WO2010005088A1 - Electronic component and method for manufacturing the same - Google Patents
Electronic component and method for manufacturing the same Download PDFInfo
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- WO2010005088A1 WO2010005088A1 PCT/JP2009/062639 JP2009062639W WO2010005088A1 WO 2010005088 A1 WO2010005088 A1 WO 2010005088A1 JP 2009062639 W JP2009062639 W JP 2009062639W WO 2010005088 A1 WO2010005088 A1 WO 2010005088A1
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- plating layer
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- conductive member
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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
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
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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
- C25D5/615—Microstructure of the layers, e.g. mixed structure
- C25D5/617—Crystalline layers
Definitions
- the present invention relates to an electronic component including at least a conductive member and a manufacturing method thereof.
- an Au layer is generally provided on a conductive material in order to obtain low contact resistance and high corrosion resistance.
- an electrolytic Ni plating layer is provided between the conductive material and the Au layer. It is known to be advantageous.
- Ni plating layer when the Ni plating layer is provided, for example, moisture such as moisture exists, and when chlorine and sulfur are dissolved in the moisture, an electrolyte solution is generated. Furthermore, since the electrolyte solution enters through the grain boundary (pinhole) of the Au layer and forms a local battery between Ni and Au, Ni which is a base metal than Au elutes. At this time, Ni corrosion products appear on the Au plating layer through the pin holes of the Au layer. On the same principle, the components contained in the copper alloy are also eluted, and corrosives are generated (chlorides and sulfides). Since this is an insulator, there has been a problem that problems such as contact failure occur.
- Patent Document 1 discloses a terminal for preventing the above-described corrosion by providing an electroless Ni—P layer between copper or a copper alloy and a gold plating layer.
- the electroless Ni-P layer is formed by an electroless plating method using hypophosphite as a reducing agent, and the plating bath composition varies with time, and the amount of P in the bath is adjusted. It is difficult to do and is not suitable for mass production.
- Patent Document 2 an electrolytic Ni layer and an electrolytic Ni—P layer are sequentially provided between a base material and a gold alloy layer, and the gold alloy layer is subjected to sealing treatment, thereby providing wear resistance. An improved electrical contact is disclosed.
- Patent Document 2 requires an electrolytic Ni layer for reasons such as extending the life of a sliding electrical contact, and the problem of Ni corrosion as described above still remains. It remains.
- An object of the present invention is to prevent or suppress corrosion by providing an appropriate layer between the conductive material and a main plating layer formed above the conductive material in an electronic component including at least a conductive member.
- An object of the present invention is to provide an electronic component capable of having connection reliability and a method for manufacturing the same.
- the gist of the present invention is as follows. (1) An electronic component including at least a conductive member, wherein an electronic component including a base plating layer and a main plating layer formed on the base plating layer on a surface portion of the conductive member, An electronic component characterized by being an electrolytic Ni-P plating layer.
- the main plating layer is made of any one of Au-containing material, Ag-containing material, Pd-containing material, Pd—Ni, Sn and Sn-based alloy plating.
- An electrolytic Ni—P plating layer is formed on a surface portion of the conductive member of an electronic component including at least a conductive member, and a main plating layer is formed on the electrolytic Ni—P plating layer. Manufacturing method of electronic components.
- the electrolytic Ni—P plating layer is a bath based on sulfuric acid having a pH of 2.4 to 2.8 and a bath temperature of 50 to 65 ° C., and a current density of 0.1 to 20 A / dm 2 .
- the electronic component of the present invention includes at least a conductive member, and has an electrolytic Ni—P plating layer and a main plating layer formed on the electrolytic Ni—P plating layer on the surface portion of the conductive member, thereby preventing corrosion. It is possible to prevent or suppress and improve connection reliability.
- an electrolytic Ni—P plating layer is formed on a surface portion of the conductive member of an electronic component including at least a conductive member, and a main plating layer is formed on the electrolytic Ni—P plating layer.
- FIG. 1 shows a general contact as an example of an electronic component
- FIG. 2 is a schematic diagram showing a cross section taken along line II of FIG.
- the contact 1 includes at least a conductive member 2 and is formed on the surface portion of the conductive material 2 on the electrolytic Ni—P plating layer 3 and on the electrolytic Ni—P plating layer.
- the main plating layer 4 is provided, and by adopting such a configuration, corrosion can be prevented or suppressed and connection reliability can be improved.
- the anti-corrosion treatment formed on the main plating layer 4 by, for example, a rust prevention treatment using a carboxylic acid-type or thiol-type anti-rust treatment solution. It is preferable to provide a rust coating layer.
- the conductive material 2 is preferably made of copper or a copper alloy, and is made of, for example, phosphor bronze, beryllium copper, brass or pure copper, but more preferably made of phosphor bronze when considering only corrosion resistance.
- the main plating layer 4 is preferably made of any of an Au-containing material, an Ag-containing material, a Pd-containing material, Pd—Ni, Sn, and Sn-based alloy plating. This is because the contact stability, corrosion resistance, and solder wettability are good. Further, the main plating layer 4 is more preferably made of an Au-containing material from the viewpoint that the corrosion resistance is very good.
- the P concentration of the electrolytic Ni—P plating layer 3 is preferably 5.0% by mass or more. This is because if the P concentration is less than 5.0% by mass, the corrosion resistance may decrease. Further, if the P concentration exceeds 18% by mass, the ductility becomes poor and cracks such as cracks may occur. Therefore, the P content is more preferably 18% by mass or less.
- the thickness of the electrolytic Ni—P plating layer 3 is preferably 0.1 ⁇ m or more. This is because if the thickness is less than 0.1 ⁇ m, corrosion resistance may decrease due to diffusion of copper and zinc contained in the copper alloy. Further, if the thickness exceeds 6.0 ⁇ m, the ductility becomes poor, and cracks such as cracks may occur. Therefore, the thickness is more preferably 6.0 ⁇ m or less.
- the thickness of the main plating layer 4 is preferably 0.07 to 6.0 ⁇ m although it depends on the type of the main plating layer.
- the thickness is about 0.1 to 1.0 ⁇ m for a portion requiring electrical reliability, and 0 for a portion requiring soldering reliability. It is desirable that the thickness is about 07 to 0.20 ⁇ m.
- the thickness of the main plating layer made of Au or Pd plating may be more than 1.0 ⁇ m. However, in consideration of cost, it is in the range of 0.1 to 1.0 ⁇ m. Is more preferable.
- the thickness is preferably 2.0 to 6.0 ⁇ m in order to ensure good electrical reliability and soldering reliability.
- the electrolytic Ni—P plating layer 3 can be formed by, for example, an electrolytic plating method using a watt bath or a sulfamine bath. In particular, it is preferably formed by an electrolytic plating method using a bath based on sulfuric acid obtained by adding phosphorous acid to a Watt bath. This is because it is possible to form a layer in which the crystal is dense and the surface activity is high and the interface reactivity with the main plating layer such as Au is good.
- the manufacturing method of the contact 1 which is an example of the electronic component according to the present invention, forms the electrolytic Ni—P plating layer 3 on the surface portion of the conductive material 2 of the contact 1 including at least the conductive member.
- the main plating layer 4 By providing the main plating layer 4 on the electrolytic Ni—P plating layer 3 and adopting such a configuration, an electronic component capable of preventing or suppressing corrosion and improving connection reliability is provided. That made it possible.
- the main plating layer 4 is preferably made of any of an Au-containing material, an Ag-containing material, a Pd-containing material, Pd—Ni, Sn, and Sn-based alloy plating. This is because the contact stability, corrosion resistance, and solder wettability are good.
- the main plating layer 4 is more preferably made of Au, particularly in terms of very good corrosion resistance.
- the electrolytic Ni—P plating layer 3 is cathodic electrolyzed at a current density of 0.1 to 20 A / dm 2 in a sulfuric acid base bath having a pH of 2.4 to 2.8 and a bath temperature of 50 to 65 ° C. Preferably it is formed. If the pH is less than 2.4, the current efficiency may decrease and the phosphorus content may exceed 18% by mass. If the pH exceeds 2.8, poor adhesion and the phosphorus content may be less than 2.0% by mass. Because there is.
- the current efficiency may decrease and the phosphorus content may exceed 18% by mass, and if it exceeds 65 ° C., the phosphorus content may be less than 2.0% by mass, Furthermore, if the current density is less than 0.1 A / dm 2 , the phosphorus content may exceed 18% by mass, and if it exceeds 20 A / dm 2 , the phosphorus content may be less than 2.0% by mass. Because there is.
- the composition of the sulfuric acid base bath preferably contains at least metal nickel ions (Ni 2+ ): 10 to 20 g / l and phosphorous acid 25 to 250 g / l. If the metal nickel ion is less than 10 g / l, the phosphorus content is high, so that cracks are likely to occur, and if it exceeds 20 g / l, the phosphorus content is low and corrosion resistance may be deteriorated. Because there is. In addition, if the phosphorous acid is less than 25 g / l, the phosphorus content may be less than 2.0% by mass, and if it exceeds 250 g / l, the phosphorus content may exceed 18% by mass. is there. As what satisfies such a composition condition, for example, a sulfuric acid base bath manufactured by Uemura Kogyo Co., Ltd. or a sulfuric acid base bath manufactured by Atotech Japan Co., Ltd. may be mentioned.
- composition and conditions of the sulfuric acid base bath can be set as follows.
- the main plating layer 4 in order to prevent or suppress corrosion, it is preferable to subject the main plating layer 4 to a rust prevention treatment using, for example, a carboxylic acid or sulfonic acid rust prevention treatment liquid.
- the rust prevention treatment is performed, for example, by an immersion treatment method or an electrolytic treatment method.
- the immersion treatment method is a method of forming a rust-preventing film layer by immersing the object to be treated in the treatment liquid
- the electrolytic treatment method further comprises applying a predetermined voltage after immersing the object to be treated in the treatment liquid.
- This is a method of applying polarity to promote the formation of a rust preventive film layer.
- FIG. 1 and 2 show an example of a typical embodiment, and the present invention is not limited to this embodiment. Further, an example is shown in FIG. 3, FIG. 4, and FIG. As shown respectively, the electronic component can be applied to, for example, a shell, a shield case, and a fixture. Of course, it goes without saying that the connector including the above-described contact, shell, shield case, fixture and the like is also included in the electronic component.
- Sample 1 is a sulfuric acid base bath having a pH of 2.5 and a bath temperature of 60 ° C. on a surface portion of phosphor bronze corresponding to the contact portion of a contact having a contact portion made of phosphor bronze.
- an electrolytic Ni—P plating layer (layer thickness: 1.20 ⁇ m) having a P concentration of 12% by mass was formed, and an Au layer (layer thickness: 0.85 ⁇ m) was formed.
- the composition of the bath is as follows. [Bath composition] Metallic nickel: 12.5g / l Phosphorous acid: 130 g / l
- Sample 2 and Sample 3 were formed by the same method as Sample 1 except that a Pd layer (film thickness: 0.20 ⁇ m or 0.85 ⁇ m) was formed on the electrolytic Ni—P plating layer, respectively.
- Samples 4 and 5 were formed by the same method as Sample 1, except that Sn—Ag layers (film thickness: 2.00 ⁇ m or 5.00 ⁇ m) were formed on the electrolytic Ni—P plating layer, respectively.
- Samples 6 and 7 were prepared in the same manner as Sample 1, except that electrolytic Ni—P plating layers (layer thickness: 1.20 ⁇ m) with P concentrations of 4.5, 5.0, 6.0, 8.0, 10, and 15% by mass were formed, respectively. 8, 9, 10, and 11 were formed, respectively.
- Samples 12, 13, 14, 15 and 16 were formed by the same method as Sample 1 except that the thickness of the electrolytic Ni—P plating layer was 0.05, 0.10, 0.50, 2.00 and 5.00 ⁇ m, respectively.
- Samples 17, 18, 19, and 20 were formed in the same manner as Sample 1, except that the thickness of the Au layer was 0.10, 0.24, 0.40, and 1.00 ⁇ m, respectively.
- a rust preventive film layer (several tens of thousands) formed by rust prevention treatment using a thiol-based rust prevention treatment liquid was formed on the Au layer, the same as Samples 17, 18, 19, and 20, respectively. Samples 21, 22, 23, and 24 were formed by the method.
- Samples 25, 26, 27, and 28 were formed by the same method as Sample 1, except that the conductive members were pure copper, brass, beryllium copper, and Corson copper, respectively.
- Sample 1 except that an electrolytic Ni plating layer (layer thickness: 1.20 ⁇ m) was formed by cathodic electrolysis at a current density of 10 A / dm 2 in a sulfuric acid base bath with a pH of 2.5 and a bath temperature of 50 ° C.
- Sample 29 was formed by the same method.
- Sample 15 except that an electrolytic Ni plating layer (layer thickness: 2.00 ⁇ m) was formed by cathodic electrolysis at a current density of 10 A / dm 2 in a sulfuric acid base bath with a pH of 2.5 and a bath temperature of 50 ° C.
- Sample 30 was formed by the same method.
- Sample 25 except that an electrolytic Ni plating layer (layer thickness: 1.20 ⁇ m) was formed by cathodic electrolysis at a current density of 10 A / dm 2 in a sulfuric acid base bath of pH 2.5 and bath temperature 50 ° C., respectively.
- Samples 31, 32, 33, and 34 were formed by the same method as that of No. 26, 27, and 28.
- Sample 17 except that an electrolytic Ni plating layer (layer thickness: 1.20 ⁇ m) was formed by cathodic electrolysis at a current density of 10 A / dm 2 in a sulfuric acid base bath each having a pH of 2.5 and a bath temperature of 50 ° C. Samples 35, 36 and 37 were formed by the same method as in FIGS.
- Sample 21 except that an electrolytic Ni plating layer (layer thickness: 1.20 ⁇ m) was formed by cathodic electrolysis at a current density of 10 A / dm 2 in a sulfuric acid-based bath having a pH of 2.5 and a bath temperature of 50 ° C., respectively.
- Samples 38, 39, 40, and 41 were formed in the same manner as in FIGS.
- Electrolytic Ni plating layer (layer thickness: 1.20 ⁇ m) and P concentration of 10 mass% on it by cathodic electrolysis with sulfuric acid base bath at pH: 2.5, bath temperature: 60 ° C, current density: 10A / dm 2
- Sample 42 was formed by the same method as Sample 10 except that the electrolytic Ni—P plating layer (layer thickness: 1.20 ⁇ m) was formed.
- Sample 43 was formed by the same method as Sample 10, except that an electroless Ni—P plating layer (layer thickness: 1.20 ⁇ m) with a P concentration of 10 mass% was formed.
- Electrolytic Ni plating layer (layer thickness: 1.20 ⁇ m) and P concentration of 10 mass% on it by cathodic electrolysis with sulfuric acid base bath at pH: 2.5, bath temperature: 50 ° C, current density: 10A / dm 2
- Sample 44 was formed by the same method as Sample 10, except that the electroless Ni—P plating layer (layer thickness: 1.20 ⁇ m) was formed.
- Sample 2 except that an electrolytic Ni plating layer (layer thickness: 1.20 ⁇ m) was formed by cathodic electrolysis at a current density of 10 A / dm 2 in a sulfuric acid-based bath with a pH of 2.5 and a bath temperature of 50 ° C., respectively.
- Samples 45, 46, 47 and 48 were formed in the same manner as in 3, 4, and 5.
- FIG. 6 to FIG. 6 For these samples 1 to 48, the results of external observation using a microscope (optical microscope) and cross-sectional observation using a focused ion beam processing apparatus (FIB) are shown in FIG. 6 to FIG. These comprehensive evaluations are shown in Table 1. For example, in FIGS. 6 (a) to 6 (e), the left of FIG. 6 (a) shows a photograph of appearance observation, and the right shows a photograph of cross-sectional observation, whereas FIG. 6 (b). As described above, all photographs having only one photograph are photographs of external appearance observation. The evaluation criteria are as follows.
- the diameter of one corrosive is 0.5mm or less, or the diameter of the corroded corrodes is 0.5mm or less
- the diameter of one corrosive is 0.5mm to 0.8mm or less
- the diameter of one corroded material exceeds 0.8mm, or the diameter of the corroded corroded materials exceeds 0.8mm.
- the base plating layer is all amorphous ⁇ : The base plating layer is not partly amorphous ⁇ : The base plating layer is not all amorphous Cost evaluation When the main plating layer is a noble metal such as Au or Pd, ⁇ : The thickness of the main plating layer is 0.2 ⁇ m or less and the thickness of the base plating layer is less than 2 ⁇ m. ⁇ : The thickness of the main plating layer exceeds 0.2 ⁇ m.
- ⁇ Thickness of the base plating layer is less than 2 ⁇ m
- Thickness of the base plating layer is 2 ⁇ m or more
- the electronic component of the present invention includes at least a conductive member, and has an electrolytic Ni—P plating layer and a main plating layer formed on the electrolytic Ni—P plating layer on the surface portion of the conductive member, thereby preventing corrosion. It is possible to prevent or suppress and improve connection reliability.
- an electrolytic Ni—P plating layer is formed on a surface portion of the conductive member of an electronic component including at least a conductive member, and a main plating layer is formed on the electrolytic Ni—P plating layer.
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Abstract
Disclosed is an electronic component comprising at least a conductive member, wherein corrosion is prevented or suppressed and high connection reliability is achieved by providing an adequate layer between the conductive member and a main plating layer formed on top of the conductive member. A method for manufacturing the electronic component is also disclosed. The electronic component comprising at least a conductive member is provided, on the surface of the conductive member, with a base plating layer and a main plating layer formed on the base plating layer, and is characterized in that the base plating layer is an electrolytic Ni-P plating layer.
Description
本発明は、少なくとも導電部材を含む電子部品およびその製造方法に関する。
The present invention relates to an electronic component including at least a conductive member and a manufacturing method thereof.
従来、例えばコネクタ等の電子部品には高接続信頼性が求められ、低接触抵抗および高耐食性を得るため、導電材料上にAu層を具えるのが一般的である。また、前記導電材料と前記Au層との密着性を向上させ、かつ前記導電材料の前記Au層への拡散を防止するため、前記導電材料と前記Au層との間に、電解Niめっき層を設けるのが有利であることが知られている。
Conventionally, for example, electronic components such as connectors are required to have high connection reliability, and an Au layer is generally provided on a conductive material in order to obtain low contact resistance and high corrosion resistance. In order to improve adhesion between the conductive material and the Au layer and prevent diffusion of the conductive material into the Au layer, an electrolytic Ni plating layer is provided between the conductive material and the Au layer. It is known to be advantageous.
しかしながら、Niめっき層を設けた場合、例えば湿気等の水分が存在し、前記水分に塩素および硫黄などが溶解した場合、電解質溶液が生成されることになる。さらに、電解質溶液がAu層の粒界(ピンホール)を通じて進入し、NiとAuとの間で局部電池を形成するため、Auよりも卑な金属であるNiが溶出する。このとき、前記Au層のピンホールを通じてNiの腐食成生物がAuめっき層上に現れる。同様な原理で、銅合金中に含まれる成分も溶出し、腐食物が生成(塩化物や硫化物)することになる。これは絶縁体であるため、接点不良等の不具合が生じるという問題があった。
However, when the Ni plating layer is provided, for example, moisture such as moisture exists, and when chlorine and sulfur are dissolved in the moisture, an electrolyte solution is generated. Furthermore, since the electrolyte solution enters through the grain boundary (pinhole) of the Au layer and forms a local battery between Ni and Au, Ni which is a base metal than Au elutes. At this time, Ni corrosion products appear on the Au plating layer through the pin holes of the Au layer. On the same principle, the components contained in the copper alloy are also eluted, and corrosives are generated (chlorides and sulfides). Since this is an insulator, there has been a problem that problems such as contact failure occur.
このような問題を解決するため、特許文献1には、銅または銅合金と金メッキ層との間に、無電解Ni-P層を設け、上述した腐食を防止する端子が開示されている。
In order to solve such a problem, Patent Document 1 discloses a terminal for preventing the above-described corrosion by providing an electroless Ni—P layer between copper or a copper alloy and a gold plating layer.
しかしながら、前記無電解Ni-P層は、還元剤として次亜リン酸塩を使用した無電解めっき法によって形成されたものであり、時間と共にめっき浴組成が変動し、浴中のP量を調整することが難しく、大量生産には不向きであるという問題がある。
However, the electroless Ni-P layer is formed by an electroless plating method using hypophosphite as a reducing agent, and the plating bath composition varies with time, and the amount of P in the bath is adjusted. It is difficult to do and is not suitable for mass production.
一方、特許文献2には、基材と金合金層との間に、電解Ni層および電解Ni-P層を順次設け、かつ前記金合金層に封孔処理を施すことにより、耐摩耗性を向上させた電気接点が開示されている。
On the other hand, in Patent Document 2, an electrolytic Ni layer and an electrolytic Ni—P layer are sequentially provided between a base material and a gold alloy layer, and the gold alloy layer is subjected to sealing treatment, thereby providing wear resistance. An improved electrical contact is disclosed.
しかしながら、特許文献2に記載された発明は、摺動型電気接点の寿命を長くする等の理由から電解Ni層を必須としたものであり、上述したようなNiの腐食の問題は依然残されたままである。
However, the invention described in Patent Document 2 requires an electrolytic Ni layer for reasons such as extending the life of a sliding electrical contact, and the problem of Ni corrosion as described above still remains. It remains.
本発明の目的は、少なくとも導電部材を含む電子部品において、前記導電材料とこの導電材料の上方に形成した主めっき層との間に適切な層を設けることにより、腐食を防止または抑制し、高接続信頼性を有することができる電子部品およびその製造方法を提供することにある。
An object of the present invention is to prevent or suppress corrosion by providing an appropriate layer between the conductive material and a main plating layer formed above the conductive material in an electronic component including at least a conductive member. An object of the present invention is to provide an electronic component capable of having connection reliability and a method for manufacturing the same.
上記目的を達成するため、本発明の要旨構成は以下の通りである。
(1)少なくとも導電部材を含む電子部品であって、前記導電部材の表面部分に、下地めっき層および該下地めっき層上に形成した主めっき層を具える電子部品において、前記下地めっき層が、電解Ni-Pめっき層であることを特徴とする電子部品。 In order to achieve the above object, the gist of the present invention is as follows.
(1) An electronic component including at least a conductive member, wherein an electronic component including a base plating layer and a main plating layer formed on the base plating layer on a surface portion of the conductive member, An electronic component characterized by being an electrolytic Ni-P plating layer.
(1)少なくとも導電部材を含む電子部品であって、前記導電部材の表面部分に、下地めっき層および該下地めっき層上に形成した主めっき層を具える電子部品において、前記下地めっき層が、電解Ni-Pめっき層であることを特徴とする電子部品。 In order to achieve the above object, the gist of the present invention is as follows.
(1) An electronic component including at least a conductive member, wherein an electronic component including a base plating layer and a main plating layer formed on the base plating layer on a surface portion of the conductive member, An electronic component characterized by being an electrolytic Ni-P plating layer.
(2)前記主めっき層が、Au含有物、Ag含有物、Pd含有物、Pd-Ni、SnおよびSn系合金めっきのいずれかからなる上記(1)に記載の電子部品。
(2) The electronic component according to (1), wherein the main plating layer is made of any one of Au-containing material, Ag-containing material, Pd-containing material, Pd—Ni, Sn and Sn-based alloy plating.
(3)前記電解Ni-Pめっき層のP濃度が、5.0質量%以上である上記(1)または(2)に記載の電子部品。
(3) The electronic component according to (1) or (2), wherein the electrolytic Ni—P plating layer has a P concentration of 5.0% by mass or more.
(4)前記電解Ni-Pめっき層の厚さが、0.1μm以上である上記(1)、(2)または(3)に記載の電子部品。
(4) The electronic component according to (1), (2) or (3), wherein the thickness of the electrolytic Ni—P plating layer is 0.1 μm or more.
(5)前記主めっき層の厚さが、0.07~6.0μmである上記(1)~(4)のいずれか一に記載の電子部品。
(5) The electronic component according to any one of (1) to (4), wherein the main plating layer has a thickness of 0.07 to 6.0 μm.
(6)前記電解Ni-Pめっき層が、硫酸をベースとする浴を用いて形成される上記(1)~(5)のいずれか一に記載の電子部品。
(6) The electronic component according to any one of (1) to (5), wherein the electrolytic Ni—P plating layer is formed using a bath based on sulfuric acid.
(7)前記主めっき層上に、防錆皮膜層をさらに有する上記(1)~(6)のいずれか一に記載の電子部品。
(7) The electronic component according to any one of (1) to (6), further including a rust preventive film layer on the main plating layer.
(8)前記導電材料が、銅または銅合金からなる上記(1)~(7)のいずれか一に記載の電子部品。
(8) The electronic component according to any one of (1) to (7), wherein the conductive material is made of copper or a copper alloy.
(9)少なくとも導電部材を含む電子部品の、前記導電部材の表面部分に、電解Ni-Pめっき層を形成し、該電解Ni-Pめっき層上に主めっき層を形成することを特徴とする電子部品の製造方法。
(9) An electrolytic Ni—P plating layer is formed on a surface portion of the conductive member of an electronic component including at least a conductive member, and a main plating layer is formed on the electrolytic Ni—P plating layer. Manufacturing method of electronic components.
(10)前記電解Ni-Pめっき層が、pH:2.4~2.8、浴温:50~65℃の硫酸をベースとする浴で、電流密度:0.1~20A/dm2で陰極電解することにより形成される上記(9)に記載の電子部品の製造方法。
(10) The electrolytic Ni—P plating layer is a bath based on sulfuric acid having a pH of 2.4 to 2.8 and a bath temperature of 50 to 65 ° C., and a current density of 0.1 to 20 A / dm 2 . The method for producing an electronic component according to (9), which is formed by cathodic electrolysis.
(11)前記硫酸ベース浴の組成が少なくとも、金属ニッケルイオン:10~20g/lおよび亜リン酸:25~250g/lを含有する上記(10)に記載の電子部品の製造方法。
(11) The method for producing an electronic component according to (10), wherein the sulfuric acid base bath contains at least metallic nickel ions: 10 to 20 g / l and phosphorous acid: 25 to 250 g / l.
本発明の電子部品は、少なくとも導電部材を含み、前記導電部材の表面部分に、電解Ni-Pめっき層および該電解Ni-Pめっき層上に形成した主めっき層を具えることにより、腐食を防止または抑制し、接続信頼性を向上させることができる。
The electronic component of the present invention includes at least a conductive member, and has an electrolytic Ni—P plating layer and a main plating layer formed on the electrolytic Ni—P plating layer on the surface portion of the conductive member, thereby preventing corrosion. It is possible to prevent or suppress and improve connection reliability.
本発明の電子部品の製造方法は、少なくとも導電部材を含む電子部品の、前記導電部材の表面部分に、電解Ni-Pめっき層を形成し、該電解Ni-Pめっき層上に主めっき層を形成することにより、腐食を防止または抑制し、接続信頼性を向上させることができる電子部品を製造することができる。
According to the method of manufacturing an electronic component of the present invention, an electrolytic Ni—P plating layer is formed on a surface portion of the conductive member of an electronic component including at least a conductive member, and a main plating layer is formed on the electrolytic Ni—P plating layer. By forming, it is possible to manufacture an electronic component capable of preventing or suppressing corrosion and improving connection reliability.
次に、本発明の電子部品の実施形態について図面を参照しながら説明する。図1は、電子部品の一例として、一般的なコンタクトを示したものであり、図2は、図1のI-I線上の断面を示す模式図である。
Next, an embodiment of an electronic component according to the present invention will be described with reference to the drawings. FIG. 1 shows a general contact as an example of an electronic component, and FIG. 2 is a schematic diagram showing a cross section taken along line II of FIG.
本発明に従うコンタクト1は、図2に示すように、少なくとも導電部材2を含み、この導電材料2の表面部分に、電解Ni-Pめっき層3、および、該電解Ni-Pめっき層上に形成した主めっき層4を具え、このような構成を採用することにより、腐食を防止または抑制し、接続信頼性を向上させることを可能にしたものである。また、図面には示されないが、より腐食を防止または抑制するために、前記主めっき層4上には、例えばカルボン酸系やチオール系の防錆処理液を用いた防錆処理により形成した防錆皮膜層を具えるのが好ましい。
As shown in FIG. 2, the contact 1 according to the present invention includes at least a conductive member 2 and is formed on the surface portion of the conductive material 2 on the electrolytic Ni—P plating layer 3 and on the electrolytic Ni—P plating layer. The main plating layer 4 is provided, and by adopting such a configuration, corrosion can be prevented or suppressed and connection reliability can be improved. Although not shown in the drawings, in order to prevent or suppress corrosion, the anti-corrosion treatment formed on the main plating layer 4 by, for example, a rust prevention treatment using a carboxylic acid-type or thiol-type anti-rust treatment solution. It is preferable to provide a rust coating layer.
前記導電材料2は、銅または銅合金からなるのが好ましく、例えば、リン青銅、ベリリウム銅、黄銅または純銅からなるが、耐食性のみを考慮する場合、リン青銅からなるのがより好ましい。
The conductive material 2 is preferably made of copper or a copper alloy, and is made of, for example, phosphor bronze, beryllium copper, brass or pure copper, but more preferably made of phosphor bronze when considering only corrosion resistance.
前記主めっき層4は、Au含有物、Ag含有物、Pd含有物、Pd-Ni、SnおよびSn系合金めっきのいずれかからなるのが好ましい。接触安定性、耐食性、はんだぬれ性が良好のためである。また、特に耐食性において非常に良好という点から、前記主めっき層4は、Au含有物からなるのがより好ましい。
The main plating layer 4 is preferably made of any of an Au-containing material, an Ag-containing material, a Pd-containing material, Pd—Ni, Sn, and Sn-based alloy plating. This is because the contact stability, corrosion resistance, and solder wettability are good. Further, the main plating layer 4 is more preferably made of an Au-containing material from the viewpoint that the corrosion resistance is very good.
前記電解Ni-Pめっき層3のP濃度は、5.0質量%以上であるのが好ましい。前記P濃度が5.0質量%未満だと、耐食性が低下するおそれがあるためである。また、前記P濃度が18質量%を超えると、延性に乏しくなり、クラックなどの割れが発生するおそれがあるため、18質量%以下とするのがより好ましい。
The P concentration of the electrolytic Ni—P plating layer 3 is preferably 5.0% by mass or more. This is because if the P concentration is less than 5.0% by mass, the corrosion resistance may decrease. Further, if the P concentration exceeds 18% by mass, the ductility becomes poor and cracks such as cracks may occur. Therefore, the P content is more preferably 18% by mass or less.
前記電解Ni-Pめっき層3の厚さは、0.1μm以上であるのが好ましい。前記厚さが0.1μm未満だと、銅合金に含まれる銅および亜鉛などの拡散により耐食性が低下するおそれがあるためである。また、前記厚さが6.0μmを超えると、延性に乏しくなり、クラックなどの割れが発生するおそれがあるため、6.0μm以下とするのがより好ましい。
The thickness of the electrolytic Ni—P plating layer 3 is preferably 0.1 μm or more. This is because if the thickness is less than 0.1 μm, corrosion resistance may decrease due to diffusion of copper and zinc contained in the copper alloy. Further, if the thickness exceeds 6.0 μm, the ductility becomes poor, and cracks such as cracks may occur. Therefore, the thickness is more preferably 6.0 μm or less.
前記主めっき層4の厚さは、主めっき層の種類にもよるが、0.07~6.0μmであるのが好ましい。例えば、主めっき層をAu含有物めっきとした場合、その厚さは、電気的信頼性が必要な部分には0.1~1.0μm程度、はんだ付けの信頼性が必要な部分には0.07~0.20μm程度とするのが望ましい。また、主めっき層4をPd含有物またはPd-Niめっきとした場合においても、同様に考えることができる。また、耐食性を向上させるため、前記AuまたはPdめっきからなる主めっき層の厚さが1.0μmを超えるものとすることもできるが、コスト面を考慮すると、0.1~1.0μmの範囲とするのがより好ましい。一方、Ag含有物、SnおよびSn系合金めっきにおいては、良好な電気的信頼性やはんだ付け信頼性を確保するため、2.0~6.0μmの厚さとするのが好ましい。
The thickness of the main plating layer 4 is preferably 0.07 to 6.0 μm although it depends on the type of the main plating layer. For example, when the main plating layer is made of an Au-containing material, the thickness is about 0.1 to 1.0 μm for a portion requiring electrical reliability, and 0 for a portion requiring soldering reliability. It is desirable that the thickness is about 07 to 0.20 μm. The same can be considered when the main plating layer 4 is made of Pd-containing material or Pd—Ni plating. In order to improve the corrosion resistance, the thickness of the main plating layer made of Au or Pd plating may be more than 1.0 μm. However, in consideration of cost, it is in the range of 0.1 to 1.0 μm. Is more preferable. On the other hand, in the Ag-containing material, Sn and Sn-based alloy plating, the thickness is preferably 2.0 to 6.0 μm in order to ensure good electrical reliability and soldering reliability.
前記電解Ni-Pめっき層3は、例えばワット浴またはスルファミン浴を用いた電解めっき法により形成されることができる。特に、ワット浴に亜リン酸を添加した硫酸をベースとする浴を用いた電解めっき法により形成されるのが好ましい。結晶が緻密で、かつ表面活性度が高く、上層のAuのような主めっき層との界面反応性が良い層を形成することができるためである。
The electrolytic Ni—P plating layer 3 can be formed by, for example, an electrolytic plating method using a watt bath or a sulfamine bath. In particular, it is preferably formed by an electrolytic plating method using a bath based on sulfuric acid obtained by adding phosphorous acid to a Watt bath. This is because it is possible to form a layer in which the crystal is dense and the surface activity is high and the interface reactivity with the main plating layer such as Au is good.
次に、本発明の電子部品の製造方法の実施形態について説明する。図2に示すように、本発明に従う電子部品の一例であるコンタクト1の製造方法は、少なくとも導電部材を含むコンタクト1の、導電材料2の表面部分に、電解Ni-Pめっき層3を形成し、該電解Ni-Pめっき層3上に主めっき層4を形成し、このような構成を採用することにより、腐食を防止または抑制し、接続信頼性を向上させることができる電子部品を提供することを可能にしたものである。
Next, an embodiment of an electronic component manufacturing method according to the present invention will be described. As shown in FIG. 2, the manufacturing method of the contact 1, which is an example of the electronic component according to the present invention, forms the electrolytic Ni—P plating layer 3 on the surface portion of the conductive material 2 of the contact 1 including at least the conductive member. By providing the main plating layer 4 on the electrolytic Ni—P plating layer 3 and adopting such a configuration, an electronic component capable of preventing or suppressing corrosion and improving connection reliability is provided. That made it possible.
前記主めっき層4は、Au含有物、Ag含有物、Pd含有物、Pd-Ni、SnおよびSn系合金めっきのいずれかからなるのが好ましい。接触安定性、耐食性、はんだぬれ性が良好のためである。また、特に耐食性において非常に良好という点から、前記主めっき層4は、Auからなるのがより好ましい。
The main plating layer 4 is preferably made of any of an Au-containing material, an Ag-containing material, a Pd-containing material, Pd—Ni, Sn, and Sn-based alloy plating. This is because the contact stability, corrosion resistance, and solder wettability are good. In addition, the main plating layer 4 is more preferably made of Au, particularly in terms of very good corrosion resistance.
前記電解Ni-Pめっき層3は、pH:2.4~2.8、浴温:50~65℃の硫酸ベース浴で、電流密度:0.1~20A/dm2で陰極電解することにより形成されるのが好ましい。前記pHが2.4未満だと、電流効率の低下およびリン含有率が18質量%を超えるおそれがあり、2.8を超えると、密着不良およびリン含有率が2.0質量%を下回るおそれがあるためである。また、前記浴温が50℃未満だと、電流効率の低下およびリン含有率が18質量%を超えるおそれがあり、65℃を超えるとリン含有率が2.0質量%を下回るおそれがあり、さらに、前記電流密度が0.1A/dm2未満だと、リン含有率が18質量%を超えるおそれがあり、20A/dm2を超えると、リン含有率が2.0質量%を下回るおそれがあるためである。
The electrolytic Ni—P plating layer 3 is cathodic electrolyzed at a current density of 0.1 to 20 A / dm 2 in a sulfuric acid base bath having a pH of 2.4 to 2.8 and a bath temperature of 50 to 65 ° C. Preferably it is formed. If the pH is less than 2.4, the current efficiency may decrease and the phosphorus content may exceed 18% by mass. If the pH exceeds 2.8, poor adhesion and the phosphorus content may be less than 2.0% by mass. Because there is. Further, if the bath temperature is less than 50 ° C., the current efficiency may decrease and the phosphorus content may exceed 18% by mass, and if it exceeds 65 ° C., the phosphorus content may be less than 2.0% by mass, Furthermore, if the current density is less than 0.1 A / dm 2 , the phosphorus content may exceed 18% by mass, and if it exceeds 20 A / dm 2 , the phosphorus content may be less than 2.0% by mass. Because there is.
前記硫酸ベース浴の組成は少なくとも、金属ニッケルイオン(Ni2+):10~20g/l、亜リン酸25~250g/lを含有するのが好ましい。前記金属ニッケルイオンが10g/l未満だと、リン含有率が高くなるためにクラックが発生し易くなるおそれがあり、20g/lを超えると、リン含有率が低くなるために耐食性が悪くなるおそれがあるためである。また、前記亜リン酸が25g/l未満だと、リン含有率が2.0質量%を下回るおそれがあり、250g/lを超えると、リン含有率が18質量%を超えるおそれがあるためである。このような組成条件を満たすものとしては、例えば、上村工業株式会社製の硫酸ベース浴またはアトテックジャパン株式会社製の硫酸ベース浴等が挙げられる。
The composition of the sulfuric acid base bath preferably contains at least metal nickel ions (Ni 2+ ): 10 to 20 g / l and phosphorous acid 25 to 250 g / l. If the metal nickel ion is less than 10 g / l, the phosphorus content is high, so that cracks are likely to occur, and if it exceeds 20 g / l, the phosphorus content is low and corrosion resistance may be deteriorated. Because there is. In addition, if the phosphorous acid is less than 25 g / l, the phosphorus content may be less than 2.0% by mass, and if it exceeds 250 g / l, the phosphorus content may exceed 18% by mass. is there. As what satisfies such a composition condition, for example, a sulfuric acid base bath manufactured by Uemura Kogyo Co., Ltd. or a sulfuric acid base bath manufactured by Atotech Japan Co., Ltd. may be mentioned.
前記硫酸ベース浴の組成および条件は、一例として、下記に示すような組成とすることができる。
金属ニッケルイオン:12.5g/l
亜リン酸 :130g/l
浴温 :60℃
pH :2.5
電流密度 :10A/dm2 As an example, the composition and conditions of the sulfuric acid base bath can be set as follows.
Metallic nickel ion: 12.5 g / l
Phosphorous acid: 130 g / l
Bath temperature: 60 ° C
pH: 2.5
Current density: 10 A / dm 2
金属ニッケルイオン:12.5g/l
亜リン酸 :130g/l
浴温 :60℃
pH :2.5
電流密度 :10A/dm2 As an example, the composition and conditions of the sulfuric acid base bath can be set as follows.
Metallic nickel ion: 12.5 g / l
Phosphorous acid: 130 g / l
Bath temperature: 60 ° C
pH: 2.5
Current density: 10 A / dm 2
また、腐食を防止または抑制するため、前記主めっき層4上には、例えばカルボン酸系やスルホン酸系の防錆処理液を用いた防錆処理を施すのが好ましい。前記防錆処理は、例えば浸漬処理法または電解処理法により行う。前記浸漬処理法は、被処理物を処理液に浸漬させることにより防錆皮膜層を形成する方法であり、電解処理法は、被処理物を処理液に浸漬させた後、さらに所定の電圧を印加して極性を与え、防錆皮膜層の形成を促進させる方法である。後者の電解処理法は、被処理物に応じて印加する電圧の条件を選択する必要があることから、本発明では、比較的防錆皮膜層の形成が容易な浸漬処理法を用いるのが好ましい。
Further, in order to prevent or suppress corrosion, it is preferable to subject the main plating layer 4 to a rust prevention treatment using, for example, a carboxylic acid or sulfonic acid rust prevention treatment liquid. The rust prevention treatment is performed, for example, by an immersion treatment method or an electrolytic treatment method. The immersion treatment method is a method of forming a rust-preventing film layer by immersing the object to be treated in the treatment liquid, and the electrolytic treatment method further comprises applying a predetermined voltage after immersing the object to be treated in the treatment liquid. This is a method of applying polarity to promote the formation of a rust preventive film layer. In the latter electrolytic treatment method, it is necessary to select the condition of the voltage to be applied according to the object to be treated. Therefore, in the present invention, it is preferable to use an immersion treatment method in which formation of a rust-proof coating layer is relatively easy. .
なお、図1および図2は、代表的な実施形態の例を示したものであって、本発明はこの実施形態に限定されるものではなく、さらに、図3、図4および図5に一例としてそれぞれ示されるように、前記電子部品は、例えばシェル、シールドケースおよび固定具等にも適用することができる。当然、上述したコンタクト、シェル、シールドケースや固定具等を含むコネクタについても、前記電子部品に含まれることは言うまでもない。
1 and 2 show an example of a typical embodiment, and the present invention is not limited to this embodiment. Further, an example is shown in FIG. 3, FIG. 4, and FIG. As shown respectively, the electronic component can be applied to, for example, a shell, a shield case, and a fixture. Of course, it goes without saying that the connector including the above-described contact, shell, shield case, fixture and the like is also included in the electronic component.
(実施例)
試料1は、導電部材がリン青銅からなり、接点部を有するコンタクトの少なくとも前記接点部に対応するリン青銅の表面部分に、pH:2.5、浴温:60℃の硫酸ベース浴で、電流密度:10A/dm2で陰極電解することにより、P濃度が12質量%の電解Ni-Pめっき層(層厚:1.20μm)を形成し、この電解Ni-Pめっき層上にAu層(層厚:0.85μm)を形成した。前記浴の組成は次のとおりである。
[浴組成]
金属ニッケル:12.5g/l
亜リン酸:130g/l (Example)
Sample 1 is a sulfuric acid base bath having a pH of 2.5 and a bath temperature of 60 ° C. on a surface portion of phosphor bronze corresponding to the contact portion of a contact having a contact portion made of phosphor bronze. By performing cathodic electrolysis at 10 A / dm 2 , an electrolytic Ni—P plating layer (layer thickness: 1.20 μm) having a P concentration of 12% by mass was formed, and an Au layer (layer thickness: 0.85 μm) was formed. The composition of the bath is as follows.
[Bath composition]
Metallic nickel: 12.5g / l
Phosphorous acid: 130 g / l
試料1は、導電部材がリン青銅からなり、接点部を有するコンタクトの少なくとも前記接点部に対応するリン青銅の表面部分に、pH:2.5、浴温:60℃の硫酸ベース浴で、電流密度:10A/dm2で陰極電解することにより、P濃度が12質量%の電解Ni-Pめっき層(層厚:1.20μm)を形成し、この電解Ni-Pめっき層上にAu層(層厚:0.85μm)を形成した。前記浴の組成は次のとおりである。
[浴組成]
金属ニッケル:12.5g/l
亜リン酸:130g/l (Example)
[Bath composition]
Metallic nickel: 12.5g / l
Phosphorous acid: 130 g / l
電解Ni-Pめっき層上にそれぞれPd層(膜厚:0.20μmまたは0.85μm)を形成したこと以外は、試料1と同様の方法により試料2および試料3を形成した。
前記電解Ni-Pめっき層上にそれぞれSn-Ag層(膜厚:2.00μmまたは5.00μm)を形成したこと以外は、試料1と同様の方法により試料4および試料5を形成した。Sample 2 and Sample 3 were formed by the same method as Sample 1 except that a Pd layer (film thickness: 0.20 μm or 0.85 μm) was formed on the electrolytic Ni—P plating layer, respectively.
Samples 4 and 5 were formed by the same method as Sample 1, except that Sn—Ag layers (film thickness: 2.00 μm or 5.00 μm) were formed on the electrolytic Ni—P plating layer, respectively.
前記電解Ni-Pめっき層上にそれぞれSn-Ag層(膜厚:2.00μmまたは5.00μm)を形成したこと以外は、試料1と同様の方法により試料4および試料5を形成した。
P濃度がそれぞれ4.5, 5.0, 6.0, 8.0, 10, 15質量%の電解Ni-Pめっき層(層厚:1.20μm)を形成したこと以外は、試料1と同様の方法により試料6、7、8、9、10,および11をそれぞれ形成した。
Samples 6 and 7 were prepared in the same manner as Sample 1, except that electrolytic Ni—P plating layers (layer thickness: 1.20 μm) with P concentrations of 4.5, 5.0, 6.0, 8.0, 10, and 15% by mass were formed, respectively. 8, 9, 10, and 11 were formed, respectively.
電解Ni-Pめっき層の層厚をそれぞれ0.05, 0.10, 0.50, 2.00, 5.00μmとしたこと以外は、試料1と同様の方法により試料12、13、14、15および16を形成した。
Samples 12, 13, 14, 15 and 16 were formed by the same method as Sample 1 except that the thickness of the electrolytic Ni—P plating layer was 0.05, 0.10, 0.50, 2.00 and 5.00 μm, respectively.
Au層の層厚をそれぞれ0.10, 0.20, 0.40, 1.00μmとしたこと以外は、試料1と同様の方法により試料17、18、19、および20を形成した。
Samples 17, 18, 19, and 20 were formed in the same manner as Sample 1, except that the thickness of the Au layer was 0.10, 0.24, 0.40, and 1.00 μm, respectively.
Au層上に、チオール系の防錆処理液を用いた防錆処理により形成した防錆皮膜層(数十Å)を形成したこと以外は、それぞれ試料17、18、19、および20と同様の方法により試料21、22、23、および24をそれぞれ形成した。
Except that a rust preventive film layer (several tens of thousands) formed by rust prevention treatment using a thiol-based rust prevention treatment liquid was formed on the Au layer, the same as Samples 17, 18, 19, and 20, respectively. Samples 21, 22, 23, and 24 were formed by the method.
導電部材がそれぞれ純銅、黄銅、ベリリウム銅、コルソン銅であること以外は、試料1と同様の方法により試料25、26、27および28を形成した。
Samples 25, 26, 27, and 28 were formed by the same method as Sample 1, except that the conductive members were pure copper, brass, beryllium copper, and Corson copper, respectively.
(比較例)
pH:2.5、浴温:50℃の硫酸ベース浴で、電流密度:10A/dm2で陰極電解することにより、電解Niめっき層(層厚:1.20μm)を形成したこと以外は、試料1と同様の方法により試料29を形成した。 (Comparative example)
Sample 1 except that an electrolytic Ni plating layer (layer thickness: 1.20 μm) was formed by cathodic electrolysis at a current density of 10 A / dm 2 in a sulfuric acid base bath with a pH of 2.5 and a bath temperature of 50 ° C. Sample 29 was formed by the same method.
pH:2.5、浴温:50℃の硫酸ベース浴で、電流密度:10A/dm2で陰極電解することにより、電解Niめっき層(層厚:1.20μm)を形成したこと以外は、試料1と同様の方法により試料29を形成した。 (Comparative example)
pH:2.5、浴温:50℃の硫酸ベース浴で、電流密度:10A/dm2で陰極電解することにより、電解Niめっき層(層厚:2.00μm)を形成したこと以外は、試料15と同様の方法により試料30を形成した。
Sample 15 except that an electrolytic Ni plating layer (layer thickness: 2.00 μm) was formed by cathodic electrolysis at a current density of 10 A / dm 2 in a sulfuric acid base bath with a pH of 2.5 and a bath temperature of 50 ° C. Sample 30 was formed by the same method.
それぞれpH:2.5、浴温:50℃の硫酸ベース浴で、電流密度:10A/dm2で陰極電解することにより、電解Niめっき層(層厚:1.20μm)を形成したこと以外は、試料25、26、27および28と同様の方法により試料31、32、33および34を形成した。
Sample 25 except that an electrolytic Ni plating layer (layer thickness: 1.20 μm) was formed by cathodic electrolysis at a current density of 10 A / dm 2 in a sulfuric acid base bath of pH 2.5 and bath temperature 50 ° C., respectively. Samples 31, 32, 33, and 34 were formed by the same method as that of No. 26, 27, and 28.
それぞれpH:2.5、浴温:50℃の硫酸ベース浴で、電流密度:10A/dm2で陰極電解することにより、電解Niめっき層(層厚:1.20μm)を形成したこと以外は、試料17、19および20と同様の方法により試料35、36および37を形成した。
Sample 17 except that an electrolytic Ni plating layer (layer thickness: 1.20 μm) was formed by cathodic electrolysis at a current density of 10 A / dm 2 in a sulfuric acid base bath each having a pH of 2.5 and a bath temperature of 50 ° C. Samples 35, 36 and 37 were formed by the same method as in FIGS.
それぞれpH:2.5、浴温:50℃の硫酸ベース浴で、電流密度:10A/dm2で陰極電解することにより、電解Niめっき層(層厚:1.20μm)を形成したこと以外は、試料21、22、23および24と同様の方法により試料38、39、40および41を形成した。
Sample 21 except that an electrolytic Ni plating layer (layer thickness: 1.20 μm) was formed by cathodic electrolysis at a current density of 10 A / dm 2 in a sulfuric acid-based bath having a pH of 2.5 and a bath temperature of 50 ° C., respectively. Samples 38, 39, 40, and 41 were formed in the same manner as in FIGS.
pH:2.5、浴温:60℃の硫酸ベース浴で、電流密度:10A/dm2で陰極電解することにより、電解Niめっき層(層厚:1.20μm)およびその上にP濃度が10質量%の電解Ni-Pめっき層(層厚:1.20μm)を形成したこと以外は、試料10と同様の方法により試料42を形成した。
P濃度が10質量%の無電解Ni-Pめっき層(層厚:1.20μm)を形成したこと以外は、試料10と同様の方法により試料43を形成した。
pH:2.5、浴温:50℃の硫酸ベース浴で、電流密度:10A/dm2で陰極電解することにより、電解Niめっき層(層厚:1.20μm)およびその上にP濃度が10質量%の無電解Ni-Pめっき層(層厚:1.20μm)を形成したこと以外は、試料10と同様の方法により試料44を形成した。 Electrolytic Ni plating layer (layer thickness: 1.20 μm) and P concentration of 10 mass% on it by cathodic electrolysis with sulfuric acid base bath at pH: 2.5, bath temperature: 60 ° C, current density: 10A / dm 2 Sample 42 was formed by the same method as Sample 10 except that the electrolytic Ni—P plating layer (layer thickness: 1.20 μm) was formed.
Sample 43 was formed by the same method as Sample 10, except that an electroless Ni—P plating layer (layer thickness: 1.20 μm) with a P concentration of 10 mass% was formed.
Electrolytic Ni plating layer (layer thickness: 1.20 μm) and P concentration of 10 mass% on it by cathodic electrolysis with sulfuric acid base bath at pH: 2.5, bath temperature: 50 ° C, current density: 10A / dm 2 Sample 44 was formed by the same method as Sample 10, except that the electroless Ni—P plating layer (layer thickness: 1.20 μm) was formed.
P濃度が10質量%の無電解Ni-Pめっき層(層厚:1.20μm)を形成したこと以外は、試料10と同様の方法により試料43を形成した。
pH:2.5、浴温:50℃の硫酸ベース浴で、電流密度:10A/dm2で陰極電解することにより、電解Niめっき層(層厚:1.20μm)およびその上にP濃度が10質量%の無電解Ni-Pめっき層(層厚:1.20μm)を形成したこと以外は、試料10と同様の方法により試料44を形成した。 Electrolytic Ni plating layer (layer thickness: 1.20 μm) and P concentration of 10 mass% on it by cathodic electrolysis with sulfuric acid base bath at pH: 2.5, bath temperature: 60 ° C, current density: 10A / dm 2 Sample 42 was formed by the same method as Sample 10 except that the electrolytic Ni—P plating layer (layer thickness: 1.20 μm) was formed.
Sample 43 was formed by the same method as Sample 10, except that an electroless Ni—P plating layer (layer thickness: 1.20 μm) with a P concentration of 10 mass% was formed.
Electrolytic Ni plating layer (layer thickness: 1.20 μm) and P concentration of 10 mass% on it by cathodic electrolysis with sulfuric acid base bath at pH: 2.5, bath temperature: 50 ° C, current density: 10A / dm 2 Sample 44 was formed by the same method as Sample 10, except that the electroless Ni—P plating layer (layer thickness: 1.20 μm) was formed.
それぞれpH:2.5、浴温:50℃の硫酸ベース浴で、電流密度:10A/dm2で陰極電解することにより、電解Niめっき層(層厚:1.20μm)を形成したこと以外は、試料2、3、4および5と同様の方法により試料45、46、47および48を形成した。
Sample 2 except that an electrolytic Ni plating layer (layer thickness: 1.20 μm) was formed by cathodic electrolysis at a current density of 10 A / dm 2 in a sulfuric acid-based bath with a pH of 2.5 and a bath temperature of 50 ° C., respectively. Samples 45, 46, 47 and 48 were formed in the same manner as in 3, 4, and 5.
(評価)
これら試料1~48について、マイクロスコープ(光学顕微鏡)を用いた外観観察および集束イオンビーム加工装置(FIB)を用いた断面観察の結果を図6~図17に示し、これらの評価およびコスト評価ならびにこれらの総合評価を表1に示す。なお、例えば、図6(a)~図6(e)において、図6(a)の左が外観観察の写真を示し、右が断面観察の写真を示すのに対し、図6(b)のように写真が1つしかないものは、全て外観観察の写真を示したものである。
評価基準は次の通りである。
外観観察
◎:1つの腐食物の径が0.5mm以下、または連なった腐食物同士の径が0.5mm以下
○:1つの腐食物の径が0.5mm超え0.8mm以下、または連なった腐食物同士の径が0.5mm超え0.8mm以下
×:1つの腐食物の径が0.8mm超え、または連なった腐食物同士の径が0.8mm超え
FIB断面観察
◎:下地めっき層がすべて非晶質であるもの
○:下地めっき層が一部非晶質でないもの
×:下地めっき層がすべて非晶質でないもの
コスト評価
主めっき層がAuやPd等の貴金属である場合は、
○:主めっき層の層厚が0.2μm以下で、かつ下地めっき層の層厚が2μm未満のもの
×:主めっき層の層厚が0.2μmを超えるもの、
または、主めっき層の層厚が0.2μm以下で、かつ、下地めっき層の層厚が2μm以上のもの
主めっき層がSn系めっきである場合は、
○:下地めっき層の層厚が2μm未満のもの
×:下地めっき層の層厚が2μm以上のもの (Evaluation)
For thesesamples 1 to 48, the results of external observation using a microscope (optical microscope) and cross-sectional observation using a focused ion beam processing apparatus (FIB) are shown in FIG. 6 to FIG. These comprehensive evaluations are shown in Table 1. For example, in FIGS. 6 (a) to 6 (e), the left of FIG. 6 (a) shows a photograph of appearance observation, and the right shows a photograph of cross-sectional observation, whereas FIG. 6 (b). As described above, all photographs having only one photograph are photographs of external appearance observation.
The evaluation criteria are as follows.
Appearance observation ◎: The diameter of one corrosive is 0.5mm or less, or the diameter of the corroded corrodes is 0.5mm or less ○: The diameter of one corrosive is 0.5mm to 0.8mm or less, Diameter: 0.5mm to 0.8mm or less ×: The diameter of one corroded material exceeds 0.8mm, or the diameter of the corroded corroded materials exceeds 0.8mm. FIB cross-sectional observation ◎: The base plating layer is all amorphous ○ : The base plating layer is not partly amorphous ×: The base plating layer is not all amorphous Cost evaluation When the main plating layer is a noble metal such as Au or Pd,
○: The thickness of the main plating layer is 0.2 μm or less and the thickness of the base plating layer is less than 2 μm. ×: The thickness of the main plating layer exceeds 0.2 μm.
Or, when the main plating layer thickness is 0.2 μm or less and the base plating layer thickness is 2 μm or more, when the main plating layer is Sn-based plating,
○: Thickness of the base plating layer is less than 2 μm ×: Thickness of the base plating layer is 2 μm or more
これら試料1~48について、マイクロスコープ(光学顕微鏡)を用いた外観観察および集束イオンビーム加工装置(FIB)を用いた断面観察の結果を図6~図17に示し、これらの評価およびコスト評価ならびにこれらの総合評価を表1に示す。なお、例えば、図6(a)~図6(e)において、図6(a)の左が外観観察の写真を示し、右が断面観察の写真を示すのに対し、図6(b)のように写真が1つしかないものは、全て外観観察の写真を示したものである。
評価基準は次の通りである。
外観観察
◎:1つの腐食物の径が0.5mm以下、または連なった腐食物同士の径が0.5mm以下
○:1つの腐食物の径が0.5mm超え0.8mm以下、または連なった腐食物同士の径が0.5mm超え0.8mm以下
×:1つの腐食物の径が0.8mm超え、または連なった腐食物同士の径が0.8mm超え
FIB断面観察
◎:下地めっき層がすべて非晶質であるもの
○:下地めっき層が一部非晶質でないもの
×:下地めっき層がすべて非晶質でないもの
コスト評価
主めっき層がAuやPd等の貴金属である場合は、
○:主めっき層の層厚が0.2μm以下で、かつ下地めっき層の層厚が2μm未満のもの
×:主めっき層の層厚が0.2μmを超えるもの、
または、主めっき層の層厚が0.2μm以下で、かつ、下地めっき層の層厚が2μm以上のもの
主めっき層がSn系めっきである場合は、
○:下地めっき層の層厚が2μm未満のもの
×:下地めっき層の層厚が2μm以上のもの (Evaluation)
For these
The evaluation criteria are as follows.
Appearance observation ◎: The diameter of one corrosive is 0.5mm or less, or the diameter of the corroded corrodes is 0.5mm or less ○: The diameter of one corrosive is 0.5mm to 0.8mm or less, Diameter: 0.5mm to 0.8mm or less ×: The diameter of one corroded material exceeds 0.8mm, or the diameter of the corroded corroded materials exceeds 0.8mm. FIB cross-sectional observation ◎: The base plating layer is all amorphous ○ : The base plating layer is not partly amorphous ×: The base plating layer is not all amorphous Cost evaluation When the main plating layer is a noble metal such as Au or Pd,
○: The thickness of the main plating layer is 0.2 μm or less and the thickness of the base plating layer is less than 2 μm. ×: The thickness of the main plating layer exceeds 0.2 μm.
Or, when the main plating layer thickness is 0.2 μm or less and the base plating layer thickness is 2 μm or more, when the main plating layer is Sn-based plating,
○: Thickness of the base plating layer is less than 2 μm ×: Thickness of the base plating layer is 2 μm or more
表1に示すように、試料1~28は、試料29~48と比較して、耐食性が向上していることがわかる。
As shown in Table 1, it can be seen that Samples 1 to 28 have improved corrosion resistance compared to Samples 29 to 48.
本発明の電子部品は、少なくとも導電部材を含み、前記導電部材の表面部分に、電解Ni-Pめっき層および該電解Ni-Pめっき層上に形成した主めっき層を具えることにより、腐食を防止または抑制し、接続信頼性を向上させることができる。
The electronic component of the present invention includes at least a conductive member, and has an electrolytic Ni—P plating layer and a main plating layer formed on the electrolytic Ni—P plating layer on the surface portion of the conductive member, thereby preventing corrosion. It is possible to prevent or suppress and improve connection reliability.
本発明の電子部品の製造方法は、少なくとも導電部材を含む電子部品の、前記導電部材の表面部分に、電解Ni-Pめっき層を形成し、該電解Ni-Pめっき層上に主めっき層を形成することにより、腐食を防止または抑制し、接続信頼性を向上させることができる電子部品を製造することができる。
According to the method of manufacturing an electronic component of the present invention, an electrolytic Ni—P plating layer is formed on a surface portion of the conductive member of an electronic component including at least a conductive member, and a main plating layer is formed on the electrolytic Ni—P plating layer. By forming, it is possible to manufacture an electronic component capable of preventing or suppressing corrosion and improving connection reliability.
1 コンタクト
2 導電材料
3 電解Ni-Pめっき層
4 主めっき層 1Contact 2 Conductive Material 3 Electrolytic Ni-P Plating Layer 4 Main Plating Layer
2 導電材料
3 電解Ni-Pめっき層
4 主めっき層 1
Claims (11)
- 少なくとも導電部材を含む電子部品であって、前記導電部材の表面部分に、下地めっき層および該下地めっき層上に形成した主めっき層を具える電子部品において、
前記下地めっき層が、電解Ni-Pめっき層であることを特徴とする電子部品。 In an electronic component including at least a conductive member, the electronic component including a base plating layer and a main plating layer formed on the base plating layer on a surface portion of the conductive member,
An electronic component, wherein the base plating layer is an electrolytic Ni-P plating layer. - 前記主めっき層が、Au含有物、Ag含有物、Pd含有物、Pd-Ni、SnおよびSn系合金めっきのいずれかからなる請求項1に記載の電子部品。 The electronic component according to claim 1, wherein the main plating layer is made of any one of Au-containing material, Ag-containing material, Pd-containing material, Pd-Ni, Sn and Sn-based alloy plating.
- 前記電解Ni-Pめっき層のP濃度が、5.0質量%以上である請求項1または2に記載の電子部品。 The electronic component according to claim 1 or 2, wherein the electrolytic Ni-P plating layer has a P concentration of 5.0 mass% or more.
- 前記電解Ni-Pめっき層の厚さが、0.1μm以上である請求項1、2または3に記載の電子部品。 The electronic component according to claim 1, 2, or 3, wherein the thickness of the electrolytic Ni-P plating layer is 0.1 µm or more.
- 前記主めっき層の厚さが、0.07~6.0μmである請求項1~4のいずれか一項に記載の電子部品。 5. The electronic component according to claim 1, wherein the main plating layer has a thickness of 0.07 to 6.0 μm.
- 前記電解Ni-Pめっき層が、硫酸をベースとする浴を用いて形成される請求項1~5のいずれか一項に記載の電子部品。 The electronic component according to any one of claims 1 to 5, wherein the electrolytic Ni-P plating layer is formed using a bath based on sulfuric acid.
- 前記主めっき層上に、防錆皮膜層をさらに有する請求項1~6のいずれか一項に記載の電子部品。 The electronic component according to any one of claims 1 to 6, further comprising a rust preventive film layer on the main plating layer.
- 前記導電材料が、銅または銅合金からなる請求項1~7のいずれか一項に記載の電子部品。 The electronic component according to any one of claims 1 to 7, wherein the conductive material is made of copper or a copper alloy.
- 少なくとも導電部材を含む電子部品の、前記導電部材の表面部分に、電解Ni-Pめっき層を形成し、該電解Ni-Pめっき層上に主めっき層を形成することを特徴とする電子部品の製造方法。 An electronic component comprising at least a conductive member, wherein an electrolytic Ni-P plating layer is formed on a surface portion of the conductive member, and a main plating layer is formed on the electrolytic Ni-P plating layer. Production method.
- 前記電解Ni-Pめっき層が、pH:2.4~2.8、浴温:50~65℃の硫酸をベースとする浴で、電流密度:0.1~20A/dm2で陰極電解することにより形成される請求項9に記載の電子部品の製造方法。 The electrolytic Ni—P plating layer is a cathodic electrolysis at a current density of 0.1 to 20 A / dm 2 in a sulfuric acid-based bath having a pH of 2.4 to 2.8 and a bath temperature of 50 to 65 ° C. The manufacturing method of the electronic component of Claim 9 formed by this.
- 前記硫酸ベース浴の組成が少なくとも、金属ニッケルイオン:10~20g/lおよび亜リン酸:25~250g/lを含有する請求項10に記載の電子部品の製造方法。 11. The method of manufacturing an electronic component according to claim 10, wherein the composition of the sulfuric acid base bath contains at least metallic nickel ions: 10 to 20 g / l and phosphorous acid: 25 to 250 g / l.
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WO2014208610A1 (en) * | 2013-06-28 | 2014-12-31 | 日本軽金属株式会社 | Conductive member |
US10164162B2 (en) | 2016-09-30 | 2018-12-25 | Nichia Corporation | Light emitting device, package for light emitting device, and method for manufacturing light emitting device |
WO2019031549A1 (en) * | 2017-08-08 | 2019-02-14 | 三菱マテリアル株式会社 | Terminal material with silver coating film, and terminal with silver coating film |
JP2019031732A (en) * | 2017-08-08 | 2019-02-28 | 三菱マテリアル株式会社 | Silver film-fitted terminal material, and silver film-fitted terminal |
JP7121881B2 (en) | 2017-08-08 | 2022-08-19 | 三菱マテリアル株式会社 | Terminal material with silver film and terminal with silver film |
US11530490B2 (en) | 2017-08-08 | 2022-12-20 | Mitsubishi Materials Corporation | Terminal material with silver coating film and terminal with silver coating film |
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