JP4863434B2 - 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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本発明は低吸湿で線膨張率が低く耐熱性の高い硬化物を与えるエポキシ樹脂及びエポキシ樹脂組成物に関する。 The present invention relates to an epoxy resin and an epoxy resin composition that give a cured product with low moisture absorption, low linear expansion coefficient and high heat resistance.
エポキシ樹脂としては、一般にビスフェノールＡのジグリシジルエーテルが広く知られており、更に高耐熱性が要求される分野においてはフェノールノボラックやクレゾールノボラックのポリグリシジルエーテル化物が主に用いられている。また、近年では電気・電子部品用途においては配線の微細化に伴い、線膨張率の低減が求められている。このような要求に対して、例えば特許文献１においてはビナフタレン骨格を有するエポキシ樹脂が低線膨張率化に有効であることが開示されている。 As the epoxy resin, diglycidyl ether of bisphenol A is generally widely known, and in the field where high heat resistance is required, a polyglycidyl etherified product of phenol novolak or cresol novolak is mainly used. Further, in recent years, reduction of the linear expansion coefficient has been demanded with the miniaturization of wiring in electrical / electronic component applications. In response to such a demand, for example, Patent Document 1 discloses that an epoxy resin having a binaphthalene skeleton is effective in reducing the linear expansion coefficient.
しかしながら、特許文献１において開示されているエポキシ樹脂は、低線膨張率化は達成しているものの、耐熱性の面で不十分である。また、機械強度の面で問題がある。 However, although the epoxy resin disclosed in Patent Document 1 has achieved a low linear expansion coefficient, it is insufficient in terms of heat resistance. There is also a problem in terms of mechanical strength.
本発明者らはこうした実状に鑑み、線膨張率が低くしかも耐熱性、耐水性、強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、本発明を完成させるに到った。 In light of these circumstances, the present inventors have intensively studied for an epoxy resin that has a low coefficient of linear expansion and is excellent in heat resistance, water resistance, and toughness. As a result, the present invention has been completed. .
すなわち本発明は
（１）下記式（１）
That is, the present invention provides (1) the following formula (1)
（式中、ｎは平均値で０．５〜１０を表す。Ｘは水素原子或いはグリシジル基を表す。）
で表されるエポキシ樹脂、
（２）上記（１）記載のエポキシ樹脂及び硬化剤を含むエポキシ樹脂組成物、
（３）硬化促進剤を含有する（２）記載のエポキシ樹脂組成物、
（４）無機充填剤を含有する上記（２）または（３）記載のエポキシ樹脂組成物、
（５）上記（２）、（３）または（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。
(In the formula, n represents an average value of 0.5 to 10. X represents a hydrogen atom or a glycidyl group.)
Epoxy resin represented by
(2) An epoxy resin composition comprising the epoxy resin and the curing agent according to (1) above,
(3) The epoxy resin composition according to (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) or (4),
Is provided.
本発明のエポキシ樹脂はナフタレン骨格を含むため、その硬化物は線膨張率が低く耐水性に優れ、しかも多官能であるため耐熱性に優れており、高度な信頼性を要求される分野に適している。 Since the epoxy resin of the present invention contains a naphthalene skeleton, its cured product has a low coefficient of linear expansion, excellent water resistance, and is multifunctional, so it has excellent heat resistance and is suitable for fields that require high reliability. ing.
本発明において原料としては１，２−ジヒドロキシナフタレン、１，３−ジヒドロキシナフタレン、１，５−ジヒドロキシナフタレン、１，６−ジヒドロキシナフタレン、２，３−ジヒドロキシナフタレン、２，６−ジヒドロキシナフタレン、２，７−ジヒドロキシナフタレン等が挙げられる。これらのジヒドロキシナフタレン化合物は１種のみを使用してもよく、２種以上を併用しても構わないが、１，５−ジヒドロキシナフタレン、１，６−ジヒドロキシナフタレンが特に好ましい。 In the present invention, raw materials include 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2, Examples include 7-dihydroxynaphthalene. These dihydroxynaphthalene compounds may be used alone or in combination of two or more, but 1,5-dihydroxynaphthalene and 1,6-dihydroxynaphthalene are particularly preferred.
これらのジヒドロキシナフタレン化合物とエピハロヒドリンとをアルカリ金属水酸化物の存在下で反応させ低分子量のグリシジルエーテル化物を調製した後、更にジヒドロキシナフタレンと反応させ高分子量化させた後、分子中に含まれるアルコール性水酸基をグリシジルエーテル化す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。ジヒドロキシナフタレンのグリシジルエーテル化物は、粘度が高く扱いにくいため、このような手法を採用することが好ましい。 These dihydroxynaphthalene compounds and epihalohydrin are reacted in the presence of an alkali metal hydroxide to prepare a low molecular weight glycidyl ether, and further reacted with dihydroxynaphthalene to increase the molecular weight, followed by alcohol contained in the molecule. The epoxy resin of the present invention can be obtained by glycidyl etherification of the functional hydroxyl group. Since the glycidyl etherified product of dihydroxynaphthalene has a high viscosity and is difficult to handle, it is preferable to employ such a method.
この製法においてエピハロヒドリンとしてはエピクロルヒドリンやエピブロムヒドリンを用いることが出来る。エピハロヒドリンの量はナフタレン化合物の水酸基１当量に対し通常２〜１５モル、好ましくは３〜１２モルである。 In this production method, epichlorohydrin or epibromohydrin can be used as the epihalohydrin. The amount of epihalohydrin is usually 2 to 15 mol, preferably 3 to 12 mol, per 1 equivalent of the hydroxyl group of the naphthalene compound.
アルカリ金属水酸化物としては水酸化ナトリウム、水酸化カリウム等が挙げられ固体でも、その水溶液を使用しても良く、水溶液を使用する場合は連続的に反応系内に添加すると同時に減圧下、または常圧下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。アルカリ金属水酸化物の使用量は当該ジヒドロキシナフタレン化合物の水酸基１モルに対して通常０．９〜１．２モルであり、好ましくは０．９５〜１．１５モルである。反応温度は通常２０〜１１０℃であり、好ましくは２５〜１００℃である。反応時間は通常０．５〜１５時間であり、好ましくは１〜１０時間である。 Examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide and the like, and may be solid or an aqueous solution thereof. When an aqueous solution is used, it is continuously added to the reaction system and simultaneously under reduced pressure, or Ordinary pressure sewage and epihalohydrin may be allowed to flow out and separated, water may be removed, and epihalohydrin may be continuously returned to the reaction system. The usage-amount of an alkali metal hydroxide is 0.9-1.2 mol normally with respect to 1 mol of hydroxyl groups of the said dihydroxy naphthalene compound, Preferably it is 0.95-1.15 mol. The reaction temperature is usually 20 to 110 ° C, preferably 25 to 100 ° C. The reaction time is usually 0.5 to 15 hours, preferably 1 to 10 hours.
メタノール、エタノール、プロパノール、ブタノールなどのアルコール類、或いはジメチルスルホキシド、ジメチルスルホンなどの非プロトン性極性溶媒を添加することは反応を促進させる上で好ましい。 Addition of alcohols such as methanol, ethanol, propanol and butanol, or aprotic polar solvents such as dimethyl sulfoxide and dimethyl sulfone is preferable for promoting the reaction.
アルコール類を使用する場合、その使用量はエピクロルヒドリンの量に対し通常３〜３０重量％、好ましくは５〜２０重量％である。非プロトン性極性溶媒を使用する場合、その使用量はエピハロヒドリンの量に対して通常１０〜１５０重量％、好ましくは１５〜１２０重量％である。 When using alcohol, the amount of its use is 3-30 weight% normally with respect to the quantity of epichlorohydrin, Preferably it is 5-20 weight%. When an aprotic polar solvent is used, the amount used is usually 10 to 150% by weight, preferably 15 to 120% by weight, based on the amount of epihalohydrin.
また、エピハロヒドリンと当該ジヒドロキシナフタレン化合物の溶液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などの４級アンモニウム塩触媒として添加し３０〜１１０℃で０．５〜８時間反応させて得られるハロヒドリンエーテル化合物にアルカリ金属水酸化物の固体または水溶液を加え２０〜１００℃で１〜１０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。 Moreover, it is obtained by adding a quaternary ammonium salt catalyst such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride to a solution of epihalohydrin and the dihydroxynaphthalene compound and reacting at 30 to 110 ° C. for 0.5 to 8 hours. A method of adding a solid or aqueous solution of an alkali metal hydroxide to the halohydrin ether compound and reacting at 20 to 100 ° C. for 1 to 10 hours to dehydrohalogenate (ring closure) may be used.
これらのエポキシ化反応の反応物を水洗後、或いは水洗無しに加熱減圧下で過剰のエピハロヒドリン及び溶剤などで除去する。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トルエン、メチルイソブチルケトンなどに溶解させ、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の水溶液を加えて閉環を確実にすることも出来る。この場合、アルカリ金属水酸化物の使用量はジヒドロキシナフタレン化合物の水酸基１モルに対して通常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。 The reaction product of these epoxidation reactions is removed with excess epihalohydrin and a solvent under heating and reduced pressure after washing with water or without washing with water. Furthermore, in order to make an epoxy resin with less hydrolyzable halogen, the recovered epoxy resin is dissolved in toluene, methyl isobutyl ketone, etc., and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to perform ring closure. Can also be ensured. In this case, the usage-amount of an alkali metal hydroxide is 0.01-0.3 mol normally with respect to 1 mol of hydroxyl groups of a dihydroxy naphthalene compound, Preferably it is 0.05-0.2 mol. The reaction temperature is usually 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours.
反応終了後、生成した塩を濾過、水洗などにより除去し加熱減圧下で溶剤を除去することにより低分子量のジグリシジルエーテル化物が得られる。この工程で得られるジグリシジルエーテル化物のエポキシ当量は通常１３６〜２００ｇ／ｅｑである。 After completion of the reaction, the produced salt is removed by filtration, washing with water, etc., and the solvent is removed under reduced pressure by heating to obtain a low molecular weight diglycidyl etherified product. The epoxy equivalent of the diglycidyl etherified product obtained in this step is usually 136 to 200 g / eq.
次いで、ジヒドロキシナフタレン化合物と上述の低分子量ジグリシジルエーテル化物を反応させ高分子量化エポキシ化物を得る。ジヒドロキシナフタレン化合物の使用量は通常、ジグリシジルエーテル化物１エポキシ当量に対して０．０５〜０．９水酸基当量であり、好ましくは０．１〜０．８水酸基当量である。 Next, the dihydroxynaphthalene compound and the above-described low molecular weight diglycidyl etherified product are reacted to obtain a high molecular weight epoxidized product. The amount of the dihydroxynaphthalene compound used is usually 0.05 to 0.9 hydroxyl equivalents, preferably 0.1 to 0.8 hydroxyl equivalents relative to 1 epoxy equivalent of diglycidyl ether compound.
高分子量化反応において触媒を添加することは反応速度を速める上で好ましい。添加し得る触媒の例としてはテトラメチルアンモニウムクロライド、トリフェニルホスフィン、水酸化ナトリウム、水酸化カリウム等が挙げられる。触媒の添加量は通常反応系に含まれるエポキシ基１モルに対して０．００５〜１重量部であり、好ましくは０．０１〜０．５重量部である。 Addition of a catalyst in the high molecular weight reaction is preferable for increasing the reaction rate. Examples of the catalyst that can be added include tetramethylammonium chloride, triphenylphosphine, sodium hydroxide, potassium hydroxide and the like. The amount of the catalyst added is usually 0.005 to 1 part by weight, preferably 0.01 to 0.5 part by weight, based on 1 mol of the epoxy group contained in the reaction system.
高分子量化反応は無溶剤下でも、溶剤の存在下でも可能である。反応物の粘度が高くなり撹拌が困難な状況では溶剤を用いることが好ましい。溶剤を用いる場合はメチルイソブチルケトン、メチルエチルケトン、シクロペンタノン、シクロヘキサノン、トルエン等が挙げられる。溶剤の使用量は低分子量ジグリシジルエーテル化物とジヒドロキシナフタレン化合物の合計使用量に対して通常５〜１５０重量％であり、好ましくは１０〜１００重量％である。反応温度は通常８０〜２００℃であり、好ましくは９０〜１８０℃である。反応は例えばＧＰＣ（ゲルパーミエーションクロマトグラフィー）で一部サンプリングしながら、ジヒドロキシナフタレン化合物が、完全に消失するまで行われる。反応時間は通常１〜２０時間、好ましくは２〜１５時間である。 The high molecular weight reaction can be performed in the absence of a solvent or in the presence of a solvent. In a situation where the viscosity of the reaction product is high and stirring is difficult, it is preferable to use a solvent. When a solvent is used, methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, cyclohexanone, toluene and the like can be mentioned. The usage-amount of a solvent is 5-150 weight% normally with respect to the total usage-amount of a low molecular-weight diglycidyl ether compound and a dihydroxy naphthalene compound, Preferably it is 10-100 weight%. The reaction temperature is usually 80 to 200 ° C, preferably 90 to 180 ° C. The reaction is carried out until the dihydroxynaphthalene compound completely disappears while partially sampling by GPC (gel permeation chromatography), for example. The reaction time is usually 1 to 20 hours, preferably 2 to 15 hours.
次いで、溶剤を用いた場合は加熱減圧下で溶剤を留去することにより、高分子量のグリシジルエーテル化物を単離することが出来る。高分子量化物の好ましいエポキシ当量は通常２００〜１０００ｇ／ｅｑであり、より好ましくは２５０〜８００ｇ／ｅｑである。 Next, when a solvent is used, a high molecular weight glycidyl ether compound can be isolated by distilling off the solvent under reduced pressure by heating. The preferable epoxy equivalent of the high molecular weight product is usually 200 to 1000 g / eq, more preferably 250 to 800 g / eq.
得られた高分子量グリシジルエーテル化物を、再度エピハロヒドリンに溶解せしめ、アルカリ金属水酸化物を添加することにより樹脂中に含まれるアルコール性水酸基のグリシジルエーテル化反応を行う。 The obtained high molecular weight glycidyl etherified product is dissolved again in epihalohydrin, and an alkali metal hydroxide is added to carry out a glycidyl etherification reaction of an alcoholic hydroxyl group contained in the resin.
エピハロヒドリンとしてはエピクロルヒドリン、エピブロモヒドリンなどが使用できるが、エピクロルヒドリンが特に好ましい。エピハロヒドリンの使用量としては高分子量グリシジルエーテル化物のアルコール性水酸基１モルに対して通常２〜３０倍モルであり、好ましくは４〜２５倍モルである。 As epihalohydrin, epichlorohydrin, epibromohydrin, and the like can be used, and epichlorohydrin is particularly preferable. The usage-amount of epihalohydrin is 2-30 times mole normally with respect to 1 mol of alcoholic hydroxyl groups of high molecular weight glycidyl etherification thing, Preferably it is 4-25 times mole.
上述の反応においては、反応を促進させるために触媒を使用する。触媒としては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などの４級アンモニウム塩、もしくはジメチルスルホキシド、ジメチルスルホンなどの非プロトン性極性溶媒が挙げられる。４級アンモニウム塩を使用する場合、その使用量は、前記アルコール性水酸基１モルに対して、通常０．１〜２０部が好ましく、０．５〜１５部が特に好ましい。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使用量に対して通常５〜１００重量％であり、好ましくは１０〜７５重量％である。 In the above reaction, a catalyst is used to accelerate the reaction. Examples of the catalyst include quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide, and trimethylbenzylammonium chloride, or aprotic polar solvents such as dimethyl sulfoxide and dimethyl sulfone. When using a quaternary ammonium salt, the amount used is usually preferably 0.1 to 20 parts, particularly preferably 0.5 to 15 parts, per 1 mol of the alcoholic hydroxyl group. When using an aprotic polar solvent, it is 5-100 weight% normally with respect to the usage-amount of epihalohydrin, Preferably it is 10-75 weight%.
高分子量グリシジルエーテル化物中に含まれるアルコール性水酸基の内、グリシジルエーテル化する割合に点に関しては、添加するアルカリ金属水酸化物の添加量により任意にコントロールすることが出来る。アルカリ金属水酸化物としては水酸化ナトリウムが好ましく、特に固形でフレーク状のものが好ましい。アルコール性水酸基のグリシジルエーテル化率（式（１）における全Ｘがグリシジル基であるモル％、以下同様）としては通常、５〜９５％であり、好ましくは１０〜９０％である。アルカリ金属水酸化物は所定量を通常１０分〜５時間かけて、反応系中に添加される。 Among the alcoholic hydroxyl groups contained in the high molecular weight glycidyl ether product, the ratio of glycidyl etherification can be arbitrarily controlled by the amount of alkali metal hydroxide added. As the alkali metal hydroxide, sodium hydroxide is preferable, and a solid and flaky shape is particularly preferable. The glycidyl etherification rate of the alcoholic hydroxyl group (mol% in which all Xs in the formula (1) are glycidyl groups, hereinafter the same) is usually 5 to 95%, preferably 10 to 90%. The predetermined amount of the alkali metal hydroxide is usually added to the reaction system over 10 minutes to 5 hours.
反応温度は通常２０〜１２０℃であり、好ましくは３０〜１００℃である。アルカリ金属水酸化物を添加した後の反応時間は通常０．５〜１０時間であり、好ましくは１〜８時間である。 The reaction temperature is usually 20 to 120 ° C, preferably 30 to 100 ° C. The reaction time after adding the alkali metal hydroxide is usually 0.5 to 10 hours, preferably 1 to 8 hours.
反応終了後、水洗によって生成塩、触媒、未反応のアルカリ金属水酸化物などを除去する。次いで加熱減圧下で過剰のエピハロヒドリン及び溶剤などを除去する。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トルエン、メチルイソブチルケトンなどに溶解させ、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の水溶液を加えて閉環を確実にすることも出来る。この場合、アルカリ金属水酸化物の使用量は高分子量グリシジルエーテル化物のアルコール性水酸基１モルに対して通常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。 After completion of the reaction, the produced salt, catalyst, unreacted alkali metal hydroxide and the like are removed by washing with water. Next, excess epihalohydrin, solvent and the like are removed under heating and reduced pressure. Furthermore, in order to make an epoxy resin with less hydrolyzable halogen, the recovered epoxy resin is dissolved in toluene, methyl isobutyl ketone, etc., and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to perform ring closure. Can also be ensured. 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, per 1 mol of the alcoholic hydroxyl group of the high molecular weight glycidyl ether compound. The reaction temperature is usually 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours.
反応終了後、生成した塩を濾過、水洗などにより除去し加熱減圧下で溶剤を除去することにより本発明のエポキシ樹脂が得られる。 After completion of the reaction, the produced salt is removed by filtration, washing with water, etc., and the solvent is removed under reduced pressure by heating to obtain the epoxy resin of the present invention.
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は硬化剤、硬化促進剤、シアネート樹脂などと組み合わせることにより、硬化性樹脂組成物として使用することが出来る。具体的な用途例としては、半導体用封止材、プリント配線基板、ソルダーレジストなどである。 Hereinafter, the epoxy resin composition of the present invention will be described. The epoxy resin of the present invention can be used as a curable resin composition by combining with a curing agent, a curing accelerator, a cyanate resin and the like. Specific examples of applications are semiconductor sealing materials, printed wiring boards, solder resists, and the like.
本発明のエポキシ樹脂組成物は、本発明のエポキシ樹脂及び硬化剤を含有する。本発明のエポキシ樹脂組成物において本発明のエポキシ樹脂は単独で、または他のエポキシ樹脂と併用して用いることが出来る。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。 The epoxy resin composition of the present invention contains the epoxy resin of the present invention and a curing agent. 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.
本発明のエポキシ樹脂と併用し得るエポキシ樹脂の具体例としてはビスフェノールＡ型エポキシ樹脂、フェノールノボラック型樹脂、ビフェノール型エポキシ樹脂、トリフェニルメタン型エポキシ樹脂、ビフェニルノボラック型エポキシ樹脂、脂環式エポキシ樹脂等が挙げられるが、これらは単独で使用してもよく、２種以上併用してもよい。 Specific examples of the epoxy resin that can be used in combination with the epoxy resin of the present invention include bisphenol A type epoxy resin, phenol novolac type resin, biphenol type epoxy resin, triphenylmethane type epoxy resin, biphenyl novolac type epoxy resin, and alicyclic epoxy resin. However, these may be used alone or in combination of two or more.
本発明のエポキシ樹脂組成物が含有する硬化剤としては、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種以上併用してもよい。 Examples of the curing agent contained 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, a polyamide resin synthesized from linolenic acid and ethylenediamine, phthalic anhydride, triethylene anhydride. Meritic acid, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, phenol novolac, 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.
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、或いは１．２当量を越える場合、いずれも硬化が不完全になり、良好な硬化物性が得られない恐れがある。 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 with respect to 1 equivalent of epoxy groups, or when exceeding 1.2 equivalent, in any case, curing may be incomplete, and good cured properties may not be obtained.
また本発明のエポキシ樹脂組成物においては硬化促進剤を使用することも出来る。用い得る硬化促進剤の例としては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などのイミダゾール類、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などのホスフィン類、オクチル酸スズ等の金属化合物が挙げられる。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。 A curing accelerator can also be used in the epoxy resin composition of the present invention. Examples of curing accelerators that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, 1,8-diaza-bicyclo (5 , 4, 0) tertiary amines such as 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.
本発明のエポキシ樹脂組成物は必要により無機充填剤を含有し得る。用い得る無機充填剤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。無機充填剤は本発明のエポキシ樹脂組成物において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、パルチミン酸、ステアリン酸亜鉛、ステアリン酸カルシウム等の離型剤、顔料などの種々の配合剤を添加することが出来る。 The epoxy resin composition of the present invention may contain 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.
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出来る。例えば本発明のエポキシ樹脂と硬化剤ならびに必要により硬化促進剤、無機充填剤及び配合剤とを必要に応じて押出機、ニーダ、ロールなどを用いて均一になるまで十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ー成型機などを用いて成型し、更に８０〜２００℃で２〜１０時間加熱することにより硬化物を得ることが出来る。 The epoxy resin composition of this invention is obtained by mixing each component uniformly. 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 composition of the present invention is mixed thoroughly with an epoxy resin, a curing agent and, if necessary, a curing accelerator, an inorganic filler and a compounding agent as necessary, using an extruder, kneader, roll, etc. until uniform. A cured product can be obtained by melting the epoxy resin composition after melting, molding it using a casting or transfer molding machine, and heating at 80 to 200 ° C. for 2 to 10 hours.
次に本発明を更に実施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。 EXAMPLES Next, the present invention will be described more specifically with reference to examples. In the following, parts are parts by weight unless otherwise specified.
実施例１
温度計、冷却管、分留管、撹拌機を取り付けたフラスコに窒素パージを施しながら、１，６−ジヒドロキシナフタレン８０部に対しエピクロルヒドリン３７０部、ジメチルスルホキシド９２．５部を仕込み撹拌下で４５℃まで昇温し、完全に溶解せしめた後、フレーク状水酸化ナトリウム４０．４部を１００分かけて分割添加した。その後、更に４５℃で３時間、７０℃で１時間後反応を行った。次いでロータリーエバポレーターを用いて過剰のエピクロルヒドリンやジメチルスルホキシドなどを除去した。残留分にメチルイソブチルケトン２７２部を加えて溶解し、７０℃で３０重量％水酸化ナトリウム水溶液１０部を加えて１時間反応を行った。反応後水洗を３回行い、精製塩などを除去した。加熱減圧下でメチルイソブチルケトンを留去し、下記式（２）
Example 1
While purging a flask equipped with a thermometer, condenser, fractionator, and stirrer with nitrogen purge, 370 parts epichlorohydrin and 92.5 parts dimethyl sulfoxide were charged to 80 parts 1,6-dihydroxynaphthalene and stirred at 45 ° C. The solution was heated up to complete dissolution, and then 40.4 parts of flaky sodium hydroxide was added in portions over 100 minutes. Thereafter, the reaction was further carried out at 45 ° C. for 3 hours and at 70 ° C. for 1 hour. Next, excess epichlorohydrin, dimethyl sulfoxide, and the like were removed using a rotary evaporator. To the residue, 272 parts of methyl isobutyl ketone was added and dissolved, and 10 parts of a 30% by weight aqueous sodium hydroxide solution were added at 70 ° C. and reacted for 1 hour. After the reaction, washing with water was performed 3 times to remove purified salts and the like. Methyl isobutyl ketone was distilled off under reduced pressure by heating, and the following formula (2)
で表されるエポキシ樹脂（Ａ）１２９部を得た。得られたエポキシ樹脂（Ａ）のエポキシ当量は１５２ｇ／ｅｑであり常温において半固形であった。 129 parts of epoxy resin (A) represented by The epoxy equivalent of the obtained epoxy resin (A) was 152 g / eq, and it was semisolid at room temperature.
次いで、上述のエポキシ樹脂（Ａ）７６部及び１，６−ジヒドロキシナフタレン２０部を仕込み、窒素雰囲気下で完全に溶解するまで撹拌した。１５０℃まで昇温しトリフェニルホスフィン０．０８部を添加し３時間縮合反応を行い、ＧＰＣにて未反応の１，６−ジヒドロキシナフタレンが完全に消失したことを確認した上で更に1時間反応を継続し、下記式（３） Subsequently, 76 parts of the above-mentioned epoxy resin (A) and 20 parts of 1,6-dihydroxynaphthalene were charged and stirred under nitrogen atmosphere until completely dissolved. The temperature was raised to 150 ° C., 0.08 part of triphenylphosphine was added and a condensation reaction was performed for 3 hours. After confirming that unreacted 1,6-dihydroxynaphthalene had completely disappeared by GPC, the reaction was continued for another 1 hour. And the following formula (3)
で表されるエポキシ樹脂（Ｂ）９６部を得た。得られたエポキシ樹脂（Ｂ）はエポキシ当量３８６ｇ／ｅｑ、軟化点９２．５℃の固体であり、ｎの値はエポキシ当量（ＪＩＳ−７２３６）から計算したところ２．３であった。 96 parts of an epoxy resin (B) represented by The obtained epoxy resin (B) was a solid having an epoxy equivalent of 386 g / eq and a softening point of 92.5 ° C., and the value of n calculated from the epoxy equivalent (JIS-7236) was 2.3.
次いで、前記で得られたエポキシ樹脂（Ｂ）６６．８部をエピクロルヒドリン１８５部に溶解し、テトラメチルアンモニウムクロライド１部を加えて８０℃で撹拌した。次いでフレーク状の固形水酸化ナトリウム８部を添加し、更に８０℃で３時間後反応を行い、水部を加えて水洗を２回行った。ロータリーエバポレーターを用いて１３０℃で、減圧下で過剰のエピクロルヒドリン等を除去した。 Next, 66.8 parts of the epoxy resin (B) obtained above was dissolved in 185 parts of epichlorohydrin, 1 part of tetramethylammonium chloride was added, and the mixture was stirred at 80 ° C. Next, 8 parts of flaky solid sodium hydroxide was added, the reaction was further carried out at 80 ° C. for 3 hours, and the water part was added, followed by washing twice with water. Excess epichlorohydrin and the like were removed under reduced pressure at 130 ° C. using a rotary evaporator.
残留分にメチルイソブチルケトン８０部を加えて溶解し、７０℃で３０重量％水酸化ナトリウム水溶液２部を加えて１時間反応を行った。反応後水洗を３回行い、生成塩などを除去した。加熱減圧下でメチルイソブチルケトンを留去し、下記式（６） To the residue, 80 parts of methyl isobutyl ketone was added and dissolved, and 2 parts of a 30 wt% aqueous sodium hydroxide solution were added at 70 ° C. and reacted for 1 hour. After the reaction, washing with water was performed three times to remove the generated salt and the like. Methyl isobutyl ketone was distilled off under reduced pressure by heating, and the following formula (6)
で表される本発明のエポキシ樹脂（Ｃ）６９．８部を得た。得られたエポキシ樹脂（Ｃ）のエポキシ当量は２５０．６ｇ／ｅｑであり、軟化点は６１．５℃であった。 69.8 parts of epoxy resin (C) of this invention represented by these were obtained. The epoxy equivalent of the obtained epoxy resin (C) was 250.6 g / eq, and the softening point was 61.5 ° C.
実施例２
実施例１で得られたエポキシ樹脂（Ｃ）部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℃）を２１部、硬化促進剤としてトリフェニルホスフィンを０．５部配合し、１５０℃で１５分ロールで混練し、１７５℃、成形圧力７０Ｋｇ／ｃｍ２の条件で１８０秒間トランスファー成型し、その後１６０℃で２時間、更に１８０℃で８時間硬化させて試験片を作成し、下記の条件でガラス転移温度を測定したところ１８２℃であり、ガラス領域における線膨張率は５８ｐｐｍであった。また、下記条件において吸水率を測定したところ０．９５％であった。
Example 2
21 parts of phenol novolak (hydroxyl equivalent 106 g / eq, softening point 83 ° C.) as a curing agent and 0.5 part of triphenylphosphine as a curing accelerator are blended with the epoxy resin (C) part obtained in Example 1. Knead with a roll at 150 ° C. for 15 minutes, transfer mold for 180 seconds under conditions of 175 ° C. and molding pressure of 70 kg / cm 2 , and then cure at 160 ° C. for 2 hours and further at 180 ° C. for 8 hours to prepare a test piece. When the glass transition temperature was measured under the following conditions, it was 182 ° C., and the linear expansion coefficient in the glass region was 58 ppm. In addition, the water absorption measured under the following conditions was 0.95%.
ガラス転移点・線膨張率
熱機械測定装置（ＴＭＡ）：真空理工（株）製 ＴＭ−７０００
昇温速度：２℃／分
吸水率
直径５ｃｍ×厚み４ｍｍの円盤状の試験片を１００℃の水中で２４時間煮沸した後
の重量増加率（％）
Glass transition point / linear expansion coefficient Thermomechanical measurement device (TMA): TM-7000, manufactured by Vacuum Riko Co., Ltd.
Rate of temperature increase: 2 ° C./min water absorption rate Weight increase (%) after boiling a disk-shaped test piece having a diameter of 5 cm × thickness of 4 mm in water at 100 ° C. for 24 hours
このように本発明のエポキシ樹脂の硬化物は、低膨張率を有し、しかも吸水性が低い。 Thus, the cured product of the epoxy resin of the present invention has a low expansion rate and low water absorption.
Claims (4)
で表されるエポキシ樹脂であって、アルコール性水酸基のグリシジルエーテル化率が１０〜９０％であるエポキシ樹脂及び硬化剤を含むエポキシ樹脂組成物であって、エポキシ樹脂のエポキシ基１当量に対して０．７〜１．２当量の硬化剤を含有するエポキシ樹脂組成物。 A dihydroxynaphthalene compound and a diglycidyl etherified product of dihydroxynaphthalene are reacted to give an epoxy equivalent of 386 to 800 g / eq. After obtaining high molecular weight glycidyl etherified product of the following formula (1) obtained by reacting with epihalohydrin
An epoxy resin composition comprising an epoxy resin having a glycidyl etherification rate of an alcoholic hydroxyl group of 10 to 90% and a curing agent, and with respect to 1 equivalent of an epoxy group of the epoxy resin An epoxy resin composition containing 0.7 to 1.2 equivalents of a curing agent.
Hardened | cured material formed by hardening | curing the epoxy resin composition of any one of Claim 2 or 3.
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