JP3659533B2 - Epoxy resin, epoxy resin composition and cured product thereof - Google Patents
Epoxy resin, epoxy resin composition and cured product thereof Download PDFInfo
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- JP3659533B2 JP3659533B2 JP21596496A JP21596496A JP3659533B2 JP 3659533 B2 JP3659533 B2 JP 3659533B2 JP 21596496 A JP21596496 A JP 21596496A JP 21596496 A JP21596496 A JP 21596496A JP 3659533 B2 JP3659533 B2 JP 3659533B2
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- 0 C**c1ccc(C2(c3ccccc3-c3c2cccc3)c2cc(*C)c(C)cc2)cc1* Chemical compound C**c1ccc(C2(c3ccccc3-c3c2cccc3)c2cc(*C)c(C)cc2)cc1* 0.000 description 1
Description
【０００１】
【発明の属する技術分野】
本発明は耐熱性及び耐水性に優れる硬化物を与えるエポキシ樹脂、およびエポキシ樹脂組成物に関する。
【０００２】
【従来の技術】
エポキシ樹脂は種々の硬化剤で硬化させることにより、一般的に機械的性質、耐水性、耐薬品性、耐熱性、電気的性質などに優れた硬化物となり、接着剤、塗料、積層板、成形材料、注型材料などの幅広い分野に利用されている。従来、工業的に最も使用されているエポキシ樹脂としてビスフェノ−ルＡにエピクロルヒドリンを反応させて得られる液状および固形のビスフェノ−ルＡ型エポキシ樹脂がある。その他液状のビスフェノ−ルＡ型エポキシ樹脂にテトラブロムビスフェノ−ルＡを反応させて得られる難燃性固形エポキシ樹脂などが汎用エポキシ樹脂として工業的に使用されている。
【０００３】
【発明が解決しようとする課題】
しかしながら、前記したような汎用エポキシ樹脂は分子量が大きくなるにつれて、それを使用して得られる硬化物の靭性は向上するものの耐熱性が低下するという欠点がある。また、汎用エポキシ樹脂にｏ−クレゾールノボラックエポキシ樹脂などの多官能エポキシ樹脂を添加した場合、その硬化物の耐熱性は向上するものの、耐水性及び靭性が低下するという問題がある。
【０００４】
【課題を解決するための手段】
本発明者らはこうした実状に鑑み、耐熱性、耐水性及び靭性に優れた硬化物を与えるエポキシ樹脂を求めて鋭意研究した結果、特定の分子構造を有するエポキシ樹脂が、その硬化物において優れた耐熱性、耐水性及び靭性を発現するものであることを見いだし本発明を完成させるに到った。
【０００５】
すなわち本発明は
（１）式（１）
【０００６】
【化２】
（式中、Ｒは水素原子または炭素数１〜４のアルキル基を表し、Ｇはグリシジル基を表す。）
【０００８】
で表されるエポキシ樹脂、
（２）上記（１）記載のエポキシ樹脂、硬化剤を含有してなるエポキシ樹脂組成物、
（３）硬化促進剤を含有する上記（２）記載のエポキシ樹脂組成物、
（４）無機充填材を含有する上記（２）または（３）記載のエポキシ樹脂組成物、
（５）上記（２）、（３）及び（４）のいずれか１項に記載のエポキシ樹脂組成物を硬化してなる硬化物、
を提供するものである。
【０００９】
【発明の実施の形態】
【００１０】
前記（１）記載の式（１）で表される本発明のエポキシ樹脂は例えば、式（２）
【００１１】
【化３】
（式中、Ｒは式（１）におけるのと同じ意味を表す。）
【００１３】
で表される化合物とエピハロヒドリンとの反応をアルカリ金属水酸化物の存在下で行うことにより得ることができる。式（２）におけるＲとしては、水素原子、メチル基、エチル基、プロピル基、ブチル基等が好ましい基として挙げられ、水素原子またはメチル基が特に好ましい。
【００１４】
式（２）で表される化合物から本発明のエポキシ樹脂を得る方法としては公知の方法が採用できる。例えば式（２）の化合物と過剰のエピクロルヒドリン、エピブロムヒドリン等のエピハロヒドリンの溶解混合物に水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物を一括で添加し、または添加しながら２０〜１２０℃で１〜１０時間反応させることにより本発明のエポキシ樹脂を得ることが出来る。
【００１５】
本発明のエポキシ樹脂を得る反応において、アルカリ金属水酸化物はその水溶液を使用してもよく、その場合は該アルカリ金属水酸化物の水溶液を連続的に反応系内に添加すると共に減圧下、または常圧下連続的に水及びエピハロヒドリンを流出させ、更に分液し水は除去しエピハロヒドリンは反応系内に連続的に戻す方法でもよい。
【００１６】
また、式（２）で表される化合物とエピハロヒドリンの溶解混合物にテトラメチルアンモニウムクロライド、テトラメチルアンモニウムブロマイド、トリメチルベンジルアンモニウムクロライド等の４級アンモニウム塩を触媒として添加し、更にアルカリ金属水酸化物の固体または水溶液を加え、２０〜１２０℃で０．５〜８時間反応させ脱ハロゲン化水素（閉環）させる方法でもよい。
【００１７】
通常これらの反応において使用されるエピハロヒドリンの量は式（２）で表される化合物の水酸基１当量に対し通常１〜２０モル、好ましくは２〜１０モルである。アルカリ金属水酸化物の使用量は式（２）で表される化合物中の水酸基１当量に対し通常０．８〜２．０モル、好ましくは０．９〜１．８モルである。また、反応を円滑に進行させるためにジメチルスルホン、ジメチルスルホキシド等の非プロトン性極性溶媒などを添加して反応を行うことが好ましい。
【００１８】
非プロトン性極性溶媒を使用する場合はエピハロヒドリンの量に対し通常５〜１５０重量％、好ましくは１０〜１４０重量％である。
【００１９】
これらのエポキシ化反応の反応物を水洗後、または水洗無しに加熱減圧下、１００〜１５０℃、圧力１０ｍｍＨｇ以下でエピハロヒドリンや溶媒などを除去する。また更に加水分解性ハロゲンの少ないエポキシ樹脂とするために、得られたエポキシ樹脂をトルエン、メチルイソブチルケトン、メチルエチルケトンなどの溶剤に溶解し、水酸化ナトリウム、水酸化カリウムなどのアルカリ金属水酸化物の水溶液を加えて更に反応を行い閉環を確実なものにすることもできる。この場合アルカリ金属水酸化物の使用量はエポキシ化に使用した式（２）の化合物の水酸基１当量に対して通常０．０１〜０．３モル、好ましくは０．０５〜０．２モルである。反応温度は通常５０〜１２０℃、反応時間は通常０．５〜２時間である。
【００２０】
反応終了後、生成した塩を濾過、水洗などにより除去し、更に、加熱減圧下トルエン、メチルイソブチルケトン、メチルエチルケトンなどの溶剤を留去することにより加水分解性ハロゲンの少ない本発明のエポキシ樹脂が得られる。
【００２１】
以下、本発明のエポキシ樹脂組成物について説明する。本発明のエポキシ樹脂組成物において本発明のエポキシ樹脂は単独でまた他のエポキシ樹脂と併用して使用することが出来る。併用する場合、本発明のエポキシ樹脂の全エポキシ樹脂中に占める割合は３０重量％以上が好ましく、特に４０重量％以上が好ましい。
【００２２】
本発明のエポキシ樹脂と併用しうる他のエポキシ樹脂の具体例としてはノボラック型エポキシ樹脂、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、ビフェニル型エポキシ樹脂などが挙げられるがこれらは単独で用いてもよく、２種以上併用してもよい。
【００２３】
本発明のエポキシ樹脂組成物は硬化剤を含有する。本発明のエポキシ樹脂組成物において使用される硬化剤としては、例えばアミン系化合物、酸無水物系化合物、アミド系化合物、フェノ−ル系化合物などが挙げられる。用い得る硬化剤の具体例としては、ジアミノジフェニルメタン、ジエチレントリアミン、トリエチレンテトラミン、ジアミノジフェニルスルホン、イソホロンジアミン、ジシアンジアミド、リノレン酸の２量体とエチレンジアミンとより合成されるポリアミド樹脂、無水フタル酸、無水トリメリット酸、無水ピロメリット酸、無水マレイン酸、テトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、無水メチルナジック酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、フェノ−ルノボラック、及びこれらの変性物、イミダゾ−ル、ＢＦ3 −アミン錯体、グアニジン誘導体などが挙げられるが、エポキシ樹脂の硬化剤として通常使用されるものであればこれらに限定されるものではない。これらは単独で用いてもよく、２種以上併用してもよい。
【００２４】
本発明のエポキシ樹脂組成物において硬化剤の使用量は、エポキシ樹脂のエポキシ基１当量に対して０．７〜１．２当量が好ましい。エポキシ基１当量に対して、０．７当量に満たない場合、あるいは１．２当量を超える場合、いずれも硬化が不完全となり良好な硬化物性が得られない恐れがある。
【００２５】
また上記硬化剤を用いる際に硬化促進剤を併用しても差し支えない。用いうる硬化促進剤の具体例としては２−メチルイミダゾール、２−エチルイミダゾール、２−エチル−４−メチルイミダゾール等のイミダゾ−ル類、２−（ジメチルアミノメチル）フェノール、１，８−ジアザ−ビシクロ（５，４，０）ウンデセン−７等の第３級アミン類、トリフェニルホスフィン等のホスフィン類、オクチル酸スズ等の金属化合物等が挙げられる。硬化促進剤はエポキシ樹脂１００重量部に対して０．１〜５．０重量部が必要に応じ用いられる。
【００２６】
本発明のエポキシ樹脂は必要により無機充填材を含有する。用いうる無機充填材の具体例としてはシリカ、アルミナ、タルク等が挙げられる。無機充填材は本発明のエポキシ樹脂組成物中において０〜９０重量％を占める量が用いられる。更に本発明のエポキシ樹脂組成物には、シランカップリング剤、ステアリン酸、パルミチン酸、ステアリン酸亜鉛、ステアリン酸カルシウム等の離型剤、顔料等の種々の配合剤を添加することができる。
【００２７】
本発明のエポキシ樹脂組成物は、各成分を所定の割合で均一に混合することにより得られる。本発明のエポキシ樹脂組成物は従来知られている方法と同様の方法で容易にその硬化物とすることができる。例えば本発明のエポキシ樹脂と硬化剤、必要により硬化促進剤、無機充填材並びに配合材とを必要に応じて押出機、ニ−ダ、ロ−ル等を用いて均一になるまで充分に混合してエポキシ樹脂組成物を得、そのエポキシ樹脂組成物を溶融後注型あるいはトランスファ−成形機などを用いて成形し、さらに８０〜２００℃で２〜１０時間加熱することにより本発明の硬化物を得ることができる。
【００２８】
また本発明のエポキシ樹脂組成物をトルエン、キシレン、アセトン、メチルエチルケトン、メチルイソブチルケトン等の溶剤に溶解させ、ガラス繊維、カ−ボン繊維、ポリエステル繊維、ポリアミド繊維、アルミナ繊維、紙などの基材に含浸させ加熱乾燥して得たプリプレグを熱プレス成形して硬化物を得ることもできる。この際の溶剤は、本発明のエポキシ樹脂組成物と該溶剤の混合物中で通常１０から７０重量％、好ましくは１５〜７０重量％、このましくは１５〜６５重量％を占める量を用いる。
【００２９】
こうして得られる硬化物は本発明の耐熱性に優れており、硬化前のエポキシ樹脂及びエポキシ樹脂組成物は低粘度で作業性が良好であるため、耐熱性、低粘度の要求される広範な分野で用いることができる。具体的には封止材料、積層板、絶縁材料などのあらゆる電気・電子材料として有用である。また、成型材料、接着剤、複合材料、塗料などの分野にも用いることができる。
【００３０】
【実施例】
次に本発明を実施例、比較例により具体的に説明するが、以下において部は特に断わりのない限り重量部である。
【００３１】
実施例１
温度計、滴下ロート、冷却管、撹拌器を取り付けたフラスコに窒素ガスパージを施しながら下記式（３）
【００３２】
【化４】
で表される化合物２２０部をエピクロルヒドリン３７０部に溶解させ、テトラメチルアンモニウムクロライド５部を添加した。更に４５℃に加熱しフレーク状水酸化ナトリウム６０部を１００分かけて分割添加し、その後、更に４５℃で３時間反応させた。反応終了後水洗を２回行い生成塩などを除去した後、ロータリーエバポレーターを使用し、１３０℃に加熱し減圧下で過剰のエピクロルヒドリン等を留去し、残留物に５５２部のメチルイソブチルケトンを加え溶解した。
【００３４】
このメチルイソブチルケトンの溶液を７０℃に加熱し３０重量％の水酸化ナトリウム水溶液１０部を添加し１時間反応させた後、洗浄液のｐＨが中性となるまで水洗を繰り返した。更に水層は分離除去し、ロータリエバポレーターを使用して油層から加熱減圧下メチルイソブチルケトンを留去し、下記式（４）
【００３５】
【化５】
（式中、Ｇはグリシジル基を表す。）
【００３７】
で表される本発明のエポキシ樹脂（Ａ）２５３部を得た。得られたエポキシ樹脂は固形でありエポキシ当量は２９４ｇ／ｅｑであった。
【００３８】
実施例２
実施例１において式（３）で表される化合物の代わりに下記式（５）
【００３９】
【化６】
で表される化合物２３３部を用いた以外は実施例１と同様にエポキシ化反応を行い、下記式（６）
【００４１】
【化７】
（式中、Ｇはグリシジル基を表す。）
【００４３】
で表されるエポキシ樹脂（Ｂ）２６８部を得た。得られたエポキシ樹脂は固形でありエポキシ当量は３０７ｇ／ｅｑであった。
【００４４】
実施例３〜４
実施例１〜２で得られたエポキシ樹脂（Ａ）及び（Ｂ）に対し硬化剤としてフェノールノボラック（水酸基当量１０６ｇ／ｅｑ、軟化点８３℃、日本化薬（株）製）を、また硬化促進剤としてトリフェニルホスフィン（ＴＰＰ）を用いて表１の配合物の組成の欄に示す割合で配合して、７０℃で１５分ロールで混練し１５０℃、成型圧力５０ｋｇ／ｃｍ2 で１８０秒間トランスファー成型して、その後１６０℃で２時間、更に１８０℃で８時間硬化せしめて試験片を作成し、ガラス転移点及び吸水率を測定した。結果を表１に示す。尚、表中配合物の組成の欄の数値は部を表す。
【００４５】
ガラス転移点
熱機械測定装置（ＴＭＡ）：真空理工（株）製 ＴＭ−７０００
昇温速度：２℃／ｍｉｎ
吸水率
【００４６】
【表１】
表１より本発明のエポキシ樹脂の硬化物は、高いガラス転移点及び低い吸水率を示すことが明らかである。
【００４８】
【発明の効果】
本発明のエポキシ樹脂は、従来一般的に使用されてきたエポキシ樹脂と比較して、耐熱性及び耐水性に優れた硬化物を与えることができ、成形材料、注型材料、積層材料、塗料、接着剤、レジストなどの広範囲の用途にきわめて有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an epoxy resin that provides a cured product having excellent heat resistance and water resistance, and an epoxy resin composition.
[0002]
[Prior art]
Epoxy resins are generally cured with various curing agents, resulting in cured products with excellent mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, etc., adhesives, paints, laminates, moldings It is used in a wide range of fields such as materials and casting materials. Conventionally, epoxy resins most industrially used include liquid and solid bisphenol A type epoxy resins obtained by reacting bisphenol A with epichlorohydrin. In addition, a flame retardant solid epoxy resin obtained by reacting tetrabromobisphenol A with a liquid bisphenol A type epoxy resin is industrially used as a general-purpose epoxy resin.
[0003]
[Problems to be solved by the invention]
However, the general-purpose epoxy resin as described above has a drawback that although the toughness of a cured product obtained by using it increases as the molecular weight increases, the heat resistance decreases. In addition, when a polyfunctional epoxy resin such as o-cresol novolac epoxy resin is added to a general-purpose epoxy resin, the heat resistance of the cured product is improved, but there is a problem that water resistance and toughness are lowered.
[0004]
[Means for Solving the Problems]
In light of these circumstances, the present inventors have eagerly studied for an epoxy resin that gives a cured product excellent in heat resistance, water resistance, and toughness. As a result, an epoxy resin having a specific molecular structure is excellent in the cured product. It has been found that it exhibits heat resistance, water resistance and toughness, and the present invention has been completed.
[0005]
That is, the present invention relates to (1) formula (1)
[0006]
[Chemical formula 2]
(In the formula, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and G represents a glycidyl group.)
[0008]
Epoxy resin represented by
(2) The epoxy resin composition comprising the epoxy resin and the curing agent according to (1) above,
(3) The epoxy resin composition according to the above (2), which contains a curing accelerator,
(4) The epoxy resin composition according to the above (2) or (3), which contains an inorganic filler,
(5) Hardened | cured material formed by hardening | curing the epoxy resin composition of any one of said (2), (3) and (4),
Is to provide.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
[0010]
The epoxy resin of the present invention represented by the formula (1) described in the above (1) is, for example, the formula (2)
[0011]
[Chemical 3]
(In the formula, R represents the same meaning as in formula (1).)
[0013]
It can obtain by performing reaction of the compound represented by and epihalohydrin in presence of an alkali metal hydroxide. Examples of R in the formula (2) include a hydrogen atom, a methyl group, an ethyl group, a propyl group, and a butyl group, and a hydrogen atom or a methyl group is particularly preferable.
[0014]
As a method for obtaining the epoxy resin of the present invention from the compound represented by the formula (2), a known method can be adopted. For example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to a dissolved mixture of the compound of formula (2) and an excess of epihalohydrin such as epichlorohydrin or epibromhydrin in one batch, or while adding 20 to 120 The epoxy resin of this invention can be obtained by making it react at 1 degreeC for 1 to 10 hours.
[0015]
In the reaction for obtaining the epoxy resin of the present invention, an aqueous solution of the alkali metal hydroxide may be used. In that case, the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system and under reduced pressure. Alternatively, water and epihalohydrin are allowed to flow out continuously under normal pressure, followed by liquid separation, removal of water, and epihalohydrin being continuously returned to the reaction system.
[0016]
Further, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride is added as a catalyst to a dissolved mixture of the compound represented by formula (2) and epihalohydrin, and further an alkali metal hydroxide. A method of adding a solid or an aqueous solution and reacting at 20 to 120 ° C. for 0.5 to 8 hours to dehydrohalogenate (ring closure) may be used.
[0017]
Usually, the amount of epihalohydrin used in these reactions is usually 1 to 20 mol, preferably 2 to 10 mol, relative to 1 equivalent of the hydroxyl group of the compound represented by formula (2). The usage-amount of an alkali metal hydroxide is 0.8-2.0 mol normally with respect to 1 equivalent of hydroxyl groups in the compound represented by Formula (2), Preferably it is 0.9-1.8 mol. In order to make the reaction proceed smoothly, it is preferable to carry out the reaction by adding an aprotic polar solvent such as dimethylsulfone or dimethylsulfoxide.
[0018]
When an aprotic polar solvent is used, it is usually 5 to 150% by weight, preferably 10 to 140% by weight, based on the amount of epihalohydrin.
[0019]
After the reaction product of these epoxidation reactions is washed with water or without washing, the epihalohydrin, the solvent, and the like are removed at 100 to 150 ° C. and a pressure of 10 mmHg or less under reduced pressure by heating. Further, in order to obtain an epoxy resin with less hydrolyzable halogen, the obtained epoxy resin is dissolved in a solvent such as toluene, methyl isobutyl ketone, or methyl ethyl ketone, and an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is dissolved. An aqueous solution can be added to carry out further reaction to ensure ring closure. In this case, the amount of alkali metal hydroxide used is usually 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, relative to 1 equivalent of the hydroxyl group of the compound of formula (2) used for epoxidation. is there. The reaction temperature is usually 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours.
[0020]
After completion of the reaction, the produced salt is removed by filtration, washing with water, and the like, and further, the epoxy resin of the present invention with less hydrolyzable halogen is obtained by distilling off a solvent such as toluene, methyl isobutyl ketone, methyl ethyl ketone under heating and reduced pressure. It is done.
[0021]
Hereinafter, the epoxy resin composition of the present invention will be described. In the epoxy resin composition of the present invention, the epoxy resin of the present invention can be used alone or in combination with other epoxy resins. When used in combination, the proportion of the epoxy resin of the present invention in the total epoxy resin is preferably 30% by weight or more, particularly preferably 40% by weight or more.
[0022]
Specific examples of other epoxy resins that can be used in combination with the epoxy resin of the present invention include novolac type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, biphenyl type epoxy resins, and the like. It may also be used in combination of two or more.
[0023]
The epoxy resin composition of the present invention contains a curing agent. Examples of the curing agent used in the epoxy resin composition of the present invention include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, and the like. Specific examples of curing agents that can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, polyamide resin synthesized from linolenic acid and ethylenediamine, phthalic anhydride, triethylene anhydride. Merit acid, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, phenol novolac, and modified products thereof, Examples include imidazole, BF 3 -amine complexes, guanidine derivatives, and the like, but are not limited to these as long as they are usually used as a curing agent for epoxy resins. These may be used alone or in combination of two or more.
[0024]
In the epoxy resin composition of the present invention, the amount of the curing agent used is preferably 0.7 to 1.2 equivalents relative to 1 equivalent of the epoxy group of the epoxy resin. When less than 0.7 equivalent or more than 1.2 equivalent with respect to 1 equivalent of epoxy group, curing may be incomplete and good cured properties may not be obtained.
[0025]
Moreover, when using the said hardening | curing agent, a hardening accelerator may be used together. Specific examples of the curing accelerator that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, 1,8-diaza- And tertiary amines such as bicyclo (5,4,0) undecene-7, phosphines such as triphenylphosphine, and metal compounds such as tin octylate. The curing accelerator is used as necessary in an amount of 0.1 to 5.0 parts by weight based on 100 parts by weight of the epoxy resin.
[0026]
The epoxy resin of the present invention contains an inorganic filler as necessary. Specific examples of the inorganic filler that can be used include silica, alumina, talc and the like. The inorganic filler is used in an amount of 0 to 90% by weight in the epoxy resin composition of the present invention. Furthermore, various compounding agents such as a silane coupling agent, a release agent such as stearic acid, palmitic acid, zinc stearate, and calcium stearate, and a pigment can be added to the epoxy resin composition of the present invention.
[0027]
The epoxy resin composition of the present invention can be obtained by uniformly mixing each component at a predetermined ratio. The epoxy resin composition of the present invention can be easily made into a cured product by a method similar to a conventionally known method. For example, the epoxy resin of the present invention and a curing agent, if necessary, a curing accelerator, an inorganic filler, and a compounding material are mixed sufficiently until uniform using an extruder, kneader, roll, etc. as necessary. An epoxy resin composition is obtained, the epoxy resin composition is melted and then molded using a casting or transfer molding machine, and further heated at 80 to 200 ° C. for 2 to 10 hours to obtain the cured product of the present invention. Can be obtained.
[0028]
In addition, the epoxy resin composition of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc., and is applied to a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. A prepreg obtained by impregnation and drying by heating can be subjected to hot press molding to obtain a cured product. The solvent used in this case is usually 10 to 70% by weight, preferably 15 to 70% by weight, preferably 15 to 65% by weight in the mixture of the epoxy resin composition of the present invention and the solvent.
[0029]
The cured product thus obtained is excellent in the heat resistance of the present invention, and since the epoxy resin and epoxy resin composition before curing have low viscosity and good workability, a wide range of fields requiring heat resistance and low viscosity are required. Can be used. Specifically, it is useful as any electrical / electronic material such as a sealing material, a laminate, and an insulating material. It can also be used in fields such as molding materials, adhesives, composite materials and paints.
[0030]
【Example】
Next, the present invention will be specifically described with reference to examples and comparative examples. In the following, parts are parts by weight unless otherwise specified.
[0031]
Example 1
While applying a nitrogen gas purge to a flask equipped with a thermometer, dropping funnel, condenser, and stirrer, the following formula (3)
[0032]
[Formula 4]
Was dissolved in 370 parts of epichlorohydrin, and 5 parts of tetramethylammonium chloride was added. The mixture was further heated to 45 ° C., 60 parts of flaky sodium hydroxide was added in portions over 100 minutes, and then further reacted at 45 ° C. for 3 hours. After the completion of the reaction, washing with water is performed twice to remove the generated salt, etc., and then using a rotary evaporator, heating to 130 ° C. to distill off excess epichlorohydrin and the like under reduced pressure, adding 552 parts of methyl isobutyl ketone to the residue. Dissolved.
[0034]
This methyl isobutyl ketone solution was heated to 70 ° C., 10 parts of a 30 wt% aqueous sodium hydroxide solution was added and allowed to react for 1 hour, and then washing with water was repeated until the pH of the washing solution became neutral. Further, the aqueous layer was separated and removed, and methyl isobutyl ketone was distilled off from the oil layer under heating and reduced pressure using a rotary evaporator.
[0035]
[Chemical formula 5]
(In the formula, G represents a glycidyl group.)
[0037]
253 parts of the epoxy resin (A) of the present invention represented by the formula: The obtained epoxy resin was solid and the epoxy equivalent was 294 g / eq.
[0038]
Example 2
Instead of the compound represented by the formula (3) in Example 1, the following formula (5)
[0039]
[Chemical 6]
An epoxidation reaction was carried out in the same manner as in Example 1 except that 233 parts of the compound represented by formula (1) was used.
[0041]
[Chemical 7]
(In the formula, G represents a glycidyl group.)
[0043]
268 parts of an epoxy resin (B) represented by The obtained epoxy resin was solid and the epoxy equivalent was 307 g / eq.
[0044]
Examples 3-4
For the epoxy resins (A) and (B) obtained in Examples 1 and 2, phenol novolak (hydroxyl equivalent: 106 g / eq, softening point: 83 ° C., manufactured by Nippon Kayaku Co., Ltd.) as a curing agent, and curing acceleration Using triphenylphosphine (TPP) as the agent, blended at the ratio shown in the composition column of Table 1, kneaded with a roll at 70 ° C. for 15 minutes at 150 ° C. and molding pressure of 50 kg / cm 2 for 180 seconds. Molded, and then cured at 160 ° C. for 2 hours and further at 180 ° C. for 8 hours to prepare a test piece, and the glass transition point and water absorption were measured. The results are shown in Table 1. In addition, the numerical value of the column of the composition of the compound in a table | surface represents a part.
[0045]
Glass transition point thermomechanical measurement device (TMA): TM-7000, manufactured by Vacuum Riko Co., Ltd.
Temperature increase rate: 2 ° C / min
Water absorption
[0046]
[Table 1]
From Table 1, it is clear that the cured product of the epoxy resin of the present invention exhibits a high glass transition point and a low water absorption.
[0048]
【The invention's effect】
The epoxy resin of the present invention can give a cured product excellent in heat resistance and water resistance as compared with epoxy resins that have been generally used in the past, and can be used as a molding material, a casting material, a laminated material, a paint, It is extremely useful for a wide range of applications such as adhesives and resists.
Claims (5)
で表されるエポキシ樹脂。Formula (1)
Epoxy resin represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21596496A JP3659533B2 (en) | 1996-07-30 | 1996-07-30 | Epoxy resin, epoxy resin composition and cured product thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21596496A JP3659533B2 (en) | 1996-07-30 | 1996-07-30 | Epoxy resin, epoxy resin composition and cured product thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1045871A JPH1045871A (en) | 1998-02-17 |
| JP3659533B2 true JP3659533B2 (en) | 2005-06-15 |
Family
ID=16681166
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21596496A Expired - Lifetime JP3659533B2 (en) | 1996-07-30 | 1996-07-30 | Epoxy resin, epoxy resin composition and cured product thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3659533B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012111543A1 (en) | 2011-02-18 | 2012-08-23 | 三菱瓦斯化学株式会社 | Resin composition, prepreg, and metal-foil-cladded laminate board |
| US11067889B2 (en) | 2015-09-03 | 2021-07-20 | Mitsubishi Gas Chemical Company, Inc. | Compound, composition, and method for producing same, underlayer film forming material for lithography, composition for underlayer film formation for lithography, and purification method |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4186257B2 (en) * | 1998-06-18 | 2008-11-26 | 東レ株式会社 | Thermosetting resin solution composition for color filter, color filter, and liquid crystal display device |
| JP5363704B2 (en) * | 2006-09-19 | 2013-12-11 | 大阪瓦斯株式会社 | Epoxy resin for sealing and its use |
| JP5249578B2 (en) * | 2007-12-26 | 2013-07-31 | 大阪瓦斯株式会社 | Epoxy compound having fluorene skeleton |
| JP5129624B2 (en) * | 2008-03-24 | 2013-01-30 | 大阪瓦斯株式会社 | Epoxy compound |
| WO2014129877A1 (en) * | 2013-02-25 | 2014-08-28 | 한국생산기술연구원 | Epoxy compound having alkoxysilyl group, method for manufacturing same, composition and cured product including same, and use thereof |
| KR102232340B1 (en) | 2019-11-15 | 2021-03-26 | 한국생산기술연구원 | Composition of alkoxysilyl-functionalized epoxy resin and composite thereof |
-
1996
- 1996-07-30 JP JP21596496A patent/JP3659533B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012111543A1 (en) | 2011-02-18 | 2012-08-23 | 三菱瓦斯化学株式会社 | Resin composition, prepreg, and metal-foil-cladded laminate board |
| US11067889B2 (en) | 2015-09-03 | 2021-07-20 | Mitsubishi Gas Chemical Company, Inc. | Compound, composition, and method for producing same, underlayer film forming material for lithography, composition for underlayer film formation for lithography, and purification method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH1045871A (en) | 1998-02-17 |
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