WO2011065166A1 - リフローSnめっき部材 - Google Patents
リフローSnめっき部材 Download PDFInfo
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- WO2011065166A1 WO2011065166A1 PCT/JP2010/068901 JP2010068901W WO2011065166A1 WO 2011065166 A1 WO2011065166 A1 WO 2011065166A1 JP 2010068901 W JP2010068901 W JP 2010068901W WO 2011065166 A1 WO2011065166 A1 WO 2011065166A1
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- reflow
- layer
- plating
- less
- plane
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
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- 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
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- 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
- H01R13/035—Plated dielectric material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/922—Static electricity metal bleed-off metallic stock
- Y10S428/9265—Special properties
- Y10S428/929—Electrical contact feature
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12708—Sn-base component
- Y10T428/12715—Next to Group IB metal-base component
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12708—Sn-base component
- Y10T428/12722—Next to Group VIII metal-base component
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12861—Group VIII or IB metal-base component
- Y10T428/12903—Cu-base component
- Y10T428/1291—Next to Co-, Cu-, or Ni-base component
Definitions
- the present invention relates to a reflow Sn plated member suitably used for conductive spring materials such as connectors, terminals, relays, switches, etc., and having a reflow Sn layer formed on the surface of a substrate made of Cu or a Cu-based alloy.
- a plated member plated with a copper alloy is used for conductive parts such as connectors, terminals, and relays.
- an Sn plated material obtained by plating Sn with a copper alloy is frequently used for automotive connectors.
- In-vehicle connectors tend to be multipolar due to an increase in in-vehicle electrical components, and the insertion / extraction force increases when the connectors are fitted.
- the connector is fitted manually, there is a problem that the work load increases.
- the Sn plating material does not generate whiskers and that solder wettability and contact resistance do not easily deteriorate in a high temperature environment.
- the plated parts are stored for a long time in high-temperature and high-humidity areas overseas, or heated inside the mounting furnace during soldering, resulting in deterioration of solder wettability and contact resistance.
- the Sn plating material is exposed to a high temperature such as in an engine room of an automobile, copper may diffuse from the copper base material into the Sn plating layer, or the Sn plating layer may be oxidized to deteriorate the contact resistance.
- an Sn plating material in which the orientation index of the (321) plane in the Sn plating layer is controlled to 2.5 or more and 4.0 or less and whisker generation in the Sn plating layer is suppressed is disclosed (patent) Reference 1). Further, a reflow Sn plating material is disclosed in which a Ni layer is provided between the Sn plating layer and the copper base material so that the copper does not diffuse from the copper base material even if the Sn plating material is exposed to a high temperature (Patent Document). 2).
- a reflow Sn plating material is disclosed in which the average roughness of the Cu—Sn alloy phase that appears when the Sn plating layer is dissolved is controlled to 0.05 to 0.3 ⁇ m to improve the insertion / removability and heat resistance. (See Patent Document 3). Further, an Sn plating material is disclosed in which the orientation index of the (101) plane in the Sn plating layer without reflowing is controlled to 2.0 or less, and the press punchability and whisker resistance are improved (see Patent Document 4). .
- the inventors have succeeded in reducing the insertion / extraction force by controlling the orientation of the surface of the reflow Sn layer formed on the surface of the substrate. That is, in the reflow Sn plated member of the present invention, the reflow Sn layer is formed on the surface of the substrate made of Cu or a Cu-based alloy, and the orientation index of the (101) plane of the surface of the reflow Sn layer is 2.0 or more and 5 0.0 or less.
- the reflow Sn layer is preferably formed by forming a Cu plating layer on the surface of the substrate and reflowing the Sn plating layer formed on the surface of the Cu plating layer. It is preferable that a Ni layer is formed between the reflow Sn layer and the base material.
- a reflow Sn-plated member that suppresses whisker generation and reduces insertion / extraction force can be obtained.
- % means “% by mass” unless otherwise specified.
- a reflow Sn layer is formed on the surface of a substrate made of Cu or a Cu-based alloy, and the orientation index of the (101) plane of the surface of the reflow Sn layer is 2. 0 or more and 5.0 or less.
- Cu—Ni—Si based alloys include C70250 (CDA number, hereinafter the same; Cu-3% Ni-0.5% Si-0.1 Mg), C64745 (Cu-1 .6% Ni-0.4% Si-0.5% Sn-0.4% Zn).
- Brass Examples of brass include C26000 (Cu-30% Zn) and C26800 (Cu-35% Zn).
- Danzoku Examples of Danzoku include C21000, C22000, and C23000.
- Titanium copper Examples of titanium copper include C19900 (Cu-3% Ti).
- Phosphor bronze Examples of phosphor bronze include C51020, C51910, C52100, and C52400.
- the reflow Sn layer is obtained by performing reflow treatment after Sn plating is performed on the surface of the substrate.
- Cu in the base material diffuses to the surface by reflow, and a layer structure is formed in the order of the Sn layer, the Cu—Sn alloy layer, and the base material from the surface side of the reflow Sn layer.
- Sn alloy such as Sn—Cu, Sn—Ag, Sn—Pb, etc. can be used in addition to the composition of Sn alone.
- a Cu underlayer and / or a Ni underlayer may be provided between the Sn layer and the base material.
- the orientation index of the (101) plane on the surface of the reflow Sn layer By setting the orientation index of the (101) plane on the surface of the reflow Sn layer to 2.0 or more and 5.0 or less, the insertion / extraction property when used for a connector or the like is improved.
- the orientation index of the (101) plane on the surface of the reflow Sn layer is less than 2.0, the desired insertion / removability cannot be obtained, and when it exceeds 5.0, the insertion / removability becomes good, but the solder wettability after heating is improved. to degrade.
- the reason why the insertion / extraction is improved by controlling the orientation of the (101) plane on the surface of the reflow Sn layer is not clear, but the following may be considered.
- orientation index of the (101) plane of the surface of the reflow Sn layer In order to control the orientation index of the (101) plane of the surface of the reflow Sn layer within the above range, it is necessary to change the orientation of the surface of the base material and perform reflow treatment under appropriate conditions. Although the orientation index of the (101) plane of the surface of the base material itself is about 1.5, even if such a base material is directly subjected to Sn plating and reflowed, the (101) plane of the surface of the reflow Sn layer The orientation index cannot be controlled to 2.0 or more.
- the temperature during reflow (in the reflow furnace) is 450 to 600 ° C.
- the reflow process is performed under the condition that the reflow time is 8 to 20 seconds, the desired contact resistance and solder wettability are satisfied, and the orientation index of the (101) plane of the surface of the reflow Sn layer is 2.0 or more.
- Cu plating formed by electroplating may be consumed for forming a Cu—Sn alloy layer during reflow, and the thickness thereof may be zero.
- the thickness of the Cu plating layer before reflow is 1.0 ⁇ m or more, the thickness of the Cu—Sn alloy layer after reflow increases, and the contact resistance and the solder wettability are significantly increased when heated. And heat resistance may be reduced. This is presumably because the Cu plating layer formed by electroplating has Cu as electrodeposited grains and is more easily diffused to the surface by heat compared to Cu in the base material which is a rolled material.
- the reflow temperature is less than 450 ° C. or when the reflow time is less than 8 seconds, the inheritance of the orientation to the plating layer is insufficient, the orientation index of the (101) plane is less than 2.0, and the desired insertion / extraction property is achieved. I can't get it.
- the orientation index of the (101) plane exceeds 5.0 and the insertion / extraction property is good, but the solder wettability after heating is deteriorated. To do.
- colloidal silica and / or halide ions may be added to the Cu plating bath and Cu plating may be performed. It is preferable to use chloride ions as halide ions.
- the concentration of chloride ions can be adjusted, for example, by adding potassium chloride to the plating bath, but is not limited to the potassium salt as long as it is a compound that ionizes to chloride ions in the plating bath.
- a copper sulfate bath can be used as the Cu plating bath.
- colloidal silica When colloidal silica alone is used in the bath, the volume of colloidal silica is 10 mL / L or more (specific gravity: 1.12 g / m 3 and silica content of 20 wt%). In the case of chloride ion alone, addition of 25 mg / L or more makes it possible to control the orientation of the Cu plating layer. Colloidal silica and halide ions may be co-added.
- the thickness of the Cu plating with the (101) plane preferentially oriented is in the range of 0.2 ⁇ m or more and less than 1.0 ⁇ m, and Sn plating with a thickness of 0.7 to 2.0 ⁇ m is applied thereon, and the reflow temperature is set to 450.
- the above plating structure can be obtained by reflow treatment at a temperature of 600 ° C. and a reflow time of 8-20 seconds.
- the average thickness of the reflow Sn layer is preferably 0.2 to 1.8 ⁇ m.
- the thickness of the Cu—Sn alloy layer formed between the reflow Sn layer and the substrate is preferably 0.5 to 1.9 ⁇ m. Since the Cu—Sn alloy layer is hard, it exists in a thickness of 0.5 ⁇ m or more, which contributes to a reduction in insertion force. On the other hand, when the thickness of the Cu—Sn alloy layer exceeds 1.9 ⁇ m, the contact resistance increases when heated and the solder wettability deteriorates, and the heat resistance may decrease.
- Ni layer may be formed between the reflow Sn layer and the base material.
- the Ni layer is obtained by performing reflow treatment after sequentially performing Ni plating, Cu plating, and Sn plating on the surface of the substrate.
- the Cu in the base material diffuses to the surface by reflow, and the layer structure is constructed in the order of Sn layer, Cu—Sn alloy layer, Ni layer, and base material from the surface side of the reflow Sn layer. Since Cu diffusion from the material is prevented, the Cu—Sn alloy layer does not become thick.
- Cu plating is performed in order to make the orientation of the (101) plane of the surface of the reflow Sn layer 2.0 or more.
- the thickness of the Ni layer after reflow is preferably 0.1 to 0.5 ⁇ m.
- the thickness of the Ni layer is less than 0.1 ⁇ m, the corrosion resistance and heat resistance may decrease.
- the thickness of the Ni layer after reflow exceeds 0.5 ⁇ m, the heat resistance improving effect is saturated and the cost is increased, so the upper limit of the Ni layer thickness is preferably 0.5 ⁇ m.
- Example 1> After applying 0.5 ⁇ m thick Cu plating and 1.0 ⁇ m Sn plating by electroplating on one side of the base material (Cu-1.6% Ni-0.4% Si alloy with 0.3 mm thickness) The reflow treatment was performed under the conditions shown in Table 1 to obtain a reflow Sn plated member.
- a copper sulfate bath having a sulfuric acid concentration of 60 g / L, a copper sulfate concentration of 200 g / L, and a bath temperature of 50 ° C. was used, and colloidal silica (“Snowtex O” manufactured by Nissan Chemical Industries, Ltd.) at the ratio shown in Table 1.
- the current density of Cu plating was 5 A / dm 2, and plating was performed while stirring the plating bath with a stirring blade having a rotation speed of 200 rpm.
- As the Sn plating bath a bath of methanesulfonic acid 80 g / L, tin methanesulfonate 250 g / L, bath temperature 50 ° C., nonionic surfactant 5 g / L was used.
- the current density of Sn plating was 8 A / dm 2, and plating was performed while stirring the plating bath with a stirring blade having a rotation speed of 200 rpm.
- ⁇ Evaluation> 1 Measurement of orientation index The obtained reflow Sn plated member was cut into a test piece having a width of 20 mm and a length of 20 mm, and the orientation of the surface of the reflow Sn layer was standardly measured ( ⁇ -2 ⁇ scan) with an X-ray diffractometer. Measurement was carried out at a tube current of 100 mA and a tube voltage of 30 kV using CuK ⁇ rays as a radiation source. The orientation index K was calculated using the following formula.
- K ⁇ A / B ⁇ / ⁇ C / D ⁇
- D Sum of intensities of orientation plane (plane defined by B) in standard data of X-ray diffraction (powder method)
- the contact resistance is an electric contact simulator CRS-113-Au type manufactured by Yamazaki Seiki Laboratories.
- the voltage is 200 mV
- the current is 10 mA
- the sliding load is 0.49 N
- the sliding speed is 1 mm / min
- the sliding distance is 1 mm.
- the insertion / extraction property was evaluated by the dynamic friction coefficient of the surface of the reflow Sn layer of the obtained reflow Sn plating member.
- a sample was fixed on a sample stage, and a stainless steel ball having a diameter of 7 mm was pressed from the base material side of the sample so that the surface of the reflow Sn layer swelled in a hemisphere.
- the bulging portion on the surface of the reflow Sn layer is the “female” side.
- the same sample which did not press a stainless steel ball was attached to the moving stand so that the reflow Sn layer surface might be exposed. This side is the “male” side.
- the bulging portion on the “female” side was placed on the reflow Sn layer on the “male” side, and both were brought into contact with each other.
- W 4.9 N
- the resistance load F accompanying the movement in the horizontal direction is set. Measured with a load cell.
- the sliding speed of the sample horizontal moving speed of the moving table) was 50 mm / min, and the sliding direction was parallel to the rolling direction of the sample.
- the sliding distance was 100 mm, and the average value of F during this period was obtained.
- soldering test method Equilibrium method of JIS-C60068
- the Sn-plated member was a strip-shaped test piece having a width of 10 mm and a length of 50 mm, and the test was performed under the following conditions using a SAT-20 solder checker manufactured by Reska.
- the zero cross time was determined from the obtained load / time curve.
- the wettability was judged as ⁇ when the zero cross time was 6 seconds or less, and as x when it exceeded 6 seconds.
- Flux 25% rosin-ethanol
- flux temperature room temperature
- flux depth 20 mm
- flux immersion time 5 seconds.
- soldering Solder composition: Sn-3.0% Ag-0.5% Cu (manufactured by Senju Metal Industry Co., Ltd.), solder temperature: 250 ° C., solder immersion speed: 4 mm / s, solder immersion depth: 2 mm, solder immersion time: It took 10 seconds.
- Example 2 One side of the substrate was subjected to Ni plating with a thickness of 0.3 ⁇ m by electroplating, and then subjected to Cu plating with a thickness of 0.5 ⁇ m and Sn plating with a thickness of 1.0 ⁇ m in the same manner as in Example 1. Then, the reflow process was performed on the conditions shown in Table 2, and the reflow Sn plating member was obtained.
- the Ni plating bath a bath having nickel sulfate: 250 g / L, nickel chloride: 45 g / L, boric acid: 30 g / L, and a bath temperature of 50 ° C. was used.
- the current density of Ni plating was 5 A / dm 2, and plating was performed while stirring the plating bath with a stirring blade having a rotation speed of 200 rpm.
- Ni plating, Cu plating, and Sn plating were performed in the same manner as in Example 1 and Example 2 except that the thicknesses of Ni plating, Cu plating, and Sn plating were changed as shown in Table 3. Then, the reflow process was performed on conditions of 550 degreeC x 15 sec, and the reflow Sn plating member was obtained.
- a copper sulfate bath having a sulfuric acid concentration of 60 g / L, a copper sulfate concentration of 200 g / L, and a bath temperature of 50 ° C.
- colloidal silica (“Snowtex O” manufactured by Nissan Chemical Industries, Ltd.) 15 mL / L (specific gravity) : The volume of colloidal silica having a silica content of 20 wt% at 1.12 g / m 3 was shown, silica particle diameter: 10-20 nm) and chloride ion (potassium chloride) 25 mg / L were added.
- the current density of Cu plating was 5 A / dm 2, and plating was performed while stirring the plating bath with a stirring blade having a rotation speed of 200 rpm.
- Comparative Example 52 In the case of Comparative Example 52 in which the thickness of the Cu plating layer at the time of Cu plating (before reflow) was 1.0 ⁇ m or more, the contact resistance exceeded 0.95 m ⁇ and the solder wettability was inferior. This is because the Cu plating layer by electroplating has Cu as electrodeposited grains, and is more easily diffused to the surface by heat compared to Cu in the base material which is a rolled material, and the thickness of the Cu—Sn alloy layer after reflow is large. It is thought that it became thick.
- Comparative Example 53 In the case of Comparative Example 53 in which the thickness of the Sn plating layer at the time of Sn plating (before reflowing) was less than 0.7 ⁇ m, the contact resistance exceeded 0.95 m ⁇ and the solder wettability was inferior. This is presumably because the Sn plating layer was thin, and the amount of metal Sn remaining on the surface was reduced by Cu diffusion and Sn layer oxidation by reflow. In the case of Comparative Example 54 in which the thickness of the Sn plating layer at the time of Sn plating (before reflow) exceeded 2.0 ⁇ m, the orientation index of the (101) plane of the surface of the reflow Sn layer was less than 2.0, and the dynamic friction coefficient was 0. .5 was exceeded. This is presumably because the friction of the surface was increased by soft Sn because the Sn plating layer was thick.
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Abstract
Description
一方、Snめっき材には、ウィスカが発生せず、高温環境下で半田濡れ性や接触抵抗が劣化しにくいことも必要とされている。特に、コネクタメーカーの製造工場の海外移転に伴い、めっき後の部材が海外の高温多湿地域で長期保管されたり、はんだ付け時に実装炉内部で加熱されて、はんだ濡れ性、接触抵抗が劣化する事が報告されている。さらに、自動車のエンジンルーム等の高温にSnめっき材が曝されることで、Snめっき層に銅基材から銅が拡散したり、Snめっき層が酸化され、接触抵抗が劣化することがある。
又、コネクタ嵌合時の挿抜力を低減する方法として、Snめっき厚みを薄くする方法があるが、Snめっき厚みを薄くすると、加熱後の半田濡れ性が劣化するため、Snめっき厚みの減少による挿抜力低減には限界があり、新たな手法による挿抜力の低減が求められている。
本発明は上記の課題を解決するためになされたものであり、ウィスカ発生を抑制すると共に、挿抜力を低減させたリフローSnめっき部材の提供を目的とする。
すなわち、本発明のリフローSnめっき部材は、Cu又はCu基合金からなる基材の表面にリフローSn層が形成され、該リフローSn層の表面の(101)面の配向指数が2.0以上5.0以下である。
前記リフローSn層と前記基材との間にNi層が形成されていることが好ましい。
(1)Cu-Ni-Si系合金
Cu-Ni-Si系合金としては、C70250(CDA番号、以下同様;Cu-3%Ni-0.5%Si-0.1Mg),C64745(Cu-1.6%Ni-0.4%Si-0.5%Sn-0.4%Zn)を挙げることができる。
(2)黄銅
黄銅としては、C26000(Cu-30%Zn),C26800(Cu-35%Zn)を挙げることができる。
(3)丹銅
丹銅としては、C21000、C22000、C23000を挙げることができる。
(4)チタン銅
チタン銅としては、C19900(Cu-3%Ti)を挙げることができる。
(5)りん青銅
りん青銅としては、C51020、C51910、C52100、C52400を挙げる事ができる。
リフローSn層の表面の(101)面の配向指数を2.0以上5.0以下にすることにより、コネクタ等に用いたときの挿抜性が改善される。リフローSn層表面の(101)面の配向指数が2.0未満の場合、所望の挿抜性が得られず、5.0を超えると挿抜性は良好となるが、加熱後の半田濡れ性が劣化する。
リフローSn層表面の(101)面の配向を制御することで挿抜性が改善される理由は明確ではないが、次のことが考えられる。まず、Sn相のすべり系は、{110}[001],{100}[001], {111}[101],{101}[101],{121}[101]の5組であり、{101}面はSnのすべり面となる。従って、{101}面を多く(2.0以上)することで、リフローSn層表面と平行なすべり面の比率が高くなる。このため、コネクタ嵌合時にSnめっき表面にせん断応力が加わった際、比較的低い応力でめっき表面が変形すると考えられる。
電気めっきで形成したCuめっきは、リフロー時にCu-Sn合金層の形成に消費され、その厚みがゼロになってもよい。但し、リフロー前のCuめっき層の厚みが1.0μm以上であると、リフロー後のCu-Sn合金層の厚みが厚くなり、加熱したときの接触抵抗の増大や半田濡れ性の劣化が顕著になり、耐熱性が低下する場合がある。これは、電気めっきによるCuめっき層はCuが電着粒として存在し、圧延材である基材中のCuに比べ熱により表面に拡散しやすいためと考えられる。
リフロー温度が450℃未満の場合、または、リフロー時間が8秒未満の場合、めっき層への配向継承が不十分で、(101)面の配向指数は2.0未満となり、所望の挿抜性が得られない。リフロー温度が600℃を超える場合、または、リフロー時間が20秒を超える場合、(101)面の配向指数は5.0を超え、挿抜性は良好となるが、加熱後の半田濡れ性が劣化する。
リフローSn層と基材との間に形成されるCu-Sn合金層の厚みは0.5~1.9μmとすることが好ましい。Cu-Sn合金層は硬質なため、0.5μm以上の厚さで存在すると、挿入力の低減に寄与する。一方、Cu-Sn合金層の厚さが1.9μmを超えると、加熱したときの接触抵抗の増大や半田濡れ性の劣化が顕著になり、耐熱性が低下する場合がある。
リフロー後のNi層の厚みは0.1~0.5μmとすることが好ましい。Ni層の厚みが0.1μm未満では耐食性や耐熱性が低下する場合がある。一方、リフロー後のNi層の厚みが0.5μmを超えると、耐熱性の改善効果は飽和し、コストアップとなるため、Ni層の厚みの上限は0.5μmとする事が好ましい。
基材(板厚0.3mmのCu-1.6%Ni-0.4%Si合金)の片面に、電気めっきにより厚み0.5μmのCuめっき、1.0μmのSnめっきをそれぞれ施した後、表1に示す条件でリフロー処理し、リフローSnめっき部材を得た。
Cuめっき浴としては、硫酸濃度60g/L、硫酸銅濃度200g/L、浴温50℃の硫酸銅浴を用い、さらに表1に示す割合でコロイダルシリカ(日産化学工業社製「スノーテックスO」,比重:1.12でシリカ含有率20wt%,シリカ粒子径:10-20nm)、及び/又は塩化物イオン(塩化カリウム)を添加した。Cuめっきの電流密度を5A/dm2とし、めっき浴を回転数200rpmの攪拌羽根で攪拌しながらめっきした。
Snめっき浴としては、メタンスルホン酸80g/L、メタンスルホン酸錫250g/L、浴温50℃、ノニオン系界面活性剤5g/Lの浴を用いた。Snめっきの電流密度を8A/dm2とし、めっき浴を回転数200rpmの攪拌羽根で攪拌しながらめっきした。
1.配向指数の測定
得られたリフローSnめっき部材を幅20mm×長さ20mmの試験片に切り出し、リフローSn層表面の配向をX線ディフラクトメータにより標準測定(θ-2θスキャン)した。線源としてCuKα線を用い、管電流100mA,管電圧30kVで測定を実施した。配向指数Kは次式を用いて算出した。
K={A/B}/{C/D}
A:(101)面のピーク強度(cps)
B:考慮した配向面((200),(101),(220),(211),(301),(112),(400),(321),(420),(411),(312),(431),(103),(332))のピーク強度の和(cps)
C:X線回折の標準データ(粉末法)における(101)面の強度
D:X線回折の標準データ(粉末法)における配向面(Bで規定した面)の強度の総和
耐熱性の評価として、得られたリフローSnめっき部材を145℃で500時間加熱後、リフローSn層表面の接触抵抗を測定した。接触抵抗は、山崎精機研究所製電気接点シミュレータCRS-113-Au型を用い、四端子法により、電圧200mV、電流10mA、摺動荷重0.49N、摺動速度1mm/min、摺動距離1mmで測定した。
得られたリフローSnめっき部材のリフローSn層表面の動摩擦係数により、挿抜性を評価した。まず、試料を試料台上に固定し、リフローSn層表面が半球状に膨らむよう、試料の基材側から直径7mmのステンレス球を押し付けた。このリフローSn層表面の膨出部が「メス」側となる。次に、ステンレス球を押し付けない同一試料を、リフローSn層表面が露出するよう移動台に取り付けた。この面が「オス」側となる。
そして、「メス」側の膨出部を、「オス」側のリフローSn層の上に載置し、両者を接触させた。この状態で、膨出部の裏側(基材側)に所定加重W(=4.9N)を掛けつつ、移動台を水平方向に移動させ、このとき水平方向への移動に伴う抵抗加重Fをロードセルにより測定した。試料の摺動速度(移動台の水平移動速度)は50mm/minとし、摺動方向は試料の圧延方向に対し平行な方向とした。摺動距離は100mmとし、この間のFの平均値を求めた。そして、動摩擦係数μをμ=F/Wより算出した。
JIS-C60068のはんだ付け試験方法(平衡法)に準じ、得られたリフローSnめっき部材と鉛フリーはんだとの濡れ性を評価した。Snめっき部材は幅10mm×長さ50mmの短冊状試験片とし、試験はレスカ社製SAT-20ソルダチェッカーを用い、下記条件でおこなった。得られた荷重/時間曲線からゼロクロスタイムを求めた。濡れ性はゼロクロスタイムが6秒以下なら○、6秒を超える場合は×と判定した。
(フラックス塗布)
フラックス:25%ロジンーエタノール、フラックス温度:室温、フラックス深さ:20mm、フラックス浸漬時間:5秒とした。又、たれ切り方法は、ろ紙にエッジを5秒当てて、フラックスを除去し、装置に固定して30秒保持して行った。
(はんだ付け)
はんだ組成: Sn-3.0%Ag-0.5%Cu(千住金属工業社製)、はんだ温度:250℃、はんだ浸漬速さ:4mm/s、はんだ浸漬深さ:2mm、はんだ浸漬時間:10秒で行った。
上記基材の片面に、電気めっきにより厚み0.3μmのNiめっきを施した後、実施例1と同様にして厚み0.5μmのCuめっき、1.0μmのSnめっきをそれぞれ施した。その後、表2に示す条件でリフロー処理し、リフローSnめっき部材を得た。
Niめっき浴としては、硫酸ニッケル:250g/L,塩化ニッケル:45g/L,ホウ酸:30g/L,浴温50℃の浴を用いた。Niめっきの電流密度を5A/dm2とし、めっき浴を回転数200rpmの攪拌羽根で攪拌しながらめっきした。
Niめっき、Cuめっき、および、Snめっきの厚みを表3に示すように変化させたこと以外は実施例1および実施例2と同様にしてNiめっき、Cuめっき、Snめっきをそれぞれ施した。その後、550℃×15secの条件でリフロー処理し、リフローSnめっき部材を得た。Cuめっき浴としては、硫酸濃度60g/L、硫酸銅濃度200g/L、浴温50℃の硫酸銅浴を用い、さらにコロイダルシリカ(日産化学工業社製「スノーテックスO」)15mL/L(比重:1.12g/m3でシリカ含有率20wt%のコロイダルシリカの体積を示し、シリカ粒子径:10-20nm)及び塩化物イオン(塩化カリウム)25mg/Lを添加した。Cuめっきの電流密度を5A/dm2とし、めっき浴を回転数200rpmの攪拌羽根で攪拌しながらめっきした。
なお、表1の発明例1~7、比較例8~14は、実施例1の条件で行った結果である。表2の発明例20~23、比較例30~35は、実施例2の条件で行った結果である。表3の発明例40~49、比較例50~54は、実施例3の条件で行った結果である。
リフロー時間が8秒未満である比較例10、及びリフロー温度が450℃未満である比較例12、14の場合、いずれもリフロー処理が不十分となり、リフローSn層の表面の(101)面の配向指数が2.0未満となり、動摩擦係数が0.5を超えた。これは、リフロー時にSnめっき層が十分に溶融しなかったため、Sn層の再配向が生じ難くなったためと考えられる。
リフロー時間が20秒を超えた比較例11、及びリフロー温度が600℃を超えた比較例13の場合、いずれもリフロー処理が過度となり、接触抵抗が0.95mΩを超えるとともに、はんだ濡れ性が劣った。これは、過度なリフロー処理により、リフローSn層に下地からCuが拡散したり、Sn層が酸化されて表面に残存する金属Sn量が減少したためと考えられる。
リフロー時間が8秒未満である比較例32、及びリフロー温度が450℃未満である比較例34の場合、いずれもリフロー処理が不十分となり、リフローSn層の表面の(101)面の配向指数が2.0未満となり、動摩擦係数が0.5を超えた。
リフロー時間が20秒を超えた比較例33、及びリフロー温度が600℃を超えた比較例35の場合、いずれもリフロー処理が過度となり、接触抵抗が0.95mΩを超えるとともに、はんだ濡れ性が劣った。
Cuめっき時(リフロー前)のCuめっき層の厚みが1.0μm以上である比較例52の場合、接触抵抗が0.95mΩを超えるとともに、はんだ濡れ性が劣った。これは、電気めっきによるCuめっき層はCuが電着粒として存在し、圧延材である基材中のCuに比べて熱により表面に拡散しやすく、リフロー後のCu-Sn合金層の厚みが厚くなったためと考えられる。
Snめっき時(リフロー前)のSnめっき層の厚みが0.7μm未満である比較例53の場合、接触抵抗が0.95mΩを超えるとともに、はんだ濡れ性が劣った。これは、Snめっき層の厚みが薄いため、リフローによるCuの拡散やSn層酸化により、表面に残存する金属Sn量が減少したためと考えられる。
Snめっき時(リフロー前)のSnめっき層の厚みが2.0μmを超えた比較例54の場合、リフローSn層の表面の(101)面の配向指数が2.0未満となり、動摩擦係数が0.5を超えた。これは、Snめっき層の厚みが厚いため、柔らかいSnによって表面の摩擦が大きくなったためと考えられる。
Claims (3)
- Cu又はCu基合金からなる基材の表面にリフローSn層が形成され、該リフローSn層の表面の(101)面の配向指数が2.0以上5.0以下であるリフローSnめっき部材。
- 前記リフローSn層は、前記基材の表面にCuめっき層を形成し、該Cuめっき層の表面に形成されたSnめっき層をリフローして形成されたものである請求項1に記載のリフローSnめっき部材。
- 前記リフローSn層と前記基材との間にNi層が形成されている請求項1又は2に記載のリフローSnめっき部材。
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