JPH1034376A - Lead-free solder - Google Patents

Lead-free solder

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Publication number
JPH1034376A
JPH1034376A JP19762596A JP19762596A JPH1034376A JP H1034376 A JPH1034376 A JP H1034376A JP 19762596 A JP19762596 A JP 19762596A JP 19762596 A JP19762596 A JP 19762596A JP H1034376 A JPH1034376 A JP H1034376A
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Japan
Prior art keywords
solder
lead
wt
free solder
solder alloy
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JP19762596A
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Japanese (ja)
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JP3693762B2 (en
Inventor
Hideo Chagi
Toshiyuki Moribayashi
Toshiaki Ogura
Yozo Yoshiura
陽三 吉浦
利明 小倉
俊之 盛林
英雄 茶木
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Nippon Genma:Kk
株式会社ニホンゲンマ
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Priority to JP19762596A priority Critical patent/JP3693762B2/en
Publication of JPH1034376A publication Critical patent/JPH1034376A/en
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Publication of JP3693762B2 publication Critical patent/JP3693762B2/en
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Application status is Expired - Fee Related legal-status Critical

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Abstract

PROBLEM TO BE SOLVED: To provide a lead-free soldering alloy specially having an excellent heat resistant fatigue characteristic and holding as much as possible such a characteristic as a Pb contained soldering alloy in spite of not containing Pb. SOLUTION: This lead-free solder is composed of, by wt., 0.1-10% Bi, 0.1-5% Ag, 0.05-2% Cu, 0.0005-0.1% Ni, 0.0005-0.01% P and the balance Sn. Also, further, by wt., 0.01-0.5%. In is added into this composition. Also, a cream solder containing the powder of the soldering alloy, a formed solder using the soldering alloy and a resin flux cored solder using the soldering alloy are included in this lead-free solder.

Description

【発明の詳細な説明】 DETAILED DESCRIPTION OF THE INVENTION

【0001】 [0001]

【発明の属する技術分野】本発明はPbを含まないはんだ付け用の無鉛はんだ合金に関する。 The present invention relates to relates to a lead-free solder alloy for soldering which does not contain Pb.

【0002】 [0002]

【従来の技術】従来のはんだはSn(スズ)をベースとし、またはSn+Bi(ビスマス)を配合したものをベースとして、これにPb(鉛)を加えた合金が用いられて来た。 Conventional solder is based on the Sn (tin), or a material obtained by mixing the Sn + Bi (bismuth) as the base, alloys have been used to this was added Pb (the lead). Pbは合金中に於いてSnの融点232℃を下げる作用をし、Pbを37重量%配合した合金は融点が183℃の共晶はんだを形成し、その適切な融点のため広く使用されてきた。 Pb is the effect of lowering the melting point 232 ° C. of Sn at in the alloy, 37 wt% compounded alloy Pb forms a eutectic solder having a melting point of 183 ° C., have been widely used because of its appropriate melting point . このようにPbははんだ合金組成において不可欠の成分であった。 Thus Pb were essential ingredients in the solder alloy composition.

【0003】しかしPbは人畜にとって有害な元素であり、Pbを含むはんだが廃棄されると、Pb成分が酸性雨等により徐々に溶け出し、地下水中に浸透するなどの重大な環境汚染を引き起こすことは明らかである。 [0003] However, Pb is a harmful element for humans and animals, the solder containing Pb is discarded, Pb component out gradually dissolved by acid rain, etc., can cause serious environmental pollution, such as to penetrate into the ground water it is clear. このようなPbによる環境汚染を防止すべきであるという世界的な要請に応えるために、はんだ業界を中心に、Pb In order to meet the global demands that such should prevent environmental pollution caused by Pb, in the center of the solder industry, Pb
を含まない無鉛はんだの研究が進められ、既に多くの技術が開示されてきている。 Underway is included not lead-free solder research of the, have been already a lot of technology is disclosed. これらの技術においては、P In these techniques, P
bの働きを代替するために、銀(Ag)、ビスマス(B To replace the function of b, silver (Ag), bismuth (B
i)、アンチモン(Sb)、亜鉛(Zn)、カドミウム(Cd)、銅(Cu)、マグネシウム(Mg)、ニッケル(Ni)、チタン(Ti)、インジウム(Ti)等が組み合わせて使用されている。 i), antimony (Sb), zinc (Zn), cadmium (Cd), copper (Cu), magnesium (Mg), nickel (Ni), titanium (Ti), indium (Ti) or the like in combination is used . しかし、これらの元素の中には、有毒なものや極めて高価なものもあり、しかも必ずしも十分にPbの果していた機能を代替するものではなかった。 However, some of these elements, there are also those things Ya very expensive toxic, yet was not necessarily considered as a substitute for enough had played of Pb function.

【0004】 [0004]

【発明が解決しようとする課題】本発明の目的は、Pb An object of the present invention is to solve the above, Pb
を含まず、しかもPb含有はんだ合金のもっていた特性をできるだけ保持した、特に耐熱疲労特性に優れた無鉛はんだ合金を提供するものである。 Not including, moreover was maintained as much as possible the properties had a Pb-containing solder alloys, and in particular, to provide a good lead-free solder alloy thermal fatigue resistance.

【0005】 [0005]

【課題を解決するための手段】本発明の無鉛はんだは、 The lead-free solder of the present invention, in order to solve the problems],
上記課題を解決するため、その成分がBi0.1〜10 To solve the above problems, its components Bi0.1~10
重量%、Ag0.1〜5重量%、Cu0.05〜2重量%、Ni0.0005〜0.1重量%、P0.0005〜 Weight%, Ag0.1~5 weight%, Cu0.05~2 weight%, Ni0.0005~0.1 weight%, P0.0005~
0.01重量%および残部がSnからなることを特徴とする。 0.01 wt% and the balance being made of Sn. さらに本発明は、上記組成にIn0.01〜0.5 The present invention is, In0.01~0.5 the above composition
重量%を添加したはんだ合金に関する。 It relates solder alloy containing by weight%. また本発明は、 Further, the present invention is,
上記はんだ合金の粉末を含有するクリームはんだ、上記はんだ合金を用いた成形はんだおよび上記はんだ合金を用いたヤニ入りはんだを含む。 Cream solder containing powder of the solder alloy, including tar-containing solder with the molding solder and the solder alloy with the solder alloy.

【0006】本発明のはんだは上記構成をとることにより、有害なPbをまったく含有することなく、優れた特性を発現することができる。 [0006] The solder of the present invention by the above configuration, without any containing harmful Pb, it is possible to exhibit excellent properties. 以下にそれぞれの構成元素のはんだ特性に及ぼす特徴を説明する。 Characterized on the solder characteristics of each constituent element will be described below. Snははんだ合金の主成分であり、それ自体毒性がなく、接合母材へのヌレ性に優れるという特性を有し、はんだ基材として不可欠な成分である。 Sn is the main component of the solder alloy, without itself toxic, has properties of excellent wettability to the bonding base material, is an essential component as a solder substrate. SnにAgを添加することにより、 By adding Ag to Sn,
機械的特性を改善することおよび融点を低下させることができる。 It can be lowered and that the melting point to improve the mechanical properties. Agの配合量は、はんだ合金中0.1〜5重量%、好ましくは0.7〜3重量%である。 The amount of Ag is 0.1 to 5 wt% in the solder alloy is preferably 0.7 to 3 wt%. 0.1重量% 0.1% by weight
より少ない場合はその効果は不十分であり、5重量%を越えると溶融温度が高くなり、またコスト面でも不利となる。 If less its effect is insufficient, it becomes high and melting temperature exceeds 5 wt%, also is disadvantageous in cost.

【0007】SnにAgを添加したものにBiを添加すると、機械的強度が向上し、溶融温度を低下させることができる。 [0007] The addition of Bi to the material obtained by adding Ag to Sn, the mechanical strength is improved, and it is possible to lower the melting temperature. Biの配合量は0.1〜10重量%、好ましくは0.5〜5重量%である。 The amount of Bi is 0.1 to 10% by weight, preferably 0.5 to 5 wt%. Biの配合量が0.1重量%より低いとその効果は不十分であり、10重量%より多いと機械的強度は向上するが、機械的伸びが極端に低下し、熱疲労が起きやすい。 When the amount of Bi is less than 0.1 wt%, the effect is insufficient, although the mechanical strength is more than 10 wt% improves the mechanical elongation is extremely reduced, thermal fatigue tends to occur. SnにAg、Biを添加したものに更にCuを添加すると、機械的強度と耐疲労強度を改善することができる。 Ag to Sn, further addition of Cu to a material obtained by adding Bi, it is possible to improve the mechanical strength and fatigue strength. Cuは配合物中0.05〜 Cu is 0.05 to formulation
2重量%添加する。 Adding 2 wt%. 0.05重量%より少ないとその効果は少なく、2重量%より多くなると溶融温度が上昇し、従来の使用条件では使用できなかったり、また基板に搭載された部品に熱的損傷を与える。 Less than 0.05% by weight, the effect is less, it is more than 2 wt% and the melt temperature is raised, or not available in conventional use conditions, also provide the thermal damage to the components mounted on the substrate.

【0008】本発明の特徴は特にPおよびNiの配合による優れた効果の発現である。 [0008] Features of the present invention is particularly expression of excellent effect by the addition of P and Ni. Pははんだの耐熱疲労特性と機械的特性(強度および伸び)を改善することができる。 P can improve the solder thermal fatigue resistance and mechanical properties (strength and elongation). しかもこれらの特性はPの配合量の増加と共に著しく改良される。 Moreover these properties are greatly improved with the increase in the amount of P. Pの配合量は0.0005〜0.01重量%である。 The amount of P is 0.0005 to 0.01 wt%. 配合量が0.0005重量%未満ではその効果はなく、0.01重量%を越えると機械的強度は改善されるが、溶融したはんだの表面張力が大きくなり、 The amount is not the effect is less than 0.0005%, although the mechanical strength exceeds 0.01 wt% improves, the greater the surface tension of the molten solder,
大気中でのヌレに問題が生じる。 There is a problem in the wetting in the atmosphere. またNiを添加することにより、耐熱疲労特性がより向上することが判明した。 Also by the addition of Ni, it was found that thermal fatigue resistance is further improved. その効果はNiをPとともに配合することにより一層顕著となる。 Its effect becomes more remarkable by compounding Ni with P. Niの配合量は0.0005〜0.1重量%である。 The amount of Ni is 0.0005 wt%. 0.0005重量%より少ない場合はその効果はなく、0.1重量%より多い場合は熱疲労特性の向上は少なくなる。 If less than 0.0005% by weight is not the effect, if more than 0.1 wt% improvement in thermal fatigue resistance is reduced. Inも耐熱疲労特性と機械的特性を改良することができる。 In can also be improved thermal fatigue resistance and mechanical properties. Inを配合することにより他の特性を損なうことなくこれらの特性を改善する。 To improve these properties without impairing other properties by incorporating In. Inの配合量ははんだ組成物中0.01〜0.5重量%、好ましくは0.01〜0.3重量%である。 The amount of In in the solder composition 0.01 to 0.5 wt%, preferably from 0.01 to 0.3 wt%. 0.01重量%より少ないとその効果は現れず、0.5重量%より多いと酸化物の生成が多くなって好ましくない。 If less than 0.01 wt%, the effect does not appear, undesirably increasingly formation of oxides is more than 0.5 wt%. 本発明はSn、A The present invention is Sn, A
g、Bi、Cu、Ni、Pを上記範囲に設定することにより、従来のSn−Ag、Sn−Zn、Sn−Sb系の無鉛はんだよりも熱疲労特性に優れた無鉛はんだを提供することができる。 g, Bi, Cu, Ni, by setting the P in the above range, the conventional Sn-Ag, Sn-Zn, is to provide a lead-free solder having excellent thermal fatigue properties than the lead-free solder of Sn-Sb-based it can.

【0009】本発明の組成の金属原料からはんだ合金を得るには、通常のはんだの製造方法を用いて行えばよい。 [0009] a metal raw material in the composition of the present invention to obtain a solder alloy may be performed using conventional solder manufacturing method. 本発明のはんだ合金を含有するクリームはんだを得るには、一般に行われているように、はんだ合金を粉末化して粉末はんだとし、これをロジン等の適切な樹脂、 To give a cream solder containing a solder alloy of the present invention, as is typical, the solder powder was triturated solder alloy, suitable resins such as rosin to this,
グリコール類、多価アルコール類等の溶媒を主成分とし、更に活性剤、粘度調整剤および酸化防止剤などの添加剤を含有するフラックスとともに常法により均一に混練して得ることができる。 Glycol, a main component of solvent such as polyhydric alcohols, can be obtained by uniformly kneading further active agent, by a conventional method with a flux containing an additive such as viscosity modifiers and antioxidants. 成形はんだおよびヤニ入りはんだの業界で公知の一般な方法で作成することができる。 It can be prepared by a known general method in forming the solder and tar containing solder industry.

【0010】 [0010]

【実施例】 実施例 1〜4表1に記載した組成の各金属原料を400℃で20分間溶融して均一な合金とした。 EXAMPLES obtain a uniform alloy was melted for 20 minutes at 400 ° C. Each metal raw material in the composition described in Examples 1-4 Table 1. (できれば溶融容器、装置等を含め、代表的なはんだ合金の製造方法を具体的に記載して下さい。) 得られた合金を以下に示す評価方法を採用して、引張強度および伸び、ヌレ性(ヌレ時間およびヌレ応力)および耐熱疲労特性を評価した。 (Melting vessel if possible, including devices such as, please specifically describes a process for the preparation of a representative solder alloy.) The obtained alloy adopted evaluation methods described below, tensile strength and elongation, wettability It was evaluated (wetting time and wetting stress) and thermal fatigue resistance. これらの結果を表1および表2に示した。 The results are shown in Table 1 and Table 2.

【0011】 比較例 1〜6表1に記載した組成で比較例1〜6のはんだを作成した。 [0011] creating the solder of Comparative Examples 1-6 with the composition described in Comparative Examples 1-6 in Table 1. 比較例1〜6のはんだについても実施例と同じようにその特性を評価し、結果を表1および2に示した。 The solder Comparative Examples 1-6 also evaluated the properties as in Example, and the results are shown in Table 1 and 2.

【0012】 [0012]

【表1】 [Table 1]

【0013】 [0013]

【表2】 [Table 2]

【0014】〔はんだ合金の評価方法〕 引張強度および伸び:はんだ合金を400℃に保持し、 [0014] [Evaluation method of the solder alloy] tensile strength and elongation: holding the solder alloy to 400 ℃,
270℃に加熱した黒鉛製の鋳型に流し込み、6℃/秒で冷却して、図1に示す形状の引張試験片を得た。 It poured into graphite molds heated to 270 ° C., and cooled at 6 ° C. / sec, to obtain a tensile test specimen having the shape shown in FIG. この試験片を常温で5mm/分の引張速度で引張試験を行い、破断時の伸びと強度を求めた。 The specimen subjected to tensile test at a tensile rate of 5 mm / min at room temperature, was determined elongation and strength at break. ヌレ特性(銅に対して):メニスコグラフ法により、2 Wetting properties (relative to copper): the meniscograph method, 2
30〜270℃でのヌレ時間およびヌレ応力を評価した。 Wetting time and wetting stress at 30~270 ℃ were evaluated. ヌレ時間:(ヌレ時間の評価法、および判定基準について) ヌレ応力:(ヌレ応力の 〃 〃 Wetting time :( wetting time evaluation methods, and the criterion) of wetting stress :( wetting stress undefined undefined
)

【0015】 熱疲労特性:はんだ合金を100mm×1 [0015] The thermal fatigue characteristics: 100mm solder alloy × 1
00mm×1.8mmの紙フェノール基板(裏面:銅箔)上に8ピンのコネクター8個を250℃ではんだ付けした。 300 mm × 1.8 mm of paper-phenol substrate (Back: copper foil) was soldered eight 8-pin connector at 250 ° C. on. この取り付け態様は図2に示すとおりである。 The attachment embodiment is shown in FIG.
この試料を+80℃(30分)〜−40℃(30分)を1サイクルとし熱衝撃試験にかけ、500サイクルまで50サイクル毎にクラックの発生したピンの本数を調べた。 The sample + 80 ° C. (30 minutes) ~-40 ° C. (30 min) subjected to a thermal shock test as one cycle, examined the number of the generated pin cracks every 50 cycles to 500 cycles. 次の式により、クラック発生率を表した。 By the following equation, representing the crack generation rate. (クラック発生率)=(クラックの発生したピンの本数)/(全ピン数) (Crack generation rate) = (generated pin number of cracks) / (total number of pins)

【0016】 [0016]

【発明の効果】本発明の無鉛はんだ合金は、全く鉛を含有せず、熱疲労特性に優れ、はんだ付け性も良好である。 Lead-free solder alloy of the present invention exhibits, at all does not contain lead, excellent thermal fatigue characteristics, a solderability even better.

【図面の簡単な説明】 BRIEF DESCRIPTION OF THE DRAWINGS

【図1】 はんだの引張特性評価用試験片形状を示す平面および側面図。 Figure 1 is a plan and side view showing a solder tensile properties evaluation specimen geometry.

【図2】 はんだの熱衝撃試験評価用試験片の取り付け態様を示す断面図。 2 is a cross-sectional view showing the manner of mounting solder thermal shock test specimen for evaluation.

【符号の説明】 DESCRIPTION OF SYMBOLS

1:はんだ 2:ランド部(銅箔) 3:フェノール樹脂基板 4:コネクター樹脂 5:ピン 1: Solder 2: land portion (copper foil) 3: a phenolic resin substrate 4: Connector Resin 5: pin

───────────────────────────────────────────────────── フロントページの続き (72)発明者 吉浦 陽三 大阪府大阪市淀川区三津屋中3丁目8番10 号 株式会社ニホンゲンマ内 (72)発明者 盛林 俊之 大阪府大阪市淀川区三津屋中3丁目8番10 号 株式会社ニホンゲンマ内 ────────────────────────────────────────────────── ─── of the front page continued (72) inventor Yozo Yoshiura Osaka Yodogawa-ku, Osaka Mitsuyanaka 3-chome, No. 8, No. 10 Co., Ltd. in the Nihongenma (72) inventor Sheng Lin Toshiyuki Osaka Yodogawa-ku, Osaka Mitsuyanaka 3-chome No. 8 No. 10 Co., Ltd. in the Nihongenma

Claims (7)

    【特許請求の範囲】 [The claims]
  1. 【請求項1】 Bi0.1〜10重量%、Ag0.1〜5 1. A Bi0.1~10 wt%, Ag0.1~5
    重量%、Cu0.05〜2重量%、Ni0.0005〜 Weight%, Cu0.05~2 weight%, Ni0.0005~
    0.1重量%、P0.0005〜0.01重量%および残部がSnからなる無鉛はんだ合金。 0.1 wt%, P0.0005~0.01 wt% and lead-free solder alloy and the balance being Sn.
  2. 【請求項2】 更にIn0.01〜0.5重量%を添加した請求項1記載の無鉛はんだ合金。 2. A further In0.01~0.5 wt% claim 1, wherein the lead-free solder alloy obtained by adding.
  3. 【請求項3】 請求項1または2記載の無鉛はんだ合金の粉末を含有するクリームはんだ。 3. A cream solder containing powder of the lead-free solder alloy of claim 1 or 2 wherein.
  4. 【請求項4】 請求項1または2記載の無鉛はんだ合金を用いた成形はんだ。 4. A molded solders with lead-free solder alloy of claim 1 or 2 wherein.
  5. 【請求項5】 請求項1または2記載の無鉛はんだ合金を用いたヤニ入りはんだ。 5. A tar-containing solders with lead-free solder alloy of claim 1 or 2 wherein.
  6. 【請求項6】 請求項1記載の無塩はんだ合金を用いた基板。 Substrate using 6. unsalted solder alloy of claim 1, wherein.
  7. 【請求項7】 請求項1記載の無塩はんだ合金を用いた電子製品。 7. An electronic products using a salt-free solder alloy of claim 1, wherein.
JP19762596A 1996-07-26 1996-07-26 Lead-free solder Expired - Fee Related JP3693762B2 (en)

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WO2001003878A1 (en) * 1999-07-07 2001-01-18 Multicore Solders Limited Solder alloy
WO2002022302A1 (en) * 2000-09-18 2002-03-21 Matsushita Electric Industrial Co., Ltd. Solder material and electric or electronic device in which the same is used
US6365097B1 (en) 1999-01-29 2002-04-02 Fuji Electric Co., Ltd. Solder alloy
US6440360B1 (en) * 1999-02-08 2002-08-27 Tokyo First Trading Company Pb-free soldering alloy
EP1273384A1 (en) 2001-06-28 2003-01-08 Senju Metal Industry Co., Ltd. Lead-free solder alloy
US6692691B2 (en) * 2000-06-30 2004-02-17 Nihon Alimit Co., Ltd. Pb-free soldering alloy
GB2421030A (en) * 2004-12-01 2006-06-14 Alpha Fry Ltd Solder alloy
JP2006524572A (en) * 2003-04-25 2006-11-02 クックソン・エレクトロニクス・アッセンブリー・マテリアルズ・グループ・アルファ・メタルズ・レートジュステーメ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツングCookson Electronics Assembly Materials Group Alpha Metals Loetsysteme Gmbh Sn, solder material composed of Ag and Cu
GB2431412A (en) * 2005-10-24 2007-04-25 Alpha Fry Ltd Lead-free solder alloy
WO2007045191A2 (en) * 2005-10-19 2007-04-26 Jan Jenik Lead-free solder alloy
CN101767253A (en) * 2008-12-26 2010-07-07 Nec照明株式会社 Solder for lead wire of cold-cathode fluorescent lamp, lead wire of cold-cathode fluorescent lamp and connection thereof
CN102085604A (en) * 2011-03-04 2011-06-08 上海交通大学 Sn-Ag-Cu-Bi-Cr low-silver and lead-free solder
JP4787384B1 (en) * 2010-10-29 2011-10-05 ハリマ化成株式会社 Low silver solder alloy and solder paste composition
US8641964B2 (en) 2005-08-24 2014-02-04 Fry's Metals, Inc. Solder alloy
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US10124154B2 (en) 2005-06-10 2018-11-13 Acclarent, Inc. Catheters with non-removable guide members useable for treatment of sinusitis
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US9610428B2 (en) 2004-04-21 2017-04-04 Acclarent, Inc. Devices, systems and methods useable for treating frontal sinusitis
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US9649477B2 (en) 2004-04-21 2017-05-16 Acclarent, Inc. Frontal sinus spacer
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US9820688B2 (en) 2006-09-15 2017-11-21 Acclarent, Inc. Sinus illumination lightwire device
US10271719B2 (en) 2008-07-30 2019-04-30 Acclarent, Inc. Paranasal ostium finder devices and methods
US9750401B2 (en) 2008-07-30 2017-09-05 Acclarent, Inc. Paranasal ostium finder devices and methods
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