JPH1192727A - Conductive adhesive - Google Patents
Conductive adhesiveInfo
- Publication number
- JPH1192727A JPH1192727A JP25230897A JP25230897A JPH1192727A JP H1192727 A JPH1192727 A JP H1192727A JP 25230897 A JP25230897 A JP 25230897A JP 25230897 A JP25230897 A JP 25230897A JP H1192727 A JPH1192727 A JP H1192727A
- Authority
- JP
- Japan
- Prior art keywords
- particles
- nickel
- conductive adhesive
- adhesive
- base metal
- 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.)
- Pending
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
- H05K3/321—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、電子部品の実装の
分野において、はんだに代えて、電子部品のプリント基
板への接合に用いるための導電性接着剤に関するもので
ある。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive adhesive used for bonding electronic components to a printed circuit board instead of solder in the field of electronic component mounting.
【０００２】[0002]
【従来の技術】最近の環境問題への認識の高まりから、
エレクトロニクス実装の分野では、はんだ合金中の鉛に
対する規制が行われようとしており、電子部品の実装に
鉛を用いない接合技術の確立が急務となっている。鉛フ
リー実装技術としては、主として鉛フリーはんだおよび
導電性接着剤が挙げられるが、接合部の柔軟性、実装温
度の低温化等のメリットが期待される導電性接着剤によ
り注目が集まっている。2. Description of the Related Art Recently, awareness of environmental issues has increased,
In the field of electronics mounting, regulations on lead in solder alloys are about to be enforced, and there is an urgent need to establish a joining technology that does not use lead for mounting electronic components. Lead-free mounting techniques mainly include lead-free solder and conductive adhesives. Attention has been paid to conductive adhesives, which are expected to have advantages such as flexibility of bonding portions and lower mounting temperatures.
【０００３】従来の導電性接着剤は、一般的に、樹脂系
接着成分中に導電性粒子を分散させたものであり、接着
剤により電極を接続した後に樹脂を硬化させ、粒子同士
の接触により、接続部の導通を確保するものである。従
って、接合部が樹脂で接着されるため、熱や外力による
変形に対して柔軟に対応し、導通部が合金であるはんだ
と比較して、接合部に亀裂が発生しにくいというメリッ
トを有していることから、はんだの代替材料として期待
されている。A conventional conductive adhesive is generally one in which conductive particles are dispersed in a resin-based adhesive component. After connecting electrodes with the adhesive, the resin is cured, and the particles are brought into contact with each other. , To ensure conduction of the connecting portion. Therefore, since the joint is bonded with a resin, it has a merit that the joint can be flexibly responded to deformation due to heat or external force, and a crack is less likely to occur in the joint as compared with a solder in which the conductive part is an alloy. Therefore, it is expected as a substitute material for solder.
【０００４】[0004]
【発明が解決しようとする問題】導電性接着剤の導電性
粒子として一般的に用いられるフィラーの金属として
は、銀とニッケルが挙げられる。例えば、特公昭６３−
５３２３４号公報に開示されているように、銀を用いた
導電性接着剤が多数報告されているが、銀は、マイグレ
ーションを起こしやすいため、はんだ代替材料として
は、実用化が困難であるという問題があった。The filler metals generally used as the conductive particles of the conductive adhesive include silver and nickel. For example,
As disclosed in Japanese Patent No. 53234, a large number of conductive adhesives using silver have been reported. However, silver is liable to cause migration, so that it is difficult to put it into practical use as a solder substitute material. was there.
【０００５】一方、特開平３−４０８９９号公報に示さ
れるように、ニッケルを用いた導電性接着剤はマイグレ
ーションを起こさないため、はんだ代替材料として最も
期待されている。しかしながら、ニッケルを用いた導電
性接着剤には、体積抵抗値が銀を用いた接着剤と比較し
て極めて高く、体積抵抗値を低下させるための改善が望
まれていた。そこで本発明は、体積抵抗率のより低いニ
ッケル系導電性接着剤を提供することを目的とする。On the other hand, as disclosed in JP-A-3-40899, a conductive adhesive using nickel does not cause migration, and is therefore most expected as a solder substitute material. However, the conductive adhesive using nickel has an extremely high volume resistance value as compared with the adhesive using silver, and an improvement for lowering the volume resistance value has been desired. Therefore, an object of the present invention is to provide a nickel-based conductive adhesive having a lower volume resistivity.
【０００６】[0006]
【課題を解決するための手段】上記課題を解決するため
に、本発明の導電性接着剤は、樹脂バインダーに、ニッ
ケル粒子と共に表面が親油性の粒子を含有することを特
徴とする。In order to solve the above-mentioned problems, the conductive adhesive of the present invention is characterized in that the resin binder contains lipophilic particles together with nickel particles.
【０００７】本発明においては、ニッケル粒子とともに
添加する粒子を表面が親油性のある物質とするのは、バ
インダーのの樹脂が油性物質であり、表面親油性の粒子
は、ニッケル粒子よりも樹脂バインダーとの濡れ性が優
れており、表面親油性の粒子を添加することにより、バ
インダー中でこれら粒子を均質に分散させるためであ
る。表面親油性の粒子とともにニッケル粒子を樹脂バイ
ンダーに練り込むことにより、ニッケル粒子のみを導電
性粒子とした場合よりも、導電性粒子の樹脂バインダー
中での分散性が高くなり、且つそれに従って接着剤は硬
化過程の体積収縮が大きくなるので、ニッケル粒子相互
の接触頻度が相対的に高くなり、接着剤硬化後には、ニ
ッケル粒子のみの場合よりも接着剤の体積抵抗値を低下
させることができるのである。In the present invention, the particles to be added together with the nickel particles are made of a substance having a lipophilic surface because the resin of the binder is an oleaginous substance. The reason for this is that, by adding particles having a surface lipophilic property, the particles are uniformly dispersed in the binder. By kneading the nickel particles into the resin binder together with the surface lipophilic particles, the dispersibility of the conductive particles in the resin binder becomes higher than when only the nickel particles are used as the conductive particles, and the adhesive accordingly. Since the volume shrinkage during the curing process increases, the frequency of contact between nickel particles becomes relatively high, and after the adhesive is cured, the volume resistance value of the adhesive can be reduced as compared with the case of only nickel particles. is there.
【０００８】本発明において、第１に、表面親油性粒子
には、固形の樹脂粒子が含まれる。樹脂粒子は、樹脂バ
インダーとの濡れ性が大きく、導電性粒子の樹脂への分
散性を高め、これにより、ニッケル粒子の分散性が高く
なる。In the present invention, first, the surface lipophilic particles include solid resin particles. The resin particles have high wettability with the resin binder and enhance the dispersibility of the conductive particles in the resin, thereby increasing the dispersibility of the nickel particles.
【０００９】本発明は、第２に、表面が親油性である粒
子には、銀を基準とした卑金属粒子を含む。ここに、卑
金属とは、銀を基準として電気化学的に卑な金属であっ
て、銀を含み、銀よりイオン化傾向の大きい金属をいう
が、但し、アルカリ金属、アルカリ土類金属及びＮｉを
含まないものと規定する。このような卑金属は、表面に
自然酸化皮膜を形成し易いこと、及び、卑金属の酸化皮
膜の含有酸素が、樹脂バインダーに対する濡れ性を大き
くすることを利用して、樹脂バインダー中で卑金属粒子
の分散性を良くし、これに伴ってニッケルの分散性も良
好にする。In the present invention, second, the particles whose surface is lipophilic include silver-based base metal particles. Here, the term “base metal” refers to a metal that is electrochemically base on the basis of silver, contains silver, and has a greater ionization tendency than silver, but includes alkali metals, alkaline earth metals, and Ni. Not specified. Such a base metal disperses the base metal particles in the resin binder by utilizing the fact that a natural oxide film is easily formed on the surface and the oxygen content of the oxide film of the base metal increases the wettability to the resin binder. And the dispersibility of nickel is also improved accordingly.
【００１０】本発明の導電性接着剤は、第３に、ニッケ
ル粒子が表面に突起を有することを特徴とする。表面に
突起を有するニッケル粒子は、先ず、多数のニッケル粒
子がそれぞれの突起との接触により、粒子相互の接触頻
度が高まり、導電性を高める。さらに、表面突起状のニ
ッケル粒子は、表面酸化性の卑金属粒子との共存によ
り、卑金属粒子との導通の頻度を大きくする作用効果を
もたらす。Third, the conductive adhesive of the present invention is characterized in that the nickel particles have projections on the surface. In the nickel particles having projections on the surface, a large number of nickel particles first come into contact with the respective projections, thereby increasing the frequency of contact between the particles and increasing the conductivity. Further, the surface-projecting nickel particles have an effect of increasing the frequency of conduction with the base metal particles by coexistence with the surface oxidizable base metal particles.
【００１１】球状のニッケル粒子に対してはその酸化皮
膜により絶縁性物質として働いく卑金属粒子も、突起状
ニッケル粒子に対しては導電性物質として作用するよう
になる。この理由により、突起状ニッケル粒子と表面酸
化性金属粒子との共存により、接着剤の体積抵抗を一層
低下させることができるのである。本発明において、特
に粒子表面に突起を有するニッケル粒子としては、四脚
状の酸化亜鉛ウイスカの表面にニッケルを被覆したもの
が利用できる。このような四脚状のニッケル粒子は、図
１に模式的に示すように、樹脂バインダー３中でニッケ
ル粒子１の突起１１が、卑金属粒子２の酸化皮膜２１と
点接触し、さらに、皮膜を機械的に突き破って、ニッケ
ル粒子２の内部金属２０即ち金属ニッケルと接触して導
通し、卑金属粒子も導電に寄与することになる。The base metal particles, which act as an insulating material due to the oxide film on spherical nickel particles, also act as a conductive material on the protruding nickel particles. For this reason, the volume resistance of the adhesive can be further reduced due to the coexistence of the protruding nickel particles and the surface oxidizable metal particles. In the present invention, as the nickel particles having projections on the particle surface, those obtained by coating the surface of a quadruped zinc oxide whisker with nickel can be used. As shown schematically in FIG. 1, such quadruped nickel particles have the protrusions 11 of the nickel particles 1 in the resin binder 3 in point contact with the oxide film 21 of the base metal particles 2. It penetrates mechanically and comes into contact with the internal metal 20 of the nickel particles 2, that is, metal nickel, and conducts, and the base metal particles also contribute to conductivity.
【００１２】[0012]
【発明の実施の形態】本発明の導電性接着剤について、
図面を参照しながら説明する。本発明においては、第１
は、樹脂バインダー中にニッケル粒子と表面親油性の粒
子として樹脂粒子を混練して、接着剤ペーストとするも
のである。樹脂粒子は、特に限定されないが、その中で
も樹脂バインダーとの濡れ性の大きいものがよく、樹脂
粒子は、この点から、好ましくは、樹脂バインダーと同
じ種類の樹脂が使用される。本発明で使用される樹脂バ
インダーには、熱硬化型樹脂の中から、接着強度が大き
く、特に耐熱強度の大きい樹脂が選ばれるが、特に、エ
ポキシ系、アクリル系など樹脂が利用される。樹脂粒子
は、この樹脂バインダーに対応して、同じ種類の樹脂の
固体粒子、例えば、上例のエポキシ系、アクリル系など
の樹脂が利用できる。BEST MODE FOR CARRYING OUT THE INVENTION The conductive adhesive of the present invention is described below.
This will be described with reference to the drawings. In the present invention, the first
Is to knead resin particles as nickel particles and surface lipophilic particles in a resin binder to obtain an adhesive paste. The resin particles are not particularly limited, but among them, those having high wettability with a resin binder are preferable, and from this point, the same type of resin as the resin binder is preferably used for the resin particles. As the resin binder used in the present invention, a resin having a high adhesive strength and particularly a high heat resistance is selected from thermosetting resins. In particular, a resin such as an epoxy resin or an acrylic resin is used. As the resin particles, corresponding to the resin binder, solid particles of the same type of resin, for example, the above-mentioned epoxy-based or acrylic-based resin can be used.
【００１３】表面が親油性である粒子として卑金属粒子
には、銀よりイオン化傾向の大きい金属の粒子が広く利
用可能である。このような金属の例には、Ｍｎ、Ｃｒ、
Ｆｅ、Ｃｏ、Ｚｎ、Ｃｄ、Ｓｎ、Ｐｂ、Ｃｕ、Ａｇなど
が挙げられるが、これらに制限されるものではない。但
し、アルカリ金属、アルカリ土類金属、及び、ニッケル
を除く。卑金属には、特に、銅、亜鉛、錫、鉄が好まし
く使用される。As base metal particles having a lipophilic surface, metal particles having a greater ionization tendency than silver are widely available. Examples of such metals include Mn, Cr,
Examples include, but are not limited to, Fe, Co, Zn, Cd, Sn, Pb, Cu, and Ag. However, alkali metals, alkaline earth metals, and nickel are excluded. In particular, copper, zinc, tin, and iron are preferably used as the base metal.
【００１４】これらの卑金属は、その表面には、常温で
大気中において酸化皮膜が形成され易いものであり、こ
の酸化皮膜は、空気中でその金属粒子表面の酸化により
生じた自然酸化皮膜が利用される。本発明において、酸
化皮膜厚みは、酸化皮膜が樹脂バインダーに対して濡れ
性を高めるに十分な程度の厚みであればよい。このよう
な酸化皮膜を確保すれば、後述するように、表面に突起
を有するニッケル粒子を適用する場合には、樹脂バイン
ダーに対して濡れ性を確保して、同時に、ニッケル粒子
の突起尖端での皮膜の接触と破壊を容易にし、これにニ
ッケル粒子と卑金属内部との導通を確保することができ
る。These base metals are apt to form an oxide film on the surface in the air at room temperature, and a natural oxide film formed by oxidation of the surface of the metal particles in the air is used as the oxide film. Is done. In the present invention, the thickness of the oxide film may be a thickness enough for the oxide film to increase the wettability to the resin binder. If such an oxide film is secured, as will be described later, when nickel particles having protrusions on the surface are applied, the wettability to the resin binder is ensured, and at the same time, the protrusions of the nickel particles are formed at the tips of the protrusions. This facilitates contact and destruction of the coating, which can ensure conduction between the nickel particles and the inside of the base metal.
【００１５】卑金属粒子の酸化皮膜をさらに厚くしても
よく、このために、卑金属粒子は、表面清浄な金属粒子
をあらかじめ室温以上の温度で加熱処理して表面酸化さ
せて形成することもできる。加熱処理は、室温以上の適
当な温度で、例えば、５０〜２００℃程度の温度で、空
気中ないしは適当な酸化性雰囲気中で加熱して、酸化皮
膜を形成し成長させるものである。このように形成成長
させた酸化皮膜により、導電性粒子の樹脂への分散性が
さらに向上し、体積抵抗値の低下の度合いを大きくでき
る。The oxide film of the base metal particles may be further thickened. For this purpose, the base metal particles may be formed by subjecting the surface-cleaned metal particles to a heat treatment at room temperature or higher in advance to oxidize the surface. In the heat treatment, an oxide film is formed and grown by heating at an appropriate temperature of room temperature or higher, for example, at a temperature of about 50 to 200 ° C. in air or an appropriate oxidizing atmosphere. By the oxide film formed and grown in this manner, the dispersibility of the conductive particles in the resin is further improved, and the degree of reduction in the volume resistance value can be increased.
【００１６】本発明の導電性接着剤において、ニッケル
粒子は、その形状について特に限定されるものではない
が、通常は、粒状ないし球状のものが利用できる。ニッ
ケル粒子は、特に、表面に外方向に向けて突起を有する
ものが利用される。In the conductive adhesive of the present invention, the shape of the nickel particles is not particularly limited, but usually, granular or spherical particles can be used. As the nickel particles, those having projections outward on the surface are used.
【００１７】このような突起を有するニッケル粒子とし
て、四脚状の酸化亜鉛ウイスカの表面にニッケル層を被
覆したものを用いることができる。四脚状の酸化亜鉛
は、酸化亜鉛の結晶が、中心位置から四方に放射状に伸
びるような針条を有し、各針条間が等角的に配向してい
るものである。As the nickel particles having such projections, those obtained by coating the surface of a quadruped zinc oxide whisker with a nickel layer can be used. The quadruped zinc oxide has needles in which zinc oxide crystals radially extend from a center position in four directions, and the intervals between the needles are equiangularly oriented.
【００１８】このような酸化亜鉛結晶粒子の表面に、蒸
着法その他の方法でＮｉ皮膜を形成して、ニッケル粒子
とするのである。酸化亜鉛上のＮｉ皮膜が導電性を与え
るが、酸化亜鉛ウイスカの突条は鋭く、より効果的に卑
金属粒子の薄い酸化皮膜を突き破ることができるので、
粒状ないし表面突起状ニッケル粒子を使用する導電性接
着剤の場合よりも体積抵抗をさらに低下させることがで
きる。A nickel film is formed on the surface of such zinc oxide crystal particles by a vapor deposition method or other methods to obtain nickel particles. Although the Ni film on the zinc oxide provides conductivity, the ridges of the zinc oxide whiskers are sharp and can more effectively penetrate the thin oxide film of the base metal particles,
The volume resistivity can be further reduced as compared with the case of a conductive adhesive using granular or surface-protruding nickel particles.
【００１９】他方、卑金属粒子の形状は、粒状、特に、
球状としたものが良い。球状粒子は、数ある形状の中で
最も比表面積が小さく、樹脂との濡れ性が優れるため、
導電性粒子のニッケル粒子を、球状粒子の卑金属粒子と
共に樹脂バインダー中に練り込むことにより、導電性粒
子の樹脂への分散性が最も優れるため、上述した導電性
接着剤の中では、体積抵抗値の低下度合が最も大きくな
る。On the other hand, the shape of the base metal particles is granular,
A spherical shape is better. Spherical particles have the smallest specific surface area among many shapes and have excellent wettability with resin,
By kneading the nickel particles of the conductive particles together with the base metal particles of the spherical particles into the resin binder, the dispersibility of the conductive particles in the resin is most excellent. Is the largest.
【００２０】本発明の導電性接着剤は、ニッケル粒子と
して粒径が３〜２０μm の範囲とし、卑金属粒子として
粒径が３〜１５μｍの範囲とするのが好ましい。この条
件の粒径を有する場合、導電性粒子の樹脂への分散性が
最も向上するため、体積抵抗値が最も低くなる。The conductive adhesive of the present invention preferably has a particle size of 3 to 20 μm as nickel particles and a particle size of 3 to 15 μm as base metal particles. In the case where the particle diameter has the above condition, the dispersibility of the conductive particles in the resin is most improved, and the volume resistance value is lowest.
【００２１】本発明において、表面親油性の粒子とニッ
ケル粒子との配合割合については、表面親油性の粒子体
積のニッケル粒子体積に対する割合が、好ましくは、
０．０５〜０．１５の範囲に採用される。この体積割合
が０．０５未満である場合は、導電性粒子の樹脂への分
散性の向上が期待できず、体積抵抗値の低下の度合が小
さく好ましくない。In the present invention, the mixing ratio of the surface lipophilic particles to the nickel particles is preferably a ratio of the surface lipophilic particle volume to the nickel particle volume,
It is adopted in the range of 0.05 to 0.15. If the volume ratio is less than 0.05, improvement in dispersibility of the conductive particles in the resin cannot be expected, and the degree of decrease in the volume resistance value is unfavorably small.
【００２２】また、この体積割合が０．１５を超える
と、卑金属粒子の量が多すぎて、卑金属粒子同士の接触
確率が増え、ニッケル粒子同士の接触頻度を低下させ、
体積抵抗値の低下の度合が小さくなるため好ましくな
い。特に、表面親油性の粒子として、銅、銀等の卑金属
を利用する場合には、卑金属粒子重量のニッケル粒子重
量との重量割合を、上記体積割合の範囲に対応して、
０．０５〜０．１５の範囲とするのが好ましい。If the volume ratio exceeds 0.15, the amount of the base metal particles is too large, the probability of contact between the base metal particles increases, and the frequency of contact between the nickel particles decreases.
It is not preferable because the degree of decrease in the volume resistance value becomes small. In particular, when a base metal such as copper or silver is used as the surface lipophilic particles, the weight ratio of the base metal particles to the nickel particles is determined in accordance with the range of the volume ratio,
It is preferred to be in the range of 0.05 to 0.15.
【００２３】また、接着剤中の表面親油性の粒子及びニ
ッケル粒子の含有量については、表面親油性の粒子の体
積とニッケル粒子の体積との合計の、接着剤の全体積に
対する割合が、０．２５〜０．４０の範囲にするのがよ
い。この体積割合が０．２５未満では、接着剤中でのニ
ッケル粒子の相互の接触頻度が低下し、この容積割合
０．４０を超すと、接着剤ペーストは粘度が高すぎて、
取扱い難くなる。特に、表面親油性の粒子として、銅、
銀等の卑金属を利用する場合には、上記の体積割合０．
２５〜０．４０に対応して、ニッケル粒子と卑金属粒子
の合計重量の、接着剤全体の重量に対する重量割合に換
算して、０．７５〜０．８５になるように組成を調製す
ることが好ましい。As for the content of the surface lipophilic particles and the nickel particles in the adhesive, the ratio of the total of the volume of the surface lipophilic particles and the volume of the nickel particles to the total volume of the adhesive is 0. .25 to 0.40. If this volume ratio is less than 0.25, the frequency of mutual contact of nickel particles in the adhesive decreases, and if this volume ratio exceeds 0.40, the adhesive paste has too high a viscosity,
It becomes difficult to handle. In particular, copper,
When a base metal such as silver is used, the above volume ratio of 0.1 is used.
It is possible to adjust the composition so that the total weight of the nickel particles and the base metal particles is 0.75 to 0.85 in terms of the weight ratio to the total weight of the adhesive corresponding to 25 to 0.40. preferable.
【００２４】本発明の導電性接着剤は、上記の如く、ニ
ッケル粒子と表面親油性の粒子とを樹脂バインダー中に
混練して、ペースト状に調製し、基板上の電極と電子部
品の電極との接着固定に使用する。この導電性接着剤
は、従来のニッケルのみを導電性粒子とした導電性接着
剤と比較して、著しく体積抵抗値が低くなり、実用性の
高い導電性接着剤としての利用が可能となる。As described above, the conductive adhesive of the present invention is prepared by kneading nickel particles and surface lipophilic particles in a resin binder, preparing a paste, and forming an electrode on a substrate and an electrode of an electronic component. Used for adhesive fixation. This conductive adhesive has a remarkably low volume resistance value as compared with a conventional conductive adhesive using only nickel as conductive particles, and can be used as a highly practical conductive adhesive.
【００２５】[0025]
【実施例】次に、本発明の導電性粒子について実施例を
示して説明する。先ず、以下の実施例で使用した接着剤
の構成材料を以下に示す。Next, the conductive particles of the present invention will be described with reference to examples. First, the constituent materials of the adhesive used in the following examples are shown below.
【００２６】ａ樹脂バインダー； ・エポキシ／アクリル系樹脂（日本ロックタイト（株）
製造、 商品名「ロックタイト３０１６」）A resin binder; epoxy / acrylic resin (Nippon Loctite Co., Ltd.)
Manufacturing, product name "Loctite 3016")
【００２７】ｂニッケル粒子； ・球状粒子；平均粒径１μｍ、５μｍ、３０μｍの３種
（インコ・エス・ピー・ピー社製） ・突起状粒子；平均粒径５μｍ（ニューメタルズ・エン
ド・ケミカルス・コーポレーション製） ・四脚状粒子；平均長さ５μｍの酸化亜鉛ウイスカ（松
下アムテック（株）製） ウイスカ粒子表面にニッケルの無電解メッキしたものB Nickel particles; ・ Spherical particles; three types having average particle diameters of 1 μm, 5 μm, and 30 μm (manufactured by Inco SP Co.) ・ Protruding particles; average particle diameter of 5 μm (New Metals End Chemicals Corporation) ・ Legged particles; zinc oxide whiskers with an average length of 5 μm (manufactured by Matsushita Amtech Co., Ltd.) Whisker particles whose surface is electrolessly plated with nickel
【００２８】ｃ表面親油性物質の粒子； 樹脂粒子； ・球状エポキシ粒子（平均粒径５μｍ） 卑金属粒子； ・銅粒子；球状粒子； 平均粒径１μｍ及び５μｍの二種（京都エレックス製） 平均粒径２０μｍ（ニューメタルズ・エン・ケミカルス
・コーポレーション製） 燐片状粒子；平均粒径５μｍ ・銀粒子；平均粒径５μｍの球状粒子（福田金属箔粉工
業製）C Particles of lipophilic substance on the surface; Resin particles; Spherical epoxy particles (average particle size: 5 μm) Base metal particles; Copper particles; Spherical particles; Two types having average particle sizes of 1 μm and 5 μm (manufactured by Kyoto Elex) 20 μm diameter (New Metals En Chemicals Corporation) Scaly particles; average particle size 5 μm ・ Silver particles: spherical particles with average particle size 5 μm (manufactured by Fukuda Metal Foil & Powder Co., Ltd.)
【００２９】実施例として、後述のように、上記の材料
から、樹脂バインダーにニッケル粒子と表面親油性粒子
とを表１に示す配合で混練してペースト状の導電性接着
剤を調製した。As an example, as described below, a paste-like conductive adhesive was prepared by kneading nickel particles and surface lipophilic particles in a resin binder from the above-mentioned materials in the composition shown in Table 1.
【００３０】比較例は、粒径が５μｍの球状ニッケル粒
子のみを、樹脂バインダーとしてエポキシ／アクリル系
樹脂と混練して、ペースト状の導電性接着剤を調製し
た。In the comparative example, only a spherical nickel particle having a particle diameter of 5 μm was kneaded with an epoxy / acrylic resin as a resin binder to prepare a paste-like conductive adhesive.
【００３１】実施例及び比較例の導電性接着剤につい
て、以下に述べる方法で体積抵抗測定および硬化収縮率
測定を行った。The conductive adhesives of Examples and Comparative Examples were measured for volume resistance and cure shrinkage by the methods described below.
【００３２】（体積抵抗測定方法）体積抵抗測定方法
は、模式的に図２に示すが、セラミックス基材４上に配
設した銀−パラジウムの電極５、６上に交叉するよう
に、各調製した導電性接着剤７をメタル版を用いて印刷
した。これを、１５０℃で３０分間熱処理して接着剤を
完全に硬化させ、次に、電極５、６間の抵抗値を４端子
法により測定し、接着剤の厚みを測定して、体積抵抗値
を計算によって求めた。体積抵抗値の測定結果を表１に
示す。(Method of Measuring Volume Resistance) The method of measuring volume resistance is schematically shown in FIG. 2, and each of the preparations is performed so as to cross the silver-palladium electrodes 5 and 6 provided on the ceramic substrate 4. The obtained conductive adhesive 7 was printed using a metal plate. This is heat-treated at 150 ° C. for 30 minutes to completely cure the adhesive, and then the resistance between the electrodes 5 and 6 is measured by a four-terminal method, the thickness of the adhesive is measured, and the volume resistance is measured. Was determined by calculation. Table 1 shows the measurement results of the volume resistance value.
【００３３】[0033]
【表１】 [Table 1]
【００３４】（硬化収縮率測定方法）上述した体積抵抗
測定方法において、接着剤の硬化前後での断面積の大き
さを、非接触型表面粗さ計（ローデンストック製）を用
いて測定し、硬化体積収縮率を計算によって求めた。い
くつかの実施例についての接着剤の硬化収縮率の測定結
果を表２に示す。(Measurement Method of Curing Shrinkage Ratio) In the above-described volume resistance measuring method, the size of the cross-sectional area of the adhesive before and after curing is measured by using a non-contact type surface roughness meter (manufactured by Rodenstock) and cured. The volume shrinkage was calculated. Table 2 shows the measurement results of the cure shrinkage of the adhesive for some examples.
【００３５】[0035]
【表２】 [Table 2]
【００３６】表１、表２を参照して実施例の内容につい
て、以下に詳しく述べる。 （実施例１）導電性粒子として、平均粒径５μm の球状
ニッケル粒子と、平均粒径５μm の球状エポキシ粒子を
重量比で７：１に調製し、樹脂バインダーのエポキシ／
アクリル系樹脂に、導電性粒子の重量を、接着剤全体の
重量の８０％になるように混練して導電性接着剤を調製
した。比較例と比較して低い体積抵抗が得られた。The contents of the embodiment will be described in detail below with reference to Tables 1 and 2. (Example 1) As conductive particles, spherical nickel particles having an average particle size of 5 µm and spherical epoxy particles having an average particle size of 5 µm were prepared at a weight ratio of 7: 1.
A conductive adhesive was prepared by kneading an acrylic resin such that the weight of the conductive particles was 80% of the total weight of the adhesive. A lower volume resistance was obtained as compared with the comparative example.
【００３７】（実施例２）実施例１におけるエポキシ粒
子を、銅粒子に代えて、従来の粒径が５μｍの球状ニッ
ケル粒子のみを導電性粒子として用いて、その他の点は
実施例１と同様にして導電性接着剤を調製した。比較例
と比較して、低い体積抵抗が得られた。Example 2 In place of the copper particles in place of the epoxy particles in Example 1, only conventional spherical nickel particles having a particle size of 5 μm were used as conductive particles, and the other points were the same as in Example 1. To prepare a conductive adhesive. As compared with the comparative example, a lower volume resistance was obtained.
【００３８】（実施例３）実施例２における銅粒子を予
め１００℃で３時間加熱処理した点を除いて、その他は
実施例２と同様にして導電性接着剤を調製した。比較例
及び実施例１と比較して、低い体積抵抗が得られた。Example 3 A conductive adhesive was prepared in the same manner as in Example 2 except that the copper particles in Example 2 were heat-treated at 100 ° C. for 3 hours in advance. Compared with the comparative example and the example 1, a lower volume resistance was obtained.
【００３９】（実施例４）実施例２における球状ニッケ
ル粒子に代えて、平均粒径５μm の突起を有する球状の
ニッケル粒子を使用して導電性粒子とし、その他の点は
実施例２と同様にして導電性接着剤を調製した。この接
着剤は、比較例および実施例２と比較して、低い体積抵
抗が得られた。(Example 4) In place of the spherical nickel particles in Example 2, spherical nickel particles having projections having an average particle diameter of 5 µm were used as conductive particles, and the other points were the same as in Example 2. Thus, a conductive adhesive was prepared. With this adhesive, a lower volume resistance was obtained as compared with Comparative Example and Example 2.
【００４０】（実施例５）実施例２における球状ニッケ
ル粒子に代えて、平均粒径５μm の四脚状酸化亜鉛粒子
にニッケルの無電解メッキを行った粒子を用いて、その
他の点は実施例２と同様にして導電性接着剤を調製し
た。この接着剤は、一連の実施例の中で最も低い体積抵
抗率が得られた。(Example 5) In place of the spherical nickel particles in Example 2, tetrapod-shaped zinc oxide particles having an average particle diameter of 5 µm were subjected to electroless plating of nickel. In the same manner as in Example 2, a conductive adhesive was prepared. This adhesive provided the lowest volume resistivity in the series of examples.
【００４１】（実施例６）実施例２における銅粒子の形
状を燐片状に変更して、その他の点は実施例２と同様に
して導電性接着剤を調製した。この接着剤は、従来の粒
径が５μｍの球状ニッケル粒子のみを導電性粒子として
用いた比較例と比較して、低い体積抵抗が得られたが、
実施例１及び同２と比較すると体積抵抗が高くなった。Example 6 A conductive adhesive was prepared in the same manner as in Example 2 except that the shape of the copper particles in Example 2 was changed to a scaly shape. This adhesive had a lower volume resistance than the conventional comparative example using only spherical nickel particles having a particle size of 5 μm as conductive particles.
The volume resistance was higher than those of Examples 1 and 2.
【００４２】（実施例７）実施例２におけるニッケル粒
子の粒径５μｍに代えてその平均粒径を１μｍとした点
を除いて、その他の点は実施例２と同様にして導電性接
着剤を調製した。この接着剤は、ニッケル粒子の粒径が
３μｍよりも小さいので、従来の粒径が５μｍの球状ニ
ッケル粒子のみを導電性粒子として用いた比較例よりは
低い体積抵抗が得られたが、実施例１よりは高くなっ
た。Example 7 A conductive adhesive was used in the same manner as in Example 2 except that the average particle diameter of nickel particles in Example 2 was changed to 5 μm and the average particle diameter was changed to 1 μm. Prepared. In this adhesive, since the particle size of the nickel particles was smaller than 3 μm, a lower volume resistance was obtained than the conventional comparative example using only spherical nickel particles having a particle size of 5 μm as the conductive particles. It was higher than 1.
【００４３】（実施例８）実施例２におけるニッケル粒
子の平均粒径５μｍを２５μｍに変更した点を除いて、
実施例２と同様にして導電性接着剤を調製した。この接
着剤は、従来の粒径が５μｍの球状ニッケル粒子のみを
導電性粒子として用いた比較例よりは低い体積抵抗が得
られたが、ニッケル粒子の粒径が２０μｍよりも大きい
ため、実施例２よりは体積抵抗が高くなった。Example 8 Except that the average particle size of nickel particles in Example 2 was changed from 5 μm to 25 μm,
A conductive adhesive was prepared in the same manner as in Example 2. This adhesive obtained a lower volume resistance than the conventional comparative example using only spherical nickel particles having a particle size of 5 μm as conductive particles, but the particle size of the nickel particles was larger than 20 μm. Volume resistance was higher than 2.
【００４４】（実施例９）この実施例は、銅粒子の粒径
を変更したもので、実施例２における銅粒子の平均粒径
５μｍに代えて銅粒子の平均粒径を１μｍとし、その他
の点は実施例２と同様にして導電性接着剤を調製した。
この接着剤は、従来の粒径が５μｍの球状ニッケル粒子
のみを導電性粒子として用いた比較例よりは低い体積抵
抗が得られたが、卑金属粒子の粒径が３μｍよりも小さ
いので、実施例２よりは体積抵抗が高くなった(Example 9) In this example, the average particle diameter of copper particles was changed to 1 μm instead of the average particle diameter of copper particles of 5 μm in Example 2, except that the average particle diameter of copper particles was changed to 5 μm. A conductive adhesive was prepared in the same manner as in Example 2.
This adhesive had a lower volume resistance than the conventional comparative example using only spherical nickel particles having a particle size of 5 μm as conductive particles, but the particle size of the base metal particles was smaller than 3 μm. Volume resistance is higher than 2
【００４５】（実施例１０）実施例２における銅粒子の
平均粒径５μｍに代えて平均粒径を２５μｍとしその他
の点は実施例２と同様にして導電性接着剤を調製した。
この接着剤は、従来の粒径が５μｍの球状ニッケル粒子
のみを導電性粒子として用いた場合（比較例）よりは低
い体積抵抗が得られたが、卑金属粒子の粒径が１５μｍ
よりも大きいため、実施例２よりは体積抵抗が高くなっ
た。Example 10 A conductive adhesive was prepared in the same manner as in Example 2 except that the average particle diameter of the copper particles in Example 2 was changed to 25 μm instead of 5 μm.
This adhesive had a lower volume resistance than the conventional case where only spherical nickel particles having a particle size of 5 μm were used as the conductive particles (Comparative Example), but the particle size of the base metal particles was 15 μm.
Therefore, the volume resistance was higher than that of Example 2.
【００４６】（実施例１１）実施例２の配合を、ニッケ
ル粒子と、平均粒径５μm の球状銅粒子と、の重量比
が、８：１になるように変更して、導電性接着剤を調製
したもので、比較例よりは低い体積抵抗が得られたが、
卑金属粒子の重量の、ニッケル粒子の重量に対する割合
が０．０５よりも小さくなるため、実施例２よりは高く
なった。Example 11 The composition of Example 2 was changed so that the weight ratio of nickel particles to spherical copper particles having an average particle diameter of 5 μm was 8: 1, and the conductive adhesive was used. Although it was prepared, a lower volume resistance was obtained than the comparative example,
Since the ratio of the weight of the base metal particles to the weight of the nickel particles was smaller than 0.05, the ratio was higher than that of Example 2.
【００４７】（実施例１２）実施例２の配合を、ニッケ
ル粒子と、平均粒径５μm の球状銅粒子と、の重量比が
４：１になるように変更して、導電性接着剤を調製した
もので、比較例よりは低い体積抵抗が得られたが、卑金
属粒子の重量の、ニッケル粒子の重量に対する割合が
０．１５よりも大きくなるため、実施例２よりは高くな
った。Example 12 A conductive adhesive was prepared by changing the composition of Example 2 so that the weight ratio of nickel particles to spherical copper particles having an average particle size of 5 μm was 4: 1. Although the volume resistance was lower than that of the comparative example, the ratio of the weight of the base metal particles to the weight of the nickel particles was larger than 0.15, and was higher than that of the second embodiment.
【００４８】（実施例１３）実施例２の配合を、ニッケ
ル粒子と銅粒子との合計重量の、接着剤の総重量に対す
る割合が０．６０になるように変更して、導電性接着剤
を調製したもので、比較例よりは低い体積抵抗が得られ
たが、ニッケル粒子と卑金属粒子の合計重量の接着剤重
量に対する割合が０．７５より小さくなるため、実施例
２よりは体積抵抗が高くなった。Example 13 The composition of Example 2 was changed so that the ratio of the total weight of nickel particles and copper particles to the total weight of the adhesive was 0.60, and the conductive adhesive was changed. Although it was prepared, the volume resistance was lower than that of the comparative example, but the ratio of the total weight of the nickel particles and the base metal particles to the weight of the adhesive was smaller than 0.75, so that the volume resistance was higher than that of Example 2. became.
【００４９】（実施例１４）実施例２の配合を、ニッケ
ル粒子と銅粒子の合計重量の、接着剤の総重量に対する
割合が０．９０になるように導電性接着剤を調製したも
ので、、ニッケル粒子と卑金属粒子の合計重量の接着剤
重量に対する割合が０．８５を超えるため、比較例より
は低い体積抵抗が得られたが、実施例２よりは体積抵抗
が高くなった。(Example 14) A conductive adhesive was prepared by mixing the composition of Example 2 so that the ratio of the total weight of nickel particles and copper particles to the total weight of the adhesive was 0.90. Since the ratio of the total weight of nickel particles and base metal particles to the weight of the adhesive exceeded 0.85, a lower volume resistance was obtained than in the comparative example, but the volume resistance was higher than in Example 2.
【００５０】以上の実施例から、本発明の導電性接着剤
の中でも、四脚状突起を有するニッケル粒子と銅粒子の
組合せの実施例５が最も体積抵抗が低くなっており、接
続信頼性に優れるために、本発明の導電性接着剤として
最も好ましい。From the above examples, among the conductive adhesives of the present invention, Example 5 in which a combination of nickel particles and copper particles each having a quadruple-shaped projection has the lowest volume resistance has the lowest connection reliability. Because it is excellent, it is most preferable as the conductive adhesive of the present invention.
【００５１】さらに、表２から明らかなように、硬化収
縮率と体積抵抗値は良好な相関関係を有しており、本発
明の導電性接着剤は、従来の導電性接着剤よりも硬化収
縮性が高い。従って、本発明の導電性接着剤は、従来の
導電性接着剤の濡れ性を改善し、硬化収縮性を高めるこ
とによって、低抵抗化を実現できたことが判る。Further, as is clear from Table 2, the curing shrinkage ratio and the volume resistance value have a good correlation, and the conductive adhesive of the present invention has a higher curing shrinkage than the conventional conductive adhesive. High in nature. Therefore, it can be seen that the conductive adhesive of the present invention was able to reduce the resistance by improving the wettability of the conventional conductive adhesive and increasing the curing shrinkage.
【００５２】なお、本実施例では、樹脂バインダーの合
成樹脂成分としてエポキシ／アクリル系樹脂を用いた
が、絶縁性に優れ接着力が十分に確保できる樹脂なら良
いので、これに限定されない。また、樹脂粒子としてエ
ポキシ粒子を用いたが、樹脂であれば良いため、これに
限定されない。In this embodiment, an epoxy / acrylic resin is used as a synthetic resin component of the resin binder. However, the resin is not limited to this as long as it is a resin having excellent insulating properties and sufficient adhesive strength. Although epoxy particles were used as the resin particles, any resin may be used, and the present invention is not limited to this.
【００５３】[0053]
【発明の効果】本発明の導電性接着剤は、樹脂バインダ
ー中に、導電性粒子としてのニッケル粒子と表面が親油
性物質である粒子とを含むので、導電性粒子の樹脂バイ
ンダー中での分散性が高くなり、且つ硬化過程の体積収
縮が大きくなり、ニッケル粒子相互の接触頻度が相対的
に高くなり、体積抵抗値が低下した接着剤硬化体を得る
ことができる。The conductive adhesive of the present invention contains nickel particles as conductive particles and particles whose surface is a lipophilic substance in the resin binder, so that the conductive particles are dispersed in the resin binder. The adhesive property is increased, the volume shrinkage during the curing process is increased, the frequency of contact between the nickel particles is relatively increased, and a cured adhesive having a reduced volume resistance value can be obtained.
【００５４】また、本発明は、表面が親油性物質である
粒子が、固形樹脂粒子または、銅などの卑金属粒子とす
るので、簡単な配合で効果的に体積抵抗値が低下した導
電性接着剤を調製することができる。Further, according to the present invention, since the particles whose surface is a lipophilic substance are solid resin particles or base metal particles such as copper, the conductive adhesive having a effectively reduced volume resistance value by a simple blending. Can be prepared.
【００５５】本発明においては、特に、ニッケル粒子と
して、ニッケル被覆四脚形状酸化亜鉛ウイスカを利用す
ることにより、体積抵抗値の低い導電性接着剤を得るこ
とができる。In the present invention, in particular, a conductive adhesive having a low volume resistance can be obtained by using nickel-coated quadruped zinc oxide whiskers as nickel particles.
【図１】本発明の電導性設着剤中の四脚状突起を有する
ニッケル粒子と酸化皮膜を有する銅粒との相互関係を図
示した模式図である。FIG. 1 is a schematic diagram illustrating the interrelationship between nickel particles having tetrapod projections and copper particles having an oxide film in the conductive adhesive of the present invention.
【図２】本発明の実施例で利用した体積抵抗測定方法を
示す模式図である。FIG. 2 is a schematic view showing a volume resistance measuring method used in an example of the present invention.
１ ニッケル粒子 ２ 銅粒子 ３ 突起 ４ セラミック基材 ５ 銀−パラジウム電極 ６ 銀−パラジウム電極 ７ 導電性接着剤 ８ 樹脂バインダー DESCRIPTION OF SYMBOLS 1 Nickel particle 2 Copper particle 3 Projection 4 Ceramic base material 5 Silver-palladium electrode 6 Silver-palladium electrode 7 Conductive adhesive 8 Resin binder
Claims (12)
親油性の粒子とを含むことを特徴とする導電性接着剤。1. A conductive adhesive comprising nickel particles and surface lipophilic particles in a resin binder.
る請求項１記載の導電性接着剤。2. The conductive adhesive according to claim 1, wherein the surface lipophilic particles are resin particles.
金属（但しニッケルを含まず）の粒子である請求項１記
載の導電性接着剤。3. The conductive adhesive according to claim 1, wherein the surface lipophilic particles are particles of a base metal (but not containing nickel) based on silver.
び鉄の中の１種以上の金属の粒子である請求項３の導電
性接着剤。4. The conductive adhesive according to claim 3, wherein said base metal particles are particles of one or more metals among silver, copper, zinc, tin and iron.
３の導電性接着剤。5. The conductive adhesive according to claim 3, wherein said base metal particles are copper particles.
膜が形成されている請求項３ないし５何れか記載の導電
性接着剤。6. The conductive adhesive according to claim 3, wherein a natural oxide film is formed on the surface of the base metal particles.
高い温度で加熱処理されて表面酸化皮膜が形成されたこ
とを特徴とする請求項３ないし６いずれかに記載の導電
性接着剤。7. The conductive adhesive according to claim 3, wherein the base metal particles are previously heat-treated at a temperature higher than room temperature to form a surface oxide film.
を特徴とする請求項１ないし７何れかに記載の導電性接
着剤。8. The conductive adhesive according to claim 1, wherein the nickel particles have projections on the surface.
イスカの表面にニッケルを被覆したものであることを特
徴とする請求項８に記載の導電性接着剤。9. The conductive adhesive according to claim 8, wherein the nickel particles are formed by coating a surface of a quadruped zinc oxide whisker with nickel.
属粒子の形状が球状であることを特徴とする請求項３な
いし７に記載の導電性接着剤。10. The conductive adhesive according to claim 3, wherein the shape of the metal particles having at least the surface oxide film is spherical.
あり、且つ、少なくとも表面に酸化皮膜を形成した金属
粒子の粒径が３〜１５μｍであることを特徴とする請求
項３ないし１０いずれかに記載の導電性接着剤。11. The method according to claim 3, wherein the nickel particles have a particle size of 3 to 20 μm, and the metal particles having an oxide film formed on at least the surface thereof have a particle size of 3 to 15 μm. 3. The conductive adhesive according to 1.).
子の重量に対する割合が０．０５〜０．１５であり、且
つ、前記ニッケル粒子と該卑金属粒子の合計重量の、接
着剤重量に対する割合が０．７５〜０．８５であること
を特徴とする請求項３ないし１０いずれかに記載の記載
の導電性接着剤。12. The ratio of the weight of the base metal particles to the weight of the nickel particles is 0.05 to 0.15, and the ratio of the total weight of the nickel particles and the base metal particles to the weight of the adhesive is 0. The conductive adhesive according to any one of claims 3 to 10, wherein the conductive adhesive has a ratio of 0.75 to 0.85.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25230897A JPH1192727A (en) | 1997-09-17 | 1997-09-17 | Conductive adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25230897A JPH1192727A (en) | 1997-09-17 | 1997-09-17 | Conductive adhesive |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH1192727A true JPH1192727A (en) | 1999-04-06 |
Family
ID=17235453
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25230897A Pending JPH1192727A (en) | 1997-09-17 | 1997-09-17 | Conductive adhesive |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH1192727A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003041218A (en) * | 2000-08-31 | 2003-02-13 | Matsushita Electric Ind Co Ltd | Conductive adhesive agent and packaging structure using the same |
| US6916433B2 (en) * | 2000-02-29 | 2005-07-12 | Matsushita Electric Industrial Co., Ltd. | Conductive adhesive, apparatus for mounting electronic component, and method for mounting the same |
| EP1616217A2 (en) * | 2003-03-27 | 2006-01-18 | E Ink Corporation | Electro-optic assemblies |
| JP2010151760A (en) * | 2008-12-26 | 2010-07-08 | Fujitsu Ltd | Method for evaluation of reliability of electronic component |
| CN114806336A (en) * | 2022-05-10 | 2022-07-29 | 浙江华普环保材料有限公司 | Special color steel plate for livestock raising and processing technology thereof |
-
1997
- 1997-09-17 JP JP25230897A patent/JPH1192727A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6916433B2 (en) * | 2000-02-29 | 2005-07-12 | Matsushita Electric Industrial Co., Ltd. | Conductive adhesive, apparatus for mounting electronic component, and method for mounting the same |
| JP2003041218A (en) * | 2000-08-31 | 2003-02-13 | Matsushita Electric Ind Co Ltd | Conductive adhesive agent and packaging structure using the same |
| EP1616217A2 (en) * | 2003-03-27 | 2006-01-18 | E Ink Corporation | Electro-optic assemblies |
| EP1616217A4 (en) * | 2003-03-27 | 2007-04-11 | E Ink Corp | Electro-optic assemblies |
| JP2011081407A (en) * | 2003-03-27 | 2011-04-21 | E Ink Corp | Electro-optic assembly |
| JP2010151760A (en) * | 2008-12-26 | 2010-07-08 | Fujitsu Ltd | Method for evaluation of reliability of electronic component |
| CN114806336A (en) * | 2022-05-10 | 2022-07-29 | 浙江华普环保材料有限公司 | Special color steel plate for livestock raising and processing technology thereof |
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