JP2006316163A - Liquid epoxy resin, epoxy resin composition and its cured material - Google Patents
Liquid epoxy resin, epoxy resin composition and its cured material Download PDFInfo
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本発明は結晶性が低く低粘度で、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 crystallinity, low viscosity, and high heat resistance.
液状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、更に低粘度が要求される分野においてはビスフェノールＦのジ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更なる低粘度化の要求が高まっており、例えばは４，４’−ビフェノールのみをジグリシジルエーテル化して得られる下記式（２） As the liquid epoxy resin, diglycidyl ether of bisphenol A is generally widely known, and diglycidyl etherified product of bisphenol F is mainly used in a field where low viscosity is required. In recent years, there has been an increasing demand for lower viscosity in electrical / electronic component applications. For example, the following formula (2) obtained by diglycidyl etherification of only 4,4'-biphenol:
で表されるエポキシ樹脂などが知られている（特許文献１）。 The epoxy resin etc. which are represented by these are known (patent document 1).
しかしながら、特許文献１で開示されているエポキシ樹脂は溶融状態での粘度は低いものの結晶性が高く、しかも融点が約４０℃以上であるため完全に液状化させるためには６０〜８０℃で加熱する必要があり、現場での作業では扱い難い点が指摘されている。現在の電気・電子部品用途では粘度が低く作業性に優れた液状エポキシ樹脂が望まれている。 However, although the epoxy resin disclosed in Patent Document 1 has a low viscosity in a molten state, it has high crystallinity and has a melting point of about 40 ° C. or higher, so that it is heated at 60 to 80 ° C. to be completely liquefied. It has been pointed out that it is difficult to handle in the field. In current electrical and electronic component applications, liquid epoxy resins having low viscosity and excellent workability are desired.
本発明者らはこうした実状に鑑み、作業性に優れた低粘度の液状の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 view of such a situation, the present inventors have intensively studied for a low-viscosity liquid epoxy resin excellent in workability, and as a result, completed the present invention.
すなわち本発明は、
（１）ビスフェノールＦ型エポキシ樹脂において、下記式（１）
That is, the present invention
(1) In the bisphenol F type epoxy resin, the following formula (1)
（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上記（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。
(2) An 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) A cured product obtained by curing the epoxy resin composition according to any one of (2), (3) or (4) above,
It is to provide.
本発明のエポキシ樹脂は低粘度の液状（もしくは融点０〜４０℃の結晶状）であるため、低粘度の液状組成物が容易に調製出来、複雑微細な形状の電気・電子部品に適用可能であり、更に耐熱性に優れるため高度な信頼性を要求される分野にも適している。 Since the epoxy resin of the present invention is a low-viscosity liquid (or a crystalline form having a melting point of 0 to 40 ° C.), a low-viscosity liquid composition can be easily prepared and applied to electrical and electronic parts having complicated and fine shapes. In addition, since it has excellent heat resistance, it is suitable for fields that require high reliability.
本発明において原料成分の一つとしては下記式（３） In the present invention, as one of the raw material components, the following formula (3)
で表されるフェノール系化合物が用いられる。当該化合物は融点が１６３℃の結晶であり、市販品が購入できる。商品名としてはｐ，ｐ’−ＢＰＦ（本州化学株式会社製）が挙げられる。このフェノール系化合物と汎用のビスフェノールＦとの混合物（以下、フェノール混合物という）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。汎用のビスフェノールＦは前記式（３）のような４，４’−ジヒドロキシジフェニルメタンだけではなく２，４’−ジヒドロキシジフェニルメタン、２，２’−ジヒドロキシジフェニルメタンなどの二量体および三量体、四量体の混合物である。本発明のエポキシ樹脂を得る反応において、式（３）の化合物と汎用ビスフェノールFとの仕込み比率は重量比で通常５０：５０〜９０：１０であり、好ましくは５５：４５〜８５〜１５である。この仕込み割合を調整することで、得られるエポキシ樹脂中の式（１）の化合物の量を調整することができる。 The phenol type compound represented by these is used. The compound is a crystal having a melting point of 163 ° C., and a commercially available product can be purchased. Examples of the product name include p, p′-BPF (manufactured by Honshu Chemical Co., Ltd.). The epoxy resin of the present invention can be obtained by reacting a mixture of this phenolic compound and general-purpose bisphenol F (hereinafter referred to as a phenol mixture) and epihalohydrin in the presence of an alkali metal hydroxide. General-purpose bisphenol F includes not only 4,4′-dihydroxydiphenylmethane as in the above formula (3) but also dimers, trimers, tetramers such as 2,4′-dihydroxydiphenylmethane and 2,2′-dihydroxydiphenylmethane. It is a mixture of bodies. In the reaction for obtaining the epoxy resin of the present invention, the charging ratio of the compound of formula (3) and the general-purpose bisphenol F is usually 50:50 to 90:10, preferably 55:45 to 85-15 in terms of weight ratio. . By adjusting this charging ratio, the amount of the compound of the formula (1) in the obtained epoxy resin can be adjusted.
本発明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仕込んだフェノール混合物の水酸基１モルに対し通常２〜１５モル、好ましくは３〜１２モルである。 In the production method of the present invention, epichlorohydrin or epibromohydrin can be used as the epihalohydrin. The amount of epihalohydrin is usually 2 to 15 mol, preferably 3 to 12 mol, relative to 1 mol of hydroxyl group in the charged phenol mixture.
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フェノール混合物の水酸基１当量に対して通常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 equivalent of hydroxyl groups of the said phenol mixture, 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フェノール系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。 In addition, it is obtained by adding as a quaternary ammonium salt catalyst such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride to a solution of epihalohydrin and the phenolic compound and reacting at 30-110 ° C. for 0.5-8 hours. A method of adding a solid or aqueous solution of an alkali metal hydroxide to the halohydrin ether compound to be reacted 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フェノール系化合物の水酸基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。 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 equivalent of hydroxyl groups of a phenol type 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本発明のエポキシ樹脂が得られる。こうして得られた本発明のエポキシ樹脂中の式（１）の化合物の割合は、通常５０〜８０％（（液体クロマトグラフィーによる面積％、以下同様）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 the epoxy resin of the present invention. The proportion of the compound of formula (1) in the epoxy resin of the present invention thus obtained is usually 50 to 80% ((area% by liquid chromatography, the same applies hereinafter).
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％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 together, 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% 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 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, 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 with a curing agent and, if necessary, a curing accelerator, an inorganic filler and a compounding agent, if necessary, using an extruder, a kneader, a roll, etc., until they are uniformly mixed to form an epoxy resin composition. A cured product can be obtained by melting the epoxy resin composition after molding and molding it using a casting or transfer molding machine and further 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、前記式（３）で表されるフェノール系化合物（商品名ｐ，ｐ’−ＢＰＦ 本州化学株式会社製）３０部及び汎用のビスフェノールＦ７０部に対しエピクロルヒドリン４６３部、ジメチルスルホキシド４６３部を仕込み撹拌下で３５℃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３５℃で４時間、４５℃で１時間、７０℃で３０分後反応を行った。次いで水を７００部加えて水洗を行い、油層から過剰のエピクロルヒドリンなどを除去した。残留分にメチルイソブチルケトン３１２部を加えて溶解し、７０℃で３０％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、本発明のエポキシ樹脂（Ａ）１４７部を得た。エポキシ樹脂（Ａ）につき液体クロマトグラフィーで分析した結果、得られたエポキシ樹脂中に前記式（１）で表される成分は６６．７％含まれていた。またこのエポキシ樹脂のエポキシ当量は１６４ｇ／ｅｑ、２５℃における粘度は１８３０ｍＰ・ｓ、全塩素量は４６０ｐｐｍ、融点は２２℃であった。
Example 1
A phenolic compound represented by the above formula (3) (trade name p, p′-BPF, manufactured by Honshu Chemical Co., Ltd.) while purging nitrogen to a flask equipped with a thermometer, a condenser, a fractionator, and a stirrer. 463 parts of epichlorohydrin and 463 parts of dimethyl sulfoxide were added to 30 parts and 70 parts of general-purpose bisphenol F, and the temperature was raised to 35 ° C. with stirring. After complete dissolution, 40.4 parts of flaky sodium hydroxide was added over 100 minutes. Were added in portions. Thereafter, the reaction was further performed at 35 ° C. for 4 hours, at 45 ° C. for 1 hour, and at 70 ° C. for 30 minutes. Next, 700 parts of water was added and washed with water to remove excess epichlorohydrin and the like from the oil layer. 312 parts of methyl isobutyl ketone was added to the residue and dissolved, and 10 parts of 30% aqueous sodium hydroxide solution was added at 70 ° C. for 1 hour to react. 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 to obtain 147 parts of the epoxy resin (A) of the present invention. As a result of analyzing the epoxy resin (A) by liquid chromatography, the obtained epoxy resin contained 66.7% of the component represented by the formula (1). The epoxy equivalent of this epoxy resin was 164 g / eq, the viscosity at 25 ° C. was 1830 mP · s, the total chlorine content was 460 ppm, and the melting point was 22 ° C.
実施例２、比較例１
実施例２として実施例１で得られたエポキシ樹脂（Ａ）、比較例としてビスフェノールＦ型エポキシ樹脂ＲＥ−３０４Ｓ（日本化薬株式会社製）を用いてエポキシ樹脂組成物を調製した。ＲＥ−３０４Ｓ中には前記式（１）で表される成分が２６％含有されていた。ＲＥ−３０４Ｓのエポキシ当量は１７１ｇ／ｅｑ、２５℃における粘度は３５００ｍＰａ・ｓであった。これらのエポキシ樹脂に対し硬化剤としてカヤハードＡ−Ａ（日本化薬株式会社製）を用い、表１の配合物の組成の欄に示す重量比で配合し均一に混合した後、金型に注型し８０℃で２時間、１２０℃で２時間、１８０℃で４時間硬化せしめて試験片を作成し、下記の条件でガラス転移温度を測定し表１の硬化物の物性の欄に示した。
Example 2 and Comparative Example 1
An epoxy resin composition was prepared using the epoxy resin (A) obtained in Example 1 as Example 2 and the bisphenol F type epoxy resin RE-304S (manufactured by Nippon Kayaku Co., Ltd.) as a comparative example. RE-304S contained 26% of the component represented by the formula (1). The epoxy equivalent of RE-304S was 171 g / eq, and the viscosity at 25 ° C. was 3500 mPa · s. Kayahard A-A (manufactured by Nippon Kayaku Co., Ltd.) is used as a curing agent for these epoxy resins, blended at a weight ratio shown in the composition column of Table 1 and mixed uniformly, and then poured into a mold. Molded and cured at 80 ° C. for 2 hours, 120 ° C. for 2 hours, and 180 ° C. for 4 hours to prepare a test piece. The glass transition temperature was measured under the following conditions, and the physical properties of the cured product in Table 1 are shown in the column of physical properties. .
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．
Glass transition point Thermomechanical measurement device (TMA): TM-7000, manufactured by Vacuum Riko Co., Ltd.
Temperature increase rate: 2 ° C./min.
表１
実施例２ 比較例１
配合物の組成
エポキシ樹脂（Ａ） １００
ＹＤＦ−８１７０Ｃ １００
カヤハードＡ−Ａ ３９ ３７
硬化物の物性
ガラス転移温度（℃） １２６ １２１
Table 1
Example 2 Comparative Example 1
Composition of the compound Epoxy resin (A) 100
YDF-8170C 100
Kayahard A-A 39 37
Physical properties of cured product Glass transition temperature (° C.) 126 121
表１から明らかなように本発明のエポキシ樹脂の硬化物は、汎用のビスフェノールＦ型エポキシ樹脂の硬化物にくらべ耐熱性が高い。しかも本発明のエポキシ樹脂は、融点が低く、溶融後の粘度も低いため作業性に優れる。 As is apparent from Table 1, the cured product of the epoxy resin of the present invention has higher heat resistance than the cured product of general-purpose bisphenol F type epoxy resin. Moreover, since the epoxy resin of the present invention has a low melting point and a low viscosity after melting, it is excellent in workability.
Claims (5)
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| JP2001316566A (en) * | 2000-05-10 | 2001-11-16 | Nagase Chemtex Corp | One pack epoxy resin composition and epoxy resin composition for semiconductor sealing use using the same |
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| JP2003286331A (en) * | 2002-03-29 | 2003-10-10 | Sumitomo Bakelite Co Ltd | Method for producing one-pack type liquid epoxy resin composition |
| JP2004146629A (en) * | 2002-10-25 | 2004-05-20 | Toray Ind Inc | Semiconductor device and its fabricating `process |
| WO2005035617A1 (en) * | 2003-10-10 | 2005-04-21 | Asahi Kasei Chemicals Corporation | Latent curing agent and composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001316566A (en) * | 2000-05-10 | 2001-11-16 | Nagase Chemtex Corp | One pack epoxy resin composition and epoxy resin composition for semiconductor sealing use using the same |
| JP2003231735A (en) * | 2002-02-08 | 2003-08-19 | Toray Ind Inc | Epoxy resin composition and resin-sealed semiconductor device made by using it |
| JP2003252960A (en) * | 2002-03-05 | 2003-09-10 | Toray Ind Inc | Epoxy resin composition and resin-sealed semiconductor device |
| JP2003286331A (en) * | 2002-03-29 | 2003-10-10 | Sumitomo Bakelite Co Ltd | Method for producing one-pack type liquid epoxy resin composition |
| JP2004146629A (en) * | 2002-10-25 | 2004-05-20 | Toray Ind Inc | Semiconductor device and its fabricating `process |
| WO2005035617A1 (en) * | 2003-10-10 | 2005-04-21 | Asahi Kasei Chemicals Corporation | Latent curing agent and composition |
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