JPH1158065A - Solder paste - Google Patents
Solder pasteInfo
- Publication number
- JPH1158065A JPH1158065A JP9227095A JP22709597A JPH1158065A JP H1158065 A JPH1158065 A JP H1158065A JP 9227095 A JP9227095 A JP 9227095A JP 22709597 A JP22709597 A JP 22709597A JP H1158065 A JPH1158065 A JP H1158065A
- Authority
- JP
- Japan
- Prior art keywords
- solder
- zinc
- solder paste
- alloy
- weight
- 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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
- H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
- H05K3/3457—Solder materials or compositions; Methods of application thereof
- H05K3/3485—Applying solder paste, slurry or powder
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は半田合金の粉末とフ
ラックスとを混合してペースト状としたソルダペースト
に関するものであって、特に亜鉛を含む半田合金を使用
したソルダペーストの改良に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solder paste made by mixing a solder alloy powder and a flux, and more particularly to an improvement of a solder paste using a solder alloy containing zinc. .
【０００２】[0002]
【従来の技術】従来一般に使用されているソルダペース
トは、半田合金として錫−鉛系合金を使用したものが広
く使用されている。しかしながら半田合金に含まれる鉛
が毒性を有するため、鉛を含まない無鉛半田が検討され
ている。2. Description of the Related Art As a solder paste generally used conventionally, a solder paste using a tin-lead alloy as a solder alloy is widely used. However, since lead contained in the solder alloy has toxicity, lead-free solder containing no lead has been studied.
【０００３】特に錫−亜鉛系共晶合金は、従来の錫−鉛
合金と融点が同等であり、また機械的強度やクリープ特
性においても優れているため、無鉛半田を構成する合金
として有望視されている。In particular, tin-zinc eutectic alloys have the same melting point as conventional tin-lead alloys, and are also excellent in mechanical strength and creep characteristics, and therefore are promising as alloys constituting lead-free solder. ing.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら錫−亜鉛
系半田合金においては、亜鉛のイオン化傾向が大きく反
応性に富んでいるため、半田付けした状態において高温
下に放置すると、半田中の亜鉛が基板の銅の表面に拡散
して、銅−亜鉛金属間化合物（Ｃｕ5Ｚｎ8）を生成し、
銅の表面に当該化合物の生成が進行する。However, in the case of tin-zinc solder alloys, zinc ionization tends to be large and the reactivity is high. Therefore, when left at a high temperature in a soldered state, zinc in the solder becomes zinc on the substrate. diffuse on the surface of copper, copper - produces zinc intermetallic compound (Cu 5 Zn 8),
The formation of the compound proceeds on the surface of the copper.
【０００５】そのため時間の経過と共に前記半田中の亜
鉛が減少してその箇所における半田組織が破壊され、亀
裂が生じて強度が低下すると共に、当該半田と前記金属
間化合物との間の強度差が大きくなり、接合強度が低下
するのである。[0005] Therefore, as time passes, zinc in the solder decreases, the solder structure at that location is broken, cracks are generated, the strength is reduced, and the strength difference between the solder and the intermetallic compound is reduced. It becomes large, and the bonding strength decreases.
【０００６】従って錫−亜鉛系半田においては、半田付
けの後に高温下に放置すると、半田と銅基板との間にお
ける前記金属間化合物層の形成が進行し、半田と銅との
間の接合強度が経時的に低下するという問題が生じてい
たのである。Accordingly, in the case of a tin-zinc solder, if the solder is left at a high temperature after soldering, the formation of the intermetallic compound layer between the solder and the copper substrate proceeds, and the bonding strength between the solder and copper is increased. However, there has been a problem that the temperature decreases with time.
【０００７】本発明はかかる事情に鑑みなされたもので
あって、錫−亜鉛系半田合金のソルダペーストにおい
て、前記金属間化合物層の進行を抑制し、経時的な接合
強度の低下を防止することを目的とするものである。The present invention has been made in view of the above circumstances, and it is an object of the present invention to suppress the progress of the intermetallic compound layer in a solder paste of a tin-zinc-based solder alloy and to prevent a decrease in bonding strength over time. It is intended for.
【０００８】[0008]
【課題を解決するための手段】而して本発明は、亜鉛を
含む半田合金の粉末とフラックスとよりなるソルダペー
ストにおいて、亜鉛よりイオン化傾向の小さい金属の塩
を添加したことを特徴とするものである。前記亜鉛を含
む半田合金としては、錫８８〜９５重量％と亜鉛５〜１
２重量％とを主体とする合金が適当である。The present invention is characterized in that a salt of a metal having a lower ionization tendency than zinc is added to a solder paste comprising a solder alloy powder containing zinc and a flux. It is. As the solder alloy containing zinc, 88 to 95% by weight of tin and 5 to 1% of zinc are used.
An alloy based on 2% by weight is suitable.
【０００９】本発明における前記金属塩としては、ビス
マス、インジウム、金、銀、銅、錫、アンチモン、ニッ
ケル、コバルト又は白金の塩が適当である。またソルダ
ペーストに対する前記金属塩の量は、０．５重量％以上
であり且つ、ソルダペースト中の亜鉛と同イオン当量以
下とするのが好ましい。As the metal salt in the present invention, a bismuth, indium, gold, silver, copper, tin, antimony, nickel, cobalt or platinum salt is suitable. Further, the amount of the metal salt with respect to the solder paste is preferably 0.5% by weight or more and the same ion equivalent as zinc in the solder paste or less.
【００１０】本発明における半田合金は、亜鉛を含むも
のであることが必要である。亜鉛を含む半田合金として
は、前述した錫−亜鉛共晶合金すなわち、錫９１．２％
と亜鉛８．８％との合金が好ましい。さらに錫８８〜９
５重量％と亜鉛５〜１２重量％とを主体として、これに
２重量％以下のビスマス、インジウム、銅、銀、アンチ
モンなどを添加したものも適当である。[0010] The solder alloy in the present invention must contain zinc. As the solder alloy containing zinc, the above-described tin-zinc eutectic alloy, that is, tin 91.2%
An alloy of zinc and 8.8% of zinc is preferred. Further tin 88-9
It is also suitable to use 5% by weight and 5 to 12% by weight of zinc, to which 2% by weight or less of bismuth, indium, copper, silver, antimony and the like are added.
【００１１】またこれらの錫−亜鉛系合金に限らず、他
の亜鉛を含む半田合金について、広く使用することがで
きる。またこれらの半田合金の粉末としては、粒径２０
〜４０μｍ程度のものが適当である。In addition to these tin-zinc alloys, other zinc-containing solder alloys can be widely used. The powder of these solder alloys has a particle size of 20%.
Those having a thickness of about 40 μm are suitable.
【００１２】本発明におけるフラックスとしては、金属
塩を添加することを除いて、通常のソルダペーストにお
けるフラックスをそのまま使用することができる。例え
ばロジンに適量のワックス及び活性剤を添加し、溶剤に
分散したものを使用することができる。As the flux in the present invention, a flux in a usual solder paste can be used as it is, except that a metal salt is added. For example, rosin obtained by adding appropriate amounts of wax and activator and dispersing in a solvent can be used.
【００１３】そしてそのフラックスに金属塩を添加す
る。その金属塩を構成する金属は、亜鉛よりイオン化傾
向が小さい金属であることを要し、例えばビスマス、イ
ンジウム、金、銀、銅、錫、アンチモン、ニッケル、コ
バルト又は白金などの塩が適当である。Then, a metal salt is added to the flux. The metal constituting the metal salt needs to be a metal having a lower ionization tendency than zinc, and for example, a salt such as bismuth, indium, gold, silver, copper, tin, antimony, nickel, cobalt or platinum is suitable. .
【００１４】これらの金属の有機酸塩及び無機酸塩を使
用することができ、具体的には、塩化ビスマス、塩化イ
ンジウム、ロジン酸ビスマス、ロジン酸インジウム、ロ
ジン酸銅、ロジン酸銀、ステアリン酸銅、クエン酸ビス
マス、酢酸銀、２エチルヘキサン酸インジウムなどを挙
げることができる。Organic and inorganic acid salts of these metals can be used, and specific examples thereof include bismuth chloride, indium chloride, bismuth rosinate, indium rosinate, copper rosinate, silver rosinate, and stearic acid. Examples include copper, bismuth citrate, silver acetate, and indium 2-ethylhexanoate.
【００１５】これらの金属塩をフラックスに添加し、そ
のフラックスと半田合金の粉末とを混合してソルダペー
ストとする。半田合金とフラックスとの混合比率は、通
常のソルダペーストと同程度であり、半田合金９２〜８
０重量％に対し、フラックス８〜２０重量％程度が適当
である。[0015] These metal salts are added to the flux, and the flux and the powder of the solder alloy are mixed to form a solder paste. The mixing ratio between the solder alloy and the flux is almost the same as that of a normal solder paste.
An appropriate flux is about 8 to 20% by weight with respect to 0% by weight.
【００１６】本発明のソルダペーストにおける前記金属
塩の添加量は、少なくとも０．５重量％以上添加するの
が好ましい。０．５重量％未満では前記金属間化合物層
の進行を抑制する効果が生じない。The amount of the metal salt in the solder paste of the present invention is preferably at least 0.5% by weight or more. If it is less than 0.5% by weight, the effect of suppressing the progress of the intermetallic compound layer does not occur.
【００１７】また金属塩の最大量としては、当該金属塩
中の金属が半田合金中の亜鉛と置換可能の量とするのが
よい。すなわち、ソルダペースト中の亜鉛と同イオン当
量以下とするのが好ましい。金属塩の量がこれを超える
と、金属塩中の金属と亜鉛との置換反応が過度に生じ、
半田合金中の亜鉛の量が不足して、適切に半田付けがで
きなくなる可能性がある。The maximum amount of the metal salt is preferably such that the metal in the metal salt can be replaced with zinc in the solder alloy. That is, it is preferable that the ion equivalent is equal to or less than the ion equivalent of zinc in the solder paste. If the amount of the metal salt exceeds this, the substitution reaction between the metal in the metal salt and zinc occurs excessively,
There is a possibility that the amount of zinc in the solder alloy may be insufficient and soldering may not be performed properly.
【００１８】[0018]
【作用】本発明においては、銅と亜鉛との金属間化合物
層の進行が抑制され、経時的に接合強度が低下すること
がない。本発明により前記金属間化合物層の進行が抑制
されるメカニズムは必ずしも明確ではないが、半田付け
時の熱により金属塩中の金属と金属間化合物中の亜鉛と
の置換反応が生じて金属間化合物を減少させると共に、
当該置換反応により遊離した金属が銅と亜鉛との反応を
抑制するのではないかと考えられる。In the present invention, the progress of the intermetallic compound layer of copper and zinc is suppressed, and the bonding strength does not decrease with time. The mechanism by which the progress of the intermetallic compound layer is suppressed by the present invention is not always clear, but heat at the time of soldering causes a substitution reaction between the metal in the metal salt and the zinc in the intermetallic compound, resulting in an intermetallic compound. Together with
It is considered that the metal released by the substitution reaction suppresses the reaction between copper and zinc.
【００１９】[0019]
【発明の効果】本発明によれば、半田付けした後に加熱
雰囲気下に放置した状態においても、銅−亜鉛の金属間
化合物層が進行することがなく、半田と銅との接合状態
が維持され、接合強度が低下することがない。According to the present invention, even in a state in which the solder is left in a heating atmosphere after soldering, the copper-zinc intermetallic compound layer does not advance, and the bonding state between the solder and copper is maintained. The joining strength does not decrease.
【００２０】[0020]
［フラックスの調製］次の組成の各成分を加熱溶解して
混合し、冷却してフラックスを調製した。比較例におい
ては金属塩を添加せず、ガムロジンの量を７２％とし
た。なお各成分の％は、いずれも重量％である。[Preparation of Flux] Each component having the following composition was dissolved by heating, mixed, and cooled to prepare a flux. In the comparative example, no metal salt was added, and the amount of gum rosin was 72%. In addition,% of each component is all weight%.
【００２１】 ガムロジン ４２％ カスターワックス ４％ ヘキシルカルビトール ２０％ セバシン酸 ２％ エチルアミンＨＢｒ ２％ 金属塩 ３０％ 計 １００％Gum rosin 42% Castor wax 4% Hexyl carbitol 20% Sebacic acid 2% Ethylamine HBr 2% Metal salt 30% Total 100%
【００２２】金属塩は、次の通りのものを使用した。 実施例１ ロジン酸ビスマス 実施例２ ロジン酸インジウム 実施例３ ロジン酸銀 比較例 添加せずThe following metal salts were used. Example 1 Bismuth rosinate Example 2 Indium rosinate Example 3 Silver rosinate Comparative Example No Addition
【００２３】［ソルダペーストの調製］上記フラックス
を１２重量％と、錫−亜鉛共晶合金（錫９１．２重量％
−亜鉛８．８重量％）の粒径２０〜４０μｍの粉末とを
混合し、混練機で撹拌してソルダペーストを調製した。[Preparation of solder paste] 12% by weight of the above flux and a tin-zinc eutectic alloy (91.2% by weight of tin)
-8.8% by weight of zinc) having a particle size of 20 to 40 μm, and the mixture was stirred with a kneader to prepare a solder paste.
【００２４】［試験方法］上記のソルダペーストを使用
して、基板上にセラミックコンデンサーを半田付けして
接合した。その基板を１００℃の条件下に５００時間放
置し、その初期と５００時間経過後における基板と接合
部品との接合強度及び、金属間化合物層の厚みを測定し
た。[Test Method] Using the above-mentioned solder paste, a ceramic capacitor was soldered and bonded on a substrate. The substrate was left under the condition of 100 ° C. for 500 hours, and the bonding strength between the substrate and the bonding component at the initial stage and after 500 hours, and the thickness of the intermetallic compound layer were measured.
【００２５】［試験結果］試験結果を表１に示す。[Test Results] The test results are shown in Table 1.
【００２６】[0026]
【表１】 [Table 1]
【００２７】以上の結果からも明らかなように、比較例
においては５００時間経過後に金属間化合物層の厚みが
大幅に増加しており、接合強度が著しく低下しているの
に対し、金属塩を添加した実施例においては、化合物層
の進行は僅かであり、また接合強度も殆ど低下していな
い。As is clear from the above results, in the comparative example, the thickness of the intermetallic compound layer was significantly increased after 500 hours, and the bonding strength was significantly reduced. In the added example, the progress of the compound layer is slight, and the bonding strength is hardly reduced.
Claims (4)
とよりなるソルダペーストにおいて、亜鉛よりイオン化
傾向の小さい金属の塩を添加したことを特徴とする、ソ
ルダペースト1. A solder paste comprising a solder alloy powder containing zinc and a flux, wherein a salt of a metal having a lower ionization tendency than zinc is added.
５重量％と亜鉛５〜１２重量％とを主体とする合金であ
ることを特徴とする、請求項１に記載のソルダペースト2. The method according to claim 2, wherein the solder alloy containing zinc is tin 88 to 9
The solder paste according to claim 1, wherein the solder paste is an alloy mainly containing 5% by weight and 5 to 12% by weight of zinc.
金、銀、銅、錫、アンチモン、ニッケル、コバルト又は
白金の塩であることを特徴とする、請求項１又は２に記
載のソルダペースト3. The method according to claim 2, wherein the metal salt is bismuth, indium,
The solder paste according to claim 1, wherein the solder paste is a salt of gold, silver, copper, tin, antimony, nickel, cobalt or platinum.
０．５重量％以上であり且つ、ソルダペースト中の亜鉛
と同イオン当量以下であることを特徴とする、請求項
１、２又は３に記載のソルダペースト4. The metal salt for a solder paste,
4. The solder paste according to claim 1, wherein the content is 0.5% by weight or more and the same ion equivalent or less as zinc in the solder paste. 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22709597A JP4017088B2 (en) | 1997-08-07 | 1997-08-07 | Solder paste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22709597A JP4017088B2 (en) | 1997-08-07 | 1997-08-07 | Solder paste |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1158065A true JPH1158065A (en) | 1999-03-02 |
| JP4017088B2 JP4017088B2 (en) | 2007-12-05 |
Family
ID=16855421
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22709597A Expired - Lifetime JP4017088B2 (en) | 1997-08-07 | 1997-08-07 | Solder paste |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4017088B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001232496A (en) * | 2000-02-23 | 2001-08-28 | Taiho Kogyo Co Ltd | Flux for soldering and solder paste |
| US6923875B2 (en) | 2002-02-28 | 2005-08-02 | Harima Chemicals, Inc. | Solder precipitating composition |
| US7180495B1 (en) | 1999-10-18 | 2007-02-20 | Seiko Epson Corporation | Display device having a display drive section |
| CN100455400C (en) * | 2007-01-16 | 2009-01-28 | 大连理工大学 | Soldering flux in use for SnZn series solder with no lead, and preparation method |
| WO2010008752A3 (en) * | 2008-06-23 | 2010-03-25 | Williams Advanced Materials, Inc. | Gold-tin-indium solder for processing compatibility with lead-free tin-based solder |
| CN115178910A (en) * | 2017-11-08 | 2022-10-14 | 阿尔法装配解决方案公司 | Cost-effective lead-free solder alloys for electronic applications |
-
1997
- 1997-08-07 JP JP22709597A patent/JP4017088B2/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7180495B1 (en) | 1999-10-18 | 2007-02-20 | Seiko Epson Corporation | Display device having a display drive section |
| JP2001232496A (en) * | 2000-02-23 | 2001-08-28 | Taiho Kogyo Co Ltd | Flux for soldering and solder paste |
| US6923875B2 (en) | 2002-02-28 | 2005-08-02 | Harima Chemicals, Inc. | Solder precipitating composition |
| CN100455400C (en) * | 2007-01-16 | 2009-01-28 | 大连理工大学 | Soldering flux in use for SnZn series solder with no lead, and preparation method |
| WO2010008752A3 (en) * | 2008-06-23 | 2010-03-25 | Williams Advanced Materials, Inc. | Gold-tin-indium solder for processing compatibility with lead-free tin-based solder |
| CN115178910A (en) * | 2017-11-08 | 2022-10-14 | 阿尔法装配解决方案公司 | Cost-effective lead-free solder alloys for electronic applications |
| CN115178910B (en) * | 2017-11-08 | 2024-04-16 | 阿尔法装配解决方案公司 | Cost-effective lead-free solder alloy for electronic applications |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4017088B2 (en) | 2007-12-05 |
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