JP2003020326A - Curing accelerator for epoxy resin and liquid epoxy resin composition - Google Patents
Curing accelerator for epoxy resin and liquid epoxy resin compositionInfo
- Publication number
- JP2003020326A JP2003020326A JP2001210392A JP2001210392A JP2003020326A JP 2003020326 A JP2003020326 A JP 2003020326A JP 2001210392 A JP2001210392 A JP 2001210392A JP 2001210392 A JP2001210392 A JP 2001210392A JP 2003020326 A JP2003020326 A JP 2003020326A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- methylphenyl
- curing accelerator
- resin composition
- curing
- 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.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、エポキシ樹脂の硬
化促進剤として有用なテトラフェニルホスホニウムテト
ラ（４−メチルフェニル）ボレートを提供することに関
する。また、本発明は電気、電子部品、半導体チップ等
の絶縁封止、注型において速硬化性と貯蔵安定性のバラ
ンスに優れる液状エポキシ樹脂組成物の提供にも関す
る。TECHNICAL FIELD The present invention relates to providing tetraphenylphosphonium tetra (4-methylphenyl) borate useful as a curing accelerator for epoxy resins. The present invention also relates to the provision of a liquid epoxy resin composition which is excellent in the balance between quick-curing property and storage stability in insulating sealing of electric, electronic parts, semiconductor chips and the like, and casting.
【０００２】[0002]
【従来の技術】エポキシ樹脂組成物は、優れた機械的、
化学的、電気的性質が得られるために接着剤、塗料、注
型材料の形態でコイル、コンデンサーなどの各種の電気
部品や半導体素子、集積回路の絶縁封止に広く使用され
ている。2. Description of the Related Art Epoxy resin compositions have excellent mechanical properties,
Since it has chemical and electrical properties, it is widely used in the form of adhesives, paints, and casting materials for various electrical parts such as coils and capacitors, semiconductor elements, and insulating encapsulation of integrated circuits.
【０００３】近年、エレクトロニクスの発展に伴い、こ
れら電子機器の高性能化の要求が高く、ＴＣＰ（テープ
キャリアーパッケージ）、ＣＳＰ（チップサイズパッケ
ージ）等の実装の場面では従来の粉末固形エポキシ樹脂
を用いたトランスファー成形に代わり、一般的に樹脂粘
度が低く流動性の高い液状エポキシ樹脂組成物が用いら
れている。そして、この液状エポキシ樹脂組成物の構成
成分であるエポキシ樹脂硬化促進剤として、一般にトリ
フェニルホスフィンやイミダゾール類が広く知られてい
る。しかしながら、それらは貯蔵安定性に劣るため、液
状エポキシ樹脂組成物の調合後、短時間で使用するか、
または冷蔵保存しなければならないという問題がある。
したがって、室温での貯蔵安定性に優れ、実際の硬化温
度では短時間に硬化しうる潜在性硬化促進剤を使用した
液状エポキシ樹脂組成物の開発が行なわれている。In recent years, with the development of electronics, there is a strong demand for higher performance of these electronic devices, and conventional powder solid epoxy resin is used for mounting TCP (tape carrier package), CSP (chip size package) and the like. In place of the transfer molding described above, a liquid epoxy resin composition having a low resin viscosity and a high fluidity is generally used. Then, triphenylphosphine and imidazoles are generally widely known as an epoxy resin curing accelerator which is a constituent component of the liquid epoxy resin composition. However, since they are inferior in storage stability, they are used in a short time after preparation of the liquid epoxy resin composition, or
Or there is a problem that it must be kept refrigerated.
Therefore, a liquid epoxy resin composition using a latent curing accelerator which has excellent storage stability at room temperature and can be cured in a short time at an actual curing temperature has been developed.
【０００４】その一つとして、特開平８−１６５３３
１号公報には、硬化性と貯蔵安定性のバランスが優れた
エポキシ樹脂組成物を与えるために、硬化促進剤として
次式（Ａ）で表わされるテトラフェニルホスホニウムテ
トラ（メチルフェニル）ボレートを用いることが記載さ
れている。As one of them, Japanese Patent Laid-Open No. 16533/1996
JP-A No. 1-1999 discloses the use of tetraphenylphosphonium tetra (methylphenyl) borate represented by the following formula (A) as a curing accelerator in order to provide an epoxy resin composition having an excellent balance between curability and storage stability. Is listed.
【化２】 [Chemical 2]
【０００５】しかしながら、ボレートに結合しているフ
ェニル基のメチル置換基の位置について具体的な記述が
なく、また液状エポキシ樹脂組成物への適用の可能性に
ついての記載もない。However, there is no specific description about the position of the methyl substituent of the phenyl group bonded to borate, and there is no description about the possibility of application to a liquid epoxy resin composition.
【０００６】また、特開平８−１６９８９２号公報に
は、上記一般式（Ａ）で表わされるテトラフェニルホス
ホニウムテトラ（メチルフェニル）ボレートが工業用防
腐防黴剤として有用であることが記載されている。しか
し、エポキシ樹脂硬化促進剤としての可能性については
示唆されていない。Further, JP-A-8-169892 describes that tetraphenylphosphonium tetra (methylphenyl) borate represented by the above general formula (A) is useful as an industrial antiseptic / antifungal agent. . However, the possibility as an epoxy resin curing accelerator has not been suggested.
【０００７】[0007]
【発明が解決しようとする課題】上記の事情にあって、
速硬化性と貯蔵安定性とのバランスに優れた新しい液状
エポキシ樹脂組成物の開発が要望されている。[Problems to be Solved by the Invention] Under the above circumstances,
There is a demand for the development of a new liquid epoxy resin composition having an excellent balance between fast curing property and storage stability.
【０００８】本発明は、このような要望に合致した速硬
化性を有するエポキシ樹脂硬化促進剤を提供することを
目的としており、また速硬化性と貯蔵安定性とのバラン
スに優れた新しい液状エポキシ樹脂組成物を提供するこ
とを目的とする。An object of the present invention is to provide an epoxy resin curing accelerator having a quick-curing property which meets such a demand, and a new liquid epoxy having an excellent balance between the fast-curing property and the storage stability. An object is to provide a resin composition.
【０００９】[0009]
【課題を解決するための手段】このような状況に鑑み、
本発明者らは上記の目的を達成しようと鋭意研究を進め
てきた。その結果、封止材として常用される硬化性エポ
キシ樹脂に対して配合される硬化剤と硬化促進剤との組
み合わせにおいて、硬化剤として酸無水物系の硬化剤を
選択しかつ硬化促進剤として上記の特開平８−１６５
３３１号公報に記載されているテトラフェニルホスホニ
ウムテトラ（メチルフェニル）ボレート化合物類の中か
ら、式（１）で示される特定のテトラフェニルホスホニ
ウムテトラ（４−メチルフェニル）ボレート化合物を選
択し、これを硬化性エポキシ樹脂に対して配合すると、
速硬化性と保存安定性とのバランスに優れた液状エポキ
シ樹脂組成物が提供できることを、本発明者らは見出し
た。また、式（１）で示される特定のテトラフェニルホ
スホニウムテトラ（４−メチルフェニル）ボレート化合
物は、酸無水物系の硬化剤、特にヒドロフタル酸無水物
系の硬化剤中に高い溶解性（相溶性）を示すことも見出
された。これらの知見に基づいて、本発明は完成された
のである。[Means for Solving the Problems] In view of such a situation,
The inventors of the present invention have conducted earnest research to achieve the above object. As a result, in the combination of the curing agent and the curing accelerator compounded with the curable epoxy resin that is commonly used as the encapsulant, an acid anhydride-based curing agent is selected as the curing agent and the above curing accelerator is used. Japanese Patent Laid-Open No. 8-165
From the tetraphenylphosphonium tetra (methylphenyl) borate compounds described in Japanese Patent No. 331, a specific tetraphenylphosphonium tetra (4-methylphenyl) borate compound represented by the formula (1) is selected. When mixed with a curable epoxy resin,
The present inventors have found that it is possible to provide a liquid epoxy resin composition having an excellent balance between fast curing property and storage stability. Further, the specific tetraphenylphosphonium tetra (4-methylphenyl) borate compound represented by the formula (1) has high solubility (compatibility) in an acid anhydride-based curing agent, particularly a hydrophthalic anhydride-based curing agent. ) Has also been found. The present invention has been completed based on these findings.
【００１０】したがって、第１の本発明においては次式
（１）で示されるテトラフェニルテトラ（４−メチルフ
ェニル）ボレートを有効成分するエポキシ樹脂硬化促進
剤が提供される。Therefore, in the first aspect of the present invention, an epoxy resin curing accelerator containing tetraphenyltetra (4-methylphenyl) borate represented by the following formula (1) as an active ingredient is provided.
【化３】 [Chemical 3]
【００１１】第１の本発明によるエポキシ樹脂硬化促進
剤は、テトラフェニルホスホニウムテトラ（メチルフェ
ニル）ボレート類の中で、特定の式（１）の化合物、す
なわちボレートのフェニル基のメチル基が４−位に結合
しているテトラフェニルホスホニウムテトラ（４−メチ
ルフェニル）ボレートを有効成分として含有することが
必須である。Among the tetraphenylphosphonium tetra (methylphenyl) borates, the epoxy resin curing accelerator according to the first aspect of the present invention is a compound of the specific formula (1), that is, the methyl group of the phenyl group of borate is 4- It is essential to contain tetraphenylphosphonium tetra (4-methylphenyl) borate bonded to the position as an active ingredient.
【００１２】メチル基が３−位に結合しているテトラフ
ェニルホスホニウム（テトラ−３−メチルフェニル）ボ
レート化合物をエポキシ樹脂硬化促進剤として用いた場
合は硬化性が劣り、メチル基が２−位に結合しているテ
トラフェニルホスホニウム（テトラ−２−メチルフェニ
ル）ボレート化合物は、実際的には化合物そのものの合
成が困難である。When a tetraphenylphosphonium (tetra-3-methylphenyl) borate compound having a methyl group bonded at the 3-position is used as an epoxy resin curing accelerator, the curability is poor and the methyl group is at the 2-position. The bound tetraphenylphosphonium (tetra-2-methylphenyl) borate compound is practically difficult to synthesize.
【００１３】なお、式（１）のテトラフェニルホスホニ
ウム（テトラ−４−メチルフェニル）ボレート化合物
は、そのままエポキシ樹脂硬化促進剤として使用できる
が、硬化特性を損なわない範囲で必要により他の公知の
硬化促進剤、例えばトリフェニルホスフィン等を含有し
てもよい。The tetraphenylphosphonium (tetra-4-methylphenyl) borate compound of the formula (1) can be used as it is as an epoxy resin curing accelerator, but other known curing agents can be used as needed as long as the curing characteristics are not impaired. Accelerators such as triphenylphosphine may also be included.
【００１４】第２の本発明においては、第１の本発明に
係る式（１）で示されるエポキシ樹脂硬化促進剤（Ｃ）
と、硬化性エポキシ樹脂（Ａ）と、該エポキシ樹脂の硬
化を起こさせる作用を持つ酸無水物系硬化剤（Ｂ）と
を、組成物の構成成分として含有することを特徴とす
る、液状エポキシ樹脂組成物が提供される。In the second aspect of the present invention, the epoxy resin curing accelerator (C) represented by the formula (1) according to the first aspect of the present invention.
And a curable epoxy resin (A) and an acid anhydride-based curing agent (B) having a function of causing curing of the epoxy resin as constituent components of the composition. A resin composition is provided.
【００１５】第２の本発明による液状エポキシ樹脂組成
物中に（Ａ）成分として配合される硬化性エポキシ樹脂
（Ａ）はビスフェノールＡ型エポキシ樹脂、ビスフェノ
ールＦ型エポキシ樹脂または脂環式エポキシ樹脂である
か、もしくはこれらエポキシ樹脂の２つまたはそれ以上
の混合物から成ることが好ましい。The curable epoxy resin (A) blended as the component (A) in the liquid epoxy resin composition according to the second aspect of the present invention is a bisphenol A type epoxy resin, a bisphenol F type epoxy resin or an alicyclic epoxy resin. It is preferably present or consists of a mixture of two or more of these epoxy resins.
【００１６】第２の本発明による液状エポキシ樹脂組成
物において（Ｂ）成分として配合される硬化剤（Ｂ）は
ヒドロフタル酸無水物、特に４−メチルヘキサヒドロフ
タル酸無水物、テトラヒドロフタル酸無水物またはナジ
ック酸無水物であり、もしくはこれら酸無水物の２つま
たはそれ以上の混合物から成ることが好まれる。The curing agent (B) compounded as the component (B) in the liquid epoxy resin composition according to the second aspect of the present invention is hydrophthalic anhydride, particularly 4-methylhexahydrophthalic anhydride and tetrahydrophthalic anhydride. It is also preferred that it is nadic acid anhydride, or consists of a mixture of two or more of these acid anhydrides.
【００１７】第２の本発明の組成物で（Ｃ）成分、すな
わちエポキシ樹脂硬化促進剤として配合される式（１）
のテトラフェニルホスホニウムテトラ（４−メチルフェ
ニル）ボレートは公知物質である。この化合物は特開平
８−１６９８９２号公報に記載の方法に基づいて合成す
ることができる。Formula (1) compounded as the component (C), that is, the epoxy resin curing accelerator in the second composition of the present invention.
Tetraphenylphosphonium tetra (4-methylphenyl) borate is a known substance. This compound can be synthesized based on the method described in JP-A-8-169892.
【００１８】第２の本発明によるエポキシ樹脂組成物に
おいて、硬化性エポキシ樹脂（Ａ）は組成物全体の重量
に基づいて３０〜７０％、好ましくは４０〜６０％の範
囲で配合され、硬化剤（Ｂ）は組成物全体の重量に基づ
いて３０〜７０％、好ましくは３５〜５５％の範囲の割
合で配合され、しかも硬化剤（Ｂ）がエポキシ樹脂
（Ａ）の１化学等量に対して０．５〜１．６等量の割合
で混合されてあり、さらに硬化促進剤（Ｃ）としての式
（１）のテトラフェニルホスホニウムテトラ（４−メチ
ルフェニル）ボレートが組成物全体の重量に基づいて
０．３〜５％、好ましくは０．５〜３％の割合で配合さ
せることができる。In the epoxy resin composition according to the second aspect of the present invention, the curable epoxy resin (A) is added in an amount of 30 to 70%, preferably 40 to 60%, based on the total weight of the composition. (B) is blended in a proportion in the range of 30 to 70%, preferably 35 to 55%, based on the weight of the entire composition, and the curing agent (B) is based on 1 chemical equivalent of the epoxy resin (A). 0.5 to 1.6 equivalents, and tetraphenylphosphonium tetra (4-methylphenyl) borate of the formula (1) as a curing accelerator (C) is added to the weight of the entire composition. Based on the above, it can be added in a proportion of 0.3 to 5%, preferably 0.5 to 3%.
【００１９】（Ｃ）成分としての硬化促進剤の配合量が
エポキシ樹脂組成物の全体の重量について０．３％より
小さいときは、組成物は十分に高い速硬化性を示すこと
ができず、また５％より多いときは、貯蔵安定性が悪化
することが認められた。When the content of the curing accelerator as the component (C) is less than 0.3% based on the total weight of the epoxy resin composition, the composition cannot show sufficiently high fast curing property, Further, when it was more than 5%, it was observed that the storage stability deteriorated.
【００２０】さらに、第２の本発明による液状エポキシ
樹脂組成物は、所望により、追加成分として充填剤、難
燃剤および有機溶剤の少なくともひとつを含有できる
が、これらの追加成分は、本発明の目的を損なわない範
囲で配合される。Further, the liquid epoxy resin composition according to the second aspect of the present invention can optionally contain at least one of a filler, a flame retardant and an organic solvent as an additional component. These additional components are the objects of the present invention. It is blended within a range that does not impair
【００２１】充填剤としては、溶融シリカ、結晶シリ
カ、アルミナ、ボロンナイトライド、窒化アルミ、窒化
珪素、グラファイト、その他であることができる。The filler can be fused silica, crystalline silica, alumina, boron nitride, aluminum nitride, silicon nitride, graphite, and the like.
【００２２】難燃剤は金属水和物、ホスフィンオキサイ
ド、その他であることができる。The flame retardant can be a metal hydrate, phosphine oxide, etc.
【００２３】有機溶剤としては、トルエン、キシレン、
メチルイソブチルケトン、酢酸エチル、酢酸ブチル等が
挙げられるが、これらに特に限定されるものではない。As the organic solvent, toluene, xylene,
Examples thereof include methyl isobutyl ketone, ethyl acetate, butyl acetate, etc., but are not particularly limited thereto.
【００２４】第２の本発明によるエポキシ樹脂組成物の
調製は、まず所定量の硬化剤（Ｂ）と所定量の硬化促進
剤（Ｃ）とを加熱および攪拌下に混合し、得られた均質
な混合物に対して所定量のエポキシ樹脂を加えて真空ニ
ーダー中で均一に攪拌、混合することにより行なうのが
便利である。In the preparation of the epoxy resin composition according to the second aspect of the present invention, first, a predetermined amount of the curing agent (B) and a predetermined amount of the curing accelerator (C) are mixed under heating and stirring to obtain a homogenous mixture. It is convenient to add a predetermined amount of epoxy resin to such a mixture and uniformly stir and mix in a vacuum kneader.
【００２５】[0025]
【発明の実施の形態】次に、本発明を実施例によって更
に具体的に説明するが、本発明はこれらの実施例により
限定されるものではない。BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to these Examples.
【００２６】（参考製造例１）テトラフェニルホスホニ
ウムテトラ（４−メチルフェニル）ボレート［式
（１）］の合成
特開平８−１６９８９２号公報の記載に基づいて合成を
行なった（収率８５％）。得られた結晶の融点は２４７
℃であり、上記文献記載の値と一致した。Reference Production Example 1 Synthesis of Tetraphenylphosphonium Tetra (4-methylphenyl) borate [Formula (1)] Synthesis was carried out based on the description in JP-A-8-169892 (yield 85%). . The melting point of the obtained crystals is 247.
The temperature was in ° C., which was in agreement with the value described in the above literature.
【００２７】（参考製造例２）テトラフェニルホスホニ
ウムテトラ（３−メチルフェニル）ボレートの合成
特開平８−１６９８９２号公報の記載に基づいて合成を
行なった（収率７１％）。得られた結晶の融点は１９５
℃であり、上記文献記載の値と一致した。(Reference Production Example 2) Synthesis of tetraphenylphosphonium tetra (3-methylphenyl) borate Synthesis was carried out based on the description in JP-A-8-169892 (71% yield). The melting point of the obtained crystal is 195.
The temperature was in ° C., which was in agreement with the value described in the above literature.
【００２８】（参考製造例３）テトラフェニルホスホニ
ウムテトラ（２−メチルフェニル）ボレートの合成
特開平８−１６９８９２の記載に基づいて合成を行なっ
た。しかし、中間体のソジウムテトラ（２−メチルフェ
ニル）ボレートが全く生成せず、目的の化合物は合成で
きなかった。(Reference Production Example 3) Synthesis of tetraphenylphosphonium tetra (2-methylphenyl) borate Synthesis was carried out based on the description in JP-A-8-169892. However, the intermediate compound sodium tetra (2-methylphenyl) borate was not produced at all, and the target compound could not be synthesized.
【００２９】実施例１
硬化剤として、４−メチルヘキサヒドロフタル酸無水物
（東京化成株式会社製）８．６ｇを、また硬化促進剤と
してテチラフェニルホスホニウムテトラ（４−メチルフ
ェニル）ボレート０．２ｇを秤取り、これらを混合して
から加熱攪拌によって硬化剤中に硬化促進剤を均一に溶
解して成る混合物を調製した。この硬化剤と硬化促進剤
との均質な混合物を室温に冷却し、その後にこの混合物
に対して液状の硬化性ビスフェノールＡ型エポキシ樹脂
（商品名エピコート８２８：油化シェルエポキシ株式会
社製）１０．０ｇを加え、攪拌することにより第２の本
発明の液状エポキシ樹脂組成物１８．８ｇを得た。Example 1 8.6 g of 4-methylhexahydrophthalic anhydride (manufactured by Tokyo Kasei Co., Ltd.) as a curing agent, and 0.2 g of tetilaphenylphosphonium tetra (4-methylphenyl) borate as a curing accelerator. Were weighed and mixed, and then the mixture was prepared by heating and stirring to uniformly dissolve the curing accelerator in the curing agent. 10. A homogeneous mixture of this curing agent and a curing accelerator is cooled to room temperature, and then a curable bisphenol A type epoxy resin (trade name Epicoat 828: manufactured by Yuka Shell Epoxy Co., Ltd.) which is liquid to this mixture. 0 g was added and stirred to obtain 18.8 g of the second liquid epoxy resin composition of the present invention.
【００３０】実施例２
硬化促進剤の配合量を０．３ｇとした以外は実施例１と
同様にして所要な３成分を混合し、これにより液状エポ
キシ樹脂組成物を調製した。Example 2 The required three components were mixed in the same manner as in Example 1 except that the amount of the curing accelerator compounded was 0.3 g, whereby a liquid epoxy resin composition was prepared.
【００３１】比較例１
実施例１において硬化促進剤として用いたテトラフェニ
ルホスホニウム（４−メチルフェニル）ボレートの代わ
りに、トリフェニルホスフィン０．１ｇを用いた以外
は、実施例１と同様にして所要の３成分を混和すること
により硬化性の液状エポキシ樹脂組成物を調製した。Comparative Example 1 The same procedure as in Example 1 was carried out except that 0.1 g of triphenylphosphine was used instead of the tetraphenylphosphonium (4-methylphenyl) borate used as the curing accelerator in Example 1. A curable liquid epoxy resin composition was prepared by mixing the above three components.
【００３２】比較例２
実施例１において硬化促進剤として用いたテトラフェニ
ルホスホニウム（４−メチルフェニル）ボレートの代わ
りに、テトラフェニルホスホニウムテトラフェニルボレ
ートを用いた以外は、実施例１と同様にして所要の３成
分を混和することにより硬化性の液状エポキシ樹脂組成
物を調製した。Comparative Example 2 The same procedure as in Example 1 was carried out except that tetraphenylphosphonium tetraphenylborate was used instead of the tetraphenylphosphonium (4-methylphenyl) borate used as the curing accelerator in Example 1. A curable liquid epoxy resin composition was prepared by mixing the above three components.
【００３３】比較例３
実施例１において硬化促進剤として用いたテトラフェニ
ルホスホニウム（４−メチルフェニル）ボレートの代わ
りに、テトラフェニルホスホニウム（３−メチルフェニ
ル）ボレートを用いた以外は、実施例１と同様にして所
要の３成分を混和することにより液状エポキシ樹脂組成
物を調製した。Comparative Example 3 As Example 1 except that tetraphenylphosphonium (3-methylphenyl) borate was used instead of the tetraphenylphosphonium (4-methylphenyl) borate used as the curing accelerator in Example 1. Similarly, a liquid epoxy resin composition was prepared by mixing the required three components.
【００３４】試験例１〜２および比較試験例１〜３
（ａ）エポキシ樹脂組成物の硬化試験
上記の実施例１〜２および比較例１〜３で得られた液状
エポキシ樹脂組成物のゲル化時間をＪＩＳ Ｋ５０５９
に準じ１５０℃で熱板法により測定した。Test Examples 1 and 2 and Comparative Test Examples 1 to 3 (a) Curing Test of Epoxy Resin Composition Gelation of the liquid epoxy resin compositions obtained in the above Examples 1 and 2 and Comparative Examples 1 to 3 Time to JIS K5059
The hot plate method was used for measurement at 150 ° C.
【００３５】なお、ゲル化試験器は日新科学社製ＧＴ−
Ｄを使用した。The gelation tester is a GT-manufactured by Nisshin Kagaku Co.
D was used.
【００３６】（ｂ）貯蔵安定性試験
上記の実施例１〜２および比較例１〜３で得られたエポ
キシ樹脂組成物の４０℃での貯蔵安定性試験を実施し
た。粘度測定は２５℃において実施した。粘度計はマル
コム社製共軸二重円筒型回転式粘度計ＰＭ−２Ａを使用
し、樹脂粘度が１０Ｐａ・ｓに到達（２５℃で測定）し
た日数を貯蔵安定性の日数とした。(B) Storage stability test The epoxy resin compositions obtained in the above Examples 1-2 and Comparative Examples 1-3 were subjected to a storage stability test at 40 ° C. Viscosity measurements were performed at 25 ° C. As the viscometer, a coaxial double cylindrical rotary viscometer PM-2A manufactured by Malcolm was used, and the number of days when the resin viscosity reached 10 Pa · s (measured at 25 ° C) was defined as the number of days of storage stability.
【００３７】これら試験で得られた結果を次に表１に要
約して示す。The results obtained in these tests are summarized in Table 1 below.
【００３８】[0038]
【表１】 [Table 1]
【００３９】表１の実施例１〜２に示すように、本発明
の液状エポキシ樹脂組成物は、硬化速度が速く、かつ優
れた貯蔵安定性を示す。一方、比較例１では硬化性は実
施例１と同程度であるが貯蔵安定性は著しく劣る。ま
た、比較例２では実施例１と同重量の促進剤を用いた場
合、貯蔵安定性は優れるものの速硬化性に劣る。比較例
３においても実施例１と同重量の促進剤を用いた場合、
実施例１と比較して貯蔵安定性は同程度であるものの、
速硬化性に劣る。促進剤の量を増やせば硬化性はよくな
るが、コストパフォーマンスにおいて劣ることとなる。As shown in Examples 1 and 2 of Table 1, the liquid epoxy resin composition of the present invention has a fast curing rate and excellent storage stability. On the other hand, in Comparative Example 1, the curability is similar to that in Example 1, but the storage stability is significantly poor. Further, in Comparative Example 2, when the same weight of the accelerator as in Example 1 was used, the storage stability was excellent, but the fast curing property was poor. Also in Comparative Example 3, when the same weight of the accelerator as in Example 1 was used,
Although the storage stability is similar to that of Example 1,
Inferior in fast curing property. If the amount of the accelerator is increased, the curability will be improved, but the cost performance will be poor.
【００４０】[0040]
【発明の効果】本発明の特定のエポキシ樹脂硬化促進剤
を使用すると、樹脂の硬化促進性、貯蔵安定性がいずれ
も優れていることが明らかである。また本発明の液状エ
ポキシ樹脂組成物は４０℃という過酷な保存条件でも貯
蔵安定性に優れており、硬化性も良好であることから各
種の小型の電気・電子部品や半導体部品の微妙な樹脂封
止において作業性の優れた樹脂を提供するものである。It is apparent that the use of the specific epoxy resin curing accelerator of the present invention is excellent in both the curing acceleration and the storage stability of the resin. Further, the liquid epoxy resin composition of the present invention has excellent storage stability even under a severe storage condition of 40 ° C. and has good curability, so that it is a delicate resin sealant for various small electric / electronic parts and semiconductor parts. It provides a resin having excellent workability in stopping.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4J036 AA01 AD08 AJ08 DB15 DB21 GA04 GA06 GA23 JA07 KA01 4M109 EA02 EB04 ─────────────────────────────────────────────────── ─── Continued front page F term (reference) 4J036 AA01 AD08 AJ08 DB15 DB21 GA04 GA06 GA23 JA07 KA01 4M109 EA02 EB04
Claims (2)
スホニウムテトラ（４−メチルフェニル）ボレートを有
効成分とするエポキシ樹脂硬化促進剤 【化１】 1. An epoxy resin curing accelerator containing tetraphenylphosphonium tetra (4-methylphenyl) borate represented by the following formula (1) as an active ingredient:
シ樹脂の硬化を起させる作用を持つ酸無水物系硬化剤
（Ｂ）と、請求項１に記載の式（１）で示されるテトラ
フェニルホスホニウムテトラ（４−メチルフェニル）ボ
レート（Ｃ）とを、組成物の構成成分として含有するこ
とを特徴とする、液状エポキシ樹脂組成物。2. A curable epoxy resin (A), an acid anhydride-based curing agent (B) having a function of causing curing of the epoxy resin, and a tetracarboxylic acid represented by the formula (1) according to claim 1. A liquid epoxy resin composition comprising phenylphosphonium tetra (4-methylphenyl) borate (C) as a constituent of the composition.
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| JP2001210392A JP3638258B2 (en) | 2001-07-11 | 2001-07-11 | Epoxy resin curing accelerator and liquid epoxy resin composition |
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|---|---|---|---|
| JP2001210392A JP3638258B2 (en) | 2001-07-11 | 2001-07-11 | Epoxy resin curing accelerator and liquid epoxy resin composition |
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| Publication Number | Publication Date |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004352871A (en) * | 2003-05-29 | 2004-12-16 | Nitto Denko Corp | Adhesive composition, adhesive film, and semiconductor device using the same |
| JP2006249149A (en) * | 2005-03-08 | 2006-09-21 | Nitto Denko Corp | Manufacturing method of epoxy resin composition for sealing semiconductor, epoxy resin composition for sealing semiconductor obtained thereby and semiconductor device using it |
| WO2009084096A1 (en) * | 2007-12-27 | 2009-07-09 | Panasonic Electric Works Co., Ltd. | Liquid epoxy resin composition for chip-on film and semiconductor device |
| JP2010199626A (en) * | 2010-06-03 | 2010-09-09 | Nitto Denko Corp | Adhesive film for die bonding, and semiconductor device using the same |
-
2001
- 2001-07-11 JP JP2001210392A patent/JP3638258B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004352871A (en) * | 2003-05-29 | 2004-12-16 | Nitto Denko Corp | Adhesive composition, adhesive film, and semiconductor device using the same |
| JP4603774B2 (en) * | 2003-05-29 | 2010-12-22 | 日東電工株式会社 | Adhesive composition and adhesive film using the same |
| JP2006249149A (en) * | 2005-03-08 | 2006-09-21 | Nitto Denko Corp | Manufacturing method of epoxy resin composition for sealing semiconductor, epoxy resin composition for sealing semiconductor obtained thereby and semiconductor device using it |
| WO2009084096A1 (en) * | 2007-12-27 | 2009-07-09 | Panasonic Electric Works Co., Ltd. | Liquid epoxy resin composition for chip-on film and semiconductor device |
| JP2010199626A (en) * | 2010-06-03 | 2010-09-09 | Nitto Denko Corp | Adhesive film for die bonding, and semiconductor device using the same |
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| Publication number | Publication date |
|---|---|
| JP3638258B2 (en) | 2005-04-13 |
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