TWI548512B - Metal materials for electronic components - Google Patents

Metal materials for electronic components Download PDF

Info

Publication number
TWI548512B
TWI548512B TW102102406A TW102102406A TWI548512B TW I548512 B TWI548512 B TW I548512B TW 102102406 A TW102102406 A TW 102102406A TW 102102406 A TW102102406 A TW 102102406A TW I548512 B TWI548512 B TW I548512B
Authority
TW
Taiwan
Prior art keywords
layer
metal material
patent application
electronic parts
substrate
Prior art date
Application number
TW102102406A
Other languages
Chinese (zh)
Other versions
TW201341171A (en
Inventor
Yoshitaka Shibuya
Kazuhiko Fukamachi
Atsushi Kodama
Original Assignee
Jx Nippon Mining & Metals Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jx Nippon Mining & Metals Corp filed Critical Jx Nippon Mining & Metals Corp
Publication of TW201341171A publication Critical patent/TW201341171A/en
Application granted granted Critical
Publication of TWI548512B publication Critical patent/TWI548512B/en

Links

Classifications

    • 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
    • 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
    • B32B15/017—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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Insulated Conductors (AREA)
  • Conductive Materials (AREA)
  • Non-Insulated Conductors (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)
  • Contacts (AREA)

Description

電子零件用金屬材料 Metal materials for electronic parts

本發明係有關於一種電子零件用金屬材料。 The present invention relates to a metal material for electronic parts.

於作為民生用及車載用電子機器用連接零件之連接器中，使用有於黃銅或磷青銅之表面實施有Ni或Cu之基底鍍敷，進而於其上實施有Sn或Sn合金鍍敷之材料。通常要求Sn或Sn合金鍍敷具有低接觸電阻及高焊料潤濕性之特性，進而，近年來對於鍍敷材經壓製加工而成形所得之公端子及母端子亦要求其插合時之***力降低。又，有於製造步驟中在鍍敷表面產生引起短路等問題之針狀結晶即晶鬚之情況，從而亦必需良好地抑制該晶鬚。 In the connector for connecting components for consumer electronics and automotive electronic equipment, base plating of Ni or Cu is applied to the surface of brass or phosphor bronze, and Sn or Sn alloy plating is applied thereto. material. Generally, Sn or Sn alloy plating is required to have low contact resistance and high solder wettability. Further, in recent years, the male terminal and the female terminal which are formed by press working of a plating material are also required to have an insertion force at the time of insertion. reduce. Further, there is a case where a needle crystal which is a problem of a short circuit or the like is generated on the plating surface in the manufacturing step, and it is necessary to suppress the whisker well.

又根據連接器(尤其是車載用電子機器用連接設備)而要求有考慮振動等影響之高耐微滑動磨耗性或高耐插拔性(即便反覆將公端子與母端子插合及脫離亦不增加接觸電阻)等特性。 In addition, depending on the connector (especially the connection device for electronic devices for vehicles), it is required to have high resistance to micro-sliding wear and high insertion resistance in consideration of vibration or the like (even if the male terminal and the female terminal are repeatedly inserted and detached from each other. Increase the contact resistance and other characteristics.

針對於此，於專利文獻1中，揭示有如下之被覆有銀之電子材料：於自表面起厚度為0.05μm以上之表層由Ni、Co或該等之合金所構成之基材上，局部被覆有Ag或Ag合金，且於露出之基材表面與局部被覆之Ag或Ag合金層上，以0.01~1.0μm之厚度被覆有In、Zn、Sn、Pd或該等之合金。而且，記載有藉此可長期維持作為電子材料之優異之焊接性及機械電性連接之連接性。 In this regard, Patent Document 1 discloses an electronic material coated with silver which is partially coated on a substrate composed of Ni, Co or alloys having a thickness of 0.05 μm or more from the surface. There is an Ag or Ag alloy, and on the surface of the exposed substrate and the partially coated Ag or Ag alloy layer, In, Zn, Sn, Pd or the like is coated with a thickness of 0.01 to 1.0 μm. Further, it is described that the excellent solderability and mechanical electrical connection as an electronic material can be maintained for a long period of time.

又，於專利文獻2中，揭示有如下之被覆有Sn或Sn合金之材料：於Cu或Cu合金基材表面設置有Ni、Co或包含該等之合金之第1被覆層，並於其表面設置有Ag或Ag合金之第2被覆層，進而於其表面設置有Sn或Sn合金之被覆層而成。而且，記載有藉此可提供即便於高溫下使用亦無表面之氧化變色且接觸電阻之增加較少、外觀及接觸特性長期良好之被覆有Sn或Sn合金之材料。 Further, Patent Document 2 discloses a material coated with a Sn or a Sn alloy in which Ni, Co or a first coating layer containing the alloy is provided on the surface of a Cu or Cu alloy substrate, and is coated on the surface thereof. A second coating layer of Ag or an Ag alloy is provided, and a coating layer of Sn or a Sn alloy is provided on the surface thereof. Further, it is described that a material coated with Sn or a Sn alloy, which has no surface oxidative discoloration, has little increase in contact resistance, and has excellent appearance and contact characteristics for a long period of time, can be provided.

又，於專利文獻3中，揭示有如下之被覆有Sn或Sn合金之材料：於Cu或Cu合金基材表面設置有Ni、Co或包含該等之合金之第1被覆層，並於其表面設置有Ag或Ag合金之第2被覆層，進而於其表面設置有Sn或Sn合金之熔融凝固被覆層而成。而且，記載有藉此可提供即便於高溫下使用亦無表面之氧化變色且接觸電阻之增加較少、外觀及接觸特性長期良好之被覆有Sn或Sn合金之材料。 Further, Patent Document 3 discloses a material coated with a Sn or a Sn alloy in which Ni, Co or a first coating layer containing the alloy is provided on the surface of a Cu or Cu alloy substrate, and is coated on the surface thereof. A second coating layer of Ag or an Ag alloy is provided, and a molten solidified coating layer of Sn or a Sn alloy is provided on the surface thereof. Further, it is described that a material coated with Sn or a Sn alloy, which has no surface oxidative discoloration, has little increase in contact resistance, and has excellent appearance and contact characteristics for a long period of time, can be provided.

又，於專利文獻4中，揭示有一種藉由預處理之錫晶鬚防止方法，其特徵在於：(a)於被鍍敷物上形成選自由銀、鈀、鉑、鉍、銦、鎳、鋅、鈦、鋯、鋁、鉻、銻所構成之群中之基底用金屬薄膜中之任一者後，(b)於上述基底用金屬薄膜上形成錫或錫合金之鍍敷皮膜。而且記載有藉此可藉簡便之操作而於錫系皮膜有效地防止錫晶鬚，該錫系皮膜係為了良好地確保焊接性等而形成於例如銅系基底等被鍍敷物之表面上者。 Further, in Patent Document 4, there is disclosed a method for preventing tin whisker by pretreatment, characterized in that: (a) forming on the object to be plated is selected from the group consisting of silver, palladium, platinum, rhodium, indium, nickel, and zinc. And (b) forming a plating film of tin or a tin alloy on the metal film for the base, after any one of the metal thin films for the base in the group consisting of titanium, zirconium, aluminum, chromium, and antimony. In addition, it is described that the tin-based film can be effectively prevented from being formed on the surface of the object to be plated such as a copper-based substrate in order to secure the weldability and the like by a simple operation.

又，於專利文獻5中，揭示有如下之鍍敷構造：係於鍍敷用基體之表面形成有銀鍍敷層，進而於該銀鍍敷層之表面形成有厚度為0.001~0.1μm之錫或銦或者鋅之鍍敷層而成，再對該鍍銀構造體進行熱處理而獲得。而且記載有藉此可提供耐熱性優異且因銀硫化引起之反射率降低較 少之發光元件收納用支撐體，及不易因硫化而變色、具有銀本身之光澤且接觸電阻較小之電子零件用被覆方法。 Further, Patent Document 5 discloses a plating structure in which a silver plating layer is formed on the surface of a plating substrate, and a tin having a thickness of 0.001 to 0.1 μm is formed on the surface of the silver plating layer. Or a plating layer of indium or zinc, which is obtained by heat-treating the silver-plated structure. Further, it is described that the heat resistance is excellent and the reflectance due to silver vulcanization is lowered. A light-emitting element storage support body and a coating method for an electronic component which are less likely to be discolored by vulcanization, have a gloss of silver, and have a small contact resistance.

[專利文獻1]日本特開昭61-124597號公報 [Patent Document 1] Japanese Patent Laid-Open No. 61-124597

[專利文獻2]日本特開平1-306574號公報 [Patent Document 2] Japanese Patent Laid-Open No. Hei 1-306574

[專利文獻3]日本特開平2-301573號公報 [Patent Document 3] Japanese Patent Laid-Open No. Hei 2-301573

[專利文獻4]日本特開2003-129278號公報 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2003-129278

[專利文獻5]日本特開2011-122234號公報 [Patent Document 5] Japanese Patent Laid-Open Publication No. 2011-122234

然而，於專利文獻1~5所記載之技術中，為未能充分地滿足耐微滑動磨耗性、耐插拔性、低晶鬚性及低插拔性等特性者。 However, in the techniques described in Patent Documents 1 to 5, the characteristics such as micro-sliding abrasion resistance, insertion resistance, low whisker property, and low plug-in property are not sufficiently satisfied.

如此，先前之具有Sn/Ag/Ni基底鍍敷構造之電子零件用金屬材料中，於耐微滑動磨耗性、耐插拔性、低晶鬚性及低插拔性等存在問題，改善該等全部之方針尚不明確。 As described above, in the metal material for electronic parts having the Sn/Ag/Ni underlying plating structure, there are problems such as micro sliding wear resistance, insertion resistance, low whisker property, and low insertion and removal properties, and the like is improved. The overall policy is not clear.

本發明係為了解決上述問題而完成者，其課題在於提供一種具有耐微滑動磨耗性、耐插拔性、低晶鬚性及低插拔性之電子零件用金屬材料及其之製造方法。 The present invention has been made in order to solve the above problems, and an object of the invention is to provide a metal material for an electronic component having micro sliding wear resistance, insertion resistance, low whisker property, and low pluggability, and a method for producing the same.

再者所謂之耐微滑動磨耗性，係指於使公端子與母端子插合之連接器中，即便插合部微滑動(滑動距離1.0mm以下)接觸電阻亦不易增加之性質。 In addition, the micro-sliding wear resistance refers to a property in which the contact resistance is not easily increased even if the insertion portion is slightly slid (sliding distance of 1.0 mm or less) in the connector in which the male terminal and the female terminal are inserted.

所謂之耐插拔性，係指即便反覆進行將公端子與母端子之複數次之插拔，連接器之接觸電阻亦難以增加之性質。 The plug-in resistance means that the contact resistance of the connector is hard to increase even if the male terminal and the female terminal are repeatedly inserted and removed.

所謂之低晶鬚性，係指難以產生晶鬚之性質。 The so-called low whisker property refers to the property that it is difficult to generate whiskers.

所謂之低插拔性，係指使公端子與母端子插合時產生之***力較低。 The so-called low insertion and removal means that the insertion force generated when the male terminal and the female terminal are inserted is low.

本發明者等人進行了努力研究，結果發現藉由於基材上依順序設置由特定之金屬所構成之C層、B層、A層，並分別以特定之厚度或附著量形成，且藉由將A層與B層之厚度比或附著量比控制於特定範圍，可製作高耐微滑動磨耗性、高耐插拔性、低晶鬚性及低插拔性均得以具備之電子零件用金屬材料。 The inventors of the present invention conducted diligent research and found that the C layer, the B layer, and the A layer composed of a specific metal are sequentially disposed on the substrate, and are respectively formed with a specific thickness or adhesion amount, and by By controlling the thickness ratio or the adhesion ratio of the A layer and the B layer to a specific range, it is possible to produce a metal for electronic parts having high micro-sliding wear resistance, high insertion resistance, low whisker property, and low plug-in property. material.

基於以上之見解而完成之本發明之一態樣中係一種電子零件用金屬材料，其中，由Sn、In或該等之合金所構成之A層形成於基材上；由Ag、Au、Pt、Pd、Ru、Rh、Os、Ir或該等之合金所構成之B層形成於該基材與該A層之間；由選自由Ni、Cr、Mn、Fe、Co、Cu所組成之群中之1種或2種以上所構成之C層形成於該基材與該B層之間，且；該A層之厚度為0.01~0.3μm，該B層之厚度為0.05~0.5μm，該C層之厚度為0.05μm以上，該A層之厚度/該B層之厚度比為0.02~4.00。 One aspect of the present invention which is completed based on the above findings is a metal material for an electronic component in which an A layer composed of Sn, In or an alloy thereof is formed on a substrate; by Ag, Au, Pt a layer B composed of Pd, Ru, Rh, Os, Ir, or the like is formed between the substrate and the layer A; and is selected from the group consisting of Ni, Cr, Mn, Fe, Co, and Cu. One or two or more C layers are formed between the substrate and the B layer, and 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 thickness of the C layer is 0.05 μm or more, and the thickness of the A layer/the thickness ratio of the B layer is 0.02 to 4.00.

本發明於另一態樣中係一種電子零件用金屬材料，其中，由Sn、In或該等之合金所構成之A層形成於基材上；由Ag、Au、Pt、Pd、Ru、Rh、Os、Ir或該等之合金所構成之B層形成於該基材與該A層之間；由選自由Ni、Cr、Mn、Fe、Co、Cu所組成之群中之1種或2種以上所構成之C層形成於該基材與該B層之間，且；該A層之附著量為7~230μg/cm2，該B層之附著量為50~550μg/cm2，該C層之附著為0.03mg/cm2以上，且該A層之附著量/該B層之附著量比為0.10~3.00。 In another aspect, the present invention is a metal material for an electronic component, wherein an A layer composed of Sn, In, or the like is formed on a substrate; and Ag, Au, Pt, Pd, Ru, Rh a layer B composed of Os, Ir, or the like is formed between the substrate and the layer A; and one or two selected from the group consisting of Ni, Cr, Mn, Fe, Co, and Cu The above-mentioned C layer is formed between the substrate and the B layer, and the adhesion amount of the A layer is 7 to 230 μg/cm 2 , and the adhesion amount of the B layer is 50 to 550 μg/cm 2 . The adhesion of the layer C is 0.03 mg/cm 2 or more, and the adhesion amount of the layer A / the adhesion ratio of the layer B is 0.10 to 3.00.

本發明之電子零件用金屬材料於一實施型態中，藉由XPS (X-ray Photoelectron Spectroscopy，X射線光電子光譜)進行Depth(深度)分析時，於自最表側至C層之濃度成為20at%之範圍中，滿足下式。 The metal material for electronic parts of the present invention is in an embodiment, by XPS (X-ray Photoelectron Spectroscopy, X-ray photoelectron spectroscopy) When the Depth (depth) analysis is performed, the concentration is 20 in% from the most front side to the C layer, and the following formula is satisfied.

A層濃度(at%)<B層濃度(at%)+30 A layer concentration (at%) <B layer concentration (at%) + 30

本發明之電子零件用金屬材料於又一實施型態中，該A層之合金組成為，Sn、In或Sn與In之合計為50質量%以上，其餘合金成分由As、Bi、Cd、Co、Cr、Cu、Fe、Mn、Mo、Ni、Sb、W、Zn所組成之群中之1種或2種以上之金屬構成。 In still another embodiment of the metal material for electronic parts of the present invention, the alloy composition of the layer A is such that the total of Sn, In or Sn and In is 50% by mass or more, and the remaining alloy components are As, Bi, Cd, Co. One or two or more kinds of metals composed of a group consisting of Cr, Cu, Fe, Mn, Mo, Ni, Sb, W, and Zn.

本發明之電子零件用金屬材料於又一實施型態中，該B層之合金組成為Ag、Au、Pt、Pd、Ru、Rh、Os、Ir，或Ag、Au、Pt、Pd、Ru、Rh、Os及Ir之合計為50質量%以上，其餘合金成分由選自由Bi、Cd、Co、Cu、Fe、Mn、Mo、Ni、Pb、Sb、Se、W、Tl、Zn所組成之群中之1種或2種以上之金屬構成。 In 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, Ru, The total of Rh, Os, and Ir is 50% by mass or more, and the remaining alloy components are selected from the group consisting of Bi, Cd, Co, Cu, Fe, Mn, Mo, Ni, Pb, Sb, Se, W, Tl, and Zn. One or two or more metals are used.

本發明之電子零件用金屬材料於又一實施型態中，該C層之合金組成為Ni、Cr、Mn、Fe、Co、Cu之合計為50質量%以上，進而由選自由B、P、Zn所組成之群中之1種或2種以上之金屬所構成。 In 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, and Cu, and further selected from B, P, and One or two or more kinds of metals composed of Zn.

本發明之電子零件用金屬材料於又一實施型態中，表面之維式硬度為Hv100以上。 In still another embodiment of the metal material for electronic parts of the present invention, the Vickers hardness of the surface is Hv100 or more.

本發明之電子零件用金屬材料於又一實施型態中，藉由超微小硬度試驗以負重0.1mN，於表面壓入壓頭而測定時之表面的壓痕硬度為1000MPa以上。 In still another embodiment, the metal material for electronic parts of the present invention has an indentation hardness of 1000 MPa or more on the surface when the surface is pressed into the indenter by a micro-hardness test at a load of 0.1 mN.

本發明之電子零件用金屬材料於又一實施型態中，表面之維式硬度為Hv1000以下。 In still another embodiment of the metal material for electronic parts of the present invention, the Vickers hardness of the surface is Hv 1000 or less.

本發明之電子零件用金屬材料於又一實施型態中，藉由超微小硬度試驗以負重0.1mN，於表面壓入壓頭而測定時之表面的壓痕硬度為10000MPa以下。 In another embodiment of the metal material for electronic parts of the present invention, the indentation hardness of the surface when the surface is pressed into the indenter by the ultra-fine hardness test at a load of 0.1 mN is 10000 MPa or less.

本發明之電子零件用金屬材料於又一實施型態中，表面之算數平均高度(Ra)為0.1μm以下。 In still another embodiment of the metal material for electronic parts of the present invention, the arithmetic mean height (Ra) of the surface is 0.1 μm or less.

本發明之電子零件用金屬材料於又一實施型態中，表面之最大高度(Rz)為1μm以下。 In still another embodiment of the metal material for electronic parts of the present invention, the maximum height (Rz) of the surface is 1 μm or less.

本發明之電子零件用金屬材料於又一實施型態中，藉由XPS(X-ray Photoelectron Spectroscopy，X射線光電子光譜)進行Depth(深度)分析時，表示該A層之Sn或In之原子濃度(at%)之最高值的位置(D1)、表示該B層之Ag、Au、Pt、Pd、Ru、Rh、Os或Ir之原子濃度(at%)之最高值的位置(D2)、及表示該C層之Ni、Cr、Mn、Fe、Co或Cu之原子濃度(at%)之最高值的位置(D3)係自最表面起以D1、D2、D3之順序存在。 In another embodiment of the metal material for electronic parts of the present invention, when Depth (depth) analysis is performed by XPS (X-ray Photoelectron Spectroscopy), the atomic concentration of Sn or In of the layer A is expressed. The position (D 1 ) of the highest value of (at%), the position (D 2 ) indicating the highest value of the atomic concentration (at%) of Ag, Au, Pt, Pd, Ru, Rh, Os or Ir of the B layer (D 2 ) And the position (D 3 ) indicating the highest value of the atomic concentration (at%) of Ni, Cr, Mn, Fe, Co or Cu of the C layer is in the order of D 1 , D 2 , and D 3 from the outermost surface. presence.

本發明之電子零件用金屬材料於又一實施型態中，藉由XPS(X射線光電子光譜)進行Depth分析時，該A層之Sn或In之原子濃度(at%)之最高值、及該B層之Ag、Au、Pt、Pd、Ru、Rh、Os或Ir之原子濃度(at%)之最高值分別為10 at%以上，且該C層之Ni、Cr、Mn、Fe、Co或Cu之原子濃度(at%)為25%以上之深度為50 nm以上。 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 highest value of the atomic concentration (at%) of Sn or In of the A layer, and the The highest atomic concentration (at%) of Ag, Au, Pt, Pd, Ru, Rh, Os or Ir in layer B is 10 at% or more, and the C layer is Ni, Cr, Mn, Fe, Co or The atomic concentration (at%) of Cu is 25% or more and the depth is 50 nm or more.

本發明於又一態樣中係一種連接器端子，其係於接點部分使用有本發明之電子零件用金屬材料。 In still another aspect of the invention, a connector terminal is used in which a metal material for an electronic component of the invention is used in a contact portion.

本發明於又一態樣中係一種連接器，其係使用有本發明之連接器端子。 In another aspect, the invention is a connector that uses the connector terminal of the present invention.

本發明於又一態樣中係一種FFC(Flat Flexible Cable，帶狀撓性電纜)端子，其係於接點部分使用有本發明之電子零件用金屬材料。 In still another aspect of the invention, an FFC (Flat Flexible Cable) terminal is used in which a metal material for an electronic component of the invention is used in a contact portion.

本發明於又一態樣中係一種FPC(Flexible Printed Circuit，撓性印刷電路)端子，其係於接點部分使用有本發明之電子零件用金屬材料。 In another aspect, the present invention is an FPC (Flexible Printed Circuit) terminal in which a metal material for an electronic component of the present invention is used in a contact portion.

本發明於又一態樣中係一種FFC，其係使用有本發明之FFC端子。 In another aspect, the invention is an FFC using the FFC terminal of the invention.

本發明於又一態樣中係一種FPC，其係使用有本發明之FPC端子。 In another aspect, the invention is an FPC using the FPC terminal of the invention.

本發明於又一態樣中係一種電子零件，其係於外部連接用電極使用有本發明之電子零件用金屬材料。 In still another aspect of the invention, an electronic component is used for the external connection electrode, and the metal material for an electronic component of the invention is used.

本發明於又一態樣中係一種電子零件，其係於壓入型端子使用有本發明之電子零件用金屬材料，該壓入型端子係分別於安裝在殼體(housing)之裝置部的一側設有母端子連接部、另一側設有基板連接部，且將該基板連接部壓入形成於基板之通孔而安裝於該基板。 In still another aspect of the invention, an electronic component is used in the push-in type terminal, wherein the press-fit type terminal is respectively mounted on a device portion of a housing. A female terminal connection portion is provided on one side, and a substrate connection portion is provided on the other side, and the substrate connection portion is press-fitted into a through hole formed in the substrate to be mounted on the substrate.

根據本發明，可提供一種具有高耐微滑動磨耗性、高耐插拔性、低晶鬚性及低***力性之電子零件用金屬材料。 According to the present invention, it is possible to provide a metal material for an electronic component which has high micro-sliding abrasion resistance, high insertion resistance, low whisker property and low insertion force.

10‧‧‧電子零件用金屬材料 10‧‧‧Metal materials for electronic parts

11‧‧‧基材 11‧‧‧Substrate

12‧‧‧C層 12‧‧‧C layer

13‧‧‧B層 13‧‧‧B layer

14‧‧‧A層 14‧‧‧A floor

圖1係表示本發明之實施形態之電子零件用金屬材料之構成之示意圖。 Fig. 1 is a schematic view showing the configuration of a metal material for an electronic component according to an embodiment of the present invention.

圖2係實施例2之XPS(X射線光電子光譜)之Depth測定結果。 Fig. 2 is a result of Depth measurement of XPS (X-ray photoelectron spectroscopy) of Example 2.

以下，對本發明之實施形態之電子零件用金屬材料進行說 明。如圖1所示，實施形態之電子零件用金屬材料10係於基材11之表面形成有C層12，於C層12之表面形成有B層13，於B層13之表面形成有A層14。 Hereinafter, the metal material for electronic parts according to the embodiment of the present invention will be described. Bright. As shown in FIG. 1, the metal material 10 for electronic parts of the embodiment is formed with a C layer 12 formed on the surface of the substrate 11, a B layer 13 formed on the surface of the C layer 12, and an A layer formed on the surface of the B layer 13. 14.

<電子零件用金屬材料之構成> <Composition of Metal Materials for Electronic Parts>

(基材) (substrate)

作為基材11並無特別限定，例如可使用銅及銅合金、Fe系材料、不鏽鋼、鈦及鈦合金、鋁及鋁合金等金屬基材。又，亦可為於金屬基材複合有樹脂層者。作為於金屬基材複合有樹脂層者之例，有FPC或FFC基材上之電極部分等。 The substrate 11 is not particularly limited, and for example, a metal substrate such as copper, a copper alloy, a Fe-based material, stainless steel, titanium or a titanium alloy, or aluminum or an aluminum alloy can be used. Further, it may be a resin layer laminated on a metal substrate. As an example of a resin substrate laminated with a metal substrate, there are an electrode portion on an FPC or FFC substrate.

(A層) (A layer)

A層14必需為Sn、In或該等之合金。Sn及In之特徵在於，雖為具有氧化性之金屬，但於金屬中相對柔軟。因此，即便於Sn及In表面形成有氧化膜，例如於將電子零件用金屬材料作為接點材料而插合公端子與母端子時，氧化膜容易被削去，從而使接點均成為金屬，因此可獲得低接觸電阻。 The A layer 14 must be Sn, In or an alloy of these. Sn and In are characterized by being oxidizing metals but relatively soft in metals. Therefore, even if an oxide film is formed on the surfaces of Sn and In, for example, when the male terminal and the female terminal are inserted as a contact material for the electronic component, the oxide film is easily cut off, and the contacts are both made of metal. Therefore, low contact resistance can be obtained.

又，Sn及In對於氯氣、亞硫酸氣體、硫化氫氣體等氣體之耐氣體腐蝕性優異，例如於使用耐氣體腐蝕性較差之Ag作為B層13、耐氣體腐蝕性較差之Ni作為C層12、耐氣體腐蝕性較差之銅及銅合金作為基材11之情形時，有提高電子零件用金屬材料之耐氣體腐蝕性之作用。再者，於Sn及In中，基於厚生勞動省之關於防止健康損害之技術方針，In受到嚴格規範，因此較佳為Sn。 Further, Sn and In are excellent in gas corrosion resistance to gases such as chlorine gas, sulfurous acid gas, and hydrogen sulfide gas, and for example, Ag which is inferior in gas corrosion resistance is used as the B layer 13, and Ni which is poor in gas corrosion resistance is used as the C layer 12 When copper or a copper alloy having poor gas corrosion resistance is used as the substrate 11, there is an effect of improving the gas corrosion resistance of the metal material for electronic parts. Further, in Sn and In, In is strictly regulated according to the technical policy for preventing health damage in the Ministry of Health, Labour and Welfare, and therefore Sn is preferable.

A層14之組成為，Sn、In或Sn與In之合計為50質量%以上，其餘合金成分亦可由選自由As、Bi、Cd、Co、Cr、Cu、Fe、Mn、Mo、 Ni、Pb、Sb、W、Zn所組成之群中之1種或2種以上之金屬構成。存在藉由使A層14之組成成為合金，例如實施Sn-Ag鍍敷等，而使高耐微滑動磨耗性、高耐插拔性、低晶鬚性及低插拔性等提高之情形。 The composition of the A layer 14 is such that the total of Sn, In or Sn and In is 50% by mass or more, and the remaining alloy components may be selected from the group consisting of As, Bi, Cd, Co, Cr, Cu, Fe, Mn, Mo, One or two or more metals of the group consisting of Ni, Pb, Sb, W, and Zn. In the case where the composition of the A layer 14 is alloyed, for example, Sn-Ag plating or the like is performed, and high micro-sliding abrasion resistance, high insertion resistance, low whisker property, and low insertion and the like are improved.

A層14之厚度必需為0.01~0.3μm。若A層14之厚度未達0.01 μm，則無法獲得充分之耐氣體腐蝕性，當對電子零件用金屬材料進行氯氣、亞硫酸氣體、硫化氫氣體等之氣體腐蝕試驗時會被腐蝕，而與氣體腐蝕試驗前相比接觸電阻大幅增加。又，無法得到充分的耐插拔性，且多數之鍍敷被削去而增加接觸電阻。又，若厚度變大，則Sn、In之凝著磨耗變大，耐微滑動磨耗性變差，插拔力變大，亦容易產生晶鬚。為獲得更充分之耐微滑動磨耗性、低插拔性、低晶鬚性，設為0.3μm以下。晶鬚係因發生螺旋差排(screw dislocation)而產生，但要發生螺旋差排需要數百nm以上之厚度之塊材。A層14之厚度為0.3μm以下，則不為足夠發生螺旋差排之厚度，基本上不會產生晶鬚。又，A層14與B層13於常溫下易進行短路擴散(short circuit diffusion)，而容易形成合金，因此不會產生晶鬚。 The thickness of the A layer 14 must be 0.01 to 0.3 μm. If the thickness of the A layer 14 is less than 0.01 μm, sufficient gas corrosion resistance cannot be obtained, and when the metal material for electronic parts is subjected to a gas corrosion test of chlorine gas, sulfurous acid gas, hydrogen sulfide gas or the like, it is corroded, and The contact resistance was significantly increased before the gas corrosion test. Moreover, sufficient plugging resistance cannot be obtained, and most of the plating is cut off to increase the contact resistance. Further, when the thickness is increased, the condensed abrasion of Sn and In is increased, the micro-sliding abrasion resistance is deteriorated, the insertion force is increased, and whiskers are likely to be generated. In order to obtain more sufficient micro-sliding abrasion resistance, low insertion and release property, and low whisker property, it is set to 0.3 μm or less. The whisker system is generated by the occurrence of a screw dislocation, but a block having a thickness of several hundred nm or more is required to cause a spiral difference. When the thickness of the A layer 14 is 0.3 μm or less, the thickness of the spiral difference row is not sufficiently generated, and whiskers are hardly generated. Further, the A layer 14 and the B layer 13 are easily subjected to short circuit diffusion at normal temperature, and an alloy is easily formed, so that whiskers are not generated.

A層14之Sn、In之附著量必需為7~230μg/cm2。此處，說明以附著量進行定義之原因。例如，於利用螢光X射線膜厚計測定A層14之厚度之情形時，存在因形成於A層與其下之B層之間之合金層而引起所測定之厚度值產生誤差之情形。另一方面，於以附著量進行控制之情形時，可不受合金層之形成狀況影響而更準確地進行品質管理。若A層14之Sn、In之附著量未達7μg/cm2，則無法獲得充分之耐氣體腐蝕性，當對電子零件用金屬材料進行氯氣、亞硫酸氣體、硫化氫氣體等之氣體腐蝕試驗時會被腐蝕，而與氣體腐蝕試驗前相比接觸電阻大幅增加。又，無法得到充分的 耐插拔性，且多數之鍍敷被削去而增加接觸電阻。又，若附著量變大，則Sn、In之凝著磨耗變大，耐微滑動磨耗性變差，插拔力變大，亦容易產生晶鬚。為獲得更充分之耐微滑動磨耗性、低插拔性、低晶鬚性，設為230μg/cm2以下。晶鬚係因發生螺旋差排而產生，但要發生螺旋差排需要數百μg/cm2以上之附著量之塊材。A層14之附著量為230μg/cm2以下，則非足以發生螺旋差排之附著量，基本上不會產生晶鬚。又，A層14與B層13於常溫下易進行短路擴散，而容易形成合金，因此不會產生晶鬚。 The amount of Sn and In adhered to the A layer 14 must be 7 to 230 μg/cm 2 . Here, the reason why the amount of adhesion is defined will be described. For example, when the thickness of the A layer 14 is measured by a fluorescent X-ray film thickness meter, there is a case where an error occurs in the thickness value measured due to the alloy layer formed between the layer A and the layer B below. On the other hand, in the case of controlling by the amount of adhesion, quality management can be performed more accurately without being affected by the formation state of the alloy layer. When the adhesion amount of Sn and In in the A layer 14 is less than 7 μg/cm 2 , sufficient gas corrosion resistance cannot be obtained, and gas corrosion test of chlorine gas, sulfurous acid gas, hydrogen sulfide gas, or the like is performed on a metal material for electronic parts. It is corroded and the contact resistance is greatly increased compared to before the gas corrosion test. Moreover, sufficient plugging resistance cannot be obtained, and most of the plating is cut off to increase the contact resistance. Further, when the amount of adhesion is increased, the condensed abrasion of Sn and In is increased, the micro-sliding abrasion resistance is deteriorated, and the insertion and extraction force is increased, and whiskers are likely to be generated. In order to obtain more sufficient micro-sliding abrasion resistance, low insertion and release property, and low whisker property, it is set to 230 μg/cm 2 or less. The whisker system is generated by the occurrence of a spiral difference, but a block in which the amount of adhesion of several hundred μg/cm 2 or more is required for the spiral difference row occurs. When the adhesion amount of the A layer 14 is 230 μg/cm 2 or less, the adhesion amount of the spiral difference row is not enough, and whiskers are hardly generated. Further, the A layer 14 and the B layer 13 are easily subjected to short-circuit diffusion at normal temperature, and an alloy is easily formed, so that whiskers are not generated.

(B層) (B layer)

B層13必需由Ag、Au、Pt、Pd、Ru、Rh、Os、Ir或該等之合金形成。Ag、Au、Pt、Pd、Ru、Rh、Os、Ir之特徵在於，在金屬之中相對具有耐熱性。因此，抑制基材11或C層12之組成向A層14側擴散從而提高耐熱性。又，該等金屬會與A層14之Sn、In形成化合物而抑制Sn、In之氧化膜形成，從而使焊料潤濕性提高。再者，於Ag、Au、Pt、Pd、Ru、Rh、Os、Ir之中，自導電率之觀點而言更理想為Ag。Ag之導電率較高。例如於將Ag用於高頻之訊號用途時，阻抗(電阻)會因集膚效應(skin effect)而降低。 The B layer 13 must be formed of Ag, Au, Pt, Pd, Ru, Rh, Os, Ir, or the like. Ag, Au, Pt, Pd, Ru, Rh, Os, and Ir are characterized by relatively high heat resistance among metals. Therefore, the composition of the substrate 11 or the C layer 12 is suppressed from diffusing toward the A layer 14 side to improve heat resistance. Further, these metals form a compound with Sn and In of the A layer 14 to suppress formation of an oxide film of Sn and In, thereby improving solder wettability. Further, among Ag, Au, Pt, Pd, Ru, Rh, Os, and Ir, Ag is more preferable from the viewpoint of conductivity. Ag has a high conductivity. For example, when Ag is used for high frequency signal use, the impedance (resistance) is lowered by the skin effect.

B層13之合金組成為，Ag、Au、Pt、Pd、Ru、Rh、Os、Ir、或Ag、Au、Pt、Pd、Ru、Rh、Os及Ir之合計為50質量%以上，其餘合金成分亦可由選自由Bi、Cd、Co、Cu、Fe、In、Mn、Mo、Ni、Pb、Sb、Se、Sn、W、Tl、Zn所組成之群中之1種或2種以上之金屬構成。也有因為B層13是以例如Sn-Ag鍍敷所形成等，故其組成成為合金，而使高耐微滑動磨耗性、高耐插拔性等提高之情形。 The alloy composition of the B layer 13 is such that Ag, Au, Pt, Pd, Ru, Rh, Os, Ir, or Ag, Au, Pt, Pd, Ru, Rh, Os, and Ir are 50% by mass or more in total. The component may be one or more metals selected from the group consisting of Bi, Cd, Co, Cu, Fe, In, Mn, Mo, Ni, Pb, Sb, Se, Sn, W, Tl, and Zn. Composition. In addition, since the B layer 13 is formed by, for example, Sn-Ag plating, the composition thereof becomes an alloy, and the high micro-sliding abrasion resistance and the high insertion resistance are improved.

B層13之厚度必需為0.05~0.5μm。若厚度未達0.05μm， 則無法獲得充分之高耐微滑動磨耗性、耐插拔性，且多數之鍍敷被削去而增加接觸電阻。又，若厚度變大，利用較硬之基材11或C層之薄膜潤滑效果下降，而插拔力變得大於目標(較比較例1減少15%以上)，故為了得到更充分之低插拔性而必需為0.5μm以下。 The thickness of the B layer 13 must be 0.05 to 0.5 μm. If the thickness is less than 0.05μm, However, sufficient high scratch resistance and insertion resistance are not obtained, and most of the plating is cut off to increase the contact resistance. Further, when the thickness is increased, the lubricating effect of the film using the hard substrate 11 or the C layer is lowered, and the insertion force is larger than the target (reduced by 15% or more compared with Comparative Example 1), so that a lower full insertion is required. The pullability must be 0.5 μm or less.

B層13之Ag、Au、Pt、Pd、Ru、Rh、Os、Ir或該等合金之附著量必需為50~550μg/cm2。此處，說明以附著量進行定義之原因。例如，於利用螢光X射線膜厚計測定B層13之厚度之情形時，存在因形成於A層14與其下之B層13之間之合金層而引起所測定之厚度值產生誤差之情形。另一方面，於以附著量進行控制之情形時，可不受合金層之形成狀況影響而更準確地進行品質管理。為了獲得更充分之高耐微滑動磨耗性、耐插拔性，附著量較佳為50 μg/cm2以上。又，若附著量較多，則較硬之基材11或C層所致之薄膜潤滑效果會下降，而插拔力變得大於目標(較比較例1減少15%以上)，故為了得到更充分之低插拔性而必需為550μg/cm2以下。 The adhesion amount of Ag, Au, Pt, Pd, Ru, Rh, Os, Ir or the alloy of the B layer 13 must be 50 to 550 μg/cm 2 . Here, the reason why the amount of adhesion is defined will be described. For example, when the thickness of the B layer 13 is measured by a fluorescent X-ray film thickness meter, there is a case where an error occurs in the thickness value measured due to the alloy layer formed between the A layer 14 and the B layer 13 below it. . On the other hand, in the case of controlling by the amount of adhesion, quality management can be performed more accurately without being affected by the formation state of the alloy layer. In order to obtain more sufficient micro-sliding abrasion resistance and insertion resistance, the adhesion amount is preferably 50 μg/cm 2 or more. Further, when the amount of adhesion is large, the film lubrication effect by the hard substrate 11 or the C layer is lowered, and the insertion force is larger than the target (reduced by 15% or more compared with Comparative Example 1), so that in order to obtain more It is necessary to have a low insertion and removal property of 550 μg/cm 2 or less.

(C層) (C layer)

於基材11與B層13之間，必需形成由選自由Ni、Cr、Mn、Fe、Co、Cu所組成之群中之1種或2種以上所構成的C層12。藉由使用選自由Ni、Cr、Mn、Fe、Co、Cu所組成之群中之1種或2種以上的金屬形成C層12，因較硬之C層之形成，會使薄膜潤滑效果提高，從而低插拔性提高，且C層12防止基材11之構成金屬向B層擴散，抑制耐熱性試驗或耐氣體腐蝕性試驗後之接觸電阻增加及焊料潤濕性劣化等，而耐久性提高。 Between the substrate 11 and the B layer 13, it is necessary to form the C layer 12 composed of one or more selected from the group consisting of Ni, Cr, Mn, Fe, Co, and Cu. The C layer 12 is formed by using one or two or more metals selected from the group consisting of Ni, Cr, Mn, Fe, Co, and Cu, and the formation of the hard C layer improves the lubrication effect of the film. In addition, the C layer 12 prevents the constituent metal of the substrate 11 from diffusing into the B layer, and suppresses an increase in contact resistance and deterioration in solder wettability after the heat resistance test or the gas corrosion resistance test, and durability. improve.

C層12之合金組成為，Ni、Cr、Mn、Fe、Co、Cu之合計為50質量%以上，且進而包含選自由B、P、Sn、Zn所組成之群中之1種或2 種以上亦可。藉由使C層12之合金組成成為此種構成，使C層12進一步硬化，藉此進一步提高薄膜潤滑效果，從而低插拔性提高，且C層12之合金化進一步防止基材11之構成金屬向B層擴散，抑制耐熱性試驗或耐氣體腐蝕性試驗後之接觸電阻增加及焊料潤濕性劣化等，而耐久性提高。 The alloy composition of the C layer 12 is such that the total of Ni, Cr, Mn, Fe, Co, and Cu is 50% by mass or more, and further includes one or two selected from the group consisting of B, P, Sn, and Zn. More than one species can be used. By making the alloy composition of the C layer 12 into such a configuration, the C layer 12 is further cured, whereby the film lubricating effect is further improved, and the low insertion and removal property is improved, and the alloying of the C layer 12 further prevents the composition of the substrate 11. The metal diffuses into the layer B, and the contact resistance after the heat resistance test or the gas corrosion resistance test is increased, and the solder wettability is deteriorated, and the durability is improved.

C層12之厚度必需為0.05μm以上。若C層12之厚度未達0.05μm，則利用較硬之C層之薄膜潤滑效果降低，從而低插拔性變差，且基材11之構成金屬易向B層擴散，耐熱性試驗或耐氣體腐蝕性試驗後之接觸電阻易於增加及焊料潤濕性易於劣化等，而耐久性變差。 The thickness of the C layer 12 must be 0.05 μm or more. If the thickness of the C layer 12 is less than 0.05 μm, the film lubrication effect by the hard C layer is lowered, so that the low insertion and removal property is deteriorated, and the constituent metal of the substrate 11 is easily diffused to the B layer, and the heat resistance test or resistance is resistant. The contact resistance after the gas corrosion test is liable to increase and the solder wettability is liable to be deteriorated, and the durability is deteriorated.

C層12之Ni、Cr、Mn、Fe、Co、Cu之附著量必需為0.03 mg/cm2以上。此處，說明以附著量進行定義之原因。例如，於利用螢光X射線膜厚計測定C層12之厚度之情形時，存在因與A層14、B層13、及基材11等形成之合金層而引起所測定之厚度值產生誤差之情形。另一方面，於以附著量進行控制之情形時，可不受合金層之形成狀況影響而更準確地進行品質管理。又，若附著量未達0.03 mg/cm2，則基於較硬之C層之薄膜潤滑效果降低，低插拔性變差，且基材11之構成金屬易向B層擴散，耐熱性試驗或耐氣體腐蝕性試驗後之接觸電阻易於增加及焊料潤濕性易於劣化等，而耐久性變差。 The adhesion amount of Ni, Cr, Mn, Fe, Co, and Cu of the C layer 12 must be 0.03 mg/cm 2 or more. Here, the reason why the amount of adhesion is defined will be described. For example, when the thickness of the C layer 12 is measured by a fluorescent X-ray film thickness meter, there is an error in the measured thickness value due to the alloy layer formed with the A layer 14, the B layer 13, and the substrate 11 or the like. The situation. On the other hand, in the case of controlling by the amount of adhesion, quality management can be performed more accurately without being affected by the formation state of the alloy layer. Moreover, if the adhesion amount is less than 0.03 mg/cm 2 , the film lubrication effect based on the hard C layer is lowered, the low insertion and removal property is deteriorated, and the constituent metal of the substrate 11 is easily diffused to the B layer, and the heat resistance test or The contact resistance after the gas corrosion resistance test is liable to increase, the solder wettability is liable to be deteriorated, and the durability is deteriorated.

(A層與B層之關係) (Relationship between A and B)

A層14之厚度[μm]/B層13之厚度[μm]之比必需為0.02~4.00。若A層14之厚度[μm]/B層13之厚度[μm]之比未達0.02，則無法獲得充分之耐氣體腐蝕性，當對電子零件用金屬材料進行氯氣、亞硫酸氣體、硫化氫氣體等之氣體腐蝕試驗時會被腐蝕，而與氣體腐蝕試驗前相比接觸電阻大幅 增加。又，若A層14之厚度[μm]/B層13之厚度[μm]之比超過4.00，則於表層大量存在A層14，耐微滑動磨耗性變差。 The ratio of the thickness [μm] of the A layer 14 / the thickness [μm] of the B layer 13 must be 0.02 to 4.00. If the ratio of the thickness [μm] of the A layer 14 / the thickness [μm] of the B layer 13 is less than 0.02, sufficient gas corrosion resistance cannot be obtained, and chlorine, sulfurous acid gas, hydrogen sulfide is used for the metal material for electronic parts. Gases such as gases are corroded during the corrosion test, and the contact resistance is significantly higher than before the gas corrosion test. increase. Further, when the ratio of the thickness [μm] of the A layer 14 / the thickness [μm] of the B layer 13 exceeds 4.00, the A layer 14 is present in a large amount in the surface layer, and the micro sliding wear resistance is deteriorated.

A層14之附著量[μg/cm2]/B層13之附著量[μg/cm2]之比必需為0.10~3.00。若A層14之附著量[μg/cm2]/B層13之附著量[μg/cm2]之比未達0.10，則無法獲得充分之耐氣體腐蝕性，當對電子零件用金屬材料進行氯氣、亞硫酸氣體、硫化氫氣體等之氣體腐蝕試驗時會被腐蝕，而與氣體腐蝕試驗前相比接觸電阻大幅增加。又，若A層14之附著量[μg/cm2]/B層13之附著量[μg/cm2]之比超過3.00，則於表層大量存在A層14，耐微滑動磨耗性變差。 The ratio of the adhesion amount of the A layer 14 [μg/cm 2 ] / the adhesion amount of the B layer 13 [μg/cm 2 ] must be 0.10 to 3.00. If the ratio of the adhesion amount of the A layer 14 [μg/cm 2 ]/the adhesion amount of the B layer 13 [μg/cm 2 ] is less than 0.10, sufficient gas corrosion resistance cannot be obtained, and when the metal material for electronic parts is used, Gases such as chlorine gas, sulfurous acid gas, and hydrogen sulfide gas are corroded during the corrosion test, and the contact resistance is greatly increased as compared with the gas corrosion test. In addition, when the ratio of the adhesion amount of the A layer 14 [μg/cm 2 ]/the adhesion amount of the B layer 13 [μg/cm 2 ] exceeds 3.00, the A layer 14 is present in a large amount in the surface layer, and the micro sliding wear resistance is deteriorated.

藉由XPS(X射線光電子光譜)進行Depth分析時，自最表側至C層之濃度成為20at%之範圍中，較佳為A層濃度(at%)<〔B層濃度(at%)+30〕。若A層濃度(at%)≧〔B層濃度(at%)+30〕，則於表層大量存在A層14，耐微滑動磨耗性變差。 When Depth analysis is performed by XPS (X-ray photoelectron spectroscopy), the concentration from the most front side to the C layer is in the range of 20 at%, preferably the A layer concentration (at%) < [B layer concentration (at%) + 30 ]. When the A layer concentration (at%) ≧ [B layer concentration (at%) + 30], the A layer 14 is present in a large amount in the surface layer, and the micro sliding wear resistance is deteriorated.

<電子零件用金屬材料之特性> <Characteristics of Metal Materials for Electronic Parts>

A層14之表面(自A層之表面測定)之維式硬度較佳為Hv100以上。若A層14之表面之維式硬度為Hv100以上，則會因較硬之A層造成薄膜潤滑效果提高，並提高插拔性。另一方面，A層14之表面(自A層之表面測定)之維式硬度較佳為Hv1000以下。若A層14之表面之維式硬度為Hv1000以下，則提高彎曲加工性，於加壓成形本發明之電子零件用金屬材料之情形時，於已成形之部分不易形成裂痕，從而抑制耐氣體腐蝕性(耐久性)之降低。 The Vickers hardness of the surface of the A layer 14 (measured from the surface of the A layer) is preferably Hv100 or more. If the Vickers hardness of the surface of the A layer 14 is Hv100 or more, the film lubrication effect is improved due to the hard A layer, and the insertion and removal 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 Hv 1000 or less. When the Vickers hardness of the surface of the A layer 14 is Hv1000 or less, the bending workability is improved, and when the metal material for electronic parts of the present invention is press-formed, cracks are less likely to be formed in the formed portion, thereby suppressing gas corrosion resistance. Reduced sex (durability).

A層14之表面(自A層之表面測定)之壓痕硬度較佳為1000 MPa以 上。若A層14之表面之壓痕硬度為1000 MPa以上，則會因較硬之A層造成薄膜潤滑效果提高，並提高低插拔性。另一方面，A層14之表面(自A層之表面測定)之壓痕硬度較佳為10000 MPa以下。若A層14之表面之壓痕硬度為10000 MPa以下，則彎曲加工性提高，於加壓成形本發明之電子零件用金屬材料之情形時，於已成形之部分不易形成裂痕，從而抑制耐氣體腐蝕性(耐久性)之降低。 The surface of the A layer 14 (measured from the surface of the A layer) preferably has an indentation hardness of 1000 MPa. on. If the indentation hardness of the surface of the A layer 14 is 1000 MPa or more, the film lubrication effect is improved due to the hard A layer, and the low insertion and removal 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, the bending workability is improved, and when the metal material for electronic parts of the present invention is press-formed, cracks are less likely to be formed in the formed portion, thereby suppressing gas resistance. Corrosion (durability) is reduced.

A層14之表面之算術平均高度(Ra)較佳為0.1μm以下。若A層14之表面之算術平均高度(Ra)為0.1μm以下，則相對易受腐蝕之凸部會減少而變得平滑，因此耐氣體腐蝕性提高。 The arithmetic mean height (Ra) of the surface of the A layer 14 is preferably 0.1 μm or less. When the arithmetic mean height (Ra) of the surface of the A layer 14 is 0.1 μm or less, the convex portion which is relatively susceptible to corrosion is reduced and smoothed, so that the gas corrosion resistance is improved.

A層14之表面之最大高度(Rz)較佳為1μm以下。若A層14之表面之最大高度(Rz)為1μm以下，則相對易受腐蝕之凸部會減少而變得平滑，因此耐氣體腐蝕性提高。 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 convex portion which is relatively susceptible to corrosion is reduced and smoothed, so that the gas corrosion resistance is improved.

於以XPS(X射線光電子光譜)進行Depth分析時，較佳為表示最表層(A層)14之Sn、In之原子濃度(at%)之最高值的位置(D1)、表示中層(B層)13之Ag、Au、Pt、Pd、Ru、Rh、Os或Ir之原子濃度(at%)之最高值的位置(D2)、及表示下層(C層)12之Ni、Cr、Mn、Fe、Co或Cu之原子濃度(at%)之最高值的位置(D3)係自最表面起以D1、D2、D3之順序存在。於自最表面起未以D1、D2、D3之順序存在之情形時，有以下顧慮：無法獲得充分之耐氣體腐蝕性，當對電子零件用金屬材料進行氯氣、亞硫酸氣體、硫化氫氣體等之氣體腐蝕試驗時會被腐蝕，而與氣體腐蝕試驗前相比接觸電阻大幅增加。 When Depth analysis is performed by XPS (X-ray photoelectron spectroscopy), it is preferably a position (D 1 ) indicating the highest value of the atomic concentration (at%) of Sn and In in the outermost layer (A layer) 14, indicating the middle layer (B). The position (D 2 ) of the highest value of the atomic concentration (at%) of Ag, Au, Pt, Pd, Ru, Rh, Os or Ir of the layer 13 and the Ni, Cr, Mn of the lower layer (C layer) 12. The position (D 3 ) of the highest value of the atomic concentration (at%) of Fe, Co or Cu exists in the order of D 1 , D 2 , and D 3 from the outermost surface. When there is no D 1 , D 2 , or D 3 in the order from the outermost surface, there are the following concerns: sufficient gas corrosion resistance cannot be obtained, and chlorine, sulfurous acid gas, and sulfurization are performed on the metal material for electronic parts. The gas corrosion test of hydrogen gas or the like is corroded, and the contact resistance is greatly increased as compared with the gas corrosion test.

於以XPS(X射線光電子光譜)進行Depth分析時，較佳為最表層(A 層)14之Sn、In之原子濃度(at%)、及中層(B層)13之Ag、Au、Pt、Pd、Ru、Rh、Os或Ir之原子濃度(at%)之最高值為10 at%以上，且下層(C層)12之Ni、Cr、Mn、Fe、Co或Cu之原子濃度(at%)為25 at%以上之深度為50 nm以上。於最表層(A層)14之Sn、In之原子濃度(at%)之最高值、及中層(B層)13之Ag、Au、Pt、Pd、Ru、Rh、Os或Ir之原子濃度(at%)之最高值分別未達10 at%，且下層(C層)12之Ni、Cr、Mn、Fe、Co或Cu之原子濃度(at%)為25 at%以上之深度未達50 nm之情形時，有基材成分向最表層(A層)14或中層(B層)13擴散而使低插拔性、耐久性(耐熱性、耐氣體腐蝕性、焊料潤濕性等)變差之虞。 When performing Depth analysis by XPS (X-ray photoelectron spectroscopy), it is preferably the outermost layer (A The atomic concentration (at%) of Sn, In, and the atomic concentration (at%) of Ag, Au, Pt, Pd, Ru, Rh, Os or Ir in the middle layer (B layer) 13 is 10 Above at%, and the atomic concentration (at%) of Ni, Cr, Mn, Fe, Co or Cu of the lower layer (C layer) 12 is 25 at% or more and the depth is 50 nm or more. The atomic concentration of the atomic concentration (at%) of Sn and In in the outermost layer (layer A) 14 and the atomic concentration of Ag, Au, Pt, Pd, Ru, Rh, Os or Ir in the middle layer (layer B) 13 ( The highest value of 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) is 25 at% or more and the depth is less than 50 nm. In the case where the base material component is diffused to the outermost layer (layer A) 14 or the intermediate layer (layer B) 13, the low insertion and the removal property, durability (heat resistance, gas corrosion resistance, solder wettability, etc.) are deteriorated. After that.

<電子零件用金屬材料之用途> <Use of Metal Materials for Electronic Parts>

本發明之電子零件用金屬材料之用途並無特別限定，但例如可列舉將電子零件用金屬材料用於接點部分之連接器端子、將電子零件用金屬材料用於接點部分之FFC端子或FPC端子、及將電子零件用金屬材料用於外部連接用電極之電子零件等。再者，關於端子，有壓接端子、焊接端子、壓入配合(press fit)端子等，不受與配線側之接合方法限制。於外部連接用電極，有對引板(tab)實施有表面處理而成之連接零件或為了用於半導體之凸塊下金屬(Under Bump Metal)而實施有表面處理之材料等。 The use of the metal material for an electronic component of the present invention is not particularly limited. For example, a metal material for an electronic component is used for a connector terminal of a contact portion, and a metal material for an electronic component is used for an FFC terminal of a contact portion or The FPC terminal and the electronic component for the electronic component are used for the electronic component of the external connection electrode. Further, regarding the terminals, there are crimp terminals, solder terminals, press fit terminals, and the like, and are not limited by the bonding method with the wiring side. The external connection electrode may be a surface-treated connection member for a tab or a surface-treated material for use in a semiconductor under bump metal.

又，既可使用以此種方式形成之連接器端子製作連接器，亦可使用FFC端子或FPC端子製作FFC或FPC。 Further, the connector can be made using the connector terminal formed in this manner, or the FFC terminal or the FPC terminal can be used to fabricate the FFC or FPC.

以下之壓入型端子亦為本發明之電子零件用金屬材料：分別於在殼體安裝有電子零件用金屬材料之裝置部其一側上設置母端子連接部、於另一側設置基板連接部，且將該基板連接部壓入形成於基板之通孔而安裝於該 基板。 The push-in type terminal is also a metal material for an electronic component according to the present invention: a female terminal connecting portion is provided on one side of the device portion in which the metal material for electronic components is mounted on the casing, and a substrate connecting portion is provided on the other side. And pressing the substrate connecting portion into the through hole formed in the substrate and mounting on the substrate Substrate.

連接器既可使公端子與母端子兩者均為本發明之電子零件用金屬材料，亦可僅使公端子或母端子之一者為本發明之電子零件用金屬材料。再者，藉由將公端子與母端子兩者均設為本發明之電子零件用金屬材料，而進一步提高低插拔性。 The connector may have both the male terminal and the female terminal as the metal material for the electronic component of the present invention, or only one of the male terminal or the female terminal may be the metal material for the electronic component of the present invention. Furthermore, both the male terminal and the female terminal are made of the metal material for electronic parts of the present invention, and the low insertion and removal property is further improved.

<電子零件用金屬材料之製造方法> <Method of Manufacturing Metal Material for Electronic Parts>

作為本發明之電子零件用金屬材料之製造方法，可使用濕式(電鍍、無電電鍍)、乾式(濺鍍、離子電鍍等)等。有以下之方法作為具體之方法：於素材11上成膜C層12，於C層12上成膜B層13，於B層13上成膜A層14，且A層14與B層13藉由擴散而形成合金層。若為此種製造方法，Sn之凝著力進一步變小，藉此獲得高耐微滑動磨耗性及高耐插拔性，且提高低插拔性、低晶鬚等特性。 As a method of producing the metal material for an electronic component of the present invention, wet (electroplating, electroless plating), dry (sputtering, ion plating, etc.), or the like can be used. The following method is used as a specific method: a C layer 12 is formed on the material 11, a B layer 13 is formed on the C layer 12, and an A layer 14 is formed on the B layer 13, and the A layer 14 and the B layer 13 are borrowed. An alloy layer is formed by diffusion. According to this manufacturing method, the condensing power of Sn is further reduced, thereby obtaining high micro-sliding abrasion resistance and high insertion resistance, and improving characteristics such as low insertion and low whiskers.

(熱處理) (heat treatment)

於形成A層14後，為了提高高耐微滑動磨耗性、高耐插拔性、低晶鬚性及低插拔性亦可實施熱處理。藉由熱處理容易使A層14與B層13形成合金層，而使Sn之凝著力進一步變小，藉此獲得高耐微滑動磨耗性及高耐插拔性，且提高低插拔性、低晶鬚等特性。再者，關於該熱處理可適當選擇處理條件(溫度×時間)。又，尤其亦可不進行該熱處理。 After the formation of the A layer 14, heat treatment can be performed in order to improve high micro-sliding abrasion resistance, high insertion resistance, low whisker property, and low plug-in property. By forming an alloy layer between the A layer 14 and the B layer 13 by heat treatment, the condensing power of Sn is further reduced, thereby obtaining high micro-sliding abrasion resistance and high insertion resistance, and low insertion and lowness are improved. Characteristics such as whiskers. Further, the treatment conditions (temperature × time) can be appropriately selected for the heat treatment. Further, in particular, the heat treatment may not be performed.

較佳為於溫度500℃以下、12小時以內進行熱處理。若超過500℃，則存在有產生接觸電阻變高，焊料潤濕性變差等問題之情形。若熱處理超過12小時，則存在有產生接觸電阻變高，焊料潤濕性變差等問題。 It is preferred to carry out heat treatment at a temperature of 500 ° C or less and within 12 hours. When it exceeds 500 ° C, there are cases where the contact resistance is high and the solder wettability is deteriorated. When the heat treatment is carried out for more than 12 hours, there is a problem that the contact resistance becomes high and the solder wettability is deteriorated.

為了提高高耐微滑動磨耗性、高耐插拔性、低插拔性及高耐 久性(耐熱性、耐氣體腐蝕性、焊料潤濕性等)亦可於A層14上、或於實施熱處理後之A層14上實施後處理。藉由後處理而提高潤滑性，獲得更低插拔性，且A層與B層之氧化受到抑制，提高耐熱性、耐氣體腐蝕性及焊料潤濕性等耐久性。作為具體之後處理有使用抑制劑(inhibitor)之磷酸鹽處理、潤滑處理、矽烷偶合劑處理等。再者，關於該後處理可適當選擇處理條件(溫度×時間)。又，尤其亦可不進行該後處理。 In order to improve high scratch resistance, high insertion resistance, low insertion and high resistance The durability (heat resistance, gas corrosion resistance, solder wettability, etc.) may also be post-treated on the A layer 14 or on the A layer 14 after the heat treatment. Lubricity is improved by post-treatment, and lower insertion and removal properties are obtained, and oxidation of the A layer and the B layer is suppressed, and durability such as heat resistance, gas corrosion resistance, and solder wettability is improved. As a specific post-treatment, there are a phosphate treatment using an inhibitor, a lubrication treatment, a decane coupling agent treatment, and the like. Further, the processing conditions (temperature × time) can be appropriately selected for the post-processing. Further, in particular, the post-processing may not be performed.

【實施例】 [Examples]

以下，一併表示本發明之實施例與比較例，但該等係為了更好地理解本發明而提供者，並不意在限定本發明。 In the following, the embodiments and the comparative examples of the present invention are shown, but are not intended to limit the present invention in order to provide a better understanding of the present invention.

作為實施例及比較例，於以下之表1~7中所示之條件下分別製作藉由依序設置基材、C層、B層、A層並進行熱處理而形成之試樣。 As examples and comparative examples, samples prepared by sequentially providing a base material, a C layer, a B layer, and an A layer in a heat treatment were prepared under the conditions shown in Tables 1 to 7 below.

分別於表1中表示基材之製作條件，於表2中表示C層之製作條件，於表3中表示B層之製作條件，於表4中表示A層之製作條件，於表5中表示熱處理條件。又，分別於表6(表6-1、表6-2、表6-3)中表示各實施例中使用之各層之製作條件及熱處理之條件，於表7中表示各比較例中使用之各層之製作條件及熱處理之條件。 Table 1 shows the production conditions of the substrate, Table 2 shows the production conditions of the C layer, Table 3 shows the production conditions of the B layer, and Table 4 shows the production conditions of the A layer, and Table 5 shows the production conditions of the substrate. Heat treatment conditions. Further, Table 6 (Table 6-1, Table 6-2, Table 6-3) shows the production conditions and heat treatment conditions of the respective layers used in the respective examples, and Table 7 shows the use of each of the comparative examples. The production conditions of each layer and the conditions of the heat treatment.

(厚度之測定) (Measurement of thickness)

A層、B層、C層之厚度係對不具有A層、B層、C層之元素的基材分別實施表面處理，並分別利用螢光X射線膜厚計(Seiko Instruments製造之SFT9500X，準直器0.1 mm Φ)測定實際之厚度。例如，於Sn鍍敷之情形時，若基材為Cu-10質量%Sn-0.15質量%P，則於基材具有Sn，而無法得知準確之Sn鍍敷之厚度，因此以基材之組成中不具有Sn之Cu-30質量%Zn測定厚度。 The thickness of the A layer, the B layer, and the C layer is subjected to surface treatment for each of the substrates having no elements of the A layer, the B layer, and the C layer, and is respectively subjected to a fluorescent X-ray film thickness meter (SFT9500X manufactured by Seiko Instruments, Straight 0.1 mm Φ) Determine the actual thickness. For example, in the case of Sn plating, if the substrate is Cu-10% by mass Sn-0.15 mass% P, Sn is present on the substrate, and the thickness of the accurate Sn plating cannot be known, so the substrate is Cu-30 mass% Zn having no Sn in the composition was measured for thickness.

(附著量之測定) (Measurement of adhesion amount)

以硫酸或硝酸等對各試樣進行酸分解，藉由ICP(Inductive Coupling Plasma，電感耦合電漿)發光分光分析而測定各金屬之附著量。再者，具體使用之酸係根據各樣本所具有之組成而不同。 Each sample was subjected to acid decomposition by sulfuric acid, nitric acid or the like, and the amount of adhesion of each metal was measured by ICP (Inductive Coupling Plasma) luminescence spectroscopic analysis. Further, the acid to be specifically used differs depending on the composition of each sample.

(組成之決定) (decide of composition)

基於測定出之附著量，算出各金屬之組成。 The composition of each metal was calculated based on the measured adhesion amount.

(層構造之決定) (Decision of layer structure)

所得之試樣之層構造係以藉由XPS(X射線光電子光譜)分析所得之深度(Depth)分佈而決定。分析出之元素係A層、B層、C層之組成、與C及O。將該等元素設為指定元素。又，將指定元素之合計設為100%，分析各元素之濃度(at%)。XPS(X射線光電子光譜)分析下之厚度對應於藉由分析所得之圖表之橫軸之距離(以SiO2換算計之距離)。 The layer structure of the obtained sample was determined by the depth (Depth) distribution obtained by XPS (X-ray photoelectron spectroscopy) analysis. The elements analyzed are the composition of layer A, layer B, layer C, and C and O. These elements are set as the specified elements. Further, the total of the designated elements was set to 100%, and the concentration (at%) of each element was analyzed. The thickness under XPS (X-ray photoelectron spectroscopy) analysis corresponds to the distance (the distance in terms of SiO 2 ) of the horizontal axis of the graph obtained by the analysis.

又，亦對所得之試樣之表面以藉由XPS(X射線光電子光譜)分析之Survey測定進行定性分析。定性分析之濃度之解析力設為0.1 at%。 Further, the surface of the obtained sample was also qualitatively analyzed by Survey measurement by XPS (X-ray photoelectron spectroscopy) analysis. The resolution of the concentration of the qualitative analysis was set to 0.1 at%.

作為XPS裝置，使用ULVAC-PHI股份有限公司製造之5600MC，設為極限真空度：5.7×10-9 Torr、激發源：單色化AlK α、輸出：210 W、檢測面積：800μm Φ、入射角：45度、掠出角：45度、無中和槍，並於以下之濺鍍條件下進行測定。 As the XPS device, 5600MC manufactured by ULVAC-PHI Co., Ltd. was used, and the ultimate vacuum degree was 5.7×10 -9 Torr, excitation source: monochromatic AlK α, output: 210 W, detection area: 800 μm Φ, incident angle : 45 degrees, sweep angle: 45 degrees, no neutral gun, and measured under the following sputtering conditions.

離子種類：Ar+ Ion species: Ar +

加速電壓：3 kV Acceleration voltage: 3 kV

掃掠區域：3 mm×3 mm Sweep area: 3 mm × 3 mm

速率：2.8 nm/min.(SiO2換算) Rate: 2.8 nm/min. (SiO 2 conversion)

(評價) (Evaluation)

對各試樣進行以下之評價。 Each sample was subjected to the following evaluation.

A.耐微滑動磨耗性 A. Micro sliding wear resistance

耐微滑動磨耗性係使用山崎精機研究所製造之精密滑動試驗裝置CRS-G2050型，以滑動距離0.5mm、滑動速度1mm/s、接觸負重1N、來回滑動500次之條件來評價滑動次數與接觸電阻之關係。樣本數設為5個，採用自各樣品之最小值至最大值之範圍。目標特性設為於滑動次數100次時接觸電阻為50m Ω以下。接觸電阻係以<50、50~200m Ω來區分。 The micro-sliding wear resistance was evaluated using the CRS-G2050 precision sliding test device manufactured by Yamazaki Seiki Co., Ltd., with sliding distance of 0.5 mm, sliding speed of 1 mm/s, contact weight of 1 N, and sliding back and forth 500 times. The relationship of resistance. The number of samples was set to five, ranging from the minimum to the maximum of each sample. The target characteristic is set to a contact resistance of 50 m Ω or less when the number of slides is 100 times. Contact resistance is distinguished by <50, 50~200m Ω.

B.耐插拔性 B. Pluggability resistance

藉於後述之「C.插拔力」所記載之方法進行10次插拔試驗，以插拔試驗後之接觸電阻進行評價。目標特性係設為接觸電阻為10m Ω以下。接觸電阻係以1~5、2~7、3~9、10<m Ω來區分。 The plugging test was carried out 10 times by the method described in "C. Insertion force" described later, and the contact resistance after the plugging test was evaluated. The target characteristic is set to a contact resistance of 10 m Ω or less. The contact resistance is distinguished by 1 to 5, 2 to 7, 3 to 9, and 10 < m Ω.

C.插拔力 C. Insertion force

插拔力係藉由使用市售之回焊鍍Sn母端子(090型住友TS/矢崎090II 系列母端子非防水/F090-SMTS)，與實施例及比較例之經鍍敷之公端子進行插拔試驗而進行評價。 The insertion force is based on the use of a commercially available reflow-plated Sn female terminal (090 Sumitomo TS/Yagasaki 090II) The series mother terminal non-waterproof/F090-SMTS) was evaluated by inserting and pulling tests with the plated male terminals of the examples and the comparative examples.

試驗所使用之測定裝置係Aikoh Engineering製造之1311NR，以公接腳(male pin)之滑動距離5 mm進行評價。樣本數設為5個，插拔力係***力與拔出力相等，因此採用各樣本之最大***力之值的平均值。作為插拔力之空白材料，採用比較例1之樣本。 The measuring device used in the test was 1311NR manufactured by Aikoh Engineering, and was evaluated by a sliding distance of 5 mm from a male pin. The number of samples was set to five, and the insertion force was equal to the insertion force, so the average value of the maximum insertion force of each sample was used. As a blank material for the insertion force, the sample of Comparative Example 1 was used.

插拔力之目標係與比較例1之最大插拔力相比為未達85%。其因比較例4與比較例1之最大***力相比為90%，故目標設為與該比較例4相比插拔力之減少更大。 The target of the insertion force was less than 85% compared with the maximum insertion force of Comparative Example 1. Since the maximum insertion force of Comparative Example 4 and Comparative Example 1 was 90%, the target was set to have a larger reduction in the insertion force than Comparative Example 4.

D.晶鬚 D. Whisker

晶鬚係藉由JEITA RC-5241之負重試驗(ball indenter method，球壓頭法)進行評價。即，對各樣本進行負重試驗，利用SEM(Scanning Electron Microscope，掃描式電子顯微鏡)(JEOL公司製造，型號JSM-5410)以100~10000倍之倍率觀察結束負重試驗之樣本，以觀察晶鬚之產生狀況。於以下表示負重試驗條件。 The whiskers were evaluated by the ball indenter method of JEITA RC-5241. In other words, each sample was subjected to a load-bearing test, and a sample of the end load test was observed by a SEM (Scanning Electron Microscope) (manufactured by JEOL Co., Ltd., model JSM-5410) at a magnification of 100 to 10,000 times to observe the whiskers. Produce the situation. The load test conditions are indicated below.

球壓頭之直徑：Φ 1 mm±0.1 mm Ball indenter diameter: Φ 1 mm ± 0.1 mm

試驗負重：2 N±0.2 N Test load: 2 N ± 0.2 N

試驗時間：120小時 Test time: 120 hours

樣本數：10 Number of samples: 10

目標特性係不產生長度20 μm以上之晶鬚，但最大目標係設為完全不產生晶鬚。 The target characteristic is that whiskers with a length of 20 μm or more are not produced, but the maximum target is set to be completely free of whiskers.

E.接觸電阻 E. Contact resistance

接觸電阻係使用山崎精機製造之接點模擬器CRS-113-Au型，於接點負重50 g之條件下藉由4端子法進行測定。樣本數設為5個，並採用自各樣本之最小值至最大值之範圍。目標特性係設為接觸電阻為10 m Ω以下。 The contact resistance was measured by a 4-terminal method using a contact simulator CRS-113-Au manufactured by Yamazaki Seiki Co., Ltd. under a load of 50 g. The number of samples is set to 5 and ranges from the minimum to the maximum of each sample. The target characteristic is set to a contact resistance of 10 m Ω or less.

F.耐熱性 F. Heat resistance

耐熱性係測定大氣加熱(155℃×500 h)試驗後之樣本之接觸電阻並進行評價。目標特性係設為接觸電阻為10 m Ω以下，最大目標係設為接觸電阻於耐熱性試驗前後無變化(相等)。耐熱性係以接觸電阻1~3、2~4、3~7、10<m Ω來區分。 The heat resistance was measured by measuring the contact resistance of the sample after the atmospheric heating (155 ° C × 500 h) test. The target characteristic was set to a contact resistance of 10 m Ω or less, and the maximum target was set as the contact resistance without change (equal) before and after the heat resistance test. The heat resistance is distinguished by contact resistances 1 to 3, 2 to 4, 3 to 7, and 10 < m Ω.

G.耐氣體腐蝕性 G. Gas corrosion resistance

耐氣體腐蝕性係於下述之試驗環境下進行評價。耐氣體腐蝕性之評價係以結束環境試驗的試驗後之樣本之接觸電阻與外觀。再者，目標特性係設為接觸電阻為10 m Ω以下，且外觀無變色。然而最大目標係設為接觸電阻於耐氣體腐蝕性試驗前後無變化(相等)。耐氣體腐蝕性係以接觸電阻1~3、2~4、6~9、10<m Ω來區分。 Gas corrosion resistance was evaluated in the test environment described below. The gas corrosion resistance was evaluated by the contact resistance and appearance of the sample after the end of the environmental test. Further, the target characteristics were such that the contact resistance was 10 m Ω or less, and the appearance was not discolored. However, the maximum target is to set the contact resistance to be unchanged (equal) before and after the gas corrosion resistance test. Gas corrosion resistance is distinguished by contact resistances 1 to 3, 2 to 4, 6 to 9, and 10 < m Ω.

硫化氫氣體腐蝕試驗 Hydrogen sulfide gas corrosion test

硫化氫濃度：3 ppm Hydrogen sulfide concentration: 3 ppm

溫度：40℃ Temperature: 40 ° C

濕度：80%RH Humidity: 80% RH

曝露時間：96 h Exposure time: 96 h

樣本數：5個 Number of samples: 5

H.焊料潤濕性 H. Solder wettability

焊料潤濕性係對鍍敷後之樣本進行評價。使用焊料測試儀(solder checker)(Rhesca公司製造之SAT-5000)，並使用市售之25%松香甲醇焊劑作為焊劑(flux)，藉由彎面(meniscograph)法測定焊料潤濕時間。焊料係使用Sn-3Ag-0.5Cu(250℃)。樣本數設為5個，並採用自各樣本之最小值至最大值之範圍。目標特性係沾錫時間(zero cross time)設為5秒以下。沾錫時間係以1~3、5<s來區分。 Solder wettability is evaluated on the plated sample. Using a solder tester (solder Checker) (SAT-5000 manufactured by Rhesca) and using a commercially available 25% rosin methanol flux as a flux, the solder wetting time was determined by the meniscograph method. The solder system used Sn-3Ag-0.5Cu (250 ° C). The number of samples is set to 5 and ranges from the minimum to the maximum of each sample. The target characteristic is zero cross time set to 5 seconds or less. Zinc tin time is distinguished by 1~3 and 5<s.

I.彎曲加工性 I. Bending workability

彎曲加工性係使用W字型之模具以試樣之板厚與彎曲半徑之比成為1之條件下彎曲90°而進行評價。評價係以光學顯微鏡觀察彎曲加工部表面，未觀察到裂痕而判斷為實用上無問題之情形時設為○，將確認有裂痕之情形設為×。再者，樣本數設為3個。 The bending workability was evaluated by bending a 90° condition using a W-shaped mold under the condition that the ratio of the thickness of the sample 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 problem in the case where no crack was observed, it was set to ○, and the case where cracks were confirmed was set to ×. Furthermore, the number of samples is set to three.

J.維氏硬度 J. Vickers hardness

最表層(A層)之維氏硬度係以負重980.7 mN(Hv0.1)、負重保持時間15秒對樣本表面壓入壓頭而進行測定。 The Vickers hardness of the outermost layer (layer A) was measured by pressing the indenter on the sample surface with a load of 980.7 mN (Hv 0.1) and a load holding time of 15 seconds.

K.壓痕硬度 K. Indentation hardness

最表層(A層)之壓痕硬度係藉由超微小硬度試驗(elionix製造之ENT-2100)，以負重0.1 mN對樣本表面壓入壓頭而進行測定。再者，每一試樣進行5次之測定。 The indentation hardness of the outermost layer (layer A) was measured by an ultra-micro hardness test (ENT-2100 manufactured by Elionix) with a load of 0.1 mN on the surface of the sample. Furthermore, each sample was measured 5 times.

L.表面粗糙度 L. Surface roughness

表面粗糙度(算術平均高度(Ra)及最大高度(Rz))之測定係依照JIS B 0601，使用非接觸式三維測定裝置(三鷹光器公司製造，型號NH-3)而進行。以截止點(cut-off)為0.25 mm，測定長度為1.50 mm，對每一試樣測定5次。 The measurement of the surface roughness (arithmetic mean height (Ra) and maximum height (Rz)) was carried out in accordance with JIS B 0601 using a non-contact three-dimensional measuring apparatus (manufactured by Sanying Optical Co., Ltd., model NH-3). The cut-off was 0.25 mm, the length was measured to be 1.50 mm, and each sample was measured 5 times.

將各條件下之評價結果示於表8~16。 The evaluation results under each condition are shown in Tables 8 to 16.

實施例1~76為耐微滑動磨耗性、耐插拔性均優異之電子零件金屬材料。 Examples 1 to 76 are metal parts for electronic parts excellent in micro sliding wear resistance and insertion resistance.

比較例1為空白材料。 Comparative Example 1 was a blank material.

比較例2為將比較例1之空白材料之Sn鍍敷設為較薄而製作者，但其焊料潤濕性較差。 In Comparative Example 2, the Sn plating of the blank material of Comparative Example 1 was made thin, but the solder wettability was inferior.

比較例3為與比較例2相比未實施熱處理而製作者，但其插拔力亦高於目標。 Comparative Example 3 was produced without heat treatment as compared with Comparative Example 2, but the insertion force was also higher than the target.

比較例4為與比較例2相比於中層實施Cu鍍敷而製作者，但其插拔力與比較例1相比為90%。 Comparative Example 4 was produced by performing Cu plating on the middle layer as compared with Comparative Example 2, but the insertion force was 90% as compared with Comparative Example 1.

比較例5為與比較例4相比將Sn鍍敷設為較薄而製作者，但其焊料潤濕性較差。 In Comparative Example 5, the Sn plating was made thinner than Comparative Example 4, but the solder wettability was inferior.

比較例6為與比較例5相比未實施熱處理而製作者，但其插拔力亦高於目標。 Comparative Example 6 was produced without heat treatment as compared with Comparative Example 5, but the insertion force was also higher than the target.

比較例7為與比較例1之空白材料相比於下層實施Cu鍍敷而製作者，但其與比較例1之間無特性變化。 Comparative Example 7 was produced by performing Cu plating on the lower layer than the blank material of Comparative Example 1, but there was no change in characteristics between Comparative Example 1.

比較例8為與比較例1之空白材料相比實施較厚之下層之Ni鍍敷而製作者，但其與比較例1之間無特性變化。 Comparative Example 8 was produced by performing Ni plating of a thicker underlayer than the blank of Comparative Example 1, but there was no change in characteristics between Comparative Example 1.

比較例9~13為B層之厚度、附著量比目標較薄、較少者，但微滑動磨耗性較差，且耐插拔性亦較高。 In Comparative Examples 9 to 13, the thickness of the layer B and the adhesion amount were thinner and smaller than the target, but the micro-sliding wear property was poor, and the plugging resistance was also high.

比較例14為A層之厚度、附著量比目標較薄、較少者，但確認到耐氣體腐蝕性較差，且試驗後之外觀變色。 In Comparative Example 14, the thickness of the layer A and the amount of adhesion were smaller than the target, and it was found to be less. However, it was confirmed that the gas corrosion resistance was poor, and the appearance after the test was discolored.

比較例15為A層之厚度、附著量比目標較厚、較多者，但於A層與B 層之關係中，A層之比率較多，且於藉由XPS(X射線光電子光譜)之Depth測定中，A層以較目標高之濃度存在，因此耐微滑動磨耗性較差。 In Comparative Example 15, the thickness of the layer A and the amount of adhesion were thicker than the target, but in the case of layer A and B. In the relationship of the layers, the ratio of the A layer is large, and in the Depth measurement by XPS (X-ray photoelectron spectroscopy), the A layer exists at a concentration higher than the target, and thus the micro sliding wear resistance is inferior.

比較例16為A層之厚度、附著量比目標較薄、較少者，但確認到耐氣體腐蝕性較差，且試驗後之外觀變色。 In Comparative Example 16, the thickness of the layer A and the amount of adhesion were thinner than the target, and it was found to be less. However, it was confirmed that the gas corrosion resistance was poor, and the appearance after the test was discolored.

比較例17為A層之厚度、附著量比目標較厚、較多者，雖A層與B層之關係係如目標者，但還是因A層之厚度、附著量比目標較厚、較多而耐微滑動磨耗性較差。 In Comparative Example 17, the thickness of the layer A and the amount of adhesion were thicker than the target. Although the relationship between the layer A and the layer B was as the target, the thickness of the layer A and the amount of adhesion were thicker than the target. The micro-sliding wear resistance is poor.

比較例18為A層之厚度、附著量比目標較薄、較少者，但確認到耐氣體腐蝕性較差，且試驗後之外觀變色。 In Comparative Example 18, the thickness of the layer A and the amount of adhesion were smaller than the target, and it was found to be less. However, it was confirmed that the gas corrosion resistance was poor, and the appearance after the test was discolored.

比較例19為A層之厚度、附著量比目標較厚、較多者，雖A層與B層之關係係如目標者，但還是因A層之厚度、附著量比目標較厚、較多而耐微滑動磨耗性較差。且插拔力亦較高。 In Comparative Example 19, the thickness of the layer A and the adhesion amount were thicker than the target, and the relationship between the layer A and the layer B was as the target, but the thickness of the layer A and the amount of adhesion were thicker than the target, and more. The micro-sliding wear resistance is poor. And the insertion force is also high.

比較例20~22為B層之厚度、附著量比目標較厚、較多者，但***力較高。 In Comparative Examples 20 to 22, the thickness of the layer B and the adhesion amount were thicker than the target, but the insertion force was high.

比較例23為C層之厚度、附著量比目標較薄、較少者，但***力較高，耐熱性及焊料潤濕性亦較差。 In Comparative Example 23, the thickness of the layer C and the amount of adhesion were thinner and smaller than the target, but the insertion force was high, and the heat resistance and the solder wettability were also inferior.

比較例24為進行較目標之熱處理之時間更長者，但焊料無潤濕。 Comparative Example 24 was carried out for a longer period of time than the intended heat treatment, but the solder was not wetted.

比較例25為進行較目標之熱處理之溫度更高者，但焊料無潤濕。 Comparative Example 25 was performed at a higher temperature than the target heat treatment, but the solder was not wetted.

比較例26為A層之厚度、附著量比目標較薄、較少者，但於藉由XPS(X射線光電子光譜)之Depth測定中，上述A層之Sn或In之原子濃度(at%)之最高值為10 at%以下，耐氣體腐蝕性較差，硫化氫氣體腐蝕試驗後之接觸電阻高於目標。 In Comparative Example 26, the thickness of the layer A and the amount of adhesion were smaller than the target, and the atomic concentration (at%) of Sn or In of the layer A was measured by Depth by XPS (X-ray photoelectron spectroscopy). The highest value is below 10 at%, and the gas corrosion resistance is poor. The contact resistance after the hydrogen sulfide gas corrosion test is higher than the target.

比較例27為B層之厚度、附著量比目標較薄、較少者，但於藉由XPS(X射線光電子光譜)之Depth測定中，上述B層之原子濃度(at%)之最高值為10 at%以下，耐熱性、焊料潤濕性較差。 In Comparative Example 27, the thickness of the layer B and the amount of adhesion were thinner than the target, but the highest value of the atomic concentration (at%) of the layer B was measured by Depth by XPS (X-ray photoelectron spectroscopy). Below 10 at%, heat resistance and solder wettability are poor.

比較例28為C層之厚度、附著量比目標較薄、較少者，但***力較高，耐熱性及焊料潤濕性亦較差。 In Comparative Example 28, the thickness of the layer C and the amount of adhesion were thinner and smaller than the target, but the insertion force was high, and the heat resistance and the solder wettability were also inferior.

比較例29為與實施例2相比，係使Sn與Ag之鍍敷順序相反而製作者，但於藉由XPS(X射線光電子光譜)之Depth測定中，表示上述最表層(A層)之Sn或In之原子濃度(at%)之最高值的位置(D1)、與表示上述中層(B層)之Ag、Au、Pt、Pd、Ru、Rh、Os或Ir之原子濃度(at%)之最高值的位置(D2)係以D2、D1之順序存在，因此耐氣體腐蝕性較差，硫化氫氣體腐蝕試驗後之接觸電阻高於目標。 In Comparative Example 29, the plating order of Sn and Ag was reversed as compared with Example 2. However, in the Depth measurement by XPS (X-ray photoelectron spectroscopy), the above-mentioned outermost layer (layer A) was shown. The position (D 1 ) of the highest value of the atomic concentration (at%) of Sn or In, and the atomic concentration of Ag, Au, Pt, Pd, Ru, Rh, Os or Ir representing the above intermediate layer (B layer) (at%) The position (D 2 ) of the highest value exists in the order of D 2 and D 1 , so that the gas corrosion resistance is poor, and the contact resistance after the hydrogen sulfide gas corrosion test is higher than the target.

又，於圖2中表示實施例2之XPS(X射線光電子光譜)之Depth測定結果。根據圖2可知，自最表側至C層成為20at%之範圍中，滿足A層之濃度(at%)<〔B層之濃度(at%)+30〕。 Further, the results of Depth measurement of XPS (X-ray photoelectron spectroscopy) of Example 2 are shown in Fig. 2 . As can be seen from Fig. 2, the concentration (at%) of the layer A (the concentration of the layer B (at%) + 30) is satisfied in the range of 20 at% from the most front side to the C layer.

又，可知表示A層之Sn或In之原子濃度(at%)之最高值的位置(D1)、與表示B層之Ag、Au、Pt、Pd、Ru、Rh、Os或Ir之原子濃度(at%)之最高值的位置(D2)、表示C層之Ni、Cr、Mn、Fe、Co或Cu之原子濃度(at%)之最高值的位置(D3)係自最表面起以D1、D2、D3之順序存在，A層之Sn或In之原子濃度(at%)之最高值、及B層之Ag、Au、Pt、Pd、Ru、Rh、Os或Ir之原子濃度(at%)之最高值分別為10 at%以上，且上述C層之Ni、Cr、Mn、Fe、Co或Cu之原子濃度(at%)為25 at%以上之深度為50 nm以上。 Further, it is known that the position (D 1 ) indicating the highest value of the atomic concentration (at%) of Sn or In of the A layer, and the atomic concentration of Ag, Au, Pt, Pd, Ru, Rh, Os or Ir indicating the B layer. position (at%) of the maximum value (D 2), indicates the position of Ni C layers, Cr, Mn, Fe, Co, or the concentration of atoms as Cu (at%) of the maximum value (D 3) lines from the outermost surface from In the order of D 1 , D 2 , and D 3 , the highest value of atomic concentration (at %) of Sn or In of layer A, and Ag, Au, Pt, Pd, Ru, Rh, Os, or Ir of layer B The highest value of atomic concentration (at%) is 10 at% or more, and the atomic concentration (at%) of Ni, Cr, Mn, Fe, Co or Cu in the above C layer is 25 at% or more and the depth is 50 nm or more. .

10‧‧‧電子零件用金屬材料 10‧‧‧Metal materials for electronic parts

11‧‧‧基材 11‧‧‧Substrate

12‧‧‧C層 12‧‧‧C layer

13‧‧‧B層 13‧‧‧B layer

14‧‧‧A層 14‧‧‧A floor

Claims (22)

一種電子零件用金屬材料，其中，由Sn、In或該等之合金所構成之A層形成於基材上；由Ag、Au、Pt、Pd、Ru、Rh、Os、Ir或該等之合金所構成之B層形成於該基材與該A層之間；由選自由Ni、Cr、Mn、Fe、Co、Cu所組成之群中之1種或2種以上所構成之C層形成於該基材與該B層之間，且；該A層之厚度為0.01~0.3μm，該B層之厚度為0.05~0.5μm，該C層之厚度為0.05μm以上，該A層之厚度/該B層之厚度比為0.02~4.00。 A metal material for an electronic component, wherein an A layer composed of Sn, In, or the like is formed on a substrate; and Ag, Au, Pt, Pd, Ru, Rh, Os, Ir, or the like The layer B is formed between the substrate and the layer A, and a layer C composed of one or more 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 more, and the thickness of the A layer/ The thickness ratio of the B layer is 0.02 to 4.00. 一種電子零件用金屬材料，其中，由Sn、In或該等之合金所構成之A層形成於基材上；由Ag、Au、Pt、Pd、Ru、Rh、Os、Ir或該等之合金所構成之B層形成於該基材與該A層之間；由選自由Ni、Cr、Mn、Fe、Co、Cu所組成之群中之1種或2種以上所構成之C層形成於該基材與該B層之間，且；該A層之附著量為7~230μg/cm2，該B層之附著量為50~550μg/cm2，該C層之附著量為0.03mg/cm2以上，該A層之附著量/該B層之附著量比為0.10~3.00。 A metal material for an electronic component, wherein an A layer composed of Sn, In, or the like is formed on a substrate; and Ag, Au, Pt, Pd, Ru, Rh, Os, Ir, or the like The layer B is formed between the substrate and the layer A, and a layer C composed of one or more selected from the group consisting of Ni, Cr, Mn, Fe, Co, and Cu is formed. Between the substrate and the layer B, the adhesion amount of the layer A is 7 to 230 μg/cm 2 , the adhesion amount of the layer B is 50 to 550 μg/cm 2 , and the adhesion amount of the layer C is 0.03 mg / Above cm 2 or more, the adhesion amount of the A layer/the adhesion ratio of the B layer is 0.10 to 3.00. 如申請專利範圍第1或第2項之電子零件用金屬材料，藉由XPS(X 射線光電子光譜)進行Depth(深度)分析時，於自最表側至C層之濃度成為20at%之範圍中，滿足下式：A層濃度(at%)<B層濃度(at%)+30。 For example, apply for metal materials for electronic parts according to item 1 or 2 of the patent, by XPS (X When the Depth (depth) analysis is performed, the concentration in the range from the most front side to the C layer is 20 at%, and the following formula: A layer concentration (at%) < B layer concentration (at%) + 30 is satisfied. 如申請專利範圍第1或第2項之電子零件用金屬材料，該A層之合金組成為，Sn、In或Sn與In之合計為50質量%以上，其餘合金成分由As、Bi、Cd、Co、Cr、Cu、Fe、Mn、Mo、Ni、Sb、W、Zn所組成之群中之1種或2種以上之金屬構成。 For the metal material for electronic parts according to the first or second aspect of the patent application, the alloy composition of the layer A is such that the total of Sn, In or Sn and In is 50% by mass or more, and the remaining alloy components are As, Bi, Cd, One or two or more kinds of metals composed of a group consisting of Co, Cr, Cu, Fe, Mn, Mo, Ni, Sb, W, and Zn. 如申請專利範圍第1或第2項之電子零件用金屬材料，該B層之合金組成為Ag、Au、Pt、Pd、Ru、Rh、Os、Ir，或Ag、Au、Pt、Pd、Ru、Rh、Os及Ir之合計為50質量%以上，其餘合金成分由選自由Bi、Cd、Co、Cu、Fe、Mn、Mo、Ni、Pb、Sb、Se、W、Tl、Zn所組成之群中之1種或2種以上之金屬構成。 For the metal material for electronic parts according to the first or second aspect of the patent application, the alloy composition of the B layer is Ag, Au, Pt, Pd, Ru, Rh, Os, Ir, or Ag, Au, Pt, Pd, Ru. The total of Rh, Os, and Ir is 50% by mass or more, and the remaining alloy components are selected from the group consisting of Bi, Cd, Co, Cu, Fe, Mn, Mo, Ni, Pb, Sb, Se, W, Tl, and Zn. One or two or more metals in the group. 如申請專利範圍第1或第2項之電子零件用金屬材料，該C層之合金組成為Ni、Cr、Mn、Fe、Co、Cu之合計為50質量%以上，進而由選自由B、P、Zn所組成之群中之1種或2種以上之金屬所構成。 In the metal material for electronic parts according to the first or second aspect of the patent application, the alloy composition of the C layer is 50% by mass or more in total of Ni, Cr, Mn, Fe, Co, and Cu, and further selected from B and P. And one or two or more kinds of metals composed of Zn. 如申請專利範圍第1或第2項之電子零件用金屬材料，其表面之維式硬度為Hv100以上。 For example, in the metal material for electronic parts according to the first or second aspect of the patent application, the surface hardness of the surface is Hv100 or more. 如申請專利範圍第1或第2項之電子零件用金屬材料，其藉由超微小硬度試驗以負重0.1mN，於表面壓入壓頭而測定時之表面的壓痕硬度為1000MPa以上。 For example, in the metal material for electronic parts according to the first or second aspect of the patent application, the indentation hardness of the surface measured by the ultra-micro hardness test at a load of 0.1 mN and the surface is pressed into the indenter is 1000 MPa or more. 如申請專利範圍第1或第2項之電子零件用金屬材料，其表面之維式硬度為Hv1000以下。 For the metal material for electronic parts according to the first or second aspect of the patent application, the dimensional hardness of the surface is Hv1000 or less. 如申請專利範圍第1或第2項之電子零件用金屬材料，其藉由超微小硬度試驗以負重0.1mN，於表面壓入壓頭而測定時之表面的壓痕硬度為10000MPa以下。 For example, in the metal material for electronic parts according to the first or second aspect of the patent application, the indentation hardness of the surface when the surface is pressed into the indenter by the ultra-fine hardness test is 0.1 mN or less, and the indentation hardness is 10000 MPa or less. 如申請專利範圍第1或第2項之電子零件用金屬材料，其表面之算數平均高度(Ra)為0.1μm以下。 The metal material for electronic parts according to the first or second aspect of the patent application has an arithmetic mean height (Ra) of 0.1 μm or less on the surface. 如申請專利範圍第1或第2項之電子零件用金屬材料，其表面之最大高度(Rz)為1μm以下。 For the metal material for electronic parts according to the first or second aspect of the patent application, the maximum height (Rz) of the surface is 1 μm or less. 如申請專利範圍第1或第2項之電子零件用金屬材料，其藉由XPS(X射線光電子光譜)進行Depth(深度)分析時，表示該A層之Sn或In之原子濃度(at%)之最高值的位置(D1)、表示該B層之Ag、Au、Pt、Pd、Ru、Rh、Os或Ir之原子濃度(at%)之最高值的位置(D2)、及表示該C層之Ni、Cr、Mn、Fe、Co或Cu之原子濃度(at%)之最高值的位置(D3)係自最表面起以D1、D2、D3之順序存在。 For the metal material for electronic parts according to the first or second aspect of the patent application, when the Depth (depth) analysis is performed by XPS (X-ray photoelectron spectroscopy), the atomic concentration of Sn or In of the A layer (at%) is indicated. a position (D 1 ) of the highest value, a position (D 2 ) indicating the highest value of the atomic concentration (at%) of Ag, Au, Pt, Pd, Ru, Rh, Os or Ir of the B layer, and indicating the position The position (D 3 ) of the highest value of the atomic concentration (at %) of Ni, Cr, Mn, Fe, Co or Cu of the C layer exists in the order of D 1 , D 2 , and D 3 from the outermost surface. 如申請專利範圍第1或第2項之電子零件用金屬材料，其藉由XPS(X射線光電子光譜)進行Depth分析時，該A層之Sn或In之原子濃度(at%)之最高值、及該B層之Ag、Au、Pt、Pd、Ru、Rh、Os或Ir之原子濃度(at%)之最高值分別為10at%以上，且該C層之Ni、Cr、Mn、Fe、Co或Cu之原子濃度(at%)為25at%以上之深度為50nm以上。 For the metal material for electronic parts according to the first or second aspect of the patent application, when the Depth analysis is performed by XPS (X-ray photoelectron spectroscopy), the atomic concentration (at%) of Sn or In of the A layer is the highest, And the highest 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, Fe, Co of the C layer Or the atomic concentration (at%) of Cu is 25 at% or more and the depth is 50 nm or more. 一種連接器端子，其係於接點部分使用有申請專利範圍第1或第2項之電子零件用金屬材料。 A connector terminal for use in a contact portion using a metal material for an electronic component according to the first or second aspect of the patent application. 一種連接器，其係使用有申請專利範圍第15項之連接器端子。 A connector using the connector terminal of claim 15 of the patent application. 一種帶狀撓性電纜端子，其係於接點部分使用有申請專利範圍第1 或第2項之電子零件用金屬材料。 A strip-shaped flexible cable terminal, which is used in the joint portion, has the patent application scope 1 Or the metal material for electronic parts of item 2. 一種撓性印刷電路端子，其係於接點部分使用有申請專利範圍第1或第2項之電子零件用金屬材料。 A flexible printed circuit terminal using a metal material for electronic parts according to the first or second aspect of the patent application in the contact portion. 一種帶狀撓性電纜，其係使用有申請專利範圍第17項之帶狀撓性電纜端子。 A ribbon flexible cable using a ribbon flexible cable terminal of claim 17 of the patent application. 一種撓性印刷電路，其係使用有申請專利範圍第18項之撓性印刷電路端子。 A flexible printed circuit using a flexible printed circuit terminal of claim 18 of the patent application. 一種電子零件，其係於外部連接用電極使用有申請專利範圍第1或第2項之電子零件用金屬材料。 An electronic component for use in an external connection electrode using a metal material for an electronic component according to the first or second aspect of the patent application. 一種電子零件，其係於壓入型端子使用有申請專利範圍第1或第2項之電子零件用金屬材料，該壓入型端子係分別於安裝在殼體之裝置部的一側設有母端子連接部、另一側設有基板連接部，且將該基板連接部壓入形成於基板之通孔而安裝於該基板。 An electronic component for use in a press-in type terminal using a metal material for an electronic component according to the first or second aspect of the patent application, wherein the press-in type terminal is respectively provided with a mother side mounted on a device portion of the housing A substrate connection portion is provided on the other end side of the terminal connection portion, and the substrate connection portion is press-fitted into the through hole formed in the substrate to be mounted on the substrate.
TW102102406A 2012-04-13 2013-01-23 Metal materials for electronic components TWI548512B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2012092240A JP5968668B2 (en) 2012-04-13 2012-04-13 Metal materials for electronic parts

Publications (2)

Publication Number Publication Date
TW201341171A TW201341171A (en) 2013-10-16
TWI548512B true TWI548512B (en) 2016-09-11

Family

ID=49327413

Family Applications (1)

Application Number Title Priority Date Filing Date
TW102102406A TWI548512B (en) 2012-04-13 2013-01-23 Metal materials for electronic components

Country Status (5)

Country Link
JP (1) JP5968668B2 (en)
KR (1) KR101688290B1 (en)
CN (1) CN104204296B (en)
TW (1) TWI548512B (en)
WO (1) WO2013153832A1 (en)

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5700183B1 (en) * 2013-10-22 2015-04-15 Ｊｆｅスチール株式会社 Stainless steel foil for separator of polymer electrolyte fuel cell
JP6503159B2 (en) * 2014-04-22 2019-04-17 Ｊｘ金属株式会社 Metal material for electronic parts, connector terminal using the same, connector and electronic parts
JP6553333B2 (en) * 2014-06-05 2019-07-31 Ｊｘ金属株式会社 Metal material for electronic parts, connector terminal using the same, connector and electronic parts
JP6374718B2 (en) * 2014-07-14 2018-08-15 矢崎総業株式会社 Electrical element
WO2016010053A1 (en) * 2014-07-14 2016-01-21 矢崎総業株式会社 Electric element
JP6268055B2 (en) * 2014-07-15 2018-01-24 矢崎総業株式会社 Terminals and connectors
JP6268070B2 (en) * 2014-09-16 2018-01-24 矢崎総業株式会社 Plating material and terminal fitting
JP6272744B2 (en) * 2014-10-24 2018-01-31 矢崎総業株式会社 Plate-like conductor and surface treatment method for plate-like conductor
JP2016113666A (en) * 2014-12-15 2016-06-23 矢崎総業株式会社 Electrical element, and connector
KR20170075800A (en) * 2014-12-15 2017-07-03 센주긴조쿠고교 가부시키가이샤 Solder alloy for plating and electronic component
JP2016115542A (en) * 2014-12-15 2016-06-23 矢崎総業株式会社 Electric element and connector
JP6655325B2 (en) * 2015-08-25 2020-02-26 株式会社エンプラス Electrical contacts and sockets for electrical components
JP6624999B2 (en) * 2016-03-31 2019-12-25 日鉄日新製鋼株式会社 Automotive terminals
KR101797660B1 (en) * 2016-04-25 2017-11-15 (주)인광 Electronic component with indium alloy electric plating layer having excellent blackening resistance and method using the same
CN106364055A (en) * 2016-11-24 2017-02-01 苏州华意铭铄激光科技有限公司 Composite metal product with low friction coefficient
JP6763463B1 (en) * 2018-09-27 2020-09-30 Toto株式会社 Faucet fitting
KR102550912B1 (en) * 2018-11-30 2023-07-05 다나카 기킨조쿠 고교 가부시키가이샤 Conductive material with excellent wear resistance and heat resistance
CN110438365B (en) * 2019-09-06 2020-07-24 内蒙古自治区国际蒙医医院(内蒙古自治区蒙医药研究所) Mongolian medicine acupuncture needle and preparation method thereof
KR102092574B1 (en) * 2019-11-21 2020-03-26 주식회사 지오스토리 Operating system of Mobile device for presenting and real time renewing electronic navigational chart

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002352540A (en) * 2001-05-22 2002-12-06 Mitsui Chemicals Inc Flexible metallic laminate
JP2011037255A (en) * 2009-07-15 2011-02-24 Kiyoshi Chiba Laminate

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61124597A (en) 1984-11-20 1986-06-12 Furukawa Electric Co Ltd:The Silver-coated electric material
JP2726434B2 (en) 1988-06-06 1998-03-11 古河電気工業株式会社 Sn or Sn alloy coating material
JP2670348B2 (en) 1989-05-15 1997-10-29 古河電気工業株式会社 Sn or Sn alloy coating material
JP2925986B2 (en) * 1995-09-08 1999-07-28 古河電気工業株式会社 Fixed contact material or electrical contact parts consisting of a contact part and a terminal part
JPH11350188A (en) * 1998-06-03 1999-12-21 Furukawa Electric Co Ltd:The Material for electric and electronic parts, its production, and electric and electronic parts lising the same
EP1352993B1 (en) * 2001-01-19 2011-05-11 The Furukawa Electric Co., Ltd. A method for preparation of metal-plated material
JP3513709B2 (en) 2001-10-16 2004-03-31 石原薬品株式会社 Preventing tin whiskers by pretreatment
JP4111522B2 (en) * 2004-11-30 2008-07-02 日鉱金属株式会社 Sn coated copper material and terminal
JP5396139B2 (en) * 2009-05-08 2014-01-22 株式会社神戸製鋼所 Press-fit terminal
JP4632380B2 (en) * 2009-06-04 2011-02-16 協和電線株式会社 Plating film connection terminal member, connection terminal using the same, plating film material and multilayer plating material used therefor, and method for producing plating film connection terminal member
JP2011006762A (en) * 2009-06-29 2011-01-13 Shinko Electric Ind Co Ltd Surface film structure of terminal connection part and method for forming the same
JP5612355B2 (en) * 2009-07-15 2014-10-22 株式会社Ｋａｎｚａｃｃ Plating structure and method of manufacturing electrical material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002352540A (en) * 2001-05-22 2002-12-06 Mitsui Chemicals Inc Flexible metallic laminate
JP2011037255A (en) * 2009-07-15 2011-02-24 Kiyoshi Chiba Laminate

Also Published As

Publication number Publication date
KR20150002803A (en) 2015-01-07
JP2013221166A (en) 2013-10-28
KR101688290B1 (en) 2016-12-20
WO2013153832A1 (en) 2013-10-17
JP5968668B2 (en) 2016-08-10
CN104204296B (en) 2016-09-14
CN104204296A (en) 2014-12-10
TW201341171A (en) 2013-10-16

Similar Documents

Publication Publication Date Title
TWI548512B (en) Metal materials for electronic components
TWI432316B (en) Electronic parts with a metallic material, using the same connector terminals, connectors and electronic components
JP5086485B1 (en) Metal material for electronic parts and method for producing the same
JP5284526B1 (en) Metal material for electronic parts and method for producing the same
TWI488733B (en) Metal material for electronic parts and manufacturing method thereof
TWI485930B (en) Metal material for electronic parts and manufacturing method thereof
JP5298233B2 (en) Metal material for electronic parts and method for producing the same