WO2009123144A1 - 耐摩耗性、挿入性及び耐熱性に優れた銅合金すずめっき条 - Google Patents

耐摩耗性、挿入性及び耐熱性に優れた銅合金すずめっき条 Download PDF

Info

Publication number
WO2009123144A1
WO2009123144A1 PCT/JP2009/056544 JP2009056544W WO2009123144A1 WO 2009123144 A1 WO2009123144 A1 WO 2009123144A1 JP 2009056544 W JP2009056544 W JP 2009056544W WO 2009123144 A1 WO2009123144 A1 WO 2009123144A1
Authority
WO
WIPO (PCT)
Prior art keywords
plating
layer
phase
alloy
thickness
Prior art date
Application number
PCT/JP2009/056544
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
健志 小池
Original Assignee
日鉱金属株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日鉱金属株式会社 filed Critical 日鉱金属株式会社
Priority to JP2009541670A priority Critical patent/JPWO2009123144A1/ja
Priority to CN2009801115368A priority patent/CN101981234B/zh
Priority to KR1020107021439A priority patent/KR101243454B1/ko
Publication of WO2009123144A1 publication Critical patent/WO2009123144A1/ja

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • C25D5/505—After-treatment of electroplated surfaces by heat-treatment of electroplated tin coatings, e.g. by melting
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
    • C25D5/611—Smooth layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of 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

Definitions

  • the present invention relates to a tin plating strip that is suitable as a conductive spring material for connectors, terminals, relays, switches, etc. and has excellent wear resistance, insertability, and heat resistance.
  • Conductive spring materials for electronic parts such as connectors, terminals, relays and switches for automobiles and consumer use are plated with Sn, taking advantage of Sn's excellent corrosion resistance, solder wettability, and electrical connectivity. Copper or copper alloy strips are used.
  • the Sn plating strip of a copper alloy is formed in a continuous plating line after degreasing and pickling, forming a Cu undercoat phase by electroplating, and then forming an Sn plating phase by electroplating. It is manufactured in a process in which a reflow treatment is applied to melt the Sn plating phase.
  • the base material and the base plating components diffuse into the Sn layer to form an alloy phase, so that the Sn layer disappears, and the base material and the base plating components become oxides on the entire surface. Since it is formed thick, various characteristics such as contact resistance and solderability deteriorate.
  • this alloy phase is mainly an intermetallic compound such as Cu 3 Sn or Cu 6 Sn 5 . The deterioration of characteristics with time is accelerated as the temperature increases, and becomes particularly noticeable around an automobile engine.
  • the number of connectors for supplying electrical signals to the circuits has been increasing.
  • the Sn plating material adopts a gas tight structure in which male and female are adhered to each other at the contact point of the connector because of its softness, the insertion force of the connector is higher than that of a connector constituted by gold plating or the like. For this reason, an increase in connector insertion force due to the increase in the number of connectors is a problem. For example, in an automobile assembly line, the work of fitting a connector is currently almost done manually. When the insertion force of the connector is increased, a burden is imposed on the worker on the assembly line, which directly leads to a decrease in work efficiency. Furthermore, it has been pointed out that it may impair the health of workers. For this reason, reduction of the insertion force of Sn plating material is strongly desired.
  • the contact point of the spring material slides due to engine vibration, vibration due to on-vehicle traveling, thermal expansion / contraction of the terminal material, and the like.
  • the characteristics such as excellent solder wettability, corrosion resistance, and electrical connectivity that are characteristic of Sn deteriorate.
  • an oxide of Sn plating material generated due to wear accumulates, and this oxide has characteristics close to insulation, resulting in poor contact. (Increased contact resistance) occurs.
  • reduction of insertion force, improvement of heat resistance and wear resistance have become issues in recent years.
  • Patent Document 1 a base material having a specific surface roughness is used to control the surface roughness of the Sn coating layer, and the surface of the base material is subjected to ion etching, electrolytic polishing, rolling, polishing, shot blasting, etc. Therefore, there is a problem that the equipment costs are increased due to the necessity of roughening treatment, and the manufacturing cost is high (Patent Document 2, “0032” to “0033”). Further, in Patent Document 2, the larger the average roughness of the Cu—Sn alloy phase, the better the insertion / extraction, while the smaller the average roughness, the better the heat resistance. Therefore, these conflicting effects are adjusted.
  • Patent Document 1 As described above, a Sn-plated strip having a low insertion force, maintaining excellent corrosion resistance and low contact resistance even after high temperature and / or for a long time, and having good wear resistance is manufactured by an industrially easy operation. Was an issue in the field.
  • the present inventor has obtained excellent wear resistance, insertability and heat resistance when the unevenness of the interface between the Cu-Sn alloy phase of the copper alloy tin plating strip and the pure Sn phase is dense and large.
  • the present invention has been made based on this discovery, and has the following configuration.
  • the height difference y from the outermost surface of the alloy phase is 0.1 to 0.5 ⁇ m;
  • the maximum height Rz of the roughness curve of this Cu—Sn alloy phase is 0.6 to 1.2 ⁇ m
  • Cu A copper alloy tin plating strip characterized in that the average length Rsm of the roughness curve of the Sn alloy phase is 2.0 to 5.0 ⁇ m;
  • a plating film is composed of the Sn layer, the Cu—Sn alloy layer, and the Cu layer from the surface to the base material, the thickness of the Sn layer is 0.5 to 1.5 ⁇ m, and the thickness of the Cu—Sn alloy layer is The copper alloy tin plating strip according to (1) or (2) above, wherein the copper layer has a thickness of 0.6 to 2.0 ⁇ m and a Cu layer thickness of 0 to 0.8 ⁇ m.
  • a plating film is composed of the Sn layer, the Cu—Sn layer, and the Ni layer, the thickness of the Sn layer is 0.5 to 1.5 ⁇ m, and the thickness of the Cu—Sn alloy layer is 0
  • the tin plating strip of the present invention is suitable as a conductive spring material for connectors, terminals, relays, switches, etc., and is excellent in wear resistance, insertability, and heat resistance.
  • 3 is an uneven SEM image in which a Cu—Sn alloy phase appears on the surface.
  • 3 is a roughness curve of a Cu—Sn alloy phase measured along the measurement line of FIG. 2.
  • It is a comparison schematic diagram of Sn plating material section of a conventional example (a) and an example of the present invention (b). It is the schematic which shows the dynamic friction coefficient measuring method. It is the schematic which shows the processing method of a contactor tip.
  • FIG. 1 is a schematic cross-sectional view of a Cu-base Sn-plated strip after reflow treatment according to the present invention.
  • the height difference “y” between the outermost surface of the Sn plating and the outermost point of the Cu—Sn alloy phase, and the Cu—Sn alloy phase The maximum height “Rz” of the roughness curve and the average length “Rsm” of the roughness curve are schematically shown.
  • a method for determining the roughness curve of the Cu—Sn alloy phase, the maximum height “Rz” and the average length “Rsm” of the roughness curve is shown below.
  • the Sn phase on the surface of the tin plating strip was dissolved and removed to reveal the Cu—Sn alloy phase on the surface, and then obtained with a commercially available uneven SEM (scanning electron microscope) (ERA-8000) apparatus.
  • FIG. 3 shows a roughness curve of the Cu—Sn alloy phase measured along the measurement line of FIG.
  • the maximum heights of the peaks appearing on the roughness curve are averaged to obtain the maximum height “Rz” of the roughness curve of the Cu—Sn alloy phase.
  • the intervals between peaks appearing on the roughness curve are averaged to obtain the average length “Rsm” of the roughness curve of the Cu—Sn alloy phase.
  • (a) is a schematic cross-sectional view of a conventional Cu base Sn plating strip, in which the peak maximum height “Rz” is small and the peak average length “Rsm” is large.
  • (B) is a schematic cross-sectional view of the Cu-base Sn-plated strip of the present invention having the same average Sn phase thickness (i) and average Cu—Sn alloy phase thickness (ii) as in the prior art, with a large Rz and Rsm Is small.
  • the maximum Cu—Sn alloy phase thickness (iii) is larger than the peak maximum height “Rz”.
  • the altitude difference y between the outermost surface of the conventional Sn plating and the outermost point of the Cu—Sn alloy phase is larger than that of the present invention.
  • the pure Sn phase is easily deformed and removed by a single connector insertion or the like, the state in which the Cu—Sn alloy phase appears on the surface is important in the examination of wear resistance.
  • the peak interval of the hard Cu—Sn alloy phase is short and the valley is deep, wear of the pure Sn phase in the valley is less likely to disappear and the wear resistance is excellent.
  • the maximum height Rz of the roughness curve of the Cu—Sn alloy phase of the tin plating strip of the present invention is 0.6 to 1.2 ⁇ m. Within this range, the pure Sn phase present in the valleys of the Cu—Sn alloy phase interface exhibits a lubricating action, and wear resistance is improved. When Rz is less than 0.6 ⁇ m, the Cu—Sn alloy phase is brittlely fractured and the wear resistance is poor as the pure Sn phase present at the valley of the Cu—Sn alloy phase interface wears away. When Rz exceeds 1.2 ⁇ m, it is difficult to achieve the following Rsm range.
  • the average length Rsm of the roughness curve of the Cu—Sn alloy phase of the tin plating strip of the present invention is 2.0 to 5.0 ⁇ m. Within this range, there are many valleys with an appropriate depth at the Cu—Sn alloy phase interface, and a pure Sn phase exhibiting a lubricating action is secured.
  • Rsm exceeds 5.0 ⁇ m, the interval between the peaks of the hard Cu—Sn alloy phase that supports the load during insertion / extraction increases, and the pure Sn phase in the troughs easily loses wear and is inferior in wear resistance.
  • Rsm is less than 2.0, it is difficult to achieve the above Rz range.
  • the height difference y between the outermost surface of the Sn plating and the outermost surface of the Cu—Sn alloy phase is 0.1 to 0.5 ⁇ m in the cross section perpendicular to the plating surface.
  • y is less than 0.1 ⁇ m, the heat resistance is poor.
  • the Cu—Sn alloy phase is exposed on the surface and the contact resistance increases.
  • y exceeds 0.5 ⁇ m, deformation resistance due to digging of Sn plating and shear resistance for shearing adhesion are increased at the time of terminal insertion, and as a result, a large insertion force is required.
  • y can be obtained by cutting the reflowed sample in the rolling parallel direction and measuring and averaging by observing the cross section at a magnification of 10,000 times.
  • the tin-plated strip of the present invention has severe irregularities at the interface of the Sn phase / Cu—Sn alloy phase, that is, Rsm is small and Rz is large. Therefore, the frictional resistance is low, and the peak of the Cu—Sn alloy phase interface acts as a support during wear, and the required insertion / extraction force is low.
  • Rsm, y and Rz of the present invention preferably have the following relationship.
  • 2.0 ⁇ Rsm / (y + Rz) ⁇ 4.0 (Y + Rz) is the sum of “the height difference y between the outermost surface of the Sn plating and the outermost surface of the Cu—Sn alloy phase” and “the maximum height of the roughness curve of the Cu—Sn alloy phase”. This represents the distance between the interface between the phase and the Cu base material or the base plating phase and the outermost surface of the Sn plating. Therefore, the average length Rsm of the roughness curve of the Cu—Sn alloy phase is preferably 2 to 5 times the distance from the lowermost part of the Cu—Sn alloy phase to the outermost surface of the Sn plating.
  • a plating film is composed of a Sn phase, a Cu—Sn alloy phase, and a Cu phase from the surface to the base material.
  • This plating film structure can be obtained by performing electroplating in the order of Cu base plating and Sn plating and performing reflow treatment.
  • the average thickness of the Sn phase after reflow is preferably 0.5 to 1.5 ⁇ m. When the Sn phase is less than 0.5 ⁇ m, the solder wettability decreases, and when it exceeds 1.5 ⁇ m, the necessary insertion force increases.
  • the thickness of the Cu—Sn alloy phase after reflow is preferably 0.6 to 2.0 ⁇ m. Since the Cu—Sn alloy phase is hard, when the interface with the Sn phase is the structure of the present invention, if it has a thickness of 0.6 ⁇ m or more, it contributes to a reduction in insertion force and wear resistance and heat resistance. Excellent. On the other hand, when the thickness of the Cu—Sn alloy phase exceeds 2.0 ⁇ m, mechanical properties such as bendability deteriorate.
  • the average thickness of the Cu—Sn alloy phase (diffusion layer) of the present invention can be made thicker than before because the interface between the Sn phase and the Cu—Sn alloy phase has irregularities. Therefore, the plating strip of the present invention in which a Cu—Sn alloy phase harder than a pure Sn layer or a base material can be made thick has excellent wear resistance. Furthermore, the plating strip of the present invention has improved heat resistance due to the thick Cu—Sn alloy phase. Although the present invention is not limited by theory, it is thought that the reason is the inhibition of Cu diffusion. That is, Cu supplied from the base material reaches the interface between the Cu—Sn alloy phase and the Sn phase and combines with Sn in the Sn phase to grow the Cu—Sn alloy phase.
  • the distance between the Cu base material interface and the Cu—Sn alloy phase / Sn phase interface becomes longer, and Cu diffuses to the Cu—Sn alloy phase / Sn phase interface.
  • the time required is longer.
  • the thickness of the Cu—Sn alloy phase between the Cu base material and the outermost point of the Cu—Sn alloy phase is the largest, Cu reaches the outermost point of the alloy phase from the base material, and as a result, Cu It is difficult for the Sn alloy phase to grow and the Sn phase to disappear even under severe conditions at a high temperature for a long time. Therefore, the plating strip of the present invention has very excellent heat resistance.
  • the Cu base plating formed by electroplating may be consumed to form a Cu—Sn alloy (phase) during reflow, and the thickness thereof may be zero.
  • the Rz and Rsm of the Cu—Sn alloy phase after reflow are out of the scope of the present invention. This is presumably because Cu electrodeposited grains are locally coarsened as the thickness of the Cu undercoat increases, which adversely affects the growth of the Cu—Sn alloy phase.
  • the inventive plating structure is obtained.
  • the reflow treatment of the present invention is carried out in the range of 230 to 600 ° C. for 3 to 30 seconds, but is rapidly heated at a temperature rising rate of 20 to 100 ° C./sec, preferably 30 to 70 ° C./sec, and a cooling rate of 100 to 100 ° C. 300 ° C / sec, heating is performed using appropriate heat transfer means such as a circulation fan or a radiation plate, such as conduction, convection, and radiation. Cooling is performed by water cooling, for example, regardless of both ends and the center of the plating strip. Cooling.
  • the present invention is not limited by theory, by the reflow process, a relatively small amount of Sn-Cu phase nuclei initially generated between the Sn plating phase and the Cu phase generate new new nuclei. It is considered that the Sn—Cu phase / Sn phase interface structure of the present invention is formed by growing in the Sn phase faster and faster and rapidly cooling at a predetermined time. In the conventional reflow treatment, there is no need for rapid heating as intended in the present invention, and even if the rapid heating is performed simply by increasing the line speed, uniform heating cannot be performed. It was difficult to obtain a uniform plating thickness in the direction.
  • a plating film is composed of each of the Sn phase, Cu—Sn alloy phase, and Ni phase.
  • This plating film structure is obtained by performing electroplating in the order of Ni base plating, Cu base plating, and Sn plating, and performing reflow treatment.
  • the average thickness of the Sn phase after reflow is preferably 0.5 to 1.5 ⁇ m. When the Sn phase is less than 0.5 ⁇ m, the solder wettability decreases, and when it exceeds 1.5 ⁇ m, the insertion force increases.
  • the thickness of the Cu—Sn alloy phase after reflow is preferably 0.4 to 2.0 ⁇ m.
  • the Cu—Sn alloy phase Since the Cu—Sn alloy phase is hard, if it exists in a thickness of 0.4 ⁇ m or more, it contributes to a reduction in insertion force. On the other hand, when the thickness of the Cu—Sn alloy phase exceeds 2.0 ⁇ m, mechanical properties such as bendability deteriorate.
  • the thickness of the Ni phase after reflow is preferably 0.1 to 0.8 ⁇ m. If the thickness of Ni is less than 0.1 ⁇ m, the corrosion resistance and heat resistance of the plating deteriorate. On the other hand, in the plated material having a Ni thickness after reflow exceeding 0.8 ⁇ m, the thermal stress generated inside the plated layer when heated is increased, and the plating peeling is promoted. Adjust the thickness of each electroplating appropriately within the range of 0.6 to 2.0 ⁇ m for Sn plating, 0.1 to 1.5 ⁇ m for Cu plating, and 0.1 to 0.8 ⁇ m for Ni plating. Then, by performing a reflow process in the same manner as described above, the plating structure of the present invention can be obtained.
  • the Cu plating phase may be completely converted into a Cu—Sn alloy phase after reflow, or may remain in a thickness of 0.4 ⁇ m or less.
  • the thickness of each of the Sn phase, Cu—Sn alloy phase, Cu phase, and Ni phase after the reflow is mainly measured using an electrolytic film thickness meter, a fluorescent X-ray film thickness meter, SEM observation from a cross section, GDS (glow discharge emission spectroscopy analyzer) analysis from the surface was also used as needed. Details are described in the Examples.
  • Types of Copper Alloy Base Material examples include, but are not limited to, the following.
  • Cu-Ni-Si alloy Corson alloy
  • Ni and Si compound particles are precipitated in Cu, and high strength and electrical conductivity are obtained.
  • Practical alloys include C70250, C64725, C64760 (CDA number, the same applies hereinafter) and the like.
  • Zn, Sn, Mg, Co, Ag, Cr and Mn In order to improve properties such as strength and heat resistance, one or more selected from the group of Zn, Sn, Mg, Co, Ag, Cr and Mn can be added as necessary.
  • Phosphor bronze Practical alloys include C52400, C52100, C51910, C51020 and the like. In order to improve properties such as strength and heat resistance, one or more selected from the group of Zn, Ni, Co, Fe, Ag, and Mn can be further added as necessary.
  • Brass Examples of practical alloys include C26000 and C26800. In order to improve properties such as strength and heat resistance, one or more selected from the group of Ni, Cr, Co, Sn, Fe, Ag, and Mn can be added as necessary.
  • Red copper There are C23000, C22000, C21000, etc. as practical alloys. In order to improve properties such as strength and heat resistance, one or more selected from the group of Ni, Cr, Co, Sn, Fe, Ag, and Mn can be added as necessary.
  • Titanium copper Examples of practical alloys include C19900. By performing the aging treatment, a compound of Ti and Cu is precipitated in Cu, and a very high strength is obtained. In order to improve properties such as strength and heat resistance, one or more selected from the group of Zn, Ni, Co, P, Cr, Fe, Ag, and Mn can be added as necessary.
  • the tin plating strip of the present invention is excellent in wear resistance, insertability and heat resistance, and is suitable as a conductive spring material for connectors, terminals, relays, switches and the like.
  • excellent in wear resistance means a case where the maximum depth of the sliding trace obtained by the following wear resistance test is 3 ⁇ m or less.
  • Excellent insertability means that the insertion force required when used as a connector is low, and means that the dynamic friction coefficient ⁇ is 0.50 or less.
  • “Excellent heat resistance” means that the contact resistance after heating for 1000 h at 145 ° C. for Cu undercoat and 175 ° C. for Cu / Ni undercoat is 8 m ⁇ or less.
  • Electrolytic degreasing is performed using a sample as a cathode in an alkaline aqueous solution. Pickling is performed using a 10% by mass aqueous sulfuric acid solution.
  • Ni base plating conditions -Plating bath composition: nickel sulfate 250 g / L, nickel chloride 45 g / L, boric acid 30 g / L ⁇ Plating bath temperature: 50 °C ⁇ Current density: 5 A / dm 2 ⁇ Ni plating thickness is adjusted by electrodeposition time
  • Plating bath composition stannous oxide 41 g / L, phenol sulfonic acid 268 g / L, surfactant 5 g / L.
  • -Plating bath temperature 50 ° C.
  • Current density 9A / dm 2. ⁇ Sn plating thickness is adjusted by electrodeposition time.
  • Sn plating layer when electrolysis is performed with the electrolytic solution R-50, the Sn plating layer is first electrolyzed and the electrolysis stops before the Cu-Sn alloy layer, and the displayed value of the device here is the Sn plating layer thickness. It becomes. Next, the electrolysis is started again and the Cu—Sn alloy layer is electrolyzed until the next time the apparatus is stopped, and the displayed value at the end time corresponds to the thickness of the Cu—Sn alloy layer.
  • the thickness of the Ni plating layer in the case of the Cu / Ni undercoat layer is determined by first measuring the thickness of the Sn plating layer and the Cu—Sn alloy layer as described above using the electrolytic solution R-50, and then using the dropper to prepare the electrolytic solution. The R-50 is sucked out, washed thoroughly with pure water and then replaced with the electrolytic solution R-54, and the thickness of the Ni plating layer is measured.
  • the reflected electron image in the case of Cu plating, for example, in the case of Cu underlayer Sn plating, color contrast is given in the order of the plating surface layer to the Sn plating layer, the Cu—Sn alloy layer, the Cu plating layer, and the base material.
  • the Sn plating layer is only Sn
  • the Cu—Sn alloy layer is Sn and Cu
  • the base material is detected of its contained components. Therefore, the layer in which only Cu is detected is the Cu plating layer. It can be seen that it is.
  • the thickness of the Cu plating layer can be obtained by measuring the thickness of a layer in which only Cu is detected in the characteristic X-ray image and having a color contrast different from that of the other by a reflected electron image.
  • the thickness is arbitrarily measured at five locations on the reflected electron image, and the average value is defined as the Cu plating layer thickness.
  • this method can determine only a very narrow thickness compared to the electrolytic film thickness method. Therefore, this observation was performed for 10 cross sections, and the average value was defined as the Cu plating thickness.
  • FIG. Rsm and Rz were calculated from this profile.
  • the y was obtained by cutting the reflowed sample in the rolling parallel direction and measuring the cross section using an uneven SEM (ERA-8000) manufactured by ELIONIX, measuring 4 points for each of 5 visual fields at a magnification of 10,000 times.
  • a brass-Sn plating material having a thickness of 0.2 mm was prepared.
  • the brass-Sn plated material is subjected to an embossing process with a height of 0.2 mm and a radius of 0.6 mm to produce a terminal with a hemispherical protrusion.
  • the terminal and the Sn plating material of the present invention are arranged as shown in FIG. 5, and the Sn plating material of the present invention is reciprocated 150 times at a speed of 5 mm / sec while applying a load of 300 g to the terminal.
  • the maximum depth ( ⁇ m) of the sliding portion was measured using a surface roughness meter (manufactured by Kosaka Laboratory Ltd., Surfcoder SE1600). It was judged that good wear resistance was obtained when the maximum depth of the sliding trace was 3 ⁇ m or less.
  • Example 2 Examples of the Cu base plating shown in Table 1 and the Ni / Cu base plating shown in Table 2 were performed.
  • Comparative Examples 9 to 13 where the interface of the diffusion layer (Cu—Sn phase) was smooth due to the slow reflow heating rate were inferior in wear resistance, heat resistance and insertability to Invention Examples 1 to 6.
  • Invention Example 7 and Comparative Example 14 have the same Sn layer thickness, but Comparative Example 14 was inferior in heat resistance with respect to contact resistance because the diffusion layer (Cu—Sn phase) thickness was thin.
  • Invention Example 8 and Comparative Example 15 have the same conditions except for the height difference y, but Comparative Example 15 was inferior in heat resistance regarding contact resistance because y was small.
  • Comparative Examples 24-27 in which the interface of the diffusion layer (Cu—Sn phase) was smooth due to the slow reflow heating rate were inferior in wear resistance, heat resistance, and insertability to Invention Examples 16-21.
  • Inventive Example 22 and Comparative Example 28 have the same Sn layer thickness, but Comparative Example 28 was slightly inferior in heat resistance with respect to contact resistance because of the thin diffusion layer (Cu—Sn phase) thickness.
  • Invention Example 23 and Comparative Example 29 have the same conditions except for the height difference y, but Comparative Example 29 was inferior in heat resistance regarding contact resistance because y was small.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating Methods And Accessories (AREA)
PCT/JP2009/056544 2008-03-31 2009-03-30 耐摩耗性、挿入性及び耐熱性に優れた銅合金すずめっき条 WO2009123144A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2009541670A JPWO2009123144A1 (ja) 2008-03-31 2009-03-30 耐摩耗性、挿入性及び耐熱性に優れた銅合金すずめっき条
CN2009801115368A CN101981234B (zh) 2008-03-31 2009-03-30 耐磨损性、插入性及耐热性优异的铜合金镀锡条
KR1020107021439A KR101243454B1 (ko) 2008-03-31 2009-03-30 내마모성, 삽입성 및 내열성이 우수한 구리 합금 주석 도금조

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2008-093903 2008-03-31
JP2008093903 2008-03-31

Publications (1)

Publication Number Publication Date
WO2009123144A1 true WO2009123144A1 (ja) 2009-10-08

Family

ID=41135518

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2009/056544 WO2009123144A1 (ja) 2008-03-31 2009-03-30 耐摩耗性、挿入性及び耐熱性に優れた銅合金すずめっき条

Country Status (5)

Country Link
JP (1) JPWO2009123144A1 (ko)
KR (1) KR101243454B1 (ko)
CN (1) CN101981234B (ko)
TW (1) TW200948526A (ko)
WO (1) WO2009123144A1 (ko)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009249716A (ja) * 2008-04-10 2009-10-29 Sumitomo Kinzoku Kozan Shindo Kk 錫めっき銅合金材
EP2369688A1 (en) * 2010-03-26 2011-09-28 Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) Copper alloy and electrically conductive material for connecting parts, and mating-type connecting part and method for producing the same
EP2644750A1 (en) * 2012-03-30 2013-10-02 Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) Electroconductive material for connection component
WO2013150690A1 (ja) * 2012-04-06 2013-10-10 株式会社オートネットワーク技術研究所 めっき部材、コネクタ用めっき端子、めっき部材の製造方法、及びコネクタ用めっき端子の製造方法
JP2014208878A (ja) * 2013-03-25 2014-11-06 三菱マテリアル株式会社 挿抜性に優れた錫めっき銅合金端子材
CN110199054A (zh) * 2017-01-30 2019-09-03 Ｊｘ金属株式会社 表面处理镀敷材料、连接器端子、连接器、ffc端子、ffc、fpc及电子零件
CN112912546A (zh) * 2018-10-18 2021-06-04 Ｊｘ金属株式会社 导电性材料、成型品以及电子部件

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102234827B (zh) * 2010-04-20 2014-01-08 Jx日矿日石金属株式会社 焊料润湿性、插拔性能优良的铜合金镀锡条
JP5140171B2 (ja) * 2011-03-18 2013-02-06 Ｊｘ日鉱日石金属株式会社 充電用電池タブ材に用いられる銅合金条
TW201311944A (zh) * 2011-08-12 2013-03-16 Mitsubishi Materials Corp 插拔性優異的鍍錫銅合金端子材及其製造方法
JPWO2014034460A1 (ja) * 2012-08-31 2016-08-08 株式会社オートネットワーク技術研究所 コネクタ用めっき端子および端子対
JP6100203B2 (ja) * 2014-05-19 2017-03-22 日新製鋼株式会社 接続部品用材料
JP6662685B2 (ja) * 2016-03-31 2020-03-11 Ｊｘ金属株式会社 めっき層を有するチタン銅箔
JP6423383B2 (ja) * 2016-03-31 2018-11-14 日新製鋼株式会社 接続部品用材料
CN109267119B (zh) * 2018-11-05 2020-06-23 深圳和而泰智能控制股份有限公司 磷青铜工件及其制作方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007063624A (ja) * 2005-08-31 2007-03-15 Nikko Kinzoku Kk 挿抜性及び耐熱性に優れる銅合金すずめっき条

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3926355B2 (ja) * 2004-09-10 2007-06-06 株式会社神戸製鋼所 接続部品用導電材料及びその製造方法
JP4771970B2 (ja) 2006-02-27 2011-09-14 株式会社神戸製鋼所 接続部品用導電材料

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007063624A (ja) * 2005-08-31 2007-03-15 Nikko Kinzoku Kk 挿抜性及び耐熱性に優れる銅合金すずめっき条

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009249716A (ja) * 2008-04-10 2009-10-29 Sumitomo Kinzoku Kozan Shindo Kk 錫めっき銅合金材
US8940405B2 (en) 2010-03-26 2015-01-27 Kobe Steel, Ltd. Copper alloy and electrically conductive material for connecting parts, and mating-type connecting part and method for producing the same
EP2369688A1 (en) * 2010-03-26 2011-09-28 Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) Copper alloy and electrically conductive material for connecting parts, and mating-type connecting part and method for producing the same
US9373925B2 (en) 2010-03-26 2016-06-21 Kobe Steel, Ltd. Method for producing a mating-type connecting part
US8956735B2 (en) 2010-03-26 2015-02-17 Kabushiki Kaisha Kobe Seiko Sho Copper alloy and electrically conductive material for connecting parts, and mating-type connecting part and method for producing the same
US9449728B2 (en) 2012-03-30 2016-09-20 Kobe Steel, Ltd. Electroconductive material for connection component
EP2644750A1 (en) * 2012-03-30 2013-10-02 Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) Electroconductive material for connection component
JP2013231228A (ja) * 2012-04-06 2013-11-14 Autonetworks Technologies Ltd めっき部材、コネクタ用めっき端子、めっき部材の製造方法、及びコネクタ用めっき端子の製造方法
WO2013150690A1 (ja) * 2012-04-06 2013-10-10 株式会社オートネットワーク技術研究所 めっき部材、コネクタ用めっき端子、めっき部材の製造方法、及びコネクタ用めっき端子の製造方法
US9755343B2 (en) 2012-04-06 2017-09-05 Autonetworks Technologies, Ltd. Plated member and plated terminal for connector
JP2014208878A (ja) * 2013-03-25 2014-11-06 三菱マテリアル株式会社 挿抜性に優れた錫めっき銅合金端子材
CN110199054A (zh) * 2017-01-30 2019-09-03 Ｊｘ金属株式会社 表面处理镀敷材料、连接器端子、连接器、ffc端子、ffc、fpc及电子零件
CN112912546A (zh) * 2018-10-18 2021-06-04 Ｊｘ金属株式会社 导电性材料、成型品以及电子部件
CN112912546B (zh) * 2018-10-18 2024-01-12 Ｊｘ金属株式会社 导电性材料、成型品以及电子部件

Also Published As

Publication number Publication date
KR20100118147A (ko) 2010-11-04
CN101981234B (zh) 2013-06-12
KR101243454B1 (ko) 2013-03-13
JPWO2009123144A1 (ja) 2011-07-28
CN101981234A (zh) 2011-02-23
TWI366498B (ko) 2012-06-21
TW200948526A (en) 2009-12-01

Similar Documents

Publication Publication Date Title
WO2009123144A1 (ja) 耐摩耗性、挿入性及び耐熱性に優れた銅合金すずめっき条
JP5319101B2 (ja) 電子部品用Ｓｎめっき材
EP2620275B1 (en) Tin-plated copper-alloy material for terminal and method for producing the same
EP2743381B1 (en) Tin-plated copper alloy terminal member with outstanding insertion and removal characteristics
US9748683B2 (en) Electroconductive material superior in resistance to fretting corrosion for connection component
JP6445895B2 (ja) Ｓｎめっき材およびその製造方法
EP3192896B1 (en) Tin-plated copper alloy terminal material and method for producing same
EP2682263A2 (en) Tin-plated copper-alloy material for terminal and method for producing the same
EP2843086A2 (en) Tin-plated copper-alloy material for terminal having excellent insertion/extraction performance
KR20140117274A (ko) 삽입 발출성이 우수한 주석 도금 구리 합금 단자재
JP5313773B2 (ja) めっき付き銅条材及びその製造方法
KR20150050397A (ko) 주석 도금 구리 합금 단자재
JP4489738B2 (ja) Ｃｕ−Ｎｉ−Ｓｉ−Ｚｎ系合金すずめっき条
JP4247256B2 (ja) Ｃｕ−Ｚｎ−Ｓｎ系合金すずめっき条
JP5984980B2 (ja) 電子部品用Ｓｎめっき材
JP4611419B2 (ja) はんだ濡れ性、挿抜性に優れた銅合金すずめっき条
JP4964795B2 (ja) 耐磨耗性に優れた銅合金すずめっき条
JP4538424B2 (ja) Ｃｕ−Ｚｎ−Ｓｎ系合金すずめっき条
JP6793618B2 (ja) Ｓｎめっき材およびその製造方法
JP5442385B2 (ja) 導電部材及びその製造方法
JP5897082B1 (ja) 耐微摺動摩耗性に優れる接続部品用導電材料
EP4012075A1 (en) Terminal material for connectors
JP2017082307A (ja) 表面被覆層付き銅又は銅合金板条

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200980111536.8

Country of ref document: CN

WWE Wipo information: entry into national phase

Ref document number: 2009541670

Country of ref document: JP

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

Ref document number: 09727184

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20107021439

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 09727184

Country of ref document: EP

Kind code of ref document: A1