JP5861600B2 - Conductive adhesive composition and electronic device using the same - Google Patents
Conductive adhesive composition and electronic device using the same Download PDFInfo
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- JP5861600B2 JP5861600B2 JP2012193914A JP2012193914A JP5861600B2 JP 5861600 B2 JP5861600 B2 JP 5861600B2 JP 2012193914 A JP2012193914 A JP 2012193914A JP 2012193914 A JP2012193914 A JP 2012193914A JP 5861600 B2 JP5861600 B2 JP 5861600B2
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Description
本発明は、導電性接着剤組成物及びそれを用いた電子素子に関するもので、詳しくは、プリント基板のスルーホールやビアホールの電極用として低抵抗で、高密着性で、且つ保存安定性の優れた導電性接着剤組成物及びそれを用いた電子素子に関する。 The present invention relates to a conductive adhesive composition and an electronic device using the same, and more specifically, low resistance, high adhesion, and excellent storage stability for electrodes of through holes and via holes in printed circuit boards. The present invention relates to a conductive adhesive composition and an electronic device using the same.
従来、導電性接着剤組成物は、ハンダ代替品として電子素子などのチップ部品をリードフレームや各種基板に接着し、電気的もしくは熱的に導通させる材料として使用されている（例えば、特許文献１）。そして近年では、電子素子内部の電極やスルーホールやビアホールを埋め層間の電気的接続として使用されるようになってきた。 Conventionally, a conductive adhesive composition is used as a material for bonding a chip component such as an electronic element to a lead frame or various substrates as a solder substitute and electrically or thermally conducting (for example, Patent Document 1). ). In recent years, electrodes, through holes, and via holes inside electronic elements have been filled and used as electrical connections between layers.
スルーホールやビアホールを通じて多層プリント基板を導通する手段としては、メッキ工程によるものが多かったが、湿式プロセスであるため製造工程が複雑となったり、部品実装に制約が加えられることがあり、高密度の部品実装が難しい。 As a means of conducting a multilayer printed circuit board through a through hole or via hole, the plating process is often used. However, since it is a wet process, the manufacturing process may be complicated and component mounting may be restricted, resulting in high density. It is difficult to mount parts.
そこで、層間の電気接続を導電性樹脂ペーストで行なう方法が提案され、実用化されている。この方法によって個々の層間および任意の位置で電気接続が可能となり、実装密度は飛躍的に向上した。 Therefore, a method of performing electrical connection between layers with a conductive resin paste has been proposed and put into practical use. This method enables electrical connection between individual layers and at any position, and the mounting density has been dramatically improved.
これらの導電性樹脂ペーストでは、導電性粉末として銀粉末が主に使用されていたが、昨今の銀価格の高騰もあり、安価な金属の適用範囲が拡がっている。前記チップ部品の導電性接着剤として、これまでに低体積抵抗率、高信頼性といった観点から銀粉末が必要とされてきたが、例えば、特許文献２では、銀粉だけでなく銀被覆銅粉を使用して低体積抵抗率を維持するようにしている。ただ、銀粉も銀被覆銅粉とほぼ同量程度と多量に使用しているためコストが十分には低減しない。 In these conductive resin pastes, silver powder is mainly used as the conductive powder. However, due to the recent increase in silver prices, the range of application of inexpensive metals is expanding. As a conductive adhesive for the chip component, silver powder has been required so far from the viewpoint of low volume resistivity and high reliability. For example, in Patent Document 2, not only silver powder but also silver-coated copper powder is used. Used to maintain low volume resistivity. However, since silver powder is used in a large amount of about the same amount as silver-coated copper powder, the cost is not reduced sufficiently.
一方、スルーホールやビアホールの充填用でもコスト低減が要請されていて、例えば、特許文献３では、銀被覆銅粉が使用されている。ただ、特許文献３では特定のエポキシ樹脂に対して樹脂の硬化剤として、カチオン重合開始剤を使用しているので、環境問題の懸念があり体積抵抗率も十分ではない。また、特許文献４では銀被覆銅粉を例示しているが、その銀含有量や粉末の密度など詳細は明らかにしておらず、銀被覆銅粉の最適化が記載されていないという点で、やはり体積抵抗率が十分に得られるものではない。また、キシレン樹脂を配合する場合があるが環境や人体に有害である。 On the other hand, cost reduction is also demanded for filling through holes and via holes. For example, in Patent Document 3, silver-coated copper powder is used. However, in Patent Document 3, since a cationic polymerization initiator is used as a resin curing agent for a specific epoxy resin, there is a concern about environmental problems and the volume resistivity is not sufficient. Moreover, although patent document 4 has illustrated silver-coated copper powder, details, such as the silver content and the density of powder, are not clarified, and the optimization of silver-coated copper powder is not described, After all, the volume resistivity is not sufficiently obtained. Moreover, although a xylene resin may be mix | blended, it is harmful to an environment or a human body.
また、特許文献５では、電磁波シールド用として、銅粉を使用しているのでコスト低減が実現されるが、銀被覆銅粉を使用していないことから、体積抵抗率が十分ではない。 Moreover, in patent document 5, since copper powder is used for electromagnetic shielding, cost reduction is implement | achieved, However, Since silver coating copper powder is not used, volume resistivity is not enough.
こうした状況の下、半導体などのチップ部品やスルーホールやビアホールの充填用、電磁波シールド用に使用される低抵抗且つ、低コスト、高密着性の導電性接着剤が切望されていた。 Under such circumstances, a low-resistance, low-cost, high-adhesive conductive adhesive used for filling semiconductor chip components, through holes and via holes, and for electromagnetic wave shielding has been desired.
本発明の課題は、前述した従来技術の問題点に鑑み、低体積抵抗率で低コスト化、保存安定性に優れた導電性接着剤組成物及びそれを用いた電子素子を提供することにある。 An object of the present invention is to provide a conductive adhesive composition having low volume resistivity, low cost, and excellent storage stability, and an electronic device using the same, in view of the above-described problems of the prior art. .
本発明者は、上記課題を解決するために鋭意研究を重ねた結果、銀被覆金属粉末、エポキシ樹脂化合物、フェノール樹脂化合物および硬化促進剤を必須成分とする導電性接着剤において、銀被覆金属粉末として、特定量の銀を含有しタップ密度が３〜８ｇ／ｃｍ３であるものを特定量使用し、低粘度のエポキシ樹脂化合物にフェノール樹脂化合物および硬化促進剤を特定量配合すると、低体積抵抗率、低コスト化、保存安定性に優れた導電性接着剤樹脂組成物が得られることを見出し、本発明を完成するに至った。 As a result of intensive studies in order to solve the above-mentioned problems, the present inventor has obtained a silver-coated metal powder in a conductive adhesive containing silver-coated metal powder, an epoxy resin compound, a phenol resin compound and a curing accelerator as essential components. When a specific amount of silver containing a specific amount of silver and having a tap density of 3 to 8 g / cm 3 is used, and a specific amount of a phenol resin compound and a curing accelerator is blended with a low viscosity epoxy resin compound, a low volume resistance is obtained. It has been found that a conductive adhesive resin composition excellent in rate, cost reduction, and storage stability can be obtained, and the present invention has been completed.
すなわち、本発明の第１の発明によれば、銀被覆金属粉末（Ａ）、エポキシ樹脂化合物（Ｂ）、フェノール樹脂化合物（Ｃ）、硬化促進剤（Ｄ）を必須成分とする導電性接着剤であって、
銀被覆金属粉末（Ａ）は、平均粒径が、１〜１０μｍの金属粒子表面に銀が被覆され、金属粒子と銀の合計量に対する銀の割合が１０〜３０重量％、かつタップ密度が３〜８ｇ／ｃｍ３、また、エポキシ樹脂化合物（Ｂ）は、２５℃での粘度が３Ｐａ．ｓ以下、またフェノール樹脂化合物（Ｃ）は、軟化点が５０℃以上のノボラックフェノール樹脂であり、さらに硬化促進剤（Ｄ）は、２−フェニル−４−メチル−５−ヒドロキシメチルイミダゾール、２−フェニル−４，５−ジヒドロキシメチルイミダゾール、または２，４−ジアミノ−６−〔２’−メチルイミダゾリル−（１’）〕−エチル−ｓ−トリアジンイソシアヌル酸付加物から選ばれるイミダゾール系化合物であり、
各成分の含有量は、銀被覆金属粉末（Ａ）が、全量に対して７０〜９５重量％、フェノール樹脂化合物（Ｃ）が、エポキシ樹脂化合物（Ｂ）の１００重量部に対して１０〜６０重量部、また、硬化促進剤（Ｄ）がエポキシ樹脂化合物（Ｂ）の１００重量部に対して０．０５〜５重量部であることを特徴とする導電性接着剤組成物が提供される。
That is, according to the first invention of the present invention, the conductive adhesive comprising silver-coated metal powder (A), epoxy resin compound (B), phenol resin compound (C), and curing accelerator (D) as essential components. Because
In the silver-coated metal powder (A), silver is coated on the surface of metal particles having an average particle diameter of 1 to 10 μm, the ratio of silver to the total amount of metal particles and silver is 10 to 30% by weight, and the tap density is 3 To 8 g / cm 3 , and the epoxy resin compound (B) has a viscosity at 25 ° C. of 3 Pa.s. s or less , and the phenol resin compound (C) is a novolak phenol resin having a softening point of 50 ° C. or higher, and the curing accelerator (D) is 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2- An imidazole compound selected from phenyl-4,5-dihydroxymethylimidazole, or 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct,
The content of each component is such that the silver-coated metal powder (A) is 70 to 95% by weight with respect to the total amount, and the phenol resin compound (C) is 10 to 60 with respect to 100 parts by weight of the epoxy resin compound (B). Provided is a conductive adhesive composition characterized in that the amount of the curing accelerator (D) is 0.05 to 5 parts by weight with respect to 100 parts by weight of the epoxy resin compound (B).
また、本発明の第２の発明によれば、第１の発明において、前記の銀が被覆される金属粉末（Ａ）は、比重が６以上の金属または合金であることを特徴とする導電性接着剤組成物が提供される。 According to a second aspect of the present invention, in the first aspect, the metal powder (A) coated with silver is a metal or alloy having a specific gravity of 6 or more. An adhesive composition is provided.
また、本発明の第３の発明によれば、第１の発明において、前記エポキシ樹脂化合物（Ｂ）の含有量は、全量に対して２〜２０重量％であることを特徴とする導電性接着剤組成物が提供される。 According to a third aspect of the present invention, in the first aspect, the content of the epoxy resin compound (B) is 2 to 20% by weight with respect to the total amount. An agent composition is provided.
一方、本発明の第４の発明によれば、第１〜３の発明のいずれかの導電性接着剤組成物をプリント基板のスルーホール又はビアホールの電極用として用いてなる電子素子が提供される。
On the other hand, according to the fourth invention of the present invention, there is provided an electronic device using the conductive adhesive composition of any one of the first to third inventions as an electrode for a through hole or a via hole of a printed board. .
以下、本発明の実施形態について詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
Ｉ．導電性接着剤組成物
本発明に係る導電性接着剤組成物は、銀被覆金属粉末（Ａ）、エポキシ樹脂化合物（Ｂ）、フェノール樹脂化合物（Ｃ）、硬化促進剤（Ｄ）を必須成分とする導電性接着剤であって、銀被覆金属粉末（Ａ）は、平均粒径が、１〜１０μｍの金属粒子表面に銀が被覆され、金属粒子と銀の合計量に対する銀の割合が１０〜３０重量％、かつタップ密度が３〜８ｇ／ｃｍ３、また、エポキシ樹脂化合物（Ｂ）は、２５℃での粘度が３Ｐａ．ｓ以下、またフェノール樹脂化合物（Ｃ）は、軟化点が５０℃以上のノボラックフェノール樹脂であり、さらに硬化促進剤（Ｄ）は、２−フェニル−４−メチル−５−ヒドロキシメチルイミダゾール、２−フェニル−４，５−ジヒドロキシメチルイミダゾール、または２，４−ジアミノ−６−〔２’−メチルイミダゾリル−（１’）〕−エチル−ｓ−トリアジンイソシアヌル酸付加物から選ばれるイミダゾール系化合物であり、各成分の含有量は、銀被覆金属粉末（Ａ）が、全量に対して７０〜９５重量％、フェノール樹脂化合物（Ｃ）が、エポキシ樹脂化合物（Ｂ）の１００重量部に対して１０〜６０重量部、また、硬化促進剤（Ｄ）がエポキシ樹脂化合物（Ｂ）の１００重量部に対して０．０５〜５重量部であることを特徴としている。
I. Conductive adhesive composition The conductive adhesive composition according to the present invention comprises a silver-coated metal powder (A), an epoxy resin compound (B), a phenol resin compound (C), and a curing accelerator (D) as essential components. In the silver-coated metal powder (A), the surface of the metal particles having an average particle diameter of 1 to 10 μm is coated with silver, and the ratio of silver to the total amount of metal particles and silver is 10 to 10 . 30 wt%, the tap density is 3 to 8 g / cm 3 , and the epoxy resin compound (B) has a viscosity at 25 ° C. of 3 Pa.s. s or less , and the phenol resin compound (C) is a novolak phenol resin having a softening point of 50 ° C. or higher, and the curing accelerator (D) is 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2- An imidazole compound selected from phenyl-4,5-dihydroxymethylimidazole, or 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct, The content of each component is such that the silver-coated metal powder (A) is 70 to 95% by weight with respect to the total amount, and the phenol resin compound (C) is 10 to 60 with respect to 100 parts by weight of the epoxy resin compound (B). Part by weight, and the curing accelerator (D) is 0.05 to 5 parts by weight with respect to 100 parts by weight of the epoxy resin compound (B).
Ａ．銀被覆金属粉末
本発明において重要な銀被覆金属粉末（以下、銀粉末ともいう）は、導電性接着剤組成物の導電性成分である。該銀粉末は、タップ密度や粒径の大きさによって特性が異なることが究明され、タップ密度３〜８ｇ／ｃｍ３の銀被覆金属粉末を使用する必要がある。なお、上記を満たすのであれば、粒径や銀含有量の異なる銀被覆金属粉末を２種類以上入れても差し支えない。
A. Silver-coated metal powder The silver-coated metal powder important in the present invention (hereinafter also referred to as silver powder) is a conductive component of the conductive adhesive composition. It has been determined that the silver powder has different characteristics depending on the tap density and the particle size, and it is necessary to use a silver-coated metal powder having a tap density of 3 to 8 g / cm 3 . If the above conditions are satisfied, two or more kinds of silver-coated metal powders having different particle sizes and silver contents may be added.
ここで、タップ密度とは、金属粉末などの粉体の嵩密度であり、ＪＩＳ Ｚ２５００に準拠し、シリンダー容量：２０ｍｍ、タップストローク：２０ｍｍ、ストローク回数：５０回の条件で測定した数値である。また、平均粒径は、マイクロトラックで測定した時の値を示す。タップ密度が３〜８ｇ／ｃｍ３の銀被覆金属粉末は分散性が優れている。一方、３ｇ／ｃｍ３より小さいと分散性が劣るので、導電性接着剤組成物中に高充填できない。また，タップ密度が８ｇ／ｃｍ３以上の銀被覆金属粉末は現在のところ入手困難であり、調製も容易ではない。好ましいタップ密度は３．５〜７ｇ／ｃｍ３で、より好ましいタップ密度は４〜６ｇ／ｃｍ３である。 Here, the tap density is a bulk density of a powder such as metal powder, and is a numerical value measured under the conditions of cylinder capacity: 20 mm, tap stroke: 20 mm, and stroke number: 50 in accordance with JIS Z2500. Moreover, an average particle diameter shows the value when measured by a micro track. Silver-coated metal powder having a tap density of 3 to 8 g / cm 3 has excellent dispersibility. On the other hand, if it is less than 3 g / cm 3 , the dispersibility is poor, so that the conductive adhesive composition cannot be highly filled. Also, silver-coated metal powder having a tap density of 8 g / cm 3 or more is currently difficult to obtain and is not easy to prepare. A preferable tap density is 3.5 to 7 g / cm 3 , and a more preferable tap density is 4 to 6 g / cm 3 .
また、銀被覆金属粉末の配合割合は、７０〜９５重量％の範囲内とする。銀被覆金属粉末が７０重量％未満であると電気伝導性が著しく劣り、９５重量％を超えるとペースト化し辛く、また、密着力も著しく低下し、導電性接着剤組成物としての役割を果たさなくなる。銀被覆金属粉末の配合割合は、７５〜９４重量％の範囲が好ましい。より好ましくは、８０〜９３重量％である。 The blending ratio of the silver-coated metal powder is in the range of 70 to 95% by weight. If the silver-coated metal powder is less than 70% by weight, the electrical conductivity is remarkably inferior, and if it exceeds 95% by weight, it is difficult to form a paste, and the adhesive strength is remarkably lowered, so that it does not serve as a conductive adhesive composition. The blending ratio of the silver-coated metal powder is preferably in the range of 75 to 94% by weight. More preferably, it is 80 to 93% by weight.
銀が被覆される金属の平均粒径は、１〜１０μｍの範囲に限定される。平均粒径が１μｍ未満であると金属同士の接触抵抗が増えるので電気伝導性が劣ったり、比表面積が大きくなるのでペースト化が難しくなり、一方、１０μｍを超えるとペースト化はできるが、微細塗布が難しくなるからである。銀が被覆される金属の平均粒径は、２〜７μｍの範囲が好ましい。 The average particle diameter of the metal coated with silver is limited to a range of 1 to 10 μm. If the average particle size is less than 1 μm, the contact resistance between metals increases, resulting in inferior electrical conductivity, and the specific surface area increases, making pasting difficult. On the other hand, if the average particle size exceeds 10 μm, pasting is possible, but fine coating Because it becomes difficult. The average particle diameter of the metal coated with silver is preferably in the range of 2 to 7 μm.
金属粉末への銀被覆率は、０．５〜３０重量％の範囲に限定される。銀被覆率が０．５重量％未満であると被覆が不十分で電気伝導性が劣り、３０重量％を超えると低コストでなくなる。銀被覆率は、１〜２０重量％の範囲が好ましく、５〜１５重量％の範囲がより好ましい。なお、本発明の目的を損なわない範囲で銀粉を入れてもよい。 The silver coverage on the metal powder is limited to the range of 0.5 to 30% by weight. If the silver coverage is less than 0.5% by weight, the coating is insufficient and the electrical conductivity is inferior, and if it exceeds 30% by weight, the cost is not low. The silver coverage is preferably in the range of 1 to 20% by weight, and more preferably in the range of 5 to 15% by weight. In addition, you may put silver powder in the range which does not impair the objective of this invention.
銀を被覆する粉末は、比重が６以上の金属または合金が好ましい。例えば、銅、ニッケル、亜鉛、錫、鉄、コバルトなど、またそれらの合金とすることができる。比重が６未満の金属は、融点が低いものが多く、銀被覆には適しておらず、また、本発明を満足させるための必要量を添加すると、比重が６以上のものに比して体積換算で多く添加することになって、ペースト化することが困難になる。上記を満足するのであれば、銅、ニッケル、亜鉛などから選ばれる２種類以上の金属や合金を選択しても構わない。但し、低コストという観点から、銀より安価な金属や合金を選択するのが望ましい。 The powder covering silver is preferably a metal or alloy having a specific gravity of 6 or more. For example, copper, nickel, zinc, tin, iron, cobalt, etc., and alloys thereof can be used. Metals having a specific gravity of less than 6 are often low in melting point and are not suitable for silver coating, and when a necessary amount for satisfying the present invention is added, the volume is higher than that having a specific gravity of 6 or more. It becomes difficult to form a paste because a large amount is added in conversion. If the above is satisfied, two or more kinds of metals or alloys selected from copper, nickel, zinc, etc. may be selected. However, from the viewpoint of low cost, it is desirable to select a metal or alloy that is less expensive than silver.
Ｂ．エポキシ樹脂化合物
エポキシ樹脂化合物は、２５℃での粘度が３Ｐａ．ｓ以下のものを使用する。粘度が、３Ｐａ．ｓを超えるとペースト化が難しくなりやすいためである。粘度が２Ｐａ．ｓ以下のエポキシ樹脂化合物が好ましく、１Ｐａ．ｓ以下のエポキシ樹脂化合物がより好ましい。
エポキシ樹脂は、その構造によって限定されないが、２官能以上のエポキシ基を有するものが好ましい。
例えば、Ｎ，Ｎ−ビス（２，３−エポキシプロピル）−４−（２，３−エポキシプロポキシ）アニリン、（３’，４’−エポキシシクロヘキサン）メチル３，４−エポキシシクロヘキサンカルボキシレートやダイマー酸のエピクロルヒドリンによるジグリシジルエステル化変性物などが挙げられる。なお、本発明の目的を損なわない範囲で２種類以上入れても構わない。
B. Epoxy resin compound The epoxy resin compound has a viscosity at 25 ° C. of 3 Pa.s. Use s or less. The viscosity is 3 Pa. This is because pasting of s tends to be difficult. The viscosity is 2 Pa. s or less epoxy resin compound is preferred, and 1 Pa. An epoxy resin compound of s or less is more preferable.
Although an epoxy resin is not limited by the structure, what has a bifunctional or more functional epoxy group is preferable.
For example, N, N-bis (2,3-epoxypropyl) -4- (2,3-epoxypropoxy) aniline, (3 ′, 4′-epoxycyclohexane) methyl 3,4-epoxycyclohexanecarboxylate and dimer acid And diglycidyl esterified modified product of epichlorohydrin. Two or more types may be added as long as the object of the present invention is not impaired.
エポキシ樹脂化合物の配合量は、全量に対して２〜２０重量％の範囲とすることが望ましい。配合量が、２重量％未満であると密着力が不十分となり、２０重量％を超えると絶縁体である樹脂成分が多くなるので電気伝導性が劣ることがある。好ましい配合量は２．５〜１５重量％、より好ましくは、３〜１０重量％である。 The compounding amount of the epoxy resin compound is desirably in the range of 2 to 20% by weight with respect to the total amount. If the blending amount is less than 2% by weight, the adhesion is insufficient, and if it exceeds 20% by weight, the resin component that is an insulator increases, so the electrical conductivity may be inferior. A preferred blending amount is 2.5 to 15% by weight, more preferably 3 to 10% by weight.
Ｃ．フェノール樹脂化合物
本発明では、エポキシ樹脂化合物の硬化剤としてフェノール樹脂化合物を使用する。フェノール樹脂化合物としては、公知の軟化点が５０℃以上のノボラックフェノールやレゾールフェノール樹脂が挙げられる。好ましいのは、軟化点が６０℃以上のノボラックフェノール樹脂、より好ましいのは軟化点が７０℃以上のノボラックフェノール樹脂である。フェノール樹脂を使用することで導電性接着剤組成物の体積抵抗率を低下させることができる。なお、フェノール樹脂には、本発明の目的を損なわない範囲で、ジシアンジアミドに代表されるアミン系、酸無水物系、カチオン重合開始剤などの硬化剤を配合しても構わない。
C. Phenol resin compound In this invention, a phenol resin compound is used as a hardening | curing agent of an epoxy resin compound. Examples of the phenol resin compound include novolak phenols and resol phenol resins having a known softening point of 50 ° C. or higher. Preferred is a novolak phenol resin having a softening point of 60 ° C. or higher, and more preferred is a novolak phenol resin having a softening point of 70 ° C. or higher. By using a phenol resin, the volume resistivity of the conductive adhesive composition can be reduced. In addition, you may mix | blend hardening | curing agents, such as an amine type represented by dicyandiamide, an acid anhydride type, and a cationic polymerization initiator, in the range which does not impair the objective of this invention to a phenol resin.
フェノール樹脂化合物は、エポキシ樹脂化合物の１００重量部に対して１０〜６０重量部の範囲に限定されるが、１０重量部未満であると硬化剤が少ないので密着性が劣り、６０重量部を超えると導電を妨げる要因となり電気伝導性が劣化する。好ましい配合量は１５〜５５重量部、より好ましくは２０〜５３重量部である。
The phenol resin compound is limited to a range of 10 to 60 parts by weight with respect to 100 parts by weight of the epoxy resin compound, but if it is less than 10 parts by weight, the adhesive is inferior because of less curing agent, and exceeds 60 parts by weight. As a result, the electrical conductivity deteriorates. The preferred amount is 15 to 55 parts by weight, more preferably 20 to 53 parts by weight.
Ｄ．硬化促進剤
また、本発明では、エポキシ樹脂化合物に対して、フェノール樹脂化合物のほかに硬化促進剤を配合する。
硬化促進剤としては、６０〜３００℃に加熱すると、エポキシ樹脂化合物とフェノール樹脂化合物との反応を速やかに促し、かつ室温で長期間の貯蔵安定性を満足できるものが使用できる。一般的には２−フェニル−４−メチル−５−ヒドロキシメチルイミダゾール、２−フェニル−４，５−ジヒドロキシメチルイミダゾール、２，４−ジアミノ−６−〔２’−メチルイミダゾリル−（１’）〕−エチル−ｓ−トリアジンイソシアヌル酸付加物などのイミダゾール系化合物が望ましい。なお、本発明の目的を損なわない範囲で２種類以上入れても構わない。
D. Curing accelerator In the present invention, a curing accelerator is added to the epoxy resin compound in addition to the phenol resin compound.
As the curing accelerator, one that can rapidly accelerate the reaction between the epoxy resin compound and the phenol resin compound when heated to 60 to 300 ° C. and can satisfy long-term storage stability at room temperature can be used. Generally 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)] Imidazole compounds such as -ethyl-s-triazine isocyanuric acid adduct are desirable. Two or more types may be added as long as the object of the present invention is not impaired.
硬化促進剤は、エポキシ樹脂化合物の１００重量部に対して０．０５〜５重量部の範囲で配合される。配合量が、０．０５重量部未満であると硬化が十分に促進されず、５重量部を超えると保存安定性が劣るし、使用時に経時粘度上昇が早くなり塗布が困難になる。好ましくは０．０７〜４重量部、より好ましくは０．１〜３重量部である。
A hardening accelerator is mix | blended in 0.05-5 weight part with respect to 100 weight part of an epoxy resin compound. If the blending amount is less than 0.05 parts by weight, curing is not sufficiently promoted, and if it exceeds 5 parts by weight, the storage stability is inferior, and the viscosity increases with time in use, which makes application difficult. Preferably it is 0.07-4 weight part, More preferably, it is 0.1-3 weight part.
Ｅ．溶剤
溶剤は本発明の組成物の任意成分であり、添加せずとも本発明を達成することが可能であるが、微量ないし少量の溶剤を添加することでペースト化が容易になる。
溶剤としては、導電性接着剤組成物が硬化する際、溶剤成分が揮発・蒸発し、又は分解して飛散してしまう有機化合物が使用できる。一般には、酢酸２−（２−エトキシエトキシ）エチル、酢酸２−（２−ｎ−ブトキシエトキシ）エチル、酢酸２−ｎ−ブトキシエチル等が挙げられる。これらは単独でも、複数種を混合して使用してもよい。
E. Solvent The solvent is an optional component of the composition of the present invention, and the present invention can be achieved without addition, but the addition of a trace amount or a small amount of solvent facilitates the formation of a paste.
As the solvent, when the conductive adhesive composition is cured, an organic compound in which the solvent component is volatilized / evaporated or decomposed and scattered can be used. In general, 2- (2-ethoxyethoxy) ethyl acetate, 2- (2-n-butoxyethoxy) ethyl acetate, 2-n-butoxyethyl acetate, and the like can be given. These may be used alone or in combination of two or more.
以下に、実施例に基づき本発明を具体的に説明するが、本発明は、これら実施例によって何ら限定されるものではない。
なお、実施例１〜１０及び、比較例１〜１２の各試料は混練後、下記に示す評価を行なった。
EXAMPLES The present invention will be specifically described below based on examples, but the present invention is not limited to these examples.
In addition, each sample of Examples 1-10 and Comparative Examples 1-12 performed the evaluation shown below after kneading | mixing.
（１）体積抵抗値の測定
アルミナ基板上に幅０．６ｍｍ、長さ６０ｍｍの長方形状に試料（導電性接着剤組成物）を印刷し、２００℃のオーブン中に６０分間放置し、硬化した後、室温まで冷却し、導電性接着剤組成物上の両端で抵抗値を測定した。続いて、印刷し硬化した導電性接着剤組成物の膜厚を測定し、抵抗値と膜厚から体積抵抗率を求めた。
(1) Measurement of volume resistance value A sample (conductive adhesive composition) was printed on an alumina substrate in a rectangular shape having a width of 0.6 mm and a length of 60 mm, and left in an oven at 200 ° C. for 60 minutes to be cured. Then, it cooled to room temperature and measured resistance value at the both ends on a conductive adhesive composition. Subsequently, the film thickness of the printed and cured conductive adhesive composition was measured, and the volume resistivity was determined from the resistance value and the film thickness.
（２）接着強度の測定
銅基板上に試料（導電性接着剤組成物）を印刷し、１．５ｍｍ角のシリコンチップを載せ、２００℃のオーブン中に６０分間放置して硬化させた。室温まで冷却した後、この基板に対し、水平方向からシリコンチップに力を加え、該シリコンチップが剥がれた時の力を接着強度として測定した。
(2) Measurement of adhesive strength A sample (conductive adhesive composition) was printed on a copper substrate, a 1.5 mm square silicon chip was placed, and allowed to cure in an oven at 200 ° C. for 60 minutes. After cooling to room temperature, a force was applied to the silicon chip from the horizontal direction on this substrate, and the force when the silicon chip was peeled was measured as the adhesive strength.
（３）塗布性の評価
試料（導電性接着剤組成物）を用いて、４００メッシュのスクリーンにて幅１００μｍ、長さ２０ｍｍの直線を１０本印刷し、印刷面に欠け、かすれ、ダレ等があるものは不可（×）、それらが確認されない場合は良（○）とした。
(3) Evaluation of coating property Using a sample (conductive adhesive composition), 10 straight lines having a width of 100 μm and a length of 20 mm were printed on a 400-mesh screen, and the printed surface was chipped, blurred, sagging, etc. Some were not acceptable (×), and when they were not confirmed, they were judged as good (◯).
（４）保存安定性の評価
試料（導電性接着剤組成物）を軟膏瓶に入れ密閉し、２５℃に５日間放置した。放置前後の粘度を粘度計で測定し、放置後の粘度が放置前の粘度に比べ１．２倍以内であれば良（○）、それを超えた場合を不可（×）とした。
(4) Evaluation of storage stability The sample (conductive adhesive composition) was put in an ointment bottle, sealed, and left at 25 ° C. for 5 days. The viscosity before and after being left was measured with a viscometer. If the viscosity after being left was within 1.2 times the viscosity before being left, it was judged as good (◯), and when it exceeded that, it was judged as impossible (×).
（５）コストメリット
銀含有率が３０ｗｔ％以下の場合を良（○）、それ以上の場合を不可（×）とした．
(5) Cost merit The case where the silver content was 30 wt% or less was judged as good (◯), and the case where the silver content was more than that was judged as impossible (×).
（６）総合評価
上記の４項目において、体積抵抗値は１×１０−４Ω・ｃｍ未満、接着強度は２０Ｎ以上、塗布性については良（○）、保存安定性については良（○）、コストメリットについては良（○）の条件を全て満たしたもののみ合格（○）とし、接着強度１つでも条件に満たさないものがある場合は不合格（×）とした。
(6) Overall Evaluation In the above four items, the volume resistance value is less than 1 × 10 −4 Ω · cm, the adhesive strength is 20 N or more, the applicability is good (◯), the storage stability is good (◯), Regarding the cost merit, only those satisfying all the conditions of good (◯) were accepted (◯), and when there was one that did not satisfy the conditions even with one adhesive strength, it was judged as unacceptable (X).
表１中、各成分の濃度は重量％で示している。銀被覆銅粉末Ａは、金属粒子（銅の平均粒径３μｍ）と銀の合計量に対する銀の割合が１０重量％、かつタップ密度が４．５ｇ／ｃｍ３であり、また、金属粒子（銅の平均粒径０．６μｍ）と銀の合計量に対する銀の割合が１０重量％の銀被覆銅粉末Ｂはタップ密度が２ｇ／ｃｍ３、金属粒子（銅の平均粒径３μｍ）と銀の合計量に対する銀の割合が０．３重量％の銀被覆銅粉末Ｃはタップ密度が４．３ｇ／ｃｍ３、金属粒子（銅の平均粒径３μｍ）と銀の合計量に対する銀の割合が４０重量％の銀被覆銅粉末Ｄはタップ密度が４．９ｇ／ｃｍ３、さらに、金属粒子（ニッケルの平均粒径５μｍ）と銀の合計量に対する銀の割合が１０重量％の銀被覆ニッケル粉末Ｅはタップ密度が４．８ｇ／ｃｍ３、金属粒子（ニッケルの平均粒径５μｍ）と銀の合計量に対する銀の割合が３０重量％の銀被覆ニッケル粉末Ｆはタップ密度が４．９ｇ／ｃｍ３、金属粒子（銅−亜鉛の平均粒径５μｍ）と銀の合計量に対する銀の割合が１０重量％の銀被覆銅−亜鉛合金粉末Ｇはタップ密度が５．７ｇ／ｃｍ３である。一方、銀粉末Ｈはタップ密度が３．８ｇ／ｃｍ３、銅粉末Ｉはタップ密度が３．２ｇ／ｃｍ３である。 In Table 1, the concentration of each component is shown in wt%. In the silver-coated copper powder A, the ratio of silver to the total amount of metal particles (copper average particle diameter 3 μm) and silver is 10% by weight, and the tap density is 4.5 g / cm 3. The silver-coated copper powder B having an average particle size of 0.6 μm) and a silver ratio of 10% by weight with respect to the total amount of silver has a tap density of 2 g / cm 3 , a total of metal particles (average particle size of copper 3 μm) and silver. Silver-coated copper powder C having a silver ratio of 0.3% by weight with respect to the amount has a tap density of 4.3 g / cm 3 , and the ratio of silver to the total amount of metal particles (average copper particle size 3 μm) and silver is 40% by weight. % Of the silver-coated copper powder D has a tap density of 4.9 g / cm 3 , and the silver-coated nickel powder E having 10% by weight of silver with respect to the total amount of metal particles (average particle diameter of nickel 5 μm) and silver is tap density 4.8 g / cm 3, average particle size 5μm of metal particles (nickel The ratio of the silver to the total amount of silver of 30 wt% silver-coated nickel powder F tap density of 4.9 g / cm 3, the metal particles - of silver to the total amount of silver (copper average particle size 5μm of zinc) The silver-coated copper-zinc alloy powder G having a ratio of 10% by weight has a tap density of 5.7 g / cm 3 . On the other hand, the silver powder H has a tap density of 3.8 g / cm 3 and the copper powder I has a tap density of 3.2 g / cm 3 .
また、エポキシ樹脂化合物Ａは、エポキシ樹脂化合物（三菱化学株式会社製：ｊＥＲ６３０、２５℃での粘度は１Ｐａ．ｓ）であり、エポキシ樹脂化合物Ｂは、エポキシ樹脂化合物（三菱化学株式会社製：ｊＥＲ８２８、２５℃での粘度１５Ｐａ．ｓ）である。 The epoxy resin compound A is an epoxy resin compound (Mitsubishi Chemical Corporation: jER630, viscosity at 25 ° C. is 1 Pa.s), and the epoxy resin compound B is an epoxy resin compound (Mitsubishi Chemical Corporation: jER828). The viscosity at 25 ° C. is 15 Pa.s).
硬化剤Ａとしてのフェノール樹脂化合物は、ノボラックフェノール樹脂化合物（明和化成株式会社製：ＭＥＨＣ−７８００Ｈ、軟化点１２０℃）で、硬化剤Ｂは液状のレゾールフェノール樹脂化合物（住友ベークライト株式会社：ＰＲ−５０６０７Ｂ）、硬化剤Ｃはジシアンジアミド（三菱化学株式会社：ＤＩＣＹ７）である。 The phenol resin compound as the curing agent A is a novolak phenol resin compound (Maywa Kasei Co., Ltd .: MEHC-7800H, softening point 120 ° C.), and the curing agent B is a liquid resol phenol resin compound (Sumitomo Bakelite Co., Ltd .: PR-). 50607B), and the curing agent C is dicyandiamide (Mitsubishi Chemical Corporation: DICY7).
さらには硬化促進剤Ａとして２−フェニル−４−メチル−５−ヒドロキシメチルイミダゾール（四国化成株式会社：キュアゾール２Ｐ４ＭＨＺ−ＰＷ）を使用した。
溶剤Ａとしては、酢酸２−（２−エトキシエトキシ）エチル（関東化学株式会社：酢酸２−（２−エトキシエトキシ）エチル）を使用した。
Furthermore, 2-phenyl-4-methyl-5-hydroxymethylimidazole (Shikoku Kasei Co., Ltd .: Curesol 2P4MHZ-PW) was used as the curing accelerator A.
As the solvent A, 2- (2-ethoxyethoxy) ethyl acetate (Kanto Chemical Co., Inc .: 2- (2-ethoxyethoxy) ethyl acetate) was used.
（実施例１）
金属粉末として、金属粒子と銀の合計量に対する銀の割合が１０重量％でタップ密度が４．５ｇ／ｃｍ３の銀被覆銅粉末Ａ、樹脂成分としてエポキシ樹脂化合物Ａ：ｐ−アミノフェノール型液状エポキシ樹脂化合物（三菱化学株式会社製：ｊＥＲ６３０）、硬化剤Ａとしてフェノール樹脂化合物（明和化成株式会社製：ＭＥＨＣ−７８００Ｈ）、硬化促進剤Ａとして２−フェニル−４−メチル−５−ヒドロキシメチルイミダゾール（四国化成株式会社：キュアゾール２Ｐ４ＭＨＺ−ＰＷ）を用意し、溶剤Ａの酢酸２−（２−エトキシエトキシ）エチル（関東化学株式会社：酢酸２−（２−エトキシエトキシ）エチル）と混合し、導電性接着剤組成物を調製し、３本ロール型混練機を使用して混練して、本発明の導電性接着剤組成物を得た。
この導電性接着剤組成物を用いて、アルミナ基板上に印刷し、上記の条件で体積抵抗率を測定した。また、銅基板上に印刷し、硬化させてから接着強度を測定した。また、本発明の導電性接着剤組成物をスクリーンによりアルミナ基板へ印刷し、塗布性を評価した。これらの結果を表１に併記した。
Example 1
As a metal powder, a silver-coated copper powder A having a silver ratio of 10% by weight and a tap density of 4.5 g / cm 3 with respect to the total amount of metal particles and silver, and an epoxy resin compound A as a resin component: p-aminophenol type liquid Epoxy resin compound (Mitsubishi Chemical Corporation: jER630), phenolic resin compound (Maywa Kasei Co., Ltd .: MEHC-7800H) as curing agent A, and 2-phenyl-4-methyl-5-hydroxymethylimidazole as curing accelerator A (Shikoku Kasei Co., Ltd .: Curesol 2P4MHZ-PW) is prepared and mixed with 2- (2-ethoxyethoxy) ethyl acetate (Kanto Chemical Co., Ltd .: 2- (2-ethoxyethoxy) ethyl acetate) as solvent A to conduct electricity. A conductive adhesive composition of the present invention was obtained by preparing a conductive adhesive composition and kneading using a three-roll type kneader.
Using this conductive adhesive composition, it printed on the alumina substrate and measured the volume resistivity on said conditions. Moreover, after printing on a copper substrate and making it harden | cure, the adhesive strength was measured. Further, the conductive adhesive composition of the present invention was printed on an alumina substrate with a screen, and the coating property was evaluated. These results are also shown in Table 1.
（実施例２〜５、１０）
表１に記載した金属粉末成分、樹脂成分、硬化剤成分、硬化促進剤成分、および溶剤成分の配合量を変えた以外は実施例１と同様にして、導電性接着剤組成物を調整し、３本ロール型混練機を使用し混練して、本発明の導電性接着剤組成物を得た。その後、この導電性接着剤組成物を用いて、アルミナ基板上に印刷し、上記の条件で体積抵抗率を測定した。また、銅基板上に印刷し、硬化させてから接着強度を測定した。また、本発明の導電性接着剤組成物をスクリーンによりアルミナ基板へ印刷し、塗布性を評価した。これらの結果を表１に併記した。
(Examples 2-5, 10)
A conductive adhesive composition was prepared in the same manner as in Example 1 except that the compounding amounts of the metal powder component, resin component, curing agent component, curing accelerator component, and solvent component described in Table 1 were changed. The conductive adhesive composition of the present invention was obtained by kneading using a three-roll kneader. Then, it printed on the alumina substrate using this conductive adhesive composition, and measured the volume resistivity on said conditions. Moreover, after printing on a copper substrate and making it harden | cure, the adhesive strength was measured. Further, the conductive adhesive composition of the present invention was printed on an alumina substrate with a screen, and the coating property was evaluated. These results are also shown in Table 1.
（実施例６〜９）
表１に記載したように、実施例１の硬化剤をレゾールフェノール樹脂化合物（住友ベークライト株式会社：ＰＲ−５０６０７Ｂ）に変えるか、実施例１の金属粉末（銀被覆銅粉末Ａ）を、金属粒子と銀の合計量に対する銀の割合が１０重量％でタップ密度が４．８ｇ／ｃｍ３の銀被覆ニッケル粉末Ｅ、又は金属粉末を金属粒子と銀の合計量に対する銀の割合が３０重量％でタップ密度が４．８ｇ／ｃｍ３の銀被覆ニッケル粉末Ｆ、あるいは金属粒子と銀の合計量に対する銀の割合が１０重量％でタップ密度が５．７ｇ／ｃｍ３の銀被覆銅−亜鉛合金粉末Ｇに変えた以外は実施例１と同様にして、導電性接着剤組成物を調製し、３本ロール型混練機を使用して混練し、本発明の導電性接着剤組成物を得た。また、
その後、この導電性接着剤組成物を用いて、アルミナ基板上に印刷し、上記の条件で体積抵抗率を測定した。また、銅基板上に印刷し、硬化させてから接着強度を測定した。また、本発明の導電性接着剤組成物をスクリーンによりアルミナ基板へ印刷し、塗布性を評価した。これらの結果を表１に併記した。
なお、このうち実施例６は参考例である。
(Examples 6 to 9)
As described in Table 1, the curing agent of Example 1 was changed to a resol phenol resin compound (Sumitomo Bakelite Co., Ltd .: PR-50607B), or the metal powder of Example 1 (silver-coated copper powder A) was replaced with metal particles. The silver-coated nickel powder E having a silver ratio of 10% by weight and a tap density of 4.8 g / cm 3 with respect to the total amount of silver and silver, or a metal powder having a ratio of silver to the total amount of metal particles and silver of 30% by weight Silver-coated nickel powder F having a tap density of 4.8 g / cm 3 , or a silver-coated copper-zinc alloy powder having a tap density of 5.7 g / cm 3 with a ratio of silver to the total amount of metal particles and silver of 10% by weight. Except for changing to G, a conductive adhesive composition was prepared in the same manner as in Example 1, and kneaded using a three-roll kneader to obtain a conductive adhesive composition of the present invention. Also,
Then, it printed on the alumina substrate using this conductive adhesive composition, and measured the volume resistivity on said conditions. Moreover, after printing on a copper substrate and making it harden | cure, the adhesive strength was measured. Further, the conductive adhesive composition of the present invention was printed on an alumina substrate with a screen, and the coating property was evaluated. These results are also shown in Table 1.
Of these, Example 6 is a reference example.
（比較例１〜５）
表２に記載したように、金属粉末成分と樹脂成分のエポキシ樹脂化合物Ａの配合量を変えるか、硬化剤Ａと硬化促進剤Ａの配合量を変えた以外は実施例１と同様にして、導電性接着剤組成物を調整し、３本ロール型混練機を使用して混練し、本発明の導電性接着剤組成物を得た。その後、この導電性接着剤組成物を用いて、アルミナ基板上に印刷し、上記の条件で体積抵抗率を測定した。また、銅基板上に印刷し、硬化させてから接着強度を測定した。また、本発明の導電性接着剤組成物をスクリーンによりアルミナ基板へ印刷し、塗布性を評価した。これらの結果を表２に併記した。
(Comparative Examples 1-5)
As described in Table 2, except that the compounding amount of the epoxy resin compound A of the metal powder component and the resin component was changed, or the compounding amount of the curing agent A and the curing accelerator A was changed, the same as in Example 1, The conductive adhesive composition was prepared and kneaded using a three-roll kneader to obtain the conductive adhesive composition of the present invention. Then, it printed on the alumina substrate using this conductive adhesive composition, and measured the volume resistivity on said conditions. Moreover, after printing on a copper substrate and making it harden | cure, the adhesive strength was measured. Further, the conductive adhesive composition of the present invention was printed on an alumina substrate with a screen, and the coating property was evaluated. These results are also shown in Table 2.
（比較例６〜１２）
表２に記載したように、銀被覆銅粉末Ａの代わりに銀被覆銅粉末Ｂや銀被覆銅粉末Ｃ、銀被覆銅粉末Ｄ、銀粉末Ｈ、銅粉末Ｉを用いたか、エポキシ樹脂Ａの代わりにエポキシ樹脂Ｂ：ビスフェノールＡジグリシジルエーテル（三菱化学株式会社：ｊＥＲ８２８）を用いたか、硬化剤Ａの代わりに硬化剤Ｃ：ジシアンジアミド（三菱化学株式会社：ＤＩＣＹ７）を使用した以外は実施例１と同様にして、導電性接着剤組成物を調製し、３本ロール型混練機を使用して混練し、本発明の導電性接着剤組成物を得た。その後、この導電性接着剤組成物を用いて、アルミナ基板上に印刷し、上記の条件で体積抵抗率を測定した。また、銅基板上に印刷し、硬化させてから接着強度を測定した。また、本発明の導電性接着剤組成物をスクリーンによりアルミナ基板へ印刷し、塗布性を評価した。これらの結果を表２に併記した。
As described in Table 2, silver-coated copper powder B, silver-coated copper powder C, silver-coated copper powder D, silver powder H, copper powder I was used instead of silver-coated copper powder A, or epoxy resin A was used instead And Example 1 except that epoxy resin B: bisphenol A diglycidyl ether (Mitsubishi Chemical Corporation: jER828) was used, or curing agent C: dicyandiamide (Mitsubishi Chemical Corporation: DICY7) was used instead of curing agent A. Similarly, a conductive adhesive composition was prepared and kneaded using a three-roll kneader to obtain a conductive adhesive composition of the present invention. Then, it printed on the alumina substrate using this conductive adhesive composition, and measured the volume resistivity on said conditions. Moreover, after printing on a copper substrate and making it harden | cure, the adhesive strength was measured. Further, the conductive adhesive composition of the present invention was printed on an alumina substrate with a screen, and the coating property was evaluated. These results are also shown in Table 2.
「評価」
上記結果を示す表１、２から明らかなように、実施例１〜１０（ただし、実施例６は参考例）の導電性接着剤組成物は、本発明の特定成分を特定量含むため導電性、接着性、塗布性、コストメリットのいずれも優れていることが分かる。なお、実施例２は、やや導電性が低いが、実用上問題の無いレベルである。実施例３、１０はやや接着性が弱いが、実用上問題の無いレベルである。
"Evaluation"
As is apparent from Tables 1 and 2 showing the above results, the conductive adhesive compositions of Examples 1 to 10 (however, Example 6 is a reference example) are conductive because they contain a specific amount of the specific component of the present invention. It can be seen that all of adhesiveness, applicability, and cost merit are excellent. In Example 2, although the conductivity is slightly low, it is at a level where there is no practical problem. In Examples 3 and 10, the adhesiveness is slightly weak, but it is a level with no practical problem.
これに対し、比較例１は銀被覆銅粉末Ａの含有量が７０重量部未満と少ないため、体積抵抗率が高く不可となった。比較例２は硬化剤Ａが６０重量部を超えているため、体積抵抗率が高く不可となった。比較例３は硬化剤Ａが１０重量部未満のため、体積抵抗率が高く不可となった。比較例４は硬化促進剤Ａが０．０５重量部未満のため、体積抵抗率が高く、接着強度が弱く不可となった。比較例５は硬化促進剤Ａが５重量部を超えているため、体積抵抗率が高く、塗布性や保存安定性も悪く不可となった。比較例６はタップ密度が２ｇ／ｃｍ３と小さい銀被覆銅粉末Ｂを使用しているため、体積抵抗率が高く、塗布性が悪く不可となった。比較例７は金属粒子と銀の合計量に対する銀の割合が０．３重量％と小さい銀被覆銅粉末Ｃを使用しているため、体積抵抗率が高く不可となった。比較例８は金属粒子と銀の合計量に対する銀の割合が４０重量％と大きすぎる銀被覆銅粉末Ｄを使用しているため、コストメリットが無く不可となった。比較例９は銀粉末Ｈが銀被覆粉末ではないため、コストメリットが無く不可となった。比較例１０は銅粉末Ｉを使用し、銀を含まないため、体積抵抗率が高く不可となった。比較例１１は粘度が高すぎるエポキシ樹脂化合物Ｂを使用しているため、体積抵抗率が高く、塗布性が悪く不可となった。比較例１２はフェノール樹脂化合物以外の硬化剤Ｃを使用しているため、体積抵抗率が高く不可となった。 On the other hand, since the content of the silver-coated copper powder A was as low as less than 70 parts by weight in Comparative Example 1, the volume resistivity was high and was impossible. In Comparative Example 2, since the curing agent A exceeds 60 parts by weight, the volume resistivity is high and cannot be used. In Comparative Example 3, since the curing agent A was less than 10 parts by weight, the volume resistivity was high and was impossible. In Comparative Example 4, since the curing accelerator A was less than 0.05 parts by weight, the volume resistivity was high, and the adhesive strength was weak, which was not possible. In Comparative Example 5, since the curing accelerator A exceeds 5 parts by weight, the volume resistivity is high, and the applicability and storage stability are also poor and cannot be used. Since Comparative Example 6 uses silver-coated copper powder B having a tap density as small as 2 g / cm 3 , the volume resistivity is high, and the applicability is poor and cannot be used. Since Comparative Example 7 uses silver-coated copper powder C having a small silver ratio of 0.3% by weight with respect to the total amount of metal particles and silver, the volume resistivity is high and cannot be used. Since Comparative Example 8 uses silver-coated copper powder D in which the ratio of silver to the total amount of metal particles and silver is too large at 40% by weight, there is no cost merit and is impossible. In Comparative Example 9, since the silver powder H was not a silver-coated powder, there was no cost merit and it was not possible. Since the comparative example 10 used the copper powder I and did not contain silver, the volume resistivity became high and became impossible. Since the comparative example 11 uses the epoxy resin compound B whose viscosity is too high, the volume resistivity is high, and the applicability is poor and cannot be used. Since the comparative example 12 uses the hardening | curing agent C other than a phenol resin compound, the volume resistivity became high and became impossible.
本発明によれば、銀被覆金属粉末、エポキシ樹脂化合物、フェノール樹脂化合物、硬化促進剤を必須成分とし、特定したタップ密度の銀被覆金属粉末を特定量組み合わせて調製したため、導電性、接着性、塗布性、保存安定性を改善することができる。 According to the present invention, silver coated metal powder, epoxy resin compound, phenol resin compound, curing accelerator as essential components, and prepared by combining a specific amount of silver coated metal powder with the specified tap density, conductivity, adhesiveness, Coating properties and storage stability can be improved.
本発明の導電性接着剤樹脂組成物は、金属粉末として特定のタップ密度で特定量銀を含有する銀被覆金属粉末を特定量配合し、樹脂成分としてエポキシ樹脂化合物を用い、硬化剤としてフェノール樹脂化合物を用い、硬化促進剤をそれぞれ特定量使用しているため、スルーホールやビアホールに充填し層間の導通や、ＩＣなど各種電子素子の接着に適用できる．また、電磁波シールド用としても適用できる。低い抵抗値が実現でき、コストメリットも高いため、高導電性や低価格が必要なスルーホールやビアホールの充填用として特に好ましく適用できる。 The conductive adhesive resin composition of the present invention comprises a specific amount of silver-coated metal powder containing a specific amount of silver at a specific tap density as a metal powder, an epoxy resin compound as a resin component, and a phenol resin as a curing agent. Since a specific amount of curing accelerator is used for each compound, it can be applied to conduction between layers by filling through holes and via holes, and adhesion of various electronic devices such as ICs. It can also be applied for electromagnetic wave shielding. Since a low resistance value can be realized and cost merit is high, it can be particularly preferably applied for filling through holes and via holes that require high conductivity and low cost.
Claims (4)
銀被覆金属粉末（Ａ）は、平均粒径が、１〜１０μｍの金属粒子表面に銀が被覆され、金属粒子と銀の合計量に対する銀の割合が１０〜３０重量％、かつタップ密度が３〜８ｇ／ｃｍ３、また、エポキシ樹脂化合物（Ｂ）は、２５℃での粘度が３Ｐａ．ｓ以下、またフェノール樹脂化合物（Ｃ）は、軟化点が５０℃以上のノボラックフェノール樹脂であり、さらに硬化促進剤（Ｄ）は、２−フェニル−４−メチル−５−ヒドロキシメチルイミダゾール、２−フェニル−４，５−ジヒドロキシメチルイミダゾール、または２，４−ジアミノ−６−〔２’−メチルイミダゾリル−（１’）〕−エチル−ｓ−トリアジンイソシアヌル酸付加物から選ばれるイミダゾール系化合物であり、
各成分の含有量は、銀被覆金属粉末（Ａ）が、全量に対して７０〜９５重量％、フェノール樹脂化合物（Ｃ）が、エポキシ樹脂化合物（Ｂ）の１００重量部に対して１０〜６０重量部、また、硬化促進剤（Ｄ）がエポキシ樹脂化合物（Ｂ）の１００重量部に対して０．０５〜５重量部であることを特徴とする導電性接着剤組成物。 A conductive adhesive comprising silver-coated metal powder (A), epoxy resin compound (B), phenol resin compound (C), and curing accelerator (D) as essential components,
In the silver-coated metal powder (A), silver is coated on the surface of metal particles having an average particle diameter of 1 to 10 μm, the ratio of silver to the total amount of metal particles and silver is 10 to 30% by weight, and the tap density is 3 To 8 g / cm 3 , and the epoxy resin compound (B) has a viscosity at 25 ° C. of 3 Pa.s. s or less , and the phenol resin compound (C) is a novolak phenol resin having a softening point of 50 ° C. or higher, and the curing accelerator (D) is 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2- An imidazole compound selected from phenyl-4,5-dihydroxymethylimidazole, or 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct,
The content of each component is such that the silver-coated metal powder (A) is 70 to 95% by weight with respect to the total amount, and the phenol resin compound (C) is 10 to 60 with respect to 100 parts by weight of the epoxy resin compound (B). The conductive adhesive composition, wherein 0.05 parts by weight and 5 parts by weight of the curing accelerator (D) are 100 parts by weight of the epoxy resin compound (B).
The electronic element which uses the conductive adhesive composition in any one of Claims 1-3 as an object for the through-hole of a printed circuit board, or a via hole .
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