WO2013153832A1 - Metal material for electronic component - Google Patents

Metal material for electronic component Download PDF

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Publication number
WO2013153832A1
WO2013153832A1 PCT/JP2013/051354 JP2013051354W WO2013153832A1 WO 2013153832 A1 WO2013153832 A1 WO 2013153832A1 JP 2013051354 W JP2013051354 W JP 2013051354W WO 2013153832 A1 WO2013153832 A1 WO 2013153832A1
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Prior art keywords
layer
metal material
electronic parts
alloy
thickness
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PCT/JP2013/051354
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French (fr)
Japanese (ja)
Inventor
澁谷　義孝
深町　一彦
篤志 児玉
Original Assignee
Jx日鉱日石金属株式会社
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Application filed by Jx日鉱日石金属株式会社 filed Critical Jx日鉱日石金属株式会社
Priority to CN201380019665.0A priority Critical patent/CN104204296B/en
Priority to KR1020147031715A priority patent/KR101688290B1/en
Publication of WO2013153832A1 publication Critical patent/WO2013153832A1/en

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/017—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of aluminium or an aluminium alloy, another layer being formed of an alloy based on a non ferrous metal other than aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/018—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of a noble metal or a noble metal alloy
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C13/00—Alloys based on tin
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C13/00—Alloys based on tin
    • C22C13/02—Alloys based on tin with antimony or bismuth as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/002—Alloys based on nickel or cobalt with copper as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/005—Alloys based on nickel or cobalt with Manganese as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/007—Alloys based on nickel or cobalt with a light metal (alkali metal Li, Na, K, Rb, Cs; earth alkali metal Be, Mg, Ca, Sr, Ba, Al Ga, Ge, Ti) or B, Si, Zr, Hf, Sc, Y, lanthanides, actinides, as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/02—Alloys based on gold
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/04—Alloys based on a platinum group metal
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/06—Alloys based on silver
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/06—Alloys based on silver
    • C22C5/08—Alloys based on silver with copper as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H01B1/026—Alloys based on copper
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/11—Printed elements for providing electric connections to or between printed circuits
    • H05K1/117—Pads along the edge of rigid circuit boards, e.g. for pluggable connectors

Definitions

  • a connector that is a connection part for consumer and in-vehicle electronic devices uses a material in which a surface of brass or phosphor bronze is plated with Ni or Cu and further plated with Sn or Sn alloy.
  • Sn or Sn alloy plating generally requires characteristics such as low contact resistance and high solder wettability, and in recent years, it is also required to reduce insertion force when mating a male terminal and a female terminal formed by plating a plated material. ing.
  • whiskers that are needle-like crystals that cause problems such as short circuits may occur on the plating surface in the manufacturing process, and it is necessary to suppress the generation of the whiskers.
  • Patent Document 1 a surface layer having a thickness of 0.05 ⁇ m or more from the surface is partially coated with Ag or an Ag alloy on a substrate made of Ni, Co or an alloy thereof, A silver-coated electric material is disclosed in which In, Zn, Sn, Pd or an alloy thereof is coated to a thickness of 0.01 to 1.0 ⁇ m on a partially coated Ag or Ag alloy layer. According to this, it is described that excellent solderability as an electrical material and connectivity in mechanical electrical connection can be maintained over a long period of time.
  • Patent Document 2 a first coating layer of Ni, Co, or an alloy containing these is provided on the surface of a Cu or Cu alloy base material, and a second coating layer of Ag or an Ag alloy is provided on the surface, and the surface is further provided.
  • a Sn or Sn alloy coating material provided with a coating layer of Sn or Sn alloy. According to this, it is possible to provide a Sn or Sn alloy coating material that has no surface oxidative discoloration, little increase in contact resistance, and good appearance and contact characteristics over a long period of time regardless of use at high temperatures. Are listed.
  • Patent Document 3 a first coating layer of Ni, Co or an alloy containing these is provided on the surface of a Cu or Cu alloy base material, a second coating layer of Ag or an Ag alloy is provided on the surface, and the surface is further provided.
  • an Sn or Sn alloy coating material provided with an Sn or Sn alloy melt-solidified coating layer. According to this, it is possible to provide a Sn or Sn alloy coating material that has no surface oxidative discoloration, little increase in contact resistance, good appearance and contact characteristics over a long period of time regardless of use at high temperatures. Are listed.
  • Patent Document 4 includes (a) any one of a metal thin film for a base selected from the group consisting of silver, palladium, platinum, bismuth, indium, nickel, zinc, titanium, zirconium, aluminum, chromium, and antimony.
  • a method for preventing tin whiskers by pretreatment is disclosed, in which a plating film of tin or a tin alloy is formed on the metal thin film for base (b) after being formed on an object to be plated. And according to this, it is possible to effectively prevent tin whiskers by a simple operation in a tin-based film formed in order to ensure good solderability on the surface of an object to be plated such as a copper-based substrate. It is stated that you can.
  • a silver plating layer is formed on the surface of a plating base, and further a tin, indium or zinc plating layer having a thickness of 0.001 to 0.1 ⁇ m is formed on the surface of the silver plating layer.
  • a plating structure obtained by heat-treating a silver plating structure is obtained.
  • Patent Documents 1 to 5 are not sufficiently satisfactory with respect to characteristics such as resistance to fine sliding wear, resistance to insertion / extraction, low whisker resistance, and low insertion / extraction.
  • the conventional metal materials for electronic parts having the Sn / Ag / Ni base plating structure have problems with respect to resistance to fine sliding wear, resistance to insertion / extraction, low whisker resistance, and low insertion / extraction, etc.
  • the policy to improve was not clear.
  • the present invention has been made to solve the above-described problems, and provides a metal material for electronic parts having fine sliding wear resistance, resistance to insertion / extraction, low whisker property, and low insertion / extraction, and a method for producing the same. Is an issue.
  • the fine sliding wear resistance is a property in which contact resistance does not easily increase even if the fitting portion is finely slid (sliding distance is 1.0 mm or less) in a connector in which a male terminal and a female terminal are fitted together.
  • the resistance to insertion / removal refers to a property that the contact resistance of the connector does not easily increase even if the male terminal and the female terminal are repeatedly inserted and extracted a plurality of times.
  • Low whisker property refers to the property that whiskers are less likely to occur.
  • the low insertion / removal property means that the insertion force generated when the male terminal and the female terminal are fitted together is low.
  • the inventors of the present invention provided a C layer, a B layer, and an A layer made of a predetermined metal on a base material in order, each formed with a predetermined thickness or adhesion amount, and the A layer and the B layer.
  • a metal material for electronic parts having high micro-sliding wear resistance, high insertion / extraction resistance, low whisker resistance, and low insertion / extraction characteristics can be obtained. It was found that it can be produced.
  • an A layer made of Sn, In, or an alloy thereof is formed on a base material, and Ag, Au, and A are formed between the base material and the A layer.
  • a B layer made of Pt, Pd, Ru, Rh, Os, Ir, or an alloy thereof is formed, and a group made of Ni, Cr, Mn, Fe, Co, Cu is formed between the base material and the B layer.
  • a C layer composed of one or more selected from the above is formed, the thickness of the A layer is 0.01 to 0.3 ⁇ m, and the thickness of the B layer is 0.05 to 0.5 ⁇ m
  • the metal material for electronic parts has a thickness of the C layer of 0.05 ⁇ m or more and a ratio of the thickness of the A layer / the thickness of the B layer of 0.02 to 4.00.
  • an A layer made of Sn, In, or an alloy thereof is formed on a base material, and Ag, Au, Pt, Pd, Ru, and the like are formed between the base material and the A layer.
  • a B layer made of Rh, Os, Ir, or an alloy thereof is formed, and one kind selected from the group consisting of Ni, Cr, Mn, Fe, Co, and Cu is formed between the base material and the B layer.
  • the deposition amount of the a layer is 7 ⁇ 230 ⁇ g / cm 2
  • the adhesion amount of the B layer becomes 50 ⁇ 550 ⁇ g / cm 2
  • the metal material for electronic parts has an amount of 0.03 mg / cm 2 or more and a ratio of the adhesion amount of the A layer / the adhesion amount of the B layer is 0.10 to 3.00.
  • the metal material for electronic parts of the present invention has a concentration of A layer (at%) within a range where the concentration of C layer is 20 at% from the outermost surface when depth analysis is performed by XPS (X-ray photoelectron spectroscopy). ) ⁇ B layer concentration (at%) + 30 Meet.
  • the alloy composition of the A layer is Sn, In, or the total of Sn and In is 50% by mass or more, and the remaining alloy component is As, Bi. , Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Sb, W, and Zn, or one or more metals selected from the group consisting of.
  • the alloy composition of the B layer is Ag, Au, Pt, Pd, Ru, Rh, Os, Ir, or Ag, Au, Pt, Pd, and Ru.
  • Rh, Os, and Ir in total are 50% by mass or more, and the remaining alloy components are made of Bi, Cd, Co, Cu, Fe, Mn, Mo, Ni, Pb, Sb, Se, W, Tl, and Zn. It consists of one or more metals selected from the group.
  • the alloy composition of the C layer is 50% by mass or more in total of Ni, Cr, Mn, Fe, Co, Cu, and further, B, P, It consists of one or more metals selected from the group consisting of Zn.
  • the surface has a Vickers hardness of Hv100 or more.
  • the indentation hardness of the surface is 1000 MPa or more when measured by applying an impact to the surface with a load of 0.1 mN by an ultra micro hardness test. It is.
  • the metal material for electronic parts of the present invention has a surface Vickers hardness of Hv1000 or less.
  • the indentation hardness of the surface is 10000 MPa or less when measured by pulverizing the surface with a load of 0.1 mN by an ultra micro hardness test. It is.
  • the arithmetic average height (Ra) of the surface is 0.1 ⁇ m or less.
  • the metal material for electronic parts of the present invention has a maximum surface height (Rz) of 1 ⁇ m or less.
  • the maximum value of the atomic concentration (at%) of Sn or In of the A layer is obtained.
  • a position (D 3 ) showing the highest atomic concentration (at%) of Cr, Mn, Fe, Co or Cu exists in the order of D 1 , D 2 and D 3 from the outermost surface.
  • the metal material for electronic parts of the present invention when depth analysis is performed by XPS (X-ray photoelectron spectroscopy), the highest value of the atomic concentration (at%) of Sn or In of the A layer, And the maximum value of the atomic concentration (at%) of Ag, Au, Pt, Pd, Ru, Rh, Os or Ir in the B layer is 10 at% or more, respectively, and the Ni, Cr, Mn, The depth at which the atomic concentration (at%) of Fe, Co or Cu is 25 at% or more is 50 nm or more.
  • the present invention is a connector terminal using the metal material for electronic parts of the present invention as a contact portion.
  • the present invention is a connector using the connector terminal of the present invention.
  • the present invention is an FFC terminal using the metal material for electronic parts of the present invention for a contact portion.
  • the present invention is an FPC terminal using the metal material for electronic parts of the present invention as a contact portion.
  • the present invention is an FFC using the FFC terminal of the present invention.
  • the present invention is an FPC using the FPC terminal of the present invention.
  • Another aspect of the present invention is an electronic component using the metal material for an electronic component of the present invention as an external connection electrode.
  • the metal material for electronic components of the present invention is provided with a female terminal connection portion on one side of a mounting portion for mounting on the housing and a substrate connection portion on the other side, and the substrate connection portion.
  • a female terminal connection portion on one side of a mounting portion for mounting on the housing and a substrate connection portion on the other side, and the substrate connection portion.
  • the present invention it is possible to provide a metal material for electronic parts having high micro-sliding wear resistance, high insertion / extraction resistance, low whisker property, and low insertion force.
  • the metal material for electronic parts As shown in FIG. 1, in the metal material 10 for an electronic component according to the embodiment, the C layer 12 is formed on the surface of the substrate 11, the B layer 13 is formed on the surface of the C layer 12, and the surface of the B layer 13 A layer 14 is formed on the substrate.
  • Base material ⁇ Configuration of metal materials for electronic parts> (Base material)
  • metal base materials such as copper and a copper alloy, Fe-type material, stainless steel, titanium and a titanium alloy, aluminum, and an aluminum alloy
  • a metal base and a resin layer may be combined. Examples of composites of metal layers and resin layers include electrode portions on FPC or FFC substrates.
  • the A layer 14 needs to be Sn, In, or an alloy thereof.
  • Sn and In are oxidizable metals, but are relatively soft among metals. Therefore, even if an oxide film is formed on the Sn and In surfaces, for example, when a male terminal and a female terminal are mated using a metal material for electronic parts as a contact material, the oxide film is easily scraped, and the contact becomes metal-to-metal. Therefore, low contact resistance is obtained.
  • Sn and In are excellent in gas corrosion resistance against gases such as chlorine gas, sulfurous acid gas, and hydrogen sulfide gas.
  • gases such as chlorine gas, sulfurous acid gas, and hydrogen sulfide gas.
  • Ag is inferior in gas corrosion resistance to the B layer 13 and inferior in gas corrosion resistance to the C layer 12.
  • the composition of the A layer 14 is 50 mass% or more in total of Sn, In, or Sn and In, and the remaining alloy components are As, Bi, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, You may be comprised by the 1 type selected from the group which consists of Pb, Sb, W, Zn, or 2 or more types of metals.
  • the A layer 14 is formed by, for example, Sn—Ag plating, and the composition thereof becomes an alloy, thereby improving high micro-sliding wear resistance, high insertion / extraction resistance, low whisker resistance, low insertion / extraction characteristics, and the like. There is a case.
  • the thickness of the A layer 14 needs to be 0.01 to 0.3 ⁇ m.
  • the thickness of the A layer 14 is less than 0.01 ⁇ m, sufficient gas corrosion resistance cannot be obtained, and the metal material for electronic parts is corroded when a gas corrosion test such as chlorine gas, sulfurous acid gas, hydrogen sulfide gas is performed.
  • a gas corrosion test such as chlorine gas, sulfurous acid gas, hydrogen sulfide gas is performed.
  • the contact resistance is greatly increased as compared to before the gas corrosion test.
  • sufficient resistance to insertion / extraction cannot be obtained, and much of the plating is scraped, resulting in increased contact resistance.
  • the adhesion wear of Sn and In is increased, the resistance to fine sliding wear is poor, the insertion / extraction force is large, and whiskers are easily generated.
  • the thickness is set to 0.3 ⁇ m or less. Whiskers are generated by the occurrence of screw dislocations. In order to generate screw dislocations, a bulk with a thickness of several hundred nm or more is required. When the thickness of the A layer 14 is 0.3 ⁇ m or less, the thickness is not sufficient to cause screw dislocation, and basically whiskers are not generated. In addition, the A layer 14 and the B layer 13 are easily diffused in a short circuit at room temperature, and an alloy is easily formed, so that no whisker is generated.
  • the amount of Sn and In deposited on the A layer 14 needs to be 7 to 230 ⁇ g / cm 2 .
  • the reason for defining the amount of adhesion will be described. For example, when the thickness of the A layer 14 is measured with a fluorescent X-ray film thickness meter, an error may occur in the measured thickness value due to the alloy layer formed between the A layer and the B layer below the A layer. . On the other hand, when controlling by the adhesion amount, more accurate quality control can be performed regardless of the formation state of the alloy layer.
  • the adhesion amount of Sn and In on the A layer 14 is less than 7 ⁇ g / cm 2 , sufficient gas corrosion resistance cannot be obtained, and the metal material for electronic parts is corroded by chlorine gas, sulfurous acid gas, hydrogen sulfide gas, etc. Corrosion occurs when the test is performed, and the contact resistance is greatly increased as compared with that before the gas corrosion test. Also, sufficient resistance to insertion / extraction cannot be obtained, and much of the plating is scraped, resulting in increased contact resistance. Further, when the adhesion amount is increased, the adhesion wear of Sn and In is increased, the resistance to fine sliding wear is poor, the insertion / extraction force is large, and whiskers are easily generated.
  • the B layer 13 needs to be formed of Ag, Au, Pt, Pd, Ru, Rh, Os, Ir, or an alloy thereof.
  • Ag, Au, Pt, Pd, Ru, Rh, Os, and Ir are characterized by having relatively heat resistance among metals. Therefore, it suppresses that the composition of the base material 11 and the C layer 12 diffuses to the A layer 14 side, and improves heat resistance. Further, these metals form a compound with Sn or In of the A layer 14 to suppress the formation of an oxide film of Sn or In, and improve solder wettability.
  • Ag is more desirable from the viewpoint of conductivity. Ag has high conductivity.
  • the alloy composition of the B layer 13 is Ag, Au, Pt, Pd, Ru, Rh, Os, Ir, or the total of Ag, Au, Pt, Pd, Ru, Rh, Os, and Ir is 50% by mass or more.
  • the residual alloy component is selected from the group consisting of Bi, Cd, Co, Cu, Fe, In, Mn, Mo, Ni, Pb, Sb, Se, Sn, W, Tl, Zn, or two or more You may be comprised with the metal.
  • the B layer 13 is formed of, for example, Sn—Ag plating, the composition of the B layer 13 becomes an alloy, which may improve the high fine sliding wear resistance and the high insertion / extraction resistance.
  • the thickness of the B layer 13 needs to be 0.05 to 0.5 ⁇ m. If the thickness is less than 0.05 ⁇ m, sufficient high fine sliding wear resistance and insertion / extraction resistance cannot be obtained, and much of the plating is scraped, resulting in increased contact resistance. Further, when the thickness is increased, the thin film lubrication effect by the hard base material 11 or the C layer is reduced, and the insertion / extraction force becomes larger than the target (15% or more reduction compared to Comparative Example 1), so that a sufficiently low insertion / extraction property is achieved. In order to obtain it, it is necessary to be 0.5 ⁇ m or less.
  • the adhesion amount of Ag, Au, Pt, Pd, Ru, Rh, Os, Ir, or their alloys on the B layer 13 needs to be 50 to 550 ⁇ g / cm 2 .
  • the reason for defining the amount of adhesion will be described. For example, when the thickness of the B layer 13 is measured with a fluorescent X-ray film thickness meter, an error occurs in the measured thickness value due to the alloy layer formed between the A layer 14 and the B layer 13 therebelow. There is. On the other hand, when controlling by the adhesion amount, more accurate quality control can be performed regardless of the formation state of the alloy layer.
  • an adhesion amount of 50 ⁇ g / cm 2 or more is preferable. Moreover, since the thin film lubrication effect by the hard base material 11 or C layer will fall and the insertion / extraction force will become larger than a target (15% or more reduction
  • C layer Between the base material 11 and the B layer 13, it is necessary to form a C layer 12 made of one or more selected from the group consisting of Ni, Cr, Mn, Fe, Co, and Cu.
  • a C layer 12 made of one or more selected from the group consisting of Ni, Cr, Mn, Fe, Co, and Cu.
  • the thin film lubrication effect is improved by forming a hard C layer.
  • C layer 12 prevents the constituent metal of base material 11 from diffusing into B layer, and suppresses increase in contact resistance and solder wettability after heat resistance test and gas corrosion resistance test. The durability is improved.
  • the alloy composition of the C layer 12 is 50% by mass or more in total of Ni, Cr, Mn, Fe, Co, and Cu, and one or two selected from the group consisting of B, P, Sn, and Zn The above may be included.
  • the C layer 12 is further cured, so that the thin film lubrication effect is further improved and the low insertion / extraction property is improved. Is further prevented from diffusing into the B layer, and an increase in contact resistance and resistance to solder wettability after the heat resistance test and gas corrosion resistance test are improved.
  • the thickness of the C layer 12 needs to be 0.05 ⁇ m or more.
  • the thickness of the C layer 12 is less than 0.05 ⁇ m, the thin film lubrication effect by the hard C layer is lowered and the low insertion / extraction property is deteriorated, and the constituent metal of the base material 11 is easily diffused into the B layer, and the heat resistance test.
  • the durability deteriorates, such as contact resistance increase and solder wettability deterioration after gas corrosion resistance test.
  • the adhesion amount of Ni, Cr, Mn, Fe, Co, and Cu on the C layer 12 needs to be 0.03 mg / cm 2 or more.
  • the reason for defining the amount of adhesion will be described. For example, when the thickness of the C layer 12 is measured with a fluorescent X-ray film thickness meter, an error occurs in the measured thickness value due to the alloy layer formed with the A layer 14, the B layer 13, the base material 11, and the like. There is. On the other hand, when controlling by the adhesion amount, more accurate quality control can be performed regardless of the formation state of the alloy layer.
  • the adhesion amount is less than 0.03 mg / cm 2 , the thin film lubrication effect by the hard C layer is lowered and the low insertion / extraction property is deteriorated, and the constituent metal of the base material 11 is easily diffused into the B layer, and is heat resistant. Durability deteriorates, such as increased contact resistance after test and gas corrosion resistance test and solder wettability.
  • the ratio of the thickness [ ⁇ m] of the A layer 14 to the thickness [ ⁇ m] of the B layer 13 needs to be 0.02 to 4.00. If the ratio of the thickness [ ⁇ m] of the A layer 14 / thickness [ ⁇ m] of the B layer 13 is less than 0.02, sufficient gas corrosion resistance cannot be obtained, and the metal material for electronic parts is made of chlorine gas, sulfurous acid gas, When a gas corrosion test such as hydrogen sulfide gas is performed, it corrodes and the contact resistance is greatly increased as compared to before the gas corrosion test.
  • the ratio of the thickness [ ⁇ m] of the A layer 14 / the thickness [ ⁇ m] of the B layer 13 exceeds 4.00, a large amount of the A layer 14 is present on the surface layer, resulting in poor resistance to fine sliding wear.
  • the ratio of the adhesion amount [ ⁇ g / cm 2 ] of the A layer 14 to the adhesion amount [ ⁇ g / cm 2 ] of the B layer 13 needs to be 0.10 to 3.00.
  • the ratio of the adhesion amount [ ⁇ g / cm 2 ] of the A layer 14 / the adhesion amount [ ⁇ g / cm 2 ] of the B layer 13 is less than 0.10, sufficient gas corrosion resistance cannot be obtained, and the metal for electronic parts
  • a gas corrosion test such as chlorine gas, sulfurous acid gas, hydrogen sulfide gas, etc., it corrodes and the contact resistance is greatly increased compared to before the gas corrosion test.
  • the ratio of the adhesion amount [ ⁇ g / cm 2 ] of the layer 14 / the adhesion amount [ ⁇ g / cm 2 ] of the B layer 13 exceeds 3.00, a large amount of the A layer 14 is present on the surface layer, and resistance to fine sliding wear Sexuality gets worse.
  • the Vickers hardness of the surface of the A layer 14 (measured from the surface of the A layer) is preferably Hv100 or more.
  • the Vickers hardness of the surface of the A layer 14 is Hv100 or more, the thin A layer improves the thin film lubrication effect, and the low insertion / extraction property is improved.
  • the Vickers hardness of the surface of the A layer 14 is preferably Hv1000 or less.
  • the indentation hardness of the surface of the A layer 14 (measured from the surface of the A layer) is preferably 1000 MPa or more.
  • the indentation hardness of the surface of the A layer 14 is 1000 MPa or more, the hard A layer improves the thin film lubrication effect, and the low insertion / extraction property is improved.
  • the indentation hardness of the surface of the A layer 14 (measured from the surface of the A layer) is preferably 10,000 MPa or less.
  • the indentation hardness of the surface of the A layer 14 is 10000 MPa or less, bending workability is improved, and when the metal material for electronic parts of the present invention is press-molded, cracks hardly occur in the molded part, and gas resistance Reduces corrosive (durability) degradation.
  • the arithmetic average height (Ra) of the surface of the A layer 14 is preferably 0.1 ⁇ m or less. When the arithmetic average height (Ra) of the surface of the A layer 14 is 0.1 ⁇ m or less, the number of convex portions that are relatively easily corroded is reduced and the surface becomes smooth, so that the gas corrosion resistance is improved.
  • the maximum height (Rz) of the surface of the A layer 14 is preferably 1 ⁇ m or less. When the maximum height (Rz) of the surface of the A layer 14 is 1 ⁇ m or less, the number of convex portions that are relatively easily corroded is reduced and smoothed, and thus the gas corrosion resistance is improved.
  • the position (D 2 ) showing the highest atomic concentration (at%) of Ag, Au, Pt, Pd, Ru, Rh, Os or Ir of Ni, Cr, Mn, Fe, Co in the lower layer (C layer) 12 or highest value indicating the position of Cu atomic concentration (at%) (D 3) is preferably present in the order of D 1, D 2, D 3 from the outermost surface.
  • the maximum value of atomic concentration (at%) of Pt, Pd, Ru, Rh, Os or Ir is 10 at% or more, respectively, and atoms of Ni, Cr, Mn, Fe, Co or Cu in the lower layer (C layer) 12
  • the depth at which the concentration (at%) is 25 at% or more is preferably 50 nm or more.
  • the maximum value of the atomic concentration (at%) of Sn or In in the outermost layer (A layer) 14 and the atomic concentration of Ag, Au, Pt, Pd, Ru, Rh, Os or Ir in the intermediate layer (B layer) ( The depth at which the maximum value of each of the atomic (at%) is less than 10 at% and the atomic concentration (at%) of Ni, Cr, Mn, Fe, Co or Cu in the lower layer (C layer) 12 is 25 at% or more is 50 nm. If it is less, the low insertion / extraction property and durability (heat resistance, gas corrosion resistance, solder wettability, etc.) are poor as the base material component diffuses into the outermost layer (A layer) 14 or the middle layer (B layer) 13. There is a risk.
  • the use of the metal material for electronic parts of the present invention is not particularly limited.
  • a connector terminal using the metal material for electronic parts as a contact part an FFC terminal or FPC terminal using the metal material for electronic parts as a contact part, and an electronic part Electronic parts using metal materials for external connection as electrodes for external connection.
  • the external connection electrode include a connection component in which a surface treatment is performed on a tab and a material in which a surface treatment is applied to a semiconductor under bump metal.
  • a connector may be produced using the connector terminal formed in this way, and an FFC or FPC may be produced using an FFC terminal or an FPC terminal.
  • the metal material for electronic parts is provided with a female terminal connection part on one side of the mounting part to be attached to the housing and a board connection part on the other side, and the board connection part is press-fitted into a through hole formed on the board.
  • the press-fit terminal attached to the substrate is also a metal material for electronic parts of the present invention.
  • both the male terminal and the female terminal may be the metal material for electronic parts of the present invention, or only one of the male terminal and the female terminal.
  • low insertion property is further improved by making both the male terminal and the female terminal into the metal material for electronic parts of the present invention.
  • ⁇ Method for producing metal material for electronic parts As a method for producing a metal material for electronic parts of the present invention, wet (electrical, electroless) plating, dry (sputtering, ion plating, etc.) plating, or the like can be used. Specifically, the C layer 12 is formed on the material 11, the B layer 13 is formed on the C layer 12, the A layer 14 is formed on the B layer 13, and the A layer 14 and the B layer are formed. There is a method in which the alloy layer is formed by diffusion of the layer 13. In this manufacturing method, by further reducing the Sn adhesion force, high micro-sliding wear resistance and high insertion / extraction resistance are obtained, and characteristics such as low insertion / extraction and low whisker are improved.
  • heat treatment After the A layer 14 is formed, heat treatment may be performed for the purpose of improving high micro-sliding wear resistance, high insertion / extraction resistance, low whisker resistance, and low insertion / extraction characteristics.
  • the heat treatment makes it easy for the A layer 14 and the B layer 13 to form an alloy layer, and by further reducing the Sn adhesion force, a high micro-sliding wear resistance and a high insertion / extraction resistance can be obtained.
  • the characteristics are improved.
  • process conditions temperature x time
  • this heat treatment is not particularly required.
  • the heat treatment is preferably performed at a temperature of 500 ° C. or less and within 12 hours. When the temperature exceeds 500 ° C., problems such as high contact resistance and poor solder wettability may occur. When the heat treatment time exceeds 12 hours, problems such as high contact resistance and poor solder wettability may occur.
  • Tables 1 to 7 samples formed by providing a base material, a C layer, a B layer, and an A layer in this order and performing a heat treatment were prepared under the conditions shown in Tables 1 to 7 below.
  • Table 1 shows the conditions for producing the substrate
  • Table 2 shows the conditions for producing the C layer
  • Table 3 shows the conditions for producing the B layer
  • Table 4 shows the conditions for producing the A layer
  • Table 5 shows the heat treatment conditions.
  • Table 6 Tables 6-1, 6-2, and 6-3
  • Table 7 shows the preparation conditions of each layer used in each comparative example. And heat treatment conditions are shown respectively.
  • the thicknesses of the A layer, the B layer, and the C layer were each subjected to surface treatment on the base material that does not have the elements of the A layer, the B layer, and the C layer, and each was subjected to a fluorescent X-ray film thickness meter
  • the actual thickness was measured at 0.1 mm ⁇ ).
  • the substrate is Cu-10 mass% Sn-0.15 mass% P, the substrate has Sn, and the exact Sn plating thickness is not known.
  • the thickness was measured with Cu-30 mass% Zn, which does not have the composition of the base material.
  • the layer structure of the obtained sample was determined by a depth profile by XPS (X-ray photoelectron spectroscopy) analysis.
  • the analyzed elements are the composition of the A layer, the B layer, and the C layer, and C and O. These elements are designated elements. Further, the concentration (at%) of each element was analyzed with the total of the designated elements as 100%.
  • the thickness in XPS (X-ray photoelectron spectroscopy) analysis corresponds to the distance on the horizontal axis of the chart by analysis (distance in terms of SiO 2 ). Further, the surface of the obtained sample was also subjected to qualitative analysis by survey measurement by XPS (X-ray photoelectron spectroscopy) analysis.
  • the resolution of the qualitative analysis concentration was 0.1 at%.
  • ULVAC-PHI Co., Ltd. 5600MC was used, ultimate vacuum: 5.7 ⁇ 10 ⁇ 9 Torr, excitation source: monochromatic AlK ⁇ , output: 210 W, detection area: 800 ⁇ m ⁇ , incident angle: 45 degrees, The take-off angle was 45 degrees, no neutralizing gun was used, and the measurement was performed under the following sputtering conditions.
  • Fine sliding wear resistance Fine sliding wear resistance is measured using a precision sliding test device CRS-G2050 manufactured by Yamazaki Seiki Laboratories, with a sliding distance of 0.5 mm, a sliding speed of 1 mm / s, and a contact load of 1 N. The relationship between the number of sliding times and the contact resistance was evaluated under the condition that the number of sliding times was 500. The number of samples was 5, and the range from the minimum value to the maximum value of each sample was adopted. The target characteristic is a contact resistance of 50 m ⁇ or less when the number of sliding times is 100. The contact resistance was classified as ⁇ 50, 50-200 m ⁇ .
  • Insertion / extraction force is tested with commercially available Sn reflow plated female terminals (090 type Sumitomo TS / Yazaki 090II series female terminal non-waterproof / F090-SMTS) with the plated male terminals according to Examples and Comparative Examples.
  • Sn reflow plated female terminals (090 type Sumitomo TS / Yazaki 090II series female terminal non-waterproof / F090-SMTS) with the plated male terminals according to Examples and Comparative Examples.
  • the measuring apparatus used for the test was 1311NR made by Ikko Engineering, and the evaluation was performed with a male spin sliding distance of 5 mm. Since the number of samples was 5, and the insertion force was the same as the insertion force, the value obtained by averaging the maximum insertion force values of each sample was adopted.
  • the sample of Comparative Example 1 was adopted as the blank material for the insertion / extraction force.
  • the target of the insertion / extraction force is less than 85% compared to the maximum insertion / extraction force of Comparative Example 1. This is 90% of Comparative Example 4 compared to the maximum insertion force of Comparative Example 1, and aimed to reduce the insertion / extraction force larger than that of Comparative Example 4.
  • Whisker Whisker was evaluated by a load test (ball indenter method) of JEITA RC-5241. That is, a load test was performed on each sample, and the sample after the load test was observed at a magnification of 100 to 10,000 times with a SEM (manufactured by JEOL, model JSM-5410) to observe the occurrence of whiskers. .
  • the load test conditions are shown below. Diameter of ball indenter: ⁇ 1mm ⁇ 0.1mm Test load: 2N ⁇ 0.2N Test time: 120 hours Number of samples: 10
  • the target characteristic is that whiskers having a length of 20 ⁇ m or more are not generated, but the maximum target is that no whisker is generated.
  • the contact resistance was measured by a 4-terminal method using a contact simulator CRS-113-Au type manufactured by Yamazaki Seiki Co., Ltd. under the condition of a contact load of 50 g. The number of samples was 5, and the range from the minimum value to the maximum value of each sample was adopted.
  • the target characteristic is a contact resistance of 10 m ⁇ or less.
  • Heat resistance was evaluated by measuring the contact resistance of a sample after an atmospheric heating (155 ° C. ⁇ 500 h) test.
  • the target characteristic is a contact resistance of 10 m ⁇ or less, and the maximum target is that the contact resistance does not change before and after the heat resistance test (is equivalent).
  • the heat resistance was classified according to contact resistance of 1 to 3, 2 to 4, 3 to 7, 10 ⁇ m ⁇ .
  • Gas corrosion resistance was evaluated in the following test environment.
  • the evaluation of gas corrosion resistance is the contact resistance and appearance of the sample after the environmental test.
  • the target characteristics are that the contact resistance is 10 m ⁇ or less and the appearance is not discolored.
  • the maximum target of contact resistance is that there is no change (equivalent) before and after the gas corrosion resistance test.
  • the gas corrosion resistance was classified according to contact resistance of 1 to 3, 2 to 4, 6 to 9, and 10 ⁇ m ⁇ .
  • Hydrogen sulfide gas corrosion test Sulfurous acid concentration: 3ppm Temperature: 40 ° C Humidity: 80% RH Exposure time: 96h Number of samples: 5
  • solder wettability was evaluated on the sample after plating.
  • Solder checker (SAT-5000 manufactured by Reska Co., Ltd.) was used, a commercially available 25% rosin methanol flux was used as the flux, and the solder wetting time was measured by the meniscograph method.
  • Sn-3Ag-0.5Cu 250 ° C.
  • the number of samples was 5, and the range from the minimum value to the maximum value of each sample was adopted.
  • the target characteristic is a zero cross time of 5 seconds (s) or less. Zero-crossing was classified as 1 to 3, 5 ⁇ s.
  • the bending workability was evaluated by bending at 90 ° using a W-shaped mold under the condition that the ratio of the plate thickness to the bending radius was 1.
  • the surface of the bent portion was observed with an optical microscope, and when it was judged that there was no practical problem when no crack was observed, it was evaluated as ⁇ , and when the crack was observed, it was evaluated as ⁇ .
  • the number of samples was three.
  • the Vickers hardness of the outermost layer (A layer) was measured from the surface of the sample with a load of 980.7 mN (Hv 0.1) and a load holding time of 15 seconds.
  • the indentation hardness of the outermost layer (A layer) was measured by hitting a root of the sample surface with a load of 0.1 mN by an ultra micro hardness test (ENTION 2100 manufactured by Elionix). In addition, it measured 5 times per sample.
  • Examples 1 to 76 were electronic component metal materials excellent in both fine sliding wear resistance and insertion / extraction resistance.
  • Comparative Example 1 is a blank material.
  • Comparative Example 2 was produced by thinning the Sn plating of the blank material of Comparative Example 1, but the solder wettability was poor.
  • the comparative example 3 was produced without performing heat processing compared with the comparative example 2, the insertion / extraction force was higher than the target.
  • Comparative Example 4 was prepared by applying Cu plating to the middle layer as compared with Comparative Example 2, but the insertion / extraction force was 90% as compared with Comparative Example 1.
  • Comparative Example 5 was prepared by making Sn plating thinner than Comparative Example 4, but the solder wettability was poor.
  • Comparative Example 6 was prepared without heat treatment as compared with Comparative Example 5, but the insertion / extraction force was higher than the target.
  • Comparative Example 7 was prepared by applying Cu plating to the lower layer as compared with the blank material of Comparative Example 1, but the characteristics were not different from Comparative Example 1.
  • Comparative Example 8 was produced by applying a lower Ni plating thicker than the blank material of Comparative Example 1, but the characteristics were not different from Comparative Example 1.
  • the thickness and adhesion amount of the B layer were thinner than the target and less, The fine sliding wear resistance was poor and the insertion / extraction resistance was also high.
  • Comparative Example 14 the thickness and adhesion amount of the A layer were thinner and less than the target, but the gas corrosion resistance was poor, and discoloration was confirmed in the appearance after the test.
  • Comparative Example 15 the thickness and adhesion amount of the A layer were thicker and larger than the target, but the ratio of the A layer was large in the relationship between the A layer and the B layer, and the depth in XPS (X-ray photoelectron spectroscopy) was high. In the measurement, the A layer was present at a higher concentration than the target, so the resistance to fine sliding wear was poor.
  • Comparative Example 16 the thickness and adhesion amount of the A layer were thinner and less than the target, but the gas corrosion resistance was poor, and discoloration was confirmed in the appearance after the test.
  • Comparative Example 17 the thickness and adhesion amount of the A layer were thicker and larger than the target, but the thickness and adhesion amount of the A layer were still larger than the target, although the relationship target of the A layer and B layer was the same as the target. It was thick and thick, so it had poor sliding resistance.
  • Comparative Example 18 the thickness and adhesion amount of the A layer were thinner and less than the target, but the gas corrosion resistance was poor, and discoloration was confirmed in the appearance after the test.
  • Comparative Example 19 the thickness and adhesion amount of the A layer were thicker and larger than the target, but the thickness and adhesion amount of the A layer were still larger than the target, although the relationship between the A layer and the B layer was as intended. It was thick and thick, so it had poor sliding resistance.
  • the insertion / extraction force was also high.
  • Comparative Examples 20 to 22 the thickness and adhesion amount of the B layer were thicker and larger than the target, but the insertion force was high.
  • Comparative Example 23 the thickness and adhesion amount of the C layer were thinner and less than the target, but the insertion force was high, and the heat resistance and solder wettability were also poor.
  • Comparative Example 24 the time was longer than the target heat treatment, but the solder did not get wet.
  • Comparative Example 25 the temperature was higher than the target heat treatment, but the solder did not get wet.
  • Comparative Example 26 the thickness and adhesion amount of the A layer were thinner and less than the target.
  • Comparative Example 28 the thickness and adhesion amount of the C layer were thinner and less than the target, but the insertion force was high, and the heat resistance and solder wettability were also poor. Comparative Example 29 was produced by reversing the plating order of Sn and Ag as compared with Example 2, but the depth of the outermost layer (A layer) was measured by Depth measurement using XPS (X-ray photoelectron spectroscopy).
  • FIG. 2 shows a depth measurement result of XPS (X-ray photoelectron spectroscopy) according to the second embodiment.
  • FIG. 2 shows that the concentration of the A layer (at%) ⁇ [the concentration of the B layer (at%) + 30] is satisfied in the range where the C layer is 20 at%. Further, the position (D 1 ) showing the highest value of Sn or In atomic concentration (at%) in the A layer, and the atomic concentration (at%) of Ag, Au, Pt, Pd, Ru, Rh, Os or Ir in the B layer.

Abstract

Provided is a metal material for an electronic component, having high fretting resistance, high insertion-extraction resistance, low whiskering, and low insertion force properties. A metal material for an electronic component, in which an A layer comprising Sn, In, or an alloy thereof is formed on a substrate, a B layer comprising Ag, Au, Pt, Pd, Ru, Rh, Os, Ir, or an alloy thereof is formed between the substrate and the A layer, a C layer comprising one or more species selected from the group consisting of Ni, Cr, Mn, Fe, Co, and Cu is formed between the substrate and the B layer, the thickness of the A layer is 0.01-0.3 µm, the thickness of the B layer is 0.05-0.5 µm, the thickness of the C layer is 0.05 µm or greater, and the ratio of the thickness of the A layer to the thickness of the B layer is 0.02-4.00.

Description

電子部品用金属材料Metal materials for electronic parts
　民生用及び車載用電子機器用接続部品であるコネクタには、黄銅やリン青銅の表面にＮｉやＣｕの下地めっきを施し、さらにその上にＳｎ又はＳｎ合金めっきを施した材料が使用されている。Ｓｎ又はＳｎ合金めっきは、一般的に低接触抵抗及び高はんだ濡れ性という特性が求められ、更に近年めっき材をプレス加工で成形したオス端子及びメス端子勘合時の挿入力の低減化も求められている。また、製造工程でめっき表面に、短絡等の問題を引き起こす針状結晶であるウィスカが発生することがあり、このウィスカの発生を抑制する必要もある。
　またコネクタ（特に車載用電子機器用接続備品）によっては、振動などの影響を考慮した高耐微摺動磨耗性や高耐挿抜性（オス端子とメス端子を勘合及び脱着を繰り返しても接触抵抗が増加しない）等の特性も求められている。 A connector that is a connection part for consumer and in-vehicle electronic devices uses a material in which a surface of brass or phosphor bronze is plated with Ni or Cu and further plated with Sn or Sn alloy. . Sn or Sn alloy plating generally requires characteristics such as low contact resistance and high solder wettability, and in recent years, it is also required to reduce insertion force when mating a male terminal and a female terminal formed by plating a plated material. ing. In addition, whiskers that are needle-like crystals that cause problems such as short circuits may occur on the plating surface in the manufacturing process, and it is necessary to suppress the generation of the whiskers.
In addition, depending on the connector (particularly for in-vehicle electronic equipment), high resistance to sliding and high resistance to insertion / removal in consideration of the effects of vibration (contact resistance even if male and female terminals are repeatedly mated and removed) Is not required to increase).
　これに対し、特許文献１には、表面から厚さ０．０５μｍ以上の表層がＮｉ，Ｃｏ又はこれらの合金からなる基材上に、Ａｇ又はＡｇ合金を部分被覆し、露出する基材表面と部分被覆したＡｇ又はＡｇ合金層上に、Ｉｎ，Ｚｎ，Ｓｎ，Ｐｄ又はこれらの合金を０．０１～１．０μｍの厚さに被覆した銀被覆電気材料が開示されている。そしてこれによれば、電気材料としての優れた半田付け性や機械的電気接続における接続性を長期にわたり維持することができると記載されている。 On the other hand, in Patent Document 1, a surface layer having a thickness of 0.05 μm or more from the surface is partially coated with Ag or an Ag alloy on a substrate made of Ni, Co or an alloy thereof, A silver-coated electric material is disclosed in which In, Zn, Sn, Pd or an alloy thereof is coated to a thickness of 0.01 to 1.0 μm on a partially coated Ag or Ag alloy layer. According to this, it is described that excellent solderability as an electrical material and connectivity in mechanical electrical connection can be maintained over a long period of time.
　また、特許文献２には、ＣｕまたはＣｕ合金基材表面にＮｉ、Ｃｏまたはこれらを含む合金の第１被覆層を設け、その表面にＡｇまたはＡｇ合金の第２被覆層を設け、さらにその表面にＳｎまたはＳｎ合金の被覆層を設けてなるＳｎまたはＳｎ合金被覆材料が開示されている。そしてこれによれば、高温における使用に拘わらず、表面の酸化変色がなく接触抵抗の増加が少なく、長期間にわたり、外観および接触特性が良好なＳｎまたはＳｎ合金被覆材料を提供することができると記載されている。 In Patent Document 2, a first coating layer of Ni, Co, or an alloy containing these is provided on the surface of a Cu or Cu alloy base material, and a second coating layer of Ag or an Ag alloy is provided on the surface, and the surface is further provided. Discloses a Sn or Sn alloy coating material provided with a coating layer of Sn or Sn alloy. According to this, it is possible to provide a Sn or Sn alloy coating material that has no surface oxidative discoloration, little increase in contact resistance, and good appearance and contact characteristics over a long period of time regardless of use at high temperatures. Are listed.
　また、特許文献３には、ＣｕまたはＣｕ合金基材表面にＮｉ，Ｃｏまたはこれらを含む合金の第１被覆層を設け、その表面にＡｇまたはＡｇ合金の第２被覆層を設け、さらにその表面にＳｎまたはＳｎ合金の溶融凝固被覆層を設けてなるＳｎまたはＳｎ合金被覆材料が開示されている。そしてこれによれば、高温における使用に拘わらず、表面の酸化変色がなく接触抵抗の増加が少なく、長期化にわたり、外観および接触特性が良好なＳｎまたはＳｎ合金被覆材料を提供することができると記載されている。 Further, in Patent Document 3, a first coating layer of Ni, Co or an alloy containing these is provided on the surface of a Cu or Cu alloy base material, a second coating layer of Ag or an Ag alloy is provided on the surface, and the surface is further provided. Discloses an Sn or Sn alloy coating material provided with an Sn or Sn alloy melt-solidified coating layer. According to this, it is possible to provide a Sn or Sn alloy coating material that has no surface oxidative discoloration, little increase in contact resistance, good appearance and contact characteristics over a long period of time regardless of use at high temperatures. Are listed.
　また、特許文献４には、（ａ）銀、パラジウム、白金、ビスマス、インジウム、ニッケル、亜鉛、チタン、ジルコニウム、アルミニウム、クロム、アンチモンよりなる群から選ばれた下地用の金属薄膜のいずれかを被メッキ物上に形成した後、（ｂ）上記下地用の金属薄膜上にスズ又はスズ合金のメッキ皮膜を形成することを特徴とする前処理によるスズホイスカーの防止方法が開示されている。そしてこれによれば、銅系素地を初めとする被メッキ物の表面上にハンダ付け性などを良好に確保するために形成するスズ系皮膜において、簡便な操作でスズホイスカーを有効に防止することができると記載されている。 Patent Document 4 includes (a) any one of a metal thin film for a base selected from the group consisting of silver, palladium, platinum, bismuth, indium, nickel, zinc, titanium, zirconium, aluminum, chromium, and antimony. A method for preventing tin whiskers by pretreatment is disclosed, in which a plating film of tin or a tin alloy is formed on the metal thin film for base (b) after being formed on an object to be plated. And according to this, it is possible to effectively prevent tin whiskers by a simple operation in a tin-based film formed in order to ensure good solderability on the surface of an object to be plated such as a copper-based substrate. It is stated that you can.
　また、特許文献５には、メッキ用基体の表面に銀メッキ層を形成し、さらに該銀メッキ層の表面に厚さ０．００１～０．１μｍの錫またはインジウムまたは亜鉛のメッキ層を形成してなる銀メッキ構造体を熱処理して得られるメッキ構造が開示されている。そしてこれによれば、耐熱性に優れ、かつ銀の硫化による反射率低下の少ない発光素子収納用支持体及び、硫化により変色しにくく、銀本来の光沢を有し、接触抵抗が小さい電気部品用被覆方法を提供することができると記載されている。 Further, in Patent Document 5, a silver plating layer is formed on the surface of a plating base, and further a tin, indium or zinc plating layer having a thickness of 0.001 to 0.1 μm is formed on the surface of the silver plating layer. A plating structure obtained by heat-treating a silver plating structure is obtained. And according to this, the support for storing a light-emitting element having excellent heat resistance and low reflectivity reduction due to silver sulfidation, and for electric parts that are hard to discolor due to sulfidation, have the original gloss of silver, and have low contact resistance It is described that a coating method can be provided.
特開昭６１－１２４５９７号公報JP 61-124597 A 特開平１－３０６５７４号公報JP-A-1-306574 特開平２－３０１５７３号公報JP-A-2-301573 特開２００３－１２９２７８号公報JP 2003-129278 A 特開２０１１－１２２２３４号公報JP 2011-122234 A
　しかしながら、特許文献１～５に記載の技術では、耐微摺動磨耗性、耐挿抜性、低ウィスカ性及び低挿抜性等の特性について、十分に満足できるものではなかった。
　このように、従来のＳｎ／Ａｇ／Ｎｉ下地めっき構造を有する電子部品用金属材料には、耐微摺動磨耗性、耐挿抜性、低ウィスカ性及び低挿抜性等について問題があり、これら全てを改善する方針が明らかになっていなかった。
　本発明は上記の課題を解決するためになされたものであり、耐微摺動磨耗性、耐挿抜性、低ウィスカ性及び低挿抜性を有する電子部品用金属材料及びその製造方法を提供することを課題とする。
　なお耐微摺動磨耗性とは、オス端子とメス端子を勘合させたコネクタにおいて、勘合部が微摺動（摺動距離１．０ｍｍ以下）しても接触抵抗が増加し難い性質をいう。
　耐挿抜性とは、オス端子とメス端子を複数回の挿抜を繰り返してもコネクタの接触抵抗が増加し難い性質をいう。
　低ウィスカ性とは、ウィスカが発生し難い性質をいう。
　低挿抜性とは、低挿抜性とは、オス端子とメス端子を勘合させた時に生じる挿入力が低いことをいう。 However, the techniques described in Patent Documents 1 to 5 are not sufficiently satisfactory with respect to characteristics such as resistance to fine sliding wear, resistance to insertion / extraction, low whisker resistance, and low insertion / extraction.
As described above, the conventional metal materials for electronic parts having the Sn / Ag / Ni base plating structure have problems with respect to resistance to fine sliding wear, resistance to insertion / extraction, low whisker resistance, and low insertion / extraction, etc. The policy to improve was not clear.
The present invention has been made to solve the above-described problems, and provides a metal material for electronic parts having fine sliding wear resistance, resistance to insertion / extraction, low whisker property, and low insertion / extraction, and a method for producing the same. Is an issue.
The fine sliding wear resistance is a property in which contact resistance does not easily increase even if the fitting portion is finely slid (sliding distance is 1.0 mm or less) in a connector in which a male terminal and a female terminal are fitted together.
The resistance to insertion / removal refers to a property that the contact resistance of the connector does not easily increase even if the male terminal and the female terminal are repeatedly inserted and extracted a plurality of times.
Low whisker property refers to the property that whiskers are less likely to occur.
The low insertion / removal property means that the insertion force generated when the male terminal and the female terminal are fitted together is low.
　本発明者らは、鋭意検討の結果、基材上に所定の金属からなるＣ層、Ｂ層、Ａ層を順に設け、それぞれ所定の厚み又は付着量で形成し、且つ、Ａ層とＢ層との厚みの比又は付着量の比を所定範囲に制御することで、高耐微摺動磨耗性、高耐挿抜性、低ウィスカ性及び低挿抜性のいずれも備えた電子部品用金属材料を作製することができることを見出した。 As a result of intensive studies, the inventors of the present invention provided a C layer, a B layer, and an A layer made of a predetermined metal on a base material in order, each formed with a predetermined thickness or adhesion amount, and the A layer and the B layer. By controlling the thickness ratio or the adhesion amount ratio within a predetermined range, a metal material for electronic parts having high micro-sliding wear resistance, high insertion / extraction resistance, low whisker resistance, and low insertion / extraction characteristics can be obtained. It was found that it can be produced.
　以上の知見を基礎として完成した本発明は一側面において、基材上にＳｎ，Ｉｎ，またはそれらの合金からなるＡ層が形成され、前記基材と前記Ａ層との間にＡｇ，Ａｕ，Ｐｔ，Ｐｄ，Ｒｕ，Ｒｈ，Ｏｓ，Ｉｒ，またはそれらの合金からなるＢ層が形成され、前記基材と前記Ｂ層との間に、Ｎｉ，Ｃｒ，Ｍｎ，Ｆｅ，Ｃｏ，Ｃｕからなる群から選択された１種、もしくは２種以上からなるＣ層が形成され、前記Ａ層の厚みが０．０１～０．３μｍであり、前記Ｂ層の厚みが０．０５～０．５μｍであり、前記Ｃ層の厚みが０．０５μm以上であり、前記Ａ層の厚み／前記Ｂ層の厚みの比が０．０２～４．００である電子部品用金属材料である。 In one aspect of the present invention completed based on the above knowledge, an A layer made of Sn, In, or an alloy thereof is formed on a base material, and Ag, Au, and A are formed between the base material and the A layer. A B layer made of Pt, Pd, Ru, Rh, Os, Ir, or an alloy thereof is formed, and a group made of Ni, Cr, Mn, Fe, Co, Cu is formed between the base material and the B layer. A C layer composed of one or more selected from the above is formed, the thickness of the A layer is 0.01 to 0.3 μm, and the thickness of the B layer is 0.05 to 0.5 μm The metal material for electronic parts has a thickness of the C layer of 0.05 μm or more and a ratio of the thickness of the A layer / the thickness of the B layer of 0.02 to 4.00.
　本発明は別の一側面において、基材上にＳｎ，Ｉｎ，またはそれらの合金からなるＡ層が形成され、前記基材と前記Ａ層との間にＡｇ，Ａｕ，Ｐｔ，Ｐｄ，Ｒｕ，Ｒｈ，Ｏｓ，Ｉｒ，またはそれらの合金からなるＢ層が形成され、前記基材と前記Ｂ層との間に、Ｎｉ，Ｃｒ，Ｍｎ，Ｆｅ，Ｃｏ，Ｃｕからなる群から選択された１種、もしくは２種以上からなるＣ層が形成され、前記Ａ層の付着量が７～２３０μｇ／ｃｍ2であり、前記Ｂ層の付着量が５０～５５０μｇ／ｃｍ2であり、前記Ｃ層の付着量が０．０３ｍｇ／ｃｍ2以上であり、前記Ａ層の付着量／前記Ｂ層の付着量の比が０．１０～３．００である電子部品用金属材料である。 In another aspect of the present invention, an A layer made of Sn, In, or an alloy thereof is formed on a base material, and Ag, Au, Pt, Pd, Ru, and the like are formed between the base material and the A layer. A B layer made of Rh, Os, Ir, or an alloy thereof is formed, and one kind selected from the group consisting of Ni, Cr, Mn, Fe, Co, and Cu is formed between the base material and the B layer. or C layer consisting of two or more is formed, the deposition amount of the a layer is 7 ~ 230μg / cm 2, the adhesion amount of the B layer becomes 50 ~ 550μg / cm 2, attachment of the C layer The metal material for electronic parts has an amount of 0.03 mg / cm 2 or more and a ratio of the adhesion amount of the A layer / the adhesion amount of the B layer is 0.10 to 3.00.
　本発明の電子部品用金属材料は一実施形態において、ＸＰＳ（Ｘ線光電子分光）でＤｅｐｔｈ分析を行ったとき、最表からＣ層の濃度が２０ａｔ％となる範囲で
　　Ａ層の濃度（ａｔ％）＜Ｂ層の濃度（ａｔ％）＋３０
を満たす。 In one embodiment, the metal material for electronic parts of the present invention has a concentration of A layer (at%) within a range where the concentration of C layer is 20 at% from the outermost surface when depth analysis is performed by XPS (X-ray photoelectron spectroscopy). ) <B layer concentration (at%) + 30
Meet.
　本発明の電子部品用金属材料は更に別の一実施形態において、前記Ａ層の合金組成がＳｎ，Ｉｎ，またはＳｎとＩｎとの合計で５０質量％以上であり、残合金成分がＡｓ，Ｂｉ，Ｃｄ，Ｃｏ，Ｃｒ，Ｃｕ，Ｆｅ，Ｍｎ，Ｍｏ，Ｎｉ，Ｓｂ，Ｗ，Ｚｎからなる群より選択される１種、もしくは２種以上の金属からなる。 In another embodiment of the metal material for electronic parts of the present invention, the alloy composition of the A layer is Sn, In, or the total of Sn and In is 50% by mass or more, and the remaining alloy component is As, Bi. , Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Sb, W, and Zn, or one or more metals selected from the group consisting of.
　本発明の電子部品用金属材料は更に別の一実施形態において、前記Ｂ層の合金組成がＡｇ，Ａｕ，Ｐｔ，Ｐｄ，Ｒｕ，Ｒｈ，Ｏｓ，Ｉｒ，またはＡｇとＡｕとＰｔとＰｄとＲｕとＲｈとＯｓとＩｒとの合計で５０質量％以上であり、残合金成分がＢｉ，Ｃｄ，Ｃｏ，Ｃｕ，Ｆｅ，Ｍｎ，Ｍｏ，Ｎｉ，Ｐｂ，Ｓｂ，Ｓｅ，Ｗ，Ｔｌ，Ｚｎからなる群より選択される１種、もしくは２種以上の金属からなる。 In still another embodiment of the metal material for electronic parts of the present invention, the alloy composition of the B layer is Ag, Au, Pt, Pd, Ru, Rh, Os, Ir, or Ag, Au, Pt, Pd, and Ru. And Rh, Os, and Ir in total are 50% by mass or more, and the remaining alloy components are made of Bi, Cd, Co, Cu, Fe, Mn, Mo, Ni, Pb, Sb, Se, W, Tl, and Zn. It consists of one or more metals selected from the group.
　本発明の電子部品用金属材料は更に別の一実施形態において、前記Ｃ層の合金組成がＮｉ，Ｃｒ，Ｍｎ，Ｆｅ，Ｃｏ，Ｃｕの合計で５０質量％以上であり、さらにＢ，Ｐ，Ｚｎからなる群から選択された１種、もしくは２種以上の金属からなる。 In yet another embodiment of the metal material for electronic parts of the present invention, the alloy composition of the C layer is 50% by mass or more in total of Ni, Cr, Mn, Fe, Co, Cu, and further, B, P, It consists of one or more metals selected from the group consisting of Zn.
　本発明の電子部品用金属材料は更に別の一実施形態において、表面のビッカース硬さがＨｖ１００以上である。 In yet another embodiment of the metal material for electronic parts of the present invention, the surface has a Vickers hardness of Hv100 or more.
　本発明の電子部品用金属材料は更に別の一実施形態において、超微小硬さ試験により、表面に荷重０．１ｍＮで打根を打って測定したときの、表面の押し込み硬さが１０００ＭＰａ以上である。 In yet another embodiment of the metal material for electronic parts according to the present invention, the indentation hardness of the surface is 1000 MPa or more when measured by applying an impact to the surface with a load of 0.1 mN by an ultra micro hardness test. It is.
　本発明の電子部品用金属材料は更に別の一実施形態において、表面のビッカース硬さがＨｖ１０００以下である。 In yet another embodiment, the metal material for electronic parts of the present invention has a surface Vickers hardness of Hv1000 or less.
　本発明の電子部品用金属材料は更に別の一実施形態において、超微小硬さ試験により、表面に荷重０．１ｍＮで打根を打って測定したときの、表面の押し込み硬さが１００００ＭＰａ以下である。 In yet another embodiment of the metal material for electronic parts according to the present invention, the indentation hardness of the surface is 10000 MPa or less when measured by pulverizing the surface with a load of 0.1 mN by an ultra micro hardness test. It is.
　本発明の電子部品用金属材料は更に別の一実施形態において、表面の算術平均高さ（Ｒａ）が０．１μｍ以下である。 In yet another embodiment of the metal material for electronic parts of the present invention, the arithmetic average height (Ra) of the surface is 0.1 μm or less.
　本発明の電子部品用金属材料は更に別の一実施形態において、表面の最大高さ（Ｒｚ）が１μｍ以下である。 In yet another embodiment, the metal material for electronic parts of the present invention has a maximum surface height (Rz) of 1 μm or less.
　本発明の電子部品用金属材料は更に別の一実施形態において、ＸＰＳ（Ｘ線光電子分光）でＤｅｐｔｈ分析を行ったとき、前記Ａ層のＳｎまたはＩｎの原子濃度（ａｔ％）の最高値を示す位置（Ｄ1）、前記Ｂ層のＡｇ，Ａｕ，Ｐｔ，Ｐｄ，Ｒｕ，Ｒｈ，ＯｓまたはＩｒの原子濃度（ａｔ％）の最高値を示す位置（Ｄ2）、前記Ｃ層のＮｉ，Ｃｒ，Ｍｎ，Ｆｅ，ＣｏまたはＣｕの原子濃度（ａｔ％）の最高値を示す位置（Ｄ3）が最表面からＤ1、Ｄ2、Ｄ3の順で存在する。 In another embodiment of the metal material for electronic parts of the present invention, when the depth analysis is performed by XPS (X-ray photoelectron spectroscopy), the maximum value of the atomic concentration (at%) of Sn or In of the A layer is obtained. Position (D 1 ), position (D 2 ) indicating the highest atomic concentration (at%) of Ag, Au, Pt, Pd, Ru, Rh, Os or Ir in the B layer, Ni in the C layer, A position (D 3 ) showing the highest atomic concentration (at%) of Cr, Mn, Fe, Co or Cu exists in the order of D 1 , D 2 and D 3 from the outermost surface.
　本発明の電子部品用金属材料は更に別の一実施形態において、ＸＰＳ（Ｘ線光電子分光）でＤｅｐｔｈ分析を行ったとき、前記Ａ層のＳｎまたはＩｎの原子濃度（ａｔ％）の最高値、及び、前記Ｂ層のＡｇ，Ａｕ，Ｐｔ，Ｐｄ，Ｒｕ，Ｒｈ，ＯｓまたはＩｒの原子濃度（ａｔ％）の最高値がそれぞれ１０ａｔ％以上であって、前記Ｃ層のＮｉ，Ｃｒ，Ｍｎ，Ｆｅ，ＣｏまたはＣｕの原子濃度（ａｔ％）が２５ａｔ％以上である深さが５０ｎｍ以上である。 In yet another embodiment, the metal material for electronic parts of the present invention, when depth analysis is performed by XPS (X-ray photoelectron spectroscopy), the highest value of the atomic concentration (at%) of Sn or In of the A layer, And the maximum value of the atomic concentration (at%) of Ag, Au, Pt, Pd, Ru, Rh, Os or Ir in the B layer is 10 at% or more, respectively, and the Ni, Cr, Mn, The depth at which the atomic concentration (at%) of Fe, Co or Cu is 25 at% or more is 50 nm or more.
　本発明は更に別の一側面において、本発明の電子部品用金属材料を接点部分に用いたコネクタ端子である。 In yet another aspect, the present invention is a connector terminal using the metal material for electronic parts of the present invention as a contact portion.
　本発明は更に別の一側面において、本発明のコネクタ端子を用いたコネクタである。 In yet another aspect, the present invention is a connector using the connector terminal of the present invention.
　本発明は更に別の一側面において、本発明の電子部品用金属材料を接点部分に用いたＦＦＣ端子である。 In still another aspect, the present invention is an FFC terminal using the metal material for electronic parts of the present invention for a contact portion.
　本発明は更に別の一側面において、本発明の電子部品用金属材料を接点部分に用いたＦＰＣ端子である。 In yet another aspect, the present invention is an FPC terminal using the metal material for electronic parts of the present invention as a contact portion.
　本発明は更に別の一側面において、本発明のＦＦＣ端子を用いたＦＦＣである。 In still another aspect, the present invention is an FFC using the FFC terminal of the present invention.
　本発明は更に別の一側面において、本発明のＦＰＣ端子を用いたＦＰＣである。 In yet another aspect, the present invention is an FPC using the FPC terminal of the present invention.
　本発明は更に別の一側面において、本発明の電子部品用金属材料を外部接続用電極に用いた電子部品である。 Further another aspect of the present invention is an electronic component using the metal material for an electronic component of the present invention as an external connection electrode.
　本発明は更に別の一側面において、本発明の電子部品用金属材料を、ハウジングに取り付ける装着部の一方側にメス端子接続部が、他方側に基板接続部がそれぞれ設けられ、前記基板接続部を基板に形成されたスルーホールに圧入して前記基板に取り付ける圧入型端子に用いた電子部品である。 In yet another aspect of the present invention, the metal material for electronic components of the present invention is provided with a female terminal connection portion on one side of a mounting portion for mounting on the housing and a substrate connection portion on the other side, and the substrate connection portion. Is an electronic component used for a press-fit terminal that is press-fitted into a through-hole formed in the substrate and attached to the substrate.
　本発明によれば、高耐微摺動磨耗性、高耐挿抜性、低ウィスカ性及び低挿入力性を有する電子部品用金属材料を提供することができる。 According to the present invention, it is possible to provide a metal material for electronic parts having high micro-sliding wear resistance, high insertion / extraction resistance, low whisker property, and low insertion force.
本発明の実施形態に係る電子部品用金属材料の構成を示す模式図である。It is a schematic diagram which shows the structure of the metal material for electronic components which concerns on embodiment of this invention. 実施例２に係るＸＰＳ（Ｘ線光電子分光）のＤｅｐｔｈ測定結果である。It is a depth measurement result of XPS (X-ray photoelectron spectroscopy) concerning Example 2.
　以下、本発明の実施形態に係る電子部品用金属材料について説明する。図１に示すように、実施形態に係る電子部品用金属材料１０は、基材１１の表面にＣ層１２が形成され、Ｃ層１２の表面にＢ層１３が形成され、Ｂ層１３の表面にＡ層１４が形成されている。 Hereinafter, the metal material for electronic parts according to the embodiment of the present invention will be described. As shown in FIG. 1, in the metal material 10 for an electronic component according to the embodiment, the C layer 12 is formed on the surface of the substrate 11, the B layer 13 is formed on the surface of the C layer 12, and the surface of the B layer 13 A layer 14 is formed on the substrate.
　＜電子部品用金属材料の構成＞
　（基材）
　基材１１としては、特に限定されないが、例えば、銅及び銅合金、Ｆｅ系材、ステンレス、チタン及びチタン合金、アルミニウム及びアルミニウム合金などの金属基材を用いることができる。また、金属基材に樹脂層を複合させたものであっても良い。金属基材に樹脂層を複合させたものとは、例としてＦＰＣまたはＦＦＣ基材上の電極部分などがある。 <Configuration of metal materials for electronic parts>
(Base material)
Although it does not specifically limit as the base material 11, For example, metal base materials, such as copper and a copper alloy, Fe-type material, stainless steel, titanium and a titanium alloy, aluminum, and an aluminum alloy, can be used. Alternatively, a metal base and a resin layer may be combined. Examples of composites of metal layers and resin layers include electrode portions on FPC or FFC substrates.
　（Ａ層）
　Ａ層１４は、Ｓｎ，Ｉｎ，またはそれらの合金である必要がある。Ｓｎ及びＩｎは、酸化性を有する金属ではあるが、金属の中では比較的柔らかいという特徴がある。よって、Ｓｎ及びＩｎ表面に酸化膜が形成されていても、例えば電子部品用金属材料を接点材料としてオス端子とメス端子を勘合する時に、容易に酸化膜が削られ、接点が金属同士となるため、低接触抵抗が得られる。
　また、Ｓｎ及びＩｎは塩素ガス、亜硫酸ガス、硫化水素ガス等のガスに対する耐ガス腐食性に優れ、例えば、Ｂ層１３に耐ガス腐食性に劣るＡｇ、Ｃ層１２に耐ガス腐食性に劣るＮｉ、基材１１に耐ガス腐食性に劣る銅及び銅合金を用いた場合には、電子部品用金属材料の耐ガス腐食性を向上させる働きがある。なおＳｎ及びＩｎでは、厚生労働省の健康障害防止に関する技術指針に基づき、Ｉｎは規制が厳しいため、Ｓｎが好ましい。 (A layer)
The A layer 14 needs to be Sn, In, or an alloy thereof. Sn and In are oxidizable metals, but are relatively soft among metals. Therefore, even if an oxide film is formed on the Sn and In surfaces, for example, when a male terminal and a female terminal are mated using a metal material for electronic parts as a contact material, the oxide film is easily scraped, and the contact becomes metal-to-metal. Therefore, low contact resistance is obtained.
Sn and In are excellent in gas corrosion resistance against gases such as chlorine gas, sulfurous acid gas, and hydrogen sulfide gas. For example, Ag is inferior in gas corrosion resistance to the B layer 13 and inferior in gas corrosion resistance to the C layer 12. When copper and copper alloy inferior in gas corrosion resistance are used for Ni and the base material 11, there exists a function which improves the gas corrosion resistance of the metal material for electronic components. For Sn and In, Sn is preferable because In is strictly regulated based on the technical guidelines for preventing health problems of the Ministry of Health, Labor and Welfare.
　Ａ層１４の組成は、Ｓｎ，Ｉｎ，またはＳｎとＩｎとの合計で５０質量％以上であり、残合金成分がＡｓ，Ｂｉ，Ｃｄ，Ｃｏ，Ｃｒ，Ｃｕ，Ｆｅ，Ｍｎ，Ｍｏ，Ｎｉ，Ｐｂ，Ｓｂ，Ｗ，Ｚｎからなる群より選択される１種、もしくは２種以上の金属で構成されていても良い。Ａ層１４が、例えばＳｎ－Ａｇめっきで形成される等により、その組成が合金になることで、高耐微摺動磨耗性、高耐挿抜性、低ウィスカ性及び低挿抜性等を向上させる場合がある。 The composition of the A layer 14 is 50 mass% or more in total of Sn, In, or Sn and In, and the remaining alloy components are As, Bi, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, You may be comprised by the 1 type selected from the group which consists of Pb, Sb, W, Zn, or 2 or more types of metals. The A layer 14 is formed by, for example, Sn—Ag plating, and the composition thereof becomes an alloy, thereby improving high micro-sliding wear resistance, high insertion / extraction resistance, low whisker resistance, low insertion / extraction characteristics, and the like. There is a case.
　Ａ層１４の厚みは０．０１～０．３μｍである必要がある。Ａ層１４の厚みが０．０１μｍ未満であると、充分な耐ガス腐食性が得られず、電子部品用金属材料を塩素ガス、亜硫酸ガス、硫化水素ガス等のガス腐食試験を行うと腐食して、ガス腐食試験前と比較して大きく接触抵抗が増加する。また、充分な耐挿抜性が得られず、めっきの多くが削れてしまって接触抵抗が増加する。また、厚みが大きくなると、ＳｎやＩｎの凝着磨耗が大きくなり、耐微摺動磨耗性が悪く、挿抜力は大きく、ウィスカも発生しやすくなる。より充分な耐微摺動磨耗性、低挿抜性及び低ウィスカ性を得るためには、０．３μｍ以下とする。ウィスカはらせん転位が生じることによって発生するが、らせん転位が生じるためには数百ｎｍ以上の厚みのバルクが必要である。Ａ層１４の厚みが０．３μｍ以下では、らせん転位が生じる十分な厚みではなく、基本的にはウィスカが発生しない。またＡ層１４とＢ層１３は常温において短回路拡散が進みやすく、合金が形成しやすいためウィスカが発生しない。 The thickness of the A layer 14 needs to be 0.01 to 0.3 μm. When the thickness of the A layer 14 is less than 0.01 μm, sufficient gas corrosion resistance cannot be obtained, and the metal material for electronic parts is corroded when a gas corrosion test such as chlorine gas, sulfurous acid gas, hydrogen sulfide gas is performed. Thus, the contact resistance is greatly increased as compared to before the gas corrosion test. Also, sufficient resistance to insertion / extraction cannot be obtained, and much of the plating is scraped, resulting in increased contact resistance. Further, when the thickness is increased, the adhesion wear of Sn and In is increased, the resistance to fine sliding wear is poor, the insertion / extraction force is large, and whiskers are easily generated. In order to obtain more sufficient fine sliding wear resistance, low insertion / extraction properties, and low whisker properties, the thickness is set to 0.3 μm or less. Whiskers are generated by the occurrence of screw dislocations. In order to generate screw dislocations, a bulk with a thickness of several hundred nm or more is required. When the thickness of the A layer 14 is 0.3 μm or less, the thickness is not sufficient to cause screw dislocation, and basically whiskers are not generated. In addition, the A layer 14 and the B layer 13 are easily diffused in a short circuit at room temperature, and an alloy is easily formed, so that no whisker is generated.
　Ａ層１４のＳｎ，Ｉｎの付着量は、７～２３０μｇ／ｃｍ2である必要がある。ここで、付着量で定義する理由を説明する。例えば、Ａ層１４の厚みを蛍光Ｘ線膜厚計で測定する場合、Ａ層とその下のＢ層との間に形成した合金層により、測定される厚みの値に誤差が生じる場合がある。一方、付着量で制御する場合、合金層の形成状況に左右されず、より正確な品質管理をすることができる。Ａ層１４のＳｎ，Ｉｎの付着量が７μｇ／ｃｍ2未満であると、充分な耐ガス腐食性が得られず、電子部品用金属材料を塩素ガス、亜硫酸ガス、硫化水素ガス等のガス腐食試験を行うと腐食して、ガス腐食試験前と比較して大きく接触抵抗が増加する。また、充分な耐挿抜性が得られず、めっきの多くが削れてしまって接触抵抗が増加する。また付着量が多くなると、ＳｎやＩｎの凝着磨耗が大きくなり、耐微摺動磨耗性が悪く、挿抜力は大きく、ウィスカも発生しやすくなる。より充分な耐微摺動磨耗性、低挿抜性及び低ウィスカ性を得るためには、２３０μｇ／ｃｍ2以下とする。ウィスカはらせん転位が生じることによって発生するが、らせん転位が生じるためには数百μｇ／ｃｍ2以上の付着量のバルクが必要である。Ａ層１４の付着量が２３０μｇ／ｃｍ2以下では、らせん転位が生じる十分な付着量ではなく、基本的にはウィスカが発生しない。またＡ層とＢ層は常温において短回路拡散が進みやすく、合金が形成しやすいためウィスカが発生しない。 The amount of Sn and In deposited on the A layer 14 needs to be 7 to 230 μg / cm 2 . Here, the reason for defining the amount of adhesion will be described. For example, when the thickness of the A layer 14 is measured with a fluorescent X-ray film thickness meter, an error may occur in the measured thickness value due to the alloy layer formed between the A layer and the B layer below the A layer. . On the other hand, when controlling by the adhesion amount, more accurate quality control can be performed regardless of the formation state of the alloy layer. When the adhesion amount of Sn and In on the A layer 14 is less than 7 μg / cm 2 , sufficient gas corrosion resistance cannot be obtained, and the metal material for electronic parts is corroded by chlorine gas, sulfurous acid gas, hydrogen sulfide gas, etc. Corrosion occurs when the test is performed, and the contact resistance is greatly increased as compared with that before the gas corrosion test. Also, sufficient resistance to insertion / extraction cannot be obtained, and much of the plating is scraped, resulting in increased contact resistance. Further, when the adhesion amount is increased, the adhesion wear of Sn and In is increased, the resistance to fine sliding wear is poor, the insertion / extraction force is large, and whiskers are easily generated. In order to obtain more sufficient fine sliding wear resistance, low insertion / extraction properties, and low whisker properties, it is 230 μg / cm 2 or less. Whiskers are generated by the occurrence of screw dislocations, but in order for the screw dislocations to occur, a bulk with an adhesion amount of several hundred μg / cm 2 or more is required. When the adhesion amount of the A layer 14 is 230 μg / cm 2 or less, the adhesion amount is not sufficient to cause screw dislocation, and basically whiskers are not generated. In addition, the A layer and the B layer easily propagate short circuit at room temperature, and an alloy is easily formed, so that no whisker is generated.
　（Ｂ層）
　Ｂ層１３は、Ａｇ，Ａｕ，Ｐｔ，Ｐｄ，Ｒｕ，Ｒｈ，Ｏｓ，Ｉｒ，またはそれらの合金で形成されている必要がある。Ａｇ，Ａｕ，Ｐｔ，Ｐｄ，Ｒｕ，Ｒｈ，Ｏｓ，Ｉｒは、金属の中では比較的耐熱性を有するという特徴がある。よって基材１１やＣ層１２の組成がＡ層１４側に拡散するのを抑制して耐熱性を向上させる。また、これら金属は、Ａ層１４のＳｎやＩｎと化合物を形成してＳｎやＩｎの酸化膜形成を抑制し、はんだ濡れ性を向上させる。なお、Ａｇ，Ａｕ，Ｐｔ，Ｐｄ，Ｒｕ，Ｒｈ，Ｏｓ，Ｉｒの中では、導電率の観点でＡｇがより望ましい。Ａｇは導電率が高い。例えば高周波の信号用途にＡｇ用いた場合、表皮効果により、インピーダンス抵抗が低くなる。
　Ｂ層１３の合金組成がＡｇ，Ａｕ，Ｐｔ，Ｐｄ，Ｒｕ，Ｒｈ，Ｏｓ，Ｉｒ，またはＡｇとＡｕとＰｔとＰｄとＲｕとＲｈとＯｓとＩｒとの合計で５０質量％以上であり、残合金成分がＢｉ，Ｃｄ，Ｃｏ，Ｃｕ，Ｆｅ，Ｉｎ，Ｍｎ，Ｍｏ，Ｎｉ，Ｐｂ，Ｓｂ，Ｓｅ，Ｓｎ，Ｗ，Ｔｌ，Ｚｎからなる群より選択される１種、もしくは２種以上の金属で構成されていても良い。Ｂ層１３が、例えばＳｎ－Ａｇめっきで形成される等により、その組成が合金になることで、高耐微摺動磨耗性及び高耐挿抜性などを向上させる場合がある。 (B layer)
The B layer 13 needs to be formed of Ag, Au, Pt, Pd, Ru, Rh, Os, Ir, or an alloy thereof. Ag, Au, Pt, Pd, Ru, Rh, Os, and Ir are characterized by having relatively heat resistance among metals. Therefore, it suppresses that the composition of the base material 11 and the C layer 12 diffuses to the A layer 14 side, and improves heat resistance. Further, these metals form a compound with Sn or In of the A layer 14 to suppress the formation of an oxide film of Sn or In, and improve solder wettability. Among Ag, Au, Pt, Pd, Ru, Rh, Os, and Ir, Ag is more desirable from the viewpoint of conductivity. Ag has high conductivity. For example, when Ag is used for high-frequency signal applications, the impedance resistance is lowered due to the skin effect.
The alloy composition of the B layer 13 is Ag, Au, Pt, Pd, Ru, Rh, Os, Ir, or the total of Ag, Au, Pt, Pd, Ru, Rh, Os, and Ir is 50% by mass or more. The residual alloy component is selected from the group consisting of Bi, Cd, Co, Cu, Fe, In, Mn, Mo, Ni, Pb, Sb, Se, Sn, W, Tl, Zn, or two or more You may be comprised with the metal. When the B layer 13 is formed of, for example, Sn—Ag plating, the composition of the B layer 13 becomes an alloy, which may improve the high fine sliding wear resistance and the high insertion / extraction resistance.
　Ｂ層１３の厚みは０．０５～０．５μｍである必要がある。厚みが０．０５μｍ未満であると、充分な高耐微摺動磨耗性や耐挿抜性が得られず、めっきの多くが削れてしまって接触抵抗が増加する。また、厚みが大きくなると、硬い基材１１またはＣ層による薄膜潤滑効果が低下して挿抜力が目標（比較例１よりも１５％以上減）よりも大きくなるため、より充分な低挿抜性を得るためには０．５μｍ以下である必要がある。 The thickness of the B layer 13 needs to be 0.05 to 0.5 μm. If the thickness is less than 0.05 μm, sufficient high fine sliding wear resistance and insertion / extraction resistance cannot be obtained, and much of the plating is scraped, resulting in increased contact resistance. Further, when the thickness is increased, the thin film lubrication effect by the hard base material 11 or the C layer is reduced, and the insertion / extraction force becomes larger than the target (15% or more reduction compared to Comparative Example 1), so that a sufficiently low insertion / extraction property is achieved. In order to obtain it, it is necessary to be 0.5 μm or less.
　Ｂ層１３のＡｇ，Ａｕ，Ｐｔ，Ｐｄ，Ｒｕ，Ｒｈ，Ｏｓ，Ｉｒ，またはそれら合金の付着量は５０～５５０μｇ／ｃｍ2である必要がある。ここで、付着量で定義する理由を説明する。例えば、Ｂ層１３の厚みを蛍光Ｘ線膜厚計で測定する場合、Ａ層１４とその下のＢ層１３との間に形成した合金層により、測定される厚みの値に誤差が生じる場合がある。一方、付着量で制御する場合、合金層の形成状況に左右されず、より正確な品質管理をすることができる。より充分な高耐微摺動磨耗性や耐挿抜性を得るためには、５０μｇ／ｃｍ2以上の付着量が好ましい。また付着量が多いと、硬い基材１１またはＣ層による薄膜潤滑効果が低下して挿抜力が目標（比較例１よりも１５％以上減）よりも大きくなるため、より充分な低挿抜性を得るためには５５０μｇ／ｃｍ2以下である必要がある。 The adhesion amount of Ag, Au, Pt, Pd, Ru, Rh, Os, Ir, or their alloys on the B layer 13 needs to be 50 to 550 μg / cm 2 . Here, the reason for defining the amount of adhesion will be described. For example, when the thickness of the B layer 13 is measured with a fluorescent X-ray film thickness meter, an error occurs in the measured thickness value due to the alloy layer formed between the A layer 14 and the B layer 13 therebelow. There is. On the other hand, when controlling by the adhesion amount, more accurate quality control can be performed regardless of the formation state of the alloy layer. In order to obtain a sufficiently high anti-sliding wear resistance and insertion / extraction resistance, an adhesion amount of 50 μg / cm 2 or more is preferable. Moreover, since the thin film lubrication effect by the hard base material 11 or C layer will fall and the insertion / extraction force will become larger than a target (15% or more reduction | decrease compared with the comparative example 1) when there is much adhesion amount, more sufficient low insertion / extraction property is achieved. In order to obtain it, it is necessary to be 550 μg / cm 2 or less.
　（Ｃ層）
　基材１１とＢ層１３との間には、Ｎｉ，Ｃｒ，Ｍｎ，Ｆｅ，Ｃｏ，Ｃｕからなる群から選択された１種、もしくは２種以上からなるＣ層１２を形成する必要がある。Ｎｉ，Ｃｒ，Ｍｎ，Ｆｅ，Ｃｏ，Ｃｕからなる群から選択された１種、もしくは２種以上の金属を用いてＣ層１２を形成することで、硬いＣ層形成により薄膜潤滑効果が向上して低挿抜性が向上し、Ｃ層１２は基材１１の構成金属がＢ層に拡散するのを防止し、耐熱性試験や耐ガス腐食性試験後の接触抵抗増加及びはんだ濡れ性劣化を抑制するなど、耐久性が向上する。 (C layer)
Between the base material 11 and the B layer 13, it is necessary to form a C layer 12 made of one or more selected from the group consisting of Ni, Cr, Mn, Fe, Co, and Cu. By forming the C layer 12 using one or more metals selected from the group consisting of Ni, Cr, Mn, Fe, Co and Cu, the thin film lubrication effect is improved by forming a hard C layer. C layer 12 prevents the constituent metal of base material 11 from diffusing into B layer, and suppresses increase in contact resistance and solder wettability after heat resistance test and gas corrosion resistance test. The durability is improved.
　Ｃ層１２の合金組成が、Ｎｉ，Ｃｒ，Ｍｎ，Ｆｅ，Ｃｏ，Ｃｕの合計で５０質量％以上であり、さらにＢ，Ｐ，Ｓｎ，Ｚｎからなる群から選択された１種、もしくは２種以上を含んでも良い。Ｃ層１２の合金組成がこのような構成となることで、Ｃ層１２がより硬化することで更に薄膜潤滑効果が向上して低挿抜性が向上し、Ｃ層１２の合金化は基材１１の構成金属がＢ層に拡散するのを更に防止し、耐熱性試験や耐ガス腐食性試験後の接触抵抗増加及びはんだ濡れ性劣化を抑制するなど、耐久性が向上する。 The alloy composition of the C layer 12 is 50% by mass or more in total of Ni, Cr, Mn, Fe, Co, and Cu, and one or two selected from the group consisting of B, P, Sn, and Zn The above may be included. When the alloy composition of the C layer 12 has such a configuration, the C layer 12 is further cured, so that the thin film lubrication effect is further improved and the low insertion / extraction property is improved. Is further prevented from diffusing into the B layer, and an increase in contact resistance and resistance to solder wettability after the heat resistance test and gas corrosion resistance test are improved.
　Ｃ層１２の厚みは０．０５μｍ以上である必要がある。Ｃ層１２の厚みが０．０５μｍ未満であると、硬いＣ層による薄膜潤滑効果が低下して低挿抜性が悪くなり、基材１１の構成金属はＢ層に拡散しやすくなり、耐熱性試験や耐ガス腐食性試験後の接触抵抗増加及びはんだ濡れ性劣化しやすいなど、耐久性が悪くなる。 The thickness of the C layer 12 needs to be 0.05 μm or more. When the thickness of the C layer 12 is less than 0.05 μm, the thin film lubrication effect by the hard C layer is lowered and the low insertion / extraction property is deteriorated, and the constituent metal of the base material 11 is easily diffused into the B layer, and the heat resistance test. In addition, the durability deteriorates, such as contact resistance increase and solder wettability deterioration after gas corrosion resistance test.
　Ｃ層１２のＮｉ，Ｃｒ，Ｍｎ，Ｆｅ，Ｃｏ，Ｃｕの付着量が、０．０３ｍｇ／ｃｍ2以上である必要がある。ここで、付着量で定義する理由を説明する。例えば、Ｃ層１２の厚みを蛍光Ｘ線膜厚計で測定する場合、Ａ層１４、Ｂ層１３、及び基材１１等と形成した合金層により、測定される厚みの値に誤差が生じる場合がある。一方、付着量で制御する場合、合金層の形成状況に左右されず、より正確な品質管理をすることができる。また付着量が０．０３ｍｇ／ｃｍ2未満であると、硬いＣ層による薄膜潤滑効果が低下して低挿抜性が悪くなり、基材１１の構成金属はＢ層に拡散しやすくなり、耐熱性試験や耐ガス腐食性試験後の接触抵抗増加及びはんだ濡れ性劣化しやすいなど、耐久性が悪くなる。 The adhesion amount of Ni, Cr, Mn, Fe, Co, and Cu on the C layer 12 needs to be 0.03 mg / cm 2 or more. Here, the reason for defining the amount of adhesion will be described. For example, when the thickness of the C layer 12 is measured with a fluorescent X-ray film thickness meter, an error occurs in the measured thickness value due to the alloy layer formed with the A layer 14, the B layer 13, the base material 11, and the like. There is. On the other hand, when controlling by the adhesion amount, more accurate quality control can be performed regardless of the formation state of the alloy layer. Further, if the adhesion amount is less than 0.03 mg / cm 2 , the thin film lubrication effect by the hard C layer is lowered and the low insertion / extraction property is deteriorated, and the constituent metal of the base material 11 is easily diffused into the B layer, and is heat resistant. Durability deteriorates, such as increased contact resistance after test and gas corrosion resistance test and solder wettability.
　（Ａ層とＢ層との関係）
　Ａ層１４の厚み［μｍ］／Ｂ層１３の厚み［μｍ］の比が０．０２～４．００である必要がある。Ａ層１４の厚み［μｍ］／Ｂ層１３の厚み［μｍ］の比が０．０２未満であると充分な耐ガス腐食性が得られず、電子部品用金属材料を塩素ガス、亜硫酸ガス、硫化水素ガス等のガス腐食試験を行うと腐食して、ガス腐食試験前と比較して大きく接触抵抗が増加する。また、Ａ層１４の厚み［μｍ］／Ｂ層１３の厚み［μｍ］の比４．００を越えると、表層にＡ層１４が多く存在し、耐微摺動磨耗性が悪くなる。
　Ａ層１４の付着量［μｇ／ｃｍ2］／Ｂ層１３の付着量［μｇ／ｃｍ2］の比が０．１０～３．００である必要がある。Ａ層１４の付着量［μｇ／ｃｍ2］／Ｂ層１３の付着量［μｇ／ｃｍ2］の比が０．１０未満であると充分な耐ガス腐食性が得られず、電子部品用金属材料を塩素ガス、亜硫酸ガス、硫化水素ガス等のガス腐食試験を行うと腐食して、ガス腐食試験前と比較して大きく接触抵抗が増加する。また層１４の付着量［μｇ／ｃｍ2］／Ｂ層１３の付着量［μｇ／ｃｍ2］の比が３．００を超えると、表層にＡ層１４が多く存在し、耐微摺動磨耗性が悪くなる。 (Relationship between layer A and layer B)
The ratio of the thickness [μm] of the A layer 14 to the thickness [μm] of the B layer 13 needs to be 0.02 to 4.00. If the ratio of the thickness [μm] of the A layer 14 / thickness [μm] of the B layer 13 is less than 0.02, sufficient gas corrosion resistance cannot be obtained, and the metal material for electronic parts is made of chlorine gas, sulfurous acid gas, When a gas corrosion test such as hydrogen sulfide gas is performed, it corrodes and the contact resistance is greatly increased as compared to before the gas corrosion test. On the other hand, if the ratio of the thickness [μm] of the A layer 14 / the thickness [μm] of the B layer 13 exceeds 4.00, a large amount of the A layer 14 is present on the surface layer, resulting in poor resistance to fine sliding wear.
The ratio of the adhesion amount [μg / cm 2 ] of the A layer 14 to the adhesion amount [μg / cm 2 ] of the B layer 13 needs to be 0.10 to 3.00. If the ratio of the adhesion amount [μg / cm 2 ] of the A layer 14 / the adhesion amount [μg / cm 2 ] of the B layer 13 is less than 0.10, sufficient gas corrosion resistance cannot be obtained, and the metal for electronic parts When the material is subjected to a gas corrosion test such as chlorine gas, sulfurous acid gas, hydrogen sulfide gas, etc., it corrodes and the contact resistance is greatly increased compared to before the gas corrosion test. Further, when the ratio of the adhesion amount [μg / cm 2 ] of the layer 14 / the adhesion amount [μg / cm 2 ] of the B layer 13 exceeds 3.00, a large amount of the A layer 14 is present on the surface layer, and resistance to fine sliding wear Sexuality gets worse.
　ＸＰＳ（Ｘ線光電子分光）でＤｅｐｔｈ分析を行ったとき、最表からＣ層の濃度が２０ａｔ％となる範囲で、Ａ層の濃度（ａｔ％）＜〔Ｂ層の濃度（ａｔ％）＋３０〕であることが好ましい。Ａ層の濃度（ａｔ％）≧〔Ｂ層の濃度（ａｔ％）＋３０〕であると表層にＡ層１４が多く存在し、耐微摺動磨耗性が悪くなる場合がある。 When depth analysis is performed by XPS (X-ray photoelectron spectroscopy), the concentration of the A layer (at%) <[concentration of the B layer (at%) + 30] in the range where the concentration of the C layer is 20 at% from the outermost table. It is preferable that If the concentration of the A layer (at%) ≧ [concentration of the B layer (at%) + 30], a large amount of the A layer 14 exists on the surface layer, and the fine sliding wear resistance may deteriorate.
　＜電子部品用金属材料の特性＞
　Ａ層１４の表面（Ａ層の表面から測定した）のビッカース硬さはＨｖ１００以上であるのが好ましい。Ａ層１４の表面のビッカース硬さがＨｖ１００以上であると、硬いＡ層によって薄膜潤滑効果が向上し、低挿抜性が向上する。また一方で、Ａ層１４表面（Ａ層の表面から測定した）のビッカース硬さはＨｖ１０００以下あるのが好ましい。Ａ層１４の表面のビッカース硬さがＨｖ１０００以下であると、曲げ加工性が向上し、本発明の電子部品用金属材料をプレス成形した場合に、成形した部分にクラックが入り難くなり、耐ガス腐食性（耐久性）低下を抑制する。
　Ａ層１４の表面（Ａ層の表面から測定した）の押し込み硬さは１０００ＭＰａ以上あるのが好ましい。Ａ層１４の表面の押し込み硬さが１０００ＭＰａ以上であると、硬いＡ層によって薄膜潤滑効果が向上し、低挿抜性が向上する。また一方でＡ層１４の表面（Ａ層の表面から測定した）の押し込み硬さは１００００ＭＰａ以下あるのが好ましい。Ａ層１４の表面の押し込み硬さが１００００ＭＰａ以下であると、曲げ加工性が向上し、本発明の電子部品用金属材料をプレス成形した場合に、成形した部分にクラックが入り難くなり、耐ガス腐食性（耐久性）低下を抑制する。 <Characteristics of metal materials for electronic parts>
The Vickers hardness of the surface of the A layer 14 (measured from the surface of the A layer) is preferably Hv100 or more. When the Vickers hardness of the surface of the A layer 14 is Hv100 or more, the thin A layer improves the thin film lubrication effect, and the low insertion / extraction property is improved. On the other hand, the Vickers hardness of the surface of the A layer 14 (measured from the surface of the A layer) is preferably Hv1000 or less. When the Vickers hardness of the surface of the A layer 14 is Hv1000 or less, bending workability is improved, and when the metal material for electronic parts of the present invention is press-molded, cracks are hardly formed in the molded part, and gas resistance Reduces corrosive (durability) degradation.
The indentation hardness of the surface of the A layer 14 (measured from the surface of the A layer) is preferably 1000 MPa or more. When the indentation hardness of the surface of the A layer 14 is 1000 MPa or more, the hard A layer improves the thin film lubrication effect, and the low insertion / extraction property is improved. On the other hand, the indentation hardness of the surface of the A layer 14 (measured from the surface of the A layer) is preferably 10,000 MPa or less. When the indentation hardness of the surface of the A layer 14 is 10000 MPa or less, bending workability is improved, and when the metal material for electronic parts of the present invention is press-molded, cracks hardly occur in the molded part, and gas resistance Reduces corrosive (durability) degradation.
　Ａ層１４の表面の算術平均高さ（Ｒａ）は０．１μｍ以下であるのが好ましい。Ａ層１４の表面の算術平均高さ（Ｒａ）が０．１μｍ以下であると比較的腐食しやすい凸部が少なくなり平滑となるため、耐ガス腐食性が向上する。
　Ａ層１４の表面の最大高さ（Ｒｚ）は１μｍ以下であるのが好ましい。Ａ層１４の表面の最大高さ（Ｒｚ）が１μｍ以下であると比較的腐食しやすい凸部が少なくなり平滑となるため、耐ガス腐食性が向上する。 The arithmetic average height (Ra) of the surface of the A layer 14 is preferably 0.1 μm or less. When the arithmetic average height (Ra) of the surface of the A layer 14 is 0.1 μm or less, the number of convex portions that are relatively easily corroded is reduced and the surface becomes smooth, so that the gas corrosion resistance is improved.
The maximum height (Rz) of the surface of the A layer 14 is preferably 1 μm or less. When the maximum height (Rz) of the surface of the A layer 14 is 1 μm or less, the number of convex portions that are relatively easily corroded is reduced and smoothed, and thus the gas corrosion resistance is improved.
　ＸＰＳ（Ｘ線光電子分光）でＤｅｐｔｈ分析を行ったとき、最表層（Ａ層）１４のＳｎまたはＩｎの原子濃度（ａｔ％）の最高値を示す位置（Ｄ1）、中層（Ｂ層）１３のＡｇ，Ａｕ，Ｐｔ，Ｐｄ，Ｒｕ，Ｒｈ，ＯｓまたはＩｒの原子濃度（ａｔ％）の最高値を示す位置（Ｄ2）、下層（Ｃ層）１２のＮｉ，Ｃｒ，Ｍｎ，Ｆｅ，ＣｏまたはＣｕの原子濃度（ａｔ％）の最高値示す位置（Ｄ3）が最表面からＤ1、Ｄ2、Ｄ3の順で存在することが好ましい。最表面からＤ1、Ｄ2、Ｄ3の順で存在しない場合、充分な耐ガス腐食性が得られず、電子部品用金属材料を塩素ガス、亜硫酸ガス、硫化水素ガス等のガス腐食試験を行うと腐食して、ガス腐食試験前と比較して大きく接触抵抗が増加するおそれがある。
　ＸＰＳ（Ｘ線光電子分光）でＤｅｐｔｈ分析を行ったとき、最表層（Ａ層）１４のＳｎまたはＩｎの原子濃度（ａｔ％）の最高値、及び、中層（Ｂ層）１３のＡｇ，Ａｕ，Ｐｔ，Ｐｄ，Ｒｕ，Ｒｈ，ＯｓまたはＩｒの原子濃度（ａｔ％）の最高値がそれぞれ１０ａｔ％以上であって、下層（Ｃ層）１２のＮｉ，Ｃｒ，Ｍｎ，Ｆｅ，ＣｏまたはＣｕの原子濃度（ａｔ％）が２５ａｔ％以上である深さが５０ｎｍ以上であることが好ましい。最表層（Ａ層）１４のＳｎまたはＩｎの原子濃度（ａｔ％）の最高値、及び、中層（Ｂ層）１３のＡｇ，Ａｕ，Ｐｔ，Ｐｄ，Ｒｕ，Ｒｈ，ＯｓまたはＩｒの原子濃度（ａｔ％）の最高値がそれぞれ１０ａｔ％未満であって、下層（Ｃ層）１２のＮｉ，Ｃｒ，Ｍｎ，Ｆｅ，ＣｏまたはＣｕの原子濃度（ａｔ％）が２５ａｔ％以上である深さが５０ｎｍ未満である場合、低挿抜性や耐久性（耐熱性、耐ガス腐食性、はんだ濡れ性等）は、基材成分が最表層（Ａ層）１４または中層（Ｂ層）１３に拡散して悪くなるおそれがある。 When the depth analysis is performed by XPS (X-ray photoelectron spectroscopy), the position (D 1 ) showing the highest value of the atomic concentration (at%) of Sn or In in the outermost layer (A layer) 14, the middle layer (B layer) 13 The position (D 2 ) showing the highest atomic concentration (at%) of Ag, Au, Pt, Pd, Ru, Rh, Os or Ir of Ni, Cr, Mn, Fe, Co in the lower layer (C layer) 12 or highest value indicating the position of Cu atomic concentration (at%) (D 3) is preferably present in the order of D 1, D 2, D 3 from the outermost surface. If there is no D 1 , D 2 , D 3 in this order from the outermost surface, sufficient gas corrosion resistance cannot be obtained, and metal materials for electronic parts are subjected to gas corrosion tests such as chlorine gas, sulfurous acid gas, hydrogen sulfide gas, etc. If it is carried out, it may corrode and the contact resistance may be greatly increased compared to before the gas corrosion test.
When depth analysis was performed by XPS (X-ray photoelectron spectroscopy), the highest value of the atomic concentration (at%) of Sn or In in the outermost layer (A layer) 14 and Ag, Au, The maximum value of atomic concentration (at%) of Pt, Pd, Ru, Rh, Os or Ir is 10 at% or more, respectively, and atoms of Ni, Cr, Mn, Fe, Co or Cu in the lower layer (C layer) 12 The depth at which the concentration (at%) is 25 at% or more is preferably 50 nm or more. The maximum value of the atomic concentration (at%) of Sn or In in the outermost layer (A layer) 14 and the atomic concentration of Ag, Au, Pt, Pd, Ru, Rh, Os or Ir in the intermediate layer (B layer) ( The depth at which the maximum value of each of the atomic (at%) is less than 10 at% and the atomic concentration (at%) of Ni, Cr, Mn, Fe, Co or Cu in the lower layer (C layer) 12 is 25 at% or more is 50 nm. If it is less, the low insertion / extraction property and durability (heat resistance, gas corrosion resistance, solder wettability, etc.) are poor as the base material component diffuses into the outermost layer (A layer) 14 or the middle layer (B layer) 13. There is a risk.
　＜電子部品用金属材料の用途＞
　本発明の電子部品用金属材料の用途は特に限定しないが、例えば電子部品用金属材料を接点部分に用いたコネクタ端子、電子部品用金属材料を接点部分に用いたＦＦＣ端子またはＦＰＣ端子、電子部品用金属材料を外部接続用電極に用いた電子部品などが挙げられる。なお、端子については、圧着端子、はんだ付け端子、プレスフィット端子等、配線側との接合方法によらない。外部接続用電極には、タブに表面処理を施した接続部品や半導体のアンダーバンプメタル用に表面処理を施した材料などがある。
　また、このように形成されたコネクタ端子を用いてコネクタを作製しても良く、ＦＦＣ端子またはＦＰＣ端子を用いてＦＦＣまたはＦＰＣを作製しても良い。
　電子部品用金属材料を、ハウジングに取り付ける装着部の一方側にメス端子接続部が、他方側に基板接続部がそれぞれ設けられ、前記基板接続部を基板に形成されたスルーホールに圧入して前記基板に取り付ける圧入型端子も本発明の電子部品用金属材料である。
　コネクタはオス端子とメス端子の両方が本発明の電子部品用金属材料であっても良いし、オス端子またはメス端子の片方だけであっても良い。なおオス端子とメス端子の両方を本発明の電子部品用金属材料にすることで、更に低挿抜性が向上する。 <Applications of metal materials for electronic parts>
The use of the metal material for electronic parts of the present invention is not particularly limited. For example, a connector terminal using the metal material for electronic parts as a contact part, an FFC terminal or FPC terminal using the metal material for electronic parts as a contact part, and an electronic part Electronic parts using metal materials for external connection as electrodes for external connection. In addition, about a terminal, it does not depend on the joining method with a wiring side, such as a crimp terminal, a solder terminal, and a press fit terminal. Examples of the external connection electrode include a connection component in which a surface treatment is performed on a tab and a material in which a surface treatment is applied to a semiconductor under bump metal.
Moreover, a connector may be produced using the connector terminal formed in this way, and an FFC or FPC may be produced using an FFC terminal or an FPC terminal.
The metal material for electronic parts is provided with a female terminal connection part on one side of the mounting part to be attached to the housing and a board connection part on the other side, and the board connection part is press-fitted into a through hole formed on the board. The press-fit terminal attached to the substrate is also a metal material for electronic parts of the present invention.
In the connector, both the male terminal and the female terminal may be the metal material for electronic parts of the present invention, or only one of the male terminal and the female terminal. In addition, low insertion property is further improved by making both the male terminal and the female terminal into the metal material for electronic parts of the present invention.
　＜電子部品用金属材料の製造方法＞
　本発明の電子部品用金属材料の製造方法としては、湿式（電気、無電解）めっき、乾式（スパッタ、イオンプレーティング等）めっき等を用いることができる。具体的な方法としては、素材１１上にＣ層１２を成膜し、Ｃ層１２上にＢ層１３を成膜し、Ｂ層１３上にＡ層１４を成膜し、Ａ層１４とＢ層１３が拡散によって合金層が形成させる方法がある。この製造方法であると、Ｓｎの凝着力を一層小さくすることにより高耐微摺動磨耗性及び高耐挿抜性が得られ、低挿抜性や低ウィスカ等の特性を向上させる。 <Method for producing metal material for electronic parts>
As a method for producing a metal material for electronic parts of the present invention, wet (electrical, electroless) plating, dry (sputtering, ion plating, etc.) plating, or the like can be used. Specifically, the C layer 12 is formed on the material 11, the B layer 13 is formed on the C layer 12, the A layer 14 is formed on the B layer 13, and the A layer 14 and the B layer are formed. There is a method in which the alloy layer is formed by diffusion of the layer 13. In this manufacturing method, by further reducing the Sn adhesion force, high micro-sliding wear resistance and high insertion / extraction resistance are obtained, and characteristics such as low insertion / extraction and low whisker are improved.
　（熱処理）
　Ａ層１４を形成させた後に、高耐微摺動磨耗性、高耐挿抜性、低ウィスカ性及び低挿抜性を向上させる目的で熱処理を施しても良い。熱処理によってＡ層１４とＢ層１３とが合金層を形成しやすくなり、Ｓｎの凝着力を一層小さくすることにより高耐微摺動磨耗性及び高耐挿抜性が得られ、低挿抜性や低ウィスカ等の特性が向上する。なお、この熱処理については、処理条件（温度×時間）は適宜選択できる。また、特にこの熱処理はしなくてもよい。
　熱処理は、温度５００℃以下、１２時間以内で行われることが好ましい。温度が５００℃を超えると、接触抵抗が高くなり、はんだ濡れ性が劣るなどの問題が発生する場合がある。熱処理時間が１２時間を超えると、接触抵抗が高くなり、はんだ濡れ性が劣るなどの問題が発生する場合がある。 (Heat treatment)
After the A layer 14 is formed, heat treatment may be performed for the purpose of improving high micro-sliding wear resistance, high insertion / extraction resistance, low whisker resistance, and low insertion / extraction characteristics. The heat treatment makes it easy for the A layer 14 and the B layer 13 to form an alloy layer, and by further reducing the Sn adhesion force, a high micro-sliding wear resistance and a high insertion / extraction resistance can be obtained. The characteristics such as whisker are improved. In addition, about this heat processing, process conditions (temperature x time) can be selected suitably. Further, this heat treatment is not particularly required.
The heat treatment is preferably performed at a temperature of 500 ° C. or less and within 12 hours. When the temperature exceeds 500 ° C., problems such as high contact resistance and poor solder wettability may occur. When the heat treatment time exceeds 12 hours, problems such as high contact resistance and poor solder wettability may occur.
　Ａ層１４上、またはＡ層１４上に熱処理を施した後に、高耐微摺動磨耗性、高耐挿抜性、低挿抜性及び高耐久性（耐熱性、耐ガス腐食性、はんだ濡れ性等）を向上させる目的で後処理を施しても良い。後処理によって潤滑性が向上し、更なる低挿抜性が得られ、またＡ層とＢ層の酸化が抑制されて、耐熱性、耐ガス腐食性及びはんだ濡れ性等の耐久性が向上する。具体的な後処理としてはインヒビターを用いた、リン酸塩処理、潤滑処理、シランカップリング処理等がある。なお、この熱処理については、処理条件（温度×時間）は適宜選択できる。また、特にこの熱処理はしなくてもよい。 After heat treatment on the A layer 14 or on the A layer 14, high micro-sliding wear resistance, high insertion / extraction resistance, low insertion / extraction characteristics and high durability (heat resistance, gas corrosion resistance, solder wettability, etc.) ) May be post-treated for the purpose of improving. Post-treatment improves lubricity, further lower insertion / removability is obtained, and oxidation of the A layer and B layer is suppressed to improve durability such as heat resistance, gas corrosion resistance, and solder wettability. Specific post-treatment includes phosphate treatment, lubrication treatment, silane coupling treatment, etc. using an inhibitor. In addition, about this heat processing, process conditions (temperature x time) can be selected suitably. Further, this heat treatment is not particularly required.
　以下、本発明の実施例を比較例と共に示すが、これらは本発明をより良く理解するために提供するものであり、本発明が限定されることを意図するものではない。 Hereinafter, examples of the present invention will be shown together with comparative examples, but these are provided for better understanding of the present invention and are not intended to limit the present invention.
　実施例及び比較例として、基材、Ｃ層、Ｂ層、Ａ層をこの順に設けて熱処理を行うことで形成した試料を、以下の表１～７に示す条件でそれぞれ作製した。
　表１に基材の作製条件を、表２にＣ層の作製条件を、表３にＢ層の作製条件を、表４にＡ層の作製条件を、表５に熱処理条件をそれぞれ示す。また、表６（表６－１、表６－２、表６－３）に各実施例で使用した各層の作製条件及び熱処理の条件を、表７に各比較例で使用した各層の作製条件及び熱処理の条件それぞれ示す。 As examples and comparative examples, samples formed by providing a base material, a C layer, a B layer, and an A layer in this order and performing a heat treatment were prepared under the conditions shown in Tables 1 to 7 below.
Table 1 shows the conditions for producing the substrate, Table 2 shows the conditions for producing the C layer, Table 3 shows the conditions for producing the B layer, Table 4 shows the conditions for producing the A layer, and Table 5 shows the heat treatment conditions. In addition, Table 6 (Tables 6-1, 6-2, and 6-3) shows the preparation conditions and heat treatment conditions of each layer used in each example, and Table 7 shows the preparation conditions of each layer used in each comparative example. And heat treatment conditions are shown respectively.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
　（厚みの測定）
　Ａ層、Ｂ層、Ｃ層の厚みは、Ａ層、Ｂ層、Ｃ層の元素を有していない基材にそれぞれ表面処理を施し、それぞれ蛍光Ｘ線膜厚計（Ｓｅｉｋｏ　Ｉｎｓｔｒｕｍｅｎｔｓ製　ＳＦＴ９５００Ｘ、コリメータ０．１ｍｍΦ）で実際の厚みを測定した。例えば、Ｓｎめっきの場合には、基材がＣｕ－１０質量％Ｓｎ－０．１５質量％Ｐであると、基材にＳｎが有しており、正確なＳｎめっきの厚みがわからないため、Ｓｎが基材の組成を有していない、Ｃｕ－３０質量％Ｚｎで厚みを測定した。 (Measurement of thickness)
The thicknesses of the A layer, the B layer, and the C layer were each subjected to surface treatment on the base material that does not have the elements of the A layer, the B layer, and the C layer, and each was subjected to a fluorescent X-ray film thickness meter The actual thickness was measured at 0.1 mmΦ). For example, in the case of Sn plating, if the substrate is Cu-10 mass% Sn-0.15 mass% P, the substrate has Sn, and the exact Sn plating thickness is not known. The thickness was measured with Cu-30 mass% Zn, which does not have the composition of the base material.
　（付着量の測定）
　各試料を硫酸や硝酸等で酸分解し、ＩＣＰ（誘導結合プラズマ）発光分光分析により各金属の付着量を測定した。なお具体的に用いる酸は、それぞれのサンプルを有する組成によって異なる。 (Measurement of adhesion amount)
Each sample was acid-decomposed with sulfuric acid, nitric acid or the like, and the adhesion amount of each metal was measured by ICP (inductively coupled plasma) emission spectroscopic analysis. In addition, the acid used concretely changes with compositions which each sample has.
　（組成の決定）
　測定した付着量に基づき、各金属の組成を算出した。 (Determination of composition)
Based on the measured adhesion amount, the composition of each metal was calculated.
　（層構造の決定）
　得られた試料の層構造は、ＸＰＳ（Ｘ線光電子分光）分析による深さ（Ｄｅｐｔｈ）プロファイルで決定した。分析した元素は、Ａ層、Ｂ層、Ｃ層の組成と、Ｃ及びＯである。これら元素を指定元素とする。また、指定元素の合計を１００％として、各元素の濃度（ａｔ％）を分析した。ＸＰＳ（Ｘ線光電子分光）分析での厚みは、分析によるチャートの横軸の距離（ＳｉＯ2換算での距離）に対応する。
　また、得られた試料の表面は、ＸＰＳ（Ｘ線光電子分光）分析によるＳｕｒｖｅｙ測定にて定性分析も行った。定性分析の濃度の分解能は０．１ａｔ％とした。
　ＸＰＳ装置としては、アルバック・ファイ株式会社製５６００ＭＣを用い、到達真空度：５．７×１０-9Ｔｏｒｒ、励起源：単色化ＡｌＫα、出力：２１０Ｗ、検出面積：８００μｍΦ、入射角：４５度、取り出し角：４５度、中和銃なしとし、以下のスパッタ条件で測定した。
　イオン種：Ａｒ+
　加速電圧：３ｋＶ
　掃引領域：３ｍｍ×３ｍｍ
　レート：２．８ｎｍ／ｍｉｎ．（ＳｉＯ2換算） (Determination of layer structure)
The layer structure of the obtained sample was determined by a depth profile by XPS (X-ray photoelectron spectroscopy) analysis. The analyzed elements are the composition of the A layer, the B layer, and the C layer, and C and O. These elements are designated elements. Further, the concentration (at%) of each element was analyzed with the total of the designated elements as 100%. The thickness in XPS (X-ray photoelectron spectroscopy) analysis corresponds to the distance on the horizontal axis of the chart by analysis (distance in terms of SiO 2 ).
Further, the surface of the obtained sample was also subjected to qualitative analysis by survey measurement by XPS (X-ray photoelectron spectroscopy) analysis. The resolution of the qualitative analysis concentration was 0.1 at%.
As an XPS device, ULVAC-PHI Co., Ltd. 5600MC was used, ultimate vacuum: 5.7 × 10 −9 Torr, excitation source: monochromatic AlKα, output: 210 W, detection area: 800 μmΦ, incident angle: 45 degrees, The take-off angle was 45 degrees, no neutralizing gun was used, and the measurement was performed under the following sputtering conditions.
Ion species: Ar +
Acceleration voltage: 3 kV
Sweep area: 3mm x 3mm
Rate: 2.8 nm / min. (SiO 2 equivalent)
　（評価）
　各試料について以下の評価を行った。 (Evaluation)
The following evaluation was performed for each sample.
　Ａ．耐微摺動磨耗性
　耐微摺動磨耗性は、山崎精機研究所製精密摺動試験装置ＣＲＳ－Ｇ２０５０型を使用し、摺動距離０．５ｍｍ、摺動速度１ｍｍ／ｓ、接触荷重１Ｎ、摺動回数５００往復条件で摺動回数と接触抵抗との関係を評価した。サンプル数は５個とし、各サンプルの最小値から最大値の範囲を採用した。目標とする特性は、摺動回数１００回時に接触抵抗が５０ｍΩ以下である。接触抵抗は、＜５０、５０～２００ｍΩで区分した。 A. Fine sliding wear resistance Fine sliding wear resistance is measured using a precision sliding test device CRS-G2050 manufactured by Yamazaki Seiki Laboratories, with a sliding distance of 0.5 mm, a sliding speed of 1 mm / s, and a contact load of 1 N. The relationship between the number of sliding times and the contact resistance was evaluated under the condition that the number of sliding times was 500. The number of samples was 5, and the range from the minimum value to the maximum value of each sample was adopted. The target characteristic is a contact resistance of 50 mΩ or less when the number of sliding times is 100. The contact resistance was classified as <50, 50-200 mΩ.
　Ｂ．耐挿抜性
　下記の「Ｃ．挿抜力」に記載の方法で１０回挿抜試験を行い、挿抜試験後の接触抵抗で評価した。目標とする特性は、接触抵抗１０ｍΩ以下である。接触抵抗は、１～５、２～７、3～９、１０＜ｍΩで区分した。 B. Insertion / extraction resistance Ten insertion / extraction tests were performed by the method described in “C. Insertion / extraction force” below, and the contact resistance after the insertion / extraction test was evaluated. The target characteristic is a contact resistance of 10 mΩ or less. The contact resistance was classified as 1-5, 2-7, 3-9, 10 <mΩ.
　Ｃ．挿抜力
　挿抜力は，市販のＳｎリフローめっきメス端子（０９０型住友ＴＳ／矢崎０９０ＩＩシリーズメス端子非防水／Ｆ０９０－ＳＭＴＳ）を用いて、実施例及び比較例に係るめっきしたオス端子と挿抜試験することによって評価した。
　試験に用いた測定装置は，アイコーエンジニアリング製１３１１ＮＲであり、オスピンの摺動距離５ｍｍで評価した。サンプル数は５個とし，挿抜力は、挿入力と抜去力が同等であるため、各サンプルの最大挿入力の値を平均した値を採用した。挿抜力のブランク材としては、比較例１のサンプルを採用した。
　挿抜力の目標は、比較例１の最大挿抜力と比較して８５％未満である。これは、比較例４が比較例１の最大挿入力と比較して９０％であり、この比較例４よりも、より大きな挿抜力の減少を目標とした。 C. Insertion / extraction force Insertion / extraction force is tested with commercially available Sn reflow plated female terminals (090 type Sumitomo TS / Yazaki 090II series female terminal non-waterproof / F090-SMTS) with the plated male terminals according to Examples and Comparative Examples. Was evaluated by
The measuring apparatus used for the test was 1311NR made by Ikko Engineering, and the evaluation was performed with a male spin sliding distance of 5 mm. Since the number of samples was 5, and the insertion force was the same as the insertion force, the value obtained by averaging the maximum insertion force values of each sample was adopted. The sample of Comparative Example 1 was adopted as the blank material for the insertion / extraction force.
The target of the insertion / extraction force is less than 85% compared to the maximum insertion / extraction force of Comparative Example 1. This is 90% of Comparative Example 4 compared to the maximum insertion force of Comparative Example 1, and aimed to reduce the insertion / extraction force larger than that of Comparative Example 4.
　Ｄ．ウィスカ
　ウィスカは、ＪＥＩＴＡ　ＲＣ－５２４１の荷重試験（球圧子法）にて評価した。すなわち、各サンプルに対して荷重試験を行い、荷重試験を終えたサンプルをＳＥＭ（ＪＥＯＬ社製、型式ＪＳＭ－５４１０）にて１００～１００００倍の倍率で観察して、ウィスカの発生状況を観察した。荷重試験条件を以下に示す。
　球圧子の直径：Φ１ｍｍ±０．１ｍｍ
　試験荷重：２Ｎ±０．２Ｎ
　試験時間：１２０時間
　サンプル数：１０
　目標とする特性は、長さ２０μｍ以上のウィスカが発生しないことであるが、最大の目標としては、ウィスカが１本も発生しないこととした。 D. Whisker Whisker was evaluated by a load test (ball indenter method) of JEITA RC-5241. That is, a load test was performed on each sample, and the sample after the load test was observed at a magnification of 100 to 10,000 times with a SEM (manufactured by JEOL, model JSM-5410) to observe the occurrence of whiskers. . The load test conditions are shown below.
Diameter of ball indenter: Φ1mm ± 0.1mm
Test load: 2N ± 0.2N
Test time: 120 hours Number of samples: 10
The target characteristic is that whiskers having a length of 20 μm or more are not generated, but the maximum target is that no whisker is generated.
　Ｅ．接触抵抗
　接触抵抗は、山崎精機製接点シミュレーターＣＲＳ－１１３－Ａｕ型を使用し、接点荷重５０ｇの条件で４端子法にて測定した。サンプル数は５個とし、各サンプルの最小値から最大値の範囲を採用した。目標とする特性は、接触抵抗１０ｍΩ以下である。 E. Contact resistance The contact resistance was measured by a 4-terminal method using a contact simulator CRS-113-Au type manufactured by Yamazaki Seiki Co., Ltd. under the condition of a contact load of 50 g. The number of samples was 5, and the range from the minimum value to the maximum value of each sample was adopted. The target characteristic is a contact resistance of 10 mΩ or less.
　Ｆ．耐熱性
　耐熱性は、大気加熱（１５５℃×５００ｈ）試験後のサンプルの接触抵抗を測定し、評価した。目標とする特性は、接触抵抗１０ｍΩ以下であるが、最大の目標としては、接触抵抗が、耐熱性試験前後で変化がない（同等である）こととした。耐熱性は、接触抵抗が１～３、２～４、３～７、１０＜ｍΩで区分した。 F. Heat resistance Heat resistance was evaluated by measuring the contact resistance of a sample after an atmospheric heating (155 ° C. × 500 h) test. The target characteristic is a contact resistance of 10 mΩ or less, and the maximum target is that the contact resistance does not change before and after the heat resistance test (is equivalent). The heat resistance was classified according to contact resistance of 1 to 3, 2 to 4, 3 to 7, 10 <mΩ.
　Ｇ．耐ガス腐食性
　耐ガス腐食性は、下記の試験環境で評価した。耐ガス腐食性の評価は、環境試験を終えた試験後のサンプルの接触抵抗と外観である。目標とする特性は、接触抵抗１０ｍΩ以下で、外観は変色がないことである。しかし接触抵抗の最大の目標としては、耐ガス腐食性試験前後で変化がない（同等である）こととした。耐ガス腐食性は、接触抵抗が１～３、２～４、６～９、１０＜ｍΩで区分した。
　　硫化水素ガス腐食試験
　　亜硫酸濃度：３ｐｐｍ
　　温度：４０℃
　　湿度：８０％ＲＨ
　　曝露時間：９６ｈ
　　サンプル数：５個 G. Gas Corrosion Resistance Gas corrosion resistance was evaluated in the following test environment. The evaluation of gas corrosion resistance is the contact resistance and appearance of the sample after the environmental test. The target characteristics are that the contact resistance is 10 mΩ or less and the appearance is not discolored. However, the maximum target of contact resistance is that there is no change (equivalent) before and after the gas corrosion resistance test. The gas corrosion resistance was classified according to contact resistance of 1 to 3, 2 to 4, 6 to 9, and 10 <mΩ.
Hydrogen sulfide gas corrosion test Sulfurous acid concentration: 3ppm
Temperature: 40 ° C
Humidity: 80% RH
Exposure time: 96h
Number of samples: 5
　Ｈ．はんだ濡れ性
　はんだ濡れ性はめっき後のサンプルを評価した。ソルダーチェッカ（レスカ社製ＳＡＴ－５０００）を使用し、フラックスとして市販の２５％ロジンメタノールフラックスを用い、メニスコグラフ法にてはんだ濡れ時間を測定した。はんだはＳｎ－３Ａｇ－０．５Ｃｕ（２５０℃）を用いた。サンプル数は５個とし、各サンプルの最小値から最大値の範囲を採用した。目標とする特性は、ゼロクロスタイム５秒（ｓ）以下である。ゼロクロスは、１～３、５＜ｓで区分した。 H. Solder wettability The solder wettability was evaluated on the sample after plating. Solder checker (SAT-5000 manufactured by Reska Co., Ltd.) was used, a commercially available 25% rosin methanol flux was used as the flux, and the solder wetting time was measured by the meniscograph method. As the solder, Sn-3Ag-0.5Cu (250 ° C.) was used. The number of samples was 5, and the range from the minimum value to the maximum value of each sample was adopted. The target characteristic is a zero cross time of 5 seconds (s) or less. Zero-crossing was classified as 1 to 3, 5 <s.
　Ｉ．曲げ加工性
　曲げ加工性は、Ｗ字型の金型を用いて試料の板厚と曲げ半径の比が１となる条件にて９０°曲げで評価した。評価は曲げ加工部表面を光学顕微鏡で観察し、クラックが観察されない場合の実用上問題ないと判断した場合には○とし、クラックが認められた場合を×とした。なお、サンプル数は３個とした。 I. Bending workability The bending workability was evaluated by bending at 90 ° using a W-shaped mold under the condition that the ratio of the plate thickness to the bending radius was 1. In the evaluation, the surface of the bent portion was observed with an optical microscope, and when it was judged that there was no practical problem when no crack was observed, it was evaluated as ◯, and when the crack was observed, it was evaluated as ×. The number of samples was three.
　Ｊ．ビッカース硬さ
　最表層（Ａ層）のビッカース硬さは、サンプル表面より荷重９８０．７ｍＮ（Ｈｖ０．１）、荷重保持時間１５秒で打根を打って測定した。 J. et al. Vickers hardness The Vickers hardness of the outermost layer (A layer) was measured from the surface of the sample with a load of 980.7 mN (Hv 0.1) and a load holding time of 15 seconds.
　Ｋ．押し込み硬さ
　最表層（Ａ層）の押し込み硬さは、超微小硬さ試験（エリオニクス製ＥＮＴ－２１００）により、サンプル表面に荷重０．１ｍＮで打根を打って測定した。なお、１試料当たり５回測定した。 K. Indentation Hardness The indentation hardness of the outermost layer (A layer) was measured by hitting a root of the sample surface with a load of 0.1 mN by an ultra micro hardness test (ENTION 2100 manufactured by Elionix). In addition, it measured 5 times per sample.
　Ｌ．表面粗さ
　表面粗さ（算術平均高さ（Ｒａ）及び最大高さ（Ｒｚ））の測定は、ＪＩＳ　Ｂ　０６０１に準拠し、非接触式三次元測定装置（三鷹光器社製、形式ＮＨ－３）を用いて行った。カットオフは０．２５ｍｍ、測定長さは１．５０ｍｍで、１試料当たり５回測定した。
　各条件及び評価結果を表８～１６に示す。 L. Surface Roughness Surface roughness (arithmetic average height (Ra) and maximum height (Rz)) is measured according to JIS B 0601, a non-contact type three-dimensional measuring device (manufactured by Mitaka Kogyo Co., Ltd., model NH- 3). The cut-off was 0.25 mm, the measurement length was 1.50 mm, and measurement was performed 5 times per sample.
Tables 8 to 16 show the conditions and evaluation results.
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000016
Figure JPOXMLDOC01-appb-T000016
Figure JPOXMLDOC01-appb-T000017
Figure JPOXMLDOC01-appb-T000017
Figure JPOXMLDOC01-appb-T000018
Figure JPOXMLDOC01-appb-T000018
　実施例１～７６は、耐微摺動磨耗性、耐挿抜性のいずれも優れた電子部品金属材料であった。
　比較例１はブランク材である。
　比較例２は、比較例１のブランク材のＳｎめっきを薄くして作製したものであるが、はんだ濡れ性が悪かった。
　比較例３は、比較例２と比較して熱処理を施さないで作製したものであるが、挿抜力が目標よりも高かった。
　比較例４は、比較例２と比較して中層にＣｕめっきを施して作製したものであるが、挿抜力は比較例１と比較して９０％であった。
　比較例５は、比較例４と比較してＳｎめっきを薄くして作製したものであるが、はんだ濡れ性が悪かった。
　比較例６は、比較例５と比較して熱処理を施さないで作製したものであるが、挿抜力が目標よりも高かった。
　比較例７は、比較例１のブランク材と比較して下層にＣｕめっきを施して作製したものであるが、比較例１と特性は変わらなかった。
　比較例８は、比較例１のブランク材と比較して下層のＮｉめっきを厚く施して作製したものであるが、比較例１と特性は変わらなかった。
　比較例９～１３は、Ｂ層の厚みや付着量が目標よりも薄く，少なかったものであるが、
耐微摺動磨耗性が悪く、耐挿抜性も高かった。
　比較例１４は、Ａ層の厚みや付着量が目標よりも薄く、少なかったものであるが、耐ガス腐食性が悪く、試験後の外観に変色が確認された。
　比較例１５は、Ａ層の厚みや付着量が目標よりも厚く、多かったものであるが、Ａ層とＢ層の関係においてＡ層の割合が多く、ＸＰＳ（Ｘ線光電子分光）でのＤｅｐｔｈ測定でＡ層が目標よりも高い濃度で存在したため、耐微摺動磨耗性が悪かった。
　比較例１６は、Ａ層の厚みや付着量が目標よりも薄く、少なかったものであるが、耐ガス腐食性が悪く、試験後の外観に変色が確認された。
　比較例１７は、Ａ層の厚みや付着量が目標よりも厚く、多かったものであるが、Ａ層とＢ層の関係目標どおりであったもののやはりＡ層の厚みや付着量が目標よりも厚く、多いために耐微摺動磨耗性が悪かった。
　比較例１８は、Ａ層の厚みや付着量が目標よりも薄く、少なかったものであるが、耐ガス腐食性が悪く、試験後の外観に変色が確認された。
　比較例１９は、Ａ層の厚みや付着量が目標よりも厚く、多かったものであるが、Ａ層とＢ層の関係目標どおりであったもののやはりＡ層の厚みや付着量が目標よりも厚く、多いために耐微摺動磨耗性が悪かった。また挿抜力も高かった。
　比較例２０～２２は、Ｂ層の厚みや付着量が目標よりも厚く、多かったものであるが、挿入力が高かった。
　比較例２３は、Ｃ層の厚みや付着量が目標よりも薄く、少なかったものであるが、挿入力が高く、耐熱性及びはんだ濡れ性も悪かった。
　比較例２４は、目標の熱処理よりも時間を長くしたものであるが、はんだが濡れなかった。
　比較例２５は、目標の熱処理よりも温度を高くしたものであるが、はんだが濡れなかった。
　比較例２６は、Ａ層の厚みや付着量が目標よりも薄く、少なかったものであるが、ＸＰＳ（Ｘ線光電子分光）でのＤｅｐｔｈ測定で、前記Ａ層のＳｎまたはＩｎの原子濃度（ａｔ％）の最高値が１０ａｔ％以下であり、耐ガス腐食性が悪く、硫化水素ガス腐食試験後の接触抵抗が目標を上回った。
　比較例２７は、Ｂ層の厚みや付着量が目標よりも薄く，少なかったものである、ＸＰＳ（Ｘ線光電子分光）でのＤｅｐｔｈ測定で、前記Ｂ層の原子濃度（ａｔ％）の最高値が１０ａｔ％以下であり、耐熱性やはんだ濡れ性が悪かった。
　比較例２８は、Ｃ層の厚みや付着量が目標よりも薄く、少なかったものであるが、挿入力が高く、耐熱性及びはんだ濡れ性も悪かった。
　比較例２９は、実施例２と比較して、ＳｎとＡｇのめっき順序を逆にして作製したものであるが、ＸＰＳ（Ｘ線光電子分光）でのＤｅｐｔｈ測定で前記最表層（Ａ層）のＳｎまたはＩｎの原子濃度（ａｔ％）の最高値を示す位置（Ｄ1）、前記中層（Ｂ層）のＡｇ，Ａｕ，Ｐｔ，Ｐｄ，Ｒｕ，Ｒｈ，ＯｓまたはＩｒの原子濃度（ａｔ％）の最高値を示す位置（Ｄ2）がＤ2、Ｄ1の順で存在するため、耐ガス腐食性が悪く、硫化水素ガス腐食試験後の接触抵抗が目標を上回った。 Examples 1 to 76 were electronic component metal materials excellent in both fine sliding wear resistance and insertion / extraction resistance.
Comparative Example 1 is a blank material.
Comparative Example 2 was produced by thinning the Sn plating of the blank material of Comparative Example 1, but the solder wettability was poor.
Although the comparative example 3 was produced without performing heat processing compared with the comparative example 2, the insertion / extraction force was higher than the target.
Comparative Example 4 was prepared by applying Cu plating to the middle layer as compared with Comparative Example 2, but the insertion / extraction force was 90% as compared with Comparative Example 1.
Comparative Example 5 was prepared by making Sn plating thinner than Comparative Example 4, but the solder wettability was poor.
Comparative Example 6 was prepared without heat treatment as compared with Comparative Example 5, but the insertion / extraction force was higher than the target.
Comparative Example 7 was prepared by applying Cu plating to the lower layer as compared with the blank material of Comparative Example 1, but the characteristics were not different from Comparative Example 1.
Comparative Example 8 was produced by applying a lower Ni plating thicker than the blank material of Comparative Example 1, but the characteristics were not different from Comparative Example 1.
In Comparative Examples 9 to 13, the thickness and adhesion amount of the B layer were thinner than the target and less,
The fine sliding wear resistance was poor and the insertion / extraction resistance was also high.
In Comparative Example 14, the thickness and adhesion amount of the A layer were thinner and less than the target, but the gas corrosion resistance was poor, and discoloration was confirmed in the appearance after the test.
In Comparative Example 15, the thickness and adhesion amount of the A layer were thicker and larger than the target, but the ratio of the A layer was large in the relationship between the A layer and the B layer, and the depth in XPS (X-ray photoelectron spectroscopy) was high. In the measurement, the A layer was present at a higher concentration than the target, so the resistance to fine sliding wear was poor.
In Comparative Example 16, the thickness and adhesion amount of the A layer were thinner and less than the target, but the gas corrosion resistance was poor, and discoloration was confirmed in the appearance after the test.
In Comparative Example 17, the thickness and adhesion amount of the A layer were thicker and larger than the target, but the thickness and adhesion amount of the A layer were still larger than the target, although the relationship target of the A layer and B layer was the same as the target. It was thick and thick, so it had poor sliding resistance.
In Comparative Example 18, the thickness and adhesion amount of the A layer were thinner and less than the target, but the gas corrosion resistance was poor, and discoloration was confirmed in the appearance after the test.
In Comparative Example 19, the thickness and adhesion amount of the A layer were thicker and larger than the target, but the thickness and adhesion amount of the A layer were still larger than the target, although the relationship between the A layer and the B layer was as intended. It was thick and thick, so it had poor sliding resistance. The insertion / extraction force was also high.
In Comparative Examples 20 to 22, the thickness and adhesion amount of the B layer were thicker and larger than the target, but the insertion force was high.
In Comparative Example 23, the thickness and adhesion amount of the C layer were thinner and less than the target, but the insertion force was high, and the heat resistance and solder wettability were also poor.
In Comparative Example 24, the time was longer than the target heat treatment, but the solder did not get wet.
In Comparative Example 25, the temperature was higher than the target heat treatment, but the solder did not get wet.
In Comparative Example 26, the thickness and adhesion amount of the A layer were thinner and less than the target. However, in the depth measurement by XPS (X-ray photoelectron spectroscopy), the atomic concentration of Sn or In (at %) Was 10 at% or less, the gas corrosion resistance was poor, and the contact resistance after the hydrogen sulfide gas corrosion test exceeded the target.
In Comparative Example 27, the maximum value of the atomic concentration (at%) of the B layer in the depth measurement by XPS (X-ray photoelectron spectroscopy), in which the thickness and adhesion amount of the B layer were thinner and less than the target. Was 10 at% or less, and heat resistance and solder wettability were poor.
In Comparative Example 28, the thickness and adhesion amount of the C layer were thinner and less than the target, but the insertion force was high, and the heat resistance and solder wettability were also poor.
Comparative Example 29 was produced by reversing the plating order of Sn and Ag as compared with Example 2, but the depth of the outermost layer (A layer) was measured by Depth measurement using XPS (X-ray photoelectron spectroscopy). Position (D 1 ) showing the maximum value of atomic concentration (at%) of Sn or In, atomic concentration (at%) of Ag, Au, Pt, Pd, Ru, Rh, Os or Ir in the middle layer (B layer) Since the position (D 2 ) showing the maximum value of D 2 exists in the order of D 2 and D 1 , the gas corrosion resistance was poor, and the contact resistance after the hydrogen sulfide gas corrosion test exceeded the target.
　また、図２に実施例２に係るＸＰＳ（Ｘ線光電子分光）のＤｅｐｔｈ測定結果を示す。図２より、最表からＣ層が２０ａｔ％となる範囲においてＡ層の濃度（ａｔ％）＜〔Ｂ層の濃度（ａｔ％）＋３０〕を満たすことが分かる。
　また、Ａ層のＳｎまたはＩｎの原子濃度（ａｔ％）の最高値を示す位置（Ｄ1）、Ｂ層のＡｇ，Ａｕ，Ｐｔ，Ｐｄ，Ｒｕ，Ｒｈ，ＯｓまたはＩｒの原子濃度（ａｔ％）の最高値を示す位置（Ｄ2）、Ｃ層のＮｉ，Ｃｒ，Ｍｎ，Ｆｅ，ＣｏまたはＣｕの原子濃度（ａｔ％）の最高値を示す位置（Ｄ3）が最表面からＤ1、Ｄ2、Ｄ3の順で存在し、Ａ層のＳｎまたはＩｎの原子濃度（ａｔ％）の最高値、及び、Ｂ層のＡｇ，Ａｕ，Ｐｔ，Ｐｄ，Ｒｕ，Ｒｈ，ＯｓまたはＩｒの原子濃度（ａｔ％）の最高値がそれぞれ１０ａｔ％以上であって、前記Ｃ層のＮｉ，Ｃｒ，Ｍｎ，Ｆｅ，ＣｏまたはＣｕの原子濃度（ａｔ％）が２５ａｔ％以上である深さが５０ｎｍ以上であることが分かる。 FIG. 2 shows a depth measurement result of XPS (X-ray photoelectron spectroscopy) according to the second embodiment. FIG. 2 shows that the concentration of the A layer (at%) <[the concentration of the B layer (at%) + 30] is satisfied in the range where the C layer is 20 at%.
Further, the position (D 1 ) showing the highest value of Sn or In atomic concentration (at%) in the A layer, and the atomic concentration (at%) of Ag, Au, Pt, Pd, Ru, Rh, Os or Ir in the B layer. ) Showing the highest value (D 2 ), and the position (D 3 ) showing the highest atomic concentration (at%) of Ni, Cr, Mn, Fe, Co or Cu in the C layer is D 1 from the outermost surface, D 2 , D 3 are present in this order, and the highest value of atomic concentration (at%) of Sn or In in the A layer, and Ag, Au, Pt, Pd, Ru, Rh, Os or Ir atoms in the B layer The maximum value of the concentration (at%) is 10 at% or more, and the depth at which the atomic concentration (at%) of Ni, Cr, Mn, Fe, Co or Cu of the C layer is 25 at% or more is 50 nm or more. It turns out that it is.
１０　電子部品用金属材料
１１　基材
１２　Ｃ層
１３　Ｂ層
１４　Ａ層 10 Metal Material for Electronic Components 11 Base Material 12 C Layer 13 B Layer 14 A Layer

Claims (22)

  1. 　基材上にＳｎ，Ｉｎ，またはそれらの合金からなるＡ層が形成され、
    　前記基材と前記Ａ層との間にＡｇ，Ａｕ，Ｐｔ，Ｐｄ，Ｒｕ，Ｒｈ，Ｏｓ，Ｉｒ，またはそれらの合金からなるＢ層が形成され、
    　前記基材と前記Ｂ層との間に、Ｎｉ，Ｃｒ，Ｍｎ，Ｆｅ，Ｃｏ，Ｃｕからなる群から選択された１種、もしくは２種以上からなるＣ層が形成され、
    　前記Ａ層の厚みが０．０１～０．３μｍであり、
    　前記Ｂ層の厚みが０．０５～０．５μｍであり、
    　前記Ｃ層の厚みが０．０５μm以上であり、
    　前記Ａ層の厚み／前記Ｂ層の厚みの比が０．０２～４．００である電子部品用金属材料。     A layer made of Sn, In, or an alloy thereof is formed on the substrate,
    A B layer made of Ag, Au, Pt, Pd, Ru, Rh, Os, Ir, or an alloy thereof is formed between the base material and the A layer,
    Between the base material and the B layer, a C layer composed of one or more selected from the group consisting of Ni, Cr, Mn, Fe, Co, Cu is formed,
    The thickness of the A layer is 0.01 to 0.3 μm,
    The thickness of the B layer is 0.05 to 0.5 μm,
    The thickness of the C layer is 0.05 μm or more;
    A metal material for electronic parts, wherein the ratio of the thickness of the A layer / the thickness of the B layer is 0.02 to 4.00.
  2. 　基材上にＳｎ，Ｉｎ，またはそれらの合金からなるＡ層が形成され、
    　前記基材と前記Ａ層との間にＡｇ，Ａｕ，Ｐｔ，Ｐｄ，Ｒｕ，Ｒｈ，Ｏｓ，Ｉｒ，またはそれらの合金からなるＢ層が形成され、
    　前記基材と前記Ｂ層との間に、Ｎｉ，Ｃｒ，Ｍｎ，Ｆｅ，Ｃｏ，Ｃｕからなる群から選択された１種、もしくは２種以上からなるＣ層が形成され、
    　前記Ａ層の付着量が７～２３０μｇ／ｃｍ2であり、
    　前記Ｂ層の付着量が５０～５５０μｇ／ｃｍ2であり、
    　前記Ｃ層の付着量が０．０３ｍｇ／ｃｍ2以上であり、
    　前記Ａ層の付着量／前記Ｂ層の付着量の比が０．１０～３．００である電子部品用金属材料。     A layer made of Sn, In, or an alloy thereof is formed on the substrate,
    A B layer made of Ag, Au, Pt, Pd, Ru, Rh, Os, Ir, or an alloy thereof is formed between the base material and the A layer,
    Between the base material and the B layer, a C layer composed of one or more selected from the group consisting of Ni, Cr, Mn, Fe, Co, Cu is formed,
    The adhesion amount of the A layer is 7 to 230 μg / cm 2 ;
    The adhesion amount of the B layer is 50 to 550 μg / cm 2 ;
    The adhesion amount of the C layer is 0.03 mg / cm 2 or more,
    A metal material for electronic parts, wherein a ratio of the adhesion amount of the A layer / the adhesion amount of the B layer is 0.10 to 3.00.
  3. 　ＸＰＳ（Ｘ線光電子分光）でＤｅｐｔｈ分析を行ったとき、最表からＣ層の濃度が２０ａｔ％となる範囲で、
    　　Ａ層の濃度（ａｔ％）＜Ｂ層の濃度（ａｔ％）＋３０
    を満たす請求項１又は２に記載の電子部品用金属材料。     When the depth analysis is performed by XPS (X-ray photoelectron spectroscopy), the concentration of the C layer is 20 at% from the outermost surface.
    A layer concentration (at%) <B layer concentration (at%) + 30
    The metal material for electronic components according to claim 1 or 2, wherein
  4. 　前記Ａ層の合金組成がＳｎ，Ｉｎ，またはＳｎとＩｎとの合計で５０質量％以上であり、残合金成分がＡｓ，Ｂｉ，Ｃｄ，Ｃｏ，Ｃｒ，Ｃｕ，Ｆｅ，Ｍｎ，Ｍｏ，Ｎｉ，Ｓｂ，Ｗ，Ｚｎからなる群より選択される１種、もしくは２種以上の金属からなる請求項１～３のいずれかに記載の電子部品用金属材料。 The alloy composition of the A layer is Sn, In, or the total of Sn and In is 50% by mass or more, and the remaining alloy components are As, Bi, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, The metal material for electronic parts according to any one of claims 1 to 3, comprising one or more metals selected from the group consisting of Sb, W, and Zn.
  5. 　前記Ｂ層の合金組成がＡｇ，Ａｕ，Ｐｔ，Ｐｄ，Ｒｕ，Ｒｈ，Ｏｓ，Ｉｒ，またはＡｇとＡｕとＰｔとＰｄとＲｕとＲｈとＯｓとＩｒとの合計で５０質量％以上であり、残合金成分がＢｉ，Ｃｄ，Ｃｏ，Ｃｕ，Ｆｅ，Ｍｎ，Ｍｏ，Ｎｉ，Ｐｂ，Ｓｂ，Ｓｅ，Ｗ，Ｔｌ，Ｚｎからなる群より選択される１種、もしくは２種以上の金属からなる請求項１～４のいずれかに記載の電子部品用金属材料。 The alloy composition of the B layer is Ag, Au, Pt, Pd, Ru, Rh, Os, Ir, or a total of Ag, Au, Pt, Pd, Ru, Rh, Os, and Ir is 50% by mass or more. The residual alloy component is composed of one or more metals selected from the group consisting of Bi, Cd, Co, Cu, Fe, Mn, Mo, Ni, Pb, Sb, Se, W, Tl, and Zn. Item 5. The metal material for electronic parts according to any one of Items 1 to 4.
  6. 　前記Ｃ層の合金組成がＮｉ，Ｃｒ，Ｍｎ，Ｆｅ，Ｃｏ，Ｃｕの合計で５０質量％以上であり、さらにＢ，Ｐ，Ｚｎからなる群から選択された１種、もしくは２種以上の金属からなる請求項１～５のいずれかに記載の電子部品用金属材料。 The alloy composition of the C layer is 50% by mass or more in total of Ni, Cr, Mn, Fe, Co, and Cu, and one or more metals selected from the group consisting of B, P, and Zn The metal material for electronic parts according to any one of claims 1 to 5, comprising:
  7. 　表面のビッカース硬さがＨｖ１００以上である請求項１～６のいずれかに記載の電子部品用金属材料。 7. The metal material for electronic parts according to claim 1, wherein the surface has a Vickers hardness of Hv 100 or more.
  8. 　超微小硬さ試験により、表面に荷重０．１ｍＮで打根を打って測定したときの、表面の押し込み硬さが１０００ＭＰａ以上である請求項１～７のいずれかに記載の電子部品用金属材料。 The metal for electronic parts according to any one of claims 1 to 7, wherein the indentation hardness of the surface is 1000 MPa or more when measured by applying a root to the surface with a load of 0.1 mN by an ultra micro hardness test. material.
  9. 　表面のビッカース硬さがＨｖ１０００以下である請求項１～８のいずれかに記載の電子部品用金属材料。 The metal material for electronic parts according to any one of claims 1 to 8, wherein the surface has a Vickers hardness of Hv1000 or less.
  10. 　超微小硬さ試験により、表面に荷重０．１ｍＮで打根を打って測定したときの、表面の押し込み硬さが１００００ＭＰａ以下である請求項１～９のいずれかに記載の電子部品用金属材料。 The metal for electronic parts according to any one of claims 1 to 9, wherein the indentation hardness of the surface is 10000 MPa or less when measured by applying a root to the surface with a load of 0.1 mN by an ultra micro hardness test. material.
  11. 　表面の算術平均高さ（Ｒａ）が０．１μｍ以下である請求項１～１０のいずれかに記載の電子部品用金属材料。 11. The metal material for an electronic component according to claim 1, wherein the arithmetic average height (Ra) of the surface is 0.1 μm or less.
  12. 　表面の最大高さ（Ｒｚ）が１μｍ以下である請求項１～１１のいずれかに記載の電子部品用金属材料。 The metal material for electronic parts according to any one of claims 1 to 11, wherein the maximum height (Rz) of the surface is 1 µm or less.
  13. 　ＸＰＳ（Ｘ線光電子分光）でＤｅｐｔｈ分析を行ったとき、前記Ａ層のＳｎまたはＩｎの原子濃度（ａｔ％）の最高値を示す位置（Ｄ1）、前記Ｂ層のＡｇ，Ａｕ，Ｐｔ，Ｐｄ，Ｒｕ，Ｒｈ，ＯｓまたはＩｒの原子濃度（ａｔ％）の最高値を示す位置（Ｄ2）、前記Ｃ層のＮｉ，Ｃｒ，Ｍｎ，Ｆｅ，ＣｏまたはＣｕの原子濃度（ａｔ％）の最高値を示す位置（Ｄ3）が最表面からＤ1、Ｄ2、Ｄ3の順で存在する請求項１～１２のいずれかに記載の電子部品用金属材料。 When the depth analysis is performed by XPS (X-ray photoelectron spectroscopy), the position (D 1 ) showing the highest value of the atomic concentration (at%) of Sn or In in the A layer, Ag, Au, Pt, Position (D 2 ) showing the highest value of atomic concentration (at%) of Pd, Ru, Rh, Os or Ir, atomic concentration (at%) of Ni, Cr, Mn, Fe, Co or Cu in the C layer The metal material for electronic parts according to any one of claims 1 to 12, wherein the position (D 3 ) exhibiting the highest value exists in the order of D 1 , D 2 , D 3 from the outermost surface.
  14. 　ＸＰＳ（Ｘ線光電子分光）でＤｅｐｔｈ分析を行ったとき、前記Ａ層のＳｎまたはＩｎの原子濃度（ａｔ％）の最高値、及び、前記Ｂ層のＡｇ，Ａｕ，Ｐｔ，Ｐｄ，Ｒｕ，Ｒｈ，ＯｓまたはＩｒの原子濃度（ａｔ％）の最高値がそれぞれ１０ａｔ％以上であって、前記Ｃ層のＮｉ，Ｃｒ，Ｍｎ，Ｆｅ，ＣｏまたはＣｕの原子濃度（ａｔ％）が２５ａｔ％以上である深さが５０ｎｍ以上である請求項１～１３のいずれかに記載の電子部品用金属材料。 When depth analysis was performed by XPS (X-ray photoelectron spectroscopy), the highest value of the atomic concentration (at%) of Sn or In in the A layer and Ag, Au, Pt, Pd, Ru, Rh in the B layer , Os or Ir atomic concentration (at%) is 10 at% or more respectively, and the atomic concentration (at%) of Ni, Cr, Mn, Fe, Co or Cu in the C layer is 25 at% or more. The metal material for electronic parts according to any one of claims 1 to 13, wherein a certain depth is 50 nm or more.
  15. 　請求項１～１４のいずれかに記載の電子部品用金属材料を接点部分に用いたコネクタ端子。 A connector terminal using the metal material for electronic parts according to any one of claims 1 to 14 as a contact portion.
  16. 　請求項１５に記載のコネクタ端子を用いたコネクタ。 A connector using the connector terminal according to claim 15.
  17. 　請求項１～１４のいずれかに記載の電子部品用金属材料を接点部分に用いたＦＦＣ端子。 15. An FFC terminal using the metal material for electronic parts according to claim 1 as a contact portion.
  18. 　請求項１～１４のいずれかに記載の電子部品用金属材料を接点部分に用いたＦＰＣ端子。 15. An FPC terminal using the metal material for electronic parts according to claim 1 as a contact portion.
  19. 　請求項１７に記載のＦＦＣ端子を用いたＦＦＣ。 FFC using the FFC terminal according to claim 17.
  20. 　請求項１８に記載のＦＰＣ端子を用いたＦＰＣ。 FPC using the FPC terminal according to claim 18.
  21. 　請求項１～１４のいずれかに記載の電子部品用金属材料を外部接続用電極に用いた電子部品。 An electronic component using the metal material for an electronic component according to any one of claims 1 to 14 as an electrode for external connection.
  22. 　請求項１～１４のいずれかに記載の電子部品用金属材料を、ハウジングに取り付ける装着部の一方側にメス端子接続部が、他方側に基板接続部がそれぞれ設けられ、前記基板接続部を基板に形成されたスルーホールに圧入して前記基板に取り付ける圧入型端子に用いた電子部品。 A female terminal connection portion is provided on one side of a mounting portion for attaching the metal material for electronic parts according to any one of claims 1 to 14 to a housing, and a substrate connection portion is provided on the other side. An electronic component used for a press-fit terminal that is press-fitted into a through-hole formed on the board and attached to the substrate.
PCT/JP2013/051354 2012-04-13 2013-01-23 Metal material for electronic component WO2013153832A1 (en)

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CN201380019665.0A CN104204296B (en) 2012-04-13 2013-01-23 Electronic component-use metal material
KR1020147031715A KR101688290B1 (en) 2012-04-13 2013-01-23 Metal material for electronic component

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KR20150002803A (en) 2015-01-07

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