JP2006326676A

JP2006326676A - Leadless solder alloy for low temperature joining of glass or ceramics

Info

Publication number: JP2006326676A
Application number: JP2005182557A
Authority: JP
Inventors: Shigenobu Sekine; 重信関根; Yurina Sekine; 由莉奈関根
Original assignee: Napra Co Ltd
Current assignee: Napra Co Ltd
Priority date: 2005-05-27
Filing date: 2005-05-27
Publication date: 2006-12-07
Anticipated expiration: 2025-05-27
Also published as: JP4627458B2

Abstract

<P>PROBLEM TO BE SOLVED: To provide a solder alloy for low temperature joining of glass or ceramics which does not include Pb harmful for the human body and further has high joining strength. <P>SOLUTION: The leadless solder alloy for low temperature joining of glass or ceramics is obtained by adding, by weight, 0.001 to 3% gallium to a low melting point leadless solder alloy which essentially consists of tin and/or bismuth, does not include lead, and has a melting point in the range of 120 to 200°C. The amount of the gallium to be added preferably lies in the range of 0.01 to 2% in particular. Even in the case the amount of the gallium to be added is 0.001%, the addition effect is recognized, and the joining strength reaches 7 kg/mm<SP>2</SP>, but, in 0.01%, it reaches the 10 kg/mm<SP>2</SP>level. Even if the amount of the gallium to be added is controlled to ≥2%, the further improvement of the joining strength is not recognized. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は、人体に有害な鉛を含有しない無鉛錫（Ｓｎ）系ハンダ合金に関し、特に、電子部品関係の金属とガラス、セラミックスとの接合への適用において有用な無鉛ハンダ合金に関するものである。 The present invention relates to a lead-free tin (Sn) -based solder alloy that does not contain lead harmful to the human body, and more particularly to a lead-free solder alloy that is useful in the application to the joining of metals related to electronic parts, glass, and ceramics.

ガラスやセラミックスの接合に用いる軟ロウ材（ハンダ合金）としては、錫（Ｓｎ）と鉛（Ｐｂ）の共晶組成付近の合金が一般に使用されてきた。特公昭４５−１７３９号にはＰｂ（４０〜９８重量％）−Ｓｎ（１．８〜５０重量％）−Ｚｎ（０．０５〜１０重量％）−Ｓｂ（０．０５〜１０重量％）系の窯業体用ハンダ、特公昭５１−４０４６号にはＰｂ（４０〜８５重量％）−Ｓｎ（５〜５０重量％）−Ｂｉ（３〜１８重量％）−Ｓｂ（０．５〜１２重量％）−Ｚｎ（０．５〜１０重量％）系のガラス用ハンダが提案されている。その後鉛の人体に対する毒性が問題になり、鉛を含まないガラス、セラミックスの用ハンダ合金として特開昭６２−２５２６９３号にはＢｉ（２５〜８５重量％）−Ｓｎ（１８〜６８重量％）−Ｚｎ（０．１〜１０重量％）−Ｓｂ（０．１〜１０重量％）系のセラミックス用ハンダ、特開平１１−７７３７０号にはＢｉ（３０〜８０重量％）−Ｓｎ（１８〜８８重量％）−Ｔｉ（０，１〜５重量％）系のガラス、セラミックス用ハンダなどが提案されているが、接合強度は鉛を含むハンダ合金に比べ劣り７ｋｇ／ｍｍ^２以上の特性が出ない。
特開昭４５−１７３９号公報特公昭５１−４０４６号公報特開昭６２−２５２６９３号公報特開平１１−７７３７０号公報 As a soft brazing material (solder alloy) used for bonding glass or ceramics, an alloy near the eutectic composition of tin (Sn) and lead (Pb) has been generally used. Japanese Patent Publication No. 45-1739 discloses a Pb (40 to 98% by weight) -Sn (1.8 to 50% by weight) -Zn (0.05 to 10% by weight) -Sb (0.05 to 10% by weight) system. No. 51-4046 is a solder for ceramics body of Pb (40-85 wt%)-Sn (5-50 wt%)-Bi (3-18 wt%)-Sb (0.5-12 wt%) ) -Zn (0.5 to 10% by weight) glass solder has been proposed. Thereafter, the toxicity of lead to the human body becomes a problem, and as a solder alloy for glass and ceramics containing no lead, JP-A-62-225293 discloses Bi (25 to 85% by weight) -Sn (18 to 68% by weight)- Solder for ceramics based on Zn (0.1 to 10% by weight) -Sb (0.1 to 10% by weight), Japanese Patent Application Laid-Open No. 11-77370 describes Bi (30 to 80% by weight) -Sn (18 to 88% by weight) %)-Ti (0, 1 to 5% by weight) based glass, solder for ceramics, etc. have been proposed, but the bonding strength is inferior to that of lead-containing solder alloys, and a characteristic of 7 kg / mm ² or more does not appear.
JP-A-45-1739 Japanese Patent Publication No.51-4046 JP-A-62-225293 JP-A-11-77370

本発明は、人体に有害なＰｂを含有せず、しかも接合強度が高い、具体的には７ｋｇ／ｍｍ^２以上あるガラス、セラミックスの低温接合用ハンダ合金を提供することを目的とする。An object of the present invention is to provide a solder alloy for low-temperature bonding of glass and ceramics that does not contain Pb harmful to the human body and has high bonding strength, specifically, 7 kg / mm ² or more.

本発明に関わるガラス又はセラミックスの低温接合用無鉛ハンダ合金は、錫及び／又はビスマスを主体とし鉛を含まない融点１２０℃〜２００℃の範囲の低融点無鉛ハンダ合金にガリウムを０．００１〜３重量％添加したものである。 The lead-free solder alloy for low-temperature bonding of glass or ceramics according to the present invention contains 0.001 to 3 gallium in a low-melting-point lead-free solder alloy having a melting point of 120 ° C. to 200 ° C. mainly containing tin and / or bismuth and not containing lead. Added by weight%.

ガラスやセラミックス相互、又はそれらと金属の接合強度が７ｋｇ／ｍｍ^２以上あるガラス、セラミックスの低温接合用ハンダ合金が得られる。A solder alloy for low-temperature bonding of glass and ceramics having a bonding strength of 7 kg / mm ² or more between glass and ceramics or between them and a metal is obtained.

本発明のベース（ガリウム添加前）となる錫及び／又はビスマスを主体とする低融点無鉛ハンダ合金としては、錫３０〜８５重量％、ビスマス１５〜６０重量％、インジウム０〜１５重量％よりなり鉛を含まない融点１２０℃〜２００℃の範囲の低融点無鉛ハンダ合金が推奨される。またこの低融点無鉛ハンダ合金に対するガリウムの添加量は０．００１〜３重量％の範囲、特に０．０１〜１重量％の範囲が好ましい。ガリウムの添加量画０．００１重量％でも添加効果が認められ接合強度７ｋｇ／ｍｍ^２となるが、０．０１重量％では１０ｋｇ／ｍｍ^２台となる。一方ガリウムの添加量を２重量％以上にしても接合強度のさらなる改善は認められない。The low melting point lead-free solder alloy mainly composed of tin and / or bismuth serving as a base (before gallium addition) of the present invention is composed of 30 to 85% by weight of tin, 15 to 60% by weight of bismuth, and 0 to 15% by weight of indium. Lead-free low melting point lead-free solder alloys with a melting point in the range of 120 ° C to 200 ° C are recommended. The amount of gallium added to the low melting point lead-free solder alloy is preferably in the range of 0.001 to 3% by weight, and more preferably in the range of 0.01 to 1% by weight. Even when the added amount of gallium is 0.001% by weight, the effect of addition is recognized and the bonding strength is 7 kg / mm ² , but at 0.01% by weight, the amount is 10 kg / mm ² . On the other hand, even if the addition amount of gallium is 2% by weight or more, no further improvement in bonding strength is observed.

表１に示す実施例１〜９の組成のハンダ合金及び比較例１〜３の組成（ガリウムを含まず）のハンダ合金を調製し、ガラス管の熱衝撃破壊指数及びガラスと金属の接合強度を測定した。結果を表１、２、３に示す。表１は実施例及び比較例の全てをまとめた表、表２は共通のベースハンダ合金（Ｂｉ：２８．０重量％、Ｉｎ：３．０重量％、Ｓｎ：残り）においてＧａの添加量の影響がわかるように編集したもの、表３は同一のＧａ添加量（０．００１重量％及び２重量％）において異なるベースハンダ合金組成の影響を示したものである。ガラス管の熱衝撃破壊指数の測定は、外径４ｍｍ、肉厚０．５ｍｍのガラス管１０本を溶融金属中に挿入し挿入２秒後に取り出し１０本中の破壊した本数で示す。ガラスと金属の接合強度の測定は、ガラス板の表面に金属線の先端をハンダ付けしたものをガラス板面に対して４５度の方向に引っ張り、剥がれたときの強度（ｋｇ／ｍｍ^２）で示す。The solder alloys having the compositions of Examples 1 to 9 shown in Table 1 and the solder alloys having the compositions of Comparative Examples 1 to 3 (not including gallium) were prepared, and the thermal shock fracture index of the glass tube and the bonding strength between the glass and the metal were determined. It was measured. The results are shown in Tables 1, 2, and 3. Table 1 is a table summarizing all of the examples and comparative examples, and Table 2 shows the amount of Ga added in a common base solder alloy (Bi: 28.0 wt%, In: 3.0 wt%, Sn: remaining). Table 3 shows the influence of different base solder alloy compositions at the same Ga addition amount (0.001 wt% and 2 wt%). The measurement of the thermal shock fracture index of a glass tube is shown by the number of 10 glass tubes having an outer diameter of 4 mm and a thickness of 0.5 mm inserted into the molten metal, taken out 2 seconds after the insertion, and broken in 10 tubes. The measurement of the bonding strength between glass and metal is the strength (kg / mm ² ) when the tip of the metal wire is soldered to the surface of the glass plate and pulled in a direction of 45 degrees with respect to the glass plate surface. Show.

表２より、ガリウムの添加量は０．００１〜３重量％の範囲、特に０．０１〜２重量％の範囲が好ましこと。ガリウムの添加量が０．００１重量％でも添加効果が認められ接合強度７ｋｇ／ｍｍ^２となるが、０．０１重量％では１０ｋｇ／ｍｍ^２台となること、ガリウムの添加量を２重量％以上にしても接合強度のさらなる改善は認められないことなどが分かる。From Table 2, the addition amount of gallium is preferably in the range of 0.001 to 3% by weight, particularly in the range of 0.01 to 2% by weight. Even if the gallium addition amount is 0.001% by weight, the addition effect is recognized and the bonding strength becomes 7 kg / mm ² , but at 0.01% by weight it becomes 10 kg / mm ² units, and the gallium addition amount is 2% by weight or more. However, it can be seen that no further improvement in bonding strength is observed.

表３の結果を見れば、ガラス管の熱衝撃破壊指数やガラスと金属の接合強度はガリウムの添加量の影響が支配的であり、ベースの錫及び／又はビスマスを主体とし鉛を含まない合金における組成の変化は支配的でないことが分かる。 According to the results in Table 3, the influence of the addition amount of gallium is dominant on the thermal shock fracture index of glass tubes and the bonding strength between glass and metal, and the alloy mainly contains tin and / or bismuth as a base and does not contain lead. It can be seen that the compositional change in is not dominant.

Claims

A glass or ceramics characterized in that 0.001 to 3% by weight of gallium is added to a low melting point lead-free solder alloy mainly composed of tin and / or bismuth and containing no melting point in the range of 120 ° C. to 200 ° C. Lead-free solder alloy for low-temperature bonding.

The lead-free solder alloy for low-temperature bonding of glass or ceramics according to claim 1, wherein the amount of gallium added is in the range of 0.01 to 2% by weight.

A low melting point lead-free solder alloy consisting of 30 to 85% by weight of tin, 15 to 60% by weight of bismuth and 0 to 15% by weight of indium and having a melting point of 120 ° C to 200 ° C containing no lead contains 0.001% to 3% of gallium. A lead-free solder alloy for low-temperature bonding of glass or ceramics, characterized in that it is added by weight%.

The lead-free solder alloy for low-temperature bonding of glass or ceramics according to claim 3, wherein the amount of gallium added is in the range of 0.01 to 2% by weight.