JP4341938B2 - Partially hydrogenated polyfunctional aromatic epoxy resin and epoxy resin composition containing the same - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は部分的に核水添された多官能性芳香族エポキシ樹脂及びこれを含有する硬化性組成物に関する。
【０００２】
【従来の技術】
多官能性芳香族エポキシ樹脂、例えばフェノ−ルノボラック、ｏ−クレゾ−ルノボラック型のエポキシ樹脂、ビフェニル、ナフト−ル骨格を有するノボラック型エポキシ樹脂、あるいはアラルキルフェノ−ル型（通称ザイロック型）エポキsシ樹脂等の多官能性芳香族エポキシ樹脂は、電子、電気材料、塗料用、材料として広く使われている。一方、芳香核が全て核水添されたノボラック型エポキシ樹脂は、特開平８−４８６７０、特開平８−５３３７０、特開平１０−２０４００２等に記載されている。
【０００３】
【発明が解決しようとしている課題】
芳香族エポキシ樹脂は、電子、電気材料用途等に詳しく研究され、各種硬化剤との組み合わせにより、種々の特性を持った硬化物が得られている。
芳香族の特性である着色しやすい傾向を嫌う光関連分野の材料としては、例えば芳香核が全て核水添されたビスフェノールＡ型のエポキシ化物が使用されている。しかし、各種の用途に応じて、軟化点、粘度、反応性、溶剤溶解性等を変える要望があり、また、反応性の違う２種類のエポキシ基を有するエポキシ化合物を作り、これらを用いてＩＰＮと略称される相互貫入型高分子や、フィルム適性を有するエポキシ基含有高分子を得る技術が望まれている。
本発明は、これらの要望を達成する方法として、芳香族性エポキシ基と脂肪族性エポキシ基を同一分子内に有するエポキシ樹脂及びこれを含有する硬化性組成物を提案するものである。
【０００４】
【課題を解決するための手段】
即ち本発明は、
（１）分子中に平均３個以上の芳香核と２個以上のエポキシ基を有する芳香族エポキシ化合物の、２０〜８０％の芳香核が水素添加され脂肪族環構造となった構造を有する芳香族エポキシ樹脂、
（２）分子中に平均３個以上の芳香核と２個以上のエポキシ基を有する芳香族エポキシ化合物を金属触媒の存在下、芳香核を全て水素添加したときの理論量の、２０〜８０％の水素を水素添加反応に使用して得られ得るエポキシ樹脂、
（３）分子中に平均３個以上の芳香核と２個以上の水酸基を有する芳香族ヒドロキシ化合物を金属触媒の存在下、芳香核を全て水素添加したときの理論量の、２０〜８０％の水素を核水添反応に使用して得られる核水添された芳香族ヒドロキシ化合物、
（４）上記（３）記載の芳香族ヒドロキシ化合物をエピクロロヒドリンによりエポキシ化して得られ得るエポキシ樹脂、
（５）上記（１）、（２）または（４）のいずれか１項に記載のエポキシ樹脂、硬化剤及び硬化触媒を含有する硬化性組成物、
（６）無機充填剤を含有する上記（５）記載の硬化性組成物
に関する。
【０００５】
【発明の実施形態】
以下本発明を詳細に説明する。
本発明の、分子中の芳香核が部分的に核水素添加（以下、核水添という）された多官能性芳香族エポキシ樹脂を得るためには、ビスフェノ−ルＡ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、ｏ−クレゾールノボラック型エポキシ樹脂、ナフトールとクレゾールの混合ノボラック型エポキシ樹脂、アラルキルフェノール型エポキシ樹脂（式（１））、ビフェニルジイルジメチレン−フェノール型エポキシ樹脂（式（２））、ビフェノールまたはビスフェノールノボラック型エポキシ樹脂(式（３））等のうち分子中に平均３個以上の芳香核と２個以上のエポキシ基を有するエポキシ化合物を原料として、核水添するか、
【０００６】
【化１】
【化２】
【化３】
【０００９】
【化４】
を表す。また、式（１）、式（２）、式（３）中、ｎは繰り返し数を表す。）
ヒドロキシ末端フェノキシ樹脂、フェノールノボラック、ｏ−クレゾールノボラック、ナフトールとクレゾールの混合ノボラック、アラルキルフェノール型フェノール樹脂、ビフェニルジイルジメチレン−フェノール樹脂、ビフェノールまたはビスフェノールノボラック等のうち分子中に平均３個以上の芳香核と２個以上の水酸基を有する芳香族ヒドロキシ化合物を部分的に核水添して得られた化合物を、エピクロロヒドリンによりエポキシ化して得ることができる。この場合は、核水添を受けてアルコール性となった水酸基が完全にエポキシ化されない場合もある。
本発明のエポキシ樹脂は上記に限定されるものでなく、平均３個以上の芳香核と２個以上のエポキシ基を有するエポキシ化合物が部分的に核水添された化合物全てを含有する。
尚、本発明における芳香核の数は、例えば、ナフタレン、ビフェニルでは２個、アンスラセンでは３個といったように数え、他の縮合環もこれに準ずる。また、核水添の割合については後述する。
【００１１】
本発明は、部分的核水添により軟化点、粘度、反応性、溶剤溶解性等を変えたり、また、反応性の違う２種類のエポキシ基を有するエポキシ樹脂を作り、これらを用いてＩＰＮと略称される相互貫入型高分子やフィルム適性を有するエポキシ基含有高分子を得るために、芳香族性エポキシ基と脂肪族性エポキシ基を同一分子内に有するエポキシ樹脂を得ることを目的としたものであり、全ての芳香核が核水添されたものと全く核水添されていない芳香族エポキシ樹脂の混合物とは、本質的に異なるものである。例えば１例として、芳香族性のエポキシ基と脂肪族性のエポキシ基の硬化剤との反応性は、場合によって２〜３倍芳香族性エポキシ基の方が速いため、上記の混合物の場合は硬化反応の過程で、芳香族性エポキシ化合物が先に反応し、脂肪族エポキシ化合物が高分子鎖に組み入れられず、完全硬化とならずに硬度が低いものしか得られないことがある。
このために、本発明では、全ての芳香核が核水添されたものを極力抑えるため、原料（芳香族エポキシ樹脂又は芳香族ヒドロキシ化合物）の分子中の芳香核の平均個数は３以上、分子中のエポキシ基又は水酸基の数は２個以上であり、芳香核の核水添の割合は、２０〜８０％、好ましくは３０〜６５％程度にする。
【００１２】
芳香族エポキシ化合物、芳香族ヒドロキシ化合物に対する核水添を行うに当たっては、いずれの場合も金属触媒を用い、例えば白金、パラジューム、ロジューム、ルテニウム、ニッケル等が使用できる。これらは単体、錯体、酸化物、炭素やアルミナ等に担持された形等いずれでも使用可能である。触媒の使用量は、金属として、水添される樹脂の０．００１〜２重量％程度である。
反応は必要により溶媒を使用する。
反応溶媒としては、ジブチルエーテル、テトラハイドロフラン、ジオキサン、ジグライム、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル又はプロピレングリコールモノメチルエーテルアセテート等のエーテル類、酢酸エチル又は酢酸ブチル等のエステル類、メタノール又はエタノール等のアルコール類、ジメチルフォルムアルデヒド、ジメチルイミダゾリジノン又はＮ−メチルピロリドン等の非プロトン性極性溶媒等が使用され、その使用量は、芳香族エポキシ化合物又は芳香族ヒドロキシ化合物の２〜１５重量倍である。
【００１３】
反応は、オートクレーブ中に原料及び触媒並びに必要により溶媒を仕込み、通常２〜２００気圧、好ましくは１０〜１００気圧の水素圧にて実施する。反応温度は、通常２５〜１５０℃、好ましくは４０〜１２０℃であり、水素の吸収を見ながら吸収された分を供給し、０．５〜２０時間かけて反応させる。水素添加率は、芳香核が全て水添されたときに必要とされる水素量と実際に反応時に供給された水素量で判定する。芳香核の水添はエポキシ環の水添に比べて速いため、上記条件を選べば、エポキシ基の水添は問題にならない。また、本発明では、部分的にしか核水添を行わないため、わずかにエポキシ基の水添が起こっても影響は少ない。
【００１４】
上記の水添法において、原料として芳香族ヒドロキシ化合物を使用すると部分的に水添された本発明の芳香族ヒドロキシ化合物が得られ、下記するようにエポキシ化して本発明のエポキシ樹脂の原料となるばかりでなく、例えばエポキシ樹脂の硬化剤として公知のエポキシ樹脂や硬化触媒と組み合わせて使用することもできる。
【００１５】
本発明の芳香族ヒドロキシ化合物のエポキシ化は、定法により行うことができる。即ち、理論量より過剰のエピクロロヒドリンの存在下、苛性ソーダ、苛性カリ等のアルカリを加えて、場合によっては反応により生成する水を共沸蒸留によって除きながら、４０〜１２０℃で、１〜１０時間反応させて行う。この際、テトラメチルアンモニウムヒドロキサイド、ベンジルトリメチルアンモニウムブロマイド等の相関移動触媒、ジメチルフォルムアルデヒド、ジメチルイミダゾリジノン、ジオキサン、メトキシエタノール、エタノール、ブタノール等の極性溶媒を少量添加することも可能である。これらの相関移動触媒は、本発明の芳香族ヒドロキシ化合物の０．０１〜０．１重量倍使用することができる。また、溶媒は、本発明の芳香族ヒドロキシ化合物に対して０．１〜１０重量倍使用することができる。
【００１６】
このようにして得られた本発明の部分核水添された芳香族エポキシ樹脂は、硬化剤、触媒とともに硬化性組成物とすることができる。ここで用いる硬化剤は、ジエチレントリアミン、ジアミノジフェニルメタン、ジアミノジフェニルスルフォン、ジシアンジアミド等のアミン系硬化剤、無水ナジック酸、無水フタル酸、無水ハイミック酸、無水マレイン酸、無水トリメリット酸等の酸無水物硬化剤、フェノールノボラック、アラルキルフェノール、トリスフェノールメタン、ナフトールとクレゾールの混合ノボラック等の多価フェノール系硬化剤等があげられ、これらの使用量はエポキシ樹脂のエポキシ当量の０．５〜１．７倍当量である。
【００１７】
硬化触媒としては、トリフェニルフォスフィン、フォスフォニウムボレート等のリン系化合物またはフォスフォニウム塩、イミダゾール類、ＤＢＵ等の３級アミン類、３フッ化ホウ素のアミン塩等が用いられる。その使用量はエポキシ樹脂に対して０．５〜５重量％である。
【００１８】
このようにして得られた本発明の硬化性組成物は、所望により、ポリアリレート、ポリエステル、ポリエーテルスルフォン、ポリイミド又はポリアミド等の熱可塑性高分子と共に、Ｎ−メチルピロリドン、メチルエチルケトン、ジメチルフォルムアルデヒド、エチレングリコールモノメチルエーテル又はプロピレングリコールモノメチルエーテルアセテート等の溶媒に溶解してキャストフィルムを得たり、シリカ、アルミナ、炭酸カルシューム等の無機充填剤と共に、封止材組成物としたり、接着材として使用することができる。これらの組成物は、１２０〜２００℃で硬化することにより硬化物を与え種々の目的に使用される。
尚、上記において無機充填剤は、封止材組成物中で０〜９０重量％を占める量が用いられる。
【００１９】
以下実施例により本発明を更に詳細に説明する。なお、実施例１〜３は参考例である。
【００２０】
実施例１
特開平１０−２０４００２に準じて調製した５％ルテニウム／カーボン触媒（５０重量％含水）を調製した。即ち、２００ｍｌのビーカーに活性炭１０ｇ、水１００ｇを加え、室温にて、ルテニウム原子として０．５ｇを含有するルテニウム（ＶＩ）酸ナトリウム水溶液を添加した。攪拌しつつ含浸させ、沈殿を濾過し、イオン交換水で洗浄した。５％ルテニウム／カーボン触媒（５０％含水）を得た。
５００ｍｌ容量のステンレス製オートクレーヴに、上記で得た触媒（５０％含水）４ｇ、ｏ−クレゾールノボラック型エポキシ樹脂（商品名：ＥＯＣＮ−４４００（日本化薬（株）製）、軟化点６２℃、１５０℃における溶融粘度は１．６ポイズ、１分子中の平均芳香核個数は約４、エポキシ基は２個以上）２０ｇ、テトラヒドロフラン１５０ｇを仕込み、窒素置換をしたあと、水素置換をして、水素圧を５０気圧とした。徐々に昇温し、９０℃で１時間水素圧を一定に保って反応し、反応終了後室温に戻したときの水素圧を測定し、空間部の容量を掛けて水素使用量を計算したところ、３８００ｍｌであった。
これは全芳香核の５０％が水添された量に相当する。反応終了後触媒を濾別し、このようにして得られた本発明のエポキシ樹脂は軟化点が５６℃であり、エポキシ当量は２１５ｇ／当量であった。
尚、得られたエポキシ樹脂の１５０℃における溶融粘度は、０．９ポイズであり、エポキシ当量は若干増えたものの、軟化点、溶融粘度が低下した部分核水添されたｏ−クレゾールノボラック型エポキシ樹脂を得た。
【００２１】
実施例２
ｏ−クレゾールノボラック（軟化点１１０℃：群栄化学工業製）２０ｇ、５％ロジューム／カーボン（５０％含水；エヌイーケムキャット社製）４ｇ、エチレングリコールモノエチルエーテル１５０ｇを５００ｍｌ容量のステンレス製オートクレーヴに仕込み、窒素置換をしたあと、水素置換をして、水素圧を５０気圧とした。徐々に昇温し、９０℃で１時間水素圧を一定に保って反応し本発明の芳香族ヒドロキシ化合物を得た。
尚、反応終了後室温に戻したときの水素圧を測定し水素使用量を計算したところ３３００ｍｌであった。
これは全芳香核の３０％が水添された量に相当する。
【００２２】
実施例３
実施例２で得られた本発明のの芳香族ヒドロキシ化合物１５．６ｇ、エピクロロヒドリン５０ｇ、テトラメチルアンモニウムクロライド０．０５ｇ、ジオキサン２０ｇを３００ｍｌ容量のフラスコ中で撹拌しながら、６０℃にて２時間にわたり、固形の苛性ソ−ダ４．９ｇを徐々に加え次いで７５℃で２時間更に反応した後、メチルイソブチルケトン１００ｇ、水５０ｇを加えて、分離した水層を除去した。水５０ｇを新たに加えて水洗した後、メチルイソブチルケトンを減圧下で留去し、本発明の部分核水添されたｏ−クレゾ−ルノボラック型エポキシ樹脂２０．５ｇを得た。
【００２３】
実施例４
５００ｍｌ容量のステンレス製オートクレーヴに、ビフェニルジイルジメチレン−フェノ−ル型エポキシ樹脂（商品名：ＮＣ−３０００Ｐ（日本化薬（株）製）、エポキシ当量２７５ｇ／当量、軟化点５８℃、１５０℃におけるＩＣＩ粘度０．９Ｐ、１分子中の平均芳香核個数６．６、エポキシ基の数２以上、平均分子量７７０）２０ｇ、５％ロジュ−ム／カ−ボン（５０％含水；エヌイーケムキャット社製）３ｇ、ジエチレングリコ−ルジメチルエ−テル１５０ｇを仕込み、窒素置換をしたあと、水素置換をして、水素圧を５０気圧とした。徐々に昇温し、８５℃で０．５時間水素圧を一定に保って反応し、反応終了後室温に戻したときの水素圧を測定し、空間部の容量を掛けて水素使用量を計算したところ、４６００ｍｌであった。これは全芳香核の４０％が水添された量に相当する。反応混合物から触媒を濾別し、濾液から反応溶媒を減圧下で留去して、２０ｇの部分核水添されたビフェニルジイルジメチレン−フェノ−ル型のエポキシ樹脂を得た。得られたエポキシ樹脂は軟化点が５５℃であり、エポキシ当量は２８８ｇ／当量であった。また、得られたエポキシ樹脂の１５０℃における溶融粘度は、０．６ポイズであり、エポキシ当量は若干増えたものの、軟化点、溶融粘度が低下した。尚、１Ｈ−ＮＭＲ測定では、ビフェニル基、フェニル基のベンゼン環共にランダムに水添されており、選択性は認められなかった。
【００２４】
実施例５
ＮＣ−３０００Ｐの代わりにアラルキルフェノ−ル型エポキシ樹脂（商品名：ＸＰ−２０３０（日本化薬（株）製）、エポキシ当量２３７、軟化点５９℃、１５０℃におけるＩＣＩ粘度１．５ポイズ）を使用した以外は実施例４と同様にして、芳香核の６０％を核水添したアラルキルフェノ−ル型エポキシ樹脂を得た。得られたエポキシ樹脂のエポキシ当量は２４８ｇ／当量、軟化点５４℃、１５０℃におけるＩＣＩ粘度０．９ポイズであった。
【００２５】
実施例６
実施例４で得られたエポキシ樹脂２０ｇ、アラルキルフェノ−ル型樹脂（商品名：ミレックスＸＬＣ−２２５−３Ｌ、三井化学（株）製）１２．８ｇ、２−エチル−４メチルイミダゾ−ル０．２ｇ、ポリエ−テルスルフォン（商品名：ＰＥＳ５００３Ｐ（ＢＡＳＦ社製））３５ｇ、Ｎ−メチルピロリドン２０ｇ、メチルエチルケトン２０ｇを室温で混合溶解させた。
この溶液から、厚さ５０μｍのキャストフィルムを作り、１７０℃で、３５μｍの厚みを有する２枚の銅箔に５０ｋｇ／ｃｍ2の圧力で圧着し３時間保持した。硬化終了後、万能引っ張り試験機で、クロスヘッドスピ−ド２００ｍｍ／ｍｉｎで剥離強度を測定したところ、２．１ｋｇ／ｃｍと良好な接着性を示した。
【００２６】
【発明の効果】
本発明によれば、同一分子内に反応性の違う２種類のエポキシ基を有する、部分的に核水添された新規な芳香族エポキシ樹脂が得られ、これは例えばホットメルト接着剤等へ応用が可能である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a partially nuclear hydrogenated polyfunctional aromatic epoxy resin and a curable composition containing the same.
[0002]
[Prior art]
Multifunctional aromatic epoxy resin, for example, phenol novolak, o-cresol novolak type epoxy resin, biphenyl, novolak type epoxy resin having naphthol skeleton, or aralkylphenol type (commonly known as zylock type) epoxy Polyfunctional aromatic epoxy resins such as resins are widely used as electronic, electrical materials, paints, and materials. On the other hand, novolac type epoxy resins in which aromatic nuclei are all hydrogenated are described in JP-A-8-48670, JP-A-8-53370, JP-A-10-204002, and the like.
[0003]
[Problems to be solved by the invention]
Aromatic epoxy resins have been studied in detail for applications such as electronic and electrical materials, and cured products having various properties have been obtained by combining with various curing agents.
As a material in the light-related field that dislikes the tendency to color, which is an aromatic characteristic, for example, bisphenol A type epoxidized products in which all aromatic nuclei are hydrogenated are used. However, there is a demand to change the softening point, viscosity, reactivity, solvent solubility, etc. according to various applications. Also, an epoxy compound having two types of epoxy groups with different reactivities is prepared and used to generate IPN. A technique for obtaining an interpenetrating polymer abbreviated as “a” and an epoxy group-containing polymer having film suitability is desired.
The present invention proposes an epoxy resin having an aromatic epoxy group and an aliphatic epoxy group in the same molecule and a curable composition containing the same as a method for achieving these demands.
[0004]
[Means for Solving the Problems]
That is, the present invention
(1) Fragrance having a structure in which 20 to 80% of aromatic nuclei are hydrogenated to form an aliphatic ring structure of an aromatic epoxy compound having an average of 3 or more aromatic nuclei and 2 or more epoxy groups in the molecule. Group epoxy resin,
(2) 20-80% of the theoretical amount when an aromatic epoxy compound having an average of 3 or more aromatic nuclei and 2 or more epoxy groups in the molecule is all hydrogenated in the presence of a metal catalyst. An epoxy resin that can be obtained using hydrogen in the hydrogenation reaction,
(3) 20-80% of the theoretical amount when an aromatic hydroxy compound having an average of 3 or more aromatic nuclei and 2 or more hydroxyl groups in the molecule is all hydrogenated in the presence of a metal catalyst. A nuclear hydrogenated aromatic hydroxy compound obtained using hydrogen for the nuclear hydrogenation reaction,
(4) An epoxy resin obtainable by epoxidizing the aromatic hydroxy compound according to (3) above with epichlorohydrin,
(5) A curable composition containing the epoxy resin according to any one of (1), (2) or (4) above, a curing agent and a curing catalyst,
(6) It relates to the curable composition according to the above (5), which contains an inorganic filler.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described in detail below.
In order to obtain a polyfunctional aromatic epoxy resin in which the aromatic nucleus in the molecule is partially hydrogenated (hereinafter referred to as nuclear hydrogenation) according to the present invention, bisphenol A type epoxy resin, phenol novolak type Epoxy resin, o-cresol novolac type epoxy resin, mixed novolak type epoxy resin of naphthol and cresol, aralkylphenol type epoxy resin (formula (1)), biphenyldiyldimethylene-phenol type epoxy resin (formula (2)), biphenol Alternatively, in the bisphenol novolac type epoxy resin (formula (3)) etc., nuclear hydrogenation is carried out using an epoxy compound having an average of 3 or more aromatic nuclei and 2 or more epoxy groups in the molecule,
[0006]
[Chemical 1]
[Chemical formula 2]
[Chemical 3]
[0009]
[Formula 4]
Represents. In the formula (1), formula (2), and formula (3), n represents the number of repetitions. )
Hydroxyl-terminated phenoxy resin, phenol novolak, o-cresol novolak, mixed novolak of naphthol and cresol, aralkylphenol type phenol resin, biphenyldiyldimethylene-phenol resin, biphenol or bisphenol novolak, etc., average 3 or more fragrances in the molecule A compound obtained by partially nuclear hydrogenating an aromatic hydroxy compound having a nucleus and two or more hydroxyl groups can be obtained by epoxidation with epichlorohydrin. In this case, the hydroxyl group that has become alcoholic as a result of nuclear hydrogenation may not be completely epoxidized.
The epoxy resin of the present invention is not limited to the above, and contains all compounds in which an epoxy compound having an average of 3 or more aromatic nuclei and 2 or more epoxy groups is partially hydrogenated.
The number of aromatic nuclei in the present invention is, for example, 2 for naphthalene and biphenyl and 3 for anthracene, and other condensed rings are the same. The ratio of nuclear hydrogenation will be described later.
[0011]
In the present invention, the softening point, viscosity, reactivity, solvent solubility, etc. are changed by partial nuclear hydrogenation, or an epoxy resin having two types of epoxy groups with different reactivities is produced. In order to obtain an abbreviated interpenetrating polymer or an epoxy group-containing polymer having film suitability, the objective is to obtain an epoxy resin having an aromatic epoxy group and an aliphatic epoxy group in the same molecule. The mixture of aromatic epoxy resins in which all aromatic nuclei have been nuclear hydrogenated and no nuclear hydrogenation is essentially different. For example, as an example, the reactivity of the aromatic epoxy group and the curing agent of the aliphatic epoxy group is 2 to 3 times faster in some cases, and in the case of the above mixture, In the course of the curing reaction, the aromatic epoxy compound may react first, and the aliphatic epoxy compound may not be incorporated into the polymer chain, and only a low hardness may be obtained without complete curing.
For this reason, in the present invention, the average number of aromatic nuclei in the molecule of the raw material (aromatic epoxy resin or aromatic hydroxy compound) is 3 or more in order to suppress as much as possible all nuclear nuclei hydrogenated. The number of epoxy groups or hydroxyl groups therein is 2 or more, and the ratio of the nuclear hydrogenation of aromatic nuclei is 20 to 80%, preferably about 30 to 65%.
[0012]
In carrying out the nuclear hydrogenation for the aromatic epoxy compound and the aromatic hydroxy compound, a metal catalyst is used in any case, and for example, platinum, palladium, rhodium, ruthenium, nickel and the like can be used. These can be used in any form such as a simple substance, a complex, an oxide, or a form supported on carbon or alumina. The amount of the catalyst used is about 0.001 to 2% by weight of the resin to be hydrogenated as a metal.
The reaction uses a solvent if necessary.
As a reaction solvent, ethers such as dibutyl ether, tetrahydrofuran, dioxane, diglyme, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether or propylene glycol monomethyl ether acetate, esters such as ethyl acetate or butyl acetate, methanol or ethanol Aprotic polar solvents such as alcohols such as dimethylformaldehyde, dimethylimidazolidinone or N-methylpyrrolidone are used, and the amount used is 2 to 15 times the amount of the aromatic epoxy compound or aromatic hydroxy compound It is.
[0013]
The reaction is carried out at a hydrogen pressure of usually 2 to 200 atm, preferably 10 to 100 atm, with raw materials, a catalyst and, if necessary, a solvent in an autoclave. The reaction temperature is usually 25 to 150 ° C., preferably 40 to 120 ° C., and the absorbed amount is supplied while observing the absorption of hydrogen, and the reaction is carried out for 0.5 to 20 hours. The hydrogenation rate is determined by the amount of hydrogen required when all the aromatic nuclei are hydrogenated and the amount of hydrogen actually supplied during the reaction. Since the hydrogenation of the aromatic nucleus is faster than the hydrogenation of the epoxy ring, the hydrogenation of the epoxy group is not a problem if the above conditions are selected. Further, in the present invention, since the nuclear hydrogenation is performed only partially, even if slight hydrogenation of the epoxy group occurs, there is little influence.
[0014]
In the above hydrogenation method, when an aromatic hydroxy compound is used as a raw material, a partially hydrogenated aromatic hydroxy compound of the present invention is obtained, and epoxidized as described below to be a raw material for the epoxy resin of the present invention. In addition, for example, it can be used in combination with a known epoxy resin or curing catalyst as a curing agent for epoxy resin.
[0015]
Epoxidation of the aromatic hydroxy compound of the present invention can be performed by a conventional method. That is, in the presence of an excess of epichlorohydrin than the theoretical amount, an alkali such as caustic soda or caustic potash is added, and in some cases, water generated by the reaction is removed by azeotropic distillation, while the temperature is 40 to 120 ° C. Let it react for hours. At this time, it is also possible to add a small amount of a phase transfer catalyst such as tetramethylammonium hydroxide or benzyltrimethylammonium bromide, or a polar solvent such as dimethylformaldehyde, dimethylimidazolidinone, dioxane, methoxyethanol, ethanol or butanol. These phase transfer catalysts can be used 0.01 to 0.1 times by weight of the aromatic hydroxy compound of the present invention. Moreover, a solvent can be used 0.1 to 10 times by weight with respect to the aromatic hydroxy compound of the present invention.
[0016]
The aromatic epoxy resin partially hydrogenated of the present invention thus obtained can be made into a curable composition together with a curing agent and a catalyst. Curing agents used here are amine curing agents such as diethylenetriamine, diaminodiphenylmethane, diaminodiphenylsulfone, and dicyandiamide, and acid anhydride curing such as nadic anhydride, phthalic anhydride, hymic anhydride, maleic anhydride, and trimellitic anhydride. Agents, phenol novolacs, aralkyl phenols, trisphenol methane, mixed novolaks of naphthol and cresol, etc., and the like, and the amount of these used is 0.5 to 1.7 times the epoxy equivalent of the epoxy resin. Is equivalent.
[0017]
As the curing catalyst, phosphorus compounds such as triphenylphosphine and phosphonium borate, phosphonium salts, tertiary amines such as imidazoles and DBU, and amine salts of boron trifluoride are used. The amount used is 0.5 to 5% by weight based on the epoxy resin.
[0018]
The curable composition of the present invention thus obtained is optionally mixed with a thermoplastic polymer such as polyarylate, polyester, polyether sulfone, polyimide or polyamide together with N-methylpyrrolidone, methyl ethyl ketone, dimethylformaldehyde, A cast film can be obtained by dissolving in a solvent such as ethylene glycol monomethyl ether or propylene glycol monomethyl ether acetate, or it can be used as an encapsulant composition or an adhesive with an inorganic filler such as silica, alumina, or calcium carbonate. Can do. These compositions give cured products by curing at 120 to 200 ° C. and are used for various purposes.
In the above, the inorganic filler is used in an amount of 0 to 90% by weight in the sealing material composition.
[0019]
Hereinafter, the present invention will be described in more detail with reference to examples. Examples 1 to 3 are reference examples.
[0020]
Example 1
A 5% ruthenium / carbon catalyst (containing 50% by weight water) prepared according to JP-A-10-204002 was prepared. That is, 10 g of activated carbon and 100 g of water were added to a 200 ml beaker, and an aqueous solution of sodium ruthenium (VI) containing 0.5 g of ruthenium atoms was added at room temperature. The mixture was impregnated with stirring, and the precipitate was filtered and washed with ion-exchanged water. A 5% ruthenium / carbon catalyst (containing 50% water) was obtained.
In a 500 ml stainless steel autoclave, 4 g of the catalyst (containing 50% water) obtained above, o-cresol novolac type epoxy resin (trade name: EOCN-4400 (manufactured by Nippon Kayaku Co., Ltd.), softening point 62 ° C., The melt viscosity at 150 ° C. is 1.6 poise, the average number of aromatic nuclei in the molecule is about 4, the epoxy group is 2 or more) 20 g, 150 g of tetrahydrofuran are charged, and after nitrogen substitution, hydrogen substitution is performed. The pressure was 50 atm. When the temperature was gradually raised, the reaction was continued for 1 hour at 90 ° C with the hydrogen pressure kept constant, the hydrogen pressure when the reaction was returned to room temperature was measured, and the amount of hydrogen used was calculated by multiplying the volume of the space 3800 ml.
This corresponds to an amount in which 50% of the total aromatic nuclei are hydrogenated. After completion of the reaction, the catalyst was filtered off, and the epoxy resin of the present invention thus obtained had a softening point of 56 ° C. and an epoxy equivalent of 215 g / equivalent.
The melt viscosity at 150 ° C. of the obtained epoxy resin was 0.9 poise, and although the epoxy equivalent was slightly increased, the softening point and the partially-nucleated hydrogenated o-cresol novolac type epoxy having a decreased melt viscosity. A resin was obtained.
[0021]
Example 2
o-Cresol novolak (softening point 110 ° C .: Gunei Chemical Co., Ltd.) 20 g, 5% rhodium / carbon (50% water content; manufactured by NV Chemcat) 4 g, ethylene glycol monoethyl ether 150 g in a 500 ml stainless steel autoclave After charging and replacing with nitrogen, replacing with hydrogen, the hydrogen pressure was adjusted to 50 atm. The temperature was gradually raised, and the reaction was carried out at 90 ° C. with the hydrogen pressure kept constant for 1 hour to obtain the aromatic hydroxy compound of the present invention.
When the hydrogen pressure was returned to room temperature after completion of the reaction and the amount of hydrogen used was calculated, it was 3300 ml.
This corresponds to an amount in which 30% of the total aromatic nuclei are hydrogenated.
[0022]
Example 3
While stirring 15.6 g of the aromatic hydroxy compound of the present invention obtained in Example 2, 50 g of epichlorohydrin, 0.05 g of tetramethylammonium chloride, and 20 g of dioxane in a 300 ml volumetric flask at 60 ° C. Over 2 hours, 4.9 g of solid caustic soda was gradually added and further reacted at 75 ° C. for 2 hours. Then, 100 g of methyl isobutyl ketone and 50 g of water were added, and the separated aqueous layer was removed. After newly adding 50 g of water and washing with water, methyl isobutyl ketone was distilled off under reduced pressure to obtain 20.5 g of the partially nuclear hydrogenated o-cresol novolak type epoxy resin of the present invention.
[0023]
Example 4
In a 500 ml stainless steel autoclave, biphenyldiyldimethylene-phenol type epoxy resin (trade name: NC-3000P (manufactured by Nippon Kayaku Co., Ltd.), epoxy equivalent 275 g / equivalent, softening point 58 ° C., 150 ° C. ICI viscosity 0.9P, average number of aromatic nuclei in molecule 6.6, number of epoxy groups 2 or more, average molecular weight 770) 20 g, 5% rhodium / carbon (50% water content; manufactured by NV Chemcat) ) 3 g and 150 g of diethylene glycol dimethyl ether were charged, and after nitrogen substitution, the hydrogen pressure was changed to 50 atm. The temperature is gradually raised, the reaction is continued at 85 ° C for 0.5 hours with the hydrogen pressure kept constant, the hydrogen pressure when the reaction is returned to room temperature is measured, and the amount of hydrogen used is calculated by multiplying the space capacity. As a result, it was 4600 ml. This corresponds to the amount of hydrogenation of 40% of the total aromatic nuclei. The catalyst was filtered off from the reaction mixture, and the reaction solvent was distilled off from the filtrate under reduced pressure to obtain 20 g of a partially nuclear hydrogenated biphenyldiyldimethylene-phenol type epoxy resin. The resulting epoxy resin had a softening point of 55 ° C. and an epoxy equivalent of 288 g / equivalent. Further, the melt viscosity at 150 ° C. of the obtained epoxy resin was 0.6 poise, and although the epoxy equivalent was slightly increased, the softening point and the melt viscosity were lowered. In 1 H-NMR measurement, both the biphenyl group and the benzene ring of the phenyl group were randomly hydrogenated, and selectivity was not recognized.
[0024]
Example 5
Aralkylphenol type epoxy resin (trade name: XP-2030 (manufactured by Nippon Kayaku Co., Ltd.), epoxy equivalent 237, softening point 59 ° C., ICI viscosity 1.5 poise at 150 ° C.) instead of NC-3000P An aralkylphenol type epoxy resin in which 60% of the aromatic nuclei were hydrogenated was obtained in the same manner as in Example 4 except that it was used. The epoxy equivalent of the obtained epoxy resin was 248 g / equivalent, the softening point was 54 ° C., and the ICI viscosity was 0.9 poise at 150 ° C.
[0025]
Example 6
20 g of the epoxy resin obtained in Example 4, 12.8 g of aralkylphenol type resin (trade name: Milex XLC-225-3L, manufactured by Mitsui Chemicals, Inc.), 2-ethyl-4 methylimidazole 2 g, 35 g of polyethersulfone (trade name: PES5003P (manufactured by BASF)), 20 g of N-methylpyrrolidone, and 20 g of methyl ethyl ketone were mixed and dissolved at room temperature.
A cast film having a thickness of 50 μm was prepared from this solution, and the film was pressed against two copper foils having a thickness of 35 μm at 170 ° C. with a pressure of 50 kg / cm 2 and held for 3 hours. After the curing, when the peel strength was measured with a universal head tester at a crosshead speed of 200 mm / min, good adhesiveness of 2.1 kg / cm was shown.
[0026]
【The invention's effect】
According to the present invention, a partially aromatic hydrogenated aromatic epoxy resin having two types of epoxy groups having different reactivities in the same molecule is obtained, which can be applied to, for example, hot melt adhesives. Is possible.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| JP23245699A JP4341938B2 (en) | 1999-08-19 | 1999-08-19 | Partially hydrogenated polyfunctional aromatic epoxy resin and epoxy resin composition containing the same |
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|---|---|---|---|
| JP23245699A JP4341938B2 (en) | 1999-08-19 | 1999-08-19 | Partially hydrogenated polyfunctional aromatic epoxy resin and epoxy resin composition containing the same |
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| JP2001055429A JP2001055429A (en) | 2001-02-27 |
| JP4341938B2 true JP4341938B2 (en) | 2009-10-14 |
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| JP2002097251A (en) * | 2000-09-21 | 2002-04-02 | New Japan Chem Co Ltd | Alicyclic compound containing glycidyl group, its production method and epoxy resin composition using the same |
| JP3904458B2 (en) * | 2002-01-17 | 2007-04-11 | 三菱化学株式会社 | Method for producing alicyclic epoxy compound |
| JP5207501B2 (en) * | 2001-08-10 | 2013-06-12 | 日本化薬株式会社 | Epoxy resin composition for optical material and cured product thereof |
| JP4623499B2 (en) * | 2004-12-17 | 2011-02-02 | 日本化薬株式会社 | Hydrogenated epoxy resin |
| JP2011089130A (en) * | 2010-12-10 | 2011-05-06 | Nippon Kayaku Co Ltd | Epoxy resin composition for optical material and cured article thereof |
| JP2011252155A (en) * | 2011-07-25 | 2011-12-15 | Nippon Kayaku Co Ltd | Epoxy resin composition for optical material, and its cured product |
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