JP2013100525A - Liquid epoxy resin composition and adhesive using the same - Google Patents

Liquid epoxy resin composition and adhesive using the same Download PDF

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JP2013100525A
JP2013100525A JP2013000714A JP2013000714A JP2013100525A JP 2013100525 A JP2013100525 A JP 2013100525A JP 2013000714 A JP2013000714 A JP 2013000714A JP 2013000714 A JP2013000714 A JP 2013000714A JP 2013100525 A JP2013100525 A JP 2013100525A
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epoxy resin
seconds
resin composition
liquid epoxy
adhesive
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JP5739917B2 (en
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Akira Taniguchi
昌 谷口
Yuichi Watanabe
裕一 渡邉
Hideki Kikuchi
秀樹 菊池
Yasuo Matsumura
泰男 松村
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Somar Corp
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Somar Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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  • Engineering & Computer Science (AREA)
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  • Power Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
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  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

PROBLEM TO BE SOLVED: To provide a liquid epoxy resin composition having high adhesive for a short curing time, can reliably bond and fix small-sized electric components, and can obtain sufficient bond strength regardless of the type of electric components.SOLUTION: The liquid epoxy resin composition contains at least an epoxy resin and two or more latent curing agents, including 50 mass% or more, based on all the latent curing agents, of a latent curing agent which has a reaction rate of 50% or more under the condition of 150°C for 30 seconds when used alone, wherein an adhesion strength (A) in the case of the curing at 150°C for 60 seconds and an adhesion strength (B) in the case of the curing at 150°C for 1 hr satisfy the following relationship: 0.6B<A.

Description

本発明は、表面実装用に好適な液状エポキシ樹脂組成物及びこれを用いた接着剤に関し、特に半導体や電子部品等の部品を各種プリント基板上に固定する際、短時間の硬化時間で各種プリント基板上に載置した電子部品等を位置ズレや剥離のない状態に保持でき、しかも小型化される電子部品においても確実に接着固定可能な液状エポキシ樹脂組成物及びこれを用いた接着剤に関するものである。   The present invention relates to a liquid epoxy resin composition suitable for surface mounting and an adhesive using the same, and in particular, when various components such as semiconductors and electronic components are fixed on various printed boards, various prints can be made with a short curing time. A liquid epoxy resin composition that can hold electronic components placed on a substrate without being displaced or peeled, and can be securely fixed even in electronic components that are miniaturized, and an adhesive using the same It is.

従来、表面実装用部品をプリント基板上に接着固定するための接着剤としては、エポキシ樹脂組成物を含有する接着剤が用いられている。このようなものとしては、例えばエポキシ樹脂と、アミン系硬化剤と、チキソ付与剤として親水性シリカ粒子とを含有するもの（特許文献１参照）や液状エポキシ樹脂とアミン系潜在性硬化剤と焼成タルクと有機系レオロジー添加剤とを含有するもの（特許文献２参照）が提案されている。   Conventionally, an adhesive containing an epoxy resin composition has been used as an adhesive for bonding and fixing a surface mounting component on a printed circuit board. Examples of such a resin include an epoxy resin, an amine curing agent, and hydrophilic silica particles as a thixotropic agent (see Patent Document 1), a liquid epoxy resin, an amine latent curing agent, and baking. A material containing talc and an organic rheology additive has been proposed (see Patent Document 2).

近時、半導体を含む電子部品は、データの大容量化や処理速度の高速化等の性能向上を目的として、小型化、高密度化が進んでいる反面、低コスト化が求められるようになり、従来とは異なる電子部品が開発されてきている。これらの電子部品はその表面（接着面）の状態も多様化してきているため、前記特許文献１や特許文献２に記載の接着剤や他の従来の接着剤では十分な接着力が得られない場合があり、電子部品の種類に関係なく安定した接着力を発現する樹脂組成物（接着剤）の開発が産業界から切望されている。   Recently, electronic components including semiconductors are becoming smaller and more dense in order to improve performance, such as increasing the data capacity and processing speed. Electronic parts different from conventional ones have been developed. Since the surface (adhesion surface) of these electronic components has also been diversified, the adhesive described in Patent Document 1 and Patent Document 2 and other conventional adhesives cannot provide sufficient adhesive force. In some cases, the development of a resin composition (adhesive) that exhibits a stable adhesive force regardless of the type of electronic component is eagerly desired by the industry.

ところで、従来は、この種の接着力を測定する方法として、ＪＩＳ Ｋ ６８５０が採用されていたが、表面実装用部品としてアルミニウム以外の材料も使用されるチップコンデンサーなどを含む各種電子部品の耐久性を評価するに当たり、この方法で接着力を評価したのでは、信頼性の高い評価が出来ないことが知られる様になってきている。従って、チップコンデンサーなどを含む各種電子部品においては、プッシュプルゲージを使用して測定する方法（特許文献３、４参照）が採用されてきている。この方法で評価したときに、一定水準以上の接着強度を示すものが望まれていることは言うまでもない。   By the way, JIS K 6850 has been conventionally used as a method for measuring this type of adhesive force, but durability of various electronic components including chip capacitors in which materials other than aluminum are also used as surface mounting components. It is becoming known that when this method is used to evaluate the adhesive strength, a highly reliable evaluation cannot be performed. Therefore, in various electronic parts including a chip capacitor and the like, a method of measuring using a push-pull gauge (see Patent Documents 3 and 4) has been adopted. Needless to say, a material exhibiting an adhesive strength of a certain level or higher when evaluated by this method is desired.

特開平０４−３３９１６号公報Japanese Unexamined Patent Publication No. 04-33916 特開平０７−３１６４００号公報JP 07-316400 A 特開平０３−３９３７８号公報Japanese Patent Laid-Open No. 03-39378 特開平１０−２７９５６号公報Japanese Patent Laid-Open No. 10-27956

本発明はこれらの問題点、すなわち、短時間の硬化時間で高い接着力を有し小型化される電子部品においても確実に接着固定可能であり、しかも電子部品の種類に関係なく、十分な接着強度が得られる液状エポキシ樹脂組成物及びこれを用いた接着剤を提供することをその課題とする。   The present invention is capable of reliably fixing even these problems, that is, electronic components that have a high adhesive force and a small size with a short curing time, and that are sufficiently bonded regardless of the type of electronic component. It is an object of the present invention to provide a liquid epoxy resin composition capable of obtaining strength and an adhesive using the same.

本発明者等は、上記の課題を解決するために鋭意検討した結果、少なくともエポキシ樹脂、２種以上の潜在性硬化剤を含有し（但し、特定の反応率を有する潜在性硬化剤を全潜在性硬化剤の５０質量％以上用いる）、硬化時間と接着力とが特定の関係を満足する液状エポキシ樹脂組成物を用いた接着剤は、短時間で高接着力を有し、サイズや種類に関係なく、各種電子部品に対して高い接着強度が得られることを見出し、本発明を完成するに至ったものである。   As a result of diligent studies to solve the above-mentioned problems, the inventors of the present invention contain at least an epoxy resin and two or more latent hardeners (however, the latent hardeners having a specific reaction rate are all latent). The adhesive using the liquid epoxy resin composition satisfying a specific relationship between the curing time and the adhesive force has a high adhesive force in a short time, Regardless, the present inventors have found that high adhesive strength can be obtained with respect to various electronic components and have completed the present invention.

なお、表面実装用に好適な液状エポキシ樹脂組成物及びこれを用いた接着剤に関し、チップコンデンサー等を含む各種電子部品の性能評価に際し、従来、硬化時間測定の指標として採用されているゲル化時間を使用したのでは、十分な性能を有する組成物を提供できないことが判明した。その理由の一つとしては、ゲル化時間は、架橋開始の時間を示す指標に過ぎず、チップコンデンサーなどを含む各種電子部品における、接着剤の硬化時間は、通常１５０℃で６０秒程度とされることから、このような条件下でも十分な接着強度を示す状態で硬化させることができるエポキシ樹脂組成物について、検討した結果、後述する反応率で規定する関係を充足させ得る初期反応率の高いエポキシ樹脂組成物であれば、サイズや種類に関係なく、各種電子部品に対して高い接着強度が得られることを見出し、本発明を完成させたものである。   In addition, regarding the liquid epoxy resin composition suitable for surface mounting and the adhesive using the same, in the performance evaluation of various electronic components including a chip capacitor etc., the gelation time that has been conventionally adopted as an index for measuring the curing time It has been found that the use of can not provide a composition with sufficient performance. One reason for this is that the gelation time is only an indicator of the time for initiation of crosslinking, and the curing time of the adhesive in various electronic parts including chip capacitors is usually about 60 seconds at 150 ° C. Therefore, as a result of studying an epoxy resin composition that can be cured in a state exhibiting sufficient adhesive strength even under such conditions, a high initial reaction rate that can satisfy the relationship defined by the reaction rate described later is high. The present inventors have found that an epoxy resin composition can provide high adhesive strength to various electronic components regardless of size and type, and have completed the present invention.

即ち、本発明は以下の液状エポキシ樹脂組成物及びこれを用いた接着剤を提供するものである。   That is, the present invention provides the following liquid epoxy resin composition and an adhesive using the same.

（１）少なくとも（ａ）エポキシ樹脂、（ｂ）２種以上の潜在性硬化剤を含有し、前記潜在性硬化剤は、全潜在性硬化剤に対して、１種類のみで使用した場合に１５０℃３０秒の条件で５０％以上の反応率を有する潜在性硬化剤を５０質量％以上用いる液状エポキシ樹脂組成物であって、当該液状エポキシ樹脂組成物を、ソルダーレジストとプリフラックスを塗布した基板上にディスペンサーを用いて、１点の塗布直径が０．７±０．１５ｍｍのものを２点塗布後、被着体として２０１２タイプの角型セラミックコンデンサーを、塗布した箇所の上に装着させ、装着後３０秒で基板の表面温度が１５０℃になるように昇温後、６０秒間又は１時間保持して硬化後、２３℃まで放冷し、部品の長軸と直角方向に押して剥離したときの強度をプッシュプルゲージにて測定する接着試験により試験したとき、１５０℃の温度下における保持時間が６０秒のときの接着力（Ａ）と、１時間保持したときの接着力（Ｂ）とが、式０．６Ｂ＜Ａで規定する関係を満たすものであることを特徴とする液状エポキシ樹脂組成物。 (1) It contains at least (a) an epoxy resin, (b) two or more latent curing agents, and the latent curing agent is 150 when only one type is used for all latent curing agents. A liquid epoxy resin composition using a latent curing agent having a reaction rate of 50% or more under the condition of 30 ° C. for 50% by mass or more, wherein the liquid epoxy resin composition is coated with a solder resist and a preflux. Using a dispenser on the top, after applying two points with an application diameter of 0.7 ± 0.15 mm, attach a 2012 type square ceramic capacitor as an adherend on the applied part, When the surface temperature of the substrate is raised to 150 ° C in 30 seconds after mounting, and after curing by holding for 60 seconds or 1 hour, cooling to 23 ° C and pressing in the direction perpendicular to the major axis of the part and peeling off The strength of When tested by an adhesion test measured with a pull gauge, the adhesive force (A) when the holding time at a temperature of 150 ° C. is 60 seconds and the adhesive force (B) when held for 1 hour are expressed by the formula 0. A liquid epoxy resin composition satisfying the relationship defined by 6B <A.

（２）前記接着力（Ａ）が３０Ｎ以上であることを特徴とする前記（１）に記載の液状エポキシ樹脂組成物。 (2) The liquid epoxy resin composition according to (1), wherein the adhesive force (A) is 30 N or more.

（３）示差走査熱量計を使用し、測定物についての等速昇温データよりピーク全体の熱量とピーク温度ならびにピークトップまでの変化率を求め、昇温スピードの常用対数値を縦軸にとり、前記ピーク温度の逆数値を横軸にとることにより小沢プロットを作成後、前記測定物についての活性化エネルギー、頻度因子、反応次数を求め、前記活性エネルギー、前記頻度因子及び前記反応次数より反応予測図を作成して算出する反応率について、１５０℃の温度下で０秒間、３０秒間、６０秒間、９０秒間硬化させた際の液状エポキシ樹脂組成物の前記反応率をそれぞれα（０）、α（３０）、α（６０）、α（９０）としたとき、これらの関係が下記式で表されることを特徴とする前記（１）又は（２）に記載の液状エポキシ樹脂組成物。 (3) Using a differential scanning calorimeter, the calorific value of the entire peak, the peak temperature, and the rate of change to the peak top are obtained from the constant speed heating data for the measured object, and the common logarithmic value of the heating speed is plotted on the vertical axis After creating an Ozawa plot by taking the reciprocal value of the peak temperature on the horizontal axis, obtain the activation energy, frequency factor, and reaction order for the measurement object, and predict the reaction from the activation energy, the frequency factor, and the reaction order Regarding the reaction rates calculated by creating a diagram, the reaction rates of the liquid epoxy resin composition when cured for 0 seconds, 30 seconds, 60 seconds, and 90 seconds at a temperature of 150 ° C. are α (0) and α, respectively. (30), α (60), α (90), the liquid epoxy resin composition according to the above (1) or (2), wherein these relationships are represented by the following formula.

Figure 2013100525
（式中、Ｘは３以上、１５以下である）
Figure 2013100525
 (Wherein X is 3 or more and 15 or less)

（４）１３０℃の温度下で０秒間、３０秒間、６０秒間、９０秒間硬化させた際の液状エポキシ樹脂組成物の前記反応率をそれぞれβ（０）、β（３０）、β（６０）、β（９０）としたとき、これらの関係が下記式で表されることを特徴とする前記（１）〜（３）のいずれかに記載の液状エポキシ樹脂組成物。 (4) The reaction rates of the liquid epoxy resin composition when cured at 130 ° C. for 0 seconds, 30 seconds, 60 seconds, and 90 seconds are β (0), β (30), and β (60), respectively. , Β (90), the liquid epoxy resin composition according to any one of the above (1) to (3), wherein these relationships are represented by the following formula.

Figure 2013100525
（式中、Ｙは２以上、１０以下である）
Figure 2013100525
 (Where Y is 2 or more and 10 or less)

（５）１５０℃の温度下で３０秒間硬化させたときの前記反応率γ（１５０）と８０℃の温度下で３０秒間硬化させたときの前記反応率γ（８０）との比Ｚ〔γ（１５０）／γ（８０）〕が１０以上であることを特徴とする前記（１）〜（４）のいずれかに記載の液状エポキシ樹脂組成物。 (5) Ratio Z [γ of the reaction rate γ (150) when cured at 150 ° C. for 30 seconds and the reaction rate γ (80) when cured at 80 ° C. for 30 seconds (150) / γ (80)] is 10 or more, The liquid epoxy resin composition as described in any one of (1) to (4) above.

（６）ＪＩＳ Ｋ ６９１１に準拠した方法により硬化した試験片（硬化条件：１２０℃で１時間さらに１５０℃で１時間）の２０℃における曲げ弾性率が５×１０8〜５×１０10Ｐａの範囲であることを特徴とする前記（１）〜（５）のいずれかに記載の液状エポキシ樹脂組成物。 (6) The bending elastic modulus at 20 ° C. of a test piece (curing condition: 1 hour at 120 ° C. and 1 hour at 150 ° C.) cured by a method according to JIS K 6911 is 5 × 10 8 to 5 × 10 10 Pa. It is a range, The liquid epoxy resin composition in any one of said (1)-(5) characterized by the above-mentioned.

（７）前記（１）〜（６）のいずれかに記載の液状エポキシ樹脂組成物を含有することを特徴とする接着剤。 (7) An adhesive comprising the liquid epoxy resin composition according to any one of (1) to (6).

本発明における反応率とは、後述するマックサイエンス社製（現ブルカー・エイエックス社製（日本国））の示差走査熱量計（ＤＳＣ）を用いて、同装置に添付されているＤＳＣ小沢法ソフトウエアのマニュアルに従い、反応予測式を導き出し、その式に基づき算出したある特定時間における反応率をいう。なお、反応率を算出するに当たっては、新版熱分析（小澤丈夫・神戸博太郎著・講談社サイエンティフィック編）、T. OZAWA, J.Thermal Anal.2.301(1970)を参考とした。上記のマニュアルの記載に従い、ＤＳＣの昇温速度を変えて、各種物性データを求め、このデータから反応率を計算した。その際、接着剤としての接着操作性、耐久性を考慮して採用した特定温度における各時間での反応率を利用することにより、より小型化され、より高集積された電子部品においても、短時間の硬化時間で、確実に接着固定可能で、かつ、高い接着力を有する接着組成物のスクリーニングの指標として有効であることを見出し、本発明を完成させたものである。この方法で求めた反応率は、ゲル化時間を指標として測定する硬化程度を推定する従来方法に比較して、誤差が少なく、特に、チップコンデンサー等の表面実装用部品をプリント基板上に接着固定するための接着剤のように、短時間で硬化することが求められる分野での使用においては、短時間での硬化の度合いをより正確に予測できるので好ましい。   The reaction rate in the present invention refers to a DSC Ozawa method software attached to the apparatus using a differential scanning calorimeter (DSC) manufactured by Mac Science (currently Bruker Ax (Japan)) described later. This refers to the reaction rate at a specific time calculated based on the formula of the reaction prediction according to the wear manual. In calculating the reaction rate, the new edition thermal analysis (Takeo Ozawa, Hirotaro Kobe, edited by Kodansha Scientific), T. OZAWA, J. Thermal Anal.2.301 (1970) was used as a reference. According to the description in the above manual, various physical property data were obtained by changing the heating rate of the DSC, and the reaction rate was calculated from this data. At that time, by using the reaction rate at each time at a specific temperature adopted in consideration of the adhesive operability and durability as an adhesive, even in electronic components that are smaller and more highly integrated, It has been found that the present invention has been completed by finding that it is effective as an index for screening an adhesive composition that can be securely fixed with a long curing time and has high adhesive strength. The reaction rate obtained by this method has fewer errors than conventional methods that estimate the degree of cure measured using gelation time as an index, and in particular, surface mount components such as chip capacitors are fixed on a printed circuit board. For use in a field that requires curing in a short time, such as an adhesive for the purpose, it is preferable because the degree of curing in a short time can be predicted more accurately.

本発明の液状エポキシ樹脂組成物及びこれを用いた接着剤は、速硬化性を有するにもかかわらず高い接着強度を有するとともに、内部応力増加に伴うクラック等の発生を防止できるので、歩留り性、製品信頼性共に向上することができる。このように、本発明の液状エポキシ樹脂組成物は、特に電子部品（半導体を含む）等をプリント基板上に表面実装する際に極めて有用な接着剤を提供することができる。   The liquid epoxy resin composition of the present invention and an adhesive using the liquid epoxy resin composition have high adhesive strength in spite of having fast curing properties, and can prevent the occurrence of cracks and the like due to an increase in internal stress. Both product reliability can be improved. As described above, the liquid epoxy resin composition of the present invention can provide an extremely useful adhesive particularly when an electronic component (including a semiconductor) or the like is surface-mounted on a printed board.

以下、本発明の液状エポキシ樹脂組成物及びこれを用いた接着剤を実施するための形態について具体的に説明するが、本発明は以下の形態に限定されるものではない。   Hereinafter, although the form for implementing the liquid epoxy resin composition of this invention and the adhesive agent using this is demonstrated concretely, this invention is not limited to the following forms.

［１］エポキシ樹脂
本発明で用いるエポキシ樹脂としては、１分子中に２個以上のエポキシ基を有するものであって、例えばビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、フェノールノボラック型又はクレゾールノボラック型エポキシ樹脂、脂環式エポキシ樹脂、水添ビスフェノールＡ型もしくはＡＤ型エポキシ樹脂、プロピレングリコールジグリシジルエーテル、ペンタエリスリトールポリグリシジルエーテル等の脂肪族系エポキシ樹脂、脂肪族若しくは芳香族カルボン酸とエピクロルヒドリンとから得られるエポキシ樹脂、脂肪族若しくは芳香族アミンとエピクロルヒドリンとから得られるエポキシ樹脂、複素環エポキシ樹脂、スピロ環含有エポキシ樹脂、エポキシ変性樹脂、ビスフェノールＳ型エポキシ樹脂、ビフェノール型エポキシ樹脂等が挙げられる。なかでも常温で液状を示すエポキシ樹脂が好ましいが、常温で固体状であっても、これを常温で液状のエポキシ樹脂に溶解することによって使用することができる。また、これらエポキシ樹脂は単独で用いてもよいが、２種以上を組み合わせて用いてもよい。硬化物の接着性、電気絶縁性、機械特性のバランスからビスフェノールＡ型エポキシ樹脂やビスフェノールＦ型エポキシ樹脂が好ましい。特にビスフェノールＡ型エポキシ樹脂とビスフェノールＦ型エポキシ樹脂との混合物が好適である。 [1] Epoxy resin The epoxy resin used in the present invention has two or more epoxy groups in one molecule. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type or cresol novolak. Type epoxy resin, cycloaliphatic epoxy resin, hydrogenated bisphenol A type or AD type epoxy resin, aliphatic epoxy resin such as propylene glycol diglycidyl ether, pentaerythritol polyglycidyl ether, aliphatic or aromatic carboxylic acid and epichlorohydrin Epoxy resin obtained from an epoxy resin obtained from an aliphatic or aromatic amine and epichlorohydrin, a heterocyclic epoxy resin, a spiro ring-containing epoxy resin, an epoxy-modified resin, a bisphenol S-type epoxy resin, A biphenol type epoxy resin etc. are mentioned. Among them, an epoxy resin that is liquid at normal temperature is preferable, but even if it is solid at normal temperature, it can be used by dissolving it in a liquid epoxy resin at normal temperature. Moreover, although these epoxy resins may be used independently, you may use in combination of 2 or more type. Bisphenol A type epoxy resin and bisphenol F type epoxy resin are preferable from the balance of adhesiveness, electrical insulation and mechanical properties of the cured product. In particular, a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin is suitable.

［２］硬化剤
発明の液状エポキシ樹脂組成物に用いられる潜在性硬化剤には、２種以上の潜在性硬化剤を用いる。潜在性硬化剤とは、常温で固体の変性アミン化合物で熱により活性化するものや所望の温度で溶解又は破壊されるマイクロカプセル中に例えば酸無水物、イミダゾール類、フェノール系化合物、アミド類等の硬化剤を含有させたマイクロカプセル型潜在性硬化剤等が挙げられる。これらのものは、硬化時間（反応性）や硬化物の物性の調整の面から２種以上を組み合わせて用いる。 [2] Curing Agent As the latent curing agent used in the liquid epoxy resin composition of the invention, two or more latent curing agents are used. The latent curing agent is, for example, acid anhydrides, imidazoles, phenolic compounds, amides, etc. in microcapsules that are activated by heat with a modified amine compound that is solid at room temperature or dissolved or destroyed at a desired temperature. And a microcapsule type latent curing agent containing the above curing agent. These are used in combination of two or more in terms of adjusting the curing time (reactivity) and the physical properties of the cured product.

前記潜在性硬化剤の中でも硬化時間（反応性）の調整や接着剤とした時の粘度調整の面からアミン系潜在性硬化剤を用いるのがさらに好ましい。アミン系潜在性硬化剤としては、２−ヘプタデシルイミダゾール、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−ベンジル−５−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−５−トリアジン及びこの２，４−ジアミノ−６−{２−メチルイミダゾリル−（１）}−エチル−５−トリアジンのイソシアヌル酸付加物等のイミダゾール化合物等が挙げられる。   Among the latent curing agents, it is more preferable to use an amine-based latent curing agent from the viewpoint of adjusting the curing time (reactivity) or adjusting the viscosity when used as an adhesive. Examples of amine-based latent curing agents include 2-heptadecylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4-benzyl-5-hydroxymethylimidazole, and 2,4-diamino-6. -{2-methylimidazolyl- (1)}-ethyl-5-triazine and the isocyanuric acid adduct of 2,4-diamino-6- {2-methylimidazolyl- (1)}-ethyl-5-triazine Examples include imidazole compounds.

アミンアダクト系化合物としては、例えば、アミキュアＰＮ−２３、アミキュアＰＮ−４０Ｊ、アミキュアＭＹ−２４（いずれも味の素ファインテクノ(株)社製。アミキュアは登録商標）、ノバキュアＨＸ−３７２１、ノバキュアＨＸ−３７４１（いずれも旭化成ケミカルズ(株)社製。ノバキュアは登録商標）等の各種市販品を用いることができる。また、スピロアセタール系化合物としては、例えばＣＴＵ、ＡＴＵ、ＣＴＵグアナミン（いずれも味の素ファインテクノ(株)社製。）等が挙げられる。特に硬化物の接着性がよく低温での硬化性と保存安定性のバランスからアミンアダクト化合物が好ましい。   Examples of the amine adduct compound include Amicure PN-23, Amicure PN-40J, Amicure MY-24 (all manufactured by Ajinomoto Fine Techno Co., Ltd., Amicure is a registered trademark), NovaCure HX-3721, NovaCure HX-3741. (All are manufactured by Asahi Kasei Chemicals Co., Ltd. NovaCure is a registered trademark). Examples of the spiroacetal compound include CTU, ATU, CTU guanamine (all of which are manufactured by Ajinomoto Fine Techno Co., Ltd.). In particular, an amine adduct compound is preferable from the viewpoint of good adhesiveness of the cured product and a balance between curability at low temperature and storage stability.

これらの潜在性硬化剤は、常温で粉末状やエポキシ樹脂中に混合されたペースト状などで市販されており、その質量平均粒径が１５μｍ以下、好ましくは１０μｍ以下が好ましい。粒径が１５μｍを超えると短時間での反応性や接着強度を上げ難くなるので好ましくない。速硬化性と接着性の面から５μｍ以下の潜在性硬化剤を用いるのが好ましい。   These latent curing agents are commercially available in the form of a powder or a paste mixed in an epoxy resin at room temperature, and the mass average particle diameter is preferably 15 μm or less, and preferably 10 μm or less. If the particle size exceeds 15 μm, it is difficult to increase the reactivity and adhesive strength in a short time, which is not preferable. It is preferable to use a latent curing agent having a thickness of 5 μm or less from the viewpoint of fast curing and adhesiveness.

また、潜在性硬化剤の使用割合は、前記エポキシ樹脂１００質量部に対し、好ましくは２０〜６０質量部、より好ましくは３６〜５０質量部の範囲である。２０質量部未満では硬化性が著しく低下することになるし、６０質量を超えると硬化物の耐湿性や電気特性が低下するとともに粘度が著しく上昇することになるからである。これらの潜在性硬化剤は２種以上を組み合わせて用いる。なお、硬化剤の選択に際しては、低温硬化速度を考慮して、プッシュプルゲージにて測定する接着試験により試験したとき、１５０℃の温度下における保持時間が６０秒のときの接着力（Ａ）と、１時間保持したときの接着力（Ｂ）とが、式０．６Ｂ＜Ａで規定する関係を満たすに充分な量を選択することが必要なことは言うまでもない。また、２種類以上組み合わせて使用するので、潜在性硬化剤を一種類のみで使用した場合に１５０℃３０秒で５０％以上の反応率を有するものを全潜在性硬化剤量の少なくとも５０質量％以上、好ましくは６０質量％を占める量となるような割合で選択する必要がある。なお、ジシアンジアミド系の潜在性硬化剤は、１５０℃での硬化速度が一般的に遅いことから、本発明の組成物に於いて、主要な潜在性硬化剤原料として使用することは好ましくない。勿論、本発明に係る組成物としての要件を満たす範囲内であれば、ジシアンジアミド系の硬化剤を保存安定性向上や接着強度増強を目的として、添加しても良いことは言うまでもない。   Moreover, the usage-amount of a latent hardening | curing agent becomes like this. Preferably it is 20-60 mass parts with respect to 100 mass parts of said epoxy resins, More preferably, it is the range of 36-50 mass parts. When the amount is less than 20 parts by mass, the curability is remarkably lowered. When the amount exceeds 60 parts by mass, the moisture resistance and electrical properties of the cured product are lowered and the viscosity is remarkably increased. These latent curing agents are used in combination of two or more. In selecting a curing agent, the adhesive strength (A) when the holding time at a temperature of 150 ° C. is 60 seconds when tested by an adhesion test measured with a push-pull gauge in consideration of the low-temperature curing rate. Needless to say, it is necessary to select an amount sufficient to satisfy the relationship defined by the formula 0.6B <A for the adhesive force (B) when held for 1 hour. In addition, since two or more types are used in combination, when only one type of latent curing agent is used, the one having a reaction rate of 50% or more at 150 ° C. for 30 seconds is at least 50% by mass of the total latent curing agent amount. As described above, it is necessary to select at a ratio that preferably accounts for 60% by mass. In addition, since the dicyandiamide-based latent curing agent generally has a slow curing rate at 150 ° C., it is not preferable to use it as a main latent curing agent raw material in the composition of the present invention. Of course, it goes without saying that a dicyandiamide-based curing agent may be added for the purpose of improving storage stability and enhancing adhesive strength as long as it satisfies the requirements of the composition according to the present invention.

［３］その他の成分
本発明の液状エポキシ樹脂組成物には、必要に応じて、他の添加物を加えることができる。添加剤としては、例えば、溶融シリカ、結晶性シリカ、低α線シリカ、ガラスフレーク、ガラスビーズ、ガラスバルーン、タルク、アルミナ、ケイ酸カルシウム、水酸化アルミニウム、炭酸カルシウム、硫酸バリウム、マグネシア、窒化ケイ素、窒化ホウ素等の無機質充填剤や、アクリル系樹脂やポリエステル系樹脂、シリコーン系樹脂等の樹脂粒子からなる充填剤、分子中に少なくとも１個のエポキシ基を有し、常温、常圧下で低粘度の化合物、具体的にはフェニルグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、メチルグリシジルエーテル、プロピルグリシジルエーテル、ペンタエリスリトールポリグリシジルエーテル、ソルビトールポリグリシジルエーテル、ｎ−ブチルグリコールグリシジルエーテル、２−エチルヘキシルグリシジルエーテル等の反応性希釈剤、トリフェニルホスフィン等のリン系化合物、例えばトリエチルアミン、テトラエタノールアミン、１，８−ジアザ−ビシクロ〔５．４．０〕−７−ウンデセン（ＤＢＵ）、Ｎ，Ｎ−ジメチルベンジルアミン、１，１，３，３−テトラメチルグアニジン、２−エチル−４−メチルイミダゾール、Ｎ−メチルピペラジン等の第３級アミン系化合物、例えば１，８−ジアザ−ビシクロ〔５．４．０〕−７−ウンデセニウムテトラフェニルボレート等のホウ素系化合物等の硬化促進剤、ニトリルゴム、ブタジエンゴム等の応力緩和剤、シラン系カップリング剤、チタネート系カップリング剤、アルミニウム系カップリング剤等のカップリング剤、染料や顔料等の着色剤、酸化安定剤、耐湿性向上剤、チキソトロピー付与剤、希釈剤、消泡剤、レベリング剤、他の各種の樹脂が挙げられる。 [3] Other components Other additives can be added to the liquid epoxy resin composition of the present invention as required. Examples of the additive include fused silica, crystalline silica, low α-ray silica, glass flake, glass beads, glass balloon, talc, alumina, calcium silicate, aluminum hydroxide, calcium carbonate, barium sulfate, magnesia, silicon nitride. Inorganic fillers such as boron nitride, fillers made of resin particles such as acrylic resins, polyester resins, silicone resins, etc., having at least one epoxy group in the molecule, and having low viscosity at normal temperature and normal pressure Compounds such as phenyl glycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, methyl glycidyl ether, propyl glycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether, n Reactive diluents such as butyl glycol glycidyl ether and 2-ethylhexyl glycidyl ether, phosphorus compounds such as triphenylphosphine, such as triethylamine, tetraethanolamine, 1,8-diaza-bicyclo [5.4.0] -7- Tertiary amine compounds such as undecene (DBU), N, N-dimethylbenzylamine, 1,1,3,3-tetramethylguanidine, 2-ethyl-4-methylimidazole, N-methylpiperazine, such as 1, Curing accelerators such as boron compounds such as 8-diaza-bicyclo [5.4.0] -7-undecenium tetraphenylborate, stress relaxants such as nitrile rubber and butadiene rubber, silane coupling agents, titanates Coupling agents, coupling agents such as aluminum coupling agents, dyes And coloring agents such as pigments, oxidation stabilizers, moisture resistance improvers, thixotropy imparting agents, diluents, antifoaming agents, leveling agents, and other various resins.

中でも反応性希釈剤は、組成物の粘度調整性に優れるため、特に本発明の液状エポキシ樹脂組成物をスクリーン印刷やディスペンサーを用いて接着剤として塗布する際に有効である。また、シラン系カップリング剤は、エポキシ樹脂と充填剤との密着性の面で用いるのが好ましい。反応性希釈剤の配合割合は、得ようとする接着剤の粘度により適宜選択すればよいが、通常エポキシ樹脂１００質量部に対して０〜２０質量部の範囲である。また、カップリング剤の配合割合は通常充填剤１００質量部に対し、０．２５〜２．０質量部の範囲である。ただし、充填剤の表面を予めカップリング剤で処理したものを用いてもよい。   Among them, the reactive diluent is excellent in viscosity adjustment of the composition, and is particularly effective when the liquid epoxy resin composition of the present invention is applied as an adhesive using screen printing or a dispenser. Further, the silane coupling agent is preferably used in terms of adhesion between the epoxy resin and the filler. The mixing ratio of the reactive diluent may be appropriately selected depending on the viscosity of the adhesive to be obtained, but is usually in the range of 0 to 20 parts by mass with respect to 100 parts by mass of the epoxy resin. Moreover, the mixture ratio of a coupling agent is the range of 0.25-2.0 mass parts normally with respect to 100 mass parts of fillers. However, you may use what processed the surface of the filler previously with the coupling agent.

本発明の液状エポキシ樹脂組成物は、エポキシ樹脂、潜在性硬化剤、必要に応じ充填剤等の各種添加剤を混合して得ることができ、本発明の接着剤は、これらの成分からなる液状エポキシ樹脂組成物を含有するものである。   The liquid epoxy resin composition of the present invention can be obtained by mixing various additives such as an epoxy resin, a latent curing agent, and a filler as required, and the adhesive of the present invention is a liquid comprising these components. It contains an epoxy resin composition.

前記エポキシ樹脂、潜在性硬化剤、及び所望により用いられる充填剤等の各種添加剤からなる液状エポキシ樹脂組成物は、下記接着試験により試験したとき、６０秒後の接着力（Ａ）と１時間後の接着力（Ｂ）との関係が０．６Ｂ＜Ａを満足するものである。本発明は、このような関係を満足しうる接着特性を有するものであれば、チップコンデンサーなどを含む各種電子部品の製造時に使用する接着剤用の原料としての液状エポキシ樹脂組成物として、十分実用性があること見出し、この事実に基づき完成させてものである。   The liquid epoxy resin composition comprising various additives such as the epoxy resin, the latent curing agent, and a filler used as required has an adhesive force (A) after 60 seconds and 1 hour when tested by the following adhesion test. The relationship with the subsequent adhesive strength (B) satisfies 0.6B <A. The present invention is sufficiently practical as a liquid epoxy resin composition as a raw material for adhesives used in the manufacture of various electronic components including chip capacitors, as long as it has adhesive properties that can satisfy such a relationship. It is the one that is found based on this fact and completed based on this fact.

即ち、通常、表面実装用部品をプリント基板上に接着固定するための接着剤としては、生産性を考慮したとき、１５０℃、６０秒程度の短時間で硬化させる必要があり、この場合にある程度反応率が高い水準でないと耐湿性等の要求水準を満足することができなくなる恐れがあるため、通常硬化が終了する１時間後の接着強度の少なくとも５０％以上の強度、好ましくは、６０％以上の強度が必要であることを見出して、本発明を完成させたものである。   That is, normally, as an adhesive for bonding and fixing a surface mounting component on a printed circuit board, it is necessary to cure in a short time of about 150 ° C. for about 60 seconds in consideration of productivity. If the reaction rate is not high, the required level such as moisture resistance may not be satisfied. Therefore, the strength is at least 50% or more, preferably 60% or more of the adhesive strength after 1 hour after normal curing is completed. The present invention has been completed by finding that the required strength is required.

［接着試験］
ソルダーレジストとプリフラックスを塗布した基板上に液状エポキシ樹脂組成物をディスペンサーにて１点の塗布直径が０．７±０．１５ｍｍで２点塗布後、被着体として２０１２タイプの角型セラミックコンデンサーを、該組成物上に装着する。装着後３０秒で基板の表面温度が１５０℃になるように昇温後、６０秒間又は１時間保持して硬化後、２３℃まで放冷し、部品の長軸と直角方向に押して剥離したときの強度をプッシュプルゲージで測定する。 [Adhesion test]
After applying a liquid epoxy resin composition on a substrate coated with a solder resist and a preflux with a dispenser at a single application diameter of 0.7 ± 0.15 mm, a 2012 type square ceramic capacitor as an adherend Is mounted on the composition. When the surface temperature of the substrate is raised to 150 ° C in 30 seconds after mounting, and after curing by holding for 60 seconds or 1 hour, cooling to 23 ° C and pressing in the direction perpendicular to the major axis of the part and peeling off The strength of is measured with a push-pull gauge.

前記接着力の関係が０．６Ｂ＜Ａを満足することにより硬化時間が短くても電子部品等を位置ズレや剥離なく次工程へ進めることができる程度の接着力が得られるが、接着力がこの関係を満足しないものである場合、所望の接着力を得るまでの硬化時間が長時間必要となるため、生産性が低下するので好ましくない。特に、電子部品等をプリント基板上に表面実装する場合、短時間に所望の強度水準に達することが好ましいことから、６０秒後の接着力（Ａ）は３０Ｎ以上が好ましく、さらに好ましくは４０Ｎ以上とするのが好ましい。   When the relationship of the adhesive force satisfies 0.6B <A, the adhesive force can be obtained to the extent that the electronic component or the like can be advanced to the next process without misalignment or peeling even if the curing time is short. If this relationship is not satisfied, the curing time required to obtain the desired adhesive force is required for a long period of time, which is not preferable because the productivity is reduced. In particular, when electronic components and the like are surface-mounted on a printed circuit board, it is preferable to reach a desired strength level in a short time. Therefore, the adhesive force (A) after 60 seconds is preferably 30 N or more, more preferably 40 N or more. Is preferable.

また、本発明の液状エポキシ樹脂組成物は、１５０℃の温度下で０秒間、３０秒間、６０秒間、９０秒間硬化させた際の液状エポキシ樹脂組成物の各反応率をそれぞれ、α（０）、α（３０）、α（６０）、α（９０）としたとき、これらの関係（Ｘ）が下記式（Ｉ）を満足するものであることが好ましい。この関係を満たす液状エポキシ樹脂組成物においては、硬化操作の際の周囲環境に影響を受けることがより少なく、かつ、短時間の内に、一定水準以上の接着力を発揮することが出来るので好ましい。   In addition, the liquid epoxy resin composition of the present invention has each reaction rate of the liquid epoxy resin composition when cured at 0, 30, 60, and 90 seconds at a temperature of 150 ° C., respectively, α (0) , Α (30), α (60), α (90), it is preferable that these relationships (X) satisfy the following formula (I). In the liquid epoxy resin composition satisfying this relationship, it is less affected by the ambient environment during the curing operation, and can exhibit an adhesive force of a certain level or more within a short time, which is preferable. .

Figure 2013100525
（式中、Ｘが３以上、１５以下である）
Figure 2013100525
 (Wherein X is 3 or more and 15 or less)

このとき、その理由は定かではないが、Ｘが３未満であると硬化物の耐湿性や絶縁特性が低下するし、１５を超えると硬化速度が速すぎて硬化物に歪が生じやすくなる。硬化物の耐湿性、絶縁特性及び歪抑制性の面から好ましくは５〜１５の範囲である。   At this time, the reason is not clear, but if X is less than 3, the moisture resistance and insulating properties of the cured product are lowered, and if it exceeds 15, the curing rate is too fast and the cured product is likely to be distorted. Preferably it is the range of 5-15 from the surface of moisture resistance of a hardened | cured material, an insulation characteristic, and distortion suppression.

さらに本発明の液状エポキシ樹脂組成物は、１３０℃の温度下での０秒間、３０秒間、６０秒間、９０秒間硬化させた際の液状エポキシ樹脂組成物の各反応率をそれぞれ、β（０）、β（３０）、β（６０）、β（９０）としたとき、これらの関係（Ｙ）が下記式（II）を満足するものであることが好ましい。このような関係を満たすものは、動作保証温度の低い特殊な半導体パッケージの接着操作の場合には、好適に使用されるからである。   Furthermore, the liquid epoxy resin composition of the present invention has a reaction rate of β (0) for each of the liquid epoxy resin compositions when cured at a temperature of 130 ° C. for 0 seconds, 30 seconds, 60 seconds, and 90 seconds. , Β (30), β (60), β (90), it is preferable that these relationships (Y) satisfy the following formula (II). This is because those satisfying such a relationship are preferably used in the case of a bonding operation of a special semiconductor package having a low guaranteed operating temperature.

Figure 2013100525
（式中、Ｙが２以上、１０以下である）
Figure 2013100525
 (Where Y is 2 or more and 10 or less)

このとき、Ｙが２未満であると硬化物の耐湿性や絶縁特性が低下するし、１０を超えると、硬化速度が速すぎて硬化物に歪が生じやすくなる。硬化物の耐湿性、絶縁特性及び歪抑制性の面から好ましくは２〜７の範囲である。   At this time, if Y is less than 2, the moisture resistance and insulating properties of the cured product are lowered, and if Y is more than 10, the curing rate is too high and the cured product is likely to be distorted. Preferably it is the range of 2-7 from the surface of the moisture resistance of a hardened | cured material, an insulation characteristic, and distortion suppression.

本発明の液状エポキシ樹脂組成物は、前記１５０℃での各時間における反応率の関係Ｘを満足すればよいが、近時、地球温暖化を含む環境問題や省資源の観点から硬化温度を低くする傾向があり、このためより低温、特に１３０℃での液状エポキシ樹脂組成物の反応率をコントロールし、各時間における反応率の関係Ｙを満足することにより、硬化温度が高温でも低温でも接着性、硬化性に優れる液状エポキシ樹脂組成物を得ることができるので好ましい。   The liquid epoxy resin composition of the present invention only needs to satisfy the relationship X of the reaction rate at each time at 150 ° C. However, recently, the curing temperature is lowered from the viewpoint of environmental problems including global warming and resource saving. Therefore, by controlling the reaction rate of the liquid epoxy resin composition at a lower temperature, particularly at 130 ° C., and satisfying the relationship Y of the reaction rate at each time, the adhesiveness can be maintained at both high and low curing temperatures. It is preferable because a liquid epoxy resin composition having excellent curability can be obtained.

また、本発明の液状エポキシ樹脂組成物は、１５０℃の温度下で３０秒間硬化させたときの反応率γ（１５０）と８０℃の温度下で３０秒間硬化させたときの反応率γ（８０）との比Ｚ〔γ（１５０）／γ（８０）〕が１０以上であるものが好ましい。この比が１０未満であると、８０℃で反応が進んでしまうために保存性が低下したり、１５０℃で６０秒後の反応率が低下、すなわち、保存時及び／又は使用時の安定性が低下するので好ましくない。長期保存性及び接着性、速硬化性の面から特に好ましくは１２以上である。   The liquid epoxy resin composition of the present invention has a reaction rate γ (150) when cured at 150 ° C. for 30 seconds and a reaction rate γ (80 when cured at 80 ° C. for 30 seconds. The ratio Z [γ (150) / γ (80)] to 10) is preferably 10 or more. If this ratio is less than 10, the reaction proceeds at 80 ° C., resulting in a decrease in storage stability, or a decrease in the reaction rate after 60 seconds at 150 ° C., that is, stability during storage and / or use. Is unfavorable because it decreases. Particularly preferred is 12 or more from the viewpoints of long-term storage, adhesion, and rapid curing.

前記式（Ｉ）で求められるＸが３以上、１５以下、前記式（II）で求められるＹが２以上、１０以下及び１５０℃での反応率と８０℃での反応率との比Ｚが１０以上である液状エポキシ樹脂組成物は、初期（０秒〜３０秒）反応率が高いために６０秒後において、高い接着力を得やすく、しかも８０℃での反応率が低いため長期保存安定性に優れるものである。その結果、このような液状エポキシ樹脂組成物を含有する接着剤は、保存安定性が高いにも係わらず、使用する場合は短時間で電子部品等の被着体を強固に接着することができるという、保存性と接着性という互いに相反する効果を高い次元で両立できるものである。   X calculated by the formula (I) is 3 or more and 15 or less, Y calculated by the formula (II) is 2 or more and 10 or less, and the ratio Z between the reaction rate at 150 ° C. and the reaction rate at 80 ° C. Since the liquid epoxy resin composition having 10 or more has a high initial (0 to 30 seconds) reaction rate, it is easy to obtain a high adhesive force after 60 seconds, and the reaction rate at 80 ° C. is low, so long-term storage stability. It has excellent properties. As a result, the adhesive containing such a liquid epoxy resin composition can firmly adhere to an adherend such as an electronic component in a short time when used even though it has high storage stability. That is, it is possible to achieve the contradictory effects of storage and adhesiveness at a high level.

さらに、本発明の液状エポキシ樹脂組成物は、次の弾性率測定試験における弾性率が５×１０8〜５×１０10Ｐａの範囲であることが好ましい。 Furthermore, the liquid epoxy resin composition of the present invention preferably has an elastic modulus in the following elastic modulus measurement test in the range of 5 × 10 8 to 5 × 10 10 Pa.

［曲げ弾性率試験］
ＪＩＳ Ｋ ６９１１に準拠した方法により曲げ弾性率を測定した。なお、試験片は１２０℃で１時間硬化後、さらに１５０℃で１時間硬化したものを使用した。 [Bending elastic modulus test]
The bending elastic modulus was measured by a method based on JIS K 6911. The test piece was cured at 120 ° C. for 1 hour and further cured at 150 ° C. for 1 hour.

曲げ弾性率が５×１０8Ｐａ未満であると接着剤として用いた場合、基板上に表面実装した電子部品等の位置ズレが生じやすくなり、その結果動作不良等の製品品質に悪影響を与える可能性があり、また、５×１０10Ｐａを超えると衝撃による電子部品等の脱落が生じやすくなり製品品質低下を招来する可能性があるので好ましくない。製品品質の面から好ましい弾性率は１×１０9〜７×１０9Ｐａの範囲である。 When used as an adhesive with a flexural modulus of less than 5 × 10 8 Pa, misalignment of surface-mounted electronic components on the substrate is likely to occur, and as a result, product quality such as malfunction may be adversely affected. In addition, if it exceeds 5 × 10 10 Pa, it is not preferable because electronic parts and the like are likely to drop off due to an impact and may cause a reduction in product quality. In terms of product quality, a preferable elastic modulus is in the range of 1 × 10 9 to 7 × 10 9 Pa.

［４］接着剤
本発明の接着剤は前記したエポキシ樹脂、潜在性硬化剤、所望により用いられる充填剤等の各種添加剤を所定の割合で、エポキシ樹脂が常温で液状の場合はそのまま、エポキシ樹脂が常温で固体の場合はエポキシ樹脂又は全ての成分を溶媒中で均一に混合させることにより得ることができるが、保存安定性や短時間での硬化性の面から次の方法により調製するのが好ましい。 [4] Adhesive The adhesive of the present invention is an epoxy resin, a latent curing agent, and various additives such as a filler that is used as required at a predetermined ratio. If the resin is solid at room temperature, it can be obtained by uniformly mixing the epoxy resin or all components in a solvent, but it can be prepared by the following method from the viewpoint of storage stability and curability in a short time. Is preferred.

（１）液状エポキシ樹脂又は予めトルエン、エタノール、セロソルブ、テトラヒドロフラン、Ｎ−メチル−２−ピロリドン、ジメチルホルムアミド等の有機溶媒に溶解したエポキシ樹脂と潜在性硬化剤及び充填剤等を撹拌機（例えばプラネタリーミキサーや万能撹拌機等、従来接着剤を製造する際に用いられているもの）に充填する。
（２）混合温度５〜４０℃、好ましくは室温（２３℃前後）の温度条件下で均一に混合する。また、充填剤としては、シリカが好ましく、この時の配合量は硬化剤の塩基度により適宜選択されるが、通常硬化剤１質量部に対して、０．０５質量部以上、好ましくは０．０７〜０．５質量部の範囲である。シリカの配合量が０．０５質量部未満であると、シリカを配合しても均一な分散性等を得ることが難しくなるので好ましくない。また、多すぎても好ましくない。 (1) A liquid epoxy resin or an epoxy resin previously dissolved in an organic solvent such as toluene, ethanol, cellosolve, tetrahydrofuran, N-methyl-2-pyrrolidone, dimethylformamide, a latent curing agent, a filler, etc. A conventional mixer such as a Lee mixer or a universal agitator).
(2) Mixing is performed uniformly at a temperature of 5 to 40 ° C., preferably room temperature (around 23 ° C.). Silica is preferable as the filler, and the blending amount at this time is appropriately selected depending on the basicity of the curing agent, but it is usually 0.05 parts by mass or more, preferably 0.8 parts per 1 part by mass of the curing agent. It is the range of 07-0.5 mass part. If the amount of silica is less than 0.05 parts by mass, it will be difficult to obtain uniform dispersibility even if silica is added, which is not preferable. Moreover, it is not preferable that there is too much.

本発明の接着剤は、ディスペンス方式、ピン転写方式、スクリーン印刷方式等の各種塗装方法に好適に用いることができる。例として、ディスペンス方式にて本発明の接着剤を用いた電子部品の固定方法について説明する。   The adhesive of the present invention can be suitably used for various coating methods such as a dispensing method, a pin transfer method, and a screen printing method. As an example, a method for fixing an electronic component using the adhesive of the present invention by a dispensing method will be described.

（１）接着剤の塗布
回路パターンを有する基板の電子部品を実装する箇所に、ディスペンサーを用いて接着剤を塗布する。ディスペンサーとしては、ねじ式（ねじの回転により接着剤を吐出させる方式）、エア式（空気圧で吐出させる方式）のいずれ方式でもよい。
（２）電子部品の固定
次に、前記接着剤上に電子部品を載せ、１３０〜１８０℃の温度で３０〜６０秒程度硬化させ、部品を固定する。
本発明の接着剤を用いた場合、加熱後６０秒間での接着力及び／又は反応率が高いため、短い硬化時間で確実に電子部品を固定できるので歩留り性に優れ、しかも次工程へ移行するまでの時間を短くすることができるため、作業効率、生産性に優れるものである。さらに、次の工程、例えばハンダディップ工程においても、接着剤の形状変化がないので、電子部品が傾いたり、位置ズレ等の発生を抑制でき、しかも吸水し難いため、電気特性低下を防止することができる。 (1) Application of adhesive Adhesive is applied using a dispenser to a place where an electronic component on a substrate having a circuit pattern is mounted. As the dispenser, any of a screw type (method of discharging an adhesive by rotating a screw) and an air type (method of discharging by air pressure) may be used.
(2) Fixing the electronic component Next, the electronic component is placed on the adhesive and cured at a temperature of 130 to 180 ° C for about 30 to 60 seconds to fix the component.
When the adhesive of the present invention is used, since the adhesive force and / or reaction rate in 60 seconds after heating is high, the electronic component can be reliably fixed in a short curing time, so that the yield is excellent and the process proceeds to the next process. Can be shortened, so that work efficiency and productivity are excellent. Furthermore, since there is no change in the shape of the adhesive in the next step, for example, the solder dipping step, it is possible to suppress the occurrence of electronic components tilting, positional misalignment, etc., and it is difficult to absorb water, thereby preventing deterioration of electrical characteristics. Can do.

以下、本発明の液状エポキシ樹脂組成物及びこれを用いた接着剤につき実施例を用いて具体的に説明するが、本発明の液状エポキシ樹脂組成物及びこれを用いた接着剤はこれらの実施例によって限定されるものではない。
なお、実施例及び比較例の接着剤については、接着力、反応率、弾性率の３項目について評価した。これらの項目については、以下の方法により評価した。 Hereinafter, the liquid epoxy resin composition of the present invention and the adhesive using the same will be specifically described with reference to examples, but the liquid epoxy resin composition of the present invention and the adhesive using the same will be described in these examples. It is not limited by.
In addition, about the adhesive agent of an Example and a comparative example, three items, the adhesive force, the reaction rate, and the elasticity modulus, were evaluated. These items were evaluated by the following methods.

［接着力（Ｎ）］
予め、ソルダーレジストとその上にプリフラックスを塗布した基板の上に、本発明の液状エポキシ樹脂組成物（接着剤）をディスペンサーにて１点の塗布直径が０．７±０．１５ｍｍで２点塗布する。この接着剤上に２０１２タイプの角型セラミックコンデンサーを装着した後、３０秒で基板の表面温度が１５０℃になるように昇温し、その後、６０秒後（Ａ）及び１時間（Ｂ）保持して硬化した（硬化炉：静止式リフロー炉ＳＡＲ−４０１Ａ（奥原電気社製））。（Ａ）と（Ｂ）の試験片を室温（２３℃）まで放冷し、部品の長軸と直角方向に押した時の剥離強度をプッシュプルゲージで測定した。品点数は１０点とし、その平均値を記録した。 [Adhesive strength (N)]
The liquid epoxy resin composition (adhesive) of the present invention is applied to a solder resist and a substrate on which a preflux has been applied in advance with a dispenser at one point with a coating diameter of 0.7 ± 0.15 mm at two points. Apply. After mounting a 2012 type square ceramic capacitor on this adhesive, the temperature was raised so that the surface temperature of the substrate reached 150 ° C. in 30 seconds, and then held for 60 seconds (A) and 1 hour (B) And cured (curing furnace: stationary reflow furnace SAR-401A (Okuhara Electric Co., Ltd.)). The specimens (A) and (B) were allowed to cool to room temperature (23 ° C.), and the peel strength when pressed in the direction perpendicular to the major axis of the component was measured with a push-pull gauge. The number of items was 10, and the average value was recorded.

［反応率］
以下の手順により算出した。
〈１〉示差走査熱量計（マックサイエンス社製示差走査熱量計ＤＳＣ３１００／３２００）を使用して、同装置に添付されているマニュアルの記述に従い、各試料についての等速昇温データ（昇温スピード５℃／分，１０℃／分，２０℃／分）よりピーク全体の熱量とピーク温度ならびにピークトップまでの変化率を求めた。ここでいう変化率は、ピーク温度までの熱量をピーク全体の熱量で除した値である。
〈２〉上記昇温スピードの常用対数値を縦軸にとり、ピーク温度の逆数値を横軸にとることにより小沢プロットを作成後、各試料についての活性化エネルギー、頻度因子、反応次数を求めた。
〈３〉前記〈２〉で求めた活性エネルギー、頻度因子及び反応次数より反応予測図を作成し、この図より８０℃、１３０℃及び１５０℃の各温度での０秒、３０秒後、６０秒後及び９０秒後の反応率を算出した。
〈４〉さらに０秒、３０秒後、６０秒後及び９０秒後の各々の反応率から以下の式により１５０℃での結果Ｘ及び１３０℃での結果Ｙを求めた。 [Reaction rate]
The calculation was performed according to the following procedure.
<1> Using a differential scanning calorimeter (Differential Scanning Calorimeter DSC3100 / 3200 manufactured by Mac Science Co., Ltd.), according to the description in the manual attached to the apparatus, constant velocity heating data (heating rate) From 5 ° C./min, 10 ° C./min, and 20 ° C./min), the heat amount and peak temperature of the entire peak and the rate of change to the peak top were determined. The rate of change here is a value obtained by dividing the amount of heat up to the peak temperature by the amount of heat of the entire peak.
<2> The Ozawa plot was created by taking the common logarithm of the temperature rise speed on the vertical axis and the reciprocal value of the peak temperature on the horizontal axis, and then the activation energy, frequency factor, and reaction order for each sample were determined. .
<3> A reaction prediction diagram is prepared from the activity energy, frequency factor and reaction order obtained in the above <2>, and from this diagram, 0 seconds at 30 ° C., 130 ° C. and 150 ° C., 30 seconds later, The reaction rate after 2 seconds and after 90 seconds was calculated.
<4> Further, the results X at 150 ° C. and the results Y at 130 ° C. were determined from the respective reaction rates after 0 seconds, 30 seconds, 60 seconds and 90 seconds, by the following equations.

Figure 2013100525
Figure 2013100525

〈５〉１５０℃で３０秒間硬化させたときの反応率と８０℃で３０秒間硬化させた時の反応率との比Ｚ（１５０℃／８０℃）を求めた。 <5> The ratio Z (150 ° C./80° C.) between the reaction rate when cured at 150 ° C. for 30 seconds and the reaction rate when cured at 80 ° C. for 30 seconds was determined.

［曲げ弾性率（Ｐａ）］
ＪＩＳ Ｋ ６９１１に準拠して測定した。なお、試験片は１２０℃で１時間硬化後さらに１５０℃で１時間硬化したものを使用した。 [Bending elastic modulus (Pa)]
Measurement was performed in accordance with JIS K 6911. The test piece was cured at 120 ° C. for 1 hour and then cured at 150 ° C. for 1 hour.

参考例１
ビスフェノールＡ型エポキシ樹脂（ジャパンエポキシレジン（株）製、商品名：エピコート８２８）５０質量部、ビスフェノールＦ型エポキシ樹脂５０質量部、潜在性硬化剤（イミダゾール系アミンアダクト硬化剤；味の素ファインテクノ（株）社製、商品名：アミキュアＰＮ−Ｈ、平均粒径１０μｍ）３５質量部及びシリカ粉末（日本アエロジル（株）社製、商品名：アエロジル＃３００）３質量部を攪拌混合し、エポキシ樹脂溶液を作製した。次に、この中にチキソ付与剤としてシリカ粉末（一次粒子径：約１０ｎｍ）７質量部を加え、ホモジナイザーで混合し、液状エポキシ樹脂組成物を調製した。このとき得られる液状エポキシ樹脂組成物は接着剤として使用できるものであった。このものの物性を表１に示す。 Reference example 1
50 parts by mass of bisphenol A type epoxy resin (trade name: Epicoat 828, manufactured by Japan Epoxy Resin Co., Ltd.), 50 parts by mass of bisphenol F type epoxy resin, latent curing agent (imidazole amine adduct curing agent; Ajinomoto Fine Techno Co., Ltd. ), Product name: Amicure PN-H, average particle size 10 μm) 35 parts by mass and silica powder (manufactured by Nippon Aerosil Co., Ltd., product name: Aerosil # 300) 3 parts by mass are stirred and mixed to obtain an epoxy resin solution Was made. Next, 7 parts by mass of silica powder (primary particle size: about 10 nm) was added as a thixotropic agent, and mixed with a homogenizer to prepare a liquid epoxy resin composition. The liquid epoxy resin composition obtained at this time could be used as an adhesive. The physical properties of this product are shown in Table 1.

実施例１
参考例１において、潜在性硬化剤をイミダゾール系アミンアダクト硬化剤（味の素ファインテクノ（株）社製、商品名：アミキュアＰＮ−２３Ｊ、平均粒径３μｍ）２０質量部と脂肪族アミン系アミンアダクト（味の素ファインテクノ（株）社製、商品名：アミキュアＭＹ−２４、平均粒径８〜１０μｍ）１５質量部に変えた以外は全て参考例１と同様にして液状エポキシ樹脂組成物からなる接着剤を調製した。このものの物性を表１に示す。 Example 1
In Reference Example 1, the latent curing agent was 20 parts by mass of an imidazole-based amine adduct curing agent (Ajinomoto Fine Techno Co., Ltd., trade name: Amicure PN-23J, average particle size 3 μm) and an aliphatic amine-based amine adduct ( Ajinomoto Fine Techno Co., Ltd., trade name: Amicure MY-24, average particle size 8-10 μm) Except for changing to 15 parts by mass, an adhesive made of a liquid epoxy resin composition was used in the same manner as in Reference Example 1. Prepared. The physical properties of this product are shown in Table 1.

実施例２
参考例１において、潜在性硬化剤をイミダゾール系アミンアダクト硬化剤（味の素ファインテクノ（株）社製、商品名：アミキュアＰＮ−２３、平均粒径１０μｍ）３０質量部と脂肪族アミン系アミンアダクト硬化剤（味の素ファインテクノ（株）社製、商品名：アミキュアＭＹ−２４、平均粒径８〜１０μｍ）１０質量部に変えた以外は全て参考例１と同様にして液状エポキシ樹脂組成物からなる接着剤を調製した。このものの物性を表１に示す。 Example 2
In Reference Example 1, the latent curing agent was 30 parts by mass of an imidazole-based amine adduct curing agent (Ajinomoto Fine Techno Co., Ltd., trade name: Amicure PN-23, average particle size 10 μm) and an aliphatic amine-based amine adduct curing. Adhesive consisting of a liquid epoxy resin composition in the same manner as in Reference Example 1 except that the agent was changed to 10 parts by mass (made by Ajinomoto Fine Techno Co., Ltd., trade name: Amicure MY-24, average particle size 8-10 μm). An agent was prepared. The physical properties of this product are shown in Table 1.

実施例３
参考例１において、潜在性硬化剤をイミダゾール系アミンアダクト硬化剤（味の素ファインテクノ（株）社製、商品名：アミキュアＰＮ−４０Ｊ、平均粒径３μｍ）３０質量部と脂肪族アミン系アミンアダクト硬化剤（味の素ファインテクノ（株）社製、商品名：アミキュアＭＹ−２４、平均粒径８〜１０μｍ）１０質量部に変えた以外は全て参考例１と同様にして液状エポキシ樹脂組成物からなる接着剤を調製した。このものの物性を表１に示す。 Example 3
In Reference Example 1, the latent curing agent was 30 parts by mass of an imidazole-based amine adduct curing agent (Ajinomoto Fine Techno Co., Ltd., trade name: Amicure PN-40J, average particle size 3 μm) and aliphatic amine-based amine adduct curing. Adhesive consisting of a liquid epoxy resin composition in the same manner as in Reference Example 1 except that the agent was changed to 10 parts by mass (made by Ajinomoto Fine Techno Co., Ltd., trade name: Amicure MY-24, average particle size 8-10 μm). An agent was prepared. The physical properties of this product are shown in Table 1.

参考例２
参考例１において、潜在性硬化剤をマイクロカプセル型硬化剤（旭化成ケミカルズ（株）社製、商品名：ノバキュアＨＸ−３７２２、平均粒径２μｍ）３５質量部に変えた以外は全て参考例１と同様にして液状エポキシ樹脂組成物からなる接着剤を調製した。このものの物性を表１に示す。 Reference example 2
Reference Example 1 is the same as Reference Example 1 except that the latent hardener was changed to 35 parts by mass of the microcapsule-type hardener (manufactured by Asahi Kasei Chemicals Corporation, trade name: NovaCure HX-3722, average particle size 2 μm). Similarly, an adhesive made of a liquid epoxy resin composition was prepared. The physical properties of this product are shown in Table 1.

比較例１
参考例１において、潜在性硬化剤をイミダゾール系アミンアダクト（味の素ファインテクノ（株）社製、商品名：アミキュアＰＮ−４０Ｊ、平均粒径３μｍ）１０質量部と脂肪族アミン系アミンアダクト（味の素ファインテクノ（株）社製、商品名：アミキュアＭＹ−２４、平均粒径８〜１０μｍ）３０質量部に変えた以外は全て参考例１と同様にして液状エポキシ樹脂組成物からなる接着剤を調製した。なお、この組成物においては、低温硬化性であるアミキュアＰＮ−４０Ｊの量が、より高温での硬化性を示す低温硬化性硬化剤であるアミキュアＭＹ−２４の量よりも少なく、全体の潜在性硬化剤量の２５質量％を占めるに過ぎないため、この組成物の接着力の関係は、０．６Ｂ＜Ａを満足するものではなかった。このものの物性を表１に示す。 Comparative Example 1
In Reference Example 1, the latent curing agent was imidazole-based amine adduct (Ajinomoto Fine Techno Co., Ltd., trade name: Amicure PN-40J, average particle size 3 μm) and aliphatic amine-based amine adduct (Ajinomoto Fine). Made of Techno Co., Ltd., trade name: Amicure MY-24, average particle size 8 to 10 μm) An adhesive comprising a liquid epoxy resin composition was prepared in the same manner as in Reference Example 1 except that the amount was changed to 30 parts by mass. . In this composition, the amount of Amicure PN-40J, which is low-temperature curable, is less than the amount of Amicure MY-24, which is a low-temperature curable curing agent that exhibits curability at higher temperatures, and the overall potential is low. Since it accounted for only 25% by mass of the amount of the curing agent, the relationship of the adhesive strength of this composition did not satisfy 0.6B <A. The physical properties of this product are shown in Table 1.

比較例２
参考例１において、潜在性硬化剤をジシアンジアミド系のマイクロカプセル型硬化剤（旭化成ケミカルズ（株）社製、商品名：ノバキュアＨＸ−３６１３、平均粒径５μｍ）３５質量部に変えた以外は全て参考例１と同様にして液状エポキシ樹脂組成物からなる接着剤を調製した。このものの物性を表１に示す。 Comparative Example 2
Reference Example 1 except that the latent curing agent was changed to 35 parts by mass of the dicyandiamide-based microcapsule type curing agent (manufactured by Asahi Kasei Chemicals Corporation, trade name: NovaCure HX-3613, average particle size 5 μm) In the same manner as in Example 1, an adhesive comprising a liquid epoxy resin composition was prepared. The physical properties of this product are shown in Table 1.

Figure 2013100525
Figure 2013100525

表１より、本発明の接着剤は、比較例１及び２に比べて短時間で接着力が高いものであることが分かる。また、実施例１〜３及び参考例１〜２のものは比較例１及び２に比べ、８０℃での反応率が低く抑えられていることがわかる。これらにより保存安定性が高く、しかも使用時には瞬時に硬化反応が起こり短時間で強固な接着力が得られる接着剤であることが分かる。このため歩留り性が向上し、かつ、高品質の製品が得られることが分かる。   From Table 1, it can be seen that the adhesive of the present invention has a higher adhesive force in a shorter time than Comparative Examples 1 and 2. Moreover, it turns out that the reaction rate in 80 degreeC is restrained low compared with the comparative examples 1 and 2 of Examples 1-3 and Reference Examples 1-2. It can be seen that these are adhesives that have high storage stability and that undergo a curing reaction instantaneously during use and can provide a strong adhesive force in a short time. Therefore, it can be seen that the yield is improved and a high quality product can be obtained.

本発明の液状エポキシ樹脂組成物及びこれに用いた接着剤は、半導体や電子部品等を回路基板上に短時間で固定できるため、次工程までの時間を短くすることができるので、作業効率、生産性が向上でき、しかも保存安定性が高い接着が得られる。このような接着剤を用いて生産すると、歩留り性の向上や高い品質の製品を得ることができる。そのため本発明の液状エポキシ樹脂組成物及びこれを用いた接着剤は、半導体や電子部品の実装分野に極めて有効なものである。   Since the liquid epoxy resin composition of the present invention and the adhesive used therefor can fix semiconductors and electronic components on the circuit board in a short time, the time to the next process can be shortened, so the work efficiency, Productivity can be improved and adhesion with high storage stability can be obtained. When produced using such an adhesive, yield can be improved and high quality products can be obtained. Therefore, the liquid epoxy resin composition and the adhesive using the same of the present invention are extremely effective in the field of mounting semiconductors and electronic components.

Claims (7)

少なくとも（ａ）エポキシ樹脂、（ｂ）２種以上の潜在性硬化剤を含有し、前記潜在性硬化剤は、全潜在性硬化剤に対して、１種類のみで使用した場合に１５０℃３０秒の条件で５０％以上の反応率を有する潜在性硬化剤を５０質量％以上用いる液状エポキシ樹脂組成物であって、
当該液状エポキシ樹脂組成物を、ソルダーレジストとプリフラックスを塗布した基板上にディスペンサーを用いて、１点の塗布直径が０．７±０．１５ｍｍのものを２点塗布後、被着体として２０１２タイプの角型セラミックコンデンサーを、塗布した箇所の上に装着させ、装着後３０秒で基板の表面温度が１５０℃になるように昇温後、６０秒間又は１時間保持して硬化後、２３℃まで放冷し、部品の長軸と直角方向に押して剥離したときの強度をプッシュプルゲージにて測定する接着試験により試験したとき、１５０℃の温度下における保持時間が６０秒のときの接着力（Ａ）と、１時間保持したときの接着力（Ｂ）とが、式０．６Ｂ＜Ａで規定する関係を満たすものであることを特徴とする液状エポキシ樹脂組成物。 It contains at least (a) an epoxy resin, and (b) two or more kinds of latent curing agents, and the latent curing agent is 150 ° C. for 30 seconds when used alone with respect to all the latent curing agents. A liquid epoxy resin composition using a latent curing agent having a reaction rate of 50% or more under the conditions of 50% by mass or more,
The liquid epoxy resin composition is applied on a substrate coated with a solder resist and a preflux using a dispenser, and two coatings having a coating diameter of one point of 0.7 ± 0.15 mm are applied as an adherend to 2012. A square ceramic capacitor of the type is mounted on the coated part, heated up so that the surface temperature of the substrate becomes 150 ° C. 30 seconds after mounting, held for 60 seconds or 1 hour, cured, and then 23 ° C. Adhesive strength when the holding time at a temperature of 150 ° C. is 60 seconds when tested by a push-pull gauge to measure the strength when peeled by pushing in a direction perpendicular to the major axis of the part. (A) and the adhesive force (B) when hold | maintaining for 1 hour satisfy | fill the relationship prescribed | regulated by Formula 0.6B <A, The liquid epoxy resin composition characterized by the above-mentioned. 前記接着力（Ａ）が３０Ｎ以上であることを特徴とする請求項１に記載の液状エポキシ樹脂組成物。   The liquid epoxy resin composition according to claim 1, wherein the adhesive force (A) is 30 N or more. 示差走査熱量計を使用し、測定物についての等速昇温データよりピーク全体の熱量とピーク温度ならびにピークトップまでの変化率を求め、昇温スピードの常用対数値を縦軸にとり、前記ピーク温度の逆数値を横軸にとることにより小沢プロットを作成後、前記測定物についての活性化エネルギー、頻度因子、反応次数を求め、前記活性エネルギー、前記頻度因子及び前記反応次数より反応予測図を作成して算出する反応率について、１５０℃の温度下で０秒間、３０秒間、６０秒間、９０秒間硬化させた際の液状エポキシ樹脂組成物の前記反応率をそれぞれα（０）、α（３０）、α（６０）、α（９０）としたとき、これらの関係が下記式で表されることを特徴とする請求項１又は２に記載の液状エポキシ樹脂組成物。
Figure 2013100525
 （式中、Ｘは３以上、１５以下である） Using a differential scanning calorimeter, the amount of heat of the entire peak, the peak temperature, and the rate of change to the peak top are obtained from the constant temperature rise data for the measurement object. After creating the Ozawa plot by taking the reciprocal value of the horizontal axis on the horizontal axis, obtain the activation energy, frequency factor, and reaction order for the measurement object, and create a reaction prediction diagram from the activation energy, the frequency factor, and the reaction order The reaction rates of the liquid epoxy resin composition when cured for 0 seconds, 30 seconds, 60 seconds, and 90 seconds at a temperature of 150 ° C. are expressed as α (0) and α (30), respectively. , Α (60), α (90), the relationship is represented by the following formula, and the liquid epoxy resin composition according to claim 1 or 2.
Figure 2013100525
 (Wherein X is 3 or more and 15 or less) １３０℃の温度下で０秒間、３０秒間、６０秒間、９０秒間硬化させた際の液状エポキシ樹脂組成物の前記反応率をそれぞれβ（０）、β（３０）、β（６０）、β（９０）としたとき、これらの関係が下記式で表されることを特徴とする請求項１〜３のいずれかに記載の液状エポキシ樹脂組成物。
Figure 2013100525
 （式中、Ｙは２以上、１０以下である） The reaction rates of the liquid epoxy resin composition when cured at 130 ° C. for 0 seconds, 30 seconds, 60 seconds, and 90 seconds are respectively represented by β (0), β (30), β (60), β ( 90), the relationship is represented by the following formula, and the liquid epoxy resin composition according to any one of claims 1 to 3.
Figure 2013100525
 (Where Y is 2 or more and 10 or less) １５０℃の温度下で３０秒間硬化させたときの前記反応率γ（１５０）と８０℃の温度下で３０秒間硬化させたときの前記反応率γ（８０）との比Ｚ〔γ（１５０）／γ（８０）〕が１０以上であることを特徴とする請求項１〜４のいずれかに記載の液状エポキシ樹脂組成物。   The ratio Z [γ (150) of the reaction rate γ (150) when cured at a temperature of 150 ° C. for 30 seconds and the reaction rate γ (80) when cured at a temperature of 80 ° C. for 30 seconds / Γ (80)] is 10 or more, The liquid epoxy resin composition according to any one of claims 1 to 4. ＪＩＳ Ｋ６９１１に準拠した方法により硬化した試験片（硬化条件：１２０℃で１時間さらに１５０℃で1時間）の２０℃における曲げ弾性率が５×１０8〜５×１０10Ｐａの範囲であることを特徴とする請求項１〜５のいずれかに記載の液状エポキシ樹脂組成物。 The bending elastic modulus at 20 ° C. of a test piece (curing condition: 120 ° C. for 1 hour and further 150 ° C. for 1 hour) cured by a method according to JIS K6911 is in the range of 5 × 10 8 to 5 × 10 10 Pa. The liquid epoxy resin composition according to any one of claims 1 to 5. 請求項１〜６のいずれかに記載の液状エポキシ樹脂組成物を含有することを特徴とする接着剤。   An adhesive comprising the liquid epoxy resin composition according to claim 1.
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