WO2021181901A1 - 銀めっき材およびその製造方法 - Google Patents

銀めっき材およびその製造方法 Download PDF

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Publication number
WO2021181901A1
WO2021181901A1 PCT/JP2021/001990 JP2021001990W WO2021181901A1 WO 2021181901 A1 WO2021181901 A1 WO 2021181901A1 JP 2021001990 W JP2021001990 W JP 2021001990W WO 2021181901 A1 WO2021181901 A1 WO 2021181901A1
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WIPO (PCT)
Prior art keywords
silver
plated
layer
plating
plating layer
Prior art date
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PCT/JP2021/001990
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English (en)
French (fr)
Inventor
悠太郎 平井
健太郎 荒井
陽介 佐藤
Original Assignee
Ｄｏｗａメタルテック株式会社
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Application filed by Ｄｏｗａメタルテック株式会社 filed Critical Ｄｏｗａメタルテック株式会社
Priority to MX2022011191A priority Critical patent/MX2022011191A/es
Priority to EP21767420.9A priority patent/EP4083271A4/en
Priority to US17/910,250 priority patent/US20230093655A1/en
Priority to CN202180019093.0A priority patent/CN115210409A/zh
Publication of WO2021181901A1 publication Critical patent/WO2021181901A1/ja

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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B15/018—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of a noble metal or a noble metal alloy
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    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y10T428/2495—Thickness [relative or absolute]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/2495—Thickness [relative or absolute]
    • Y10T428/24967—Absolute thicknesses specified
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/24975—No layer or component greater than 5 mils thick
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/264—Up to 3 mils
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/264—Up to 3 mils
    • Y10T428/265—1 mil or less

Definitions

  • the present invention relates to a silver-plated material and a method for manufacturing the same, and in particular, a silver-plated material used as a material for contacts and terminal parts such as connectors, switches, and relays used for in-vehicle and consumer electrical wiring and its manufacture. Regarding the method.
  • a tin-plated material obtained by tin-plating a material such as copper or a copper alloy or stainless steel is inexpensive, but inferior in corrosion resistance in a high-temperature environment.
  • the gold-plated material obtained by subjecting these materials to gold plating has excellent corrosion resistance and high reliability, but the cost is high.
  • the silver-plated material obtained by subjecting these materials to silver plating is cheaper than the gold-plated material and has excellent corrosion resistance as compared with the tin-plated material.
  • silver-plated material is soft and easily worn, when it is used as a material for connection terminals, it is likely to adhere and wear due to insertion and removal or sliding, and the surface is scraped when the connection terminal is inserted. There is a problem that the friction coefficient becomes high and the insertion force becomes high.
  • an object of the present invention is to provide a silver-plated material having better fine sliding wear characteristics than the conventional one and a method for producing the same.
  • the present inventors have made a first silver plating layer, a zinc plating layer as an intermediate plating layer, and a second silver plating layer as a surface layer on the base material.
  • a silver-plated material having superior fine sliding wear characteristics can be produced by forming the above in this order, and have completed the present invention.
  • the first silver plating layer, the zinc plating layer as the intermediate plating layer, and the second silver plating layer as the surface layer are formed in this order on the base material. It is characterized by.
  • the thickness of the first silver-plated layer is preferably 0.1 to 10 ⁇ m
  • the thickness of the zinc-plated layer is preferably 0.1 to 5 ⁇ m
  • the thickness of the galvanized layer is preferably 0.1 to 10.
  • the thickness of the second silver plating layer is preferably 0.1 to 10 ⁇ m.
  • a base plating layer is formed between the material and the first silver plating layer.
  • the base plating layer is preferably made of nickel or a nickel alloy, and the thickness of the base plating layer is preferably 0.1 to 5 ⁇ m.
  • the base material is preferably made of copper or a copper alloy, and the Vickers hardness HV of the silver-plated material is preferably 80 to 220.
  • a first silver-plated layer, a zinc-plated layer as an intermediate plating layer, and a second silver-plated layer as a surface layer are formed on a base material by electroplating. Is formed in this order.
  • the first silver plating layer and the second silver plating layer are electroplated in a silver plating solution composed of an aqueous solution containing silver potassium cyanide, potassium cyanide and potassium selenociate. It is preferable to form by.
  • the thickness of the first silver plating layer is preferably 0.1 to 10 ⁇ m
  • the thickness of the zinc plating layer is preferably 0.1 to 5 ⁇ m, which is the first with respect to the thickness of the zinc plating layer.
  • the ratio of the thickness of the silver-plated layer is preferably 0.1 to 10.
  • the thickness of the second silver plating layer is preferably 0.1 to 10 ⁇ m.
  • the base plating layer is preferably made of nickel or a nickel alloy, and the thickness of the base plating layer is preferably 0.1 to 5 ⁇ m. Further, the base material is preferably made of copper or a copper alloy.
  • a base plating layer 12 a first silver plating layer (lower silver plating layer) 14 made of silver, and zinc as an intermediate plating layer are placed on the base material 10.
  • the zinc plating layer 16 As an intermediate plating layer between the first silver plating layer 14 and the second silver plating layer 18 in this way, an alloy of zinc and silver is formed at the interface of each plating layer.
  • an alloy of zinc and silver is formed at the interface of each plating layer.
  • the first silver-plated layer 14 and the second silver-plated layer 18 preferably have high conductivity, are composed of 99% by mass or more of silver, and have a small amount other than silver. Other elements (for example, a small amount of elements such as Se and Sb due to brighteners, impurities, etc.) may be contained.
  • the thickness of the first silver plating layer 14 is preferably 0.1 to 10 ⁇ m, more preferably 0.2 to 8 ⁇ m, and most preferably 0.3 to 6 ⁇ m.
  • the thickness of the second silver plating layer 18 is preferably 0.1 to 10 ⁇ m, more preferably 0.2 to 8 ⁇ m, and most preferably 0.3 to 6 ⁇ m.
  • the zinc plating layer 16 is made of 95% by mass or more (preferably 99% by mass or more) of zinc, and may contain a small amount of other elements other than zinc (for example, elements caused by impurities or the like).
  • the thickness of the zinc plating layer 16 is preferably 0.1 to 5 ⁇ m, more preferably 0.2 to 3 ⁇ m, and most preferably 0.3 to 2 ⁇ m.
  • the ratio of the thickness of the first silver-plated layer 14 to the thickness of the zinc-plated layer 16 is preferably 0.1 to 10, and more preferably 0.3 to 9.
  • the base plating layer 12 is preferably made of nickel or a nickel alloy.
  • the thickness of the base plating layer 12 is preferably 0.1 to 5 ⁇ m, more preferably 0.3 to 3 ⁇ m.
  • the base material 10 is preferably made of copper or a copper alloy.
  • the Vickers hardness HV of the silver-plated material is preferably 80 to 220, more preferably 120 to 200, and most preferably 130 to 180.
  • a base plating layer 12 made of nickel or a nickel alloy and a base plating layer 12 made of silver are formed on a base material 10 made of copper or a copper alloy by electroplating.
  • the silver plating layer 14 of No. 1 the zinc plating layer 16 made of zinc as an intermediate plating layer, and the second silver plating layer 18 made of silver as a surface layer are formed in this order.
  • the first silver plating layer 14 and the second silver plating layer 18 are placed in a silver plating solution composed of an aqueous solution containing silver potassium cyanide, potassium cyanide and potassium selenociate. , It is preferable to form by performing electroplating.
  • Example 1 a rolled plate made of oxygen-free copper (C1020 1 / 2H) of 67 mm ⁇ 50 mm ⁇ 0.3 mm was prepared as a base material (material to be plated), and as a pretreatment of the material to be plated, the material to be plated and a SUS plate were prepared.
  • the material to be plated was used as a cathode
  • the SUS plate was used as an anode
  • electrolytic degreasing was performed at a voltage of 5 V for 30 seconds, washed with water, and then pickled in 3% sulfuric acid for 15 seconds.
  • a matte nickel plating solution consisting of an aqueous solution containing 540 g / L nickel sulfamate tetrahydrate, 25 g / L nickel chloride and 35 g / L boric acid.
  • a cathode the nickel electrode plate as an anode, and performing stirring solution temperature 55 ° C. 80 seconds electroplating at a current density of 5A / dm 2 in at 500rpm by stirrer (matte nickel plating), a thickness of 1 ⁇ m as a base plating film
  • stirrer mimetric nickel plating
  • a silver strike plating solution consisting of an aqueous solution containing 3 g / L of silver potassium cyanide (KAg (CN) 2 ) and 90 g / L of potassium cyanide (KCN)
  • the material to be plated having a base plating film formed is used as a cathode.
  • electroplating was performed at room temperature (25 ° C.) for 10 seconds at a current density of 1.4 A / dm 2 while stirring at 500 rpm with a stirrer to form a silver strike plating film. After that, it was washed with water to thoroughly wash away the silver strike plating solution.
  • a silver plating solution consisting of an aqueous solution containing 175 g / L of silver potassium cyanide (KAg (CN) 2 ), 95 g / L of potassium cyanide (KCN) and 102 mg / L of potassium selenocyanate (KSeCN), silver was added.
  • a first silver-plated film lower silver-plated film having a thickness of 1 ⁇ m
  • the mixture was washed with water.
  • the first silver plating film was formed in a galvanizing solution consisting of an aqueous solution containing 42 g / L of zinc oxide (ZnO), 120 g / L of potassium cyanide (KCN), and 116 g / L of potassium hydroxide (KOH).
  • the ratio of the thickness of the first silver plating film to the thickness of the zinc plating film was 2.
  • a silver plating solution consisting of an aqueous solution containing 175 g / L of potassium cyanide (KAg (CN) 2 ), 95 g / L of potassium cyanide (KCN), and 102 mg / L of potassium selenociate (KSeCN).
  • Electroplating at a current density of 5 A / dm 2 at a liquid temperature of 18 ° C. while stirring at 500 rpm with a stirrer using the material to be plated on which the plating film is formed as a cathode and a silver electrode plate as an anode.
  • a second silver-plated film (upper silver-plated film) having a thickness of 3.5 ⁇ m was formed, washed with water, and dried.
  • the Vickers hardness HV on the surface of the silver-plated material thus obtained was subjected to a measurement load of 10 gf for 10 seconds using a micro-hardness tester (HM-221 manufactured by Mitutoyo Co., Ltd.), and JIS Z2244. When measured according to the above, it was 132.
  • Example 2 By the same method as in Example 1, except that the electroplating time for forming the first silver plating film was 90 seconds and the electroplating time for forming the second silver plating film was 10 seconds. A silver-plated material was produced.
  • the thicknesses of the matte nickel plating film, the first silver plating film, the zinc plating film and the second silver plating film of this silver plating material were 1 ⁇ m, 4 ⁇ m, 0.5 ⁇ m and 0.5 ⁇ m, respectively.
  • the ratio of the thickness of the first silver plating film to the thickness of the zinc plating film was 8.
  • the Vickers hardness HV of the silver-plated film was measured by the same method as in Example 1, and the fine sliding wear characteristics were evaluated. As a result, the Vickers hardness HV was 147. Further, it was found that the number of reciprocations of the fine sliding operation until the contact resistance exceeded 0.5 m ⁇ was 10,000 times, and the fine sliding wear characteristic was excellent.
  • Example 3 By the same method as in Example 1, except that the electroplating time for forming the first silver plating film was 75 seconds and the electroplating time for forming the second silver plating film was 20 seconds. A silver-plated material was produced.
  • the thicknesses of the matte nickel plating film, the first silver plating film, the zinc plating film and the second silver plating film of this silver plating material were 1 ⁇ m, 3.5 ⁇ m, 0.5 ⁇ m and 1 ⁇ m, respectively.
  • the ratio of the thickness of the first silver plating film to the thickness of the zinc plating film was 7.
  • the Vickers hardness HV of the silver-plated film was measured by the same method as in Example 1, and the fine sliding wear characteristics were evaluated. As a result, the Vickers hardness HV was 147. Further, it was found that the number of reciprocations of the fine sliding operation until the contact resistance exceeded 0.5 m ⁇ was 10,000 times, and the fine sliding wear characteristic was excellent.
  • Example 4 By the same method as in Example 1, except that the electroplating time for forming the first silver plating film was 63 seconds and the electroplating time for forming the second silver plating film was 30 seconds. A silver-plated material was produced.
  • the thicknesses of the matte nickel plating film, the first silver plating film, the zinc plating film and the second silver plating film of this silver plating material were 1 ⁇ m, 3 ⁇ m, 0.5 ⁇ m and 1.5 ⁇ m, respectively. In this example, the ratio of the thickness of the first silver plating film to the thickness of the zinc plating film was 6.
  • the Vickers hardness HV of the silver-plated film was measured by the same method as in Example 1, and the fine sliding wear characteristics were evaluated. As a result, the Vickers hardness HV was 149. Further, the number of reciprocations of the fine sliding operation until the contact resistance exceeded 0.5 m ⁇ was 9,000 times, and it was found that the fine sliding wear characteristics were excellent.
  • the electroplating time for forming the first silver plating film is 10 seconds
  • the electroplating time for forming the zinc plating film is 40 seconds
  • the electroplating time for forming the second silver plating film is 40 seconds.
  • a silver-plated material was produced by the same method as in Example 1 except that the time was 75 seconds.
  • the thicknesses of the matte nickel plating film, the first silver plating film, the zinc plating film and the second silver plating film of this silver plating material were 1 ⁇ m, 0.5 ⁇ m, 1 ⁇ m and 3.5 ⁇ m, respectively.
  • the ratio of the thickness of the first silver plating film to the thickness of the zinc plating film was 0.5.
  • the Vickers hardness HV of the silver-plated film was measured by the same method as in Example 1, and the fine sliding wear characteristics were evaluated. As a result, the Vickers hardness HV was 152. Further, it was found that the number of reciprocations of the fine sliding operation until the contact resistance exceeded 0.5 m ⁇ was 5,000 times, and the fine sliding wear characteristic was excellent.
  • Example 6 By the same method as in Example 5, except that the electroplating time for forming the first silver plating film was 20 seconds and the electroplating time for forming the second silver plating film was 63 seconds. A silver-plated material was produced.
  • the thicknesses of the matte nickel plating film, the first silver plating film, the zinc plating film and the second silver plating film of this silver plating material were 1 ⁇ m, 1 ⁇ m, 1 ⁇ m and 3 ⁇ m, respectively.
  • the ratio of the thickness of the first silver plating film to the thickness of the zinc plating film was 1.
  • the Vickers hardness HV of the silver-plated film was measured by the same method as in Example 1, and the fine sliding wear characteristics were evaluated. As a result, the Vickers hardness HV was 159. Further, the number of reciprocations of the fine sliding operation until the contact resistance exceeded 0.5 m ⁇ was 7,000 times, and it was found that the fine sliding wear characteristics were excellent.
  • Example 7 By the same method as in Example 5, except that the electroplating time for forming the first silver plating film was 75 seconds and the electroplating time for forming the second silver plating film was 10 seconds. A silver-plated material was produced.
  • the thicknesses of the matte nickel plating film, the first silver plating film, the zinc plating film and the second silver plating film of this silver plating material were 1 ⁇ m, 3.5 ⁇ m, 1 ⁇ m and 0.5 ⁇ m, respectively.
  • the ratio of the thickness of the first silver plating film to the thickness of the zinc plating film was 3.5.
  • the Vickers hardness HV of the silver-plated film was measured by the same method as in Example 1, and the fine sliding wear characteristics were evaluated. As a result, the Vickers hardness HV was 159. Further, it was found that the number of reciprocations of the fine sliding operation until the contact resistance exceeded 0.5 m ⁇ was 5,000 times, and the fine sliding wear characteristic was excellent.
  • Example 8 By the same method as in Example 5, except that the electroplating time for forming the first silver plating film was 53 seconds and the electroplating time for forming the second silver plating film was 30 seconds. A silver-plated material was produced.
  • the thicknesses of the matte nickel plating film, the first silver plating film, the zinc plating film and the second silver plating film of this silver plating material were 1 ⁇ m, 2.5 ⁇ m, 1 ⁇ m and 1.5 ⁇ m, respectively.
  • the ratio of the thickness of the first silver plating film to the thickness of the zinc plating film was 2.5.
  • the Vickers hardness HV of the silver-plated film was measured by the same method as in Example 1, and the fine sliding wear characteristics were evaluated. As a result, the Vickers hardness HV was 151. Further, it was found that the number of reciprocations of the fine sliding operation until the contact resistance exceeded 0.5 m ⁇ was 5,000 times, and the fine sliding wear characteristic was excellent.
  • Example 9 By the same method as in Example 7, except that the electroplating time for forming the first silver plating film was 42 seconds and the electroplating time for forming the second silver plating film was 42 seconds. A silver-plated material was produced.
  • the thicknesses of the matte nickel plating film, the first silver plating film, the zinc plating film and the second silver plating film of this silver plating material were 1 ⁇ m, 2 ⁇ m, 1 ⁇ m and 2 ⁇ m, respectively.
  • the ratio of the thickness of the first silver plating film to the thickness of the zinc plating film was 2.
  • the Vickers hardness HV of the silver-plated film was measured by the same method as in Example 1, and the fine sliding wear characteristics were evaluated. As a result, the Vickers hardness HV was 155. Further, it was found that the number of reciprocations of the fine sliding operation until the contact resistance exceeded 0.5 m ⁇ was 10,000 times, and the fine sliding wear characteristic was excellent.
  • a silver-plated material was produced by the same method as in Example 7 except that the electroplating time for forming the second silver-plated film was 90 seconds without forming the first silver-plated film.
  • the thicknesses of the matte nickel plating film, the first plating film, the zinc plating film and the second silver plating film of this silver plating material were 1 ⁇ m, 0 ⁇ m, 1 ⁇ m and 4 ⁇ m, respectively.
  • the ratio of the thickness of the first silver plating film to the thickness of the zinc plating film was 0.
  • the Vickers hardness HV of the silver-plated film was measured by the same method as in Example 1, and the fine sliding wear characteristics were evaluated. As a result, the Vickers hardness HV was 144. Further, it was found that the number of reciprocations of the fine sliding operation until the contact resistance exceeded 0.5 m ⁇ was 1,000 times, and the fine sliding wear characteristic was poor.
  • the silver plating material was prepared by the same method as in Example 1 except that the electroplating time for forming the first silver plating film was 105 seconds and the zinc plating film and the second silver plating film were not formed. Made.
  • the thicknesses of the matte nickel plating film, the first plating film, the zinc plating film and the second silver plating film of this silver plating material were 1 ⁇ m, 5 ⁇ m, 0 ⁇ m and 0 ⁇ m, respectively.
  • the Vickers hardness HV of the silver-plated film was measured by the same method as in Example 1, and the fine sliding wear characteristics were evaluated. As a result, the Vickers hardness HV was 134. Further, it was found that the number of reciprocations of the fine sliding operation until the contact resistance exceeded 0.5 m ⁇ was 3,000 times, and the fine sliding wear characteristic was poor.
  • a plating material was produced by the same method as in Example 9 except that a copper plating film was formed instead of the zinc plating film as the intermediate plating film.
  • This copper plating film is made of pure copper using the material to be plated on which the first silver plating film is formed as a cathode in a copper plating solution consisting of an aqueous solution containing 260 g / L of copper cyanide and 8 g / L of potassium cyanide. It was formed by electroplating with an electrode plate as an anode at a liquid temperature of 50 ° C. and a current density of 7.4 A / dm 2 for 50 seconds while stirring with a stirrer at 500 rpm.
  • the thicknesses of the matte nickel plating film, the first plating film, the copper plating film and the second silver plating film of this silver plating material were 1 ⁇ m, 2 ⁇ m, 1 ⁇ m and 2 ⁇ m, respectively.
  • the Vickers hardness HV of the silver-plated film was measured by the same method as in Example 1, and the fine sliding wear characteristics were evaluated. As a result, the Vickers hardness HV was 136. Further, it was found that the number of reciprocations of the fine sliding operation until the contact resistance exceeded 0.5 m ⁇ was 2,000 times, and the fine sliding wear characteristic was poor.
  • a plating material was produced by the same method as in Example 9 except that a tin plating film was formed instead of the zinc plating film as the intermediate plating film.
  • a tin plating film in a tin plating solution composed of an aqueous solution containing tin organic acid and an organic acid, the material to be plated on which the first silver plating film is formed is used as a cathode, and a pure tin electrode plate is used as an anode, and stirrer is used. It was formed by electroplating at a current density of 10 A / dm 2 for 20 seconds at a liquid temperature of 25 ° C. while stirring at 500 rpm.
  • the thicknesses of the matte nickel plating film, the first plating film, the tin plating film, and the second silver plating film of this silver plating material were 1 ⁇ m, 2 ⁇ m, 1 ⁇ m, and 2 ⁇ m, respectively.
  • the Vickers hardness HV of the silver-plated film was measured by the same method as in Example 1, and the fine sliding wear characteristics were evaluated. As a result, the Vickers hardness HV was 109. Further, it was found that the number of reciprocations of the fine sliding operation until the contact resistance exceeded 0.5 m ⁇ was 2,000 times, and the fine sliding wear characteristic was poor.
  • a plating material was produced by the same method as in Example 9 except that a nickel plating film was formed instead of the zinc plating film as the intermediate plating film.
  • This nickel-plated film is the first in a matte nickel plating solution consisting of an aqueous solution containing 540 g / L of nickel sulfamate tetrahydrate, 25 g / L of nickel chloride, and 35 g / L of boric acid. It was formed by electroplating with a nickel electrode plate as an anode and a nickel electrode plate as an anode at a liquid temperature of 55 ° C. and a current density of 5 A / dm 2 for 80 seconds while stirring at 500 rpm with a stirrer.
  • the thicknesses of the matte nickel plating film as the base plating film of the silver plating material, the first plating film, the nickel plating film as the intermediate plating film, and the second silver plating film are 1 ⁇ m, 2 ⁇ m, 1 ⁇ m, and 2 ⁇ m, respectively. Met.
  • the Vickers hardness HV of the silver-plated film was measured by the same method as in Example 1, and the fine sliding wear characteristics were evaluated. As a result, the Vickers hardness HV was 171. Further, it was found that the number of reciprocations of the fine sliding operation until the contact resistance exceeded 0.5 m ⁇ was 3,000 times, and the fine sliding wear characteristic was poor.
  • Tables 1 and 2 show the production conditions and characteristics of the silver-plated materials obtained in these Examples and Comparative Examples.
  • Base material 12 Base plating layer 14 First silver plating layer 16 Intermediate plating layer 18 Second silver plating layer

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Abstract

従来よりも微摺動摩耗特性に優れた銀めっき材およびその製造方法を提供する。銅または銅合金からなる基材１０上に、電気めっきにより、ニッケルまたはニッケル合金からなる下地めっき層１２と、銀からなる第１の銀めっき層（下側銀めっき層）１４と、中間めっき層としての亜鉛からなる亜鉛めっき層１６と、表層としての銀からなる第２の銀めっき層（上側銀めっき層）１８とをこの順に形成することによって、銀めっき材を製造する。

Description

銀めっき材およびその製造方法
　本発明は、銀めっき材およびその製造方法に関し、特に、車載用や民生用の電気配線に使用されるコネクタ、スイッチ、リレーなどの接点や端子部品の材料として使用される銀めっき材およびその製造方法に関する。
　従来、コネクタやスイッチなどの接点や端子部品などの材料として、銅または銅合金やステンレス鋼などの比較的安価で耐食性や機械的特性などに優れた素材に、電気特性や半田付け性などの必要な特性に応じて、錫、銀、金などのめっきを施しためっき材が使用されている。
　銅または銅合金やステンレス鋼などの素材に錫めっきを施した錫めっき材は、安価であるが、高温環境下における耐食性に劣っている。また、これらの素材に金めっきを施した金めっき材は、耐食性に優れ、信頼性が高いが、コストが高くなる。一方、これらの素材に銀めっきを施した銀めっき材は、金めっき材と比べて安価であり、錫めっき材と比べて耐食性に優れている。
　また、コネクタやスイッチなどの接点や端子部品などの材料は、コネクタの挿抜やスイッチの摺動に伴う耐摩耗性も要求される。
　しかし、銀めっき材は、軟質で摩耗し易いため、接続端子などの材料として使用すると、挿抜や摺動により凝着して凝着摩耗が生じ易くなり、また、接続端子の挿入時に表面が削られて摩擦係数が高くなって挿入力が高くなるという問題がある。
　このような問題を解消するため、銅または銅合金からなる基材とこの基材の最表面に積層された銀被覆層との間に、銅、ニッケル、亜鉛、クロムまたはこれらの１種以上の金属を含有する合金からなるめっき層を中間層として備え、銀被覆層の表面の算術平均粗さＲａが０．１μｍ以上１０μｍ以下であり、銀被覆層の表面から厚さ方向の中央位置まで圧子を押し込んで測定した押し込み硬さが、基材の押し込み硬さの０．３倍以上１倍以下である金属材料が提案されている（例えば、特許文献１参照）。
特開２０１９－２０５６号公報（段落番号０００６）
　しかし、特許文献１に記載された金属材料を端子部品の材料として使用すると、雄端子と雌端子の接点部間の僅かな距離の摺動によって、最表層の銀めっき層が摩耗（微摺動摩耗）し易くなり、このような微摺動摩耗によって接触信頼性が損なわれるという問題がある。
　したがって、本発明は、このような従来の問題点に鑑み、従来よりも微摺動摩耗特性に優れた銀めっき材およびその製造方法を提供することを目的とする。
　本発明者らは、上記課題を解決するために鋭意研究した結果、基材上に、第１の銀めっき層と、中間めっき層としての亜鉛めっき層と、表層としての第２の銀めっき層をこの順に形成すれば、従来よりも微摺動摩耗特性に優れた銀めっき材を製造することができることを見出し、本発明を完成するに至った。
　すなわち、本発明による銀めっき材は、基材上に、第１の銀めっき層と、中間めっき層としての亜鉛めっき層と、表層としての第２の銀めっき層がこの順に形成されていることを特徴とする。
　この銀めっき材において、第１の銀めっき層の厚さは０．１～１０μｍであるのが好ましく、亜鉛めっき層の厚さは０．１～５μｍであるのが好ましく、亜鉛めっき層の厚さに対する第１の銀めっき層の厚さの比は０．１～１０であるのが好ましい。また、第２の銀めっき層の厚さは０．１～１０μｍであるのが好ましい。また、素材と第１の銀めっき層との間に下地めっき層が形成されているのが好ましい。この下地めっき層はニッケルまたはニッケル合金からなるのが好ましく、下地めっき層の厚さは０．１～５μｍであるのが好ましい。さらに、基材は銅または銅合金からなるのが好ましく、銀めっき材のビッカース硬さＨＶは８０～２２０であるのが好ましい。
　また、本発明による銀めっき材の製造方法は、基材上に、電気めっきにより、第１の銀めっき層と、中間めっき層としての亜鉛めっき層と、表層としての第２の銀めっき層とをこの順に形成することを特徴とする。
　この銀めっき材の製造方法では、第１の銀めっき層と第２の銀めっき層を、シアン化銀カリウムとシアン化カリウムとセレノシアン酸カリウムを含む水溶液からなる銀めっき液中において、電気めっきを行うことにより形成するのが好ましい。また、第１の銀めっき層の厚さは０．１～１０μｍであるのが好ましく、亜鉛めっき層の厚さは０．１～５μｍであるのが好ましく、亜鉛めっき層の厚さに対する第１の銀めっき層の厚さの比は０．１～１０であるのが好ましい。また、第２の銀めっき層の厚さは０．１～１０μｍであるのが好ましい。また、素材と第１の銀めっき層との間に、電気めっきにより、下地めっき層を形成するのが好ましい。この下地めっき層はニッケルまたはニッケル合金からなるのが好ましく、下地めっき層の厚さは０．１～５μｍであるのが好ましい。さらに、基材は銅または銅合金からなるのが好ましい。
　本発明によれば、従来よりも微摺動摩耗特性に優れた銀めっき材およびその製造方法を提供することができる。
本発明による銀めっき材の実施の形態を概略的に示す断面図である。
　以下、添付図面を参照して、本発明による銀めっき材およびその製造方法の実施の形態を詳細に説明する。
　図１に示す実施の形態の銀めっき材では、基材１０上に、下地めっき層１２と、銀からなる第１の銀めっき層（下側銀めっき層）１４と、中間めっき層としての亜鉛からなる亜鉛めっき層１６と、表層としての銀からなる第２の銀めっき層（上側銀めっき層）１８がこの順に形成されている。
　このように第１の銀めっき層１４と第２の銀めっき層１８の間に中間めっき層として亜鉛めっき層１６を形成することにより、各めっき層の界面において亜鉛と銀の合金を形成して銀めっき材の硬度を高くするとともに、銀めっき材を接続端子などの材料として使用した場合に、挿抜や摺動により凝着して凝着摩耗が生じるのを抑制することができる。
　この実施の形態の銀めっき材においてにおいて、第１の銀めっき層１４と第２の銀めっき層１８は、高い導電率を有するのが好ましく、９９質量％以上の銀からなり、銀以外の少量の他の元素（例えば、光沢剤や不純物などに起因する少量のＳｅやＳｂなどの元素）を含んでもよい。第１の銀めっき層１４の厚さは、０．１～１０μｍであるのが好ましく、０．２～８μｍであるのがさらに好ましく、０．３～６μｍであるのが最も好ましい。第２の銀めっき層１８の厚さは、０．１～１０μｍであるのが好ましく、０．２～８μｍであるのがさらに好ましく、０．３～６μｍであるのが最も好ましい。
　亜鉛めっき層１６は、９５質量％以上（好ましくは９９質量％以上）の亜鉛からなり、亜鉛以外の少量の他の元素（例えば、不純物などに起因する元素）を含んでもよい。亜鉛めっき層１６の厚さは、０．１～５μｍであるのが好ましく、０．２～３μｍであるのがさらに好ましく、０．３～２μｍであるのが最も好ましい。亜鉛めっき層１６の厚さに対する第１の銀めっき層１４の厚さの比は、０．１～１０であるのが好ましく、０．３～９であるのがさらに好ましい。
　下地めっき層１２は、ニッケルまたはニッケル合金からなるのが好ましい。下地めっき層１２の厚さは、０．１～５μｍであるのが好ましく、０．３～３μｍであるのがさらに好ましい。
　基材１０は、銅または銅合金からなるのが好ましい。また、銀めっき材のビッカース硬さＨＶは、８０～２２０であるのが好ましく、１２０～２００であるのがさらに好ましく、１３０～１８０であるのが最も好ましい。
　また、図１に示す銀めっき材の製造方法の実施の形態では、銅または銅合金からなる基材１０上に、電気めっきにより、ニッケルまたはニッケル合金からなる下地めっき層１２と、銀からなる第１の銀めっき層１４と、中間めっき層としての亜鉛からなる亜鉛めっき層１６と、表層としての銀からなる第２の銀めっき層１８とをこの順に形成する。
　この銀めっき材の製造方法の実施の形態では、第１の銀めっき層１４と第２の銀めっき層１８を、シアン化銀カリウムとシアン化カリウムとセレノシアン酸カリウムを含む水溶液からなる銀めっき液中において、電気めっきを行うことにより形成するのが好ましい。
　以下、本発明による銀めっき材およびその製造方法の実施例について詳細に説明する。
［実施例１］
　まず、基材（被めっき材）として６７ｍｍ×５０ｍｍ ×０．３ｍｍの無酸素銅（Ｃ１０２０　１／２Ｈ）からなる圧延板を用意し、この被めっき材の前処理として、被めっき材とＳＵＳ板をアルカリ脱脂液に入れ、被めっき材を陰極とし、ＳＵＳ板を陽極として、電圧５Ｖで３０秒間電解脱脂を行い、水洗した後、３％硫酸中で１５秒間酸洗を行った。
　次に、５４０ｇ／Ｌのスルファミン酸ニッケル四水和物と２５ｇ／Ｌの塩化ニッケルと３５ｇ／Ｌのホウ酸を含む水溶液からなる無光沢ニッケルめっき液中において、前処理を行った被めっき材を陰極とし、ニッケル電極板を陽極として、スターラにより５００ｒｐｍで撹拌しながら液温５５℃において電流密度５Ａ／ｄｍ２で８０秒間電気めっき（無光沢ニッケルめっき）を行って、下地めっき皮膜として厚さ１μｍの無光沢ニッケルめっき皮膜を形成した後、水洗した。
　次に、３ｇ／Ｌのシアン化銀カリウム（ＫＡｇ（ＣＮ）２）と９０ｇ／Ｌのシアン化カリウム（ＫＣＮ）を含む水溶液からなる銀ストライクめっき液中において、下地めっき皮膜を形成した被めっき材を陰極とし、白金で被覆したチタン電極板を陽極として、スターラにより５００ｒｐｍで撹拌しながら室温（２５℃）において電流密度１．４Ａ／ｄｍ２で１０秒間電気めっきを行って、銀ストライクめっき皮膜を形成した後、水洗して銀ストライクめっき液を十分に洗い流した。
　次に、１７５ｇ／Ｌのシアン化銀カリウム（ＫＡｇ（ＣＮ）２）と９５ｇ／Ｌのシアン化カリウム（ＫＣＮ）と１０２ｍｇ／Ｌのセレノシアン酸カリウム（ＫＳｅＣＮ）を含む水溶液からなる銀めっき液中において、銀ストライクめっき皮膜を形成した被めっき材を陰極とし、銀電極板を陽極として、スターラにより５００ｒｐｍで撹拌しながら液温１８℃において電流密度５Ａ／ｄｍ２で２０秒間電気めっき（第１の銀めっき）を行って、厚さ１μｍの第１の銀めっき皮膜（下側銀めっき皮膜）を形成した後、水洗した。
　次に、４２ｇ／Ｌの酸化亜鉛（ＺｎＯ）と１２０ｇ／Ｌのシアン化カリウム（ＫＣＮ）と１１６ｇ／Ｌの水酸化カリウム（ＫＯＨ）を含む水溶液からなる亜鉛めっき液中において、第１の銀めっき皮膜を形成した被めっき材を陰極とし、白金で被覆したチタン電極板を陽極として、スターラにより５００ｒｐｍで撹拌しながら液温２５℃において電流密度５Ａ／ｄｍ２で２０秒間電気めっきを行って、中間めっき皮膜として厚さ０．５μｍの亜鉛めっき皮膜を形成した後、水洗した。なお、本実施例において、亜鉛めっき皮膜の厚さに対する第１の銀めっき皮膜の厚さの比は２であった。
　次に、１７５ｇ／Ｌのシアン化銀カリウム（ＫＡｇ（ＣＮ）２）と９５ｇ／Ｌのシアン化カリウム（ＫＣＮ）と１０２ｍｇ／Ｌのセレノシアン酸カリウム（ＫＳｅＣＮ）を含む水溶液からなる銀めっき液中において、亜鉛めっき皮膜を形成した被めっき材を陰極とし、銀電極板を陽極として、スターラにより５００ｒｐｍで撹拌しながら液温１８℃において電流密度５Ａ／ｄｍ２で７５秒間電気めっき（第２の銀めっき）を行って、厚さ３．５μｍの第２の銀めっき皮膜（上側銀めっき皮膜）を形成した後、水洗し、乾燥した。
　このようにして得られた銀めっき材の表面のビッカース硬さＨＶを、微小硬さ試験機（株式会社ミツトヨ製のＨＭ－２２１）を使用して、測定荷重１０ｇｆを１０秒間加えて、ＪＩＳ　Ｚ２２４４に準じて測定したところ、１３２であった。
　また、上記の銀めっき材を２枚用意し、一方をインデント加工（内側Ｒ＝１．５ｍｍ）して圧子として使用し、他方を平板状の評価試料として使用し、精密摺動試験装置（株式会社山崎精機研究所製のＣＲＳ－Ｇ２０５０－ＤＷＡ）により、評価試料に圧子を一定の加重（５Ｎ）で押し当てながら、微摺動動作（摺動距離０．１ｍｍ、摺動速度０．２ｍｍ／ｓ）を継続し、接触抵抗が０．５ｍΩを超えるまでの微摺動動作の往復回数を数えた。その結果、接触抵抗が０．５ｍΩを超えるまでの微摺動動作の往復回数は６，０００回であり、微摺動摩耗特性に優れていることがわかった。
［実施例２］
　第１の銀めっき皮膜を形成する際の電気めっき時間を９０秒間とし、第２の銀めっき皮膜を形成する際の電気めっき時間を１０秒間とした以外は、実施例１と同様の方法により、銀めっき材を作製した。この銀めっき材の無光沢ニッケルめっき皮膜、第１の銀めっき皮膜、亜鉛めっき皮膜および第２の銀めっき皮膜の厚さは、それぞれ１μｍ、４μｍ、０．５μｍおよび０．５μｍであった。なお、本実施例において、亜鉛めっき皮膜の厚さに対する第１の銀めっき皮膜の厚さの比は８であった。
　このようにして得られた銀めっき材について、実施例１と同様の方法により、銀めっき皮膜のビッカース硬さＨＶを測定し、微摺動摩耗特性の評価を行った。その結果、ビッカース硬さＨＶは１４７であった。また、接触抵抗が０．５ｍΩを超えるまでの微摺動動作の往復回数は１０，０００回であり、微摺動摩耗特性に優れていることがわかった。
［実施例３］
　第１の銀めっき皮膜を形成する際の電気めっき時間を７５秒間とし、第２の銀めっき皮膜を形成する際の電気めっき時間を２０秒間とした以外は、実施例１と同様の方法により、銀めっき材を作製した。この銀めっき材の無光沢ニッケルめっき皮膜、第１の銀めっき皮膜、亜鉛めっき皮膜および第２の銀めっき皮膜の厚さは、それぞれ１μｍ、３．５μｍ、０．５μｍおよび１μｍであった。なお、本実施例において、亜鉛めっき皮膜の厚さに対する第１の銀めっき皮膜の厚さの比は７であった。
　このようにして得られた銀めっき材について、実施例１と同様の方法により、銀めっき皮膜のビッカース硬さＨＶを測定し、微摺動摩耗特性の評価を行った。その結果、ビッカース硬さＨＶは１４７であった。また、接触抵抗が０．５ｍΩを超えるまでの微摺動動作の往復回数は１０，０００回であり、微摺動摩耗特性に優れていることがわかった。
［実施例４］
　第１の銀めっき皮膜を形成する際の電気めっき時間を６３秒間とし、第２の銀めっき皮膜を形成する際の電気めっき時間を３０秒間とした以外は、実施例１と同様の方法により、銀めっき材を作製した。この銀めっき材の無光沢ニッケルめっき皮膜、第１の銀めっき皮膜、亜鉛めっき皮膜および第２の銀めっき皮膜の厚さは、それぞれ１μｍ、３μｍ、０．５μｍおよび１．５μｍであった。なお、本実施例において、亜鉛めっき皮膜の厚さに対する第１の銀めっき皮膜の厚さの比は６であった。
　このようにして得られた銀めっき材について、実施例１と同様の方法により、銀めっき皮膜のビッカース硬さＨＶを測定し、微摺動摩耗特性の評価を行った。その結果、ビッカース硬さＨＶは１４９であった。また、接触抵抗が０．５ｍΩを超えるまでの微摺動動作の往復回数は９，０００回であり、微摺動摩耗特性に優れていることがわかった。
［実施例５］
　第１の銀めっき皮膜を形成する際の電気めっき時間を１０秒間とし、亜鉛めっき皮膜を形成する際の電気めっき時間を４０秒間とし、第２の銀めっき皮膜を形成する際の電気めっき時間を７５秒間とした以外は、実施例１と同様の方法により、銀めっき材を作製した。この銀めっき材の無光沢ニッケルめっき皮膜、第１の銀めっき皮膜、亜鉛めっき皮膜および第２の銀めっき皮膜の厚さは、それぞれ１μｍ、０．５μｍ、１μｍおよび３．５μｍであった。なお、本実施例において、亜鉛めっき皮膜の厚さに対する第１の銀めっき皮膜の厚さの比は０．５であった。
　このようにして得られた銀めっき材について、実施例１と同様の方法により、銀めっき皮膜のビッカース硬さＨＶを測定し、微摺動摩耗特性の評価を行った。その結果、ビッカース硬さＨＶは１５２であった。また、接触抵抗が０．５ｍΩを超えるまでの微摺動動作の往復回数は５，０００回であり、微摺動摩耗特性に優れていることがわかった。
［実施例６］
　第１の銀めっき皮膜を形成する際の電気めっき時間を２０秒間とし、第２の銀めっき皮膜を形成する際の電気めっき時間を６３秒間とした以外は、実施例５と同様の方法により、銀めっき材を作製した。この銀めっき材の無光沢ニッケルめっき皮膜、第１の銀めっき皮膜、亜鉛めっき皮膜および第２の銀めっき皮膜の厚さは、それぞれ１μｍ、１μｍ、１μｍおよび３μｍであった。なお、本実施例において、亜鉛めっき皮膜の厚さに対する第１の銀めっき皮膜の厚さの比は１であった。
　このようにして得られた銀めっき材について、実施例１と同様の方法により、銀めっき皮膜のビッカース硬さＨＶを測定し、微摺動摩耗特性の評価を行った。その結果、ビッカース硬さＨＶは１５９であった。また、接触抵抗が０．５ｍΩを超えるまでの微摺動動作の往復回数は７，０００回であり、微摺動摩耗特性に優れていることがわかった。
［実施例７］
　第１の銀めっき皮膜を形成する際の電気めっき時間を７５秒間とし、第２の銀めっき皮膜を形成する際の電気めっき時間を１０秒間とした以外は、実施例５と同様の方法により、銀めっき材を作製した。この銀めっき材の無光沢ニッケルめっき皮膜、第１の銀めっき皮膜、亜鉛めっき皮膜および第２の銀めっき皮膜の厚さは、それぞれ１μｍ、３．５μｍ、１μｍおよび０．５μｍであった。なお、本実施例において、亜鉛めっき皮膜の厚さに対する第１の銀めっき皮膜の厚さの比は３．５であった。
　このようにして得られた銀めっき材について、実施例１と同様の方法により、銀めっき皮膜のビッカース硬さＨＶを測定し、微摺動摩耗特性の評価を行った。その結果、ビッカース硬さＨＶは１５９であった。また、接触抵抗が０．５ｍΩを超えるまでの微摺動動作の往復回数は５，０００回であり、微摺動摩耗特性に優れていることがわかった。
［実施例８］
　第１の銀めっき皮膜を形成する際の電気めっき時間を５３秒間とし、第２の銀めっき皮膜を形成する際の電気めっき時間を３０秒間とした以外は、実施例５と同様の方法により、銀めっき材を作製した。この銀めっき材の無光沢ニッケルめっき皮膜、第１の銀めっき皮膜、亜鉛めっき皮膜および第２の銀めっき皮膜の厚さは、それぞれ１μｍ、２．５μｍ、１μｍおよび１．５μｍであった。なお、本実施例において、亜鉛めっき皮膜の厚さに対する第１の銀めっき皮膜の厚さの比は２．５であった。
　このようにして得られた銀めっき材について、実施例１と同様の方法により、銀めっき皮膜のビッカース硬さＨＶを測定し、微摺動摩耗特性の評価を行った。その結果、ビッカース硬さＨＶは１５１であった。また、接触抵抗が０．５ｍΩを超えるまでの微摺動動作の往復回数は５，０００回であり、微摺動摩耗特性に優れていることがわかった。
［実施例９］
　第１の銀めっき皮膜を形成する際の電気めっき時間を４２秒間とし、第２の銀めっき皮膜を形成する際の電気めっき時間を４２秒間とした以外は、実施例７と同様の方法により、銀めっき材を作製した。この銀めっき材の無光沢ニッケルめっき皮膜、第１の銀めっき皮膜、亜鉛めっき皮膜および第２の銀めっき皮膜の厚さは、それぞれ１μｍ、２μｍ、１μｍおよび２μｍであった。なお、本実施例において、亜鉛めっき皮膜の厚さに対する第１の銀めっき皮膜の厚さの比は２であった。
　このようにして得られた銀めっき材について、実施例１と同様の方法により、銀めっき皮膜のビッカース硬さＨＶを測定し、微摺動摩耗特性の評価を行った。その結果、ビッカース硬さＨＶは１５５であった。また、接触抵抗が０．５ｍΩを超えるまでの微摺動動作の往復回数は１０，０００回であり、微摺動摩耗特性に優れていることがわかった。
［比較例１］
　第１の銀めっき皮膜を形成せず、第２の銀めっき皮膜を形成する際の電気めっき時間を９０秒間とした以外は、実施例７と同様の方法により、銀めっき材を作製した。この銀めっき材の無光沢ニッケルめっき皮膜、第１のめっき皮膜、亜鉛めっき皮膜および第２の銀めっき皮膜の厚さは、それぞれ１μｍ、０μｍ、１μｍおよび４μｍであった。なお、本比較例において、亜鉛めっき皮膜の厚さに対する第１の銀めっき皮膜の厚さの比は０であった。
　このようにして得られた銀めっき材について、実施例１と同様の方法により、銀めっき皮膜のビッカース硬さＨＶを測定し、微摺動摩耗特性の評価を行った。その結果、ビッカース硬さＨＶは１４４であった。また、接触抵抗が０．５ｍΩを超えるまでの微摺動動作の往復回数は１，０００回であり、微摺動摩耗特性が悪いことがわかった。
［比較例２］
　第１の銀めっき皮膜を形成する際の電気めっき時間を１０５秒間とし、亜鉛めっき皮膜と第２の銀めっき皮膜を形成しなかった以外は、実施例１と同様の方法により、銀めっき材を作製した。この銀めっき材の無光沢ニッケルめっき皮膜、第１のめっき皮膜、亜鉛めっき皮膜および第２の銀めっき皮膜の厚さは、それぞれ１μｍ、５μｍ、０μｍおよび０μｍであった。
　このようにして得られた銀めっき材について、実施例１と同様の方法により、銀めっき皮膜のビッカース硬さＨＶを測定し、微摺動摩耗特性の評価を行った。その結果、ビッカース硬さＨＶは１３４であった。また、接触抵抗が０．５ｍΩを超えるまでの微摺動動作の往復回数は３，０００回であり、微摺動摩耗特性が悪いことがわかった。
［比較例３］
　中間めっき皮膜として亜鉛めっき皮膜の代わりに銅めっき皮膜を形成した以外は、実施例９と同様の方法により、めっき材を作製した。なお、この銅めっき皮膜は、２６０ｇ／Ｌのシアン化銅カリウムと８ｇ／Ｌのシアン化カリウムを含む水溶液からなる銅めっき液中において、第１の銀めっき皮膜を形成した被めっき材を陰極とし、純銅電極板を陽極として、スターラにより５００ｒｐｍで撹拌しながら液温５０℃において電流密度７．４Ａ／ｄｍ２で５０秒間電気めっきを行うことによって形成した。この銀めっき材の無光沢ニッケルめっき皮膜、第１のめっき皮膜、銅めっき皮膜および第２の銀めっき皮膜の厚さは、それぞれ１μｍ、２μｍ、１μｍおよび２μｍであった。
　このようにして得られた銀めっき材について、実施例１と同様の方法により、銀めっき皮膜のビッカース硬さＨＶを測定し、微摺動摩耗特性の評価を行った。その結果、ビッカース硬さＨＶは１３６であった。また、接触抵抗が０．５ｍΩを超えるまでの微摺動動作の往復回数は２，０００回であり、微摺動摩耗特性が悪いことがわかった。
［比較例４］
　中間めっき皮膜として亜鉛めっき皮膜の代わりに錫めっき皮膜を形成した以外は、実施例９と同様の方法により、めっき材を作製した。なお、この錫めっき皮膜は、有機酸錫と有機酸を含む水溶液からなる錫めっき液中において、第１の銀めっき皮膜を形成した被めっき材を陰極とし、純錫電極板を陽極として、スターラにより５００ｒｐｍで撹拌しながら液温２５℃において電流密度１０Ａ／ｄｍ２で２０秒間電気めっきを行うことによって形成した。この銀めっき材の無光沢ニッケルめっき皮膜、第１のめっき皮膜、錫めっき皮膜および第２の銀めっき皮膜の厚さは、それぞれ１μｍ、２μｍ、１μｍおよび２μｍであった。
　このようにして得られた銀めっき材について、実施例１と同様の方法により、銀めっき皮膜のビッカース硬さＨＶを測定し、微摺動摩耗特性の評価を行った。その結果、ビッカース硬さＨＶは１０９であった。また、接触抵抗が０．５ｍΩを超えるまでの微摺動動作の往復回数は２，０００回であり、微摺動摩耗特性が悪いことがわかった。
［比較例５］
　中間めっき皮膜として亜鉛めっき皮膜の代わりにニッケルめっき皮膜を形成した以外は、実施例９と同様の方法により、めっき材を作製した。なお、このニッケルっき皮膜は、５４０ｇ／Ｌのスルファミン酸ニッケル四水和物と２５ｇ／Ｌの塩化ニッケルと３５ｇ／Ｌのホウ酸を含む水溶液からなる無光沢ニッケルめっき液中において、第１の銀めっき皮膜を形成した被めっき材を陰極とし、ニッケル電極板を陽極として、スターラにより５００ｒｐｍで撹拌しながら液温５５℃において電流密度５Ａ／ｄｍ２で８０秒間電気めっきを行うことによって形成した。この銀めっき材の下地めっき皮膜としての無光沢ニッケルめっき皮膜、第１のめっき皮膜、中間めっき皮膜としてのニッケルめっき皮膜および第２の銀めっき皮膜の厚さは、それぞれ１μｍ、２μｍ、１μｍおよび２μｍであった。
　このようにして得られた銀めっき材について、実施例１と同様の方法により、銀めっき皮膜のビッカース硬さＨＶを測定し、微摺動摩耗特性の評価を行った。その結果、ビッカース硬さＨＶは１７１であった。また、接触抵抗が０．５ｍΩを超えるまでの微摺動動作の往復回数は３，０００回であり、微摺動摩耗特性が悪いことがわかった。
　これらの実施例および比較例で得られた銀めっき材の製造条件および特性を表１～表２に示す。
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
　１０　基材
　１２　下地めっき層
　１４　第１の銀めっき層
　１６　中間めっき層
　１８　第２の銀めっき層

Claims (20)

  1. 基材上に、第１の銀めっき層と、中間めっき層としての亜鉛めっき層と、表層としての第２の銀めっき層がこの順に形成されていることを特徴とする、銀めっき材。
  2. 前記第１の銀めっき層の厚さが０．１～１０μｍであることを特徴とする、請求項１に記載の銀めっき材。
  3. 前記亜鉛めっき層の厚さが０．１～５μｍであることを特徴とする、請求項１に記載の銀めっき材。
  4. 前記亜鉛めっき層の厚さに対する前記第１の銀めっき層の厚さの比が０．１～１０であることを特徴とする、請求項１に記載の銀めっき材。
  5. 前記第２の銀めっき層の厚さが０．１～１０μｍであることを特徴とする、請求項１に記載の銀めっき材。
  6. 前記素材と前記第１の銀めっき層との間に下地めっき層が形成されていることを特徴とする、請求項１に記載の銀めっき材。
  7. 前記下地めっき層がニッケルまたはニッケル合金からなることを特徴とする、請求項６に記載の銀めっき材。
  8. 前記下地めっき層の厚さが０．１～５μｍであることを特徴とする、請求項６に記載の銀めっき材。
  9. 前記基材が銅または銅合金からなることを特徴とする、請求項１に記載の銀めっき材。
  10. 前記銀めっき材のビッカース硬さＨＶが８０～２２０であることを特徴とする、請求項１に記載の銀めっき材。
  11. 基材上に、電気めっきにより、第１の銀めっき層と、中間めっき層としての亜鉛めっき層と、表層としての第２の銀めっき層とをこの順に形成することを特徴とする、銀めっき材の製造方法。
  12. 前記第１の銀めっき層と前記第２の銀めっき層が、シアン化銀カリウムとシアン化カリウムとセレノシアン酸カリウムを含む水溶液からなる銀めっき液中において、前記電気めっきを行うことにより形成されることを特徴とする、請求項１１に記載の銀めっき材の製造方法。
  13. 前記第１の銀めっき層の厚さが０．１～１０μｍであることを特徴とする、請求項１１に記載の銀めっき材の製造方法。
  14. 前記亜鉛めっき層の厚さが０．１～５μｍであることを特徴とする、請求項１１に記載の銀めっき材の製造方法。
  15. 前記亜鉛めっき層の厚さに対する前記第１の銀めっき層の厚さの比が０．１～１０であることを特徴とする、請求項１１に記載の銀めっき材の製造方法。
  16. 前記第２の銀めっき層の厚さが０．１～１０μｍであることを特徴とする、請求項１１に記載の銀めっき材の製造方法。
  17. 前記素材と前記第１の銀めっき層との間に、電気めっきにより、下地めっき層を形成することを特徴とする、請求項１１に記載の銀めっき材の製造方法。
  18. 前記下地めっき層がニッケルまたはニッケル合金からなることを特徴とする、請求項１７に記載の銀めっき材の製造方法。
  19. 前記下地めっき層の厚さが０．１～５μｍであることを特徴とする、請求項１７に記載の銀めっき材の製造方法。
  20. 前記基材が銅または銅合金からなることを特徴とする、請求項１１に記載の銀めっき材の製造方法。
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