JP2005246480A - Solder alloy for preventing fe erosion and method for preventing fe erosion - Google Patents
Solder alloy for preventing fe erosion and method for preventing fe erosion Download PDFInfo
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本発明は、Ｆｅ系合金被覆した器具のＦｅ喰われ防止方法とはんだ合金に関する。特に、本発明は、マニュアルソルダリングによりプリント基板にはんだ付けを行う際に、使用される機器のＦｅ喰われ防止用はんだとＦｅ喰われ防止方法に関する。 The present invention relates to a method for preventing Fe erosion of a device coated with an Fe alloy and a solder alloy. In particular, the present invention relates to an Fe erosion prevention solder and an Fe erosion prevention method for equipment used when soldering a printed circuit board by manual soldering.
従来プリント基板のはんだ付けにはＰｂ−Ｓｎ合金を使用していた。このＰｂ−Ｓｎ合金は、共晶組成（Ｐｂ−６３Ｓｎ）では融点が１８３℃であり、熱に弱い電子部品に対しても熱影響が少なく、またはんだ付け性に優れているため未はんだやディウエット等のはんだ付け不良の発生も少ないという特長を有している。このＰｂ−Ｓｎ合金を用いてはんだ付けされた電子機器が古くなったり、故障したりした場合、機能アップや修理をせず廃棄処分されていた。プリント基板を廃棄する場合、焼却処分でなく埋め立て処分をしていたが、埋め立て処分をするのは、プリント基板の銅箔にはんだが金属的に付着しており、銅箔とはんだを分離して再使用することができないからである。この埋め立て処分されたプリント基板に酸性雨が接触すると、はんだ中のＰｂが溶出し、それが地下水を汚染するようになる。そしてＰｂを含んだ地下水を長年月にわたって人や家畜が飲用するとＰｂ中毒を起こすことが懸念されている。そこでＰｂを含まないいわゆる「鉛フリーはんだ」が、新しい電子機器の生産から使用が始まっている。 Conventionally, Pb—Sn alloys have been used for soldering printed circuit boards. This Pb—Sn alloy has a melting point of 183 ° C. in the eutectic composition (Pb-63Sn), has little thermal effect on heat-sensitive electronic components, and is excellent in soldering. It has the feature that there are few occurrences of soldering defects such as wet. When an electronic device soldered using this Pb—Sn alloy becomes old or breaks down, it has been disposed of without being upgraded or repaired. When the printed circuit board is discarded, it was disposed of in landfill instead of incineration. However, in the landfill disposal, the solder is attached to the copper foil of the printed circuit board, and the copper foil and the solder are separated. This is because it cannot be reused. When acid rain comes into contact with the printed circuit board that has been disposed of in landfill, Pb in the solder is eluted, which contaminates groundwater. There is a concern that Pb poisoning will occur if people and livestock drink groundwater containing Pb for many years. Therefore, so-called “lead-free solder” that does not contain Pb has been used since the production of new electronic devices.
鉛フリーはんだとは、Ｓｎを主成分としたものであり、現在使われている鉛フリーはんだ合金は、Ｓｎ−３．５Ａｇ（融点：２２１℃）、Ｓｎ−０．７Ｃｕ（融点：２２７℃）、Ｓｎ−９Ｚｎ（融点：１９９℃）、Ｓｎ−５８Ｂｉ（融点：１３９℃）等の二元合金の他、これらにＡｇ、Ｃｕ、Ｚｎ、Ｂｉ、Ｉｎ、Ｓｂ、Ｎｉ、Ｃｒ、Ｃｏ、Ｆｅ、Ｍｎ、Ｐ、Ｇｅ、Ｇａ等の第三元素を適宜添加したものである。なお本発明でいう「系」とは、合金そのもの、或いは二元合金を基に第三元素を一種以上添加した合金である。例えばＳｎ−Ｚｎ系とは、Ｓｎ−Ｚｎ合金そのもの、或いはＳｎ−Ｚｎに前述第三元素を一種以上添加した合金であり、Ｓｎ−Ａｇ系とはＳｎ−Ａｇ合金そのもの、或いはＳｎ−Ａｇに前述第三元素を一種以上添加した合金である。 Lead-free solder is composed mainly of Sn, and currently used lead-free solder alloys are Sn-3.5Ag (melting point: 221 ° C), Sn-0.7Cu (melting point: 227 ° C). In addition to binary alloys such as Sn-9Zn (melting point: 199 ° C), Sn-58Bi (melting point: 139 ° C), Ag, Cu, Zn, Bi, In, Sb, Ni, Cr, Co, Fe, A third element such as Mn, P, Ge, or Ga is appropriately added. The “system” referred to in the present invention is an alloy itself or an alloy to which one or more third elements are added based on a binary alloy. For example, the Sn—Zn alloy is an Sn—Zn alloy itself, or an alloy obtained by adding one or more of the above-mentioned third elements to Sn—Zn, and the Sn—Ag alloy is an Sn—Ag alloy itself or Sn—Ag. An alloy to which one or more third elements are added.
現在、Ｓｎ−Ａｇ−Ｃｕ系鉛フリーはんだ合金の主流は、Ｓｎ−３Ａｇ−０．５Ｃｕ、Ｓｎ−３．５Ａｇ−０．７５Ｃｕ などのＳｎ−Ａｇ−Ｃｕ系鉛フリーはんだとなっている。Ｓｎ−Ａｇ−Ｃｕ系鉛フリーはんだ合金は、マニュアルソルダリング、フローソルダリング、リフローソルダリングなどのあらゆる工法に対応でき、はんだ付け強度の信頼性およびはんだ付け性が良い。
他に使用されている鉛フリーはんだ合金は、低コストのフローソルダリング用はんだ合
金としてＳｎ−０．７Ｃｕ鉛フリーはんだ合金などのＳｎ−Ｃｕ系合金、および溶融温度が低いリフローソルダリング用合金としてＳｎ−Ｚｎ系はんだ合金およびＳｎ−Ｉｎ系はんだ合金などがあるが、全体からみればわずかの割合である。
At present, the mainstream of Sn-Ag-Cu-based lead-free solder alloys is Sn-Ag-Cu-based lead-free solders such as Sn-3Ag-0.5Cu and Sn-3.5Ag-0.75Cu. The Sn-Ag-Cu-based lead-free solder alloy can be applied to all methods such as manual soldering, flow soldering, and reflow soldering, and has good soldering strength reliability and solderability.
Other lead-free solder alloys are Sn-Cu alloys such as Sn-0.7Cu lead-free solder alloys as low-cost solder alloys for flow soldering, and reflow soldering alloys with a low melting temperature. There are Sn—Zn solder alloys and Sn—In solder alloys, but only a small percentage from the whole.
マニュアルソルダリングとは手作業でのはんだ付けを指し、はんだ鏝を使用して行われ
る。マニュアルソルダリングは、フローソルダリングやリフローソルダリングの修正や後
付部品のはんだ付けに対して行われる。はんだ鏝は、ヒータを内蔵するはんだ鏝本体の先
端に鏝先が取り付けられた構造をしている。鏝先の芯材には導電性の良いＣｕおよびＣｕ合金などが使用されており、そのはんだ付けを行う先端部分にはＳｎによるＣｕの喰われを防止するため、Ｎｉめっきに加えＦｅめっきをしたり、同じＦｅ系の合金であるがＣｕおよびＣｕ合金の母材の上にＳＵＳ３０４などのステンレス鋼を被覆する方法がとられている。
Manual soldering refers to manual soldering and is performed using a soldering iron. Manual soldering is performed for correction of flow soldering and reflow soldering and soldering of retrofit components. The soldering iron has a structure in which a soldering tip is attached to the tip of the soldering iron main body incorporating the heater. The core material of the tip is made of Cu or Cu alloy having good conductivity, and in order to prevent Cu from being eroded by Sn at the tip portion to be soldered, Fe plating is performed in addition to Ni plating. Alternatively, a method of coating stainless steel such as SUS304 on the base material of Cu and Cu alloy, which are the same Fe-based alloy, is employed.
Ｆｅめっきの食われが発生する原因は、ＳｎとＦｅが反応（相互拡散）することにより合金化し、これが溶融はんだ中のＳｎに溶解し易くなるからである。Ｓｎの含有量が多い程、Ｓｎ食われが顕著になる。
この現象はステンレス鋼でも同様に起きて、ステンレス鋼の喰われが発生する。
マニュアルソルダリングに使用されるはんだでは、従来のＳｎ−Ｐｂ系はんだ合金から現在使用されているＳｎ−Ａｇ−Ｃｕ系鉛フリーはんだ合金に置き換わったことにより鏝先の消耗が激しく、はんだ鏝の鏝先寿命が約１／３になったといわれている。
The reason for the occurrence of erosion of Fe plating is that Sn and Fe are reacted (interdiffusion) to form an alloy, which is easily dissolved in Sn in the molten solder. As the Sn content increases, Sn eating becomes more prominent.
This phenomenon also occurs in stainless steel, and the stainless steel is bitten.
In solder used for manual soldering, the conventional Sn-Pb solder alloy is replaced with the Sn-Ag-Cu lead-free solder alloy that is currently used, so that the wear of the solder tip is severe. It is said that the pre-life is about 1/3.
鉛フリーはんだ使用での鏝先のＦｅめっき層の浸食を抑制する方法として、はんだ鏝に使用するはんだに事前にＦｅを０．０１質量％〜０．２質量％添加しておく方法が公開されている。（特許文献１）しかし鉛フリーはんだへのＦｅの混入は、同じはんだ付け時間の当たりのＦｅめっき層の浸食抑制効果はあるが、はんだのぬれ性を著しく阻害してはんだ付け時間を延ばしてしまうため、結局Ｆｅめっき層を浸食してしまう。 As a method of suppressing erosion of the iron plating layer at the tip of the solder when using lead-free solder, a method of adding 0.01 mass% to 0.2 mass% of Fe in advance to the solder used for the soldering iron is disclosed. ing. (Patent Document 1) However, mixing Fe into lead-free solder has the effect of suppressing erosion of the Fe plating layer per the same soldering time, but significantly impedes the wettability of the solder and extends the soldering time. Therefore, the Fe plating layer is eventually eroded.
本発明の課題は、ＦｅおよびＦｅ系合金を被覆した部材を用いてＳｎを主成分としたＳｎ−Ａｇ−Ｃｕ系の鉛フリーはんだ合金ではんだ付けをする際に、ＦｅおよびＦｅ系合金被覆した部材のＦｅ喰われを防止するためのはんだ合金および防止方法を提供することである。 An object of the present invention is to coat a Fe and Fe alloy when soldering with a Sn-Ag-Cu lead-free solder alloy mainly composed of Sn using a member coated with Fe and an Fe alloy. It is providing the solder alloy for preventing Fe biting of a member, and a prevention method.
このようにＦｅ喰われ現象が顕著になった理由は、鉛フリーはんだに置き換わったことにより、はんだ中のＣｕを溶解しやすいＳｎの含有率が高くなったこと、はんだ自体のぬれ性が悪く、はんだ鏝によるはんだ付け時間が約２倍かかること、従来のＳｎ−Ｐｂ系はんだ合金の溶融温度（約１８３℃）からＳｎ−Ａｇ−Ｃｕ系鉛フリーはんだ合金の溶融温度（約２２０℃）とはんだの溶融温度が約４０℃上昇したため、鏝先の使用温度もＳｎ−Ｐｂ系はんだ合金の使用温度である３５０℃〜４２０℃から、Ｓｎ−Ａｇ−Ｃｕ系鉛フリーはんだ合金の使用温度の３８０℃〜４５０℃に上昇したことなどが挙げられ、その結果、Ｆｅとの反応が進み、被覆層が浸食されやすくなった。 The reason why the Fe erosion phenomenon became significant in this way was that the content of Sn, which easily dissolves Cu in the solder, increased due to the replacement with lead-free solder, the wettability of the solder itself was poor, Soldering time by soldering iron takes about twice, melting temperature of conventional Sn-Pb solder alloy (about 183 ° C) and melting temperature of Sn-Ag-Cu lead free solder alloy (about 220 ° C) and solder Since the melting temperature of the solder increased by about 40 ° C., the operating temperature of the tip also increased from 350 ° C. to 420 ° C., which is the operating temperature of the Sn—Pb solder alloy, to 380 ° C., the operating temperature of the Sn—Ag—Cu based lead free solder alloy. As a result, the reaction with Fe progressed, and the coating layer was easily eroded.
本発明者らは、Ｓｎ−Ａｇ−Ｃｕ系鉛フリーはんだ合金にＣｏを添加させたはんだを使用することにより、Ｓｎ−Ａｇ−Ｃｕ系鉛フリーはんだ合金中にＣｏが分散してＦｅの溶解を防止すること、はんだ鏝の鏝先のＦｅ喰われが起きにくくなることを見出し、本発明を完成させた。
本発明のＦｅ喰われ防止用はんだ合金は、Ａｇ：０．３質量％以上４．０質量％以下、Ｃｕ：０．１質量％以上１．０質量％以下、Ｃｏ：０．００１質量％以上０．５質量％以下、残部実質上ＳｎからなるＦｅ喰われ防止用はんだ合金である。
By using a solder obtained by adding Co to a Sn-Ag-Cu-based lead-free solder alloy, the present inventors dispersed Co in the Sn-Ag-Cu-based lead-free solder alloy to dissolve Fe. The present invention was completed by finding that it was difficult to prevent, and that the iron erosion at the tip of the solder iron was difficult to occur.
The solder alloy for preventing Fe erosion of the present invention is Ag: 0.3 mass% to 4.0 mass%, Cu: 0.1 mass% to 1.0 mass%, Co: 0.001 mass% or more This is an Fe erosion-preventing solder alloy consisting of 0.5 mass% or less and the remainder substantially Sn.
本発明は、ＦｅおよびＦｅ系合金を被覆したはんだ付け用部材を用いてＳｎを主成分としたＳｎ−Ａｇ−Ｃｕ系の鉛フリーはんだ合金をはんだ付けをする際に、Ｓｎ−Ａｇ−Ｃｕ系の鉛フリーはんだ合金に０．００１質量％以上０．５質量％以下のＣｏを含有したはんだを用いてはんだ付けを行うことを特徴とする、ＦｅおよびＦｅ系合金被覆したはんだ付け用部材のＦｅ喰われ防止方法である。本発明では、はんだ合金の耐疲労性向上のため、上記のはんだ合金組成にＮｉを０．０１質量％以上０．１質量％以下含有させても良い。 The present invention provides a Sn-Ag-Cu-based solder when soldering a Sn-Ag-Cu-based lead-free solder alloy mainly composed of Sn using a soldering member coated with Fe and an Fe-based alloy. Fe and a Fe-based alloy-coated soldering member, wherein a solder containing 0.001 mass% or more and 0.5 mass% or less of Co is soldered to the lead-free solder alloy of It is a biting prevention method. In the present invention, in order to improve the fatigue resistance of the solder alloy, the solder alloy composition may contain Ni in an amount of 0.01% by mass to 0.1% by mass.
また本発明は、ＦｅおよびＦｅ系合金を被覆したはんだ付け用機器を用いてＳｎを主成分としたＳｎ−Ａｇ−Ｃｕ系の鉛フリーはんだ合金をはんだ付けをする際に、Ｓｎ−Ａｇ−Ｃｕ系の鉛フリーはんだ合金に０．００１質量％以上０．５質量％以下のＣｏを含有したはんだを用いてはんだ付けを行うことを特徴とする、ＦｅおよびＦｅ系合金被覆したはんだ付け用機器部材のＦｅ喰われ防止方法である。 The present invention also provides a Sn-Ag-Cu solder when soldering a Sn-Ag-Cu-based lead-free solder alloy mainly composed of Sn using a soldering device coated with Fe and an Fe-based alloy. Soldering equipment member coated with Fe and Fe alloy, characterized in that soldering is performed using a lead-free solder alloy containing 0.001% by mass or more and 0.5% by mass or less of Co containing solder This is a method of preventing Fe erosion.
本発明の対象になるＦｅ喰われを起こしやすいはんだ付け用部材としては、マニュアルソルダリングに用いるはんだ鏝の鏝先、はんだ付けロボットに使用されるはんだ鏝の鏝先、およびリペア装置に使用されるはんだ鏝の鏝先などが挙げられる。
これらのはんだ付け用部材は、熱伝導性を求められるため芯材としてＣｕおよびＣｕ合金が使用されるが、Ｃｕははんだ中のＳｎに溶解しやすいので、使用しているうちにはんだに喰われてしまう。そのため、Ｓｎに溶解しずらいＦｅを保護膜としてＣｕ芯材表面にめっきしたり、さらに耐久性を持たせるためＣｕの芯材表面にＮｉめっきをして、さらにＦｅを保護膜としてめっきをしたものが用いられている。なおＦｅめっきとは、Ｆｅの他にＦｅ−Ｃ合金のようなＦｅ系合金めっきも含まれる。
As a soldering member that is likely to cause Fe erosion, the tip of a soldering iron used for manual soldering, a soldering iron tip used for a soldering robot, and a repair device are used. For example, the tip of a soldering iron.
Since these soldering members are required to have thermal conductivity, Cu and Cu alloys are used as the core material. However, since Cu is easily dissolved in Sn in the solder, it is eroded by the solder during use. End up. Therefore, the surface of the Cu core material is plated with Fe, which is difficult to dissolve in Sn, as a protective film, or the surface of the Cu core material is plated with Ni for further durability, and further plated with Fe as the protective film. Things are used. The Fe plating includes Fe-based alloy plating such as Fe-C alloy in addition to Fe.
本発明のＳｎ−Ａｇ−Ｃｕ系鉛フリーはんだ合金にＣｏ：０．００１質量％以上０．５質量％以下、好ましくはＣｏ：０．０１質量％以上０．１質量％以下加えたはんだ合金を使用することにより、従来のＳｎ−Ｐｂ系はんだ合金に比較してはんだによる喰われの激しいＳｎ−Ａｇ−Ｃｕ系鉛フリーはんだ合金を用いても、マニュアルソルダリングに使用するはんだ鏝の鏝先保護膜であるＦｅめっきの喰われが少なく、鏝先寿命が約３倍長くなる。 A solder alloy obtained by adding Co: 0.001% by mass to 0.5% by mass, preferably Co: 0.01% by mass to 0.1% by mass, to the Sn—Ag—Cu-based lead-free solder alloy of the present invention. By using it, it is possible to protect the tip of the soldering iron used for manual soldering even when using Sn-Ag-Cu lead-free solder alloy, which is more eroded by solder than conventional Sn-Pb solder alloy. There is little biting of the Fe plating as a film, and the tip life is about three times longer.
本発明のはんだ合金によるＦｅ喰われ防止機構については必ずしも明確になっていないが、次のように推測される。
すなわち「Ｆｅ喰われ」は、はんだに接触した部材表面に含まれるＦｅ分がはんだ中に消耗する現象であり、一般的には、溶解はんだ中にＦｅ分が溶解する現象である、。
このように、鉛フリーはんだを使ったはんだ付け中にＦｅ喰われが発生する原因は、ＳｎとＦｅが反応することによりＳｎ−Ｆｅ合金ができるが、Ｓｎ−Ｆｅ合金はＦｅより溶融温度が低いため溶融はんだ中のＳｎに溶解しやすくなるからである。そのため、鉛フリーはんだのようなＳｎ含有量が多いはんだほどＦｅ喰われが顕著に起こる。
The mechanism for preventing Fe erosion by the solder alloy of the present invention is not necessarily clear, but is presumed as follows.
That is, “Fe erosion” is a phenomenon in which the Fe content contained on the surface of the member in contact with the solder is consumed in the solder, and is generally a phenomenon in which the Fe content is dissolved in the molten solder.
As described above, the cause of Fe erosion during soldering using lead-free solder is that Sn—Fe alloy is formed by the reaction of Sn and Fe, but the melting temperature of Sn—Fe alloy is lower than that of Fe. Therefore, it becomes easy to dissolve in Sn in the molten solder. For this reason, Fe erosion occurs more markedly in a solder having a higher Sn content such as lead-free solder.
このようなＳｎに対してＦｅが溶解できる飽和量とその速度は、温度によって異なる。Ｆｅがはんだ中のＳｎへ溶解する速度を抑制するには、あらかじめＳｎにＦｅを添加することで抑制可能となるが、ＦｅはＳｎに対して殆ど固溶せず、微量でも化合物が析出する為、液相線温度の上昇に繋がる。
Ｆｅは周期表から見ると第８属に属する金属で、同じ第８属に属するＣｏおよびＮｉ、第６属に属するＣｒなどは遷移金属と呼ばれ、似た性質を持っている。多くの遷移金属は、Ｆｅと同様に、Ｓｎ中に固溶せずに、化合物として析出する為、液相線温度の上昇に繋がるが、ＮｉやＣｏは、共晶組成を作り溶融温度を低下させる性質がある。
The amount of saturation and the rate at which Fe can dissolve in such Sn vary with temperature. In order to suppress the rate at which Fe dissolves into Sn in the solder, it can be suppressed by adding Fe to Sn in advance. However, since Fe hardly dissolves in Sn, the compound precipitates even in a small amount. , Leading to an increase in liquidus temperature.
From the periodic table, Fe is a metal belonging to Group 8, Co and Ni belonging to Group 8 and Cr belonging to Group 6 are called transition metals and have similar properties. Many transition metals, like Fe, do not dissolve in Sn, but precipitate as compounds, leading to an increase in the liquidus temperature, but Ni and Co create a eutectic composition and lower the melting temperature. There is a nature to make.
Ｓｎ−Ａｇ−Ｃｕ系鉛フリーはんだ合金にＮｉやＣｏを添加すると、それらは溶融時にＳｎ中に分散する。Ｓｎ−Ａｇ−Ｃｕ系鉛フリーはんだ合金に充分な量のＣｏが固溶していると、Ｆｅ、Ｎｉ、Ｃｒなどの同種の遷移金属がそれ以上固溶できず、Ｆｅ系合金を被覆した部材の喰われが抑制される。Ｃｏと同様な効果をＮｉも示すが、ＮｉはＣｏに比較してＳｎに対する溶解性が低く、さらにＳｎ−Ａｇ−Ｃｕ系鉛フリーはんだ合金にＮｉが溶解すると、はんだの溶融温度が上昇するため、多量のＮｉは添加できない。一方、Ｃｏの添加はＮｉより微量でも効果があり、また、Ｎｉと同等の量でもはんだ合金の液相温度が上昇しないためＦｅ喰われが少なくなる。 When Ni or Co is added to the Sn-Ag-Cu-based lead-free solder alloy, they are dispersed in Sn at the time of melting. When a sufficient amount of Co is dissolved in the Sn-Ag-Cu-based lead-free solder alloy, the same type of transition metal such as Fe, Ni, Cr cannot be further dissolved, and the member coated with the Fe-based alloy Eating is suppressed. Ni also shows the same effect as Co, but Ni is less soluble in Sn than Co, and when Ni dissolves in a Sn-Ag-Cu lead-free solder alloy, the melting temperature of the solder increases. A large amount of Ni cannot be added. On the other hand, the addition of Co is effective even in a minute amount compared to Ni, and even if the amount is the same as that of Ni, the liquid phase temperature of the solder alloy does not increase, and Fe erosion is reduced.
Ｓｎ−Ａｇ−Ｃｕ系鉛フリーはんだ合金への最適なＣｏの添加量は、Ｓｎの含有量によって決定され、Ｓｎが９５％以上では、０．００１質量％以上０．５質量％以下が良く、より好ましくは、０．０１質量％以上０．１質量％以下が良い。
Ｃｏの量が、０．０１質量％以下、特に０．００１質量％より少ないと，Ｆｅ系合金を被覆した部材の喰われ抑制効果が現れず、Ｃｏの量が０．１質量％、特に０．５質量％より多いと液相線温度の上昇を引き起こし、作業性の悪化が懸念される。
The optimum amount of Co added to the Sn-Ag-Cu-based lead-free solder alloy is determined by the Sn content. When Sn is 95% or more, 0.001% by mass to 0.5% by mass is good, More preferably, 0.01 mass% or more and 0.1 mass% or less are good.
If the amount of Co is 0.01% by mass or less, particularly less than 0.001% by mass, the effect of suppressing the erosion of the Fe-coated alloy-coated member does not appear, and the amount of Co is 0.1% by mass, particularly 0%. If it is more than 5% by mass, the liquidus temperature will rise, and there is a concern that workability will deteriorate.
マニュアルソルダリングに適したやに入りはんだのはんだ合金組成の条件としては、はんだ合金のぬれ性が良いことが挙げられる。従来使用していたＳｎ−Ｐｂはんだ合金は、非常にぬれ性の良いはんだ合金であったが、鉛フリーはんだではＳｎ−Ｐｂはんだ合金ほどぬれ性の良いはんだ合金は存在しない。鉛フリーはんだで比較的ぬれ性の良い合金としてＳｎ−Ｂｉ系が挙げられる。Ｓｎ中にＢｉの添加はぬれ性の向上をもたらすが、融点低下ももたらし、リフトオフ現象などの不具合も報告されている。そのような事から、マニュアルソルダリングに適した鉛フリーやに入りはんだのはんだ合金組成としては、Ｓｎ−Ａｇ−Ｃｕ系鉛フリーはんだ合金が最適である。他にマニュアルソルダリングに使用可能な鉛フリーはんだ合金としてＳｎ−Ｃｕ系鉛フリーはんだ合金があるが、はんだ合金の溶融温度がＳｎ−Ａｇ−Ｃｕ系鉛フリーはんだ合金に比較して約１０℃高く、はんだ合金としてのぬれ性も悪い。本発明に使用する鉛フリーはんだ合金は、Ｓｎ−Ａｇ−Ｃｕ系鉛フリーはんだ合金の中でも、はんだの溶融温度が低く、Ｓｎ−Ｃｕ系鉛フリーはんだ合金よりぬれ性が良い範囲のマトリックスの中から選択されたもので、特にマニュアルソルダリングに適したはんだ合金組成が実現されるのであり、本発明にかかるはんだ合金はぬれ性が特に良い。 As a condition of the solder alloy composition of the cored solder suitable for manual soldering, the wettability of the solder alloy is good. Sn-Pb solder alloys that have been used in the past have been very wettable solder alloys, but lead-free solders do not have solder alloys that have better wettability than Sn-Pb solder alloys. Sn-Bi is an example of a lead-free solder and a relatively good wettability alloy. Addition of Bi in Sn brings about improvement in wettability, but also brings about a decrease in melting point, and problems such as a lift-off phenomenon have been reported. For this reason, Sn—Ag—Cu lead-free solder alloy is optimal as the solder alloy composition of lead-free flux cored solder suitable for manual soldering. Other lead-free solder alloys that can be used for manual soldering include Sn-Cu-based lead-free solder alloys. The melting temperature of solder alloys is about 10 ° C higher than Sn-Ag-Cu-based lead-free solder alloys. Also, the wettability as a solder alloy is poor. Among the lead-free solder alloys used in the present invention, among the Sn-Ag-Cu-based lead-free solder alloys, the melting temperature of the solder is low and the wettability is better than that of the Sn-Cu-based lead-free solder alloys. A solder alloy composition that is particularly suitable for manual soldering is realized, and the solder alloy according to the present invention has particularly good wettability.
Ｓｎ−Ａｇ−Ｃｕ系鉛フリーはんだ合金の溶融温度とメニスコグラフ法によるゼロクロス時間のグラフを表１に示す。マニュアルソルダリングに適した鉛フリーやに入りはんだの組成はゼロクロスタイムが３秒以内のはんだである。ここで、Ｓｎに対するＡｇの添加は、はんだ合金のぬれ性を著しく向上させる。Ｓｎベースの鉛フリーはんだに対するＡｇの添加は、最低０．３質量％以上加えることにより効果を顕し、特に３．０質量％以上加えるとはんだ合金のぬれ性を向上させる。Ａｇを４．０質量％以上加えてしまうとはんだ合金の溶融温度を高めるため、はんだ鏝の設定温度を上げなければならず、Ｆｅ喰われが大きくなる。また、Ｓｎベースの鉛フリーはんだに対するＣｕの微量添加は、はんだ合金の強度を向上させるとともに、はんだ合金の溶融温度を下げ、ぬれ性も向上させる。Ｃｕの添加は、０．１質量％以上加えることにより、特に０．５質量％以上加えることにより効果を顕し、１．０質量％超以上加えてしまうとはんだ合金の溶融温度を高めるため、はんだ鏝の設定温度を上げなければならず、Ｆｅ喰われが大きくなる。 Table 1 shows a graph of the melting temperature of the Sn-Ag-Cu-based lead-free solder alloy and the zero crossing time by the meniscograph method. The lead-free flux cored solder suitable for manual soldering has a zero crossing time of 3 seconds or less. Here, the addition of Ag to Sn significantly improves the wettability of the solder alloy. The addition of Ag to the Sn-based lead-free solder exhibits an effect by adding at least 0.3% by mass or more, and particularly when added by 3.0% by mass or more improves the wettability of the solder alloy. If Ag is added in an amount of 4.0% by mass or more, the melting temperature of the solder alloy is increased, so the set temperature of the soldering iron must be increased, and the Fe erosion increases. Further, addition of a small amount of Cu to the Sn-based lead-free solder improves the strength of the solder alloy, lowers the melting temperature of the solder alloy, and improves the wettability. The addition of Cu exhibits an effect by adding 0.1% by mass or more, particularly by adding 0.5% by mass or more. When adding more than 1.0% by mass, the melting temperature of the solder alloy is increased. The set temperature of the soot has to be raised, and Fe erosion increases.
マニュアルソルダリングに適したＳｎ−Ａｇ−Ｃｕ系鉛フリーはんだ合金は、Ａｇ：０．３質量％以上４．０ 質量％以下、Ｃｕ：０．１質量％以上１．０ 質量％以下、残りがＳｎの組成が好ましく、その中でさらに好ましいＳｎ−Ａｇ−Ｃｕ系鉛フリーはんだ合金の組成としては、Ａｇ３．０質量％以上４．０ 質量％以下、Ｃｕ：０．５質量％以上１．０ 質量％以下、残りがＳｎの組成である。それらの鉛フリーはんだ合金に本発明の０．００１質量％以上０．５質量％以下のＣｏ、より好ましくは０．０１質量％以上０．１質量％以下のＣｏを添加することにより、はんだ鏝の鏝先のＦｅめっきに対する喰われを少なくすることが可能になる。 Sn-Ag-Cu-based lead-free solder alloys suitable for manual soldering are: Ag: 0.3% by mass to 4.0% by mass, Cu: 0.1% by mass to 1.0% by mass, and the rest The composition of Sn is preferable, and the Sn-Ag-Cu-based lead-free solder alloy is more preferably composed of Ag 3.0% by mass or more and 4.0% by mass or less, Cu: 0.5% by mass or more and 1.0% by mass. The composition is Sn or less, and the remainder is Sn. By adding 0.001% by mass or more and 0.5% by mass or less Co of the present invention to these lead-free solder alloys, more preferably 0.01% by mass or more and 0.1% by mass or less Co. It is possible to reduce the biting of the iron tip against Fe plating.
本発明のＦｅ系合金を被覆したはんだ付け器具のＦｅ喰われ防止方法に用いるやに入りはんだのはんだ合金組成は、Ａｇ：０．３質量％以上４．０質量％以上、Ｃｕ：０．１質量％以上１．０ 質量％以下、Ｃｏ：０．００１質量％以上０．５質量％以下、残部実質上Ｓｎからなる合金組成のはんだ合金である。またより好ましくは、Ａｇ：３．０質量％以上４．０質量％以下、Ｃｕ：０．５質量％以上１．０ 質量％以下、Ｃｏ：０．０１質量％以上０．１質量％以下、残部実質上Ｓｎからなる合金組成のはんだ合金である。 The solder alloy composition of the cored solder used in the method for preventing Fe erosion of the soldering device coated with the Fe-based alloy of the present invention is as follows: Ag: 0.3% by mass or more and 4.0% by mass or more, Cu: 0.1 This is a solder alloy having an alloy composition of not less than 1.0% by mass and not more than 1.0% by mass, Co: 0.001% by mass to not more than 0.5% by mass, and the balance substantially consisting of Sn. More preferably, Ag: 3.0% by mass to 4.0% by mass, Cu: 0.5% by mass to 1.0% by mass, Co: 0.01% by mass to 0.1% by mass, This is a solder alloy having an alloy composition substantially consisting of Sn.
Ｓｎ−Ａｇ−Ｃｕ系鉛フリーはんだ合金に微量のＮｉを添加することにより、はんだ合金の耐疲労性を改善することができるが、本発明のＦｅ系合金を被覆したはんだ付け器具のＦｅ喰われ防止方法に用いるやに入りはんだのはんだ合金組成でも同様の効果が現れる。添加するＮｉは、Ｎｉが０．０１質量％より少ないと耐疲労性の改善が見込めず、Ｎｉが０．１質量％より多いとＮｉが析出し、はんだ合金の溶融温度が上昇してしまい、はんだ鏝の設定温度を上げなければならないため、Ｆｅ喰われが大きくなる。 By adding a small amount of Ni to the Sn-Ag-Cu-based lead-free solder alloy, the fatigue resistance of the solder alloy can be improved, but the Fe erosion of the soldering device coated with the Fe-based alloy of the present invention The same effect appears in the solder alloy composition of cored solder as soon as it is used in the prevention method. Ni to be added cannot be expected to improve fatigue resistance when Ni is less than 0.01% by mass, Ni is precipitated when Ni is more than 0.1% by mass, and the melting temperature of the solder alloy rises. Since the set temperature of the soldering iron has to be increased, Fe erosion increases.
本発明のはんだ合金は、使用形態はいずれであっても良いが、その使用温度がはんだの溶融温度＋１５０℃以上と他よりも高く、また必ずＦｅ被覆が行われている、はんだ鏝に用いられるやに入りはんだ用として用いられることが多い。ここで、やに入りはんだとは、線状に成型したはんだの中心部に２〜４％のフラックスを含芯させたものであり、後付や修正などに使用されるマニュアルソルダリング用に用いられる。 The solder alloy of the present invention may be used in any form, but the use temperature thereof is higher than the melting temperature of the solder + 150 ° C. or higher, and it is used for solder irons that are always coated with Fe. Often used for flux cored solder. Here, the flux cored solder is a core in which 2-4% flux is cored at the center of the solder molded into a linear shape, and is used for manual soldering used for retrofit or correction. It is done.
各はんだ合金組成のやに入りはんだを作り、プリント基板のランドをはんだ付けして、鏝先の使用可能回数を調べた。はんだ合金組成、その溶融温度、ウエッティングバランス法のゼロクロスタイムおよび鏝先の使用可能回数の結果を表１に示す。
試験条件
（１）鏝先の使用回数
ランド形状：円
ランドサイズ：０．８ｍｍφ
はんだ鏝温度：はんだ合金の溶融温度＋１６０℃
鏝先仕様：芯材 Ｃｕ
下地 Ｎｉめっき ５０μｍ
表面 Ｆｅめっき ３０μｍ
やに入りはんだ
やに入りはんだ径：０．５ｍｍφ
フラックスの等級：ＡＡ （ＪＩＳ Ｚ ３２８３）
フラックス含有量：３質量％
（２）溶融温度 （ＪＩＳ Ｚ ３１９８−１）
測定方法：示差走査熱量測定法（ＤＳＣ）
昇温速度：５℃／分 キャリアガス：Ａｉｒ
（３）ウエッティングバランス法によるぬれ性の測定 （ＪＩＳ Ｚ ３１９８−４）
浸せき深さ：２ｍｍ
浸せき速度：５ｍｍ／秒
浸漬時間：１０秒
はんだ温度：２５０℃
使用フラックス：ｗｗロジンの２５％ＩＰＡ溶液
Test conditions (1) Number of times the tip is used Land shape: Circular land size: 0.8mmφ
Solder solder temperature: Melting temperature of solder alloy + 160 ° C
Tip specifications: Core material Cu
Base Ni plating 50μm
Surface Fe plating 30μm
Flux cored solder Flux diameter: 0.5mmφ
Flux grade: AA (JIS Z 3283)
Flux content: 3% by mass
(2) Melting temperature (JIS Z 3198-1)
Measuring method: Differential scanning calorimetry (DSC)
Temperature rising rate: 5 ° C./min Carrier gas: Air
(3) Measurement of wettability by the wetting balance method (JIS Z 3198-4)
Immersion depth: 2mm
Immersion speed: 5 mm / sec Immersion time: 10 seconds Solder temperature: 250 ° C.
Flux used: 25% IPA solution of ww rosin
本発明のＣｏを０．００１質量％以上０．０５ 質量％以下を含有したはんだ合金では、鏝先の使用回数が３０００ポイント近く使用可能であったのに対して、比較例のＣｏが入っていないやに入りはんだの使用回数は１０００ポイント以下、先行文献として提示された参考文献１のやに入りはんだでも約１５００ポイントしか使用できなかった。 The solder alloy containing 0.001% by mass or more and 0.05% by mass or less of Co of the present invention can be used nearly 3000 points of the tip, whereas Co of the comparative example is contained. The number of times of use of the cored solder was 1000 points or less, and only about 1500 points could be used with the cored solder of Reference 1 presented as the prior document.
フローソルダリング用のはんだ槽は、インペラ、ダクト、整流板、噴流ノズルなどの駆動部分およびはんだ槽本体にSUS304などのFe系のステンレス鋼が使用されている。これらのＦｅの合金を使用しているものにも、本発明のはんだ合金を用いることにより、Ｆｅ喰われを防ぎ、はんだ槽を長持ちさせることができる。 The soldering bath for flow soldering uses Fe-based stainless steel such as SUS304 for driving parts such as impellers, ducts, rectifying plates, jet nozzles, and the soldering bath body. By using the solder alloy of the present invention for those using these Fe alloys, it is possible to prevent Fe erosion and extend the solder bath.
Claims (7)
When soldering with a Sn-Ag-Cu-based lead-free solder alloy containing Sn as a main component using a soldering member coated with Fe and an Fe-based alloy, Sn-Ag-Cu-based lead-free A method for preventing Fe erosion of a member coated with Fe and an Fe-based alloy, characterized in that soldering is performed using a solder alloy containing 0.001 mass% or more and 0.5 mass% or less of Co.
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| US8823245B2 (en) | 2009-11-20 | 2014-09-02 | Epcos Ag | Solder material for fastening an outer electrode on a piezoelectric component and piezoelectric component comprising a solder material |
| JP2013511392A (en) * | 2009-11-20 | 2013-04-04 | エプコス アーゲー | Solder material for joining external electrodes to piezoelectric component, and piezoelectric component having solder material |
| DE102009054068A1 (en) * | 2009-11-20 | 2011-05-26 | Epcos Ag | Solder material for fixing an outer electrode in a piezoelectric component and piezoelectric component with a solder material |
| JP2015083321A (en) * | 2009-11-20 | 2015-04-30 | エプコス アーゲーＥｐｃｏｓ Ａｇ | Solder material for bonding outer electrode to piezoelectric component, and piezoelectric component comprising solder material |
| US9527167B2 (en) | 2011-03-28 | 2016-12-27 | Senju Metal Industry Co., Ltd. | Lead-free solder ball |
| US9700963B2 (en) | 2011-03-28 | 2017-07-11 | Senju Metal Industry Co., Ltd. | Lead-free solder ball |
| JP2019072742A (en) * | 2017-10-17 | 2019-05-16 | 千住金属工業株式会社 | Wire solder, manufacturing method of solder joint and soldering method |
| JP6323606B1 (en) * | 2017-10-17 | 2018-05-16 | 千住金属工業株式会社 | Wire solder, solder joint manufacturing method and soldering method |
| JP2019093425A (en) * | 2017-11-24 | 2019-06-20 | 千住金属工業株式会社 | Discoloration-resistant solder material, and discoloration-resistant solder joint |
| JP2020015054A (en) * | 2018-07-24 | 2020-01-30 | 千住金属工業株式会社 | Solder alloy and solder joint |
| WO2020021967A1 (en) * | 2018-07-24 | 2020-01-30 | 千住金属工業株式会社 | Soldering alloy and solder joint |
| TWI694885B (en) * | 2018-07-24 | 2020-06-01 | 日商千住金屬工業股份有限公司 | Solder alloys and welded joints |
| JP2019130596A (en) * | 2019-04-02 | 2019-08-08 | 千住金属工業株式会社 | Discoloration-resistant solder material, and discoloration-resistant solder joint |
| JP7013636B2 (en) | 2019-04-02 | 2022-02-01 | 千住金属工業株式会社 | Discoloration resistant solder alloys and discoloration resistant solder joints |
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