JP2001131774A - Method of forming plated layer of silver-tin alloy - Google Patents
Method of forming plated layer of silver-tin alloyInfo
- Publication number
- JP2001131774A JP2001131774A JP31919799A JP31919799A JP2001131774A JP 2001131774 A JP2001131774 A JP 2001131774A JP 31919799 A JP31919799 A JP 31919799A JP 31919799 A JP31919799 A JP 31919799A JP 2001131774 A JP2001131774 A JP 2001131774A
- Authority
- JP
- Japan
- Prior art keywords
- tin
- silver
- plating
- alloy
- film
- Prior art date
- Legal status (The legal status 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 status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/021—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material including at least one metal alloy layer
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemically Coating (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、銀−錫合金めっき
層の形成方法に関する。更に詳しく述べると、本発明
は、プリント配線板や、電子部品の接合のために使用さ
れる、鉛を含まない、浴管理の容易な銀−錫合金めっき
層の形成方法に関する。The present invention relates to a method for forming a silver-tin alloy plating layer. More specifically, the present invention relates to a method for forming a lead-free silver-tin alloy plating layer that is used for joining printed wiring boards and electronic components and that is easy to manage in a bath.
【０００２】[0002]
【従来の技術】プリント配線板や、電子部品等には接合
のため、低コストで電気特性、はんだ付け性に優れたは
んだ、即ち、錫−鉛合金が広く利用されている。しかし
ながら、はんだには、鉛が多量に含まれており、鉛は、
作業環境保全や、自然環境の観点から問題視されてお
り、錫をベースとし、かつ鉛を含まない低融点合金皮膜
を被処理物上に形成する簡便な方法が望まれている。近
年、このような鉛を含有しない低融点合金皮膜を形成す
る方法として、鉛を含まない錫合金めっき液として、錫
−銀合金めっき液、錫−ビスマス合金めっき液、錫−銅
合金めっき液等を使用する方法が公知となっている。錫
−銀合金めっき液は、錫に対し銀が貴な金属であるた
め、錫イオンの酸化により銀イオンが還元され、金属化
した銀の沈殿物を生ずるため、錫−銀合金めっき浴の長
期使用が困難となるなど問題となっている。また、析出
電位が大きく異なる錫と銀とを合金として析出させるた
めに、沃化カリウムや、グルコン酸等の錯化剤を添加
し、銀の析出電位を卑なる方向に移して錫との共析を可
能とする方法があるが、低電流密度部においては、銀の
含有率が上昇する傾向にある。錫−銀の平衡状態図によ
れば、銀３．５重量％以上では、銀の含有率が高いほど
皮膜の融点が高くなる傾向にあり、プリント配線板のス
ルホール部分では、電流密度が低くなるため、銀の含有
量が上昇し、はんだ濡れ性が低下する問題がある。ま
た、錯化剤の添加によって析出電位が卑に移行すると、
電流効率が低下する恐れがあり、更に、錯化剤が排水処
理への大きな負担にもなる。2. Description of the Related Art A low-cost solder excellent in electrical characteristics and solderability, that is, a tin-lead alloy, is widely used for bonding to a printed wiring board, an electronic component and the like. However, solder contains a large amount of lead, and lead is
It is regarded as a problem from the viewpoints of working environment preservation and natural environment, and a simple method of forming a tin-based, lead-free low-melting alloy film on a workpiece is desired. In recent years, as a method for forming such a lead-free low melting point alloy film, tin-silver alloy plating solution, tin-bismuth alloy plating solution, tin-copper alloy plating solution, etc. Methods for using are known. Since the tin-silver alloy plating solution is a metal in which silver is noble with respect to tin, silver ions are reduced by oxidation of tin ions and metalized silver precipitates are generated. There are problems such as difficulty in use. Further, in order to deposit tin and silver as alloys having greatly different deposition potentials, a complexing agent such as potassium iodide or gluconic acid is added, and the deposition potential of silver is shifted to a lower direction to coexist with tin. Although there is a method that enables the precipitation, the silver content tends to increase in the low current density portion. According to the tin-silver equilibrium diagram, above 3.5% by weight of silver, the melting point of the coating tends to increase as the silver content increases, and the current density decreases in the through-hole portion of the printed wiring board. Therefore, there is a problem that the silver content increases and the solder wettability decreases. Also, when the precipitation potential shifts to a lower value due to the addition of the complexing agent,
Current efficiency may be reduced, and the complexing agent also imposes a heavy burden on wastewater treatment.
【０００３】一方、錫−ビスマス合金めっき液中のビス
マス、錫−銅合金めっき液中の銅は、錫に対する析出電
位が銀よりも近いため、錫−銀合金めっき液よりも浴の
安定性に優れており、各電流密度におけるビスマス又は
銅の含有率も変動が少ない。更に、錯化剤の添加も不要
であるか、又は添加量を抑えることができるため、析出
効率の低下も少なく、廃液処理への負担も低減できる。
更に、錫−銀合金皮膜は、皮膜接合強度等の特性が優れ
ているため、電子部品や、プリント配線基板用の接合材
料として最も有望である。それに対して、錫−ビスマス
合金皮膜の特性は、非常に脆いという欠点があり、錫−
銅合金皮膜は融点が高いため、この皮膜をめっきした電
子部品をプリント配線板に実装する場合、加熱温度が高
くなると、電子部品及びプリント配線板に熱ダメージを
与える恐れがある。ところで、これら錫−ビスマス合金
皮膜及び錫−銅合金皮膜の上記問題点は、銀を、その皮
膜中に析出させることにより、錫−銀合金めっき皮膜よ
りも優れた性能を示すことが知られているが、錫と銀と
が同一めっき液内に存在する合金めっき浴は、不安定で
あり、錫と銀とビスマス又は銅とを同一めっき液内に添
加した３元合金めっき浴も不安定であると共に、管理が
非常に煩雑であり、実用的ではない。[0003] On the other hand, bismuth in a tin-bismuth alloy plating solution and copper in a tin-copper alloy plating solution have a closer deposition potential to tin than silver, and therefore have lower bath stability than a tin-silver alloy plating solution. It is excellent, and the content of bismuth or copper at each current density also has little fluctuation. Further, since the addition of the complexing agent is unnecessary or the amount of addition can be suppressed, the reduction in the precipitation efficiency is small and the burden on the waste liquid treatment can be reduced.
Further, the tin-silver alloy film is most promising as a bonding material for electronic components and printed wiring boards because of its excellent properties such as film bonding strength. On the other hand, the tin-bismuth alloy film has the disadvantage that it is very brittle,
Since the copper alloy film has a high melting point, when an electronic component plated with this film is mounted on a printed wiring board, an increase in the heating temperature may cause thermal damage to the electronic component and the printed wiring board. By the way, it is known that the above-mentioned problems of the tin-bismuth alloy film and the tin-copper alloy film show higher performance than the tin-silver alloy plating film by depositing silver in the film. However, an alloy plating bath in which tin and silver are present in the same plating solution is unstable, and a ternary alloy plating bath in which tin, silver and bismuth or copper are added in the same plating solution is also unstable. At the same time, management is very complicated and impractical.
【０００４】錫−銀合金、錫−ビスマス−銀合金、錫−
銅−銀合金めっき皮膜等の錫−銀系合金めっき皮膜は、
融点、接合強度等の優れた性能を示し、鉛を含有しない
ことから、錫−鉛合金めっき皮膜の代替として有望であ
るが、錫と銀との析出電位が大きく異なるため、めっき
液は、不安定であり、長期使用が困難であり、良好なめ
っき皮膜を形成するためには、非常に煩雑な浴管理が必
要になる等多くの問題を有している。[0004] Tin-silver alloy, tin-bismuth-silver alloy, tin-
Tin-silver alloy plating films such as copper-silver alloy plating films
It shows excellent performance such as melting point and bonding strength and does not contain lead, so it is a promising alternative to tin-lead alloy plating films.However, since the deposition potential of tin and silver differs greatly, plating solutions are not suitable. It is stable and difficult to use for a long period of time, and has many problems such as the necessity of extremely complicated bath management to form a good plating film.
【０００５】[0005]
【発明が解決しようとする課題】従って、本発明は、鉛
を使用することなく、浴管理が容易な、銀−錫合金めっ
き層を形成する方法を提供することを目的とする。SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a method for forming a silver-tin alloy plating layer which is easy to manage a bath without using lead.
【０００６】[0006]
【課題を解決するための手段】発明者は、上記課題を達
成するため鋭意検討した結果、金属基材上に、銀めっき
皮膜と、錫めっき皮膜、錫−ビスマス合金めっき皮膜又
は錫−銅合金めっき皮膜とを、この順序で、又はこの逆
の順序で、形成した２層めっき皮膜を、好ましくは、加
熱することにより、錫−銀合金めっき皮膜を形成できる
ことを見出し、本発明に到達したものである。即ち、本
発明は、金属基材に、（１）銀めっき皮膜、及び（２）
錫、錫−ビスマス、又は錫−銅合金めっき皮膜を、この
順序で、又はこの逆の順序で、析出させることを特徴と
する、銀−錫合金層を形成させる方法に関するものであ
る。Means for Solving the Problems As a result of intensive studies to achieve the above object, the inventors have found that a silver plating film, a tin plating film, a tin-bismuth alloy plating film or a tin-copper alloy With the plating film, in this order, or in the reverse order, the formed two-layer plating film, preferably, by heating, found that a tin-silver alloy plating film can be formed, arrived at the present invention It is. That is, according to the present invention, (1) a silver plating film, and (2)
The present invention relates to a method for forming a silver-tin alloy layer, characterized by depositing a tin, tin-bismuth or tin-copper alloy plating film in this order or vice versa.
【０００７】[0007]
【発明の実施の形態】以下、本発明について詳細に説明
する。本発明の銀−錫合金めっき層は、はんだが使用さ
れている分野において、はんだに代替するものである。
従って、そのような分野である限り、各種の金属基材に
適用することができる。具体的には、金属基材として
は、例えば、プリント配線板や、鋼板、銅合金板、それ
らのエッチング又はプレス成形体等が挙げられる。プリ
ント配線板のような有機基材と金属基板の複合基板は、
予め酸性の洗浄剤等の水性洗浄剤を用い油脂又はレジス
トの残査除去を行なう事が好ましい。この酸性の洗浄剤
としては、硫酸や、リン酸、ギ酸又はスルファミン酸の
単独又は混合物に少量の界面活性剤を加えた水溶液が使
用できる。また、その他の金属基材に対しては、予め、
有機溶剤又はアルカリ洗浄剤等の水性洗浄剤を用いて油
脂類の除去を行うことが好ましい。有機溶剤としては、
このような予備処理に使用されている溶剤であれば、各
種の溶剤を使用することができる。好ましい溶剤として
は、例えば、ＨＦＣの様な塩素を含まないフロン系溶剤
又はエタノールや、イソプロパノールをはじめとするア
ルコール系溶剤等が挙げられる。アルカリ洗浄剤として
は、例えば、苛性ソーダや、炭酸ソーダ、ケイ酸塩ソー
ダ、リン酸塩ソーダ等を、単独で又は混合物として、少
量の界面活性剤を加えた水溶液等を使用することができ
る。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The silver-tin alloy plating layer of the present invention replaces solder in the field where solder is used.
Therefore, as long as it is such a field, it can be applied to various metal base materials. Specifically, examples of the metal substrate include a printed wiring board, a steel plate, a copper alloy plate, and an etched or press-formed product thereof. Composite substrates of organic substrates and metal substrates, such as printed wiring boards,
It is preferable to remove oils and fats or resist residues in advance using an aqueous cleaning agent such as an acidic cleaning agent. As the acidic cleaning agent, an aqueous solution in which a small amount of a surfactant is added to sulfuric acid, phosphoric acid, formic acid, or sulfamic acid alone or in a mixture can be used. In addition, for other metal substrates,
It is preferable to remove oils and fats using an aqueous solvent such as an organic solvent or an alkaline cleaner. As organic solvents,
Various solvents can be used as long as they are used for such pretreatment. Preferred examples of the solvent include a chlorine-free Freon-based solvent such as HFC, ethanol, and an alcohol-based solvent such as isopropanol. As the alkaline detergent, for example, an aqueous solution to which a small amount of a surfactant is added, alone or as a mixture of sodium hydroxide, sodium carbonate, sodium silicate, sodium phosphate and the like can be used.
【０００８】また、金属基材の表面を、ブラッシング
や、ホーニング等の物理的方法により清浄化してもよ
い。金属基材は、更に、清浄化した後、希硫酸又は希塩
酸等で酸化皮膜を除去しておくことが好ましい。このよ
うにして、清浄化等の処理を行った金属基材には、ま
ず、例えば、銀めっき処理を行う。銀めっき処理は、電
気めっき処理でもよく、無電解めっき処理でもよい。こ
れらの電気又は無電解めっき処理方法としては、公知の
処理方法を採用することができる。次いで、形成された
銀めっき皮膜上には、電気めっき処理により、錫、錫−
ビスマス合金又は錫−銅合金めっきを行なう。これらの
錫、錫−ビスマス合金又は錫−銅合金めっき処理は、公
知であり、各種の条件や方法等を採用することが可能で
ある。The surface of the metal substrate may be cleaned by a physical method such as brushing or honing. After the metal substrate is further cleaned, it is preferable to remove the oxide film with dilute sulfuric acid or dilute hydrochloric acid. First, for example, a silver plating process is performed on the metal base material that has been subjected to a process such as cleaning. The silver plating may be electroplating or electroless plating. As these electric or electroless plating treatment methods, known treatment methods can be adopted. Next, on the formed silver plating film, tin, tin-
Bismuth alloy or tin-copper alloy plating is performed. These tin, tin-bismuth alloy or tin-copper alloy plating treatments are known, and various conditions and methods can be adopted.
【０００９】本発明においては、このようにして形成し
た銀めっき皮膜及び錫、錫−ビスマス合金又は錫−銅合
金めっき皮膜は、室温等において、放置することによ
り、両皮膜を構成する金属が相互に拡散し合い合金化す
ることによって、銀−錫合金めっき層が形成される。好
ましくは、両皮膜を加熱することによって、合金化を促
進することが適当である。加熱温度は、例えば、８０〜
１９０℃、好ましくは、１００〜１７０℃、処理時間
は、通常、１０分〜１０時間、好ましくは、３０分〜８
時間であることが適当である。なお、両皮膜が溶融する
場合であっても、短時間であれば、特に問題ではない。
例えば、加熱温度は、２００〜３００℃、好ましくは、
２３０〜２７０℃、処理時間は、例えば、１〜６０秒、
好ましくは、１０〜４０秒であることが適当である。In the present invention, the silver plating film and the tin, tin-bismuth alloy or tin-copper alloy plating film formed as described above are allowed to stand at room temperature or the like so that the metals constituting the two films are mutually reciprocal. The alloy is formed by diffusion and alloying. Preferably, it is appropriate to heat the two films to promote alloying. The heating temperature is, for example, 80 to
190 ° C., preferably 100 to 170 ° C., the treatment time is usually 10 minutes to 10 hours, preferably 30 minutes to 8 hours.
Time is appropriate. In addition, even if both films are melted, there is no particular problem as long as the time is short.
For example, the heating temperature is 200 to 300 ° C., preferably,
230-270 ° C, the processing time is, for example, 1-60 seconds,
Preferably, the time is 10 to 40 seconds.
【００１０】本発明においては、両めっき皮膜は、加熱
処理により合金化するため、所望の銀の含有率に応じ
て、任意の膜厚比率で両めっき皮膜を形成すればよい。
特に、合金化後の皮膜では、はんだ接合強度や、はんだ
濡れ性等を考慮すると、銀は、例えば、２〜１０質量
％、好ましくは、３〜５質量％であることが適当であ
る。また、膜厚比率は、銀めっき皮膜：錫、錫−ビスマ
ス又は錫−銅合金めっき皮膜＝１：９９〜８：９２、好
ましくは、２：９８〜４：９６であることが適当であ
る。また、めっき皮膜の膜厚は、特に限定されることは
なく、はんだ付け性の皮膜として機能し得る範囲とすれ
ばよいが、通常、銀めっき皮膜と、錫、錫−ビスマス又
は錫−銅合金めっき皮膜との両層の合計膜厚は、例え
ば、１〜２０μｍ、好ましくは、２〜１０μｍであるこ
とが適当である。In the present invention, since both plating films are alloyed by heat treatment, both plating films may be formed at an arbitrary thickness ratio according to a desired silver content.
In particular, in the film after alloying, it is appropriate that silver is, for example, 2 to 10% by mass, and preferably 3 to 5% by mass in consideration of solder bonding strength, solder wettability, and the like. Further, it is appropriate that the thickness ratio is silver plating film: tin, tin-bismuth or tin-copper alloy plating film = 1: 99 to 8:92, preferably 2:98 to 4:96. The thickness of the plating film is not particularly limited, and may be in a range that can function as a soldering film. Usually, a silver plating film, tin, tin-bismuth, or a tin-copper alloy is used. The total film thickness of both the plating film and the two layers is, for example, 1 to 20 μm, and preferably 2 to 10 μm.
【００１１】本発明は、鉛を含有しないはんだ接合材料
として、銀めっき皮膜と、錫、錫−ビスマス合金又は錫
−銅合金めっき皮膜とからなる２層のめっき皮膜を形成
し、合金化する事を目的としているが、２層のめっき皮
膜に限定されるものではなく、銀めっき皮膜と、錫、錫
−ビスマス又は錫−銅合金めっき皮膜とを交互に行い、
多層めっき皮膜を形成する場合も包含されることは容易
に理解されるところである。また、めっき層を形成する
順序としては、最下層が銀めっき皮膜である必要はない
が、最表面に錫、錫−ビスマス合金又は錫−銅合金めっ
きを施すことにより、銀の硫化又は酸化を防止すること
ができるため、錫めっき皮膜と同等以上のはんだ濡れ性
を確保することができる。According to the present invention, as a lead-free solder bonding material, a two-layer plating film composed of a silver plating film and a tin, tin-bismuth alloy or tin-copper alloy plating film is formed and alloyed. The purpose is to be not limited to the two-layer plating film, silver plating film, tin, tin-bismuth or tin-copper alloy plating film alternately performed,
It is easily understood that the case where a multilayer plating film is formed is also included. Further, as the order of forming the plating layer, the lowermost layer does not need to be a silver plating film, but tin, tin-bismuth alloy or tin-copper alloy plating is applied to the outermost surface to suppress sulfuration or oxidation of silver. Therefore, the solder wettability equal to or higher than that of the tin plating film can be secured.
【００１２】本発明では、銀めっき皮膜、錫めっき皮
膜、錫−ビスマス合金めっき皮膜及び錫−銅合金めっき
皮膜を形成するために用いるめっき液は、特に限定はな
く、従来公知のものが使用できる。具体的には、銀めっ
き液としては、銀イオン濃度１〜６０ｇ／Ｌ、好ましく
は、２〜４０ｇ／Ｌであり、シアン浴又はシアンを含有
しない液としては、チオシアン浴や、沃化物浴、チオ硫
酸浴等がある。錫めっき液では、錫イオン濃度は、例え
ば、１０〜１００ｇ／Ｌ、好ましくは、２０〜７０ｇ／
Ｌであり、メタンスルホン酸浴や、硫酸浴及び塩化物浴
がある。また、錫−ビスマス合金めっき液及び錫−銅合
金めっき液では、ビスマスイオン濃度が、０．５〜４０
ｇ／Ｌ、好ましくは、１〜３０ｇ／Ｌ、銅イオン濃度
は、０．３〜２０ｇ／Ｌ、好ましくは、０．５〜１０ｇ
／Ｌであり、メタンスルホン酸浴及び硫酸浴がある。In the present invention, the plating solution used for forming the silver plating film, the tin plating film, the tin-bismuth alloy plating film and the tin-copper alloy plating film is not particularly limited, and a conventionally known plating solution can be used. . Specifically, the silver plating solution has a silver ion concentration of 1 to 60 g / L, preferably 2 to 40 g / L, and the cyan bath or the solution containing no cyan includes a thiocyan bath, an iodide bath, Thiosulfate bath and the like. In the tin plating solution, the tin ion concentration is, for example, 10 to 100 g / L, preferably 20 to 70 g / L.
L, including a methanesulfonic acid bath, a sulfuric acid bath, and a chloride bath. In the tin-bismuth alloy plating solution and the tin-copper alloy plating solution, the bismuth ion concentration is 0.5 to 40.
g / L, preferably 1 to 30 g / L, and the copper ion concentration is 0.3 to 20 g / L, preferably 0.5 to 10 g.
/ L, with a methanesulfonic acid bath and a sulfuric acid bath.
【００１３】[0013]
【発明の効果】本発明の銀−錫合金めっき層の形成方法
は、有害な成分である鉛を使用しないため、安全性が高
い。形成された銀めっき皮膜と、錫、錫−ビスマス又は
錫−銅合金めっき皮膜とは、好ましくは、加熱処理によ
り容易に合金化し、形成される合金皮膜は、はんだ濡れ
性に優れているため、低温接合材料として有用性の高い
ものである。また、本発明の錫−銀合金めっき皮膜は、
銀めっき皮膜と、錫又は錫合金めっき皮膜の２層で作製
されるため、銀と錫、銀と錫とビスマス又は銀と錫と銅
を同一めっき液に含有する合金めっき液よりも浴の安定
性に優れ、且つ各金属含有率の安定しためっき皮膜が得
られる。The method for forming a silver-tin alloy plating layer according to the present invention does not use lead, which is a harmful component, and therefore has high safety. The formed silver plating film and the tin, tin-bismuth or tin-copper alloy plating film are preferably easily alloyed by heat treatment, and the formed alloy film has excellent solder wettability. It is highly useful as a low-temperature bonding material. Further, the tin-silver alloy plating film of the present invention,
Because it is made of two layers of silver plating film and tin or tin alloy plating film, bath is more stable than alloy plating solution containing silver and tin, silver and tin and bismuth or silver, tin and copper in the same plating solution. A plating film having excellent properties and a stable content of each metal can be obtained.
【００１４】[0014]
【実施例】実施例１ 下記の組成を有する銀めっき液及び錫めっき液を調製
し、鉄−ニッケル合金リードフレームにめっきした。銀めっき液 シアン化銀（金属銀として） ４０ｇ／Ｌ シアン化カリウム（遊離シアン化カリウムとして） ７８ｇ／Ｌ 炭酸カリウム １０ｇ／Ｌ 蒸留水 残量錫めっき液 メタンスルホン酸 １５０ｇ／Ｌ メタンスルホン酸錫（２価錫として） ２０ｇ／Ｌ ポリオキシエチレンポリオキシプロピレングリコール ２ｇ／Ｌ （エチレンオキサイド：１０ｍｏｌ、プロピレンオキサイド：４ｍｏｌ） 蒸留水 残量 EXAMPLE 1 A silver plating solution and a tin plating solution having the following compositions were prepared and plated on an iron-nickel alloy lead frame. Silver plating solution Silver cyanide (as metallic silver) 40 g / L Potassium cyanide (as free potassium cyanide) 78 g / L Potassium carbonate 10 g / L Distilled water Remaining tin plating solution Methanesulfonic acid 150 g / L Tin methanesulfonate (as tin (II) tin) ) 20 g / L polyoxyethylene polyoxypropylene glycol 2 g / L (ethylene oxide: 10 mol, propylene oxide: 4 mol) distilled water
【００１５】めっき工程 アルカリ脱脂（５Ａ／ｄｍ2、３０秒、６０℃） 水酸化ナトリウム ４０ｇ／Ｌ、 炭酸ナトリウム ２５ｇ／Ｌ、 メタケイ珪酸ナトリウム １０ｇ／Ｌ、 ジオキシエチレンベンジルアルコールエーテル １ｇ／
Ｌ 水洗 ２０％塩酸浸漬 水洗 銀めっき（１Ａ／ｄｍ2、３０秒、２５℃） 水洗 錫めっき（１０Ａ／ｄｍ2、１２０秒、４５℃） 水洗 乾燥 加熱処理（１７０℃、１時間） Plating step Alkali degreasing (5 A / dm 2 , 30 seconds, 60 ° C.) 40 g / L sodium hydroxide, 25 g / L sodium carbonate, 10 g / L sodium metasilicate, 1 g / dioxyethylene benzyl alcohol ether
L Water washing 20% hydrochloric acid immersion Water washing Silver plating (1 A / dm 2 , 30 seconds, 25 ° C.) Water washing Tin plating (10 A / dm 2 , 120 seconds, 45 ° C.) Water washing Drying Heat treatment (170 ° C., 1 hour)
【００１６】実施例２ 下記の組成を有する銀めっき液及び錫めっき液を調製
し、リン青銅コネクターにめっきした。銀めっき液 シアン化銀（金属銀として） ４０ｇ／Ｌ シアン化カリウム（遊離シアン化カリウムとして） ７８ｇ／Ｌ 炭酸カリウム １０ｇ／Ｌ 蒸留水 残量錫めっき液 メタンスルホン酸 １５０ｇ／Ｌ メタンスルホン酸錫（２価錫として） ６０ｇ／Ｌ アセトアルデヒド ０．２ｇ／Ｌ １−ナフチルアルデヒド ０．１ｇ／Ｌ ポリオキシエチレンノニルフェニルエーテル ２ｇ／Ｌ （エチレンオキサイド：１２ｍｏｌ） 蒸留水 残量 Example 2 A silver plating solution and a tin plating solution having the following compositions were prepared and plated on a phosphor bronze connector. Silver plating solution Silver cyanide (as metallic silver) 40 g / L Potassium cyanide (as free potassium cyanide) 78 g / L Potassium carbonate 10 g / L Distilled water Remaining tin plating solution Methanesulfonic acid 150 g / L Tin methanesulfonate (as tin (II) tin) ) 60 g / L acetaldehyde 0.2 g / L 1-naphthyl aldehyde 0.1 g / L polyoxyethylene nonyl phenyl ether 2 g / L (ethylene oxide: 12 mol) distilled water
【００１７】めっき工程 アルカリ脱脂 水洗 １０％硫酸浸漬 水洗 ニッケルめっき（２Ａ／ｄｍ2、５分、５５℃） 銀めっき（１０Ａ／ｄｍ2、１秒、２５℃） 水洗 錫めっき（１０Ａ／ｄｍ2、４０秒、２０℃） 水洗 乾燥 加熱処理（１２０℃、１時間） Plating step Alkaline degreasing Water washing 10% sulfuric acid immersion Water washing Nickel plating (2 A / dm 2 , 5 minutes, 55 ° C.) Silver plating (10 A / dm 2 , 1 second, 25 ° C.) Water washing Tin plating (10 A / dm 2 , 40 seconds, 20 ° C) Rinsing, drying, heat treatment (120 ° C, 1 hour)
【００１８】実施例３ 下記の組成を有する銀めっき液及び錫めっき液を調製
し、鉄−ニッケル合金リードフレームにめっきした。銀めっき液 シアン化銀（金属銀として） ４ｇ／Ｌ シアン化カリウム（遊離シアン化カリウムとして） １０ｇ／Ｌ 炭酸カリウム １０ｇ／Ｌ 蒸留水 残量錫めっき液 硫酸 １５０ｇ／Ｌ 硫酸第一錫（２価錫として） ２０ｇ／Ｌ ポリオキシエチレンノニルフェニルエーテル ２ｇ／Ｌ （エチレンオキサイド：９ｍｏｌ） 蒸留水 残量 Example 3 A silver plating solution and a tin plating solution having the following compositions were prepared and plated on an iron-nickel alloy lead frame. Silver plating solution Silver cyanide (as metallic silver) 4 g / L Potassium cyanide (as free potassium cyanide) 10 g / L Potassium carbonate 10 g / L Distilled water Remaining tin plating solution Sulfuric acid 150 g / L Stannous sulfate (as divalent tin) 20 g / L polyoxyethylene nonyl phenyl ether 2g / L (ethylene oxide: 9mol) Distilled water
【００１９】めっき工程 アルカリ脱脂 水洗 ２０％塩酸 水洗 錫めっき（１Ａ／ｄｍ2、６００秒、２５℃） 水洗 銀めっき（０．５Ａ／ｄｍ2、６０秒、２５℃） 水洗 錫めっき（１／ｄｍ2、６００秒、２５℃） 水洗 乾燥 加熱処理（１２０℃、１時間） Plating step Alkaline degreasing Water washing 20% hydrochloric acid Water washing Tin plating (1 A / dm 2 , 600 seconds, 25 ° C.) Water washing Silver plating (0.5 A / dm 2 , 60 seconds, 25 ° C.) Water washing Tin plating (1 / dm) 2 , 600 seconds, 25 ° C) Rinsing, drying, heat treatment (120 ° C, 1 hour)
【００２０】実施例４ 下記の組成を有する銀めっき液及び錫−ビスマス合金め
っき液を調整し、鉄−ニッケルリードフレームにめっき
した。銀めっき液 シアン化銀（金属銀として） ４ｇ／Ｌ シアン化カリウム（遊離シアン化カリウムとして） １０ｇ／Ｌ 炭酸カリウム １０ｇ／Ｌ 蒸留水 残量錫−ビスマス合金めっき液 メタンスルホン酸 １５０ｇ／Ｌ メタンスルホン酸錫（２価錫として） ２５ｇ／Ｌ メタンスルホン酸ビスマス（金属ビスマスとして） １．５ｇ／Ｌ ポリオキシエチレンノニルフェニルエーテル ２ｇ／Ｌ （エチレンオキサイド：１０ｍｏｌ） カテコール ０．１ｇ／Ｌ Example 4 A silver plating solution and a tin-bismuth alloy plating solution having the following compositions were prepared and plated on an iron-nickel lead frame. Silver plating solution silver cyanide (as metallic silver) 4g / (as potassium free cyanide) L Potassium cyanide 10 g / L of potassium carbonate 10 g / L of distilled water Balance tin - bismuth alloy plating solution methanesulfonic acid 150 g / L methanesulfonic tin (2 25 g / L bismuth methanesulfonate (as metal bismuth) 1.5 g / L polyoxyethylene nonyl phenyl ether 2 g / L (ethylene oxide: 10 mol) catechol 0.1 g / L
【００２１】めっき工程 アルカリ脱脂 水洗 ２０％塩酸 水洗 銀めっき（０．５Ａ／ｄｍ2、６０秒、２５℃） 水洗 錫―ビスマス合金めっき（２Ａ／ｄｍ2、１０分、３５
℃） 水洗 乾燥 加熱処理（１２０℃、２時間） Plating step Alkaline degreasing Water washing 20% hydrochloric acid Water washing Silver plating (0.5 A / dm 2 , 60 seconds, 25 ° C.) Water washing Tin-bismuth alloy plating (2 A / dm 2 , 10 minutes, 35
℃) Rinse, dry, heat treatment (120 ℃, 2 hours)
【００２２】実験例５ 下記の組成を有する銀めっき液及び錫−銅合金めっき液
を調製し、鉄−ニッケル合金リードフレームにめっきし
た。銀めっき液 シアン化銀（金属銀として） ４ｇ／Ｌ シアン化カリウム（遊離シアン化カリウムとして） １０ｇ／Ｌ 炭酸カリウム １０ｇ／Ｌ 蒸留水 残量錫−銅合金めっき液 メタンスルホン酸 １３０ｇ／Ｌ メタンスルホン酸錫（２価錫として） ６０ｇ／Ｌ メタンスルホン酸銅（金属銅として） １ｇ／Ｌ ラウリルジメチルアミノ酢酸ベタイン ２ｇ／Ｌ ポリオキシエチレンノニルフェニルエーテル ３ｇ／Ｌ （エチレンオキサイド：１２ｍｏｌ） ハイドロキノン ０．１ｇ／Ｌ Experimental Example 5 A silver plating solution and a tin-copper alloy plating solution having the following compositions were prepared and plated on an iron-nickel alloy lead frame. Silver plating solution silver cyanide (as metallic silver) 4g / (as potassium free cyanide) L Potassium cyanide 10 g / L of potassium carbonate 10 g / L of distilled water Balance tin - copper alloy plating solution methanesulfonic acid 130 g / L methanesulfonic tin (2 60 g / L Copper methanesulfonate (as copper metal) 1 g / L Lauryl dimethylaminoacetic acid betaine 2 g / L Polyoxyethylene nonylphenyl ether 3 g / L (ethylene oxide: 12 mol) Hydroquinone 0.1 g / L
【００２３】めっき条件 アルカリ脱脂 水洗 ２０％塩酸 水洗 銀めっき（０．５Ａ／ｄｍ2、６０秒、２５℃） 水洗 錫−銅合金めっき（１５Ａ／ｄｍ2、８０秒、３５℃） 水洗 乾燥 加熱処理（１７０℃、１時間） Plating conditions Alkaline degreasing Water washing 20% hydrochloric acid Water washing Silver plating (0.5 A / dm 2 , 60 seconds, 25 ° C.) Water washing Tin-copper alloy plating (15 A / dm 2 , 80 seconds, 35 ° C.) Water washing Dry Heat treatment (170 ° C, 1 hour)
【００２４】実験例６ 実験例５の組成を有する銀めっき液及び錫−銅合金めっ
き液を用い、鉄−ニッケル合金リードフレームにめっき
した。めっき条件 アルカリ脱脂 水洗 ２０％塩酸 水洗 銀めっき（０．５Ａ／ｄｍ2、１２秒、２５℃） 水洗 錫―銅合金めっき（１５Ａ／ｄｍ2、１５秒、３５℃） 水洗 乾燥 加熱処理（２５０℃、２０秒） Experimental Example 6 Using a silver plating solution and a tin-copper alloy plating solution having the composition of Experimental Example 5, plating was performed on an iron-nickel alloy lead frame. Plating conditions Alkaline degreasing Water washing 20% hydrochloric acid Water washing Silver plating (0.5 A / dm 2 , 12 seconds, 25 ° C.) Water washing Tin-copper alloy plating (15 A / dm 2 , 15 seconds, 35 ° C.) Water washing Dry Heat treatment (250 ° C.) , 20 seconds)
【００２５】実施例７ 下記の組成を有する銀めっき液及び錫−銅合金めっき液
を調製し、鉄−ニッケル合金リードフームにめっきし
た。銀めっき液 硝酸銀（金属銀として） ８ｇ／Ｌ チオシアン酸カリウム １１０ｇ／Ｌ ｐＨ ８．０（水酸化カリウムで調整 ）錫−銅合金めっき液 メタンスルホン酸 １３０ｇ／Ｌ メタンスルホン酸錫（２価錫として） ６０ｇ／Ｌ メタンスルホン酸銅（金属銅として） １ｇ／Ｌ ラウリルジメチルアミノ酢酸ベタイン ２ｇ／Ｌ ポリオキシエチレンノニルフェニルエーテル ３ｇ／Ｌ （エチレンオキサイド：１２ｍｏｌ） ハイドロキノン ０．１ｇ／Ｌ Example 7 A silver plating solution and a tin-copper alloy plating solution having the following compositions were prepared and plated on an iron-nickel alloy lead fume. Silver plating solution Silver nitrate (as metallic silver) 8 g / L Potassium thiocyanate 110 g / L pH 8.0 (adjusted with potassium hydroxide) Tin-copper alloy plating solution Methanesulfonic acid 130 g / L Tin methanesulfonate (as tin (II) tin ) 60 g / L copper methanesulfonate (as metallic copper) 1 g / L betaine lauryl dimethylaminoacetate 2 g / L polyoxyethylene nonyl phenyl ether 3 g / L (ethylene oxide: 12 mol) hydroquinone 0.1 g / L
【００２６】めっき条件 アルカリ脱脂 水洗 ２０％塩酸 水洗 銀めっき（０．５Ａ／ｄｍ2、１２秒、２５℃） 水洗 錫−銅合金めっき液（１５Ａ／ｄｍ2、１５秒、３５
℃） 水洗 乾燥 加熱処理（１２０℃、１時間） Plating conditions Alkaline degreasing Water washing 20% hydrochloric acid Water washing Silver plating (0.5 A / dm 2 , 12 seconds, 25 ° C.) Water washing Tin-copper alloy plating solution (15 A / dm 2 , 15 seconds, 35
℃) Rinse, dry, heat treatment (120 ℃, 1 hour)
【００２７】得られためっき皮膜はいずれも良好な無光
沢又は光沢外観を有していた。これらのめっき皮膜のは
んだ濡れ性について、ソルダーチェッカーを用いたメニ
スコグラフ法により評価した。メニスコグラフの測定条
件は以下の通りである。メニスコグラフ測定条件１ はんだ槽 Ｓｎ：Ｐｂ＝６０：４０共晶はんだ 浴温 ２３０℃ 浸漬深さ ２ｍｍ 浸漬速度 １０ｍｍ／秒 浸漬時間 ５秒 フラックス ロジン系不活性タイプEach of the obtained plating films had a good matte or glossy appearance. The solder wettability of these plating films was evaluated by a meniscograph method using a solder checker. The measurement conditions of the meniscograph are as follows. Meniscograph measurement conditions 1 Solder bath Sn: Pb = 60: 40 Eutectic solder Bath temperature 230 ° C Immersion depth 2mm Immersion speed 10mm / sec Immersion time 5sec Flux rosin-based inert type
【００２８】メニスコグラフ測定条件２ はんだ槽 Ｓｎ：Ａｇ：Ｃｕ＝９５．８：３．５：０．７ 浴温 ２４５℃ 浸漬深さ ２ｍｍ 浸漬速度 １０ｍｍ／秒 浸漬時間 ５秒 フラックス ロジン系不活性タイプ Meniscograph measurement condition 2 Solder bath Sn: Ag: Cu = 95.8: 3.5: 0.7 Bath temperature 245 ° C Immersion depth 2mm Immersion speed 10mm / sec Immersion time 5sec Flux rosin-based inert type
【００２９】以上の試験により得られた結果を表１に示
す。この結果から、ゼロクロスタイムは、全て１秒未満
であり、電子部品等で要求されているはんだ濡れ性を充
分に満たしていた。Table 1 shows the results obtained by the above tests. From these results, it was found that the zero cross times were all less than 1 second, sufficiently satisfying the solder wettability required for electronic components and the like.
【００３０】[0030]
【表１】表１ [Table 1] Table 1
───────────────────────────────────────────────────── フロントページの続き (72)発明者 汲田 鉄也 東京都中央区日本橋馬喰町１−14−５ 日 本リーロナール株式会社内 Ｆターム(参考） 4K022 AA02 AA41 AA42 BA01 BA08 BA21 BA28 BA32 DA01 EA01 4K023 AA17 AA24 AB34 AB40 EA01 4K024 AA07 AA10 AA21 AA24 AB02 BA02 BA09 BB09 BB11 DB01 GA14 4K044 AA02 AA06 AB02 BA08 BA10 BB03 BC08 CA12 CA15 CA18 CA62 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Tetsuya Ukita 1-14-5, Nihonbashi Bakurocho, Chuo-ku, Tokyo F-term (reference) in Nihon Rironal Co., Ltd. 4K022 AA02 AA41 AA42 BA01 BA08 BA21 BA28 BA32 DA01 EA01 4K023 AA17 AA24 AB34 AB40 EA01 4K024 AA07 AA10 AA21 AA24 AB02 BA02 BA09 BB09 BB11 DB01 GA14 4K044 AA02 AA06 AB02 BA08 BA10 BB03 BC08 CA12 CA15 CA18 CA62
Claims (2)
（２）錫、錫−ビスマス、又は錫−銅合金めっき皮膜
を、この順序で、又はこの逆の順序で、析出させること
を特徴とする、銀−錫合金めっき層を形成させる方法。1. Depositing (1) a silver plating film and (2) a tin, tin-bismuth or tin-copper alloy plating film on a metal substrate in this order or vice versa. Forming a silver-tin alloy plating layer.
錫、錫−ビスマス、又は錫−銅合金めっき皮膜の両皮膜
を加熱する工程を含有する請求項１に記載の方法。2. The method according to claim 1, further comprising the step of heating both the silver plating film (1) and the tin, tin-bismuth or tin-copper alloy plating film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31919799A JP4465068B2 (en) | 1999-11-10 | 1999-11-10 | Method for forming silver-tin alloy plating layer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31919799A JP4465068B2 (en) | 1999-11-10 | 1999-11-10 | Method for forming silver-tin alloy plating layer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
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| JP2006037227A (en) * | 2004-06-25 | 2006-02-09 | Ormecon Gmbh | Tin-coated printed circuit board with low tendency to whisker formation |
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| US7391116B2 (en) | 2003-10-14 | 2008-06-24 | Gbc Metals, Llc | Fretting and whisker resistant coating system and method |
| JP2013221208A (en) * | 2012-04-19 | 2013-10-28 | Autonetworks Technologies Ltd | Plated terminal for connector |
| WO2014003144A1 (en) * | 2012-06-27 | 2014-01-03 | Jx日鉱日石金属株式会社 | Electronic component metal material and manufacturing method thereof, and connector terminal, connector and electronic component using said electronic component metal material |
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| KR20150053263A (en) * | 2012-06-27 | 2015-05-15 | 제이엑스 닛코 닛세키 킨조쿠 가부시키가이샤 | Electronic component metal material and manufacturing method thereof, and connector terminal, connector and electronic component using said electronic component metal material |
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