JP3659532B2 - 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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- JP3659532B2 JP3659532B2 JP21596396A JP21596396A JP3659532B2 JP 3659532 B2 JP3659532 B2 JP 3659532B2 JP 21596396 A JP21596396 A JP 21596396A JP 21596396 A JP21596396 A JP 21596396A JP 3659532 B2 JP3659532 B2 JP 3659532B2
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Description
【０００１】
【発明の属する技術分野】
本発明は機械強度に優れる硬化物を与え、しかも粘度の低いエポキシ樹脂およびエポキシ樹脂組成物およびその硬化物に関するものであり、本発明のエポキシ樹脂及びエポキシ樹脂組成物は成形材料、注型材料、積層材料、複合材料、塗料、接着剤、レジストなどの広範囲の用途に極めて有用である。
【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機械強度は向上するものの粘度も上昇し作業性が低下するという欠点がある。
【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、機械強度に優れた硬化物を与え、しかも粘度の低い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低粘度であり、その硬化物において優れた靭性（機械強度）を付与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、ｎは平均値であり正数を表し０より大きく２０以下の値を示す。Ｒは水素原子、ハロゲン原子、又は炭素数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）（ａ）上記（１）記載のエポキシ樹脂
（ｂ）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】
式（１）で表される化合物は例えば、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。
【００１４】
式（２）で表される化合物においてｎの値は平均値であり、正数を表し、０より大きく２０以下の値を示すが、好ましくは０．０１〜１５、特に好ましくは０．５〜５である。
【００１５】
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。
【００１６】
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。
【００１７】
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２０〜１２０℃でアルカリ金属水酸化物の固体または水溶液を加え、２０〜１２０℃の温度で反応させ脱ハロゲン化水素（閉環）させる方法でもよい。この場合、反応時間は通常０．５〜１０時間である。
【００１８】
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。更に、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。この場合、反応時間は通常１〜８時間である。
【００１９】
非プロトン性極性溶媒は、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％が必要に応じて使用される。
【００２０】
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添加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、回収したエポキシ樹脂を再びトルエン、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。
【００２１】
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本発明のエポキシ樹脂が得られる。
【００２２】
以下、本発明のエポキシ樹脂組成物について説明する。前記（２）、（３）、（４）記載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。
【００２３】
本発明のエポキシ樹脂と併用しうる他のエポキシ樹脂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種以上用いてもよい。
【００２４】
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種以上用いてもよい。
【００２５】
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。
【００２６】
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。
【００２７】
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。
【００２８】
本発明のエポキシ樹脂組成物は、各成分を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、硬化剤更に必要により硬化促進剤の配合された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及び充填材等の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。
【００２９】
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。
【００３０】
こうして得られる硬化物は機械強度に優れており、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、機械強度、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。
【００３１】
【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。
【００３２】
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）
【００３３】
【化４】
（式中、ｎの平均値は２．６である。）
【００３５】
で表される化合物２８９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℃で加熱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６９０部のメチルイソブチルケトンを加え溶解した。
【００３６】
更に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が中性にま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）
【００３７】
【化５】
（式中、ｎの平均値は２．６であり、Ｇはグリシジル基を表す。）
【００３９】
で表される本発明のエポキシ樹脂（Ａ）２９３部を得た。得られたエポキシ樹脂は液状でありエポキシ当量は３６３ｇ／ｅｑであった。
【００４０】
実施例２
実施例１において、式（３）におけるｎの平均値が２．６の代わりに４．８である化合物を３８５部使用した以外は合成例１と同様に反応を行い前記式（４）で表される本発明のエポキシ樹脂（Ｂ）３７４部を得た。得られたエポキシ樹脂は液状でありエポキシ当量は４５９ｇ／ｅｑであった。
【００４１】
実施例３、４、比較例１
実施例３、４として得られたエポキシ樹脂（Ａ）及びエポキシ樹脂（Ｂ）に対し硬化剤として無水メチルナジック酸（カヤハードＭＣＤ、日本化薬（株）製）を用い、硬化促進剤として２−メチル−４−エチルイミダゾール（２Ｅ４ＭＺ）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、混合した後注型し８０℃で２時間、１２０℃で２時間、２００℃で５時間硬化せしめて試験片を作成し、ＪＩＳ Ｋ−６９１１に準じて曲げ強度を測定した。結果を表１に示す。尚、表中の配合物の組成の欄の中の数値は部を表す。
【００４２】
【表１】
表１より本発明のエポキシ樹脂の硬化物は、高い曲げ強度を示すことが明らかである。
【００４４】
【発明の効果】
本発明のエポキシ樹脂は、液状でありしかも従来一般的に使用されてきたエポキシ樹脂と比較して、機械強度に優れた硬化物を与える。
すなわち本発明のエポキシ樹脂は機械強度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 and an epoxy resin composition having a low mechanical strength and a cured product having excellent mechanical strength. The epoxy resin and the epoxy resin composition of the present invention are a molding material, a casting material, It is extremely useful for a wide range of applications such as laminated materials, composite materials, paints, adhesives, and resists.
[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, as the molecular weight increases, the mechanical strength of the cured product obtained by using it increases, but the viscosity also increases and the workability decreases.
[0004]
[Means for Solving the Problems]
In view of such a situation, the present inventors have obtained a cured product having excellent mechanical strength, and have eagerly studied for an epoxy resin having a low viscosity. As a result, an epoxy resin having a specific molecular structure has a low viscosity, and its cured The present invention was completed by finding that it imparts excellent toughness (mechanical strength) to a product.
[0005]
That is, the present invention relates to (1) formula (1)
[0006]
[Chemical formula 2]
(In the formula, n represents an average value and represents a positive number and represents a value greater than 0 and 20 or less. R represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms, and G represents a glycidyl group. .)
[0008]
Epoxy resin represented by
(2) (a) an epoxy resin composition comprising the epoxy resin (b) curing agent described in (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 compound represented by the formula (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.
[0014]
In the compound represented by the formula (2), the value of n is an average value, represents a positive number, and represents a value greater than 0 and 20 or less, preferably 0.01 to 15, particularly preferably 0.5 to 5.
[0015]
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 epibromohydrin, or while adding at 20 to 120 ° C. The epoxy resin of this invention can be obtained by making it react for 1 to 10 hours.
[0016]
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.
[0017]
Further, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride or the like is added to a dissolved mixture of the compound represented by formula (2) and epihalohydrin as a catalyst, and alkali metal water is used at 20 to 120 ° C. A method of adding a solid or aqueous solution of an oxide and reacting at a temperature of 20 to 120 ° C. to dehydrohalogenate (ring closure) may be used. In this case, the reaction time is usually 0.5 to 10 hours.
[0018]
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. Furthermore, it is preferable to carry out the reaction by adding an aprotic polar solvent such as dimethylsulfone or dimethylsulfoxide in order to allow the reaction to proceed smoothly. In this case, the reaction time is usually 1 to 8 hours.
[0019]
The aprotic polar solvent is usually used in an amount of 5 to 150% by weight, preferably 10 to 140% by weight, based on the amount of epihalohydrin.
[0020]
After the reaction product of these epoxidation reactions is washed with water or without washing with water, epihalohydrin, added solvent, and the like are removed at 100 to 150 ° C. under a pressure of 10 mmHg or less under reduced pressure. Further, in order to make an epoxy resin with less hydrolyzable halogen, the recovered epoxy resin is dissolved again in a solvent such as toluene, methyl isobutyl ketone, methyl ethyl ketone, etc., 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.
[0021]
After completion of the reaction, the produced salt is removed by filtration, washing with water, etc., and the solvent of toluene, methyl isobutyl ketone, methyl ethyl ketone, etc. is distilled off under heating and reduced pressure to obtain the epoxy resin of the present invention.
[0022]
Hereinafter, the epoxy resin composition of the present invention will be described. In the epoxy resin compositions described in the above (2), (3), and (4), 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.
[0023]
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. Two or more kinds may be used.
[0024]
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 the curing agent 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 novolak, and modified products thereof, Examples include, but are not limited to, imidazole, BF 3 -amine complexes, guanidine derivatives, and the like. These may be used alone or in combination of two or more.
[0025]
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.
[0026]
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.
[0027]
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.
[0028]
The epoxy resin composition of this invention is obtained by mixing each component uniformly. The epoxy resin composition of the present invention in which the epoxy resin of the present invention, a curing agent and, if necessary, a curing accelerator are blended 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, and if necessary, a blending material such as a curing accelerator and a filler are mixed thoroughly using an extruder, kneader, roll, etc. as necessary until uniform. 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.
[0029]
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.
[0030]
The cured product thus obtained has excellent mechanical strength, and the epoxy resin and epoxy resin composition before curing have low viscosity and good workability, so they should be used in a wide range of fields where mechanical strength and low viscosity are required. Can do. 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.
[0031]
【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.
[0032]
Example 1
While applying a nitrogen gas purge to a flask equipped with a thermometer, dropping funnel, condenser, and stirrer, the following formula (3)
[0033]
[Formula 4]
(In the formula, the average value of n is 2.6.)
[0035]
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 completion of the reaction, the product was washed with water to remove the produced salt and the like, and then a rotary evaporator was used. Excess epichlorohydrin and the like were distilled off at 130 ° C. under reduced pressure by heating, and 690 parts of methyl isobutyl ketone was added to the residue and dissolved.
[0036]
Further, this methyl isobutyl ketone solution was heated to 70 ° C., 10 parts of a 30% by weight aqueous sodium hydroxide solution was added and reacted for 1 hour, and then washed with water 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.
[0037]
[Chemical formula 5]
(In the formula, the average value of n is 2.6, and G represents a glycidyl group.)
[0039]
293 parts of the epoxy resin (A) of the present invention represented by the formula: The obtained epoxy resin was liquid and the epoxy equivalent was 363 g / eq.
[0040]
Example 2
In Example 1, the reaction was performed in the same manner as in Synthesis Example 1 except that 385 parts of the compound in which the average value of n in formula (3) was 4.8 instead of 2.6 was used. 374 parts of the epoxy resin (B) of the present invention was obtained. The obtained epoxy resin was liquid and the epoxy equivalent was 459 g / eq.
[0041]
Examples 3 and 4 and Comparative Example 1
For the epoxy resin (A) and epoxy resin (B) obtained as Examples 3 and 4, methyl nadic acid anhydride (Kayahard MCD, manufactured by Nippon Kayaku Co., Ltd.) was used as the curing agent, and 2- Using methyl-4-ethylimidazole (2E4MZ), blended in the proportions shown in the composition column of Table 1, mixed, cast, and cast at 80 ° C for 2 hours, 120 ° C for 2 hours, and 200 ° C. A test piece was prepared by curing for 5 hours, and the bending strength was measured according to JIS K-6911. The results are shown in Table 1. In addition, the numerical value in the column of the composition of the compound in a table | surface represents a part.
[0042]
[Table 1]
From Table 1, it is clear that the cured product of the epoxy resin of the present invention exhibits high bending strength.
[0044]
【The invention's effect】
The epoxy resin of the present invention is liquid and gives a cured product having excellent mechanical strength as compared with epoxy resins that have been generally used.
That is, the epoxy resin of the present invention can give a cured product having excellent mechanical strength, and is extremely useful for a wide range of applications such as molding materials, casting materials, laminated materials, paints, adhesives, and resists.
Claims (5)
（ｂ）硬化剤
を含有してなるエポキシ樹脂組成物。(A) An epoxy resin composition comprising the epoxy resin according to claim 1 (b) a curing agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21596396A JP3659532B2 (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 |
|---|---|---|---|
| JP21596396A JP3659532B2 (en) | 1996-07-30 | 1996-07-30 | Epoxy resin, epoxy resin composition and cured product thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1036485A JPH1036485A (en) | 1998-02-10 |
| JP3659532B2 true JP3659532B2 (en) | 2005-06-15 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP21596396A Expired - Lifetime JP3659532B2 (en) | 1996-07-30 | 1996-07-30 | Epoxy resin, epoxy resin composition and cured product thereof |
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Families Citing this family (13)
| 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 |
| JP4646439B2 (en) * | 2001-05-23 | 2011-03-09 | 大阪瓦斯株式会社 | Photopolymerizable resin composition, cured product thereof and production method |
| TWI306463B (en) * | 2002-06-28 | 2009-02-21 | Osaka Gas Co Ltd | Resin composition containing fluorene |
| JP2004083855A (en) * | 2002-06-28 | 2004-03-18 | Osaka Gas Co Ltd | Fluorene-containing resin |
| JP5129802B2 (en) * | 2003-04-22 | 2013-01-30 | 大阪瓦斯株式会社 | Fluorene-based composition and molded article thereof |
| JP4836411B2 (en) * | 2003-04-22 | 2011-12-14 | 大阪瓦斯株式会社 | Fluorene-based composition and molded article thereof |
| JP4548647B2 (en) * | 2003-10-03 | 2010-09-22 | 日本化薬株式会社 | Liquid epoxy resin, epoxy resin composition and cured product thereof |
| JP4966484B2 (en) * | 2004-07-22 | 2012-07-04 | 大阪瓦斯株式会社 | Fluorene compound and method for producing the same |
| JP5192641B2 (en) * | 2005-10-07 | 2013-05-08 | 大阪瓦斯株式会社 | Compound having fluorene skeleton and method for producing the same |
| 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 |
| JP6435226B2 (en) * | 2015-04-01 | 2018-12-05 | 大阪ガスケミカル株式会社 | Epoxy resin having fluorene skeleton and method for producing the same |
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1996
- 1996-07-30 JP JP21596396A patent/JP3659532B2/en not_active Expired - Lifetime
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