JP2009502513A - Sn-Ag-Cu-Ni-Al lead-free solder alloy - Google Patents

Sn-Ag-Cu-Ni-Al lead-free solder alloy Download PDF

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JP2009502513A
JP2009502513A JP2008524347A JP2008524347A JP2009502513A JP 2009502513 A JP2009502513 A JP 2009502513A JP 2008524347 A JP2008524347 A JP 2008524347A JP 2008524347 A JP2008524347 A JP 2008524347A JP 2009502513 A JP2009502513 A JP 2009502513A
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キョセイ マ
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Abstract

電子材料及び電子製造の技術領域におけるＳｎ−Ａｇ−Ｃｕ−Ｎｉ−Ａｌ系無鉛はんだ合金に関するものである。はんだ合金の各化学成分の重量％はＡｇ １．５〜４．０、Ｃｕ ０．１〜２．０、Ａｌ ０．００１〜０．５、Ｎｉ：０．０１〜１．０、残りはＳｎと不可避的な不純物である。本発明の無鉛はんだ合金は、従来の制作方法により、ペースト、粉、ブロック、棒や線などの各種物理的形状を得ることが可能であり、リフローはんだ付け、ウェーブはんだ付け、手付けはんだ付けなどの多種の溶接方法により多くの需要を満足させるものである。本発明はんだ合金は、１）はんだ合金の広がり率を高める、２）溶接を行う際に溶剤を利用し酸化膜を除去し、溶接箇所の結合強度を高め、組織を均一化し、欠陥を減少させる耐酸化性が良好である、３）はんだ合金の安定性を高め、はんだの溶接特性の悪化を防ぐという特徴を備えている。  The present invention relates to an Sn—Ag—Cu—Ni—Al lead-free solder alloy in the technical field of electronic materials and electronic manufacturing. The weight percentage of each chemical component of the solder alloy is Ag 1.5-4.0, Cu 0.1-2.0, Al 0.001-0.5, Ni: 0.01-1.0, the rest is Sn And inevitable impurities. The lead-free solder alloy of the present invention can be obtained in various physical shapes such as paste, powder, block, bar and wire by conventional production methods, such as reflow soldering, wave soldering, and manual soldering. Many demands are satisfied by various welding methods. The solder alloy of the present invention 1) increases the spreading rate of the solder alloy, 2) removes the oxide film using a solvent when welding, increases the bond strength of the welded portion, homogenizes the structure, and reduces defects It has good oxidation resistance. 3) It has the characteristics of enhancing the stability of the solder alloy and preventing deterioration of the welding characteristics of the solder.

Description

本発明は電子材料及び電子製造の技術領域におけるＳｎ−Ａｇ−Ｃｕ−Ｎｉ−Ａｌ系無鉛はんだ合金、具体的には電子組立とパッケージ及び電子、電機設備、通信機材、自動車などの領域におけるろう付けはんだの使用に適した無鉛はんだに関するものである。   The present invention relates to Sn-Ag-Cu-Ni-Al-based lead-free solder alloys in the technical field of electronic materials and electronic manufacturing, specifically electronic assembly and packaging, and brazing in the fields of electronics, electrical equipment, communication equipment, automobiles, etc. The present invention relates to a lead-free solder suitable for the use of solder.

Ｓｎ−Ｐｂ合金は現代電子工業における主要な実装材料であり、電子部品の組立において主要な地位を占めている。Ｓｎ−Ｐｂ合金は優れた濡れ性及び溶接性、導電性、力学的性能、低コストなどの特徴を備えているが、これに対してＰｂ及びＰｂ化合物は有毒性を持ち、その使用により環境汚染、労働者の健康が損なわれると共に、環境保護法が日々厳格に整備されていくなか、鉛の使用禁止を叫ぶ声が日益しに高まっている。   Sn-Pb alloy is a major mounting material in the modern electronics industry and occupies a major position in the assembly of electronic components. Sn-Pb alloy has excellent wettability and weldability, electrical conductivity, mechanical performance, low cost, etc. In contrast, Pb and Pb compounds are toxic, and their use causes environmental pollution. As the health of workers is impaired and environmental protection laws are being rigorously developed every day, the voices crying out to ban the use of lead are increasing.

各国において、鉛はんだの電子産業における使用を禁止した法令が次々に制定されている。２０００年６月、アメリカＩＰＣＬｅａｄ−ＦｒｅｅＲｏａｄｍａｐ第４版は、アメリカ企業界に２００１年より電子商品の無鉛化の推進、２００４年より全面無鉛化実施の提案を発表した。ヨーロッパでは無鉛立法を推進するにあたり、より積極的な態度がとられ、２００３年２月１３日付のＥＣ官報において《電子電機設備におけるいくつかの有害物質の使用禁止指令》を公布、ＷＥＥＥ（Waste Electrical and Electronic Equipment）とＲｏｌｌｓ（Restriction of Hazardous Substances）が正式に批准され、効力が発生したことにより、２００６年７月１日よりヨーロッパ市場において販売される電子商品は無鉛の電子商品でなければならなくなった。アジア方面では、日本政府が２００３年１月より全面的な無鉛化を推進すると共に、“無鉛”表示によりアメリカ、中国、韓国、台湾地区及びヨーロッパからの有鉛電子商品の輸入品を阻止又は制限し始めた。中国政府は２００３年３月に情報産業部が《電子情報商品生産汚染予防治療管理法》を制定し、２００６年７月１日より鉛を含んだ電子商品を禁止した。
アメリカＩＰＣＬｅａｄ−ＦｒｅｅＲｏａｄｍａｐ第４版 In each country, laws and regulations prohibiting the use of lead solder in the electronics industry have been enacted one after another. In June 2000, US IPCLead-FreeRoadmap 4th edition announced to the US business community the promotion of lead-free electronic products from 2001 and the implementation of lead-free from 2004. In Europe, a more positive attitude was taken to promote lead-free legislation, and in the EC official gazette on February 13, 2003, the “Prohibition on the Use of Some Hazardous Substances in Electronic Equipment” was promulgated. and Electronic Equipment) and Rolls (Restriction of Hazardous Substances) have been officially ratified and become effective, electronic products sold in the European market from 1 July 2006 must be lead-free electronic products It was. In Asia, the Japanese government has promoted lead-free implementation in January 2003, and has blocked or restricted the import of leaded electronic products from the United States, China, South Korea, Taiwan, and Europe with the “lead-free” label. Began to do. In March 2003, the Ministry of Information Industry enacted the Law for the Prevention and Treatment of Electronic Information Product Production Pollution by the Ministry of Information Industry and banned electronic products containing lead from July 1, 2006.
US IPCLead-FreeLoadmap 4th edition

現在の無鉛はんだにおいて、Ｓｎ−Ａｇ−Ｃｕ系合金はその応用が比較的良好であるとして、アメリカＮＥＭＩ、イギリスＤＴＩ、Ｓｏｌｄｅｒｔｅｃなどの推薦を得ている。Ｓｎ−Ａｇ−Ｃｕ系について、アメリカ特許４，７７８，７３３はＳｎ−Ａｇ（０．０５−３％）−ｃｕ（０．７−６％）の組成の無鉛はんだを開示している。アメリカ特許５，５２７，６２８は組成が９３．６Ｓｎ−４．７Ａｇ−１．７Ｃｕの合金について叙述している。アメリカ特許５，８６３，４９３はＳｎ−Ａｇ（２．０−５．０％）−ｃｕ（０−２．９％）の無鉛はんだを開示している。またアメリカ特許４，７５８，４０７はＳｎ−Ａｇ（０−５．０％）−ｃｕ（３．０−５．０％）を基礎としてＮｉ元素を添加している。アメリカ特許６，１７９，９３５はＳｎ−Ａｇ（０−４．０％）−Ｃｕ（０−２．０％）を基礎として微量のＮｉとＧｅ元素を添加している。Ｓｎ−Ａｇ−Ｃｕ系はんだ合金は、総合性では比較的優れているが、濡れ性が劣り、合金の組成が粗く、分布が不均一であるという欠点がある。   In the current lead-free solder, Sn—Ag—Cu based alloys have been recommended by US NEMI, UK DTI, Soldertec, etc. for their relatively good application. For the Sn-Ag-Cu system, U.S. Pat. No. 4,778,733 discloses a lead-free solder having a composition of Sn-Ag (0.05-3%)-cu (0.7-6%). U.S. Pat. No. 5,527,628 describes an alloy having a composition of 93.6Sn-4.7Ag-1.7Cu. US Pat. No. 5,863,493 discloses a lead-free solder of Sn—Ag (2.0-5.0%)-cu (0-2.9%). U.S. Pat. No. 4,758,407 adds Ni element based on Sn-Ag (0-5.0%)-cu (3.0-5.0%). U.S. Pat. No. 6,179,935 adds a small amount of Ni and Ge elements based on Sn-Ag (0-4.0%)-Cu (0-2.0%). Sn—Ag—Cu-based solder alloys are relatively excellent in totality, but have the drawbacks of poor wettability, rough alloy composition, and non-uniform distribution.

本発明の目的は、はんだ合金のミクロ構造を最適にすることにより、はんだの応用特性を高めたＳｎ−Ａｇ−Ｃｕ−Ｎｉ−Ａｌ系無鉛はんだ合金を提供することにある。
本発明が提供しているＳｎ−Ａｇ−Ｃｕ−Ｎｉ−Ａｌ系無鉛はんだ合金における各化学成分の重量％は、
Ａｇ １．５〜４．０
Ｃｕ ０．１〜２．０
Ａｌ ０．００１〜０．５
Ｎｉ ０．０１〜１．０
残りはＳｎと不可避的な不純物である。 An object of the present invention is to provide a Sn-Ag-Cu-Ni-Al-based lead-free solder alloy with improved solder application characteristics by optimizing the microstructure of the solder alloy.
The weight% of each chemical component in the Sn—Ag—Cu—Ni—Al lead-free solder alloy provided by the present invention is as follows:
Ag 1.5-4.0
Cu 0.1-2.0
Al 0.001-0.5
Ni 0.01-1.0
The rest is Sn and inevitable impurities.

本発明が提供しているＳｎ−Ａｇ−Ｃｕ−Ｎｉ−Ａｌ系無鉛はんだ合金は、現有技術において公知の従来の製作方法により、ペースト、粉、ブロック、棒、球や線などの各種物理的形状を得ることが可能であり、リフローはんだ付け、ウェーブはんだ付けや手付けはんだ付けなどの多種の溶接方法により多くの需要を満足させるものである。   Sn-Ag-Cu-Ni-Al-based lead-free solder alloys provided by the present invention can be prepared in various physical shapes such as pastes, powders, blocks, rods, spheres and wires by conventional manufacturing methods known in the existing technology. Therefore, many demands are satisfied by various welding methods such as reflow soldering, wave soldering and manual soldering.

本発明を利用して製造したＳｎ−Ａｇ−Ｃｕ−Ｎｉ−Ａｌ系無鉛はんだ合金は、長所として、１）はんだの溶接部材における濡れ性が良好である、つまり合金はんだの広がり率を高めた。２）耐酸化性が良好である、無鉛はんだ合金中のＮｉは合金の耐酸化性を高め、Ａｌははんだ表面に厚めの酸化膜を形成し、合金を保護する、溶接時に溶剤を利用し酸化膜を除去することにより、溶接箇所の結合強度を強め、組成を均一化し、欠陥を少なくした。３）はんだの安定性を高め、はんだの溶接特性の悪化を防ぐこと、が挙げられる。   The Sn-Ag-Cu-Ni-Al-based lead-free solder alloy produced by utilizing the present invention has the following advantages: 1) Good wettability in the welded member of the solder, that is, the spreading rate of the alloy solder is increased. 2) Ni in lead-free solder alloy with good oxidation resistance enhances the oxidation resistance of the alloy, Al forms a thick oxide film on the solder surface, protects the alloy, and uses a solvent during welding to oxidize By removing the film, the bond strength at the welded portion was increased, the composition was made uniform, and defects were reduced. 3) To increase the stability of the solder and to prevent deterioration of the welding characteristics of the solder.

本発明における各添加元素の作用及び最も好ましい含有量を以下に詳細に説明する。ＡｇはＳｎ基体とＳｎ−Ａｇ共晶を形成し、はんだの融点を低下させ、はんだの力学的性能を高め、さらにＳｎ−Ａｇ系はんだは伝統的なＳｎ−Ｐｂ共晶に較べ特に優れた耐クリープ疲労特性を備えている。Ａｇの追加量が０．５％より少ない場合、これら作用ははっきり表れない。５．０％以上のＡｇを加えるとはんだ合金の液相線温度は急激に上昇し、ろう付け温度の上昇により電子構成部品が熱破壊を受ける可能性がある。好ましいＡｇの含有量は１．５〜４．０％である。Ｃｕを添加することによりＳｎ−Ａｇ−Ｃｕ間に三元共晶を形成させ、はんだの融点をさらに低下させることができる。Ｃｕ元素は更にＳｎ−Ａｇ系はんだの濡れ性を高めることが可能である。Ｃｕ元素の存在ははんだの強度を高め、Ｓｎ−Ａｇはんだの強度不足という欠点を補っている。Ｓｎ−Ａｇ−Ｃｕ共晶はんだは更に強い強度を有する。また溶融はんだ鍋に漬ける方法により、銅箔導線を設けたプリント回路板に電子部品をろう付けする際に、溶融はんだ鍋中にあるＣｕは銅箔導線における銅が溶融はんだ鍋に拡散するのを抑制するという余分な作用を有する。好ましいＣｕの含有量は０．１〜２．０％である。Ｎｉ元素はＣｕが溶融はんだに溶解することを抑制し、Ｃｕが溶融はんだに溶解する速度及び架橋を起こす可能性を低下させることが可能である。ＮｉはＳｎとＣｕが反応により形成したＣｔ−Ｓｎ５とＣｕ３Ｓｎなどの金属間の化合物を抑え、これら形成された化合物を溶解させる。Ａｌ耐酸化マイクロ構造を解析する。Ａｌは面心立方構造であり、各方向が同性の特徴を備えているため、はんだ合金が凝固時、Ａｌは高分散した微粒子の形状により合金基体中に析出分布され、各微粒子は一定範囲の合金基体の周囲に耐酸化保護作用をもたらす。この様に、比較的少量のＡｌは理想的な抗酸化効果を発揮する。   The action and most preferable content of each additive element in the present invention will be described in detail below. Ag forms a Sn-Ag eutectic with the Sn substrate, lowers the melting point of the solder, improves the mechanical performance of the solder, and Sn-Ag solder has a particularly excellent resistance to resistance compared to the traditional Sn-Pb eutectic. Has creep fatigue properties. These effects are not apparent when the added amount of Ag is less than 0.5%. When 5.0% or more of Ag is added, the liquidus temperature of the solder alloy rises rapidly, and the electronic component may be subject to thermal destruction due to the increase in brazing temperature. The preferable Ag content is 1.5 to 4.0%. By adding Cu, a ternary eutectic can be formed between Sn—Ag—Cu, and the melting point of the solder can be further lowered. Cu element can further improve the wettability of Sn-Ag solder. The presence of Cu element increases the strength of the solder and compensates for the shortage of Sn-Ag solder. Sn-Ag-Cu eutectic solder has a stronger strength. In addition, when brazing electronic components to a printed circuit board provided with a copper foil conductor by the method of immersing it in a molten solder pan, Cu in the molten solder pan prevents the copper in the copper foil conductor from diffusing into the molten solder pan. It has the extra effect of inhibiting. A preferable Cu content is 0.1 to 2.0%. Ni element suppresses that Cu melt | dissolves in a molten solder, It is possible to reduce the possibility of causing the speed | rate and bridge | crosslinking which Cu melt | dissolves in a molten solder. Ni suppresses compounds between metals such as Ct-Sn5 and Cu3Sn formed by reaction of Sn and Cu, and dissolves these formed compounds. The Al oxidation resistant microstructure is analyzed. Since Al has a face-centered cubic structure and each direction has the same characteristics, when the solder alloy solidifies, Al is precipitated and distributed in the alloy base due to the shape of highly dispersed fine particles, and each fine particle has a certain range. Provides an oxidation-resistant protective action around the alloy substrate. Thus, a relatively small amount of Al exhibits an ideal antioxidant effect.

以下は本発明の実施例であり、各実施例は、重金属原料をるつぼ又は溶解なべに入れ空気中で加熱撹拌するという従来の方法により鋳造している。しかし、空気中において原料金属を溶融し、原料金属及び合金中の不純物又は非金属物が空気と反応し、可溶性のガスとなり、可溶性窒素又は酸素ははんだ合金中に残留し、溶接性能を低下させる。よって本発明の無鉛含量合金は真空又は不活性ガス中において精錬するのが最も望ましい。   The following are examples of the present invention, and each example is cast by a conventional method in which a heavy metal raw material is placed in a crucible or a melting pan and heated and stirred in air. However, the raw metal is melted in the air, and impurities or non-metallic substances in the raw metal and the alloy react with the air to form a soluble gas, so that soluble nitrogen or oxygen remains in the solder alloy and deteriorates the welding performance. . Therefore, it is most desirable to refine the lead-free alloy of the present invention in a vacuum or an inert gas.

無鉛はんだ合金における各化学成分の重量％は、Ａｇ：３．８，Ｃｕ：０．３，Ａｌ：０．１，Ｎｉ：０．０２，残りはＳｎ。はんだ合金の固相線温度は２１６．１３℃、液相線温度は２１９．５３℃、広がり率は９１．３％である。   The weight percentage of each chemical component in the lead-free solder alloy is Ag: 3.8, Cu: 0.3, Al: 0.1, Ni: 0.02, and the rest is Sn. The solidus temperature of the solder alloy is 216.13 ° C., the liquidus temperature is 219.53 ° C., and the spreading ratio is 91.3%.

無鉛はんだ合金における各化学成分の重量％は、Ａｇ：３．５，Ｃｕ：０．７，Ａｌ：０．２，Ｎｉ：０．１０，残りはＳｎ。はんだ合金の固相線温度は２１６．１３℃、液相線温度は２１９．５３℃、広がり率は９１．３％である。   The weight percentage of each chemical component in the lead-free solder alloy is Ag: 3.5, Cu: 0.7, Al: 0.2, Ni: 0.10, and the rest is Sn. The solidus temperature of the solder alloy is 216.13 ° C., the liquidus temperature is 219.53 ° C., and the spreading ratio is 91.3%.

無鉛はんだ合金における各化学成分の重量％は、Ａｇ：３．０，Ｃｕ：１，Ａｌ：０．３，Ｎｉ：０．４０，残りはＳｎ。はんだ合金の固相線温度は２１６．９６℃、液相線温度は２２０．２０℃、広がり率は９４．３％である。     The weight percentage of each chemical component in the lead-free solder alloy is Ag: 3.0, Cu: 1, Al: 0.3, Ni: 0.40, and the rest is Sn. The solidus temperature of the solder alloy is 216.96 ° C., the liquidus temperature is 220.20 ° C., and the spreading ratio is 94.3%.

無鉛はんだ合金における各化学成分の重量％は、Ａｇ：２．０，Ｃｕ：１．５，Ａｌ：０．４，Ｎｉ：０．７０，残りはＳｎ。はんだ合金の固相線温度は２２０．６６℃、液相線温度は２２３．１２℃、広がり率は８７．１％である。     The weight percentage of each chemical component in the lead-free solder alloy is Ag: 2.0, Cu: 1.5, Al: 0.4, Ni: 0.70, and the rest is Sn. The solidus temperature of the solder alloy is 220.66 ° C., the liquidus temperature is 223.12 ° C., and the spreading ratio is 87.1%.

無鉛はんだ合金における各化学成分の重量％は、Ａｇ：２．５，Ｃｕ：１．５，Ａｌ：０．５，Ｎｉ：１．００，残りはＳｎ。はんだ合金の固相線温度は２１９．８１℃、液相線温度は２２２．４７℃、広がり率は８７．７％である。     The weight percentage of each chemical component in the lead-free solder alloy is Ag: 2.5, Cu: 1.5, Al: 0.5, Ni: 1.00, and the rest is Sn. The solidus temperature of the solder alloy is 219.81 ° C., the liquidus temperature is 222.47 ° C., and the spreading ratio is 87.7%.

無鉛はんだ合金における各化学成分の重量％は、Ａｇ：３．５，Ｃｕ：０．７５，Ａｌ：０．００１，Ｎｉ：０．１，残りはＳｎ。はんだ合金の固相線温度は２１７℃、液相線温度は２１９℃、広がり率は８８．５％である。   The weight percentage of each chemical component in the lead-free solder alloy is Ag: 3.5, Cu: 0.75, Al: 0.001, Ni: 0.1, and the rest is Sn. The solidus temperature of the solder alloy is 217 ° C., the liquidus temperature is 219 ° C., and the spreading ratio is 88.5%.

Claims (1)

はんだ合金における各化学成分の重量％が、Ａｇが１．５〜４．０、Ｃｕが０．１〜２．０、Ａｌが０．００１〜０．５、Ｎｉが０．０１〜１．０であって、残りがＳｎである
ことを特徴とするＳｎ−Ａｇ−Ｃｕ−Ｎｉ−Ａｌ系無鉛はんだ合金。 The weight percentage of each chemical component in the solder alloy is such that Ag is 1.5 to 4.0, Cu is 0.1 to 2.0, Al is 0.001 to 0.5, and Ni is 0.01 to 1.0. And the remainder is Sn. Sn-Ag-Cu-Ni-Al-based lead-free solder alloy.
JP2008524347A 2005-08-02 2006-08-02 Sn-Ag-Cu-Ni-Al lead-free solder alloy Pending JP2009502513A (en)

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CNB2005100873831A CN1313631C (en) 2005-08-02 2005-08-02 Tin silver copper nickel aluminium series leadless welding flux alloy
PCT/CN2006/001943 WO2007014530A1 (en) 2005-08-02 2006-08-02 Lead-free sn-ag-cu-ni-al system solder alloy

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JP2009502513A true JP2009502513A (en) 2009-01-29

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JP2017213602A (en) * 2016-05-31 2017-12-07 株式会社日本スペリア社 Soldering method and solder joint
JP2022515254A (en) * 2018-12-27 2022-02-17 アルファ・アセンブリー・ソリューションズ・インコーポレイテッド Lead-free solder composition

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WO2012137901A1 (en) * 2011-04-08 2012-10-11 株式会社日本スペリア社 Solder alloy
CN111112870A (en) * 2019-12-20 2020-05-08 深圳市镱豪金属有限公司 Environment-friendly tin bar

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
JP2017213602A (en) * 2016-05-31 2017-12-07 株式会社日本スペリア社 Soldering method and solder joint
JP2022515254A (en) * 2018-12-27 2022-02-17 アルファ・アセンブリー・ソリューションズ・インコーポレイテッド Lead-free solder composition

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CN1718797A (en) 2006-01-11
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