WO2016157713A1 - Matériau de placage d'argent et son procédé de fabrication - Google Patents

Matériau de placage d'argent et son procédé de fabrication Download PDF

Info

Publication number
WO2016157713A1
WO2016157713A1 PCT/JP2016/001038 JP2016001038W WO2016157713A1 WO 2016157713 A1 WO2016157713 A1 WO 2016157713A1 JP 2016001038 W JP2016001038 W JP 2016001038W WO 2016157713 A1 WO2016157713 A1 WO 2016157713A1
Authority
WO
WIPO (PCT)
Prior art keywords
plating
silver
nickel
plating layer
silver plating
Prior art date
Application number
PCT/JP2016/001038
Other languages
English (en)
Japanese (ja)
Inventor
宏▲禎▼ 高橋
Original Assignee
オリエンタル鍍金株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by オリエンタル鍍金株式会社 filed Critical オリエンタル鍍金株式会社
Priority to JP2017509209A priority Critical patent/JP6484844B2/ja
Publication of WO2016157713A1 publication Critical patent/WO2016157713A1/fr

Links

Images

Classifications

    • 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
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/64—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of silver
    • 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
    • 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
    • C25D5/18—Electroplating using modulated, pulsed or reversing current
    • 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
    • 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
    • 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
    • C25D5/615—Microstructure of the layers, e.g. mixed structure
    • C25D5/617—Crystalline 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

Definitions

  • the present invention relates to a silver plating material in which a silver plating layer is formed on the surface of a metal base material and a method for producing the same, and more specifically, silver plating that can be suitably used for various contacts, terminals, connectors, switches, and the like.
  • the present invention relates to a material and a manufacturing method thereof.
  • Silver plating has excellent properties such as electrical conductivity, low contact resistance, and heat resistance, and is widely used for electrical and electronic parts such as various contacts, terminals, connectors, and switches (for example, Patent Document 1 No. 2001-3194)).
  • Patent Document 2 Japanese Patent Laid-Open No. 2014-198895
  • Patent Document 2 Japanese Patent Laid-Open No. 2014-198895
  • a method for producing a silver plating material in which a surface layer made of silver is formed on the surface of a material or the surface of an underlayer formed on the material 1 to 25 mg
  • an aging treatment is performed.
  • a method for producing a silver-plated material having an area fraction of ⁇ 200 ⁇ orientation of the surface layer of 15% or more is disclosed.
  • the bending workability of a silver plating material becomes so favorable that the area fraction of ⁇ 200 ⁇ direction of the surface layer of a silver plating material is high, and it uses it in a high temperature environment.
  • an increase in contact resistance can be suppressed.
  • Patent Document 3 Japanese Patent Laid-Open No. 2012-184468 discloses a plating film made of Au (100-xy) -Mx-Cy. Note that M is a metal element other than Au, and 1 ⁇ x ⁇ 22, 3 ⁇ y ⁇ 30, and 4 ⁇ (x + y) ⁇ 40.
  • a plating film having high hardness and low resistance can be provided by adding metal elements and carbon that contributes to an increase in hardness of the plating film.
  • Patent Documents 2 and 3 has a higher specific resistance than silver, and a higher content of the metal in the silver plating layer means that the conductivity of the silver plating layer is reduced. is doing.
  • the metal oxide has a particularly high specific resistance, the conductivity of the silver plating layer exposed to a high temperature is remarkably lowered and the contact resistance is remarkably increased.
  • the object of the present invention is to provide silver plating that has excellent conductivity and wear resistance, and can maintain the characteristics even after being left at room temperature for a long time or exposed to high temperature. It is in providing a material and its manufacturing method.
  • the present inventor has conducted extensive research on silver plating materials and methods for producing the same, and as a result, a plating bath to which a certain amount of metal element is added can be used to perform plating using a pulse power source.
  • the inventors have found that the present invention is extremely effective, and have reached the present invention.
  • the present invention A method for producing a silver plating material for forming a silver plating layer on the surface of a metal substrate, Using a cyan-based silver plating bath containing 2.5 to 25 ppm of additive metal element, Plating using a pulse power supply, The manufacturing method of the silver plating material characterized by these is provided.
  • the additive metal element By setting the additive metal element to the plating bath to 2.5 ppm or more, it is possible to impart excellent wear resistance to the silver plating layer and to maintain the wear resistance even after high temperature exposure. Moreover, the electroconductivity and contact resistance which were excellent in the silver plating layer can be maintained because an additional metal element shall be 25 ppm or less.
  • the additive metal element is preferably one or more metal elements selected from copper, tin, nickel, cobalt, selenium, antimony, tellurium and bismuth, More preferably, it is selenium.
  • the wear resistance can be improved without impairing the conductivity of the silver plating layer, and the decrease in conductivity and wear resistance due to high-temperature exposure can be effectively suppressed. it can.
  • a nickel plating treatment is performed on an arbitrary region of the surface of the metal substrate to form a nickel plating layer.
  • a nickel plating layer By forming the nickel plating layer, atomic diffusion and reaction between the metal substrate and the silver plating layer can be prevented, and deterioration of characteristics of the silver plating layer can be suppressed.
  • a silver strike is applied to an arbitrary region on the surface of the metal substrate and / or the nickel plating layer. It is preferable to apply one or more strike plating selected from the group of plating, copper strike plating, gold strike plating, and nickel strike plating. By performing the strike plating treatment, the adhesion between the metal substrate and the nickel plating layer and the adhesion between the nickel plating layer and the silver plating layer can be improved more reliably.
  • the present invention also provides: A silver plating layer is formed on at least a part of the metal substrate, The silver plating layer contains one or more metal elements selected from copper, tin, nickel, cobalt, selenium, antimony, tellurium and bismuth, The metal element content is 0.001 to 0.025%; A silver plating material characterized by the above is also provided.
  • the silver plating layer contains 0.001 to 0.025% of one or more metal elements selected from copper, tin, nickel, cobalt, selenium, antimony, tellurium and bismuth. Therefore, it has high hardness and can maintain the high hardness even after high temperature exposure.
  • the thickness of the silver plating layer is preferably 0.1 ⁇ m to 50 ⁇ m.
  • the thickness of the silver plating layer is preferably 0.1 ⁇ m to 50 ⁇ m.
  • the silver plating layer basically has a constant thickness, but may be partially thinned or thickened within a range not impairing the effects of the present invention.
  • the Vickers hardness of the silver plating layer is preferably 80 HV to 250 HV.
  • a nickel plating layer is formed between the base material and the silver plating layer.
  • the nickel plating layer can prevent the diffusion and reaction of atoms between the metal substrate and the silver plating layer, and can suppress the deterioration of the characteristics of the silver plating layer.
  • the nickel plating layer preferably has a continuous film shape, and the thickness of the nickel plating layer is preferably 0.05 ⁇ m to 10 ⁇ m. A more preferable nickel plating layer thickness is 0.5 ⁇ m to 2 ⁇ m. If it is less than 0.05 ⁇ m, the barrier effect is poor, and if it is 10 ⁇ m or more, cracks are likely to occur during bending.
  • the nickel plating layer may have a granular or island-like discontinuous film shape as long as the effects of the present invention are not impaired. In the latter case, the granular and island portions may be partially continuous.
  • silver strike plating copper strike plating, gold at the interface between the metal substrate and the nickel plating layer and / or the interface between the nickel plating layer and the silver plating layer. It is preferable that one or more strike platings selected from the group of strike plating and nickel strike plating are formed.
  • the strike plating layer realizes excellent adhesion between the metal substrate and the nickel plating layer and excellent adhesion between the nickel plating layer and the silver plating layer.
  • the thickness of the strike plating layer is preferably 0.01 ⁇ m to 0.5 ⁇ m. Moreover, even if the strike plating layer is a continuous film shape, it may be a granular or island-like discontinuous film shape as long as the effects of the present invention are not impaired. In the latter case, the granular and island portions may be partially continuous. In addition, when performing a silver strike plating process, a silver plating layer is formed on a silver strike plating layer by the silver plating process, and it is a single silver plating layer roughly.
  • the metal interface which comprises the silver plating material of this invention, the silver plating layer, the nickel plating layer, and various strike plating layers is metallurgically joined.
  • Metallurgical bonding means that the metals are directly bonded to each other, not mechanical bonding such as an anchor effect or different bonding layers such as an adhesive.
  • Metallurgical bonding is a concept that naturally includes bonding by crystallographic matching (epitaxy), and in the present invention, it is preferable that the plating layers achieve bonding by crystallographic matching (epitaxy).
  • the silver-plated material of the present invention and the method for producing the same, the silver-plated material having excellent conductivity and wear resistance, and capable of maintaining the characteristics even after being left at room temperature for a long time or exposed to high temperature, and the production thereof A method can be provided.
  • FIG. 1 is a process diagram of a method for producing a silver-plated material of the present invention.
  • the method for producing a silver-plated material of the present invention is a method in which a silver plating process (S04) is performed on the surface of a metal substrate to form a silver plating layer. If necessary, a strike plating process on a metal substrate is performed. (S01), nickel plating treatment (S02) on the metal substrate or strike plating layer, and strike plating treatment (S03) on the nickel plating layer.
  • the metal used for the metal substrate is not particularly limited as long as it has electrical conductivity, and examples thereof include aluminum and aluminum alloys, iron and iron alloys, titanium and titanium alloys, stainless steel, copper, and copper alloys. However, among these, copper and copper alloys are preferably used because they are excellent in electrical conductivity, thermal conductivity, and spreadability.
  • a silver plating material can be obtained through a cleaning process on the metal base material and the various processing steps (S01 to S04). Hereinafter, each process will be described in detail.
  • the cleaning process is an optional process, and is a process of cleaning the surface of the metal substrate, although not shown in FIG.
  • various conventionally known cleaning processing solutions and processing conditions can be used within a range not impairing the effects of the present invention.
  • a common immersion degreasing solution or electrolytic degreasing solution for non-ferrous metals can be used as the cleaning treatment solution.
  • a cleaning treatment solution having a pH of more than 2 and less than 11 is used. It is preferable to use, and it is preferable to avoid the use of a strong acid bath having a pH of 2 or less or a strong alkali bath having a pH of 11 or more.
  • cathode electrolytic degreasing may be performed at a cathode current density of 2 to 5 A / dm 2 using an insoluble anode such as stainless steel, a titanium platinum plate, and iridium oxide as the anode.
  • an acid cleaning solution a general acid cleaning solution in which an acid such as sulfuric acid or nitric acid is diluted to 3 to 50% can be used.
  • the metal substrate is preferably subjected to strike plating (S01).
  • strike plating S01
  • one or more strike plating selected from the group of silver strike plating, copper strike plating, gold strike plating and nickel strike plating, the adhesion of the nickel plating layer or the silver plating layer can be improved more reliably. it can.
  • Silver strike plating As a silver strike plating bath, what contains silver salts, such as silver cyanide and silver cyanide potassium, and electrically conductive salts, such as potassium cyanide and potassium pyrophosphate, can be used, for example.
  • silver salts such as silver cyanide and silver cyanide potassium
  • electrically conductive salts such as potassium cyanide and potassium pyrophosphate
  • the concentration of silver salt in the plating bath is lower than that of ordinary silver plating. It is preferable to increase the concentration of the conductive salt.
  • the silver strike plating bath that can be suitably used for the silver strike plating treatment is composed of a silver salt, an alkali cyanide salt, and a conductive salt, and a brightener may be added as necessary.
  • Preferred amounts of each component are silver salt: 1 to 10 g / L, alkali cyanide salt: 80 to 200 g / L, conductive salt: 0 to 100 g / L, brightener: ⁇ 1000 ppm.
  • Examples of the silver salt include silver cyanide, silver iodide, silver oxide, silver sulfate, silver nitrate, and silver chloride.
  • Examples of the conductive salt include potassium cyanide, sodium cyanide, potassium pyrophosphate, and potassium iodide. And sodium thiosulfate.
  • a metal brightener and / or an organic brightener can be used.
  • the metallic brightener include antimony (Sb), selenium (Se), tellurium (Te), and the like
  • examples of the organic brightener include aromatic sulfonic acid compounds such as benzenesulfonic acid, mercaptans, and the like. be able to.
  • Silver strike plating conditions such as the bath temperature, anode material, and current density of the silver strike plating bath can be appropriately set according to the plating bath used, the required plating thickness, and the like.
  • the anode material is preferably an insoluble anode such as stainless steel, a titanium platinum plate, and iridium oxide.
  • Suitable plating conditions include bath temperature: 15 to 50 ° C., current density: 0.5 to 5 A / dm 2 , and processing time: 5 to 60 seconds.
  • silver strike plating may be performed on the entire surface of the metal substrate, or may be performed only on a region where a nickel plating layer or a silver plating layer is to be formed.
  • Copper strike plating Either a acidic bath or an alkaline bath may be used for the copper strike plating bath.
  • the acidic bath is composed of a copper salt and an acid, and additives may be added.
  • copper sulfate and copper sulfamate can be used as the copper salt.
  • acid for example, sulfuric acid and sulfamic acid can be used.
  • additive for example, a sulfur compound (thiourea, disulfone salt, mercaptobenzothiazole, etc.), an organic compound (polyoxyethylene glycol ether, polyethylene glycol, etc.), a selenium compound and the like can be used.
  • Suitable amounts of each component of the acidic bath that can be suitably used for the copper strike plating treatment are copper salt: 60 to 200 g / L, acid: 30 to 200 g / L, and additive: 0 to 100 ppm.
  • a cyan bath can be used as the alkaline bath.
  • the cyan bath is composed of a copper salt, an alkali cyanide salt and a conductive salt, and an additive may be added thereto.
  • copper cyanide can be used as the copper salt.
  • potassium cyanide and sodium cyanide can be used as the alkali cyanide salt.
  • potassium carbonate and sodium carbonate can be used as the conductive salt.
  • Rochelle salt, potassium selenite, sodium selenite, potassium thiocyanate, lead acetate, lead tartrate and the like can be used.
  • Suitable amounts of each component of the cyan bath that can be suitably used for the copper strike plating treatment are: copper salt: 10 to 80 g / L, alkali cyanide acid: 20 to 50 g / L, conductive salt: 10 to 50 g / L, additive: 0 to 60 g / L.
  • the copper strike plating conditions such as bath temperature, anode material, and current density of the copper strike plating bath can be appropriately set according to the plating bath used, the required plating thickness, and the like.
  • the anode material it is preferable to use a soluble anode such as electrolytic copper and / or an insoluble anode such as stainless steel, a titanium platinum plate, and iridium oxide.
  • Suitable plating conditions include bath temperature: 25 to 70 ° C., current density: 0.1 to 6.0 A / dm 2 , and processing time: 5 to 60 seconds.
  • copper strike plating may be performed on the entire surface of the metal base material, or may be performed only on a region where a nickel plating layer or a silver plating layer is to be formed.
  • (C) Gold strike plating As a gold strike plating bath, what contains a gold salt, a conductive salt, a chelating agent, and a crystal growth agent can be used, for example. Further, a brightener may be added to the gold strike plating bath.
  • the gold salt examples include gold cyanide, potassium gold cyanide, potassium gold cyanide, sodium gold sulfite, and sodium gold thiosulfate.
  • the conductive salt for example, potassium citrate, potassium phosphate, potassium pyrophosphate, potassium thiosulfate, or the like can be used.
  • ethylenediaminetetraacetic acid and methylenephosphonic acid can be used as the chelating agent.
  • the crystal growth agent examples include cobalt, nickel, thallium, silver, palladium, tin, zinc, copper, bismuth, indium, arsenic, and cadmium.
  • Suitable amounts of each component of the gold strike plating bath that can be suitably used for the gold strike plating treatment are: gold salt: 1 to 10 g / L, conductive salt: 0 to 200 g / L, chelating agent: 0 to 30 g / L, crystal growth agent: 0 to 30 g / L.
  • Gold strike plating conditions such as the bath temperature, anode material, and current density of the gold strike plating bath can be appropriately set according to the plating bath used, the required plating thickness, and the like.
  • the anode material is preferably a titanium platinum plate and an insoluble anode such as iridium oxide.
  • bath temperature 20 to 40 ° C.
  • current density 0.5 to 5.0 A / dm 2
  • treatment time 5 to 60 seconds
  • pH 0.5 to 7.0
  • the gold strike plating may be performed on the entire surface of the metal substrate, or may be performed only on a region where the nickel plating layer or the silver plating layer is to be formed.
  • Nickel strike plating As a nickel strike plating bath, what contains nickel salt, an anodic dissolution promoter, and a pH buffer can be used, for example. Further, an additive may be added to the nickel strike plating bath.
  • nickel salt for example, nickel sulfate, nickel sulfamate, nickel chloride and the like can be used.
  • anodic dissolution accelerator for example, nickel chloride and hydrochloric acid can be used.
  • pH buffering agent for example, boric acid, nickel acetate, citric acid and the like can be used.
  • additives include primary brighteners (saccharin, benzene, naphthalene (di, tri), sodium sulfonate, sulfonamide, sulfinic acid, etc.), secondary brighteners (organic compounds: butynediol, coumarin, allylaldehyde).
  • a sulfonic acid or the like, a metal salt: cobalt, lead, zinc or the like) and a pit inhibitor (such as sodium lauryl sulfate) can be used.
  • the preferred amount of each component of the nickel strike plating bath that can be suitably used for the nickel strike plating treatment is nickel salt: 200 to 600 g / L, anodic dissolution accelerator: 0 to 300 g / L, pH buffer: 0 to 50 g / L, additive: 0 to 20 g / L.
  • Nickel strike plating conditions such as bath temperature, anode material, and current density of the nickel strike plating bath can be appropriately set according to the plating bath used, the required plating thickness, and the like.
  • the anode material it is preferable to use a soluble anode such as electrolytic nickel, carbonized nickel, depolarized nickel, and sulfur nickel.
  • bath temperature 20 to 70 ° C.
  • current density 0.1 to 15.0 A / dm 2
  • treatment time 5 to 60 seconds
  • pH 0.5 to 4.5 can do.
  • the nickel strike plating may be performed on the entire surface of the metal substrate, or may be performed only on the region where the nickel plating layer or the silver plating layer is to be formed.
  • the above-described various strike plating may be performed only one kind, or a plurality of strike plating may be laminated. Further, when the adhesion state of the rough nickel plating is good without the strike plating process due to the surface state of the metal substrate, the strike plating process can be omitted.
  • Nickel plating treatment It is preferable to perform a nickel plating process (S02) on the metal substrate (a strike plating layer when the strike plating process is performed). By performing the nickel plating treatment, it is possible to prevent the diffusion and reaction of atoms between the metal substrate and the silver plating layer, and it is possible to suppress the deterioration of the characteristics of the silver plating layer.
  • the nickel plating bath for example, a bath containing a nickel salt, an anodic dissolution accelerator and a pH buffer can be used.
  • An additive may be added to the nickel plating bath.
  • nickel salt for example, nickel sulfate, nickel sulfamate, nickel chloride and the like can be used.
  • anodic dissolution accelerator for example, nickel chloride and hydrochloric acid can be used.
  • pH buffering agent for example, boric acid, nickel acetate, citric acid and the like can be used.
  • additives include primary brighteners (saccharin, benzene, naphthalene (di, tri) sodium sulfonate, sulfonamide, sulfinic acid, etc.), secondary brighteners (organic compounds: butynediol, coumarin, allylaldehyde sulfone). Acids, metal salts: cobalt, lead, zinc, etc.) and pit inhibitors (sodium lauryl sulfate, etc.) can be used.
  • the preferred amount of each component of the nickel plating bath that can be suitably used for the nickel plating treatment is nickel salt: 200 to 600 g / L, anodic dissolution accelerator: 0 to 300 g / L, pH buffer: 20 to 50 g / L, additive: 0 to 20 g / L.
  • Nickel plating conditions such as bath temperature, anode material, and current density of the nickel plating bath can be set as appropriate according to the plating bath used, the required plating thickness, and the like.
  • the anode material it is preferable to use a soluble anode such as electrolytic nickel, carbonized nickel, depolarized nickel, and sulfur nickel.
  • bath temperature 20 to 70 ° C.
  • current density 0.1 to 15.0 A / dm 2
  • treatment time 10 to 50000 seconds
  • pH 0.5 to 4.5
  • the nickel plating layer preferably has a continuous film shape, and the thickness of the nickel plating layer is preferably 0.05 ⁇ m to 10 ⁇ m. If it is less than 0.05 ⁇ m, the barrier effect is poor, and if it is 10 ⁇ m or more, cracks are likely to occur during bending.
  • the nickel plating layer may have a granular or island-like discontinuous film shape as long as the effects of the present invention are not impaired. In the latter case, the granular and island portions may be partially continuous.
  • the nickel plating layer is preferably subjected to strike plating treatment (S03).
  • strike plating treatment S03
  • strike plating treatment S03
  • the adhesion between the nickel plating layer and the silver plating layer can be improved more reliably. it can.
  • Each strike plating method is the same as the strike plating process (S01) on the metal substrate.
  • a silver plating process (S04) is a process for forming the silver plating layer which is the outermost surface of a silver plating material.
  • silver plating treatment various conventionally known silver plating methods can be used within a range not impairing the effects of the present invention, but the silver salt concentration in the plating bath is increased as compared with ordinary silver strike plating. It is preferable to reduce the concentration of the conductive salt.
  • a silver plating bath that can be suitably used for silver plating treatment is composed of a silver salt, an alkali cyanide salt, a conductive salt, and a metal additive, and an organic additive may be added as necessary.
  • the preferred amount of each component used is: silver salt: 40 to 150 g / L, alkali cyanide salt: 1 to 200 g / L, conductive salt: 10 to 250 g / L, metal additive: 2.5 to 25 ppm, organic Additive: 0 to 10 g / L.
  • Examples of the silver salt include silver cyanide and silver cyanide potassium, and examples of the alkali cyanide salt include potassium cyanide and sodium cyanide.
  • Examples of the conductive salt include potassium carbonate, potassium chloride, potassium pyrophosphate, and potassium thiosulfate.
  • Examples of the metal additive include copper, tin, nickel, cobalt, antimony, selenium, tellurium, bismuth and the like, but it is preferable to use selenium.
  • Examples of the organic additive include benzenesulfonic acid, mercaptans, and ethylenediaminetetraacetic acid.
  • an insoluble anode such as a soluble anode, stainless steel, a titanium platinum plate, and iridium oxide as the anode material.
  • the bath temperature is preferably 15 to 70 ° C. and the pH is preferably 7.0 to 10.0.
  • One of the features of the method for producing a silver plating material of the present invention is to use a pulse power supply device.
  • a pulse power supply device By performing plating using a pulse power source, a dense and uniform silver plating layer can be formed even when a plating bath to which a metal element is added is used.
  • Examples of the current density are 0.5 to 20.0 A / dm 2 , and the treatment time is 0.5 to 10,000 seconds.
  • FIG. 2 is a schematic cross-sectional view of one embodiment of the silver plating material of the present invention.
  • a silver plating layer 6 is formed on the surface of the metal base 2 via a nickel plating layer 4.
  • a strike plating layer 8 is preferably formed between the metal substrate 2 and the nickel plating layer 4 and between the nickel plating layer 4 and the silver plating layer 6.
  • the silver plating layer 6 contains one or more metal elements selected from copper, tin, nickel, cobalt, selenium, antimony, tellurium and bismuth, and the content of the metal elements is 0.001 to 0.025. %. Since the silver plating layer 6 contains one or more metal elements selected from 0.001% or more of copper, tin, nickel, cobalt, selenium, antimony, tellurium and bismuth, the silver plating layer 6 Excellent wear resistance can be imparted, and the wear resistance can be maintained even after high temperature exposure. Moreover, the electroconductivity and contact resistance which were excellent in the silver plating layer 6 can be maintained because an additive metal element shall be 0.025% or less.
  • a dense and uniform silver plating layer 6 is formed.
  • the thickness of the silver plating layer 6 is preferably 0.1 ⁇ m to 50 ⁇ m.
  • the characteristics of the silver plating layer 6 can be utilized when the silver plating material 1 is used for various contacts, terminals, connectors, switches, and the like.
  • the thickness By setting the thickness to 50 ⁇ m or less, defect formation and the like in the silver plating layer 6 can be suppressed, and efficient production becomes possible.
  • the metal of the metal substrate 2 is not particularly limited as long as it has electrical conductivity, and examples thereof include aluminum and aluminum alloys, iron and iron alloys, titanium and titanium alloys, stainless steel, copper, and copper alloys. However, among these, copper and copper alloys are preferably used because they are excellent in electrical conductivity, thermal conductivity, and spreadability.
  • the nickel plating layer 4 preferably has a continuous film shape, and the thickness of the nickel plating layer 4 is preferably 0.05 ⁇ m to 10 ⁇ m. A more preferable thickness of the nickel plating layer 4 is 0.5 ⁇ m to 2 ⁇ m.
  • the nickel plating layer 4 may be a granular or island-like discontinuous film shape as long as the effects of the present invention are not impaired. In the latter case, the granular and island portions may be partially continuous.
  • the strike plating layer 8 may be a continuous film shape or may be a granular or island-like discontinuous film shape as long as the effects of the present invention are not impaired. In the latter case, the granular and island portions may be partially continuous. Depending on the strike plating conditions, it may be difficult to identify the strike plating layer 8.
  • the thickness of the strike plating layer 8 is preferably 0.01 ⁇ m to 0.5 ⁇ m.
  • the strike plating layer 8 may be one or more strike plating layers selected from the group of silver strike plating, copper strike plating, gold strike plating, and nickel strike plating.
  • the silver plating layer 6 is formed on the surface of the strike plating layer 8.
  • the thickness of the silver plating layer 6 is preferably 0.1 ⁇ m to 50 ⁇ m, and the Vickers hardness is preferably 80 HV to 250 HV. If the thickness is less than 0.1 ⁇ m, the wear resistance of the silver plating layer 6 cannot be used.
  • the nickel plating layer 4 and the strike plating layer 8 are not essential constituent requirements of the silver plating material 1 of the present invention, but the nickel plating layer 4 causes atomic atoms between the metal substrate 2 and the silver plating layer 6 to be present. Diffusion and reaction can be prevented, and the characteristic deterioration of the silver plating layer 6 can be suppressed. Further, the strike plating layer 8 can more reliably improve the adhesion between the metal substrate 2 and the nickel plating layer 4 and the adhesion between the nickel plating layer 4 and the silver plating layer 6.
  • Metallurgical bonding means that the metals are directly bonded to each other, not mechanical bonding such as an anchor effect or different bonding layers such as an adhesive.
  • Metallurgical bonding is a concept that naturally includes bonding by crystallographic matching (epitaxy), and in the present invention, it is preferable that the plating layers achieve bonding by crystallographic matching (epitaxy).
  • the silver plating material 1 of this invention can be suitably manufactured with the manufacturing method of the silver plating material of this invention.
  • Example 1 A 30 ⁇ m silver plating layer was formed on a base material (material to be plated) made of a copper alloy by the following steps. First, as a pretreatment of the substrate surface, the material to be plated and the SUS plate were placed in an alkaline degreasing solution, and the material to be plated was used as a cathode, and the SUS plate was used as an anode, and electrolytic degreasing was performed at a voltage of 3 V for 30 seconds. After washing with water, acid washing was performed in 5% sulfuric acid for 15 seconds.
  • Ia and Ib indicate current density (A / dm 2 ), Ta and Tb indicate energization time (ms), and satisfy the following formulas (1) and (2).
  • in the equation (1) indicates an absolute value.
  • Example 2 A silver plating material was produced in the same manner as in Example 1 except that a silver plating bath composed of potassium selenocyanate equivalent to 5 ppm was used as selenium, and various evaluations were performed. The obtained results are shown in Table 1.
  • Example 3 A silver plating material was produced in the same manner as in Example 1 except that a silver plating bath composed of potassium selenocyanate equivalent to 10 ppm was used as selenium, and various evaluations were performed. The obtained results are shown in Table 1.
  • Example 4 A silver plating material was produced in the same manner as in Example 1 except that a silver plating bath composed of potassium selenocyanate equivalent to 15 ppm was used as selenium, and various evaluations were performed. The obtained results are shown in Table 1.
  • Example 5 A silver plating material was produced in the same manner as in Example 1 except that a silver plating bath composed of potassium selenocyanate equivalent to 25 ppm was used as selenium, and various evaluations were performed. The obtained results are shown in Table 1.
  • Example 3 A silver plating material was produced in the same manner as in Example 1 except that a silver plating bath made of potassium selenocyanate equivalent to 1 ppm was used as selenium, and various evaluations were performed. The obtained results are shown in Table 1.
  • Comparative Example 4 A silver plating material was produced in the same manner as in Example 1 except that a silver plating bath composed of potassium selenocyanate equivalent to 30 ppm was used as selenium, and various evaluations were performed. The obtained results are shown in Table 1.
  • the silver plating layer in the silver plating material of the present invention contains 0.001 to 0.025% selenium. Further, it can be seen that the silver plating layer has a high hardness of 100 HV or more, and the hardness is maintained even after boiling at 100 ° C. for 1 hour (Examples 1 to 5).

Abstract

L'invention concerne : un matériau de placage d'argent qui possède à la fois une excellente conductivité électrique et une excellente résistance à l'usure, et qui est capable de conserver ces caractéristiques y compris après avoir été laissé à température ambiante pendant une longue période de temps ou après avoir été exposé à des températures élevées ; et un procédé de production de ce matériau de placage d'argent. L'invention concerne un procédé de fabrication d'un matériau de placage d'argent, au cours duquel une couche de placage d'argent est formée sur la surface d'un métal de base, et qui est caractérisé en ce que le placage est réalisé à l'aide d'un bain de placage d'argent à base de cyanogène qui contient de 2,5 à 25 ppm d'un ou plusieurs éléments métalliques choisis parmi le cuivre, l'étain, le nickel, le cobalt, le sélénium, l'antimoine, le tellure et le bismuth, au moyen d'une alimentation en énergie pulsée.
PCT/JP2016/001038 2015-03-27 2016-02-26 Matériau de placage d'argent et son procédé de fabrication WO2016157713A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2017509209A JP6484844B2 (ja) 2015-03-27 2016-02-26 銀めっき材及びその製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015067533 2015-03-27
JP2015-067533 2015-03-27

Publications (1)

Publication Number Publication Date
WO2016157713A1 true WO2016157713A1 (fr) 2016-10-06

Family

ID=57004887

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/001038 WO2016157713A1 (fr) 2015-03-27 2016-02-26 Matériau de placage d'argent et son procédé de fabrication

Country Status (2)

Country Link
JP (1) JP6484844B2 (fr)
WO (1) WO2016157713A1 (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018181399A1 (fr) * 2017-03-31 2018-10-04 古河電気工業株式会社 Matériau de fil machine plaqué, son procédé de production, et câble, fil électrique, bobine et élément de ressort formés à partir de celui-ci
JP2018168423A (ja) * 2017-03-30 2018-11-01 株式会社Ｋａｎｚａｃｃ 銀メッキ銅系基材およびその製造方法
JPWO2018181190A1 (ja) * 2017-03-31 2020-02-06 メタローテクノロジーズジャパン株式会社 電解銀めっき液
WO2020153396A1 (fr) * 2019-01-24 2020-07-30 三菱マテリアル株式会社 Matériau de borne de connecteur et terminal de connecteur
JP6822618B1 (ja) * 2019-08-09 2021-01-27 三菱マテリアル株式会社 コネクタ用端子材
WO2021029254A1 (fr) * 2019-08-09 2021-02-18 三菱マテリアル株式会社 Matériau de borne pour connecteurs
JP2021130856A (ja) * 2020-02-20 2021-09-09 三菱マテリアル株式会社 コネクタ用端子材
WO2022018896A1 (fr) * 2020-07-22 2022-01-27 三菱マテリアル株式会社 Matériau de borne pour connecteurs
JP2022022071A (ja) * 2020-07-22 2022-02-03 三菱マテリアル株式会社 コネクタ用端子材
CN114758817A (zh) * 2022-03-14 2022-07-15 鼎辉光电通信(江苏)有限公司 一种耐高温低噪音半钢电缆

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61186494A (ja) * 1985-02-13 1986-08-20 Matsushita Electric Ind Co Ltd 銀メツキ法
JPH06158385A (ja) * 1992-11-27 1994-06-07 Furukawa Saakitsuto Foil Kk 通電ロール
JP2013249514A (ja) * 2012-05-31 2013-12-12 Nichia Corp 光半導体装置用電解銀めっき液
JP2014080672A (ja) * 2012-09-27 2014-05-08 Dowa Metaltech Kk 銀めっき材およびその製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61186494A (ja) * 1985-02-13 1986-08-20 Matsushita Electric Ind Co Ltd 銀メツキ法
JPH06158385A (ja) * 1992-11-27 1994-06-07 Furukawa Saakitsuto Foil Kk 通電ロール
JP2013249514A (ja) * 2012-05-31 2013-12-12 Nichia Corp 光半導体装置用電解銀めっき液
JP2014080672A (ja) * 2012-09-27 2014-05-08 Dowa Metaltech Kk 銀めっき材およびその製造方法

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018168423A (ja) * 2017-03-30 2018-11-01 株式会社Ｋａｎｚａｃｃ 銀メッキ銅系基材およびその製造方法
JP6452912B1 (ja) * 2017-03-31 2019-01-16 古河電気工業株式会社 めっき線棒材及びその製造方法、並びにこれを用いて形成されたケーブル、電線、コイル及びばね部材
JPWO2018181190A1 (ja) * 2017-03-31 2020-02-06 メタローテクノロジーズジャパン株式会社 電解銀めっき液
WO2018181399A1 (fr) * 2017-03-31 2018-10-04 古河電気工業株式会社 Matériau de fil machine plaqué, son procédé de production, et câble, fil électrique, bobine et élément de ressort formés à partir de celui-ci
WO2020153396A1 (fr) * 2019-01-24 2020-07-30 三菱マテリアル株式会社 Matériau de borne de connecteur et terminal de connecteur
JP6743998B1 (ja) * 2019-01-24 2020-08-19 三菱マテリアル株式会社 コネクタ用端子材及びコネクタ用端子
US20220294140A1 (en) 2019-08-09 2022-09-15 Mitsubishi Materials Corporation Terminal material for connectors
JP6822618B1 (ja) * 2019-08-09 2021-01-27 三菱マテリアル株式会社 コネクタ用端子材
WO2021029254A1 (fr) * 2019-08-09 2021-02-18 三菱マテリアル株式会社 Matériau de borne pour connecteurs
US11901659B2 (en) 2019-08-09 2024-02-13 Mitsubishi Materials Corporation Terminal material for connectors
JP2021130856A (ja) * 2020-02-20 2021-09-09 三菱マテリアル株式会社 コネクタ用端子材
JP7040544B2 (ja) 2020-02-20 2022-03-23 三菱マテリアル株式会社 コネクタ用端子材
JP7119267B2 (ja) 2020-07-22 2022-08-17 三菱マテリアル株式会社 コネクタ用端子材
JP2022022071A (ja) * 2020-07-22 2022-02-03 三菱マテリアル株式会社 コネクタ用端子材
WO2022018896A1 (fr) * 2020-07-22 2022-01-27 三菱マテリアル株式会社 Matériau de borne pour connecteurs
CN114758817A (zh) * 2022-03-14 2022-07-15 鼎辉光电通信(江苏)有限公司 一种耐高温低噪音半钢电缆

Also Published As

Publication number Publication date
JP6484844B2 (ja) 2019-03-20
JPWO2016157713A1 (ja) 2018-01-18

Similar Documents

Publication Publication Date Title
JP6484844B2 (ja) 銀めっき材及びその製造方法
JP6259437B2 (ja) めっき積層体
JP6466837B2 (ja) めっき材の製造方法及びめっき材
JP6665387B2 (ja) 銀めっき部材及びその製造方法
JP2007070730A (ja) 金属デュプレックス及び方法
JP2015187303A (ja) 接続部品用導電部材及びその製造方法
JPWO2018221087A1 (ja) Ｐｃｂ端子
JP2006009039A (ja) ウィスカー成長が抑制されたスズ系めっき皮膜及びその形成方法
JP6651852B2 (ja) 銀めっき部材及びその製造方法
JPH10212591A (ja) 電気ニッケルめっき浴又は電気ニッケル合金めっき浴及びそれを用いためっき方法
JP6182757B2 (ja) めっき材の製造方法及びめっき材
JP2017197788A (ja) 電子部品接点部材の製造方法及び電子部品接点部材
JP6086531B2 (ja) 銀めっき材
TWI328052B (en) Electrolyte and method for depositing tin-bismuth alloy layers
JP6268408B2 (ja) めっき材の製造方法及びめっき材
JP7162341B2 (ja) めっき積層体の製造方法及びめっき積層体
JP2022082619A (ja) Ｐｃｂ端子の製造方法及びｐｃｂ端子
JP2017218663A (ja) めっき積層体の製造方法及びめっき積層体
WO2020079904A1 (fr) Matériau conducteur électrique, article moulé et composant électronique
JP7270968B2 (ja) めっき積層体の製造方法及びめっき積層体
JP7213390B1 (ja) 銀めっき皮膜及び該銀めっき皮膜を備えた電気接点
US11686007B2 (en) Tin-indium alloy electroplating solution
TW201341598A (zh) 鍍銀電解液及其電鍍方法
JP5978439B2 (ja) 導電部材
JP2013144835A (ja) 無電解Ｎｉ−Ｐ−Ｓｎめっき液

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16771607

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2017509209

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16771607

Country of ref document: EP

Kind code of ref document: A1