WO2023234015A1 - Matériau revêtu en surface pour contacts électriques, et contact électrique, commutateur et borne de connecteur utilisant chacun celui-ci - Google Patents

Matériau revêtu en surface pour contacts électriques, et contact électrique, commutateur et borne de connecteur utilisant chacun celui-ci Download PDF

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WO2023234015A1
WO2023234015A1 PCT/JP2023/018332 JP2023018332W WO2023234015A1 WO 2023234015 A1 WO2023234015 A1 WO 2023234015A1 JP 2023018332 W JP2023018332 W JP 2023018332W WO 2023234015 A1 WO2023234015 A1 WO 2023234015A1
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Prior art keywords
silver
containing layer
electrical contacts
base material
conductive base
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PCT/JP2023/018332
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English (en)
Japanese (ja)
Inventor
義胤 鳥居
颯己 葛原
親人 菅原
圭介 池貝
裕俊 鍵田
Original Assignee
古河電気工業株式会社
古河精密金属工業株式会社
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Priority to CN202380024470.9A priority Critical patent/CN118786252A/zh
Publication of WO2023234015A1 publication Critical patent/WO2023234015A1/fr

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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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H1/00—Contacts
    • H01H1/02—Contacts characterised by the material thereof
    • H01H1/04—Co-operating contacts of different material
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
    • B21B1/22—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling plates, strips, bands or sheets of indefinite length
    • B21B1/30—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling plates, strips, bands or sheets of indefinite length in a non-continuous process
    • B21B1/32—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling plates, strips, bands or sheets of indefinite length in a non-continuous process in reversing single stand mills, e.g. with intermediate storage reels for accumulating work
    • B21B1/36—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling plates, strips, bands or sheets of indefinite length in a non-continuous process in reversing single stand mills, e.g. with intermediate storage reels for accumulating work by cold-rolling

Definitions

  • the present invention relates to a surface coating material for electrical contacts, and electrical contacts, switches, and connector terminals using the same.
  • Patent Document 1 describes a copper alloy composite foil in which a smooth layer of silver is provided on at least one surface of a copper alloy plate, and (200) crystals on the surface of the smooth layer of silver are measured by X-ray diffraction.
  • the strength of the orientation is in the range of 34 or more and 100 or less when the sum of the strength of the (220) crystal orientation and the strength of the (111) crystal orientation is 100, and the strength of the (220) crystal orientation is in the range of (111).
  • a copper alloy composite foil is described that has a crystal orientation strength in a range of 18 or more and 120 or less when the strength of crystal orientation is 100.
  • silver has the property of being easily abraded due to adhesion, so the silver (Ag) or silver alloy plating applied to the surface is abraded due to sliding due to switching on/off operations or sliding of connectors. This has the drawback of increasing contact resistance.
  • the copper alloy composite foil described in Patent Document 1 even if the hardness is increased by increasing the peak intensity derived from the Ag (220) plane obtained from the X-ray diffraction chart of the silver smooth layer, the silver Since the adhesion is not suppressed, the durability as evaluated by the keystroke test has not yet been improved.
  • peak intensities derived from the Ag (200) plane, Ag (220) plane, and Ag (111) plane obtained from the X-ray diffraction chart of the silver smooth layer It focuses only on the relationship between peak intensities derived from , and does not focus on the influence of other peak intensities.
  • the copper alloy composite foil described in Patent Document 1 was subjected to a sliding wear test using a steel ball as a mating material, but in the actual usage environment, adhesion with silver is more likely to occur than with steel balls. Since wear caused by sliding becomes a problem, there is a need to improve the wear resistance, which is evaluated by a keystroke test that matches the actual usage environment.
  • the copper alloy composite foil described in Patent Document 1 has poor bending workability, and its shape is unstable when molded into the shape of a terminal or connector.
  • the present invention is a surface coating material for electrical contacts that has a silver-containing layer on the surface that has excellent bending workability and can suppress adhesion and increase wear resistance under conditions suitable for actual usage environments. and to provide electrical contacts, switches, and connector terminals using the same.
  • the present inventors took into account all the peak intensities obtained from the X-ray diffraction chart of the silver-containing layer, and determined that the peak intensities originate from the Ag (111) plane and the peak intensities originate from the plane parallel to the Ag (111) plane.
  • the first total peak intensity which is the total value with the peak intensity, is set as h1 , and the sum of the remaining peak intensities obtained by subtracting the first total peak intensity ( h1 ) from the total value of all detected peak intensities.
  • the ratio ( h1 / h2 ) of the first total peak intensity (h1) to the second total peak intensity ( h2 ) is 1.0 or more 3
  • the gist of the present invention is as follows.
  • a surface coating material for electrical contacts comprising a conductive base material and a silver-containing layer covering at least one side of the conductive base material, the silver-containing layer being obtained from an X-ray diffraction chart.
  • the first total peak intensity which is the sum of the peak intensity originating from the Ag (111) plane and the peak intensity originating from the plane parallel to the Ag (111) plane, is h1 , and all detected
  • the second total peak intensity which is the total value of the remaining peak intensities after subtracting the first total peak intensity (h 1 ) from the total value of peak intensities
  • the second total peak intensity is h 2
  • the second total peak intensity (h 2 ) wherein the ratio (h 1 /h 2 ) of the first total peak intensity (h 1 ) to ) is in the range of 1.0 or more and 3.0 or less.
  • the silver-containing layer is the surface coating material for electrical contacts according to (1) above, wherein the half width of the peak derived from the Ag (111) plane is in the range of 0.15° or more and 0.30° or less. .
  • a surface for electrical contacts is provided with a silver-containing layer on the surface that has excellent bending workability and is capable of suppressing adhesion and increasing wear resistance under conditions consistent with the actual usage environment.
  • a coating material and electrical contacts, switches, and connector terminals using the same can be provided.
  • FIG. 1 is a schematic cross-sectional view including the thickness direction, showing an example of the surface coating material for electrical contacts of the present invention.
  • FIG. 7 is a schematic cross-sectional view including the thickness direction, showing a modification of the surface coating material for electrical contacts of the present invention including an intermediate layer.
  • the surface coating material 1 for electrical contacts of the present invention includes a conductive base material 2 and a silver-containing layer 3 covering at least one side of the conductive base material 2, and the silver-containing layer 3 includes:
  • the first total peak intensity which is the sum of the peak intensity derived from the Ag (111) plane and the peak intensity derived from the plane parallel to the Ag (111) plane, obtained from the X-ray diffraction chart, is defined as h1 .
  • the second total peak intensity which is the total value of the remaining peak intensities after subtracting the first total peak intensity (h 1 ) from the total value of all detected peak intensities
  • the second total The ratio (h 1 /h 2 ) of the first total peak intensity (h 1 ) to the peak intensity (h 2 ) is in the range of 1.0 or more and 3.0 or less.
  • the ratio of the orientation of silver contained in the silver-containing layer 3 that is non-parallel to the Ag (111) plane, which is an orientation that provides excellent keying performance, is moderately increased compared to all orientations, so that in practice Even when silver, which tends to adhere, is used as a mating material in accordance with the usage environment, it is possible to suppress adhesion of silver during a keystroke test and thereby suppress wear of the silver-containing layer 3.
  • the proportion of the orientation parallel to the Ag (111) plane is relatively decreased, and the proportion of silver oriented in other directions is relatively increased, so that the electrical contact surface coating material 1
  • the bending workability of the material is improved.
  • the surface coating material for electrical contacts has a silver-containing layer 3 on its surface that has excellent bending workability and can suppress adhesion and increase wear resistance under conditions suitable for the actual usage environment. 1 can be provided.
  • FIG. 1 is a schematic cross-sectional view including the thickness direction, showing an example of the surface coating material for electrical contacts of the present invention.
  • the surface coating material 1 for electrical contacts includes a conductive base material 2 and a silver-containing layer 3 covering at least one side of the conductive base material 2.
  • the surface coating material 1 for electrical contacts in FIG. may be coated on both sides.
  • the conductive base material 2 is made of pure copper, copper alloy, pure iron, iron alloy, pure aluminum, or aluminum alloy.
  • copper alloys include Cu-Sn-P, Cu-Zn, Cu-Ni-Si, Cu-Sn-Ni, Cu-Cr-Mg, and Cu-Ni-Si-Zn-Sn. -Mg type etc. can be mentioned.
  • iron alloys include Fe-Cr-Ni series, Fe-Cr series, and the like.
  • aluminum alloy examples include Al--Mg type, Al--Mg--Si type, and the like.
  • the shape of the conductive base material 2 is not particularly limited and may be appropriately selected depending on the application, but it is preferably a strip or a plate, and can also be a bar or wire. Moreover, it is preferable that the conductive base material 2 is manufactured by rolling.
  • the conductivity of the conductive base material 2 is not particularly limited, but it is preferably 20% IACS or more, and more preferably 25% IACS or more. Thereby, the entire electrical contact surface coating material 1 can have excellent electrical conductivity.
  • the electrical conductivity (IACS; International Annealed Copper Standard) can be determined by measuring in a constant temperature bath controlled at 20° C. ( ⁇ 1° C.) using a four-terminal method.
  • the conductive base material 2 preferably has a thickness in the range of 0.03 mm or more and 0.30 mm or less.
  • the electrical contact surface coating material 1 having the conductive base material 2 can be easily used as a contact material for a switch.
  • the thickness of the conductive base material 2 by setting the thickness of the conductive base material 2 to 0.03 mm or more, the mechanical strength of the conductive base material 2 can be increased. Note that a method for measuring the thickness of the conductive base material 2 will be described later.
  • the silver-containing layer 3 is provided to cover at least one side of the conductive base material 2 and contains silver (Ag).
  • the silver-containing layer 3 is preferably made of pure silver or a silver alloy containing 95% by mass or more of silver, and more preferably made of pure silver containing 99% by mass or more of silver.
  • the silver-containing layer 3 is made of pure silver made of silver and unavoidable impurities.
  • the silver-containing layer 3 contains one or more elements selected from the group consisting of zinc (Zn), copper (Cu), nickel (Ni), selenium (Se), antimony (Sb), and cobalt (Co). It may also contain a second element consisting of. When the silver-containing layer 3 contains such a second element, the keying performance and wear resistance of the electrical contact surface coating material 1 can be further improved. On the other hand, from the viewpoint of improving the electrical connectivity of the surface coating material 1 for electrical contacts, the silver-containing layer 3 contains zinc (Zn), copper (Cu), nickel (Ni), selenium (Se), and antimony (Sb). and cobalt (Co) in a total amount of 5% by mass or less.
  • the silver-containing layer 3 has a first total peak obtained from an X-ray diffraction chart, which is the sum of the peak intensity derived from the Ag (111) plane and the peak intensity derived from the plane parallel to the Ag (111) plane.
  • h 2 be the second total peak intensity, which is the total value of the remaining peak intensities after subtracting the first total peak intensity (h 1 ) from the total value of all detected peak intensities.
  • the ratio (h 1 /h 2 ) of the first total peak intensity (h 1 ) to the second total peak intensity (h 2 ) is in the range of 1.0 or more and 3.0 or less.
  • the orientation of the silver contained in the silver-containing layer 3 is important, and the Ag(111) plane and the plane parallel to the Ag(111) plane are on the surface of the silver-containing layer 3.
  • the exposed crystal orientation has the property of reducing the keying performance of the surface coating material 1 for electrical contacts, while the crystal orientation in which the plane that is not parallel to the Ag (111) plane is exposed on the surface of the silver-containing layer 3 is difficult for electrical contacts. It has the property of improving the keying performance of the surface coating material 1.
  • the crystals contained in the silver-containing layer 3 are It is possible to suppress a decrease in the bending workability of the surface coating material 1 for electrical contacts due to an excessive amount of strain, and in particular, it is possible to suppress cracking of the silver-containing layer 3 during bending.
  • the surface that is not parallel to the Ag (111) surface can be Since the ratio of the derived peak intensity is relatively increased, adhesion of the silver-containing layer 3 can be suppressed and wear resistance can be improved.
  • Examples of planes parallel to the Ag (111) plane include the Ag (222) plane and the Ag (333) plane, but the peak intensity of planes other than the Ag (222) plane that appears in the X-ray diffraction chart is weak. Therefore, only the Ag (222) plane may be a plane parallel to the Ag (111) plane.
  • the half width of the peak derived from the Ag (111) plane obtained from the X-ray diffraction chart is preferably in the range of 0.15° or more and 0.30° or less.
  • the amount of strain in the crystal contained in the silver-containing layer 3 becomes excessive. It is possible to suppress a decrease in bending workability.
  • the half width of the peak derived from the Ag (111) plane is set to 0.15° or more, it is possible to maintain a high amount of strain remaining in the crystals included in the silver-containing layer 3, and to increase the hardness of the silver-containing layer 3. Since this increases, the keying performance and abrasion resistance of the silver-containing layer 3 can be improved.
  • the thickness of the silver-containing layer 3 is not particularly limited, but is preferably in the range of, for example, 0.05 ⁇ m or more and 10 ⁇ m or less.
  • the thickness of the silver-containing layer 3 is preferably 0.05 ⁇ m or more, more preferably 0.10 ⁇ m or more, and even more preferably 0.15 ⁇ m or more.
  • the thickness of the silver-containing layer 3 is preferably 0.05 ⁇ m or more, more preferably 0.10 ⁇ m or more, and even more preferably 0.15 ⁇ m or more.
  • the thickness of the silver-containing layer 3 by setting the thickness of the silver-containing layer 3 to 10 ⁇ m or less, the material cost of the surface coating material 1 for electrical contacts can be suppressed.
  • the thickness of the silver-containing layer 3 is preferably 10 ⁇ m or less, more preferably 2.0 ⁇ m or less, and even more preferably 1.0 ⁇ m or less. Note that a method for measuring the thickness of the silver-containing layer 3 will be described later.
  • FIG. 2 is a schematic cross-sectional view including the thickness direction, showing a modification of the surface coating material for electrical contacts of the present invention including an intermediate layer.
  • the surface coating material 1A for electrical contacts shown in FIG. 2 further includes at least one intermediate layer 4 made of pure copper, copper alloy, pure nickel, or nickel alloy between the conductive base material 2 and the silver-containing layer 3. That is, the silver-containing layer 3 of the electrical contact surface coating material 1A covers at least one side of the conductive base material 2 with the intermediate layer 4 interposed therebetween. Since the surface coating material 1A for electrical contacts includes the intermediate layer 4, thermal diffusion of elements constituting the conductive base material 2 into the silver-containing layer 3 can be suppressed, and the conductive base material 2 and Adhesion with the silver-containing layer 3 can be improved.
  • examples of the nickel alloy include Ni--P type.
  • examples of the copper alloy include Cu--Sn type, Cu--Co type, etc.
  • the thickness of the intermediate layer 4 is not particularly limited, but is preferably in the range of 0.01 ⁇ m or more and 1.00 ⁇ m or less, for example.
  • the thickness of the intermediate layer 4 is set to 0.01 ⁇ m or more, thermal diffusion of elements constituting the conductive base material 2 to the silver-containing layer 3 can be easily suppressed, and the conductive base material 2 and the silver Adhesion with the containing layer 3 can be easily improved.
  • the thickness of the intermediate layer 4 to 1.00 ⁇ m or less, the bending workability of the surface coating material 1A for electrical contacts can be improved, and in particular, the ratio of the bending radius to the thickness (R/t) can be improved. Even when bending is performed as shown in FIG. 1, damage to the electrical contact surface coating material 1A can be made less likely to occur.
  • the surface coating materials 1 and 1A for electrical contacts configured as described above have the property that the silver-containing layer 3 is not easily worn out due to adhesion, electrical contacts are manufactured using the surface coating materials 1 and 1A for electrical contacts. It is particularly preferable that the silver-containing layer 3 is configured to be in electrical contact with the mating material. At this time, even if the mating material is silver, which tends to adhere, it is difficult to wear out due to sliding due to repeated on/off operations of a switch or sliding of a connector terminal, so it is difficult to increase the contact resistance of the electrical contact. can do.
  • the electrical contact surface coating materials 1 and 1A have excellent bending properties, so that when molded into the shape of a terminal or connector, the shape can be easily stabilized. Therefore, the surface coating materials 1 and 1A for electrical contacts of the present invention can be suitably used for switches and connector terminals having electrical contacts. Furthermore, such switches and connector terminals can be used in various consumer electronic devices and in-vehicle connection parts.
  • the silver-containing layer 3 and intermediate layer 4 coated on the conductive base material 2 only need to be formed on at least one side of the conductive base material 2. , may be formed on both sides of the conductive base material 2.
  • Method for manufacturing surface coating material for electrical contacts As an example of a method for manufacturing surface coating material 1 for electrical contacts, a silver-containing layer 3 is formed on at least one side of a conductive base material 2 that has been electrolytically degreased, and then the silver-containing layer 3 is A method of rolling the conductive base material 2 having a surface formed thereon can be mentioned.
  • the method for producing the surface coating material 1 for electrical contacts including the intermediate layer 4 includes sequentially forming the intermediate layer 4 and the silver-containing layer 3 on at least one side of the conductive base material 2 that has been subjected to electrolytic degreasing and acid cleaning. After that, the conductive base material 2 on which these are formed is subjected to a rolling process.
  • An example of pre-treatment of the conductive base material 2 includes a method of electrolytically degreasing and acid cleaning the conductive base material 2.
  • the conductive base material 2 is made of pure iron or an iron alloy
  • the oxide film on the surface is removed by performing acid electrolysis after electrolytic degreasing, and then nickel strike is performed. Plating may be applied.
  • alkali etching may be performed as a pretreatment of the conductive base material 2.
  • plating methods can be used, such as wet plating methods such as electrolytic plating and electroless plating, and dry plating methods such as vapor deposition and sputtering. can be used.
  • wet plating methods such as electrolytic plating and electroless plating
  • dry plating methods such as vapor deposition and sputtering.
  • electrolytic plating when forming the silver-containing layer 3 is performed in an alkali cyan silver bath with a bath temperature (liquid temperature) of 20° C. or more and 25° C. or less, and a current density of 5 A/dm 2 or more and 10 A/dm 2 or less.
  • electrolytic plating is performed in a copper plating bath with a bath temperature (liquid temperature) of 40°C or higher and 55°C or lower, at a rate of 5 A/dm 2 or higher and 10 A/dm or higher. It can be carried out at a current density of 2 or less.
  • electrolytic plating is performed using a nickel plating bath with a bath temperature (liquid temperature) of 45°C or higher and 60°C or lower at a rate of 5 A/dm 2 or higher and 15 A/dm or higher. It can be carried out at current densities below dm2 .
  • the orientation of silver contained in the silver-containing layer 3 can be controlled. Note that the values of bath temperature and current density in the plating method can also be adjusted in combination as appropriate.
  • the conductive base material 2 on which at least the silver-containing layer 3 is formed is cold-rolled using a work roll.
  • the amount of strain in the crystals contained in the silver-containing layer 3 can be increased appropriately.
  • the ratio (h 1 /h 2 ) of the first total peak intensity (h 1 ) to the second total peak intensity (h 2 ) described above can be adjusted to a desired magnitude.
  • the keying performance and wear resistance of the electrical contact surface coating material 1 can be improved.
  • cold rolling and heat treatment may be performed in an appropriate combination.
  • the processing rate in cold rolling is preferably in the range of 20% or more and 50% or less.
  • the processing rate in cold rolling is preferably 20% or more, more preferably 30% or more.
  • the processing rate in cold rolling is preferably 50% or less, more preferably 40% or less.
  • the diameter (roll diameter) of the rolling work roll in contact with the conductive base material 2 on which the silver-containing layer 3 is formed is the first total peak intensity (h 2 ) relative to the second total peak intensity (h 2 ).
  • the ratio (h 1 /h 2 ) of 1 ) to a desired range it can be set, for example, to a range of 70 mm or more and 90 mm or less.
  • the ratio (h 1 /h 2 ) of the first total peak intensity (h 1 ) to the second total peak intensity (h 2 ) tends to be large.
  • the conductive base material 2 on which the silver-containing layer 3 is formed may be heat-treated.
  • the orientation of the silver contained in the silver-containing layer 3 can also be controlled by performing a combination of rolling and heat treatment on the conductive base material 2 on which the silver-containing layer 3 is formed.
  • the surface of the silver-containing layer 3 of the obtained surface coating material 1 for electrical contacts was analyzed using an X-ray diffraction method, and analyzed using an X-ray diffraction device (manufactured by PANalytical, model: X'Pert PRO).
  • the sum of the peak intensity originating from the Ag (111) plane and the peak intensity originating from the plane parallel to the Ag (111) plane is calculated as the first
  • the second total peak intensity ( 2nd total peak intensity ( The ratio (h 1 /h 2 ) of the first total peak intensity (h 1 ) to h 2 ) was calculated.
  • ⁇ The ratio of the depth of the sliding part to the thickness of the silver-containing layer 3 is less than 1/10. ⁇ : The ratio of the depth of the sliding part to the thickness of the silver-containing layer 3 is 1/10 or more and less than 1/5. ⁇ : The ratio of the depth of the sliding part to the thickness of the silver-containing layer 3 is 1/5 or more
  • the surface on which the silver-containing layer 3 of the obtained surface coating material 1 for electrical contacts is formed is brought into contact with a pure silver ball as a mating material. Co., Ltd.), reciprocating sliding was performed 50 times at the same location at a contact load of 4 N, a sliding distance of 50 mm, and a sliding speed of 100 mm/min. Next, using a laser roughness meter, measure the depth of the sliding portion of the mating material from the reference surface (the surface that is not sliding back and forth), and calculate the depth of the sliding portion relative to the thickness of the silver-containing layer 3. The percentage of Based on the calculated ratio, the wear resistance of steel balls was evaluated according to the following criteria.
  • ⁇ The ratio of the depth of the sliding part to the thickness of the silver-containing layer 3 is less than 1/10. ⁇ : The ratio of the depth of the sliding part to the thickness of the silver-containing layer 3 is 1/10 or more and less than 1/5. ⁇ : The ratio of the depth of the sliding part to the thickness of the silver-containing layer 3 is 1/5 or more
  • the obtained surface coating material 1 for electrical contacts was processed into a fixed contact, and on the surface on which the silver-containing layer 3 was formed, a dome-shaped movable contact with a diameter of 4 mm made of a silver-coated stainless steel strip was used as a movable contact, and a key was pressed.
  • the test was conducted. The test conditions were as follows: 1 million keystrokes were performed at a contact pressure of 9.8 N/mm 2 and a keystroke speed of 5Hz, and the contact resistance before and after each keystroke was measured at a current of 10 mA. The amount of change in contact resistance value was evaluated based on the following criteria.
  • ⁇ The amount of change in contact resistance value is less than 15 m ⁇ .
  • ⁇ The amount of change in contact resistance value is 15 m ⁇ or more and less than 30 m ⁇ . If it becomes impossible to measure
  • the obtained surface coating material 1 for electrical contacts was subjected to a bending test based on the Japan Copper & Brass Association technical standard T307:2007 (method for evaluating bending workability of copper and copper alloy thin plate strips), and the bent portion was examined using an optical microscope.
  • the bending workability of the obtained observation results was evaluated based on the following criteria with reference to the Japan Copper & Brass Association Technical Standard T307:2007. More specifically, the bending workability of the surface coating material 1 for electrical contacts was determined by taking five test pieces with a length of 30 mm and a width of 10 mm from the surface coating material 1 for electrical contacts so that the rolling direction was the longitudinal direction.
  • the ratio of the bending radius to the thickness (R/t) is 1 and the bending angle is 90 degrees.
  • the bending workability was evaluated based on the presence or absence of wrinkles formed on the surface of the electrical contact surface coating material 1. ⁇ : No cracks or wrinkles occur on all 5 test pieces ⁇ : Wrinkles appear on the surface of one or more test pieces, but no cracks occur on all 5 test pieces ⁇ : 1 or more Cracks occur in the test piece of
  • ⁇ Contact resistance value is less than 1.0 m ⁇
  • ⁇ Contact resistance value is 1.0 m ⁇ or more and less than 5.0 m ⁇
  • Contact resistance value is 5.0 m ⁇ or more
  • the conductive base material 2 was subjected to electrolytic degreasing and acid cleaning. Further, as a pretreatment of the conductive substrate 2 in Examples 18 and 19 of the present invention, after removing the oxide film on the surface by performing acid electrolysis after electrolytic degreasing, 500 g/L of nickel sulfate hexahydrate and 30 g of nickel sulfate hexahydrate were added. Nickel strike plating was performed using a nickel plating bath containing /L of nickel chloride and 30g/L of sulfuric acid.
  • an aqueous solution containing 50 g/L of silver cyanide and 100 g/L of potassium cyanide was prepared as an electrolytic plating solution.
  • 3L of electrolytic plating solution was put into a cylindrical plating electrolytic bath with an inner diameter of 120 mm, and the conductive substrate 2 after acid washing was immersed in the resulting alkaline cyan silver bath, and at a bath temperature of 25°C, 10A/
  • a silver-containing layer 3 was formed on the surface of the conductive base material 2 by electrolytic plating.
  • Surface coating material 1 for electrical contacts was prepared.
  • Inventive Example 12 and Comparative Examples 1 and 2 in order to contain zinc (Zn) as a second element in the electrolytic plating solution, 50 g/L of silver cyanide, 100 g/L of potassium cyanide, and 10 g/L of potassium cyanide were used. An aqueous solution containing zinc chloride was prepared.
  • Inventive Example 13 and Comparative Examples 3 and 4 in order to contain copper (Cu) as a second element in the electrolytic plating solution, 50 g/L of silver cyanide, 100 g/L of potassium cyanide, and 12 g of potassium cyanide were used. /L of copper chloride dihydrate was prepared.
  • Inventive Example 14 and Comparative Examples 5 and 6 in order to contain nickel (Ni) as a second element in the electrolytic plating solution, 50 g/L of silver cyanide, 100 g/L of potassium cyanide, and 12 g of potassium cyanide were used. /L of nickel chloride was prepared.
  • Invention Example 15 and Comparative Examples 7 and 8 in order to contain selenium (Se) as a second element, 50 g/L of silver cyanide, 100 g/L of potassium cyanide, and 2.2 mg of electrolytic plating solution were used. /L of potassium selenocyanate was prepared.
  • Invention Example 16 and Comparative Examples 9 and 10 in order to contain antimony (Sb) as a second element, 50 g/L of silver cyanide, 100 g/L of potassium cyanide, and 12 g of potassium cyanide were used as the electrolytic plating solution. /L of antimony trichloride was prepared.
  • the conductive substrate 2 was subjected to electrolytic degreasing and acid cleaning as pretreatment for the conductive substrate 2. Further, as a pretreatment of the conductive substrate 2 in Inventive Example 37, after removing the oxide film on the surface by performing acid electrolysis after electrolytic degreasing, 500 g/L of nickel sulfate hexahydrate and 30 g/L of nickel sulfate hexahydrate were added. Nickel strike plating was performed using a nickel plating bath containing 30 g/L of nickel chloride and 30 g/L of sulfuric acid. Furthermore, as a pretreatment for the conductive substrate 2 in Inventive Example 38, alkaline etching was performed using an aqueous solution containing 100 g/L of sodium hydroxide and 10 g/L of sodium gluconate.
  • an electrolytic plating solution for forming the intermediate layer 4 an aqueous solution containing 23 g/L of copper cyanide, 34 g/L of sodium cyanide, and 15 g/L of sodium carbonate was prepared. 3L of electrolytic plating solution was put into a cylindrical plating electrolytic bath with an inner diameter of 120 mm, and the conductive base material 2 after acid washing was immersed in the resulting copper plating bath, and at a bath temperature of 40°C, 5A/dm 2 was applied. By applying electricity at a current density, an intermediate layer 4 made of pure copper was formed on the surface of the conductive base material 2 by electrolytic plating.
  • an electrolytic plating solution for forming the silver-containing layer 3 an aqueous solution containing 50 g/L of silver cyanide and 100 g/L of potassium cyanide was prepared. 3L of electrolytic plating solution was put into a cylindrical plating electrolytic bath with an inner diameter of 120 mm, and the conductive base material 2 having the intermediate layer 4 was immersed in the resulting alkaline cyan silver bath, and at a bath temperature of 25° C., the conductive substrate 2 was heated at 10 A/d. By applying current at a current density of 2 , the silver-containing layer 3 was formed on the surface of the intermediate layer 4 by electrolytic plating.
  • a surface coating material 1A for electrical contacts was prepared, which was provided with layer 3 and further provided with intermediate layer 4 between conductive base material 2 and silver-containing layer 3.
  • the electrolytic plating solution for forming the silver-containing layer 3 in order to include zinc (Zn) as a second element in the silver-containing layer 3.
  • An aqueous solution containing silver cyanide, 100 g/L potassium cyanide, and 10 g/L zinc chloride was prepared.
  • the electrolytic plating solution for forming the silver-containing layer 3 contained copper (Cu) as a second element in the silver-containing layer 3 at 50 g/L.
  • An aqueous solution containing silver cyanide, 100 g/L potassium cyanide, and 12 g/L copper chloride dihydrate was prepared.
  • the electrolytic plating solution for forming the silver-containing layer 3 contained nickel (Ni) as a second element in the silver-containing layer 3, so that 50 g/L was used.
  • 3L of electrolytic plating solution was put into a cylindrical plating electrolytic bath with an inner diameter of 120 mm, and the conductive base material 2 having the intermediate layer 4 was immersed in the resulting alkaline cyan silver bath, and at a bath temperature of 25° C., the conductive substrate 2 was heated at 10 A/d.
  • the silver-containing layer 3 was formed on the surface of the intermediate layer 4 by electrolytic plating.
  • cold rolling is performed using rolling work rolls having diameters shown in Tables 3 and 4 at processing rates shown in Tables 3 and 4, thereby forming a silver-containing material that coats the surface of the conductive substrate 2.
  • a surface coating material 1A for electrical contacts was prepared, which was provided with layer 3 and further provided with intermediate layer 4 between conductive base material 2 and silver-containing layer 3.
  • the electrolytic plating solution for forming the silver-containing layer 3 contained antimony (Sb) as a second element in the silver-containing layer 3 at 50 g/L.
  • aqueous solution containing silver cyanide of 100 g/L, potassium cyanide of 100 g/L, and antimony trichloride of 12 g/L was prepared.
  • the electrolytic plating solution for forming the silver-containing layer 3 contained cobalt (Co) as a second element in the silver-containing layer 3 at 50 g/L.
  • An aqueous solution containing silver cyanide, 100 g/L potassium cyanide, and 10 g/L cobalt chloride was prepared.
  • 3L of electrolytic plating solution was put into a cylindrical plating electrolytic bath with an inner diameter of 120 mm, and the conductive base material 2 having the intermediate layer 4 was immersed in the resulting alkaline cyan silver bath, and at a bath temperature of 25° C., the conductive substrate 2 was heated at 10 A/d.
  • the silver-containing layer 3 was formed on the surface of the intermediate layer 4 by electrolytic plating.
  • cold rolling is performed using rolling work rolls having diameters shown in Tables 3 and 4 at processing rates shown in Tables 3 and 4, thereby forming a silver-containing material that coats the surface of the conductive substrate 2.
  • a surface coating material 1A for electrical contacts was prepared, which was provided with layer 3 and further provided with intermediate layer 4 between conductive base material 2 and silver-containing layer 3.
  • the conductive substrate 2 was subjected to electrolytic degreasing and acid cleaning as pretreatment for the conductive substrate 2. Further, as a pretreatment of the conductive substrate 2 in Invention Example 56, after removing the oxide film on the surface by performing acid electrolysis after electrolytic degreasing, 500 g/L of nickel sulfate hexahydrate and 30 g/L of nickel sulfate hexahydrate were added. Nickel strike plating was performed using a nickel plating bath containing 30 g/L of nickel chloride and 30 g/L of sulfuric acid. Furthermore, as a pretreatment for the conductive substrate 2 in Inventive Example 57, alkaline etching was performed using an aqueous solution containing 100 g/L of sodium hydroxide and 10 g/L of sodium gluconate.
  • an electrolytic plating solution for forming the intermediate layer 4 an aqueous solution containing 500 g/L of nickel sulfate hexahydrate, 30 g/L of nickel chloride, and 30 g/L of sulfuric acid was prepared. 3L of electrolytic plating solution was put into a cylindrical plating electrolytic bath with an inner diameter of 120 mm, and the conductive base material 2 after acid washing was immersed in the resulting nickel plating bath, and at a bath temperature of 55°C, a plating solution of 15 A/dm 2 was applied. By applying electricity at a current density, an intermediate layer 4 made of pure nickel was formed on the surface of the conductive base material 2 by electrolytic plating.
  • an electrolytic plating solution for forming the silver-containing layer 3 an aqueous solution containing 50 g/L of silver cyanide and 100 g/L of potassium cyanide was prepared. 3L of electrolytic plating solution was put into a cylindrical plating electrolytic bath with an inner diameter of 120 mm, and the conductive base material 2 having the intermediate layer 4 was immersed in the resulting alkaline cyan silver bath, and at a bath temperature of 25° C., the conductive substrate 2 was heated at 10 A/d. By applying current at a current density of 2 , the silver-containing layer 3 was formed on the surface of the intermediate layer 4 by electrolytic plating.
  • a surface coating material 1A for electrical contacts was prepared, which was provided with layer 3 and further provided with intermediate layer 4 between conductive base material 2 and silver-containing layer 3.
  • the electrolytic plating solution for forming the silver-containing layer 3 was 50 g/L in order to include zinc (Zn) as a second element in the silver-containing layer 3.
  • An aqueous solution containing silver cyanide, 100 g/L potassium cyanide, and 10 g/L zinc chloride was prepared.
  • the electrolytic plating solution for forming the silver-containing layer 3 contained copper (Cu) as a second element in the silver-containing layer 3 at 50 g/L.
  • An aqueous solution containing silver cyanide, 100 g/L potassium cyanide, and 12 g/L copper chloride dihydrate was prepared.
  • the electrolytic plating solution for forming the silver-containing layer 3 contained nickel (Ni) as a second element in the silver-containing layer 3, so that 50 g/L was used.
  • 3L of electrolytic plating solution was put into a cylindrical plating electrolytic bath with an inner diameter of 120 mm, and the conductive base material 2 having the intermediate layer 4 was immersed in the resulting alkaline cyan silver bath, and at a bath temperature of 25° C., the conductive substrate 2 was heated at 10 A/d.
  • the silver-containing layer 3 was formed on the surface of the intermediate layer 4 by electrolytic plating.
  • cold rolling is performed using rolling work rolls having diameters shown in Tables 3 and 4 at processing rates shown in Tables 3 and 4, thereby forming a silver-containing material that coats the surface of the conductive substrate 2.
  • a surface coating material 1A for electrical contacts was prepared, which was provided with layer 3 and further provided with intermediate layer 4 between conductive base material 2 and silver-containing layer 3.
  • Inventive Example 53 and Comparative Examples 43 and 44 50 g/L was used as the electrolytic plating solution for forming the silver-containing layer 3 in order to include selenium (Se) as a second element in the silver-containing layer 3.
  • An aqueous solution containing silver cyanide, 100 g/L potassium cyanide, and 2.2 mg/L potassium selenocyanate was prepared.
  • antimony (Sb) was included as a second element in the silver-containing layer 3 as an electrolytic plating solution for forming the silver-containing layer 3, so that 50 g/L was used.
  • An aqueous solution containing silver cyanide of 100 g/L, potassium cyanide of 100 g/L, and antimony trichloride of 12 g/L was prepared.
  • the electrolytic plating solution for forming the silver-containing layer 3 contained cobalt (Co) as a second element in the silver-containing layer 3 at 50 g/L.
  • An aqueous solution containing silver cyanide, 100 g/L potassium cyanide, and 10 g/L cobalt chloride was prepared.
  • 3L of electrolytic plating solution was put into a cylindrical plating electrolytic bath with an inner diameter of 120 mm, and the conductive base material 2 having the intermediate layer 4 was immersed in the resulting alkaline cyan silver bath, and at a bath temperature of 25° C., the conductive substrate 2 was heated at 10 A/d.
  • the silver-containing layer 3 was formed on the surface of the intermediate layer 4 by electrolytic plating.
  • cold rolling is performed using rolling work rolls having diameters shown in Tables 3 and 4 at processing rates shown in Tables 3 and 4, thereby forming a silver-containing material that coats the surface of the conductive substrate 2.
  • a surface coating material 1A for electrical contacts was prepared, which was provided with layer 3 and further provided with intermediate layer 4 between conductive base material 2 and silver-containing layer 3.
  • the surface coating materials for electrical contacts obtained in Examples 1 to 57 of the present invention have a ratio of the first total peak intensity (h 1 ) to the second total peak intensity (h 2 ).
  • (h 1 /h 2 ) is in the range of 1.0 or more and 3.0 or less
  • the bending workability is evaluated as “ ⁇ ” or “ ⁇ ”
  • the silver content when silver is used as the counterpart material.
  • the abrasion resistance of the layer was also evaluated as " ⁇ " or " ⁇ ”.
  • the surface coating materials for electrical contacts of Examples 1 to 57 of the present invention were evaluated as " ⁇ " or " ⁇ ” in the keystroke test results.
  • the surface coating materials for electrical contacts of Examples 1 to 57 of the present invention have low contact resistance of the silver-containing layer and are evaluated as “ ⁇ ” or “ ⁇ ”, and the contact resistance of the silver-containing layer after heating is low. The resistance was also low, and the heat resistance was rated as " ⁇ " or " ⁇ ".
  • the surface coating materials for electrical contacts obtained in Examples 1 to 57 of the present invention had excellent bending workability and also had high wear resistance of the silver-containing layer.
  • the surface coating materials for electrical contacts obtained in Comparative Examples 1 to 54 have a ratio (h 1 /h 2 ) of the first total peak intensity (h 1 ) to the second total peak intensity (h 2 ).
  • the range of 1.0 to 3.0 was not satisfied, and at least one of the bending workability and the wear resistance of the silver-containing layer when silver was used as a counterpart material was evaluated as "x". .
  • the half width of the peak derived from the Ag (111) plane was 0.15° or more (present invention examples 1 to 14, 16, 18 to 33, 35, 37 to 52, 54, 56), the abrasion resistance of the silver-containing layer when silver was used as the counterpart material and the results of the keystroke test were evaluated as " ⁇ ".
  • the surface coating materials for electrical contacts obtained in the examples in which the half width of the peak derived from the Ag (111) plane was less than 0.15° (Invention Examples 15, 17, 34, 36, 53, 55) were as follows: The abrasion resistance of the silver-containing layer when using silver as a mating material and the results of the keystroke test were rated as " ⁇ ".
  • examples in which the half width of the peak derived from the Ag (111) plane was 0.30° or less present invention examples 1 to 13, 15, 17 to 32, 34, 36 to 51, Although the surface coating material for electrical contacts obtained in 53, 55) was evaluated as " ⁇ " in bending workability, the half width of the peak derived from the Ag (111) plane was 0.30°.
  • the surface covering materials for electrical contacts obtained in the examples (inventive examples 14, 16, 33, 35, 52, and 54) that exceeded the standard were evaluated as "Good” in bending workability.
  • the electrical contacts obtained in the examples in which the content of the silver-containing layer was 99% by mass or more (Examples 1 to 11, 18 to 30, 37 to 49, 56, 57)
  • the surface coating material was evaluated as " ⁇ " for the contact resistance value, but the silver-containing layer content was less than 99% by mass (invention examples 12 to 17, 31 to 36, 50 to The surface coating material for electrical contacts obtained in 55) was evaluated as "Good” in terms of contact resistance value.
  • the surface coating materials for electrical contacts obtained in the examples (present invention examples 20 to 57) in which the intermediate layer 4 was provided between the conductive base material 2 and the silver-containing layer 3 had heat resistance.
  • the surfaces for electrical contacts obtained in the examples (inventive examples 1 to 19) that did not have the intermediate layer 4 between the conductive base material 2 and the silver-containing layer 3 The coating material was rated "Good" in terms of heat resistance.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
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Abstract

La présente invention fournit : un matériau revêtu en surface pour contacts électriques, le matériau revêtu en surface présentant une excellente aptitude au pliage, tout en ayant une surface qui est pourvue d'une couche contenant de l'argent qui est capable de supprimer l'adhérence et ainsi d'améliorer la résistance à l'usure dans les conditions qui correspondent à l'environnement d'utilisation réel ; et un contact électrique, un commutateur et une borne de connecteur, chacun utilisant ce matériau revêtu en surface pour des contacts électriques.　Un matériau revêtu en surface (1) pour contacts électriques selon la présente invention comprend un matériau de base conducteur (2) et une couche contenant de l'argent (3) qui recouvre au moins une surface du matériau de base conducteur (2). Par rapport à la couche contenant de l'argent (3), si h1 est une première intensité de pic totale qui est la somme de l'intensité de pic attribuée au plan d'Ag (111) et de l'intensité de pic attribuée à un plan qui est parallèle au plan d'Ag (111) tel que déterminé à partir du diagramme de diffraction par rayons X, et h2 est une seconde intensité de pic totale qui est la somme des autres intensités de pic, c'est-à-dire la valeur obtenue en soustrayant la première intensité de pic totale h1 de la somme de toutes les intensités de pic détectées, le rapport (h1/h2) entre la première intensité de pic totale (h1) et la seconde intensité de pic totale (h2) est dans la plage comprise entre 1,0 et 3,0.
PCT/JP2023/018332 2022-05-30 2023-05-16 Matériau revêtu en surface pour contacts électriques, et contact électrique, commutateur et borne de connecteur utilisant chacun celui-ci WO2023234015A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4920127B1 (fr) * 1970-06-26 1974-05-22
WO2011099574A1 (fr) * 2010-02-12 2011-08-18 古河電気工業株式会社 Matériau composite revêtu d'argent pour composant de contact amovible, son procédé de production et composant de contact amovible
WO2013137121A1 (fr) * 2012-03-14 2013-09-19 Ｄｏｗａメタルテック株式会社 Matériau de placage d'argent
JP2015110833A (ja) * 2013-11-08 2015-06-18 Ｄｏｗａメタルテック株式会社 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
JPS4920127B1 (fr) * 1970-06-26 1974-05-22
WO2011099574A1 (fr) * 2010-02-12 2011-08-18 古河電気工業株式会社 Matériau composite revêtu d'argent pour composant de contact amovible, son procédé de production et composant de contact amovible
WO2013137121A1 (fr) * 2012-03-14 2013-09-19 Ｄｏｗａメタルテック株式会社 Matériau de placage d'argent
JP2015110833A (ja) * 2013-11-08 2015-06-18 Ｄｏｗａメタルテック株式会社 銀めっき材およびその製造方法

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