間経過後の評価サンプルについて、外観を目視により観察することで、以下の基準に従って、耐食性の評価を行った。なお、耐食性の評価は、実施例1,7,8、比較例1,2、実施例23,27,28、比較例3,4、実施例32,36,37、比較例8、比較例12~14について行った。
◎:目視上赤錆(点錆)発生無し
○:視認できる赤錆(点錆)がわずかに発生(十点未満レベル)
△:視認できる赤錆(点錆)が全体的に発生(数十点レベル)
×:全面に赤錆もしくは点状の極大赤錆が発生
基体として、低炭素アルミキルド鋼の冷間圧延板(厚さ0.1mm)を焼鈍して得られた鋼板を準備した。
<粗化ニッケルめっき条件>
浴組成:硫酸ニッケル六水和物10g/L、塩化ニッケル六水和物10g/L、硫酸アンモニウム20g/L
pH:6.0
浴温:35℃
電流密度:15A/dm2
めっき時間:20.8秒間
<亜鉛めっき条件>
浴組成:硫酸亜鉛七水和物220g/L、硫酸アンモニウム30g/L
pH:2.0
浴温:55℃
電流密度:10A/dm2
めっき時間:47.0秒間
具体的には、まず、得られた粗化めっき板と樹脂板(ナイロン6)を縦100mm、横100mmの寸法に切断し、粗化めっき板の粗化めっき層側が樹脂板と接合するように2つの材料を重ね合わせ、ホットプレスにて加熱・加圧を行うことで、積層板を作製した。
<積層条件>
1)予備加熱 ⇒ 温度:270℃、面圧:0.5MPa、保持時間:3分
2)プレス ⇒ 温度:270℃、面圧:5MPa、保持時間:7分
3)冷却/脱型 ⇒ 温度:70℃以下、面圧:5MPa
そして、得られた積層板から180°ピール試験体を作製し、上記した方法により、樹脂密着性(180°ピール強度)の評価を行った。結果を表1に示す。
粗化ニッケルめっきのめっき時間(処理時間)および亜鉛めっきのめっき時間(処理時間)を表1に示す条件に変更した以外は、実施例1と同様にして、実施例2~6、比較例1の粗化めっき板および180°ピール試験体を得て、同様に評価を行った。結果を表1に示す。
鋼板について、アルカリ電解脱脂、硫酸浸漬の酸洗を行った後、下記の浴組成の下地ニッケルめっき浴を用いて、下記条件にて、電解めっきを行うことで、鋼板の両面に、厚さ1μmの下地ニッケルめっきを形成した後、この下地ニッケルめっき層上に、実施例1と同様にして、粗化ニッケルめっき層の形成、および、亜鉛めっき被膜による被覆を行い、実施例7の粗化めっき板を得るとともに、実施例1と同様にして、180°ピール試験体を得て、同様に評価を行った。結果を表1に示す。
<下地ニッケルめっき条件>
浴組成:硫酸ニッケル六水和物250g/L、塩化ニッケル六水和物45g/L、ホウ酸30g/L
pH:4.2
浴温:60℃
電流密度:10A/dm2
鋼板について、アルカリ電解脱脂、硫酸浸漬の酸洗を行った後、下記の浴組成の下地亜鉛めっき浴を用いて、下記条件にて、電解めっきを行うことで、鋼板の両面に、厚さ1μmの下地亜鉛めっきを形成した後、この下地亜鉛めっき層上に、実施例1と同様にして、粗化ニッケルめっき層の形成、および、亜鉛めっき被膜による被覆を行い、実施例8の粗化めっき板を得るとともに、実施例1と同様にして、180°ピール試験体を得て、同様に評価を行った。結果を表1に示す。
<下地亜鉛めっき条件>
浴組成:硫酸亜鉛七水和物220g/L、硫酸アンモニウム30g/L
pH:2.0
浴温:55℃
電流密度:10A/dm2
粗化ニッケルめっきを形成せずに、鋼板上に、直接、亜鉛めっきを行った以外は、実施例1と同様にして、めっき板および180°ピール試験体を得て、同様に評価を行った。結果を表1に示す。
粗化ニッケルめっきのめっき時間(処理時間)および亜鉛めっきのめっき時間(処理時間)を表2に示す条件に変更した以外は、実施例1と同様にして、実施例9の粗化めっき板を得て、同様に評価を行った。そして、得られた粗化めっき板を用いたこと、樹脂板として、ナイロン6に代えて、エポキシ樹脂(EP、厚さ1mm)を使用したこと、および、ホットプレスにおける加熱温度を180℃に変更したこと以外は、実施例1と同様にして、180°ピール試験体を得て、上記した方法により、樹脂密着性(180°ピール強度)の評価を行った。結果を表2に示す。
粗化ニッケルめっきのめっき時間(処理時間)、亜鉛めっきのめっき時間(処理時間)、めっき浴、電流密度、pHおよび浴温を表2に示す条件に変更した以外は、実施例9と同様にして、実施例10~26、比較例3の粗化めっき板および180°ピール試験体を得て、同様に評価を行った。結果を表2に示す。
実施例7と同様にして、鋼板の両面に、厚さ1μmの下地ニッケルめっきを形成した後、この下地ニッケルめっき層上に、実施例23と同様にして、粗化ニッケルめっき層の形成、および、亜鉛めっき被膜による被覆を行い、実施例27の粗化めっき板を得るとともに、実施例9と同様にして、180°ピール試験体を得て、同様に評価を行った。結果を表2に示す。
実施例8と同様にして、鋼板の両面に、厚さ1μmの下地亜鉛めっきを形成した後、この下地亜鉛めっき層上に、実施例23と同様にして、粗化ニッケルめっき層の形成、および、亜鉛めっき被膜による被覆を行い、実施例28の粗化めっき板を得るとともに、実施例9と同様にして、180°ピール試験体を得て、同様に評価を行った。結果を表2に示す。
粗化ニッケルめっきを形成せずに、鋼板上に、直接、亜鉛めっきを行った以外は、実施例18と同様にして、めっき板および180°ピール試験体を得て、同様に評価を行った。結果を表1に示す。
180°ピール試験体を得る際に、樹脂板として、ナイロン6に代えて、ナイロン66(PA66、厚さ1mm)を使用したこと、および、ホットプレスにおける加熱温度を280℃に変更したこと以外は、実施例1と同様にして、180°ピール試験体を得て、上記した方法により、樹脂密着性(180°ピール強度)の評価を行った。結果を表3に示す。
180°ピール試験体を得る際に、樹脂板として、ナイロン6に代えて、ナイロン610(PA610、厚さ1mm)を使用したこと以外は、実施例1と同様にして、180°ピール試験体を得て、上記した方法により、樹脂密着性(180°ピール強度)の評価を行った。結果を表3に示す。
180°ピール試験体を得る際に、樹脂板として、ナイロン6に代えて、ナイロン12(PA12、厚さ1mm)を使用したこと、および、ホットプレスにおける加熱温度を240℃に変更したこと以外は、実施例1と同様にして、180°ピール試験体を得て、上記した方法により、樹脂密着性(180°ピール強度)の評価を行った。結果を表3に示す。
180°ピール試験体を得る際に、樹脂板として、ナイロン6に代えて、ポリプロピレン樹脂(PP、厚さ1mm)を使用したこと、および、ホットプレスにおける加熱温度を200℃に変更したこと以外は、実施例1と同様にして、180°ピール試験体を得て、上記した方法により、樹脂密着性(180°ピール強度)の評価を行った。結果を表3に示す。
180°ピール試験体を得る際に、樹脂板として、ナイロン6に代えて、ABS樹脂(ABS、厚さ1mm)を使用したこと、および、ホットプレスにおける加熱温度を240℃に変更したこと以外は、実施例1と同様にして、180°ピール試験体を得て、上記した方法により、樹脂密着性(180°ピール強度)の評価を行った。結果を表3に示す。
180°ピール試験体を得る際に、樹脂板として、ナイロン6に代えて、ポリメチルメタクリレート樹脂(PMMA、厚さ1mm)を使用したこと、および、ホットプレスにおける加熱温度を250℃に変更したこと以外は、実施例1と同様にして、180°ピール試験体を得て、上記した方法により、樹脂密着性(180°ピール強度)の評価を行った。結果を表3に示す。
180°ピール試験体を得る際に、樹脂板として、ナイロン6に代えて、熱可塑性ポリウレタン樹脂(TPU、厚さ1mm)を使用したこと、および、ホットプレスにおける加熱温度を220℃に変更したこと以外は、実施例1と同様にして得られた粗化めっき板を用いて、実施例1と同様にして、180°ピール試験体を得て、上記した方法により、樹脂密着性(180°ピール強度)の評価を行った。結果を表3に示す。
180°ピール試験体を得る際に、樹脂板として、ナイロン6に代えて、ポリプロピレン樹脂(PP、厚さ1mm)を使用したこと、および、ホットプレスにおける加熱温度を200℃に変更したこと以外は、実施例7と同様にして、180°ピール試験体を得て、上記した方法により、樹脂密着性(180°ピール強度)の評価を行った。結果を表3に示す。
180°ピール試験体を得る際に、樹脂板として、ナイロン6に代えて、ポリプロピレン樹脂(PP、厚さ1mm)を使用したこと、および、ホットプレスにおける加熱温度を200℃に変更したこと以外は、実施例8と同様にして、180°ピール試験体を得て、上記した方法により、樹脂密着性(180°ピール強度)の評価を行った。結果を表3に示す。
180°ピール試験体を得る際に、樹脂板として、実施例29~35でそれぞれ使用した、ナイロン66の板(比較例5)、ナイロン610の板(比較例6)、ナイロン12の板(比較例7)、ポリプロピレン樹脂の板(比較例8)、ABS樹脂の板(比較例9)、ポリメチルメタクリレート樹脂の板(比較例10)、熱可塑性ポリウレタン樹脂の板(比較例11)を使用し、ホットプレスにおける加熱温度を各樹脂板に対応する温度とした以外は、比較例2と同様にして得られためっき板を用いて、比較例2と同様にして、180°ピール試験体を得て、上記した方法により、樹脂密着性(180°ピール強度)の評価を行った。結果を表3に示す。
鋼板について、アルカリ電解脱脂、硫酸浸漬の酸洗を行った後、下記の浴組成のニッケルめっき浴を用いて、下記条件にて、電解めっきを行うことで、鋼板の両面に、厚さ1μmのニッケルめっきを形成することで、ニッケルめっき板を得た。そして、得られたニッケルめっき板について、実施例1と同様にして評価を行うとともに、得られたニッケルめっき板を用いて、実施例1と同様にして、180°ピール試験体を得て、同様に評価を行った。結果を表4に示す。
<ニッケルめっき条件>
浴組成:硫酸ニッケル六水和物250g/L、塩化ニッケル六水和物45g/L、ホウ酸30g/L
pH:4.2
浴温:60℃
電流密度:10A/dm2
めっき時間:31.2秒間
180°ピール試験体を得る際に、樹脂板として、ナイロン6に代えて、エポキシ樹脂(EP、厚さ1mm)を使用したこと、および、ホットプレスにおける加熱温度を180℃に変更したこと以外は、比較例12と同様にして、180°ピール試験体を得て、上記した方法により、樹脂密着性(180°ピール強度)の評価を行った。結果を表4に示す。
180°ピール試験体を得る際に、樹脂板として、ナイロン6に代えて、ポリプロピレン樹脂(PP、厚さ1mm)を使用したこと、および、ホットプレスにおける加熱温度を200℃に変更したこと以外は、比較例12と同様にして、180°ピール試験体を得て、上記した方法により、樹脂密着性(180°ピール強度)の評価を行った。結果を表4に示す。
一方、粗化めっき層表面の十点平均粗さRzjisが、3μm未満である場合や、粗化めっき層を形成しない場合(すなわち、粗化ニッケルめっき層を形成せず、直接、亜鉛めっき層を形成した場合)には、各種樹脂に対する密着性に劣る結果となった(比較例1~11)。
また、粗化めっき層を形成しなかった場合にも、各種樹脂に対する密着性に劣る結果となった(比較例12~14)。
また、粗化めっき層の下に、下地亜鉛めっき層を形成した場合には、耐食性に極めて優れるものであった(実施例8,28,37)。
なお、下地めっき層の有無にかかわらず、表面粗度および外観に極端な差はみられず、さらには、実施例1,実施例23,実施例32の結果より、他の実施例においても、優れた耐食性を実現できるものと考えることができる。
また、図5(B)、図5(C)において、ニッケル粒状物の表面に、亜鉛めっき被膜(亜鉛めっき層)が形成されてなる突起状の粗化めっき層について、突起の根元の位置をベースとして、基材と、粗化めっき層との界面位置を判断したところ、このような界面を境に、粗化めっき層が良好に形成されていることが確認された。
以下に、粗化めっき層の密着性の評価方法を示す。
まず、基準サンプルとして、粘着テープ(ニチバン社製、商品名「セロテープ(登録商標)」)を、台紙に貼り付けたものを準備し、分光測色計(製品名「CM-5」、コニカミノルタ社製)を使用して、明度L*、色度a*、b*を測定した。なお、測定に際しては、CIE1976L*a*b*色差モデルを用いた。
そして、実施例1,4,6~8,10,11,13,14,18~24,27~37で得られた粗化めっき板の粗化めっき層が形成された面に、粘着テープ(ニチバン社製、商品名「セロテープ」)を、幅24mm、長さ50mmの範囲となるように貼付した後、貼付した粘着テープによる剥離試験を、JIS H 8504に記載された引きはがし試験方法の要領で行った。そして、剥離試験後の粘着テープを、上記基準サンプルと同じ台紙に貼り付け、上記と同様にして、分光測色計を使用して、明度L*、色度a*、b*を測定した。そして、予め測定した、基準サンプルの明度L*、色度a*、b*の測定結果、および剥離試験後の粘着テープの明度L*、色度a*、b*の測定結果から、これらの差ΔE*ab(ΔE*ab=〔(ΔL*)2+(Δa*)2+(Δb*)2〕1/2)を算出し、以下の基準に基づいて、粗化めっき層の密着性の評価を行った。なお、ΔE*abが小さいほど、剥離試験において剥離する量が少なく、つまり、剥離試験後の、粗化ニッケル層の残存率が高く、基材に対する密着性に優れると判断することができる。
11…金属基材
12…粗化めっき層
121…粗化ニッケルめっき層
1210…ニッケル粒状物
122…亜鉛めっき層
1220…亜鉛めっき被膜
Claims (8)
- 金属基材の少なくとも一方の面に、前記金属基材側から、粗化ニッケルめっき層と、亜鉛めっき層とがこの順に形成されてなる粗化めっき層を備える粗化めっき板であって、
レーザー顕微鏡測定による、前記粗化めっき層表面の十点平均粗さRzjisが3μm以上である、粗化めっき板。 - 前記粗化めっき層表面の明度L*が83以下である請求項1に記載の粗化めっき板。
- 前記粗化めっき層表面の十点平均粗さRzjisが3~30μmである請求項1または2に記載の粗化めっき板。
- 前記粗化めっき層表面の明度L*が45~83である請求項1~3のいずれかに記載の粗化めっき板。
- 前記金属基材と、前記粗化ニッケルめっき層との間に、別のめっき層をさらに備える請求項1~4のいずれかに記載の粗化めっき板。
- 前記別のめっき層がニッケルめっき層、又は亜鉛めっき層である請求項5に記載の粗化めっき板。
- 前記粗化めっき層を構成する前記亜鉛めっき層の付着量が、3g/m2以上である請求項1~6のいずれかに記載の粗化めっき板。
- 前記金属基材が、Fe,Cu,AlおよびNiから選択される一種の純金属からなる金属板もしくは金属箔、または、Fe,Cu,AlおよびNiから選択される一種を含む合金からなる金属板もしくは金属箔である請求項1~7のいずれかに記載の粗化めっき板。
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005248323A (ja) * | 2004-02-06 | 2005-09-15 | Furukawa Circuit Foil Kk | 表面処理銅箔 |
JP2011021216A (ja) * | 2009-07-14 | 2011-02-03 | Furukawa Electric Co Ltd:The | 抵抗層付銅箔、該銅箔の製造方法および積層基板 |
JP2013095991A (ja) * | 2011-11-04 | 2013-05-20 | Fukuda Metal Foil & Powder Co Ltd | 高放射率金属箔 |
WO2016038923A1 (ja) * | 2014-09-09 | 2016-03-17 | 古河電気工業株式会社 | プリント配線板用銅箔及び銅張積層板 |
JP2016084528A (ja) * | 2014-10-22 | 2016-05-19 | Jx金属株式会社 | 銅放熱材、キャリア付銅箔、コネクタ、端子、積層体、シールド材、プリント配線板、金属加工部材、電子機器、及び、プリント配線板の製造方法 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW200535259A (en) | 2004-02-06 | 2005-11-01 | Furukawa Circuit Foil | Treated copper foil and circuit board |
JP4626390B2 (ja) * | 2005-05-16 | 2011-02-09 | 日立電線株式会社 | 環境保護を配慮したプリント配線板用銅箔 |
WO2009116484A1 (ja) | 2008-03-17 | 2009-09-24 | 大成プラス株式会社 | 亜鉛系鍍金鋼板と被着材の接合体及びその製造方法 |
JP2011162860A (ja) | 2010-02-12 | 2011-08-25 | Furukawa Electric Co Ltd:The | 表面粗化銅箔とその製造方法及び銅張積層板 |
JP5885345B2 (ja) | 2012-05-29 | 2016-03-15 | 東洋鋼鈑株式会社 | 樹脂との加工密着性に優れる容器用表面処理鋼板、その製造方法および缶 |
JP5362924B1 (ja) * | 2012-11-09 | 2013-12-11 | Jx日鉱日石金属株式会社 | 表面処理銅箔及びそれを用いた積層板 |
JP5728117B1 (ja) | 2014-09-22 | 2015-06-03 | 株式会社Shカッパープロダクツ | 表面処理銅箔、該表面処理銅箔の製造方法、および該表面処理銅箔を用いた銅張積層板 |
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005248323A (ja) * | 2004-02-06 | 2005-09-15 | Furukawa Circuit Foil Kk | 表面処理銅箔 |
JP2011021216A (ja) * | 2009-07-14 | 2011-02-03 | Furukawa Electric Co Ltd:The | 抵抗層付銅箔、該銅箔の製造方法および積層基板 |
JP2013095991A (ja) * | 2011-11-04 | 2013-05-20 | Fukuda Metal Foil & Powder Co Ltd | 高放射率金属箔 |
WO2016038923A1 (ja) * | 2014-09-09 | 2016-03-17 | 古河電気工業株式会社 | プリント配線板用銅箔及び銅張積層板 |
JP2016084528A (ja) * | 2014-10-22 | 2016-05-19 | Jx金属株式会社 | 銅放熱材、キャリア付銅箔、コネクタ、端子、積層体、シールド材、プリント配線板、金属加工部材、電子機器、及び、プリント配線板の製造方法 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116300696A (zh) * | 2023-05-17 | 2023-06-23 | 天津岳东天合科技有限公司 | 一种基于镀锌工艺优化的机加工控制方法及*** |
CN116300696B (zh) * | 2023-05-17 | 2023-11-14 | 天津岳东天合科技有限公司 | 一种基于镀锌工艺优化的机加工控制方法及*** |
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