WO2018124114A1 - 表面処理材およびこれを用いて作製した部品 - Google Patents
表面処理材およびこれを用いて作製した部品 Download PDFInfo
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- WO2018124114A1 WO2018124114A1 PCT/JP2017/046748 JP2017046748W WO2018124114A1 WO 2018124114 A1 WO2018124114 A1 WO 2018124114A1 JP 2017046748 W JP2017046748 W JP 2017046748W WO 2018124114 A1 WO2018124114 A1 WO 2018124114A1
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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
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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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- 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
- B32B15/018—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of a noble metal or a noble metal alloy
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1651—Two or more layers only obtained by electroless plating
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
- C23C18/1827—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment only one step pretreatment
- C23C18/1831—Use of metal, e.g. activation, sensitisation with noble metals
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
- C23C18/1837—Multistep pretreatment
- C23C18/1841—Multistep pretreatment with use of metal first
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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
- C25D5/02—Electroplating of selected surface areas
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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
- C25D5/34—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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- 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
- C25D5/611—Smooth layers
-
- 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
-
- 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
- C25D7/005—Jewels; Clockworks; Coins
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R13/00—Details of coupling devices of the kinds covered by groups H01R12/70 or H01R24/00 - H01R33/00
- H01R13/02—Contact members
- H01R13/03—Contact members characterised by the material, e.g. plating, or coating materials
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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
- B32B2457/00—Electrical equipment
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R43/00—Apparatus or processes specially adapted for manufacturing, assembling, maintaining, or repairing of line connectors or current collectors or for joining electric conductors
- H01R43/16—Apparatus or processes specially adapted for manufacturing, assembling, maintaining, or repairing of line connectors or current collectors or for joining electric conductors for manufacturing contact members, e.g. by punching and by bending
Definitions
- the present invention relates to a surface treatment material and a part produced using the same, and particularly at least one layer on a conductive substrate that is mainly composed of a base metal having a high ionization tendency and is difficult to form a sound plating film.
- the present invention relates to a technique for easily and easily forming a surface treatment film comprising a metal layer with good adhesion.
- Copper, copper alloy, iron, iron alloy, etc. from the viewpoint of being inexpensive and relatively excellent in properties to be plated (conductive substrate) used for forming conventional electrical contacts, etc.
- the metal materials have been widely used. Such a metal material has particularly good conductivity and workability, is relatively easy to obtain, and can be easily coated on the surface, and has a surface with excellent plating adhesion. Therefore, it is still used as a mainstream material for conductive substrates.
- copper (specific gravity 8.96) and iron (specific gravity 7.87) are materials with a relatively large specific gravity.
- magnesium (specific gravity 1.74) are increasingly used for materials with relatively low specific gravity.
- aluminum called light metal has a complicated surface plating method and it is difficult to form a plating film with good adhesion. This is because aluminum tends to form an oxide film called a passive film on its surface, and this oxide film exists in a stable state, and base metal such as aluminum is plated in a wet manner. It is difficult to do this.
- a base layer such as a nickel layer formed on the surface of an aluminum-based substrate for the purpose of improving plating adhesion, and a coating layer made of a metal (such as tin or silver) for electrical contact, for example,
- a metal such as tin or silver
- a zinc-containing solution is used to perform a zinc substitution process called a zincate process, whereby the base material and the plating film (the base layer and the coating layer) are formed.
- a zinc-containing solution is used to perform a zinc substitution process called a zincate process, whereby the base material and the plating film (the base layer and the coating layer) are formed.
- Pre-treatment for increasing adhesion strength for example, Patent Documents 2 and 3
- the adhesion strength is increased by the anchor effect of the recess (for example, Patent Document 4).
- a zinc layer formed with a thickness of, for example, about 100 nm is interposed between the substrate and the plating film, Since the main plating layer (plating film) is formed on this zinc layer, when heated, zinc in the zinc layer diffuses in the main plating layer, and further diffuses and appears to the surface layer of the main plating layer. As a result, various problems such as an increase in contact resistance, a decrease in wire bonding property, and a decrease in solder wettability are caused.
- the plating layer (underlayer) formed after the zinc replacement treatment is thinly formed, it is difficult to completely cover the zinc-containing layer due to the formation of a non-uniform plating layer or pinholes. In this case, erosion preferentially proceeds along the zinc-containing layer, and as a result, there is a problem that peeling occurs between the underlayer and the base material. For this reason, in order to prevent the above-described problems from occurring, it is desirable that there is no zinc layer between the substrate and the plating film, and when formation of the zinc layer is necessary, A zinc layer having a thickness as thin as possible is formed.
- Patent Document 4 the method of forming fine irregularities on the surface requires a processing time of several minutes and has a problem of low productivity.
- an object of the present invention is to form a surface-treated film with good adhesion and easily in a short time on a conductive substrate that is mainly composed of a base metal having a particularly high ionization tendency and is difficult to form a sound plating film. It is an object of the present invention to provide a surface treatment material that can be formed and a component manufactured using the surface treatment material.
- the inventors of the present invention directly formed on the conductive substrate out of at least one metal layer constituting the surface treatment film formed on the conductive substrate. Focusing on the bottom metal layer, which is the metal layer, and providing a surface treatment material with good adhesion by optimizing the shape of the bottom metal layer in close contact (contact) with the conductive substrate As a result, the inventors have found out that the present invention can be achieved.
- the gist configuration of the present invention is as follows. (1) A surface treatment material having a conductive substrate and a surface treatment film formed of at least one metal layer formed on the conductive substrate, wherein among the at least one metal layer, A plurality of metals in which a lowermost metal layer, which is a metal layer formed directly on the conductive substrate, is scattered on the conductive substrate and continuously extends from the surface of the conductive substrate toward the inside. A surface treatment material having an embedded portion. (2) A surface treatment material having a conductive substrate and a surface treatment film composed of one or more metal layers on the conductive substrate, wherein the conductive layer is a conductive material among the metal layers constituting the surface treatment film.
- the lowermost metal layer in contact with the conductive substrate has a plurality of metal buried portions extending from the surface of the conductive substrate toward the inside in the thickness direction.
- the metal embedded portion has an average length of 0.5 ⁇ m or more and 10 ⁇ m when measured along the thickness direction from the surface of the conductive substrate, as viewed in a vertical section of the surface treatment material.
- the average abundance of the metal-embedded portion is in the range of 1 to 10 per 50 ⁇ m in cross-sectional width of the conductive substrate, as viewed in the vertical cross section of the surface treatment material, (1) The surface treatment material as described in any one of (3).
- the surface treatment film includes the lowermost metal layer and one or more metal layers formed on the lowermost metal layer, and the one or more metal layers include nickel, a nickel alloy, Cobalt, cobalt alloy, copper, copper alloy, tin, tin alloy, silver, silver alloy, gold, gold alloy, platinum, platinum alloy, rhodium, rhodium alloy, ruthenium, ruthenium alloy, iridium, iridium alloy, palladium and palladium alloy.
- the surface treatment material according to (7), wherein the one or more metal layers are composed of two or more metal layers.
- a conductive substrate which is mainly composed of a base metal having a high ionization tendency and is difficult to form a sound plating film, for example, aluminum or an aluminum alloy, and the conductive substrate.
- the lowermost metal layer which is a layer, has a plurality of metal embedded portions that are scattered on the conductive substrate and continuously extend from the surface of the conductive substrate toward the inside thereof.
- the process is simplified compared to a conventional surface treatment material in which a zinc-containing layer (particularly a zincate treatment layer) having a thickness of about 100 nm is interposed.
- Surface treatment material that shows excellent adhesion as a result of obtaining a mechanical anchoring effect when the metal buried portion of the lower metal layer penetrates into the inside of the conductive substrate, and can also greatly reduce the manufacturing time Will be able to provide.
- the original characteristics obtained after the surface treatment film is formed can be maintained without deterioration even under a use environment at a high temperature (for example, about 200 ° C.), and the surface has high long-term reliability.
- FIG. 1 is a schematic cross-sectional view of a surface treatment material according to a first embodiment of the present invention.
- Drawing 2 is a figure for explaining extension length and existence density of a metal embedding part formed in a surface treating material which is a 1st embodiment.
- FIG. 3 is a schematic cross-sectional view of a surface treatment material according to the second embodiment.
- FIG. 4 is a SIM photograph when a cross section of a typical surface treatment material according to the present invention is observed.
- FIG. 1 is a schematic cross-sectional view of the surface treatment material of the first embodiment.
- the illustrated surface treatment material 10 includes a conductive substrate 1 and a surface treatment film 2.
- the conductive substrate 1 is not particularly limited.
- the conductive substrate 1 is mainly composed of a base metal having a high ionization tendency, and it is difficult to form a sound plating film using a wet plating method.
- Al or an aluminum alloy is preferable in that the effects of the present invention can be remarkably exhibited.
- the shape of the conductive substrate 1 is shown as an example in the drawing, it may be in the form of a plate, a wire, a bar, a tube, a foil, or the like, and can take various shapes depending on the application.
- the surface treatment film 2 is composed of at least one metal layer, in FIG. 1, one metal layer 3, and is formed on the conductive substrate 1.
- the surface treatment film 2 may be composed of one metal layer or may be composed of two or more metal layers, it is composed of one layer or two or more layers.
- the metal layer 3 (one layer) formed directly on the conductive substrate 1 is referred to as a “lowermost metal layer”. Since the surface treatment material 10 shown in FIG. 1 is composed of only one metal layer directly formed on the conductive substrate 1, the metal layer 3 is the lowermost metal layer.
- the lowermost metal layer 3 is not a zinc-containing layer formed by zincate treatment, but is a metal layer made of, for example, nickel (Ni), nickel alloy, cobalt (Co), cobalt alloy, copper (Cu), or copper alloy Is preferred.
- a suitable thickness of the lowermost metal layer 3 is 0.05 ⁇ m or more and 2.0 ⁇ m or less in consideration of solder wettability, contact resistance and bending workability after an environmental test at a high temperature (for example, 200 ° C.). Preferably, it is 0.1 ⁇ m or more and 1.5 ⁇ m or less, and more preferably 0.2 ⁇ m or more and 1.0 ⁇ m or less.
- the lowest metal layer is Ni
- good heat resistance is obtained
- Cu good
- good moldability is obtained.
- Ni or Co is used as the lowermost metal layer, there is an effect of reducing electrolytic corrosion of the aluminum base when the functional plating layer is damaged.
- the surface treatment film 2 includes a lowermost metal layer 3 and one or more metal layers 4 (for example, various functional plating layers) formed on the lowermost metal layer 3. It may be configured.
- Examples of the one or more metal layers 4 formed on the lowermost metal layer 3 include nickel (Ni), nickel alloy, cobalt (Co), cobalt alloy, copper (Cu), copper alloy, and tin (Sn). , Tin alloy, silver (Ag), silver alloy, gold (Au), gold alloy, platinum (Pt), platinum alloy, rhodium (Rh), rhodium alloy, ruthenium (Ru), ruthenium alloy, iridium (Ir), iridium Among the alloys, palladium (Pd), and palladium alloys, a metal or an alloy that is appropriately selected according to a desired property-imparting purpose can be given.
- nickel, a nickel alloy, cobalt, a cobalt alloy nickel, a nickel alloy, cobalt, a cobalt alloy
- the lowermost metal layer 3 made of copper or a copper alloy is formed, and then, on the lowermost metal layer 3, as a coating layer for imparting the surface treatment material 10 with a function required for each component ( Nickel, nickel alloy, cobalt, cobalt alloy, copper, copper alloy, tin, tin alloy, silver, silver alloy, gold, gold alloy, platinum, platinum alloy, rhodium, rhodium alloy
- a metal layer 4 made of a metal or an alloy selected from ruthenium, ruthenium alloy, iridium, iridium alloy, palladium and palladium alloy into a single layer or two or more layers, Robustness of excellent surface treatment material can be obtained (plating material) 10.
- the surface-treated film 2 includes two or more metal layers including at least a lower metal layer 3 formed for the purpose of improving adhesion to the conductive substrate 1 and a metal layer 4 as a coating layer for imparting a function. 3 or 4 is preferable.
- the surface treatment film 2 composed of the lowermost metal layer 3 and the metal layer 4 for example, after forming a nickel layer on the conductive substrate 1 as the lowermost metal layer 3, gold plating is performed as the metal layer 4 that imparts a function.
- the surface treatment film 2 can be formed by forming the layer 4 on the lowermost metal layer 3, whereby the surface treatment material (plating material) 10 having excellent corrosion resistance can be provided.
- the method for forming the metal layers 3 and 4 is not particularly limited, but is preferably performed by a wet plating method.
- the characteristic configuration of the present invention is to optimize the shape of the bottom metal layer 3 that is in close contact (contact) with the conductive substrate 1. More specifically, it is a surface treatment material 10 having a conductive substrate 1 and a surface treatment film 2 made of at least one metal layer formed on the conductive substrate 1, and having at least one layer. Among the metal layers, the lowermost metal layer 3 which is a metal layer directly formed on the conductive substrate 1 is scattered on the conductive substrate 1 and continuously from the surface of the conductive substrate 1 to the inside. This is a surface treatment material 10 having a plurality of extending metal buried portions 3a.
- the surface treatment material 10 which has the electroconductive base
- the lowermost metal layer 3 in contact with the substrate 1 is a surface treatment material 10 having a plurality of metal embedded portions 3 a extending from the surface of the conductive substrate 1 toward the inside in the thickness direction.
- a substitution treatment with zinc that is, a so-called zincate treatment.
- the thickness of the zinc-containing layer existing between the conductive substrate and the surface treatment coating (plating coating) is about 100 nm, for example, and zinc in this zinc-containing layer diffuses in the surface treatment coating.
- it may increase the contact resistance, and further deteriorate the wire bonding property, solder wettability, and corrosion resistance.
- the properties of the surface treatment material deteriorate due to use and long-term reliability is impaired.
- a zinc-containing layer does not exist between the conductive substrate 1 and the metal layer 2.
- the conductive substrate 1 It has been difficult to form a surface-treated film (plating film) with good adhesion to the conductive substrate 1 which is a base metal having a particularly high ionization tendency.
- the present inventors diligently examined, prior to forming the surface treatment film 2, by performing a new surface activation treatment step on the surface of the conductive substrate 1 (for example, an aluminum substrate), Without forming a conventional zinc-containing layer (especially a zincate treatment layer), an oxide film that is stably present on the surface of the conductive substrate 1 can be effectively removed. Even when a surface treatment film (for example, nickel plating layer) is formed, the metal atoms (for example, aluminum atoms) constituting the conductive substrate 1 and the metal atoms (for example, nickel atoms) for constituting the surface treatment film can be directly bonded. It has been found that the lower metal layer 3 can be easily formed with good adhesion to the conductive substrate 1.
- a surface treatment film for example, nickel plating layer
- the surface treatment material 10 of the present invention can form a surface treatment film having excellent adhesion without the presence of a zinc-containing layer. For example, it can be maintained without deterioration even in a use environment at about 200 ° C., and has excellent long-term reliability.
- the lowermost metal constituting the surface treatment film 2 is formed on the conductive substrate 1.
- the so-called “anchor effect” combined with the effect produced by effectively removing the oxide film stably present on the surface of the conductive substrate 1 described above.
- the adhesion of the surface treatment film 2 to the conductive substrate 1 can be remarkably improved.
- the mechanism for producing such an effect is not clear, but the surface of the conductive substrate 1 is probably removed by removing the oxide film present on the surface of the conductive substrate 1 by performing a new surface activation treatment.
- the surface treatment material of the present invention having such a configuration cannot be achieved by a method for forming a simple etching recess, and the adhesion is remarkably superior to the surface treatment material having a surface treatment film formed by a conventional method. ing. Furthermore, the method for producing the surface treatment material of the present invention is capable of producing the surface treatment material in a simple and short-time treatment without performing a complicated pretreatment process like a zincate treatment. In addition, it is possible to provide a surface treatment material (plating material) that is greatly improved from the viewpoint of production efficiency.
- the metal burying portion 3 a is a part of the lowermost metal layer 3, is scattered on the conductive base 1, and extends continuously from the surface of the conductive base 1 toward the inside.
- the metal burying portion 3a has an average value Lave.
- Lave the average value of the extension length L as measured in the thickness direction from the surface of the conductive substrate 1 when viewed in a vertical section of the surface treatment material 10 is 0.3 ⁇ m or more. It is preferable to improve the adhesion, and more preferably in the range of 0.5 ⁇ m to 10 ⁇ m. If the average value Lave. Of the extension length L of the metal burying portion 3a is less than 0.5 ⁇ m, the anchor effect may not be sufficiently exerted, and the effect of improving the adhesion may be small. When the average value Lave.
- the surface treatment material 10, particularly the conductive substrate 1 is likely to be cracked when bending is performed starting from the metal embedded portion 3 a that has penetrated. This is because the adhesiveness may decrease due to the destruction of the base material.
- the average value Lave is in the range of 1 ⁇ m to 5 ⁇ m.
- the extending length L of the metal burying portion 3 a is the distance from the surface position (surface side base portion) S of the conductive substrate 1 to the inside of the conductive substrate 1 as viewed in the vertical cross section of the surface treatment material 10. It means the straight line length measured along the thickness direction tx of the conductive substrate 1 up to the end position F of the infiltrating metal buried portion 3a.
- This extended length L is formed by forming an arbitrary cross section of the surface treatment material 1 by, for example, cross section polishing after resin filling, focused ion beam (FIB) processing, and cross section forming methods such as ion milling and cross section polisher. And the extension length L shall be measured about the metal burying part 3a which exists in the observation area
- FIB focused ion beam
- the average density P of the metal-embedded portion 3a is in the range of 1 to 10 in the observation region where the cross-sectional width W of the conductive substrate 1 is 50 ⁇ m, as viewed in the vertical cross section of the surface treatment material 10. It is preferable. If the average abundance P of the metal burying portion 3a is less than one in the observation region, that is, if the metal burying portion 3a does not exist, the anchor effect is exhibited only at the same level as the conventional technology product, and the effect of improving the adhesion is achieved. You may not get enough. Further, if the average existence density P of the metal burying portion 3a exceeds 10 in the observation region, a starting point for generating a crack is easily generated when bending or pressing is performed.
- the average existence density P of the metal burying portion 3a is more preferably in the range of 3 or more and 5 or less in the observation region.
- the observation region for measuring the number of the metal burying portions 3a is the observation region when measuring the extension length L of the metal burying portion 3a described above. It is the same.
- the shape of the metal embedding part 3a in this invention when the cross section observation of the electroconductive base
- the shape is preferably not only a straight line, a curved line, and a wedge shape, but also a light chain (zigzag shape) or the like that is continuously connected as a line segment. It is more preferable that a wedge shape or a lightning bolt shape as shown in FIG. 2 penetrates the bond at the interface between the crystal grains in FIG.
- FIG. 4 shows, as an example, a SIM photograph when a cross-section of the surface treatment material of the present invention having two metal-embedded portions 3a having extension lengths L of 3.8 ⁇ m and 4.0 ⁇ m is observed.
- the surface treatment material having the cross-sectional structure shown in FIG. 1 aluminum (for example, 1000 series aluminum such as A1100 defined by JIS H4000: 2014, and aluminum alloy (for example, defined by JIS H4000: 2014).
- the electrolytic degreasing step, the surface activation treatment step, and the surface treatment coating formation step may be sequentially performed on a plate material, rod material, or wire material that is a base material of a 6000 (Al—Mg—Si) alloy such as A6061.
- the electrolytic degreasing step is performed by, for example, immersing in an alkaline degreasing bath of 20 to 200 g / L sodium hydroxide (NaOH), using the substrate as a cathode, a current density of 2.5 to 5.0 A / dm 2 , and a bath temperature of 60.
- Examples of the method include cathodic electrolytic degreasing under the conditions of ° C and a processing time of 10 to 100 seconds.
- the surface activation treatment step is a novel activation treatment step different from the conventional activation treatment, and is the most important step among the steps for producing the surface treatment material of the present invention.
- the surface activation treatment step is performed so that the zinc-containing layer containing zinc as a main component is not formed by the zincate treatment or the like.
- the oxide film stably present on the surface of the substrate 1 can be effectively removed, and in addition, metal atoms (for example, nickel atoms) constituting the lowermost metal layer 3 directly formed on the conductive substrate 1 thereafter. ) Can be formed as crystal nuclei or thin layers on the conductive substrate 1 before the formation of the lowermost metal layer 3.
- the lowermost metal layer for example, Nick Even if the metal plating layer 3 is formed, the metal atom (for example, aluminum atom) constituting the conductive substrate 1 and the metal atom (for example, nickel atom) constituting the surface treatment film can be directly bonded. It can be easily formed with good adhesion to the conductive substrate 1.
- the surface of the conductive substrate 1 after the electrolytic degreasing step is performed by (1) any of acid solutions 10 to 10 selected from sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid, and phosphoric acid.
- a surface treatment film forming step is performed.
- the surface treatment film 2 may be formed only by the lowermost metal layer 3, but depending on the purpose of imparting characteristics (function) to the surface treatment material 10, Furthermore, one or more (other) metal layers 4 can be formed, and the surface treatment film 2 can be formed of at least two or more metal layers 3 and 4 including the lowermost metal layer 3.
- the lowermost metal layer 3 is formed by using a plating solution containing the same metal component as the main component metal in the activation treatment solution used in the surface activation treatment step, by a wet plating method of electrolytic plating or electroless plating. It can be carried out.
- Tables 1 to 3 exemplify plating bath compositions and plating conditions when the lowermost metal layer 3 is formed by nickel (Ni) plating, cobalt (Co) plating, and copper (Cu) plating, respectively.
- each metal layer 4 has characteristics (functions) in the surface treatment material.
- electroplating or electroless plating can be performed by a wet plating method.
- Tables 1 to 10 show nickel (Ni) plating, cobalt (Co) plating, copper (Cu) plating, tin (Sn) plating, silver (Ag) plating, silver (Ag) -tin (Sn) plating, and silver, respectively.
- plating bath composition and plating conditions when forming a metal layer by (Ag) -palladium (Pd) plating, gold (Au) plating, palladium (Pd) plating and rhodium (Rh) plating are shown.
- the surface treatment coating 2 has various layer configurations by appropriately combining the lowermost metal layer 3 as described above and one or more metal layers 4 formed on the lowermost metal layer 3 according to the application. It is possible to change and form. For example, when the surface treatment material of the present invention is used for a lead frame, after forming a nickel plating layer as the lowermost metal layer 3 on the conductive substrate 1, silver plating or silver is formed on the lowermost metal layer 3. By forming a metal layer (functional plating layer) composed of one or more types of plating selected from alloy plating, palladium plating, palladium alloy plating, gold plating and gold alloy plating, the surface treatment film 2 is constituted. Functions such as solder wettability, wire bondability, and reflectance improvement can be imparted.
- the metal layer (it consists of silver plating or silver alloy plating ( By forming the surface treatment film 2 by forming a functional plating layer), it is possible to provide an electrical contact material having a stable contact resistance.
- an excellent surface treatment material 10 having necessary characteristics according to each application can be obtained. Can be provided.
- the surface treatment material of the present invention is a base material such as a lighter aluminum or aluminum alloy instead of a conventionally used base material such as iron, iron alloy, copper, copper alloy as a base material (conductive base).
- Materials can be used, terminals, connectors, bus bars, lead frames, medical members (eg catheter guide wires, stents, artificial joints, etc.), shield cases (eg for electromagnetic wave prevention), coils (eg for motors), accessories (For example, necklaces, earrings, rings, etc.), contact switches, cables (for example, aircraft wire harnesses), heat pipes, memory disks, and other various parts (products) can be applied.
- the surface activation of the base material is enabled without the conventional thick zinc-containing layer of about 100 nm (particularly the zincate treatment layer) existing between the base material and the surface treatment film.
- the product group consisting of iron, iron alloy, copper, and copper alloy, and it is especially necessary to reduce the weight of automobile wire harnesses, aerospace cases, and electromagnetic shielding cases. It can be used in various products.
- Inventive Examples 1 to 46 perform an electrolytic degreasing process on the aluminum base materials (size 0.2 mm ⁇ 30 mm ⁇ 30 mm) shown in Tables 11 and 12 under the above-described conditions, and then, on the surface of the conductive substrate 1, A surface activation treatment was performed.
- the surface activation treatment is carried out using any acid solution selected from sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid and phosphoric acid, 10 to 500 mL / L, nickel sulfate and nitric acid.
- an activation treatment solution containing a nickel compound selected from the group consisting of nickel, nickel chloride and nickel sulfamate (0.1 to 500 g / L in terms of nickel metal content)
- a treatment temperature of 20 to It is performed under the conditions of treatment at 60 ° C., current density of 0.1 to 20 A / dm 2 and treatment time of 1 to 200 seconds.
- Invention Example 22 from sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid and phosphoric acid.
- Cobalt compound (cobalt selected from the group consisting of 300 mL / L of any selected acid solution and cobalt sulfate, cobalt nitrate, cobalt chloride and cobalt sulfamate Using an activation treatment solution containing 50 g / L in terms of the metal content of the metal, and under the conditions of treatment at a treatment temperature of 30 ° C., a current density of 2 A / dm 2 and a treatment time of 20 seconds.
- Examples 23 and 27 to 46 consist of 10 to 500 mL / L of any acid solution selected from sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid and phosphoric acid, and copper sulfate, copper nitrate, copper chloride and copper sulfamate.
- an activation treatment solution containing a copper compound selected from the group (0.1 to 500 g / L in terms of copper metal content) treatment temperature 20 to 60 ° C., current density 0.1 to 20 The treatment was performed under the conditions of A / dm 2 and a treatment time of 1 to 200 seconds.
- the surface treatment film 2 composed of the lowermost metal layer 3 and the surface plating layer which is the metal layer 4 formed on the lowermost metal layer 3 is formed.
- the surface treatment material 10 of the invention was produced.
- average existence density P of extension length L of metal embedded portion 3a show the types and thicknesses of the lowermost metal layer 3 and the metal layer 4.
- the formation conditions of the metal layers 3 and 4 constituting the surface treatment coating 2 were performed according to the plating conditions shown in Tables 1 to 10.
- Comparative Example 1 In Comparative Example 1, the surface activation treatment was carried out by using 200 mL / L of any acid solution selected from sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid and phosphoric acid, nickel sulfate, nickel nitrate, nickel chloride and nickel sulfamate.
- Conventional Example 1 performs an electrolytic degreasing process on the aluminum base material (size 0.2 mm ⁇ 30 mm ⁇ 30 mm) shown in Table 11 under the above-described conditions, and then performs a conventional zinc replacement process (zincate process). A zinc-containing layer having a thickness of 110 nm was formed. Then, without performing surface activation treatment, a surface treatment film composed of two metal layers consisting of a nickel plating layer and a gold plating layer is formed at the thickness shown in Table 11 by the surface treatment film formation step described above. Then, a surface treatment material was produced.
- the bending workability is determined by performing a V-bending test at a bending radius of 0.5 mm in a direction perpendicular to the rolling rebar (rolling direction).
- Tables 13 and 14 show the results of evaluating the top surface of the top with a microscope (VHX200; manufactured by Keyence Corporation) at an observation magnification of 200 times.
- the bending workability shown in Tables 13 and 14 is “ ⁇ (excellent)” when no cracks are observed on the surface of the top, and “ ⁇ (good)” when wrinkles are not generated.
- the contact resistances shown in Tables 13 and 14 are “ ⁇ (excellent)” when the resistance is 10 m ⁇ or less, “Good” when it exceeds 10 m ⁇ and 50 m ⁇ or less, and “ ⁇ (possible)” exceeding 50 m ⁇ and 100 m ⁇ or less. ) ”And“ ⁇ (impossible) ”when exceeding 100 m ⁇ , and in this test, the cases corresponding to“ ⁇ (excellent) ”,“ ⁇ (good) ”and“ ⁇ (possible) ” The resistance was evaluated as being at an acceptable level.
- solder wettability is measured after each sample material (surface treatment material) is subjected to heat treatment at 200 ° C for 24 hours with the surface treatment film formed (as it is plated) (unheated state). 2 types of samples (state after heat treatment) were prepared, and the solder wetting time was measured using a solder checker (SAT-5100 (trade name, manufactured by Reska Co., Ltd.)) and evaluated from this measured value. did. Tables 13 and 14 show the evaluation results. The solder wettability shown in Tables 13 and 14 is as follows under the details of the measurement conditions. When the solder wet time is less than 3 seconds, it is judged as “ ⁇ (excellent)”, and it is 3 seconds or more and less than 5 seconds.
- Solder type Sn-3Ag-0.5Cu Temperature: 250 ° C
- Test piece size 10 mm x 30 mm
- Flux isopropyl alcohol-25% rosin immersion speed: 25 mm / sec.
- Immersion time 10 seconds
- Immersion depth 10 mm
- a conductive substrate which is mainly composed of a base metal having a high ionization tendency and is difficult to form a sound plating film, for example, aluminum or an aluminum alloy, and the conductive material.
- the original characteristics obtained after the surface treatment film is formed can be maintained without deterioration even under a use environment at a high temperature (for example, about 200 ° C.), and the surface has high long-term reliability.
- Treatment materials and various parts (products) manufactured using them such as terminals, connectors, bus bars, lead frames, medical materials, shield cases, coils, contact switches, cables, heat pipes, memory disks, etc., can be provided Became.
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Abstract
Description
さらに、ドローンやウエアラブルデバイスでは、雨や汗がデバイス内部に入り込む可能性があり、長期信頼性を確保するためにも、高い耐食性が求められる。風力発電のような塩水環境における変圧器のモータやインバータも同様である。しかしながら、亜鉛置換処理後に形成されるめっき層(下地層)を薄く形成すると、不均一なめっき層の形成やピンホールの形成により、亜鉛含有層を完全に被覆することは困難であり、塩水環境において亜鉛含有層に沿って侵食が優先的に進行し、その結果、下地層と基材の間において剥離が生じてしまうという問題がある。このため、上述したような問題が生じないようにするためにも、基体とめっき被膜との間には、亜鉛層を存在しないことが望ましく、また、亜鉛層の形成が必要な場合には、できるだけ厚さを薄くした亜鉛層を形成する。
(1)導電性基体と、該導電性基体上に形成された少なくとも1層以上の金属層からなる表面処理被膜とを有する表面処理材であって、前記少なくとも1層以上の金属層のうち、前記導電性基体上に直接形成されている金属層である最下金属層が、前記導電性基体に点在しかつ前記導電性基体の表面から内部に向かって連続して延在する複数の金属埋設部を有することを特徴とする表面処理材。
(2)導電性基体と、該導電性基体上に1層以上の金属層からなる表面処理被膜と、を有する表面処理材であって、前記表面処理被膜を構成する金属層のうち、前記導電性基体に接する最下金属層は、前記導電性基体の表面から厚さ方向の内部に向かって延在する複数の金属埋設部を有することを特徴とする表面処理材。
(3)前記金属埋設部は、前記表面処理材の垂直断面で見て、前記導電性基体の表面から厚さ方向に沿って測定したときの延在長さの平均値が0.5μm以上10μm以下の範囲であることを特徴とする、上記(1)又は(2)に記載の表面処理材。
(4)前記金属埋設部の平均存在密度は、前記表面処理材の垂直断面で見て、前記導電性基体の断面幅50μmあたり1本以上10本以下の範囲であることを特徴とする、上記(1)乃至(3)のいずれか1つに記載の表面処理材。
(5)前記導電性基体は、アルミニウム、またはアルミニウム合金であることを特徴とする、上記(1)乃至(4)のいずれか1つに記載の表面処理材。
(6)前記最下金属層は、ニッケル、ニッケル合金、コバルト、コバルト合金、銅または銅合金であることを特徴とする、 上記(1)乃至(5)のいずれか1つに記載の表面処理材。
(7)前記表面処理被膜は、前記最下金属層と、該最下金属層上に形成された1層以上の金属層とからなり、該1層以上の金属層が、ニッケル、ニッケル合金、コバルト、コバルト合金、銅、銅合金、錫、錫合金、銀、銀合金、金、金合金、白金、白金合金、ロジウム、ロジウム合金、ルテニウム、ルテニウム合金、イリジウム、イリジウム合金、パラジウムおよびパラジウム合金の群から選択されるいずれかで形成されたものであることを特徴とする、上記(1)乃至(6)のいずれか1つに記載の表面処理材。
(8)前記1層以上の金属層が、2層以上の金属層からなることを特徴とする、上記(7)記載の表面処理材。
(9)上記(1)乃至(8)のいずれか1つに記載の表面処理材を用いて作製された端子。
(10)上記(1)乃至(8)のいずれか1つに記載の表面処理材を用いて作製されたコネクタ。
(11)上記(1)乃至(8)のいずれか1つに記載の表面処理材を用いて作製されたバスバー。
(12)上記(1)乃至(8)のいずれか1つに記載の表面処理材を用いて作製されたリードフレーム。
(13)上記(1)乃至(8)のいずれか1つに記載の表面処理材を用いて作製された医療部材。
(14)上記(1)乃至(8)のいずれか1つに記載の表面処理材を用いて作製されたシールドケース。
(15)上記(1)乃至(8)のいずれか1つに記載の表面処理材を用いて作製されたコイル。
(16)上記(1)乃至(8)のいずれか1つに記載の表面処理材を用いて作製されたコンタクトスイッチ。
(17)上記(1)乃至(8)のいずれか1つに記載の表面処理材を用いて作製されたケーブル。
(18)上記(1)乃至(8)のいずれか1つに記載の表面処理材を用いて作製されたヒートパイプ。
(19)上記(1)乃至(8)のいずれか1つに記載の表面処理材を用いて作製されたメモリーディスク。
図1は、第1実施形態の表面処理材を概略断面で示したものである。
図示の表面処理材10は、導電性基体1と表面処理被膜2とを有している。
導電性基体1は、特に限定するものではないが、例えばイオン化傾向が大きい卑な金属で主として構成され、なかでも湿式めっき法を用いて健全なめっき被膜の形成が難しいとされる、例えばアルミニウム(Al)、またはアルミニウム合金であることが、本発明の効果を顕著に奏することができる点で好ましい。さらに、導電性基体1の形状は、図面においては条での例を示しているが、板、線、棒、管、箔などの形態でもよく、用途によって様々な形状を採ることができる。
表面処理被膜2は、少なくとも1層以上の金属層、図1では1層の金属層3で構成され、導電性基体1上に形成されている。ここで、表面処理被膜2は、1層の金属層で構成される場合と2層以上の金属層で構成される場合があるため、1層で構成される場合および2層以上で構成される場合のいずれにおいても、本発明では、導電性基体1上に直接形成されている(1層の)金属層3を、「最下金属層」と呼称することとする。なお、図1に示す表面処理材10は、導電性基体1上に直接形成されている金属層の1層のみで構成されているため、この金属層3は最下金属層である。
そして、本発明の特徴的な構成は、最下金属層3の、導電性基体1に密着(接触)する部分の形状の適正化を図ることにある。より具体的には、導電性基体1と、導電性基体1上に形成された少なくとも1層以上の金属層からなる表面処理被膜2とを有する表面処理材10であって、少なくとも1層以上の金属層のうち、導電性基体1上に直接形成されている金属層である最下金属層3が、導電性基体1に点在しかつ導電性基体1の表面から内部に向かって連続して延在する複数の金属埋設部3aを有する表面処理材10である。また、導電性基体1と、導電性基体1上に1層以上の金属層からなる表面処理被膜2と、を有する表面処理材10であって、表面処理被膜を構成する金属層のうち導電性基体1に接する最下金属層3は、導電性基体1の表面から厚さ方向の内部に向かって延在する複数の金属埋設部3aを有する表面処理材10である。
次に、本発明に従う表面処理材の製造方法におけるいくつかの実施形態を以下で説明する。
電解脱脂工程は、例えば20~200g/Lの水酸化ナトリウム(NaOH)のアルカリ脱脂浴中に浸漬し、前記基材を陰極とし、電流密度2.5~5.0A/dm2、浴温60℃、処理時間10~100秒の条件で陰極電解脱脂する方法が挙げられる。
電解脱脂工程を行った後に、表面活性化処理工程を行う。表面活性化処理工程は、従来の活性化処理とは異なる新規な活性化処理工程であって、本発明の表面処理材を製造する工程の中で最も重要な工程である。
表面活性化処理工程を行った後に、表面処理被膜形成工程を行う。
表面処理被膜形成工程は、最下金属層3だけで表面処理被膜2を形成してもよいが、表面処理材10に特性(機能)を付与する目的に応じて、最下金属層3上にさらに1層以上の(他の)金属層4を形成して、最下金属層3を含む少なくとも2層以上の金属層3、4で表面処理被膜2を形成することができる。
最下金属層3の形成は、表面活性化処理工程で用いた活性化処理液中の主成分金属と同一の金属成分を含有するめっき液を用い、電解めっきまたは無電解めっきの湿式めっき法によって行うことができる。表1~表3に、それぞれニッケル(Ni)めっき、コバルト(Co)めっきおよび銅(Cu)めっきにより最下金属層3を形成する際のめっき浴組成およびめっき条件を例示する。
表面処理被膜2を構成する金属層3、4のうち、最下金属層3以外の(他の)金属層4を形成する場合には、各金属層4は、表面処理材に特性(機能)を付与する目的に応じて、電解めっきまたは無電解めっきの湿式めっき法によって行うことができる。表1~表10に、それぞれニッケル(Ni)めっき、コバルト(Co)めっき、銅(Cu)めっき、錫(Sn)めっき、銀(Ag)めっき、銀(Ag)-錫(Sn)めっき、銀(Ag)-パラジウム(Pd)めっき、金(Au)めっき、パラジウム(Pd)めっきおよびロジウム(Rh)めっきにより金属層を形成する際のめっき浴組成およびめっき条件を例示する。
発明例1~46は、表11および12に示すアルミニウム系基材(サイズ0.2mm×30mm×30mm)上に、上述した条件で電解脱脂工程を行い、その後、導電性基体1の表面に、表面活性化処理を施した。表面活性化処理は、発明例1~21および24~26では、硫酸、硝酸、塩酸、フッ酸およびリン酸の中から選択されるいずれかの酸溶液10~500mL/Lと、硫酸ニッケル、硝酸ニッケル、塩化ニッケルおよびスルファミン酸ニッケルからなる群から選択されたニッケル化合物(ニッケルのメタル分に換算して0.1~500g/L)とを含有する活性化処理液を使用し、処理温度20~60℃、電流密度0.1~20 A/dm2および処理時間1~200秒にて処理する条件で行い、また、発明例22では、硫酸、硝酸、塩酸、フッ酸およびリン酸の中から選択されるいずれかの酸溶液300mL/Lと、硫酸コバルト、硝酸コバルト、塩化コバルトおよびスルファミン酸コバルトからなる群から選択されたコバルト化合物(コバルトのメタル分に換算して50g/L)とを含有する活性化処理液を使用し、処理温度30℃、電流密度2A/dm2および処理時間20秒にて処理する条件で行い、さらに、発明例23および27~46では、硫酸、硝酸、塩酸、フッ酸およびリン酸の中から選択れるいずれかの酸溶液10~500mL/Lと、硫酸銅、硝酸銅、塩化銅およびスルファミン酸銅からなる群から選択された銅化合物(銅のメタル分に換算して0.1~500g/L)とを含有する活性化処理液を使用し、処理温度20~60℃、電流密度0.1~20 A/dm2および処理時間1~200秒にて処理する条件で行った。その後、上述した表面処理被膜形成工程によって、最下金属層3と、最下金属層3上に形成された金属層4である表層めっき層とで構成された表面処理被膜2を形成し、本発明の表面処理材10を作製した。基材(導電性基体1)の種類、表面活性化処理に用いる活性化処理液中に含有させる金属化合物の種類、金属埋設部3aの延在長さLの平均値Lave.および平均存在密度P、ならびに最下金属層3および金属層4の種類および厚さについては、表11および12に示す。また、表面処理被膜2を構成する各金属層3、4の形成条件については、表1~表10に示すめっき条件により行なった。
比較例1は、表面活性化処理を、硫酸、硝酸、塩酸、フッ酸およびリン酸の中から選択されるいずれかの酸溶液200mL/Lと、硫酸ニッケル、硝酸ニッケル、塩化ニッケルおよびスルファミン酸ニッケルからなる群から選択されたニッケル化合物(ニッケルのメタル分に換算して10g/L)とを含有する活性化処理液を使用し、処理温度30℃、電流密度0.05A/dm2および処理時間0.5秒にて処理する条件で行った。比較例1で作製した表面処理材は、電流密度が低く、処理時間も短かったため、最下金属層に金属埋設部は存在しなかった。
従来例1は、表11に示すアルミニウム基材(サイズ0.2mm×30mm×30mm)上に、上述した条件で電解脱脂工程を行い、その後、従来の亜鉛置換処理(ジンケート処理)を行なうことによって、厚さ110nmの亜鉛含有層を形成した。その後、表面活性化処理を行うことなく、上述した表面処理被膜形成工程によって、表11に示す厚さでニッケルめっき層と金めっき層からなる2層の金属層で構成される表面処理被膜を形成し、表面処理材を作製した。
<基材(導電性基体)に対する表面処理被膜の密着性>
基材に対する表面処理被膜の密着性(以下、単に「密着性」という。)は、上述した方法で作製した供試材(表面処理材)について剥離試験を行い、密着性を評価した。剥離試験は、JIS H 8504:1999に規定される「めっきの密着性試験方法」の「15.1 テープ試験方法」に基づき行なった。表12に密着性の評価結果を示す。なお、表12に示す密着性は、めっき剥離が見られなかった場合を「◎(優)」、試験面積の95%以上が良好に密着していた場合を「○(良)」、試験面積の85%以上95%未満が良好に密着していた場合を「△(可)」、そして、密着領域が試験面積の85%未満である場合を「×(不可)」とし、本試験では、「◎(優)」、「○(良)」および「△(可)」に該当する場合を、密着性が合格レベルにあるとして評価した。
曲げ加工性は、上述した方法で作製した各供試材(表面処理材)について、曲げ加工半径0.5mmにてV曲げ試験を圧延筋(圧延方向)に対して直角方向に実施した後、その頂上部をマイクロスコープ(VHX200;キーエンス社製)にて観察倍率200倍で表面観察を行い、評価した結果を表13および14に示す。表13および14に示す曲げ加工性は、頂上部の表面に全く割れが認められなかった場合を「◎(優)」と、割れではないがしわが発生している場合を「○(良)」とし、軽微な割れが生じている場合を「△(可)」とし、そして、比較的大きな割れが生じている場合を「×(不可)」とし、本試験では、「◎(優)」、「○(良)」および「△(可)」に該当する場合を、曲げ加工性が合格レベルにあるとして評価した。
作製した供試材(表面処理材)ごとに、表面処理被膜を形成した(めっきした)状態(未熱処理状態)と、大気中で200℃、24時間の熱処理を施した後の状態(熱処理後の状態)の2種類のサンプルを作製し、4端子法を用いて、未熱処理状態の表面処理材と熱処理後の状態に表面処理材について、接触抵抗の測定を行った。測定条件は、Agプローブ半径R=2mm、荷重0.1Nの条件下で10mA通電時の抵抗値を10回測定して平均値を算出した。表13および14に評価結果を示す。なお、表13および14に示す接触抵抗は、10mΩ以下である場合を「◎(優)」とし、10mΩ超え50mΩ以下である場合を「○(良)」とし、50mΩ超え100mΩ以下「△(可)」とし、そして、100mΩを超える場合を「×(不可)」とし、本試験では、「◎(優)」、「○(良)」および「△(可)」に該当する場合を、接触抵抗が合格レベルにあるとして評価した。
半田濡れ性は、作製した供試材(表面処理材)ごとに、表面処理被膜形成まま(めっきまま)の状態(未熱処理状態)と、大気中で200℃、24時間の熱処理を施した後の状態(熱処理後の状態)の2種類のサンプルを作製し、ソルダーチェッカー(SAT-5100(商品名、(株)レスカ社製))を用いて半田濡れ時間を測定し、この測定値から評価した。表13および14にその評価結果を示す。なお、表13および14に示す半田濡れ性は、測定条件詳細は以下の条件とし、はんだ濡れ時間が3秒未満である場合を「◎(優)」と判定し、3秒以上5秒未満である場合を「○(良)」と判定し、5秒以上10秒未満である場合を「△(可)」と判定し、そして、10秒浸漬しても接合しなかった場合を「×(不可)」と判定し、本試験では、「◎(優)」、「○(良)」および「△(可)」に該当する場合を、半田濡れ性が合格レベルにあるとして評価した。
温度:250℃
試験片サイズ:10mm×30mm
フラックス:イソプロピルアルコール-25%ロジン
浸漬速度:25mm/sec.
浸漬時間:10秒
浸漬深さ:10mm
実用レベルとしては「△」以上である場合を合格レベルにあるとして判断した。
これに対し、表面活性化処理工程を行っておらず、しかも従来のジンケート処理で厚さが110nmと厚い亜鉛含有層を形成した従来例1は、200℃における接触抵抗および半田濡れ性が劣っていた。また、最下金属層に金属埋設部をもたない比較例1は、密着性および曲げ加工性が合格レベルになく不良品であった。
2 表面処理被膜
3 最下金属層
4 表面処理被膜を構成する最下金属層以外の金属層
10、10A 表面処理材
F 終端位置
S 表面側根元部
Claims (19)
- 導電性基体と、該導電性基体上に形成された少なくとも1層以上の金属層からなる表面処理被膜とを有する表面処理材であって、前記少なくとも1層以上の金属層のうち、前記導電性基体上に直接形成されている金属層である最下金属層が、前記導電性基体に点在しかつ前記導電性基体の表面から内部に向かって連続して延在する複数の金属埋設部を有することを特徴とする表面処理材。
- 導電性基体と、該導電性基体上に1層以上の金属層からなる表面処理被膜と、を有する表面処理材であって、前記表面処理被膜を構成する金属層のうち、前記導電性基体に接する最下金属層は、前記導電性基体の表面から厚さ方向の内部に向かって延在する複数の金属埋設部を有することを特徴とする表面処理材。
- 前記金属埋設部は、前記表面処理材の垂直断面で見て、前記導電性基体の表面から厚さ方向に沿って測定したときの延在長さの平均値が0.5μm以上10μm以下の範囲であることを特徴とする、請求項1又は2に記載の表面処理材。
- 前記金属埋設部の平均存在密度は、前記表面処理材の垂直断面で見て、前記導電性基体の断面幅50μmあたり1本以上10本以下の範囲であることを特徴とする、請求項1乃至3の何れか1項に記載の表面処理材。
- 前記導電性基体は、アルミニウム、またはアルミニウム合金であることを特徴とする、請求項1乃至4の何れか1項に記載の表面処理材。
- 前記最下金属層は、ニッケル、ニッケル合金、コバルト、コバルト合金、銅または銅合金であることを特徴とする、請求項1乃至5の何れか1項に記載の表面処理材。
- 前記表面処理被膜は、前記最下金属層と、該最下金属層上に形成された1層以上の金属層とからなり、該1層以上の金属層が、ニッケル、ニッケル合金、コバルト、コバルト合金、銅、銅合金、錫、錫合金、銀、銀合金、金、金合金、白金、白金合金、ロジウム、ロジウム合金、ルテニウム、ルテニウム合金、イリジウム、イリジウム合金、パラジウムおよびパラジウム合金の群から選択されるいずれかで形成されたものであることを特徴とする、請求項1乃至6の何れか1項に記載の表面処理材。
- 前記1層以上の金属層が、2層以上の金属層からなることを特徴とする、請求項7に記載の表面処理材。
- 請求項1乃至8の何れか1項に記載の表面処理材を用いて作製された端子。
- 請求項1乃至8の何れか1項に記載の表面処理材を用いて作製されたコネクタ。
- 請求項1乃至8の何れか1項に記載の表面処理材を用いて作製されたバスバー。
- 請求項1乃至8の何れか1項に記載の表面処理材を用いて作製されたリードフレーム。
- 請求項1乃至8の何れか1項に記載の表面処理材を用いて作製された医療部材。
- 請求項1乃至8の何れか1項に記載の表面処理材を用いて作製されたシールドケース。
- 請求項1乃至8の何れか1項に記載の表面処理材を用いて作製されたコイル。
- 請求項1乃至8の何れか1項に記載の表面処理材を用いて作製されたコンタクトスイッチ。
- 請求項1乃至8の何れか1項に記載の表面処理材を用いて作製されたケーブル。
- 請求項1乃至8の何れか1項に記載の表面処理材を用いて作製されたヒートパイプ。
- 請求項1乃至8の何れか1項に記載の表面処理材を用いて作製されたメモリーディスク。
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JP6805217B2 (ja) * | 2018-10-18 | 2020-12-23 | Jx金属株式会社 | 導電性材料、成型品及び電子部品 |
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EP3564412A1 (en) | 2019-11-06 |
JPWO2018124114A1 (ja) | 2018-12-27 |
KR20190097023A (ko) | 2019-08-20 |
CN110114515A (zh) | 2019-08-09 |
JP6615350B2 (ja) | 2019-12-04 |
US20190337268A1 (en) | 2019-11-07 |
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