JP2001143529A - Conductive bonding agent by cream solder mixing and bonding method using the same - Google Patents
Conductive bonding agent by cream solder mixing and bonding method using the sameInfo
- Publication number
- JP2001143529A JP2001143529A JP32194999A JP32194999A JP2001143529A JP 2001143529 A JP2001143529 A JP 2001143529A JP 32194999 A JP32194999 A JP 32194999A JP 32194999 A JP32194999 A JP 32194999A JP 2001143529 A JP2001143529 A JP 2001143529A
- Authority
- JP
- Japan
- Prior art keywords
- filler
- conductive
- bonding agent
- cream solder
- parts
- 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.)
- Withdrawn
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、導電性接着剤とク
リームハンダによる導電性接合剤およびそれを使用した
接合方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive bonding agent using a conductive adhesive and cream solder, and a bonding method using the same.
【０００２】[0002]
【従来の技術】現在電子機器業界において半導体やその
他の精密電子部品の組立に導電性接着剤が使用されてお
り、この導電性接着剤は、銀、金、ニッケル、カーボン
等を導電性を発現するフィラーとし、エポキシ樹脂、フ
ェノール樹脂、ポリエステル樹脂、アクリル樹脂等をバ
インダとして、これらのフィラーとバインダを硬化剤や
溶剤と共に、目的に合わせて適当に配合して、所定の導
電性接着剤を得ている。また一方、最近の電子機器の鉛
フリー化のトレンドを契機として、これらの導電接着剤
を一般電子機器基板のアッセンブリーに、はんだ代替接
合材として利用しようとする試みがなされている。2. Description of the Related Art At present, in the electronic equipment industry, conductive adhesives are used for assembling semiconductors and other precision electronic parts, and the conductive adhesives exhibit conductivity of silver, gold, nickel, carbon, and the like. As a filler to be used, epoxy resin, phenol resin, polyester resin, acrylic resin, etc. are used as a binder, and these fillers and a binder are appropriately blended with a curing agent and a solvent according to the purpose to obtain a predetermined conductive adhesive. ing. On the other hand, with the recent trend of lead-free electronic devices, attempts have been made to use these conductive adhesives as substitutes for solders in assemblies of general electronic device substrates.
【０００３】[0003]
【発明が解決しようとする課題】導電性接着剤は、導電
性を司る金属粉末を主とする導電性粉末フィラーと接着
を司る合成樹脂バインダとを混練りして作られている。
一般にバインダとしては、エポキシ樹脂、ポリアミド樹
脂、フェノール樹脂等が使用されているが、これらの合
成樹脂は概して耐湿性が十分でなく、半導体のようにパ
ッケージングされるものでは、問題がないものの、一般
基板のように大気に露出したまま機器に組み込まれるも
のは、高温高湿度の環境下で湿気の影響により部品接合
部の導電性の低下や接着強度の低下を引き起こす嫌いが
ある。The conductive adhesive is produced by kneading a conductive powder filler mainly composed of a metal powder for controlling conductivity and a synthetic resin binder for controlling adhesion.
Generally, as a binder, epoxy resin, polyamide resin, phenol resin, etc. are used, but these synthetic resins generally do not have sufficient moisture resistance, and although there is no problem in packaging like a semiconductor, Components that are built into the device while exposed to the atmosphere, such as general substrates, do not like to cause a decrease in conductivity and a decrease in adhesive strength at the joints of parts due to the influence of moisture in an environment of high temperature and high humidity.
【０００４】即ち、これらの合成樹脂の組織が総じてミ
クロ的に粗大のため、湿気が合成樹脂組織の間隙を縫っ
て浸透し、それが基板の電極や部品電極の表面を急速に
酸化させ、更に金属フィラー表面をも酸化させて、接続
部全体の導電性の低下や接合強度の劣化を惹き起こすの
である。That is, since the structure of these synthetic resins is generally microscopically coarse, moisture penetrates through the gaps of the synthetic resin structures and rapidly oxidizes the surfaces of the electrodes of the substrate and the electrodes of the components. This also oxidizes the surface of the metal filler, causing a decrease in conductivity of the entire connection portion and a deterioration in bonding strength.
【０００５】この耐湿性の問題を改善するために過去様
々な提案がなされている。即ち、バインダ内に酸を併存
させて電極表面をクリーニングし、導電性を回復させよ
うとするものや、針状フィラーを利用し電極部への突き
刺さることで導電性や接合強度を確保しようとするも
の、更には高融点合金のフィラーと低融点のはんだ合金
フィラーと、フラックス作用を発現する潜在活性剤を含
むバインダからなる導電性接着剤により、加熱時に電極
とはんだ合金間に拡散作用を起こさせ導電性と接合強度
を確保しようとするもの等であるが、何れも方法が複雑
であるばかりか、未だ十分とは言えないものであった。Various proposals have been made in the past to improve the problem of moisture resistance. That is, the electrode surface is cleaned by allowing an acid to coexist in the binder to recover the conductivity, or the conductivity or the bonding strength is secured by piercing the electrode portion using a needle-like filler. And a conductive adhesive consisting of a high-melting-point alloy filler, a low-melting-point solder alloy filler, and a binder containing a latent activator that exhibits a flux action, causing a diffusion action between the electrode and the solder alloy during heating. Although it is intended to ensure conductivity and bonding strength, all of these methods are not only complicated but also insufficient.
【０００６】[0006]
【課題を解決するための手段】本発明は、上記の各種提
案のごとき技術的に複雑なものでなく、単に導電性接着
剤とクリームハンダとを混練りして用いることにより、
導電性接着剤の効果とクリームハンダによるハンダ付け
効果の優れた相乗効果により高湿度条件下での導電性と
接合強度の劣化の問題の解決を図るものである。即ち、
導電性フィラーと樹脂バインダとからなる導電性接着剤
に、樹脂系フラックスをベースとするクリームハンダを
混合してなる導電性接合剤、また、導電性フィラーと樹
脂バインダとからなる導電性接着剤に、錫・ビスマス合
金又は／及び錫・銀・ビスマス合金フィラーと樹脂系フ
ラックスをベースとする無鉛クリームハンダを配合して
なる導電性接合剤、また特には、前記導電性フィラーを
銀、ニッケル、銅の少なくとも１種のフィラー、また銀
フィラー及び錫合金フィラーの両方又はいずれか一方よ
りなるフィラーとすることを特徴とする導電性接合剤に
より解決を図るものである。更には、これらの導電性接
合剤を用いることを特徴とする接合方法により解決せん
とするものである。The present invention is not technically complicated as in the above-mentioned various proposals, and is achieved by simply kneading a conductive adhesive and cream solder.
An object of the present invention is to solve the problem of deterioration of conductivity and bonding strength under high humidity conditions by the excellent synergistic effect of the effect of the conductive adhesive and the soldering effect of cream solder. That is,
To a conductive adhesive consisting of a conductive filler and a resin binder, a conductive bonding agent obtained by mixing cream solder based on a resin flux, and to a conductive adhesive consisting of a conductive filler and a resin binder , A tin-bismuth alloy or / and a tin-silver-bismuth alloy filler and a lead-free cream solder based on a resin-based flux, and in particular, a conductive bonding agent comprising silver, nickel, copper The conductive bonding agent is characterized by using at least one kind of filler described above, and a filler comprising both or one of a silver filler and a tin alloy filler. Further, the present invention solves the problem by a bonding method characterized by using these conductive bonding agents.
【０００７】[0007]
【発明の実施の形態】以下、本発明を更に詳細に説明す
る。なお、以下の説明は本発明の理解を容易にするため
のものであり、本発明を限定するものではない。本発明
の導電性接合剤における導電性接着剤に要求される条件
としては、ａ）硬化温度が低すぎないこと。望ましく
は、１７０〜２２０℃程度であること。ｂ）導電性フィ
ラーは、はんだ付けし易い金属或いは合金であること。
好ましくは銀、銅、錫、ニッケル等の金属或いはそれら
の合金が望ましい。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The following description is for the purpose of facilitating the understanding of the present invention, and does not limit the present invention. The conditions required for the conductive adhesive in the conductive bonding agent of the present invention are that a) the curing temperature is not too low. Desirably, it is about 170 to 220 ° C. b) The conductive filler is a metal or alloy that is easy to solder.
Preferably, metals such as silver, copper, tin and nickel or alloys thereof are desirable.
【０００８】更に、本発明の導電性接合剤におけるクリ
ームハンダに要求される条件としては、イ）ハンダ材
は、併用する導電性接着剤の硬化温度以下で溶融するも
のであること。ロ）フラックスは、合成樹脂系であって
併用する導電性接着剤に使用されているバインダの合成
樹脂と相溶するタイプのものであること。 好ましく
は、該バインダの合成樹脂と同系の合成樹脂であること
が望ましい。以下実施例に基づき具体的に説明する。な
お、本発明はその要旨を越えない限り、以下に説明する
諸例の構成に限定されるものではない。Further, the conditions required for the cream solder in the conductive bonding agent of the present invention are as follows: a) The solder material must melt at a temperature not higher than the curing temperature of the conductive adhesive used in combination. B) The flux must be of a synthetic resin type and compatible with the synthetic resin of the binder used for the conductive adhesive used in combination. Preferably, the synthetic resin is similar to the synthetic resin of the binder. Hereinafter, a specific description will be given based on examples. The present invention is not limited to the configurations of the examples described below unless departing from the gist.
【０００９】[0009]
【実施例】実施例１：エポキシ樹脂系バインダと銀フィ
ラーからなる熱硬化性１液タイプの導電性接着剤の９０
重量部（部）に対し、ハンダの融点が１３８℃であるロ
ジン系錫・ビスマス共晶合金フィラークリームハンダを
１０重量部（部）混合し、導電性接合剤１を試作した。
なお銀フィラーの平均粒径は５μｍであった。該導電性
接合剤１を試験基板に塗布し、該導電性接着剤の硬化温
度１５０℃において２０分間加熱した。冷却後外観検査
および破壊検査を行った。外観検査において、導電性接
合剤１は試験基板上に固化し、十分な接着が確認され
た。しかし、破壊検査において接合部を拡大観察した結
果、基板の電極部分ははんだの溶融が不十分で、基板電
極に対するハンダの濡れが殆ど達成されていないことが
観察された。EXAMPLE 1 A thermosetting one-part type conductive adhesive composed of an epoxy resin binder and a silver filler was used.
10 parts by weight (parts) of a rosin-based tin-bismuth eutectic alloy filler cream solder having a melting point of 138 ° C. was mixed with parts by weight (parts) to prepare a conductive bonding agent 1.
The average particle size of the silver filler was 5 μm. The conductive bonding agent 1 was applied to a test substrate and heated at a curing temperature of the conductive adhesive of 150 ° C. for 20 minutes. After cooling, a visual inspection and a destructive inspection were performed. In the appearance inspection, the conductive bonding agent 1 solidified on the test substrate, and sufficient adhesion was confirmed. However, as a result of magnifying observation of the joint in the destructive inspection, it was observed that the solder of the electrode portion of the substrate was insufficiently melted and solder wetting on the substrate electrode was hardly achieved.
【００１０】実施例２：実施例１の結果に鑑み、前記硬
化温度を２０℃上げ、１７０℃とした以外は実施例１と
同様条件である導電性接合剤２を作成した。加熱時間は
２０分の条件で同一試験基板を加熱した。 試験基板上
の導電性接合剤の状態は微少なロジンの滲みが観察され
たが、問題となる金属粒子の滲みだしはなく、外観上は
欠陥のない接着が完成していた。この試料を破壊して基
板電極部分を詳細観察した結果、ハンダの十分な溶融が
見られ、当該加熱条件であれば、目的の接合状態、即ち
ハンダが溶融して基板と部品の電極面を濡らし、且つフ
ィラーとも部分的な濡れによる連携がみられ、接合部全
体として、単にフィラーと電極の接触による導電性だけ
でなく、ハンダの濡れによる導電性の補完とバインダに
よる接着に、更にハンダ付け接合がプラスされた接合強
度の補完関係にある接合状態が完成されていることが観
察された。Example 2 In view of the results of Example 1, a conductive bonding agent 2 was prepared under the same conditions as in Example 1 except that the curing temperature was increased by 20 ° C. and set to 170 ° C. The same test substrate was heated under a heating time of 20 minutes. Although the bleeding of the fine rosin was observed in the state of the conductive bonding agent on the test substrate, no problematic bleeding of the metal particles was observed, and adhesion without defects in appearance was completed. As a result of destroying this sample and observing the substrate electrode portion in detail, sufficient melting of the solder was observed, and under the heating conditions, the desired bonding state, that is, the solder melted and wetted the electrode surface of the substrate and the component. In addition, there is cooperation between the filler and the part due to partial wetting. As a whole, not only the conductivity due to the contact between the filler and the electrode, but also the complementation of the conductivity due to the wetting of the solder and the bonding with the binder, as well as the solder bonding It has been observed that a bonding state having a complementary relation of the bonding strength with the addition of “” has been completed.
【００１１】実施例３：銀フィラー３５重量部（部）に
錫合金フィラー４０重量部（部）及び錫フィラー５重量
部（部）を混合したタイプの導電性接着剤を９５重量部
（部）、これにロジン系低温クリームハンダを５重量部
（部）加えて混練し導電性接合剤３を試作した。これを
試験基板に塗布し、加熱温度１７０℃で２０分加熱し、
冷却後試験基板の外観検査をおこなった。結果、接合部
にロジンの滲みだしもなく形状的に欠陥のない接着が完
成していることが観察された。また当該試験基板を破壊
し基板電極部を詳細観察した。電極上にハンダの濡れが
観察され、更に周辺の錫合金フィラーとハンダとの部分
的な濡れも発達し、一部では凝集を起こしているのが観
察された。Example 3: 95 parts by weight of a conductive adhesive obtained by mixing 35 parts by weight of silver filler with 40 parts by weight of tin alloy filler and 5 parts by weight of tin filler Then, 5 parts by weight (part) of a rosin-based low-temperature cream solder was added and kneaded to produce a conductive bonding agent 3 as a trial. This is applied to a test substrate and heated at a heating temperature of 170 ° C. for 20 minutes.
After cooling, the appearance of the test substrate was inspected. As a result, it was observed that rosin did not bleed out at the joint, and that bonding without shape defects was completed. Further, the test substrate was broken, and the substrate electrode portion was observed in detail. It was observed that solder wettability was observed on the electrode, partial wettability between the surrounding tin alloy filler and the solder also developed, and aggregation occurred in part.
【００１２】実施例４：銀フィラー７５重量部（部）に
銅フィラー５重量部（部）を混合したタイプの導電性接
着剤を９５重量部（部）、これにロジン系低温クリーム
ハンダを５重量部（部）加えて混練し導電性接合剤４を
試作した。これを前述と試験基板に塗布し、加熱温度１
７０℃で２０分加熱した。冷却後試験基板の外観検査を
おこなった。結果、実施例３と略同程度で安定した接着
が認められた。また当該試験基板を破壊し基板電極部を
詳細観察した結果、電極上のハンダの良好な濡れが観察
された。Example 4: 95 parts by weight of a conductive adhesive obtained by mixing 5 parts by weight of a copper filler with 75 parts by weight of a silver filler, and 5 parts by weight of a rosin-based low-temperature cream solder A part by weight (parts) was added and kneaded to prepare a conductive bonding agent 4 as a trial. This was applied to the test substrate as described above, and a heating temperature of 1
Heated at 70 ° C. for 20 minutes. After cooling, the appearance of the test substrate was inspected. As a result, stable adhesion was observed at about the same level as in Example 3. In addition, as a result of destroying the test substrate and observing the substrate electrode portion in detail, favorable wetting of the solder on the electrode was observed.
【００１３】実施例５：銀フィラー７５重量部（部）に
ニッケルフィラー５重量部（部）を混合したタイプの導
電性接着剤を９５重量部（部）、これにロジン系低温ク
リームハンダを５重量部（部）加えて混練し導電性接合
剤５を試作した。これを試験基板に塗布し、加熱温度１
７０℃で２０分加熱した。冷却後前例と同様試験基板の
外観検査及び試験基板を破壊し基板電極部の詳細観察を
おこなった。ハンダによる基板と部品の電極面の濡れも
十分であり、接合部全体としての接着程度も良好であっ
た。Example 5: 95 parts by weight of a conductive adhesive obtained by mixing 5 parts by weight of nickel filler with 75 parts by weight of silver filler, and 5 parts by weight of a rosin-based low-temperature cream solder The conductive bonding agent 5 was prototyped by adding and kneading parts by weight (parts). This was applied to a test substrate and heated at a heating temperature of 1
Heated at 70 ° C. for 20 minutes. After cooling, the appearance of the test substrate was inspected, and the test substrate was broken to observe the electrode portions of the substrate in detail as in the previous example. The electrode surfaces of the substrate and the component were sufficiently wetted by the solder, and the degree of adhesion of the entire joint was good.
【００１４】実施例６：実施例５に対し銅フィラーを加
えることにより銀フィラーの更なる削減を目的として、
銀フィラー７０重量部（部）にニッケルフィラー５重量
部（部）と更に銅フィラー５重量部（部）を混合したタ
イプの導電性接着剤を９５重量部（部）、これにロジン
系低温クリームハンダを５重量部（部）加えて混練し導
電性接合剤６を試作した。これを試験基板に塗布し、加
熱温度１７０℃で２０分加熱した。冷却後試験基板の外
観検査及び試験基板を破壊し基板電極部を詳細観察をお
こなった。実施例５に比べて濡れ状態、接着状態とも遜
色は認められなかった。Example 6 In order to further reduce the amount of silver filler by adding a copper filler to Example 5,
95 parts by weight of a conductive adhesive obtained by mixing 5 parts by weight of nickel filler, 5 parts by weight of copper filler, 70 parts by weight of silver filler, and rosin-based low-temperature cream 5 parts by weight (parts) of solder were added and kneaded to produce a conductive bonding agent 6 as a trial. This was applied to a test substrate and heated at a heating temperature of 170 ° C. for 20 minutes. After cooling, the appearance of the test substrate was inspected, and the test substrate was destroyed to observe the substrate electrode in detail. Compared to Example 5, no inferiority was observed in the wet state and the adhesion state.
【００１５】実施例７：更に実施例６の導電性接着剤組
成と同一のものとし、加えるクリームハンダの量を増量
し、クリームハンダ量による効果を確認するために、実
施例６と同じ銀フィラー７０重量部（部）にニッケルフ
ィラー５重量部（部）、銅フィラー５重量部（部）を混
合したタイプの導電性接着剤を９０重量部（部）、これ
にロジン系低温クリームハンダを１０重量部（部）加え
て混練し導電性接合剤７を試作した。これを試験基板に
塗布し、加熱温度１７０℃で２０分加熱した。冷却後試
験基板の外観検査及び試験基板を破壊し基板電極部を詳
細観察をおこなった。接合部の接着状態及び電極上のハ
ンダの濡れ具合は、実施例６と略同一レベルであり、ク
リームハンダを増量した効果は特には見受けられなかっ
た。クリームハンダの量は５重量部（部）程度でも十分
相乗効果を期待できることがわかった。Example 7: The same silver filler as in Example 6 was used in order to further increase the amount of cream solder to be added and to confirm the effect of the amount of cream solder to be the same as the conductive adhesive composition of Example 6. 90 parts by weight of a conductive adhesive obtained by mixing 5 parts by weight of nickel filler and 5 parts by weight of copper filler in 70 parts by weight, and 10 parts by weight of rosin-based low-temperature cream solder A part by weight (parts) was added and kneaded to produce a conductive bonding agent 7 as a trial. This was applied to a test substrate and heated at a heating temperature of 170 ° C. for 20 minutes. After cooling, the appearance of the test substrate was inspected, and the test substrate was destroyed to observe the substrate electrode in detail. The bonding state of the bonding portion and the degree of wetting of the solder on the electrode were substantially the same as in Example 6, and the effect of increasing the amount of cream solder was not particularly observed. It was found that a sufficient synergistic effect can be expected even when the amount of the cream solder is about 5 parts by weight (parts).
【００１６】実施例８：銀フィラーを全く除いた場合の
効果を確認するために、錫・銀共晶合金フィラーのみを
フィラーとする導電性接着剤を９５重量部（部）、これ
にロジン系低温クリームハンダを５重量部（部）加えて
混練し導電性接合剤８を試作した。これを試験基板に塗
布し、加熱温度１７０℃で２０分加熱した。冷却後試験
基板の外観検査及び基板を破壊し基板電極部の詳細観察
をおこなった。実施例２の全て銀フィラーの場合に比べ
て、接合部の接着状態及び電極上のハンダの濡れ状態は
殆ど変わらないレベルであり、銀フィラーと錫・銀共晶
合金フィラーによる接合上の差は殆ど認められない。Example 8: To confirm the effect when the silver filler was completely removed, 95 parts by weight of a conductive adhesive containing only a tin / silver eutectic alloy filler as a filler and a rosin-based adhesive were used. 5 parts by weight (parts) of low-temperature cream solder was added and kneaded to produce a conductive bonding agent 8 as a trial. This was applied to a test substrate and heated at a heating temperature of 170 ° C. for 20 minutes. After cooling, the appearance of the test substrate was inspected, and the substrate was broken, and detailed observation of the substrate electrode was performed. Compared to the case of all the silver fillers of Example 2, the bonding state of the bonding portion and the wet state of the solder on the electrode are almost unchanged, and the difference in bonding between the silver filler and the tin / silver eutectic alloy filler is as follows. Almost no.
【００１７】実施例９：更に実施例２に対し、混練する
クリームハンダの組成を変えた場合の効果を比較するた
めに、実施例２と同様の導電性接着剤９０重量部（部）
に対し、錫・銀・ビスマス共晶合金フィラーをフィラー
とするロジン系低温クリームハンダを１０重量部（部）
加えて混練し導電性接合剤９を試作した。これを試験基
板に塗布し、加熱温度１７０℃で２０分加熱した。冷却
後試験基板の外観検査及び基板を破壊し基板電極部の詳
細観察をおこなった。実施例２に比較して接合部の接着
程度はほぼ同程度レベルであり、電極上のハンダの濡れ
状態では若干の差が認められたが、これも同程度のレベ
ルと判断される。。Example 9: In order to compare the effect when the composition of the cream solder to be kneaded was changed with respect to Example 2, 90 parts by weight (part) of the same conductive adhesive as in Example 2 was used.
10 parts by weight of rosin-based low-temperature cream solder containing eutectic tin / silver / bismuth alloy filler
In addition, the mixture was kneaded to produce a conductive bonding agent 9 as a trial. This was applied to a test substrate and heated at a heating temperature of 170 ° C. for 20 minutes. After cooling, the appearance of the test substrate was inspected, and the substrate was broken, and detailed observation of the substrate electrode was performed. Compared to Example 2, the degree of adhesion of the joints was almost the same level, and a slight difference was observed in the wet state of the solder on the electrodes, but this was also judged to be the same level. .
【００１８】実施例１０、実施例１１、実施例１２：混
練するクリームハンダの錫・ビスマス合金フィラーの組
成を変えた場合の効果を確認するため、合金の錫とビス
マスの質量比を４０／６０、７０／３０、９０／１０と
変化させたフィラーをベースとしたロジン系低温クリー
ムハンダを準備し、これを実施例２における導電性接着
剤に同様混練して、導電性接合剤１０，１１，１２を試
作した。この場合ビスマス量の減少に伴って合金の溶融
点が上がるため、試験基板に塗布後の硬化加熱条件は各
１７０℃２０分、２００℃２０分、２２０℃２０分とし
た。 前述例と同様に、冷却後験基板の外観検査及び基
板を破壊し基板電極部の詳細観察をおこなった。結果、
錫とビスマスの質量比がこの範囲では接合部の接着状態
及び電極上のハンダの濡れ状態共に殆んど有意差は認め
られない。従って、クリームハンダにおける錫・ビスマ
ス合金の組成については選択の自由度が存在する。Example 10, Example 11, Example 12 In order to confirm the effect of changing the composition of the tin / bismuth alloy filler of the kneaded cream solder, the mass ratio of tin to bismuth in the alloy was set to 40/60. , 70/30, and 90/10, a rosin-based low-temperature cream solder based on fillers was prepared and kneaded with the conductive adhesive in Example 2 in the same manner as in the conductive bonding agents 10, 11, and 10. 12 were prototyped. In this case, since the melting point of the alloy increases with the decrease in the amount of bismuth, the curing heating conditions after application to the test substrate were 170 ° C. for 20 minutes, 200 ° C. for 20 minutes, and 220 ° C. for 20 minutes. In the same manner as in the above-mentioned example, after cooling, the appearance of the substrate was inspected, and the substrate was broken to observe the electrode portion of the substrate in detail. result,
When the mass ratio of tin to bismuth is in this range, there is almost no significant difference between the adhesion state of the joint and the wet state of the solder on the electrode. Therefore, there is a degree of freedom in selecting the composition of the tin-bismuth alloy in the cream solder.
【００１９】比較例１：従来行われている導電性接着
剤、即ち、クリームハンダを添加されていないものに対
する、本発明の上述実施例２〜１２の導電性接合剤を比
較するために、導電性接合剤１３を試作した。クリーム
ハンダ混練に伴う関係条件以外は、実施例２と全く同様
である。即ち、エポキシ樹脂系バインダと銀フィラーか
らなる熱硬化性１液タイプの導電性接着剤（銀フィラー
の平均粒径５μｍ）を試験基板に塗布し、該導電性接着
剤の硬化温度１７０℃において２０分間加熱した。冷却
後外観検査および破壊検査を行った。外観検査におい
て、導電性接合剤１３は試験基板上に一様に、良好な固
化接着しているのが確認された。しかしながら、破壊検
査において接合部を拡大観察した結果は、基板の電極部
分における完全な接合は得られておらず、これよりクリ
ームハンダによる基板電極に対する濡れ及びハンダ溶融
接着による効果が極めて好ましいものであることが確認
された。Comparative Example 1 In order to compare the conductive adhesives of Examples 2 to 12 of the present invention with a conventional conductive adhesive, that is, one to which cream solder was not added, The experimental bonding agent 13 was produced. Except for the conditions involved in kneading the cream solder, the conditions are exactly the same as in Example 2. That is, a thermosetting one-pack type conductive adhesive (average particle size of silver filler: 5 μm) composed of an epoxy resin-based binder and a silver filler is applied to a test substrate. Heated for minutes. After cooling, a visual inspection and a destructive inspection were performed. In the appearance inspection, it was confirmed that the conductive bonding agent 13 was uniformly solidified and adhered on the test substrate. However, the result of magnified observation of the joints in the destructive inspection shows that complete bonding at the electrode portion of the substrate was not obtained, and the effect of wetting on the substrate electrode by cream solder and the effect of solder fusion bonding are extremely preferable. It was confirmed that.
【００２０】表１及び表２に上記実施例１乃至９及び実
施例１０乃至１３の組成内容、硬化条件及び硬化前後の
特性を示す。なお、使用されたフィラーの平均粒径に対
するアスペクト比は１：１．５以内とした。Tables 1 and 2 show the composition contents, curing conditions, and characteristics before and after curing of Examples 1 to 9 and Examples 10 to 13 described above. In addition, the aspect ratio with respect to the average particle diameter of the filler used was set to within 1: 1.5.
【００２１】[0021]
【表１】 [Table 1]
【００２２】[0022]
【表２】 [Table 2]
【００２３】本発明の実施例１〜１２における導電性接
合剤による固着強度、接触抵抗を比較試験した。２１２
５チップ部品を基板に通常の標準作業内容により接合し
て接合試験片とし、接合直後、熱衝撃試験条件（−５５
℃／１５ｍｉｎ、＋１２５℃／１５ｍｉｎ、各間室温５
ｍｉｎ繰り返し）による、２５０、５００、７５０、１
０００サイクル後の各接着強度（固着強度：ＭＰa ）及
び接触抵抗（ｍΩ）を測定した。また、該接合試験片を
高湿度環境の下（湿度条件：８５℃、８５重量部（部）
ＲＨ）、２５０、５００、７５０、１０００時間さらし
た後の固着強度（ＭＰa ）及び接触抵抗（ｍΩ）を測定
した。各測定値を表３及び表４に示す。また、この測定
値の減衰状態を容易に把握するために棒グラフに表示し
た結果を図１〜４に示す。Comparative tests were conducted on the fixing strength and contact resistance of the conductive bonding agents in Examples 1 to 12 of the present invention. 212
The five-chip component was bonded to the substrate according to the normal standard operation to form a bonded test piece. Immediately after bonding, the thermal shock test conditions (-55
° C / 15min, + 125 ° C / 15min, room temperature 5 between each
min, 250, 500, 750, 1
After 000 cycles, the adhesive strength (bonding strength: MPa) and the contact resistance (mΩ) were measured. The bonding test piece was placed in a high humidity environment (humidity condition: 85 ° C., 85 parts by weight (parts)).
RH), adhesion strength (MPa) and contact resistance (mΩ) after exposure for 250, 500, 750 and 1000 hours. Tables 3 and 4 show the measured values. FIGS. 1 to 4 show the results displayed on a bar graph in order to easily grasp the attenuation state of the measured values.
【００２４】[0024]
【表３】 [Table 3]
【００２５】[0025]
【表４】 [Table 4]
【００２６】なお、粘度の測定は、標準動粘度計（東機
産業ＲＢ８０型）により、測定容量３ｍｌ、測定温度２
５±０．３℃、回転条件２０ｒｐｍ×３ｍｉｎにて測定
した。 また、固着強度は、１００ｍｍ×４０ｍｍのガ
ラスエポキシ基板の片側に１５０μｍ厚みのメタルマス
クを用いて塗布し、チップマウンタにより２１２５チッ
プコンデンサを標準搭載した後、所定の条件にて加熱硬
化したものを試験試料とした。測定は固着強度試験機に
より押圧速度２３ｍｍ／ｍｉｎで加圧し、破断破壊した
ときの荷重ＭＰaをもって固着強度とした。The viscosity was measured by a standard kinematic viscometer (Toki Sangyo RB80 type) with a measuring volume of 3 ml and a measuring temperature of 2.
The measurement was performed at 5 ± 0.3 ° C. under a rotation condition of 20 rpm × 3 min. The adhesion strength was measured by applying a metal mask with a thickness of 150 μm to one side of a 100 mm × 40 mm glass epoxy board, mounting a 2125 chip capacitor as standard with a chip mounter, and then heating and curing it under specified conditions. A sample was used. The measurement was performed by applying a pressure at a pressing speed of 23 mm / min using a bonding strength tester, and taking the load MPa at the time of breaking and breaking as the bonding strength.
【００２７】接触抵抗の測定は、前記固着強度の場合と
どうようのガラスエポキシ基板を用い、基板中央部のラ
ンドに跨るように４ｍｍφ×１５０μｍ厚みで試料を塗
布し所定条件で加熱硬化したものを試験試料とした。測
定はデジタルマルチメータ（アドバンテスト製）を用
い、電極間５０ｍｍにおける接触抵抗値（ｍΩ）を測定
した。The contact resistance was measured by using a glass epoxy substrate having the same adhesion strength as described above, applying a sample with a thickness of 4 mmφ × 150 μm over a land at the center of the substrate, and heating and curing it under predetermined conditions. A test sample was used. The contact resistance (mΩ) was measured at a distance of 50 mm between the electrodes using a digital multimeter (Advantest).
【００２８】図１、図３に明らかなごとく、比較例１
（クリームハンダ無添加導電性接合剤）に比較して、本
発明のいずれの実施例のものも接触抵抗値（ｍΩ）が約
３０〜５０重量部（部）程度と低く、導電性接合条件と
して十分な値を示している。これは前述の接合状態の観
察結果と一致しており、クリームハンダを併用混練した
本発明が従来の導電性接着剤に比べて、接触抵抗に相当
の有位差があることがわかる。実施例におけるフィラー
組成の差、クリームハンダのフィラーの差、導電性接着
剤に混練するクリームハンダの量の差等は本実施例の範
囲では大差なく、いずれも実用に適するものである。即
ち、混練されるクリームハンダの内容如何によらず、ク
リームハンダを或程度入れること自体により、極めて大
きな効果が期待できるところに本発明の特徴がある。As apparent from FIGS. 1 and 3, Comparative Example 1
Compared to (cream solder-free conductive bonding agent), the contact resistance value (mΩ) of any of the examples of the present invention is as low as about 30 to 50 parts by weight (parts). It shows a sufficient value. This is in agreement with the above-mentioned observation result of the bonding state, and it can be seen that the present invention in which cream solder is used and kneaded together has a considerable difference in contact resistance as compared with the conventional conductive adhesive. The difference in the filler composition, the difference in the filler of the cream solder, the difference in the amount of the cream solder to be kneaded with the conductive adhesive and the like in the examples are not significantly different in the range of the present example, and all are suitable for practical use. That is, regardless of the content of the cream solder to be kneaded, the present invention is characterized in that an extremely large effect can be expected by adding cream solder to a certain degree.
【００２９】一方、固着強度については、比較例に比べ
て必ずしも優位にあるとは言えないが、通常要求される
固着強度のレベルはいずれも満足しており、実用上問題
とならない。実施例６、７（導電性フィラー：銀フィラ
ー、銅フィラー、ニッケルフィラー）のものは熱衝撃試
験、耐湿度試験による減衰率が低く安定しており、長期
使用には適していよう。On the other hand, the bonding strength is not necessarily superior to the comparative example, but all of the required bonding strength levels are satisfied, so that there is no practical problem. Examples 6 and 7 (conductive fillers: silver filler, copper filler, nickel filler) have a low and stable attenuation rate by a thermal shock test and a humidity resistance test, and thus may be suitable for long-term use.
【００３０】上記実施例２〜１２の結果から、導電性接
着剤に樹脂系クリームハンダを加えてなる導電性接合剤
は、基板電極及び部品電極へのハンダの良好な濡れ性を
発生させ、且つ導電性接着剤のフィラーとも部分的な濡
れを生じて導電効果が高められ、一般導電性接着剤によ
る接続部における、高湿度条件下において経時的に発生
する湿度の影響による導電性と接合強度の劣化に対し顕
著な効果を発揮することが確認された。また、クリーム
ハンダとの相乗効果により、導電性接着剤単体の場合に
比べ、フィラー選択の自由度が極めて大きく、高価なフ
ィラーの使用を制限することが可能であり経済的にも極
めて有利である。従って本発明の導電性接合剤は、はん
だ付け生産ラインにおける自由度を上げることができる
接合方法を提供し得るものである。From the results of Examples 2 to 12, the conductive bonding agent obtained by adding the resin-based cream solder to the conductive adhesive causes good solder wettability to the substrate electrode and the component electrode, and The conductive effect is enhanced by partial wetting with the filler of the conductive adhesive, and the conductive effect is increased. It was confirmed that a remarkable effect on deterioration was exhibited. In addition, due to the synergistic effect with cream solder, the degree of freedom in selecting fillers is extremely large as compared with the case of using a conductive adhesive alone, and it is possible to restrict the use of expensive fillers, which is extremely economical. . Therefore, the conductive bonding agent of the present invention can provide a bonding method that can increase the degree of freedom in a soldering production line.
【００３１】[0031]
【発明の効果】本発明により、地球環境汚染の問題に対
処するはんだ代替用接着剤として、安価で且つ導電性の
優れた、また湿度の影響による問題があった従来の導電
性接着剤の欠陥を十分に解決する導電性接合剤および該
導電性接合剤による優れた接合方法を提供することがで
きる。According to the present invention, a defect of a conventional conductive adhesive which is inexpensive, has excellent conductivity, and has a problem due to the influence of humidity, is used as an adhesive for solder replacement to address the problem of global environmental pollution. , And an excellent bonding method using the conductive bonding agent.
【図１】 本発明の実施例の接触抵抗試験の結果を示す
図である。FIG. 1 is a diagram showing the results of a contact resistance test according to an example of the present invention.
【図２】 本発明の実施例の接着強度試験の結果を示す
図である。FIG. 2 is a view showing a result of an adhesive strength test of an example of the present invention.
【図３】 本発明の他の実施例の接触抵抗試験の結果を
示す図である。FIG. 3 is a diagram showing the results of a contact resistance test according to another example of the present invention.
【図４】 本発明の他の実施例の接着強度試験の結果を
示す図である。FIG. 4 is a view showing a result of an adhesive strength test of another example of the present invention.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｈ０５Ｋ 3/32 Ｈ０１Ｌ 21/92 ６２１Ａ ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) H05K 3/32 H01L 21/92 621A
Claims (6)
る導電性接着剤に、樹脂系フラックスをベースとするク
リームハンダを配合してなる導電性接合剤。1. A conductive bonding agent comprising a conductive adhesive comprising a conductive filler and a resin binder, and a cream solder based on a resin-based flux.
る導電性接着剤に、錫・ビスマス合金又は／及び錫・銀
・ビスマス合金フィラーと樹脂系フラックスをベースと
する無鉛クリームハンダを配合してなる導電性接合剤。2. A conductive adhesive comprising a conductive filler and a resin binder, and a tin-bismuth alloy or / and a tin-silver-bismuth alloy filler and a lead-free cream solder based on a resin-based flux. Conductive bonding agent.
の少なくとも１種よりなる導電性フィラーであることを
特徴とする請求項１又は２に記載の導電性接合剤。3. The conductive bonding agent according to claim 1, wherein the conductive filler is a conductive filler made of at least one of silver, nickel, and copper.
合金フィラーの両方又はいずれか一方よりなることを特
徴とする請求項１又は２に記載の導電性接合剤。4. The conductive bonding agent according to claim 1, wherein the conductive filler comprises a silver filler and / or a tin alloy filler.
スマス合金粉末であり、その錫とビスマスとの質量比が
９：１乃至４：６であることを特徴とする請求項１乃至
４のいずれか１項に記載の導電性接合剤。5. The cream solder according to claim 1, wherein the filler is tin-bismuth alloy powder, and the mass ratio of tin to bismuth is 9: 1 to 4: 6. Item 2. The conductive bonding agent according to item 1.
導電性接合剤を用いることを特徴とする接合方法。6. A bonding method using the conductive bonding agent according to any one of claims 1 to 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32194999A JP2001143529A (en) | 1999-11-12 | 1999-11-12 | Conductive bonding agent by cream solder mixing and bonding method using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32194999A JP2001143529A (en) | 1999-11-12 | 1999-11-12 | Conductive bonding agent by cream solder mixing and bonding method using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001143529A true JP2001143529A (en) | 2001-05-25 |
Family
ID=18138239
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32194999A Withdrawn JP2001143529A (en) | 1999-11-12 | 1999-11-12 | Conductive bonding agent by cream solder mixing and bonding method using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001143529A (en) |
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| US7604154B2 (en) | 2003-08-08 | 2009-10-20 | Kabushiki Kaisha Toshiba | Thermosetting flux and solder paste |
| JP2010174096A (en) * | 2009-01-28 | 2010-08-12 | Fujikura Kasei Co Ltd | Anisotropic conductive adhesive |
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