JPH0812745A - Liquid epoxy resin composition - Google Patents
Liquid epoxy resin compositionInfo
- Publication number
- JPH0812745A JPH0812745A JP14837994A JP14837994A JPH0812745A JP H0812745 A JPH0812745 A JP H0812745A JP 14837994 A JP14837994 A JP 14837994A JP 14837994 A JP14837994 A JP 14837994A JP H0812745 A JPH0812745 A JP H0812745A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- curing agent
- resin composition
- liquid epoxy
- general formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Landscapes
- Epoxy Resins (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は電気・電子分野の種々の
用途、例えば、接着剤、注型材、封止材及び積層品等に
用いられる液状エポキシ樹脂組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid epoxy resin composition used for various applications in the electric and electronic fields, such as adhesives, casting materials, encapsulating materials and laminated products.
【０００２】[0002]
【従来の技術】エポキシ樹脂組成物は、優れた電気的性
能と接着力とを有するため、電気・電子分野の種々の用
途に使用されている。エポキシ樹脂組成物は、その硬化
に際して、種々の硬化剤を使用し、硬化剤の種類により
硬化物の性能が大きく異なることが知られており、用途
によって硬化剤が使い分けられている。例えば、接着剤
や積層板の用途では接着性が最も重要視されるためにア
ミン系の硬化剤が用いられ、注型材用途では電気的性能
と低粘度の点から酸無水物系が用いられ、封止材用途で
は耐水性の点からフェノール系硬化剤が用いられる。2. Description of the Related Art Epoxy resin compositions have excellent electrical performance and adhesive strength, and are therefore used in various applications in the electric and electronic fields. It is known that the epoxy resin composition uses various curing agents at the time of curing, and that the performance of the cured product greatly varies depending on the type of the curing agent, and the curing agent is properly used depending on the application. For example, in the use of adhesives and laminates, amine-based curing agents are used because adhesion is the most important, and in casting applications, acid anhydrides are used from the viewpoint of electrical performance and low viscosity. Phenolic curing agents are used for sealing materials from the viewpoint of water resistance.
【０００３】従来、無溶剤型の接着剤、電気及び電子部
品用の封止材、塗料等の液状エポキシ樹脂組成物の硬化
剤としてアミン類及び酸無水物が知られている。フェノ
ール系硬化剤を用いる場合、一般にフェノールノボラッ
ク樹脂が使用され、その分子量が大きいことと、エポキ
シ樹脂に対する上記フェノールノボラック樹脂硬化剤の
添加量が５０ＰＨＲ以上であり、大きいことから、液状
エポキシ樹脂組成物の粘度が非常に高くなって実用に供
しなくなる。しかし、接着性、耐水性、電気的性能等の
物性バランスの点では、フェノール系硬化剤が最も優れ
た硬化剤である。すなわち、液状化が困難であるという
理由からフェノール系硬化剤は一般に固形の成形材料用
途にしか使用できていない。アミン系及び酸無水物系の
硬化剤では、液状化は容易であるが、以下のような問題
点を有している。すなわち、アミン系硬化剤を用いた場
合は、硬化物の架橋構造中に３級アミン構造が存在する
ため、吸湿性が高くなる。酸無水物系の硬化剤を用いた
場合は、硬化物の架橋構造中のエステル構造が化学的に
加水分解され易いため長期耐水性に劣る上に、硬化剤の
酸無水物基とエポキシ樹脂のエポキシ基との反応によっ
て、接着に寄与するアルコール性水酸基が副生し難いこ
とから、硬化物が接着性に劣る。Conventionally, amines and acid anhydrides have been known as curing agents for liquid epoxy resin compositions such as solventless adhesives, sealing materials for electric and electronic parts, paints and the like. When a phenol-based curing agent is used, a phenol novolac resin is generally used, and the liquid epoxy resin composition has a large molecular weight and the addition amount of the phenol novolac resin curing agent to the epoxy resin is 50 PHR or more, which is large. The viscosity of is so high that it cannot be put to practical use. However, in terms of the balance of physical properties such as adhesiveness, water resistance, and electrical performance, the phenolic curing agent is the most excellent curing agent. That is, since it is difficult to liquefy, phenolic curing agents can generally be used only for solid molding materials. Amine-based and acid anhydride-based curing agents are easy to liquefy, but have the following problems. That is, when an amine-based curing agent is used, the hygroscopicity is high because a tertiary amine structure exists in the crosslinked structure of the cured product. When an acid anhydride-based curing agent is used, long-term water resistance is poor because the ester structure in the crosslinked structure of the cured product is easily chemically hydrolyzed, and the acid anhydride group of the curing agent and the epoxy resin The cured product is inferior in adhesiveness because the alcoholic hydroxyl group that contributes to adhesion is less likely to be by-produced by the reaction with the epoxy group.
【０００４】最近の電子部品は高密度化・薄型化の傾向
にあるため、従来のトランスファー成形したパッケージ
から、ベアチップを実装して液状の封止材で封止する、
いわゆるチップオンボード（ＣＯＢ）やＴＡＢ（Ｔａｐ
ｅ Ａｕｔｏｍａｔｅｄ Ｂｏｎｄｉｎｇ）という方式
に代わりつつある。従来の液状封止材としては、粘度面
の制限から、アミン系又は酸無水物系の硬化剤を用いた
エポキシ樹脂組成物が主流を占めている。しかし、アミ
ン系又は酸無水物系の硬化剤を用いたエポキシ樹脂組成
物からなる液状封止材は、前述のフェノールノボラック
樹脂硬化剤を用いたエポキシ樹脂組成物からなるトラン
スファー成形材料に比べて、総合的な信頼性に劣る。そ
のため、液状封止材の信頼性の向上が強く望まれてい
る。そこで、フェノール系硬化剤を用いたエポキシ樹脂
組成物の高粘度という欠点を補うために、溶剤の使用、
アミン系硬化剤又は酸無水物系硬化剤との併用等が行わ
れてきて取扱い性は容易になったが、液状封止材の信頼
性の点では、満足する段階には至っていない。Since recent electronic parts tend to be higher in density and thinner, a bare chip is mounted from a conventional transfer molded package and sealed with a liquid sealing material.
So-called chip-on-board (COB) and TAB (Tap)
e Automated Bonding) is being replaced. As a conventional liquid encapsulating material, an epoxy resin composition using an amine-based or acid anhydride-based curing agent is predominant because of its limited viscosity. However, the liquid encapsulant composed of the epoxy resin composition using the amine-based or acid anhydride-based curing agent is more than the transfer molding material composed of the epoxy resin composition using the phenol novolac resin curing agent described above. Poor overall reliability. Therefore, it is strongly desired to improve the reliability of the liquid sealing material. Therefore, in order to compensate for the drawback of high viscosity of the epoxy resin composition using a phenolic curing agent, the use of a solvent,
Although the handling of the liquid encapsulating material has been facilitated by using it together with an amine-based curing agent or an acid anhydride-based curing agent, the liquid sealing material has not yet reached a satisfactory stage.
【０００５】[0005]
【発明が解決しようとする課題】本発明は上述の事実に
鑑みてなされたもので、その目的とするところは、低粘
度で取扱い性が良く、樹脂封止層をスポット封止で形成
するのに適し、耐湿性及び耐熱性等に優れた信頼性の高
い硬化物を与えることができる液状エポキシ樹脂組成物
を提供することにある。SUMMARY OF THE INVENTION The present invention has been made in view of the above facts, and an object thereof is to form a resin sealing layer by spot sealing with low viscosity and good handleability. A liquid epoxy resin composition that is suitable for use as a liquid epoxy resin composition and that can provide a highly reliable cured product having excellent moisture resistance and heat resistance.
【０００６】[0006]
【課題を解決するための手段】本発明の請求項１に係る
液状エポキシ樹脂組成物は、エポキシ樹脂と硬化剤とを
含有する常温で液状エポキシ樹脂組成物において、上記
硬化剤として下記の一般式で表される化合物を含有す
ることを特徴とする。The liquid epoxy resin composition according to claim 1 of the present invention is a liquid epoxy resin composition containing an epoxy resin and a curing agent at room temperature, and the following general formula is used as the curing agent. It is characterized by containing a compound represented by.
【０００７】[0007]
【化８】 Embedded image
【０００８】本発明の請求項２に係る液状エポキシ樹脂
組成物は、エポキシ樹脂と硬化剤とを含有する常温で液
状エポキシ樹脂組成物において、上記硬化剤として下記
の一般式で表される化合物を含有することを特徴とす
る。A liquid epoxy resin composition according to a second aspect of the present invention is a liquid epoxy resin composition containing an epoxy resin and a curing agent at room temperature, which comprises a compound represented by the following general formula as the curing agent. It is characterized by containing.
【０００９】[0009]
【化９】 [Chemical 9]
【００１０】本発明の請求項３に係る液状エポキシ樹脂
組成物は、エポキシ樹脂と硬化剤とを含有する常温で液
状エポキシ樹脂組成物において、上記硬化剤として下記
の一般式で表される化合物を含有することを特徴とす
る。A liquid epoxy resin composition according to a third aspect of the present invention is a liquid epoxy resin composition containing an epoxy resin and a curing agent at room temperature, which comprises a compound represented by the following general formula as the curing agent. It is characterized by containing.
【００１１】[0011]
【化１０】 [Chemical 10]
【００１２】本発明の請求項４に係る液状エポキシ樹脂
組成物は、エポキシ樹脂と硬化剤とを含有する常温で液
状エポキシ樹脂組成物において、上記硬化剤として下記
の一般式で表される化合物を含有することを特徴とす
る。A liquid epoxy resin composition according to a fourth aspect of the present invention is a liquid epoxy resin composition containing an epoxy resin and a curing agent at room temperature, which comprises a compound represented by the following general formula as the curing agent. It is characterized by containing.
【００１３】[0013]
【化１１】 [Chemical 11]
【００１４】本発明の請求項５に係る液状エポキシ樹脂
組成物は、エポキシ樹脂と硬化剤とを含有する常温で液
状エポキシ樹脂組成物において、上記硬化剤として下記
の一般式で表される化合物を含有することを特徴とす
る。A liquid epoxy resin composition according to a fifth aspect of the present invention is a liquid epoxy resin composition containing an epoxy resin and a curing agent at room temperature, which comprises a compound represented by the following general formula as the curing agent. It is characterized by containing.
【００１５】[0015]
【化１２】 [Chemical 12]
【００１６】本発明の請求項６に係る液状エポキシ樹脂
組成物は、エポキシ樹脂と硬化剤とを含有する常温で液
状エポキシ樹脂組成物において、上記硬化剤として下記
の一般式で表される化合物を含有することを特徴とす
る。A liquid epoxy resin composition according to a sixth aspect of the present invention is a liquid epoxy resin composition containing an epoxy resin and a curing agent at room temperature, which comprises a compound represented by the following general formula as the curing agent. It is characterized by containing.
【００１７】[0017]
【化１３】 [Chemical 13]
【００１８】本発明の請求項７に係る液状エポキシ樹脂
組成物は、エポキシ樹脂と硬化剤とを含有する常温で液
状エポキシ樹脂組成物において、上記硬化剤として下記
の一般式で表される化合物を含有することを特徴とす
る。A liquid epoxy resin composition according to a seventh aspect of the present invention is a liquid epoxy resin composition containing an epoxy resin and a curing agent at room temperature, which comprises a compound represented by the following general formula as the curing agent. It is characterized by containing.
【００１９】[0019]
【化１４】 Embedded image
【００２０】以下、本発明を詳しく説明する。本発明の
液状エポキシ樹脂組成物を構成するマトリックス樹脂と
しては、液状エポキシ樹脂を使用する。この液状エポキ
シ樹脂は、１分子中に２個以上のエポキシ基を有するエ
ポキシ樹脂であって、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、ノボラッ
ク型エポキシ樹脂、ハロゲン化エポキシ樹脂、グリシジ
ルエステル型エポキシ樹脂、脂環式エポキシ樹脂、ナフ
タレン型エポキシ樹脂、ビフェニル型エポキシ樹脂等が
用いられる。The present invention will be described in detail below. A liquid epoxy resin is used as the matrix resin constituting the liquid epoxy resin composition of the present invention. This liquid epoxy resin is an epoxy resin having two or more epoxy groups in one molecule and includes, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, halogenated epoxy resin, glycidyl ester. Type epoxy resin, alicyclic epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin and the like are used.
【００２１】硬化剤としては、上記の一般式〜一般式
で表される化合物を使用することが必須である。上記
の一般式〜一般式で表される化合物は、それぞれ、
アリル化されていない多価フェノールから合成が可能で
ある。これらのアリル化されていない多価フェノール
は、高融点の固体であり、フェノールノボラック樹脂と
同様に、硬化剤として用いてもエポキシ樹脂組成物に良
好な流動性を与えることができない。しかし、上記のア
リル化されていない多価フェノールをアリル化すること
により、常温で液状を有するアリル化された多価フェノ
ールになるか、固体であっても融点が大幅に低下したア
リル化された多価フェノールになる。これらのアリル化
された多価フェノールを硬化剤として用いることによ
り、常温で低粘度の液状エポキシ樹脂組成物を得ること
ができる。As the curing agent, it is essential to use the compounds represented by the above general formulas to general formulas. The compounds represented by the above general formula to the general formula, respectively,
It can be synthesized from non-allylated polyphenols. These non-allylated polyhydric phenols are solids having a high melting point and, like the phenol novolac resin, cannot give good flowability to the epoxy resin composition even when used as a curing agent. However, by allylating the above non-allylated polyhydric phenol, it becomes an allylated polyhydric phenol that is liquid at room temperature, or even if it is a solid, the melting point is drastically reduced. Become a polyhydric phenol. A liquid epoxy resin composition having a low viscosity at room temperature can be obtained by using these allylated polyphenols as a curing agent.
【００２２】硬化剤としては、必須成分である上記の一
般式〜一般式で表される化合物以外に、特性を損な
わない範囲内で他の硬化剤と併用してもよい。As the curing agent, in addition to the compounds represented by the above-mentioned general formulas to general formulas, which are essential components, other curing agents may be used in combination within a range that does not impair the characteristics.
【００２３】硬化促進剤としては、リン系、３級アミン
系の硬化促進剤等が用いられ、特に限定するものではな
い。充填剤としては、シリカ等の無機充填剤等を用い、
必要に応じて、充填剤の表面をカップリング剤で表面処
理をすることができる。さらに、必要に応じて、反応希
釈剤、難燃剤、顔料、染料、可撓性付与剤及び離型剤等
を添加することができる。As the curing accelerator, phosphorus-based and tertiary amine-based curing accelerators are used, and the curing accelerator is not particularly limited. As the filler, an inorganic filler such as silica is used,
If necessary, the surface of the filler can be surface treated with a coupling agent. Furthermore, if necessary, a reaction diluent, a flame retardant, a pigment, a dye, a flexibility-imparting agent, a release agent, etc. can be added.
【００２４】[0024]
【実施例】以下、本発明を実施例により具体的に説明す
る。EXAMPLES The present invention will be specifically described below with reference to examples.
【００２５】まず、上記の一般式〜一般式で表され
る化合物の合成例を説明する。 （合成例）表１のそれぞれの配合量をグラム（ｇ）で表
した配合表に基づいて材料を配合し、下記の一般式
〔ｂ〕〜一般式〔ｇ〕で表される化合物である原料フェ
ノールの表１に示すそれぞれの配合量と脱水アセトン２
００ｇとを１リットル四つ口フラスコに入れ溶解させ、
表１に示す臭化アリルの配合量と同モル数の炭酸カリウ
ムとを加えた後、室温（１０〜３０℃程度）で表１に示
す配合量の臭化アリルを２０分間で滴下し、５時間アセ
トンを還流し反応させた。First, synthetic examples of the compounds represented by the above general formulas to general formulas will be described. (Synthesis Example) Raw materials that are compounds represented by the following general formula [b] to general formula [g] by blending materials based on the blending table in which each blending amount in Table 1 is expressed in grams (g). Each blending amount of phenol shown in Table 1 and dehydrated acetone 2
00g and 1 liter four-necked flask to dissolve,
After the amount of allyl bromide shown in Table 1 and the same molar number of potassium carbonate were added, the amount of allyl bromide shown in Table 1 was added dropwise at room temperature (about 10 to 30 ° C.) over 20 minutes, and 5 Acetone was refluxed for a reaction time to react.
【００２６】[0026]
【化１５】 [Chemical 15]
【００２７】[0027]
【化１６】 Embedded image
【００２８】[0028]
【化１７】 [Chemical 17]
【００２９】[0029]
【化１８】 Embedded image
【００３０】[0030]
【化１９】 [Chemical 19]
【００３１】[0031]
【化２０】 Embedded image
【００３２】なお、上記の一般式〔ｂ〕〜一般式〔ｇ〕
で表される化合物は、全て固体であり、融点がそれぞ
れ、１２５℃、１２３℃、１７７℃、１７８℃、２３２
℃、２２９℃であり、本州化学工業社から入手した。The above general formula [b] to general formula [g]
The compounds represented by are all solids and have melting points of 125 ° C., 123 ° C., 177 ° C., 178 ° C., and 232, respectively.
C., 229.degree. C., obtained from Honshu Chemical Industry Co., Ltd.
【００３３】反応終了後、１リットルビーカーに移し、
脱イオン水を５００ミリリットル加え、トルエン２００
ミリリットルで２回抽出し、トルエン溶液を１０％水酸
化ナトリウム水溶液１５０ミリリットルで３回、イオン
交換水２００ミリリットルで３回洗浄し、次いで、トル
エンを減圧留去し、上記の一般式〔ｂ〕〜一般式〔ｇ〕
で表される化合物である原料フェノールの、それぞれの
アリルエーテル化合物を得た。After the reaction, transfer to a 1 liter beaker,
Add 500 milliliters of deionized water and add toluene 200
It was extracted twice with milliliters, the toluene solution was washed three times with 150 milliliters of a 10% aqueous sodium hydroxide solution and three times with 200 milliliters of deionized water, and then toluene was distilled off under reduced pressure to obtain the above-mentioned general formula [b]- General formula [g]
Each allyl ether compound of the raw material phenol, which is a compound represented by
【００３４】これらのアリルエーテル化合物８０ｇと
Ｎ，Ｎ−ジエチルアニリン８０ｇとを２００ミリリット
ルナス型フラスコに入れ、１９０℃１９時間でクライゼ
ン転移させた。転移反応終了後、１０％水酸化ナトリウ
ム水溶液２００ミリリットルで２回抽出し、３３％塩酸
で中和し、さらにトルエン２００ミリリットルで２回抽
出し、イオン交換水２００ミリリットルで６回洗浄し、
最後に、トルエンを減圧留去し、目的生成物である上記
の一般式〜一般式で表される化合物を得た。なお、
これらの合成品で、一般式で表される化合物の粘度
は、８２０センチポイズ、一般式で表される化合物の
粘度は、４３００センチポイズ、一般式で表される化
合物の融点は、１２０℃、一般式で表される化合物の
融点は、１００℃、一般式で表される化合物の融点
は、１３０℃、一般式で表される化合物は、粘稠な液
体であった。80 g of these allyl ether compounds and 80 g of N, N-diethylaniline were placed in a 200 ml eggplant type flask, and the Claisen transfer was carried out at 190 ° C. for 19 hours. After completion of the transfer reaction, it was extracted twice with 200 ml of 10% aqueous sodium hydroxide solution, neutralized with 33% hydrochloric acid, further extracted twice with 200 ml of toluene, and washed 6 times with 200 ml of ion-exchanged water,
Finally, toluene was distilled off under reduced pressure to obtain the target product, a compound represented by the above general formula to general formula. In addition,
In these synthetic products, the viscosity of the compound represented by the general formula is 820 centipoise, the viscosity of the compound represented by the general formula is 4300 centipoise, the melting point of the compound represented by the general formula is 120 ° C., the general formula The melting point of the compound represented by was 100 ° C., the melting point of the compound represented by the general formula was 130 ° C., and the compound represented by the general formula was a viscous liquid.
【００３５】以後、上記の一般式で表される化合物を
化合物Ａ、上記の一般式で表される化合物を化合物
Ｂ、上記の一般式で表される化合物を化合物Ｃ、上記
の一般式で表される化合物を化合物Ｄ、上記の一般式
で表される化合物を化合物Ｅ、上記の一般式で表さ
れる化合物を化合物Ｆ、上記の一般式で表される化合
物を化合物Ｇ、上記の一般式〔ｂ〕で表される化合物を
化合物ｂ、上記の一般式〔ｃ〕で表される化合物を化合
物ｃ、上記の一般式〔ｄ〕で表される化合物を化合物
ｄ、上記の一般式〔ｅ〕で表される化合物を化合物ｅ、
上記の一般式〔ｆ〕で表される化合物を化合物ｆ、上記
の一般式〔ｇ〕で表される化合物を化合物ｇと称する。Hereinafter, the compound represented by the above general formula is represented by compound A, the compound represented by the above general formula is represented by compound B, the compound represented by the above general formula is represented by compound C, and the above general formula is represented. The compound represented by the above general formula is compound E, the compound represented by the above general formula is compound F, the compound represented by the above general formula is compound G, the above general formula The compound represented by [b] is a compound b, the compound represented by the above general formula [c] is a compound c, the compound represented by the above general formula [d] is a compound d, the above general formula [e] ] The compound represented by
The compound represented by the above general formula [f] is referred to as a compound f, and the compound represented by the above general formula [g] is referred to as a compound g.
【００３６】[0036]
【表１】 [Table 1]
【００３７】以下、本発明を実施例により、比較例と比
較しながら具体的に説明する。 （実施例１〜実施例１２）硬化剤として化合物Ａ〜化合
物Ｇを用いた。化合物Ａは、三井東圧化学社製のＰＦ０
１２を使用し、化合物Ｂ〜化合物Ｇは、上記の合成例で
得られたものを使用した。エポキシ樹脂としては、ビス
フェノールＡ型エポキシ樹脂（ＹＤ８１２５：東都化成
社製）とフェノールノボラック型エポキシ樹脂（ＹＤＰ
Ｎ６３８Ｐ：東都化成社製）と３官能タイプエポキシ樹
脂（Ｅ１０３２Ｈ：油化シェルエポキシ社製）とを用い
た。Hereinafter, the present invention will be specifically described with reference to Examples and comparison with Comparative Examples. (Examples 1 to 12) Compounds A to G were used as curing agents. Compound A is PF0 manufactured by Mitsui Toatsu Chemicals, Inc.
12 was used, and the compounds B to G used were those obtained in the above-mentioned synthesis example. As the epoxy resin, bisphenol A type epoxy resin (YD8125: manufactured by Tohto Kasei Co., Ltd.) and phenol novolac type epoxy resin (YDP
N638P: manufactured by Tohto Kasei Co., Ltd. and a trifunctional epoxy resin (E1032H: manufactured by Yuka Shell Epoxy Co., Ltd.) were used.
【００３８】表２に示したそれぞれの配合量を重量部で
表した配合に基づいて、エポキシ樹脂と硬化剤とを混合
し、この混合物を１２０℃に加熱して均一に溶解した。
この溶解物を５０〜６０℃に冷却後、硬化促進剤とし
て、１，８ジアザ−ビシクロ−（５，４，０）ウンデセ
ン−７〔ＤＢＵ〕のオクチル酸塩（ＳＡ１０２：サンア
プロ株式会社製）を液状エポキシ樹脂組成物の全量に対
して１重量％添加し、均一に混合して液状エポキシ樹脂
組成物を得た。この液状エポキシ樹脂組成物の２５℃で
の粘度を回転粘度計を用いて測定するとともに、２枚の
ガラス板の間に注型し、１５０℃８時間加熱することに
よって、それぞれの硬化物を得た。これらの硬化物を１
２１℃２気圧ＰＣＴ条件で１０００時間処理し、その処
理品の性状を観察した。ＰＣＴ１０００時間処理後に溶
解、粘着性を生じたものを不可、異常が認められなかっ
たものを良好とし、これらの結果を表２に示した。An epoxy resin and a curing agent were mixed based on the composition shown in parts by weight in Table 2 and the mixture was heated to 120 ° C. and uniformly dissolved.
After cooling this melt to 50 to 60 ° C., 1,8 diaza-bicyclo- (5,4,0) undecene-7 [DBU] octylate (SA102: manufactured by San-Apro Co., Ltd.) was used as a curing accelerator. 1 wt% was added to the total amount of the liquid epoxy resin composition and mixed uniformly to obtain a liquid epoxy resin composition. The viscosity of this liquid epoxy resin composition at 25 ° C. was measured using a rotational viscometer, and the liquid epoxy resin composition was cast between two glass plates and heated at 150 ° C. for 8 hours to obtain each cured product. 1 of these cured products
Treatment was performed under the conditions of 21 ° C. and 2 atm PCT for 1000 hours, and the properties of the treated product were observed. After the PCT treatment for 1000 hours, those that were dissolved and tacky were disapproved, and those that did not show any abnormality were regarded as good, and these results are shown in Table 2.
【００３９】[0039]
【表２】 [Table 2]
【００４０】（比較例１〜比較例９）化合物Ａのアリル
化されていない化合物であるビスフェノールＡ（試薬）
を化合物ａと称する。比較例１〜比較例７については、
実施例１〜実施例７において、硬化剤として化合物Ａ〜
化合物Ｇの代わりに、化合物Ａ〜化合物Ｇのアリル化さ
れていない化合物である化合物ａ〜化合物ｇをそれぞれ
用いた以外は、実施例１〜実施例７と同様にして、エポ
キシ樹脂組成物及び硬化物を得て、エポキシ樹脂組成物
の２５℃での粘度の測定及び硬化物のＰＣＴ処理を行っ
た。比較例８については、硬化剤としてフェノールノボ
ラック（ＰＳＭ６２００：群栄化学社製）を、比較例９
については、硬化剤として酸無水物（Ｂ−６５０：大日
本インキ社製）を表３に示したそれぞれの配合量を重量
部で表した配合で用いた以外は、実施例１〜実施例７と
同様にして、エポキシ樹脂組成物及び硬化物を得て、エ
ポキシ樹脂組成物の２５℃での粘度の測定及び硬化物の
ＰＣＴ処理を行った。これらの結果を表３に示した。Comparative Examples 1 to 9 Bisphenol A (reagent) which is a non-allylated compound of Compound A
Is referred to as compound a. Regarding Comparative Examples 1 to 7,
In Examples 1 to 7, compound A as a curing agent was used.
Epoxy resin compositions and curing were carried out in the same manner as in Examples 1 to 7 except that compounds a to compound g, which are non-allylated compounds of compounds A to G, were used instead of compound G, respectively. After obtaining the product, the viscosity of the epoxy resin composition at 25 ° C. was measured and the cured product was subjected to PCT treatment. In Comparative Example 8, phenol novolac (PSM6200: manufactured by Gunei Chemical Co., Ltd.) was used as a curing agent, and Comparative Example 9 was used.
About Example 1 to Example 7 except that an acid anhydride (B-650: manufactured by Dainippon Ink and Chemicals, Inc.) was used as a curing agent in a composition expressed in parts by weight for each compounding amount shown in Table 3. In the same manner as above, an epoxy resin composition and a cured product were obtained, the viscosity of the epoxy resin composition at 25 ° C. was measured, and the cured product was subjected to PCT treatment. The results are shown in Table 3.
【００４１】[0041]
【表３】 [Table 3]
【００４２】上記表２及び表３に示す結果により、比較
例１〜比較例９のエポキシ樹脂組成物の２５℃での粘度
については、比較例９のエポキシ樹脂組成物以外は、１
万ポイズ（Ｐ）を越えて粘稠物あるいは固体である。比
較例９では、硬化物のＰＣＴ処理後に溶解、粘着性を生
じて不可である。これに対して実施例１〜実施例１２で
は、液状エポキシ樹脂組成物の２５℃での粘度が、３０
Ｐ〜７０００Ｐであり、ほとんどが、低粘度で取扱い性
が良く、樹脂封止層をスポット封止で形成するのに適
し、ＰＣＴ処理という苛酷な条件下であっても安定な硬
化物を維持し、耐湿性及び耐熱性等に優れた信頼性の高
い硬化物を与えることができる液状エポキシ樹脂組成物
であることが確認できた。From the results shown in Tables 2 and 3, the viscosities of the epoxy resin compositions of Comparative Examples 1 to 9 at 25 ° C. were 1 except for the epoxy resin compositions of Comparative Example 9.
It is a viscous material or solid that exceeds 10,000 poise (P). Comparative Example 9 is not possible because the cured product is dissolved and tacky after PCT treatment. On the other hand, in Examples 1 to 12, the viscosity of the liquid epoxy resin composition at 25 ° C. was 30
P to 7,000 P, most of them have low viscosity and are easy to handle, and are suitable for forming a resin sealing layer by spot sealing, and maintain a stable cured product even under the severe condition of PCT treatment. It was confirmed that the liquid epoxy resin composition was able to give a highly reliable cured product having excellent moisture resistance and heat resistance.
【００４３】[0043]
【発明の効果】本発明の請求項１〜請求項７に係る液状
エポキシ樹脂組成物は上記のように構成されているの
で、本発明の請求項１〜請求項７に係る液状エポキシ樹
脂組成物によると、低粘度で取扱い性が良く、樹脂封止
層をスポット封止で形成するのに適し、耐湿性及び耐熱
性等に優れた信頼性の高い硬化物を与えることができる
液状エポキシ樹脂組成物が得られる。Since the liquid epoxy resin compositions according to claims 1 to 7 of the present invention are configured as described above, the liquid epoxy resin compositions according to claims 1 to 7 of the present invention. According to the above, a liquid epoxy resin composition having a low viscosity, good handleability, suitable for forming a resin encapsulating layer by spot encapsulation, and capable of giving a highly reliable cured product excellent in moisture resistance, heat resistance and the like. The thing is obtained.
Claims (7)
で液状エポキシ樹脂組成物において、上記硬化剤として
下記の一般式で表される化合物を含有することを特徴
とする液状エポキシ樹脂組成物。 【化１】 1. A liquid epoxy resin composition containing an epoxy resin and a curing agent at room temperature, which contains a compound represented by the following general formula as the curing agent. Embedded image
で液状エポキシ樹脂組成物において、上記硬化剤として
下記の一般式で表される化合物を含有することを特徴
とする液状エポキシ樹脂組成物。 【化２】 2. A liquid epoxy resin composition containing an epoxy resin and a curing agent at room temperature, which contains a compound represented by the following general formula as the curing agent. Embedded image
で液状エポキシ樹脂組成物において、上記硬化剤として
下記の一般式で表される化合物を含有することを特徴
とする液状エポキシ樹脂組成物。 【化３】 3. A liquid epoxy resin composition containing an epoxy resin and a curing agent at room temperature, which contains a compound represented by the following general formula as the curing agent. Embedded image
で液状エポキシ樹脂組成物において、上記硬化剤として
下記の一般式で表される化合物を含有することを特徴
とする液状エポキシ樹脂組成物。 【化４】 4. A liquid epoxy resin composition containing an epoxy resin and a curing agent at room temperature, which contains a compound represented by the following general formula as the curing agent. [Chemical 4]
で液状エポキシ樹脂組成物において、上記硬化剤として
下記の一般式で表される化合物を含有することを特徴
とする液状エポキシ樹脂組成物。 【化５】 5. A liquid epoxy resin composition containing an epoxy resin and a curing agent at room temperature, which contains a compound represented by the following general formula as the curing agent. Embedded image
で液状エポキシ樹脂組成物において、上記硬化剤として
下記の一般式で表される化合物を含有することを特徴
とする液状エポキシ樹脂組成物。 【化６】 6. A liquid epoxy resin composition containing an epoxy resin and a curing agent at room temperature, which contains a compound represented by the following general formula as the curing agent. [Chemical 6]
で液状エポキシ樹脂組成物において、上記硬化剤として
下記の一般式で表される化合物を含有することを特徴
とする液状エポキシ樹脂組成物。 【化７】 7. A liquid epoxy resin composition containing an epoxy resin and a curing agent at room temperature, which contains a compound represented by the following general formula as the curing agent. [Chemical 7]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14837994A JPH0812745A (en) | 1994-06-29 | 1994-06-29 | Liquid epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14837994A JPH0812745A (en) | 1994-06-29 | 1994-06-29 | Liquid epoxy resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0812745A true JPH0812745A (en) | 1996-01-16 |
Family
ID=15451452
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14837994A Withdrawn JPH0812745A (en) | 1994-06-29 | 1994-06-29 | Liquid epoxy resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0812745A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1112443A (en) * | 1997-06-25 | 1999-01-19 | Matsushita Electric Works Ltd | Liquid epoxy resin composition and semiconductor apparatus |
| JP2001106767A (en) * | 1999-10-07 | 2001-04-17 | Sumitomo Bakelite Co Ltd | Resin paste for semiconductor and semiconductor device using the same |
| JP2001106873A (en) * | 1999-10-07 | 2001-04-17 | Sumitomo Bakelite Co Ltd | Resin paste for semiconductor and semiconductor device using the same |
| JP2001106874A (en) * | 1999-10-07 | 2001-04-17 | Sumitomo Bakelite Co Ltd | Resin paste for semiconductor and semiconductor device using the same |
| JP2002194066A (en) * | 2000-12-27 | 2002-07-10 | Hitachi Chem Co Ltd | Liquid epoxy-resin composition for encapsulating and electronic parts device |
| JP2002194065A (en) * | 2000-12-27 | 2002-07-10 | Hitachi Chem Co Ltd | Liquid epoxy-resin composition for encapsulating and electronic parts device |
| EP2316810A1 (en) | 2009-10-06 | 2011-05-04 | Shin-Etsu Chemical Co., Ltd. | Alcoholic hydroxyl-containing compounds and making method |
-
1994
- 1994-06-29 JP JP14837994A patent/JPH0812745A/en not_active Withdrawn
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1112443A (en) * | 1997-06-25 | 1999-01-19 | Matsushita Electric Works Ltd | Liquid epoxy resin composition and semiconductor apparatus |
| JP2001106767A (en) * | 1999-10-07 | 2001-04-17 | Sumitomo Bakelite Co Ltd | Resin paste for semiconductor and semiconductor device using the same |
| JP2001106873A (en) * | 1999-10-07 | 2001-04-17 | Sumitomo Bakelite Co Ltd | Resin paste for semiconductor and semiconductor device using the same |
| JP2001106874A (en) * | 1999-10-07 | 2001-04-17 | Sumitomo Bakelite Co Ltd | Resin paste for semiconductor and semiconductor device using the same |
| JP2002194066A (en) * | 2000-12-27 | 2002-07-10 | Hitachi Chem Co Ltd | Liquid epoxy-resin composition for encapsulating and electronic parts device |
| JP2002194065A (en) * | 2000-12-27 | 2002-07-10 | Hitachi Chem Co Ltd | Liquid epoxy-resin composition for encapsulating and electronic parts device |
| EP2316810A1 (en) | 2009-10-06 | 2011-05-04 | Shin-Etsu Chemical Co., Ltd. | Alcoholic hydroxyl-containing compounds and making method |
| US8378148B2 (en) | 2009-10-06 | 2013-02-19 | Shin-Etsu Chemical Co., Ltd. | Alcoholic hydroxyl-containing compounds and making method |
| TWI469960B (en) * | 2009-10-06 | 2015-01-21 | Shinetsu Chemical Co | Compounds containing alcoholic hydroxyl groups and methods for their manufacture |
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| Date | Code | Title | Description |
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| A300 | Withdrawal of application because of no request for examination |
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