JP2009082986A - Lead-free solder alloy for manual soldering - Google Patents
Lead-free solder alloy for manual soldering Download PDFInfo
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- JP2009082986A JP2009082986A JP2008223211A JP2008223211A JP2009082986A JP 2009082986 A JP2009082986 A JP 2009082986A JP 2008223211 A JP2008223211 A JP 2008223211A JP 2008223211 A JP2008223211 A JP 2008223211A JP 2009082986 A JP2009082986 A JP 2009082986A
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- 229910000679 solder Inorganic materials 0.000 title claims abstract description 92
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 40
- 239000000956 alloy Substances 0.000 title claims abstract description 40
- 238000005476 soldering Methods 0.000 title claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 229910001122 Mischmetal Inorganic materials 0.000 claims abstract description 7
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 6
- 150000003624 transition metals Chemical class 0.000 claims abstract description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 120
- 229910052742 iron Inorganic materials 0.000 abstract description 64
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 51
- 239000010949 copper Substances 0.000 abstract description 50
- 229910052802 copper Inorganic materials 0.000 abstract description 42
- 239000006023 eutectic alloy Substances 0.000 abstract description 12
- 229910052732 germanium Inorganic materials 0.000 abstract description 12
- 229910052709 silver Inorganic materials 0.000 abstract description 3
- 230000003628 erosive effect Effects 0.000 description 37
- 230000000694 effects Effects 0.000 description 12
- 229910000765 intermetallic Inorganic materials 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000010828 elution Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000001629 suppression Effects 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- 238000007654 immersion Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910008433 SnCU Inorganic materials 0.000 description 3
- 229910018792 Sn—Co—Fe Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910017816 Cu—Co Inorganic materials 0.000 description 2
- 229910017061 Fe Co Inorganic materials 0.000 description 2
- 229910020816 Sn Pb Inorganic materials 0.000 description 2
- 229910020922 Sn-Pb Inorganic materials 0.000 description 2
- 229910008783 Sn—Pb Inorganic materials 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910017944 Ag—Cu Inorganic materials 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229910007116 SnPb Inorganic materials 0.000 description 1
- 229910005728 SnZn Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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Abstract
Description
この発明は、電気・電子機器の金属接合等に使用されるマニュアルソルダリング用無鉛はんだ合金に係り、詳記すれば、優れた耐こて先喰われ性と耐銅喰われ性を併有するマニュアルソルダリング用のＳｎＡｇＣｕ系無鉛はんだ合金に関する。 The present invention relates to a lead-free solder alloy for manual soldering used for metal bonding of electric / electronic devices, and more specifically, a manual having both excellent tip resistance and copper resistance. The present invention relates to a SnAgCu-based lead-free solder alloy for soldering.
従来、電気・電子機器の金属接合に使用するはんだ合金としては、Ｓｎが６３重量％、Ｐｂが３７重量％等の鉛を含有するはんだ合金が一般的に用いられてきた。 Conventionally, a solder alloy containing lead such as 63 wt% Sn and 37 wt% Pb has been generally used as a solder alloy used for metal bonding of electric / electronic devices.
しかしながら、鉛を含有するはんだは、人体に有害であることから鉛を含有しない多くの無鉛はんだ合金が検討されている。具体的には、ＳｎＣｕ系合金、ＳｎＡｇＣｕ系合金、ＳｎＺｎ系合金やこれらの合金にＢｉ、Ｉｎ等を添加したものが検討されている。 However, since lead-containing solder is harmful to the human body, many lead-free solder alloys that do not contain lead have been studied. Specifically, SnCu-based alloys, SnAgCu-based alloys, SnZn-based alloys, and alloys obtained by adding Bi, In or the like to these alloys have been studied.
この中でＳｎＡｇＣｕ系合金は、クリープ強度に代表される優れた機械特性値と濡れ性を有するところから、信頼性の高い無鉛はんだ合金として、最も実用化されている無鉛はんだ合金である。 Among these, SnAgCu-based alloys are lead-free solder alloys most practically used as lead-free solder alloys with high reliability because they have excellent mechanical property values typified by creep strength and wettability.
しかしながら、このＳｎ３Ａｇ０．５Ｃｕに代表されるＳｎＡｇＣｕ系の合金は、銅や鉄系の合金を溶食し易く、基板の銅回路の浸食、銅の細線を消失、はんだ槽の容器の浸食、はんだこて先の鉄メッキの侵食などの、いわゆる金属の溶損にかかわる問題があり、これらが実用上の障害となっている。 However, this SnAgCu-based alloy represented by Sn3Ag0.5Cu is easy to corrode copper and iron-based alloys, erosion of the copper circuit of the substrate, disappearance of the copper fine wire, erosion of the container of the solder bath, soldering iron There are problems associated with so-called metal erosion, such as the previous erosion of iron plating, which are practical obstacles.
一方、マニュアルソルダリングとは、固形フラックスをコアとした線状のはんだを、はんだこてを用いてはんだ付けする工法である。 On the other hand, manual soldering is a method of soldering linear solder with solid flux as a core using a soldering iron.
このマニュアルソルダリングで、ＳｎＡｇＣｕ系のはんだを使用する場合、ＳｎＣｕ系のはんだ合金（Ｓｎ０．７ＣｕあるいはＳｎ０．３Ａｇ０．７Ｃｕに代表される）よりは少ないが、鉄を溶解し易く、銅の表層を鉄メッキしたこて先の寿命が短くなるという、いわゆる鉄喰われあるいはこて先喰われが大きいという欠点と、径が０．２ｍｍ程度の銅の細線あるいは細線束をはんだ付けする場合に、銅の細線が消失するという欠点を持っている。この銅喰われに関しては、ＳｎＣｕ系はんだ合金よりもＳｎＡｇＣｕ系はんだ合金の方が、銅線等の銅が喰われやすい。 When using SnAgCu solder in this manual soldering, it is less than SnCu solder alloy (typified by Sn0.7Cu or Sn0.3Ag0.7Cu), but it is easy to dissolve iron and the surface layer of copper When soldering a copper wire or a bundle of wires with a diameter of about 0.2 mm, the shortage of the iron-plated tip is short, that is, the so-called iron bite or the tip bite is large. Has the disadvantage that the fine lines disappear. Regarding this copper erosion, the SnAgCu solder alloy is more easily eroded by copper, such as a copper wire, than the SnCu solder alloy.
Ｓｎベースの鉛フリーはんだは、ＳｎＰｂ系はんだに比較して、融点が高いうえに、濡れ性が悪いことから、マニュアルソルダリングにおけるこて先の温度は、Ｓｎ３７Ｐｂ（共晶合金）のはんだより高い３００〜４５０℃程度に設定されるのが一般的である。そのため、こて先の鉄メッキの浸食により、こて先の寿命はさらに短くなり、また、径０．２ｍｍ程度の銅細線をはんだ付けする場合の銅細線の消失も起こり易くなり、これが現実的な大問題となっている。 Since Sn-based lead-free solder has a higher melting point and poor wettability compared to SnPb solder, the tip temperature in manual soldering is higher than that of Sn37Pb (eutectic alloy) solder. Generally, the temperature is set to about 300 to 450 ° C. Therefore, the life of the tip is further shortened due to the erosion of the iron plating of the tip, and the loss of the copper fine wire is likely to occur when soldering the copper fine wire having a diameter of about 0.2 mm, which is realistic. It has become a big problem.
鉄喰われの問題を解決するために、Ｃｏ：０．００１〜０．５重量％、Ｎｉ：０．０１〜０．１重量％を添加するＳｎＡｇＣｕ系合金が提案されている（特許文献１参照）。しかしながらこのものは、本発明者等の研究によれば、４００℃近くの温度では、こて先の喰われを抑制する効果は少ないことが判明した。 In order to solve the problem of iron erosion, a SnAgCu-based alloy to which Co: 0.001 to 0.5 wt% and Ni: 0.01 to 0.1 wt% are added has been proposed (see Patent Document 1). ). However, according to the study by the present inventors, it has been found that the effect of suppressing the tip biting is small at a temperature close to 400 ° C.
更に、鉄喰われの問題を解決するために、Ｆｅ、ＮｉとＣｏを添加するＳｎＡｇＣｕ系の鉛フリーはんだ合金が特許されている（特許文献２参照）。このはんだは、Ｆｅ、ＮｉとＣｏを添加することでＳｎ３７Ｐｂ（共晶合金）に近いこて先喰われ抑制効果を発揮する。しかしながら、本発明者等の研究によれば、このはんだは耐鉄喰われ性は優れるが、４００℃程度の高温では銅喰われを抑制する効果が少なく、また、Ｆｅ、ＮｉとＣｏの添加量が多すぎると、ＳｎとＦｅ、Ｃｏ、Ｎｉの高融点の金属間化合物が溶解工程で生成し易くなり、金属間化合物が酸化物とともにドロスとして系外に排出され、安定した成分組成のはんだの製造が困難となることが判明した。 Furthermore, in order to solve the problem of iron erosion, a SnAgCu-based lead-free solder alloy to which Fe, Ni, and Co are added has been patented (see Patent Document 2). This solder exhibits the effect of suppressing the tip erosion close to Sn37Pb (eutectic alloy) by adding Fe, Ni and Co. However, according to the study by the present inventors, this solder is excellent in iron erosion resistance, but at a high temperature of about 400 ° C., there is little effect of suppressing copper erosion, and the addition amount of Fe, Ni and Co If there is too much, a high melting point intermetallic compound of Sn and Fe, Co, and Ni is likely to be generated in the melting process, and the intermetallic compound is discharged out of the system as dross together with the oxide, and the solder with a stable component composition Production has proved difficult.
従って、従来のＳｎＡｇＣｕ系のはんだ合金は、こて先に代表される鉄喰われの抑制、銅細線に代表される銅喰われの抑制と製造上の問題である成分組成の安定性という観点から、マニュアルソルダリング用としては未だ全く不満足であった。 Therefore, the conventional SnAgCu-based solder alloy has the viewpoint of the suppression of iron erosion represented by the tip, the suppression of copper erosion represented by the copper fine wire, and the stability of the component composition which is a problem in production. It was still unsatisfactory for manual soldering.
この発明は、このような点に鑑みなされたものであり、Ｓｎ３７Ｐｂ（共晶合金）と同レベルの耐こて先喰われ性と実用上問題のない耐銅喰われ性を有し、また、安定した成分組成のはんだの製造が可能な、ＳｎＡｇＣｕ系のマニュアルソルダリング用無鉛はんだ合金を提供することを目的とする。 This invention has been made in view of such points, and has the same level of tip erosion resistance as Sn37Pb (eutectic alloy) and copper erosion resistance with no practical problems, An object of the present invention is to provide a SnAgCu-based lead-free solder alloy for manual soldering capable of producing a solder having a stable component composition.
上記目的を達成するために本発明者等は、鋭意研究の結果、Ｃｕを０．２〜１．２重量％、Ａｇを１．０〜５．０重量％含有するＳｎＡｇＣｕ系無鉛はんだ合金に、微量のＣｏ、ＧｅとＦｅを添加し、残部がＳｎよりなるはんだ合金が、Ｓｎ３７Ｐｂ（共晶合金）と同レベルの耐こて先喰われ性と実用レベルの耐銅喰われ性を有し、安定した成分組成のはんだが製造できることを見出し、本発明に到達した。 In order to achieve the above object, as a result of intensive studies, the present inventors have developed a SnAgCu-based lead-free solder alloy containing 0.2 to 1.2% by weight of Cu and 1.0 to 5.0% by weight of Ag. A solder alloy comprising a small amount of Co, Ge and Fe and the balance being Sn has the same level of tip erosion resistance and practical level of copper erosion resistance as Sn37Pb (eutectic alloy), The inventors have found that a solder having a stable component composition can be produced, and have reached the present invention.
即ち本発明のマニュアルソルダリング用はんだは、Ｃｕを０．２〜１．２重量％、Ａｇを１．０〜５．０重量％含有するＳｎＡｇＣｕ系無鉛はんだ合金であって、Ｃｏを０.００５〜０．０３重量％、Ｇｅを０．００１〜０．０１重量％及びＦｅを０．０１〜０．０５重量％含有し、残部がＳｎよりなることを特徴とする。
さらに、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄなどの遷移金属あるいはこれらの混合物であるミッシュメタル［Mischmetall：独語、mixed metals：英語（以下ＭＭと略す場合がある）］を０．００１〜０．０５重量％添加することによって、耐こて先喰われ性と耐銅喰われ性を補完することができる。
That is, the solder for manual soldering of the present invention is a SnAgCu-based lead-free solder alloy containing 0.2 to 1.2% by weight of Cu and 1.0 to 5.0% by weight of Ag, and Co is 0.005. It is characterized by containing -0.03% by weight, Ge by 0.001-0.01% by weight and Fe by 0.01-0.05% by weight, with the balance being Sn.
Further, transition metal such as La, Ce, Pr, Nd or a mixture thereof, Misch metal [Mischmetall: German, mixed metals: English (hereinafter sometimes abbreviated as MM)] is 0.001 to 0.05% by weight. By adding, it is possible to complement the tip erosion resistance and copper erosion resistance.
本発明によれば、Ｃｕが０．２〜１．２重量％、Ａｇが１．０〜５．０重量％を含有するＳｎＡｇＣｕ系の無鉛はんだ合金に、Ｃｏを０．００５〜０．０３重量％、Ｇｅを０．００１〜０．０１重量％、Ｆｅを０．０１〜０．０５重量％含有させることによって、Ｓｎ３７Ｐｂ（共晶合金）と同レベルの耐こて先喰われ性を有し、耐銅喰われ性はＳｎ３７Ｐｂ（共晶合金）には及ばないが、実用上問題のないレベルであり、かつ安定した成分組成のはんだが製造できる。 According to the present invention, a SnAgCu-based lead-free solder alloy containing 0.2 to 1.2% by weight of Cu and 1.0 to 5.0% by weight of Ag is added 0.005 to 0.03% by weight of Co. %, Ge 0.001-0.01% by weight and Fe 0.01-0.05% by weight, the tip wear resistance of the same level as Sn37Pb (eutectic alloy) Although the copper erosion resistance does not reach that of Sn37Pb (eutectic alloy), a solder having a stable component composition can be produced at a level that is not problematic in practice.
１．０〜５．０重量％添加されているＡｇは、こて先の鉄メッキとはんだとの界面に濃縮する傾向があり、ある程度の鉄喰われの抑制効果を示すが充分ではない。
Ｃｏを０．００５〜０．０３重量％、Ｆｅを０．０１〜０．０５重量％添加することによって、こて先の鉄メッキとはんだとの界面にＳｎ−Ｆｅ−Ｃｏの金属間化合物層が形成されることと、鉄がはんだ中にあらかじめ添加されることで界面の鉄の濃度勾配が小さくなることから、鉄のはんだ中への溶出が抑制される。
Ag added in an amount of 1.0 to 5.0% by weight tends to concentrate at the interface between the iron plating of the tip and the solder, and exhibits a certain degree of iron erosion suppression effect, but is not sufficient.
By adding Co in an amount of 0.005 to 0.03% by weight and Fe in an amount of 0.01 to 0.05% by weight, an Sn—Fe—Co intermetallic compound layer is formed on the iron plating / solder interface of the tip. And the concentration gradient of iron at the interface is reduced by adding iron in advance to the solder, so that elution of iron into the solder is suppressed.
また、Ｃｕが０．２〜１．２重量％添加されているはんだ合金に、Ｃｏを０．００５〜０．０３重量％添加することで、銅とはんだの界面にはＳｎ−Ｃｕ−Ｃｏの金属間化合物が形成されることと、銅がはんだ中にあらかじめ添加されることで界面の銅の濃度勾配が小さくなることから、銅のはんだ中への溶出が抑制される。 Further, by adding Co in an amount of 0.005 to 0.03% by weight to a solder alloy to which Cu is added in an amount of 0.2 to 1.2% by weight, Sn—Cu—Co of the interface between copper and solder is added. Since the intermetallic compound is formed and copper is added to the solder in advance, the concentration gradient of copper at the interface becomes small, so that elution of copper into the solder is suppressed.
ＣｏとＦｅを含有するＳｎＡｇＣｕ系はんだ合金にＧｅを添加すると、Ｓｎ−Ｃｏ−Ｆｅの金属間化合物の生成を抑制するが、Ｃｏ、Ｆｅ、Ｇｅの含有量が多い場合は、金属間化合物が塊状のドロスとなって析出して酸化物発生量が多くなると共に、耐銅喰われ性も低下する。しかし、Ｃｏ、ＦｅとＧｅの含有量の少ない本発明の範囲内の場合には、塊状のドロスの生成が無いため、酸化物の発生量も少なく、また、鉄喰われ抑制効果と銅喰われ抑制効果が増進する。
メカニズムは不明であるが、微量のＧｅはＳｎ−Ｃｏ−Ｆｅの金属間化合物が鉄あるいは銅などとの界面でなく、溶融したはんだ中で生成するのを抑制する作用があるものと考えられる。
When Ge is added to a SnAgCu-based solder alloy containing Co and Fe, the formation of Sn—Co—Fe intermetallic compounds is suppressed, but when the contents of Co, Fe and Ge are large, the intermetallic compounds are massive. As a result, the amount of oxide generated increases and the copper erosion resistance also decreases. However, in the case of the present invention with a low content of Co, Fe and Ge, since no dross is formed, the amount of oxide generated is small, and the iron erosion suppressing effect and copper erosion are reduced. The suppression effect is increased.
Although the mechanism is unknown, it is considered that a small amount of Ge has an action of suppressing the formation of Sn—Co—Fe intermetallic compounds in molten solder, not at the interface with iron or copper.
上記したように、Ｓｎ３７Ｐｂ（共晶合金）と同レベルの耐こて先喰われ性と実用レベルの耐銅喰われ性を有し、また、安定した成分組成のはんだの製造が可能な、はんだ合金は、ＳｎＡｇＣｕ系のはんだ合金に微量のＣｏ、Ｇｅ及びＦｅを添加することによって達成される。 As described above, a solder having the same level of tip erosion resistance and practical level of copper erosion resistance as Sn37Pb (eutectic alloy) and capable of producing a solder having a stable component composition The alloy is achieved by adding trace amounts of Co, Ge and Fe to a SnAgCu based solder alloy.
また、上記のはんだ合金に、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄなどの遷移金属あるいはこれらの混合物であるミッシュメタルを添加すると、その量が多いと酸化物の発生量が増加するが、０．００１〜０．０５重量％の範囲で添加すると、鉄喰われ抑制と銅喰われ抑制が増進される。 Further, when a transition metal such as La, Ce, Pr, Nd or misch metal which is a mixture thereof is added to the above solder alloy, the amount of oxide generated increases when the amount is large. When added in the range of 0.05% by weight, iron erosion suppression and copper erosion suppression are enhanced.
特許文献１の段落［０００７］には、鉛フリーはんだへの鉄の混入は、はんだの濡れ性を著しく阻害してはんだ付け時間を延ばし、結局鉄めっき層を浸食する旨記載されている。しかしながら、本発明の組成のＳｎＡｇＣｕ系無鉛はんだに、上記少量のＣｏとＦｅを加えると、はんだの濡れ性は殆ど阻害されないことが実験により確認されている。その理由は、Ｃｏの添加ははんだの表面張力を下げることと、溶融したはんだ表面の酸化を抑制するゲルマニウム添加効果により、鉄による濡れ性の低下を補完しているものと考えている。また、特許文献２の段落［００３８］には、ＮｉにはＦｅやＣｏの添加によって低下しがちなハンダゴテのコテ先の濡れ性を高める効果がある旨記載されている。この記載から、Ｃｏの添加がＦｅによる濡れ性の低下を補完することは、予想外のことである。 In paragraph [0007] of Patent Document 1, it is described that the mixing of iron into lead-free solder significantly hinders the wettability of the solder, extends the soldering time, and eventually erodes the iron plating layer. However, it has been experimentally confirmed that when the small amount of Co and Fe is added to the SnAgCu-based lead-free solder having the composition of the present invention, the wettability of the solder is hardly inhibited. The reason is that the addition of Co complements the decrease in wettability due to iron by lowering the surface tension of the solder and the effect of adding germanium that suppresses the oxidation of the molten solder surface. Further, paragraph [0038] of Patent Document 2 describes that Ni has an effect of increasing the wettability of the soldering iron tip which tends to be lowered by the addition of Fe or Co. From this description, it is unexpected that the addition of Co complements the decrease in wettability due to Fe.
要するに本発明の効果が得られる理由は、次の理由によると考えられる。
即ち、少量のＦｅとＣｏとを添加することにより、Ｓｎ−Ｆｅ−Ｃｏの金属間化合物層が形成されることと、鉄がはんだ中にあらかじめ添加されることで界面の鉄の濃度勾配が小さくなることから、鉄のはんだ中への溶出が抑制される。また、銅が添加されているはんだにＣｏを添加することにより、銅とはんだの界面にはＳｎ−Ｃｕ−Ｃｏの金属間化合物が形成されることと、銅がはんだ中にあらかじめ添加されることで界面の銅の濃度勾配が小さくなることから、銅のはんだ中への溶出が抑制される。更に、ＣｏとＧｅの添加は、はんだの表面張力を下げ、はんだ表面の酸化物生成を抑制するので、濡れ性が向上する。
In short, the reason why the effect of the present invention can be obtained is considered to be as follows.
That is, by adding a small amount of Fe and Co, an Sn—Fe—Co intermetallic compound layer is formed, and by adding iron in advance to the solder, the concentration gradient of iron at the interface is small. Therefore, elution of iron into the solder is suppressed. Moreover, by adding Co to the solder to which copper is added, an intermetallic compound of Sn—Cu—Co is formed at the interface between the copper and the solder, and copper is added to the solder in advance. Thus, since the copper concentration gradient at the interface becomes small, elution of copper into the solder is suppressed. Furthermore, the addition of Co and Ge lowers the surface tension of the solder and suppresses the formation of oxide on the solder surface, thereby improving the wettability.
しかしながら、Ｃｏ、ＧｅとＦｅの添加量が多すぎると金属間化合物が過度に析出し、ドロスが形成する。そのため、安定的な組成のはんだを製造するためには、Ｃｏの添加量を０．０３重量％以下とし、Ｇｅの添加量を０．０１重量％以下、Ｆｅの添加量を０．０５重量％以下に制限する必要がある。その際微量のＧｅは、溶融したはんだ中でのＳｎ−Ｃｏ−Ｆｅの金属間化合物の生成を抑制するものと考えられる。 However, if the added amount of Co, Ge, and Fe is too large, intermetallic compounds are excessively precipitated and dross is formed. Therefore, in order to manufacture a solder having a stable composition, the amount of Co added is 0.03% by weight or less, the amount of Ge added is 0.01% by weight or less, and the amount of Fe added is 0.05% by weight. It is necessary to restrict to the following. At that time, a small amount of Ge is considered to suppress the formation of Sn—Co—Fe intermetallic compounds in the molten solder.
遷移金属あるいはその混合物であるミッシュメタルは、鉄喰われと銅喰われの両方を抑制する効果があるが、その効果は０．００１重量％より少ない添加では発現しないし、０．０５重量％より多く添加すると、ドロスを発生し易くなる。 The transition metal or a mixture thereof, the misch metal, has the effect of suppressing both iron and copper erosion, but the effect does not appear with less than 0.001% by weight addition, and more than 0.05% by weight. If a large amount is added, dross is likely to be generated.
以上述べた如く、所定の組成のＳｎＡｇＣｕ系合金に、Ｃｏ、Ｇｅ、Ｆｅを所定の少量添加することによって、Ｓｎ３７Ｐｂ（共晶合金）と同レベルの耐鉄喰われ性と、Ｓｎ３７Ｐｂ（共晶合金）には及ばないが、実用上問題の無いレベルの優れた耐銅喰われ性を有し、かつ安定した成分組成のはんだの製造が可能となる。このようなＳｎＡｇＣｕ系のはんだ合金は、従来強く求められていたにもかかわらず得られなかったものであるから、これは極めて画期的な効果である。 As described above, by adding a predetermined small amount of Co, Ge, and Fe to a SnAgCu alloy having a predetermined composition, the same level of iron erosion resistance as Sn37Pb (eutectic alloy) and Sn37Pb (eutectic alloy) are obtained. However, it is possible to produce a solder having a stable component composition having an excellent copper erosion resistance having a practically no problem level. Such a SnAgCu-based solder alloy has been strongly demanded in the past, but has not been obtained. This is a very innovative effect.
次に、本発明の実施の形態を説明する。 Next, an embodiment of the present invention will be described.
本発明で含有するＣｕの範囲は０．２〜１．２重量％の範囲であり、Ｃｕは０．２重量％より少ないと濡れ性が劣り、１．２重量％より多いと融点が上昇し、はんだ付けの作業性が劣る。 The range of Cu contained in the present invention is in the range of 0.2 to 1.2% by weight. When Cu is less than 0.2% by weight, the wettability is inferior, and when it exceeds 1.2% by weight, the melting point increases. , Soldering workability is inferior.
本発明で使用するＣｕの範囲は０．２〜１．２重量％であり、Ａｇの範囲は１．０〜５．０重量％である。これはこの範囲でＳｎ−Ａｇ−Ｃｕの共晶温度及びその温度近くの組成となるからである。 The range of Cu used in the present invention is 0.2 to 1.2% by weight, and the range of Ag is 1.0 to 5.0% by weight. This is because within this range, the Sn—Ag—Cu eutectic temperature and a composition close to that temperature are obtained.
Ｃｏを０．００５〜０．０３重量％、Ｇｅを０．００１〜０．０１重量％、Ｆｅを０．０１〜０．０５重量％含有させることによって、従来のＳｎ−Ｐｂ系はんだ並に鉄喰われを抑制でき、また、従来のＳｎ−Ｐｂには劣るが、実用上問題のないレベルに銅喰われも抑制できる。
ＣｏとＦｅの含有量がそれぞれ０．００５重量％、０．０１重量％より少ないと、Ｆｅとの界面に形成される金属間化合物層の厚さが薄くなり、鉄の溶出を抑制する効果が少なくなり、また銅の溶出を抑制する効果も少なくなる。また、Ｃｏの添加量を０．０３重量％より多く、Ｇｅの添加量を０．０１重量％より多く、Ｆｅの添加量を０．０５重量％より多くすると、溶融はんだ中に金属間化合物の析出によるドロスが形成され易くなり、安定した成分組成のはんだの製造が困難となる。特に、０．００１〜０．０１重量％のＧｅがドロスの形成を抑制している。
By containing Co 0.005-0.03% by weight, Ge 0.001-0.01% by weight, and Fe 0.01-0.05% by weight, it is possible to use conventional Sn-Pb solder as well as iron. The biting can be suppressed, and copper biting can also be suppressed to a level that is not problematic in practice, although inferior to conventional Sn-Pb.
When the contents of Co and Fe are less than 0.005% by weight and 0.01% by weight, respectively, the thickness of the intermetallic compound layer formed at the interface with Fe becomes thin, and the effect of suppressing elution of iron is achieved. The effect of suppressing copper elution is reduced. Further, when the addition amount of Co is more than 0.03% by weight, the addition amount of Ge is more than 0.01% by weight, and the addition amount of Fe is more than 0.05% by weight, Dross due to precipitation is likely to be formed, making it difficult to produce a solder having a stable component composition. In particular, 0.001 to 0.01% by weight of Ge suppresses the formation of dross.
次に実施例を挙げて本発明を更に説明する。 EXAMPLES Next, an Example is given and this invention is demonstrated further.
後記表１の組成となる実施例（Ｎｏ１〜Ｎｏ２）及び比較例（Ｎｏ１〜Ｎｏ５）のはんだを、それぞれ４ｋｇ作成した。尚、Sn3Ag0.5Cu0.02Co0.005Ge0.03Fe0.003MM（実施例２）は、Ａｇが３重量％、Ｃｕが０．５重量％、Ｃｏが０．０２重量％、Ｇｅが０．００５重量％、Ｆｅが０．０３重量％、ミッシュメタルが０．００３重量％、残部をＳｎとしたはんだ合金を意味する。 4 kg of each of the solders of Examples (No1 to No2) and Comparative Examples (No1 to No5) having the compositions shown in Table 1 below was prepared. In addition, Sn3Ag0.5Cu0.02Co0.005Ge0.03Fe0.003MM (Example 2), Ag is 3 wt%, Cu is 0.5 wt%, Co is 0.02 wt%, Ge is 0.005 wt%, This means a solder alloy in which Fe is 0.03% by weight, Misch metal is 0.003% by weight, and the balance is Sn.
得られたはんだについて、固相線温度／液相線温度（℃）、ゼロクロスタイム（秒）、鉄溶出量（４５０℃）、銅線残存量（％）、ドロス形成の有無を測定した。試験方法は以下のようにして行った。 The obtained solder was measured for solidus temperature / liquidus temperature (° C.), zero crossing time (seconds), iron elution amount (450 ° C.), copper wire remaining amount (%), and presence or absence of dross formation. The test method was performed as follows.
〔固相線温度／液相線温度（℃）〕
５００ｇのはんだを使用し、冷却法で融点〔固相線温度／液相線温度（℃）〕を測定した。
[Solidus temperature / Liquidus temperature (℃)]
Using 500 g of solder, the melting point [solidus temperature / liquidus temperature (° C.)] was measured by a cooling method.
〔ゼロクロスタイム（秒）〕
７×５０×０．２ｍｍの銅板を用い、浸漬深さ２ｍｍ、浸漬速度２．５ｍｍ／秒、浸漬時間１０秒の条件で濡れ性試験機を用いてゼロクロスタイム(秒）を測定した。なお、試験温度は２５５℃で行い、フラックスはハロゲン量０．１２％のＲＭＡタイプのものを使用した。
[Zero cross time (seconds)]
Using a 7 × 50 × 0.2 mm copper plate, the zero cross time (seconds) was measured using a wettability tester under conditions of an immersion depth of 2 mm, an immersion speed of 2.5 mm / second, and an immersion time of 10 seconds. The test temperature was 255 ° C., and the flux used was an RMA type with a halogen content of 0.12%.
〔鉄喰われ量（ｇ／１時間）〕
２．５ｋｇのはんだを磁性の皿に入れ、加熱溶解して４５０℃とした。このはんだ中に幅３０ｍｍ、厚さ２ｍｍのＳＰＣ鉄板を、φ６０の攪拌羽根に取り付けてＳＰＣ鉄板の先端１５ｍｍをはんだ中に浸漬した。続いて、攪拌羽根を３０ｒｐｍで１時間間攪拌した。この場合のはんだ中の鉄板の移動速度は約１ｍ／分である。試験前後の鉄板の重量を測定し、鉄のはんだ中への溶出量を求めて、鉄喰われ量とした。
[Feeding amount (g / 1 hour)]
2.5 kg of solder was placed in a magnetic dish and heated to melt at 450 ° C. In this solder, an SPC iron plate having a width of 30 mm and a thickness of 2 mm was attached to a stirring blade having a diameter of 60 mm, and the tip of the SPC iron plate was immersed in the solder. Subsequently, the stirring blade was stirred at 30 rpm for 1 hour. In this case, the moving speed of the iron plate in the solder is about 1 m / min. The weight of the iron plate before and after the test was measured, and the amount of iron eluted into the solder was determined to be the amount of iron erosion.
〔銅線残存量（％）〕
銅喰われ性を測定するために、径０．２ｍｍのウレタン被覆銅線を４００℃のはんだに２秒間浸漬した後、樹脂に埋め込み研磨して銅線の断面積を測定し、銅線残存量を以下の式で算出した。
銅線残存量（％）＝（Ａ／Ｂ）×１００
Ａ ：浸漬後の銅線の断面積
Ｂ ：元の銅線の断面積
[Remaining copper wire (%)]
In order to measure the copper erosion property, a 0.2 mm diameter urethane-coated copper wire was immersed in a solder at 400 ° C. for 2 seconds, then embedded in a resin and polished to measure the cross-sectional area of the copper wire. Was calculated by the following formula.
Copper wire remaining amount (%) = (A / B) × 100
A: Cross-sectional area of copper wire after immersion B: Cross-sectional area of original copper wire
〔ドロス形成の有無〕
２．５ｋｇのはんだを磁性の皿に入れ、加熱溶解して２７０℃とした。このはんだ中に、φ６０の攪拌羽根（３枚羽根）を用いて、６０ｒｐｍで３０分間表面を攪拌し、回収した酸化物が通常の乾いた酸化物か湿ったドロスを含む酸化物かを肉眼観察した。
2.5 kg of solder was placed in a magnetic dish and heated to melt at 270 ° C. In this solder, the surface is stirred for 30 minutes at 60 rpm using a φ60 stirring blade (three blades), and whether the recovered oxide is an ordinary dry oxide or an oxide containing wet dross is visually observed. did.
上記結果から明らかなように、実施例１〜２の鉄喰われ量は、４５０℃においては０．０１〜０．０２ｇ／１時間であり、比較例５のＳｎ３7Ｐｂ（共晶合金）よりも少ない。また、銅線の残存量は８６％、８７％であり、Ｓｎ３７Ｐｂ（共晶合金）よりは少ないが、充分実用化できるレベルであり、ドロスの発生も無い。一方、比較例１〜３はドロスの生成は無いが、銅線の残存量は７４〜７８％と実施例１〜２より少なく、４５０℃の鉄喰われ量は、０．１１〜０．２３ｇ／１時間と非常に多い。また、比較例４は４５０℃の鉄喰われ量は０．０２ｇ／１時間と少ないが、銅線の残存量は７６％と少なく、ドロスも生成する。
実施例１及び２のはんだは、前記特許文献２の記載に反して、鉄を含有しない比較例３のはんだと比べても、若干濡れ性は低下するが、実用上問題の無いレベルである。しかも本発明のはんだは、４５０℃の鉄喰われ量は、比較例３のはんだと比べて遥かに優れている。
このことから、Ｃｕが０．２〜１．２重量％、Ａｇが１．０〜５．０重量％、残部をＳｎとするはんだに、微量のＣｏ、ＧｅとＦｅを添加したはんだ、及び、さらに微量の遷移金属を添加したはんだが、良好な耐鉄喰われ性と耐銅喰われ性、さらに成分組成の安定性を達成するはんだとなし得ることがわかる。
As is clear from the above results, the amount of iron biting in Examples 1 and 2 is 0.01 to 0.02 g / 1 hour at 450 ° C., which is smaller than Sn3 7 Pb (eutectic alloy) in Comparative Example 5. . Further, the remaining amount of copper wire is 86% and 87%, which is less than Sn37Pb (eutectic alloy), but is at a level that can be sufficiently put into practical use, and no dross is generated. On the other hand, in Comparative Examples 1 to 3, no dross was produced, but the remaining amount of copper wire was 74 to 78%, less than Examples 1 and 2, and the amount of iron erosion at 450 ° C was 0.11 to 0.23 g. / 1 hour and very much. Further, in Comparative Example 4, the amount of iron erosion at 450 ° C. is as small as 0.02 g / 1 hour, but the remaining amount of copper wire is as small as 76%, and dross is also generated.
Contrary to the description in Patent Document 2, the solders of Examples 1 and 2 are slightly less wettable than the solder of Comparative Example 3 that does not contain iron, but are at a level that does not cause any practical problems. Moreover, the amount of iron bite at 450 ° C. of the solder of the present invention is far superior to that of the solder of Comparative Example 3.
From this, the solder which added trace amount Co, Ge, and Fe to the solder which makes Cu 0.2-1.2 weight%, Ag 1.0-5.0 weight%, and the remainder is Sn, and, Furthermore, it turns out that the solder which added the trace amount transition metal can be made into the solder which achieves favorable iron erosion resistance and copper erosion resistance, and also the stability of a component composition.
Claims (2)
The lead-free solder alloy according to claim 1, further comprising 0.001 to 0.05% by weight of a misch metal which is a transition metal such as La, Ce, Pr, Nd or a mixture thereof.
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| JP7376842B1 (en) * | 2023-02-21 | 2023-11-09 | 千住金属工業株式会社 | Solder alloys, solder balls, solder pastes and solder joints |
| WO2024177065A1 (en) * | 2023-02-21 | 2024-08-29 | 千住金属工業株式会社 | Solder alloy, solder ball, solder paste, and soldered joint |
| TWI866789B (en) * | 2023-02-21 | 2024-12-11 | 日商千住金屬工業股份有限公司 | Solder alloys, solder balls, solder pastes and solder joints |
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