JP4565489B2 - Curing agent for epoxy resin, epoxy resin composition, and cured product thereof - Google Patents
Curing agent for epoxy resin, epoxy resin composition, and cured product thereof Download PDFInfo
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- 0 Oc1*cccc1 Chemical compound Oc1*cccc1 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Oc1ccccc1 Chemical compound Oc1ccccc1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
Description
本発明はエポキシ樹脂用の硬化剤、及び例えば成形材料、注型材料、積層材料、塗料、接着剤、レジスト等に用いられる液状エポキシ樹脂組成物に関する。 The present invention relates to a curing agent for an epoxy resin, and a liquid epoxy resin composition used for, for example, a molding material, a casting material, a laminated material, a paint, an adhesive, a resist and the like.
エポキシ樹脂用の硬化剤としては一般に、フェノールノボラック型樹脂、アミン化合物、酸無水物などが知られている。
このうちフェノールノボラック型樹脂は硬化時にエーテル結合を形成するため信頼性の面では最も優れている。しかしながら、一般にフェノールノボラック型樹脂は比較的高軟化点の固形樹脂であり、低粘度が要求される分野には適していない。
これを解決するために、アリル基含有ノボラック型フェノール樹脂を硬化剤に用いる例（特許文献１）が提案されている。また、アミン化合物や酸無水物は液状や粉末状での使用が可能であり、エポキシ樹脂組成物の低粘度化という面では適している。
また、本発明に用いる化合物は、特許文献２に記載されている。
Of these, phenol novolac resins are most excellent in terms of reliability because they form an ether bond upon curing. However, in general, phenol novolac resins are solid resins having a relatively high softening point and are not suitable for fields requiring low viscosity.
In order to solve this, an example (Patent Document 1) in which an allyl group-containing novolak type phenol resin is used as a curing agent has been proposed. In addition, amine compounds and acid anhydrides can be used in liquid or powder form, and are suitable for reducing the viscosity of the epoxy resin composition.
The compound used in the present invention is described in Patent Document 2.
特許文献１で提案されているアリル基含有ノボラック型フェノール樹脂を硬化剤として用いたエポキシ樹脂組成物は、水酸基に対してオルソ位に位置するアリル基がエポキシ基との反応を妨害するため硬化速度が遅く耐熱性などでも不十分であることが知られている。
また、アミン化合物や酸無水物はアミン化合物は一般に低温から硬化反応が始まるためエポキシ樹脂組成物の貯蔵安定性の面で問題がある。また、酸無水物は硬化時にエステル結合を形成するため、加水分解されやすく信頼性の面で問題がある。
本発明者らはこうした実状に鑑み、液状もしくは粉末状で容易に液状エポキシ樹脂に溶解し、耐熱性、信頼性に優れた硬化物を与えるエポキシ樹脂用の硬化剤、エポキシ樹脂組成物を提供することを目的とする。
The epoxy resin composition using an allyl group-containing novolak type phenolic resin proposed in Patent Document 1 as a curing agent has a curing rate because the allyl group located in the ortho position with respect to the hydroxyl group hinders the reaction with the epoxy group. However, it is known that the heat resistance and the like are slow.
In addition, amine compounds and acid anhydrides have a problem in terms of storage stability of an epoxy resin composition because an amine compound generally starts a curing reaction at a low temperature. Moreover, since an acid anhydride forms an ester bond at the time of curing, it is easily hydrolyzed and has a problem in reliability.
In view of such a situation, the present inventors provide an epoxy resin composition and a curing agent for an epoxy resin that is easily dissolved in a liquid epoxy resin in a liquid or powder form and gives a cured product having excellent heat resistance and reliability. For the purpose.
本発明者らは前記した課題を解決すべく鋭意研究した結果、本発明を完成させるに到った。すなわち本発明は
（１）下記式（１）で表されるエポキシ樹脂用の硬化剤、
（３）エポキシ樹脂と、（１）または（２）に記載のエポキシ樹脂用の硬化剤を含有するエポキシ樹脂組成物、
（４）硬化促進剤を含有する（３）に記載のエポキシ樹脂組成物、
（５）（３）または（４）に記載のエポキシ樹脂組成物を硬化してなる硬化物、
（６）下記式（３）で表されるビスフェノール化合物とグリシドールとを反応させることにより得る、式（１）の化合物の製造方法、
を提供するものである。
As a result of intensive studies to solve the above-mentioned problems, the present inventors have completed the present invention. That is, the present invention
(1) a curing agent for epoxy resin represented by the following formula (1),
(3) An epoxy resin composition containing an epoxy resin and a curing agent for the epoxy resin according to (1) or (2),
(4) The epoxy resin composition according to (3), which contains a curing accelerator,
(5) A cured product obtained by curing the epoxy resin composition according to (3) or (4),
(6) A method for producing a compound of formula (1), obtained by reacting a bisphenol compound represented by the following formula (3) with glycidol,
Is to provide.
本発明のエポキシ樹脂用の硬化剤は通常結晶状もしくは半固形であり、液状のエポキシ樹脂と混合して得られるエポキシ樹脂組成物は通常液状である。またその組成物は硬化速度が速く、その硬化物は耐熱性に優れ信頼性に優れているため、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。
また、本発明のエポキシ樹脂用の硬化剤はアルコール性水酸基を有するため、エポキシ樹脂と混合して得られるエポキシ樹脂組成物は液晶等への溶出も妨げられ、液晶シール剤等の用途にも有用である。
The curing agent for epoxy resin of the present invention is usually crystalline or semi-solid, and the epoxy resin composition obtained by mixing with a liquid epoxy resin is usually liquid. In addition, the composition has a high curing rate, and the cured product has excellent heat resistance and reliability, so it is extremely useful for a wide range of applications such as molding materials, casting materials, laminated materials, paints, adhesives, and resists. It is.
In addition, since the curing agent for epoxy resin of the present invention has an alcoholic hydroxyl group, the epoxy resin composition obtained by mixing with the epoxy resin also prevents elution into liquid crystal and the like, and is also useful for applications such as liquid crystal sealing agents. It is.
本発明の式（１）で表されるエポキシ樹脂用の硬化剤において、Ｒはメチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｎ−ブチル基、ｉ−ブチル基、ｔ−ブチル基などの炭素数１〜４のアルキル基であり、好ましくはメチル基である。ｍ、ｎは０〜４の正数であるが、０または２が好ましく、特に０が好ましい。Ｘは前記式（２−１）〜（２−５）で表される基の内のいずれかであり、好ましくは前記式（２−１）または（２−２）である。ここで、（２−５）は直接結合を意味する。
本発明において式（１）で表される化合物は通常、下記式（３）
In the curing agent for epoxy resin represented by the formula (1) of the present invention, R is methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl. A C1-C4 alkyl group such as a group, preferably a methyl group. m and n are 0-4 positive numbers, but 0 or 2 is preferable, and 0 is particularly preferable. X is any one of the groups represented by the formulas (2-1) to (2-5), and is preferably the formula (2-1) or (2-2). Here, (2-5) means a direct bond.
In the present invention, the compound represented by the formula (1) is usually represented by the following formula (3).
（式中、Ｒ、ｍ、ｎ、Ｘは式（１）とにおけるのと同じ意味を表す。また、Ｘの結合位置は、それぞれのベンゼン環の水酸基の４位であることが好ましい。）
で表されるビスフェノール化合物とグリシドールとを反応させることにより得ることが出来る。反応における仕込み比率は、通常ビスフェノール化合物の水酸基１当量に対してグリシドール１〜２モルであり、好ましくは１．０５〜１．５モルである。
(In the formula, R, m, n, and X represent the same meaning as in formula (1). Also, the bonding position of X is preferably the 4-position of the hydroxyl group of each benzene ring.)
It can obtain by making the bisphenol compound represented by these, and glycidol react. The charge ratio in the reaction is usually 1 to 2 mol, and preferably 1.05 to 1.5 mol, of glycidol with respect to 1 equivalent of the hydroxyl group of the bisphenol compound.
使用し得るビスフェノール類の例としてはビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、ビスフェノールフルオレン、テトラメチルビフェノール、テトラメチルビスフェノールＦ等が挙げられる。 Examples of bisphenols that can be used include bisphenol A, bisphenol F, bisphenol S, bisphenol fluorene, tetramethyl biphenol, tetramethyl bisphenol F, and the like.
反応は無溶剤でも溶剤中でも行うことが出来る。溶剤を使用する場合は水、アセトン、メチルエチルケトンなどが挙げられる。溶剤を使用する場合、その使用量はビスフェノール化合物とグリシドールの仕込み総重量に対して通常５〜１００重量％であり、好ましくは１０〜５０重量％である。 The reaction can be carried out without a solvent or in a solvent. In the case of using a solvent, water, acetone, methyl ethyl ketone and the like can be mentioned. When a solvent is used, the amount used is usually 5 to 100% by weight, preferably 10 to 50% by weight, based on the total charged weight of the bisphenol compound and glycidol.
また反応に際しては触媒を用いるのが好ましい。使用し得る触媒としてはエポキシ基とフェノール性水酸基の付加反応に用い得るものであれば特に制限がないが、具体的にはテトラメチルアンモニウムクロライド、テトラエチルアンモニウムブロマイドなどの４級アンモニウム塩、水酸化ナトリウム、水酸化カリウム、トリエチルアミン等の塩基、トリフェニルホスフィン等が挙げられる。このうち、水酸化ナトリウム、水酸化カリウムは通常、水溶液で用いる。触媒の使用量としては用いるグリシドール１モルに対して通常０．００１〜５ｇであり、好ましくは０．００５〜２．５ｇである。 In the reaction, it is preferable to use a catalyst. The catalyst that can be used is not particularly limited as long as it can be used for the addition reaction of an epoxy group and a phenolic hydroxyl group. , Bases such as potassium hydroxide and triethylamine, and triphenylphosphine. Of these, sodium hydroxide and potassium hydroxide are usually used in an aqueous solution. The amount of the catalyst used is usually 0.001 to 5 g, preferably 0.005 to 2.5 g, with respect to 1 mol of glycidol used.
反応時間は通常１〜２０時間であり、好ましくは２〜１５時間である。反応温度は通常４０〜１５０℃であり、好ましくは５０〜１４０℃である。 The reaction time is usually 1 to 20 hours, preferably 2 to 15 hours. The reaction temperature is usually 40 to 150 ° C, preferably 50 to 140 ° C.
反応終了後、目的物が結晶性である場合は水などの貧溶媒を系中に加えることにより結晶を析出させ、濾過、水洗、乾燥により不純物などを除去することが出来る。また、目的物が樹脂状の場合は加熱減圧下で処理することにより未反応のグリシドールや溶剤などを除去することが出来る。加熱減圧下で精製を行う場合、反応触媒としては揮発しやすいトリエチルアミンなどの有機塩基を用いることが特に好ましい。 When the target product is crystalline after completion of the reaction, a poor solvent such as water is added to the system to precipitate the crystal, and impurities and the like can be removed by filtration, washing with water and drying. Further, when the target product is resinous, unreacted glycidol or solvent can be removed by treatment under heating and reduced pressure. When purification is performed under heating and reduced pressure, it is particularly preferable to use an organic base such as triethylamine which is easily volatilized as a reaction catalyst.
本発明のエポキシ樹脂組成物は、エポキシ樹脂と、本発明のエポキシ樹脂用の硬化剤を必須成分とする組成物である。
本発明のエポキシ樹脂組成物に用い得るエポキシ樹脂としては、１分子中にエポキシ基を２個以上有する化合物であれば特に制限はなく、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−フェノール類縮合型エポキシ樹脂、トリフェニルメタン型エポキシ樹脂、ジシクロペンタジエン・フェノール重縮合型エポキシ樹脂、フェノール・アラルキル重縮合型エポキシ樹脂等が挙げられる。
The epoxy resin composition of the present invention is a composition comprising an epoxy resin and a curing agent for the epoxy resin of the present invention as essential components.
The epoxy resin that can be used in the epoxy resin composition of the present invention is not particularly limited as long as it is a compound having two or more epoxy groups in one molecule, and is a novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy. Examples thereof include a resin, a biphenyl-phenol condensation type epoxy resin, a triphenylmethane type epoxy resin, a dicyclopentadiene / phenol polycondensation type epoxy resin, and a phenol / aralkyl polycondensation type epoxy resin.
本発明のエポキシ樹脂用の硬化剤は、他のそれ自体公知のエポキシ樹脂用の硬化剤と併用してもよい。
本発明のエポキシ樹脂用の硬化剤と併用し得る他の硬化剤としては、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。これらの併用可能な他の硬化剤は、本発明の効果を妨げない範囲、例えば本発明のエポキシ樹脂用の硬化剤の使用量を越えない範囲の割合が好ましい。
The curing agent for epoxy resins of the present invention may be used in combination with other known curing agents for epoxy resins.
Examples of other curing agents that can be used in combination with the curing agent for epoxy resins 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. These other curing agents that can be used in combination are preferably within a range that does not hinder the effects of the present invention, for example, a range that does not exceed the amount of the curing agent for epoxy resin of the present invention.
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おそれがある。 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 the amount is less than 0.7 equivalent or 1 equivalent with respect to 1 equivalent of epoxy group, 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例えば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。 In addition, a curing accelerator may be used in combination in the epoxy resin composition of the present invention. Specific examples of the curing accelerator that can be used include, for example, imidazoles such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, and 1,8-diaza. -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.
本発明のエポキシ樹脂組成物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。 The epoxy resin composition 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 silane coupling agents, mold release agents such as stearic acid, palmitic acid, zinc stearate, calcium stearate, and pigments 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、上記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できる。例えば、エポキシ樹脂と硬化剤、並びに必要により硬化促進剤及び無機充填材、配合剤とを必要に応じて押出機、ニーダ、ロール等を用いて均一になるまで充分に混合することより本発明のエポキシ樹脂組成物を得て、そのエポキシ樹脂組成物を溶融注型法あるいはトランスファー成型法やインジェクション成型法、圧縮成型法などによって成型し、更に８０〜２００℃で２〜１０時間に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。 The epoxy resin composition of the present invention can be obtained by uniformly mixing the above components. 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, the curing agent, and if necessary, the curing accelerator, the inorganic filler, and the compounding agent are mixed sufficiently until uniform using an extruder, a kneader, a roll, or the like as necessary. By obtaining an epoxy resin composition, molding the epoxy resin composition by a melt casting method, a transfer molding method, an injection molding method, a compression molding method or the like, and further heating at 80 to 200 ° C. for 2 to 10 hours The cured product of the present invention can be obtained.
また本発明のエポキシ樹脂組成物を溶剤に溶解したワニスを、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。溶剤としてはトルエン、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が挙げられる。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１０〜７０重量％、好ましくは１５〜７０重量％を占める量を用いる。 A prepreg obtained by impregnating a base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber or paper with a varnish obtained by dissolving the epoxy resin composition of the present invention in a solvent is heated. A cured product can also be obtained by press molding. Examples of the solvent include toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone and the like. The solvent used here is usually 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of the epoxy resin composition of the present invention and the solvent.
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。又％は重量％を意味する。 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. Moreover,% means weight%.
実施例１
温度計、冷却管、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、４，４'−ビスフェノールＦ１００部に対しグリシドール７４部、アセトン４４部を仕込み常温下で撹拌し、完全に溶解せしめた後、２５％水酸化ナトリウム水溶液４部を加え、６５℃まで昇温し還流下で６時間反応させた。反応終了後水３００部を加え、析出した結晶を濾過し、更にアセトン、水で洗浄した後、乾燥させ下記式（４）
Example 1
After purging nitrogen with a flask equipped with a thermometer, condenser and stirrer, 74 parts of glycidol and 44 parts of acetone were added to 100 parts of 4,4′-bisphenol F and stirred at room temperature to completely dissolve them. Then, 4 parts of 25% aqueous sodium hydroxide solution was added, the temperature was raised to 65 ° C., and the mixture was reacted under reflux for 6 hours. After completion of the reaction, 300 parts of water was added, and the precipitated crystals were filtered, further washed with acetone and water, and then dried, then the following formula (4)
実施例２
温度計、冷却管、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、ビスフェノールＡ１１４部に対しグリシドール７４部、アセトン４７部を仕込み常温下で撹拌し、完全に溶解せしめた後、トリエチルアミン１部を加え、６５℃まで昇温し還流下で６時間反応させた。反応終了後、エバポレーターを用い加熱減圧下でアセトンやトリエチルアミンなどを除去し、下記式（５）
Example 2
While purging a flask equipped with a thermometer, condenser, and stirrer with nitrogen purge, add 114 parts of glycidol and 47 parts of acetone to 114 parts of bisphenol A and stir at room temperature to completely dissolve. Then, 1 part of triethylamine is added. In addition, the temperature was raised to 65 ° C. and reacted for 6 hours under reflux. After completion of the reaction, acetone, triethylamine and the like are removed using an evaporator under heating and reduced pressure, and the following formula (5)
で表される本発明のエポキシ樹脂用の硬化剤（Ｂ）１７７部を得た。得られた化合物は常温において半固形であった。 177 parts of the curing agent (B) for the epoxy resin of the present invention represented by the formula: The obtained compound was semisolid at room temperature.
実施例３
エポキシ樹脂としてＲＥ−３０４Ｓ（日本化薬株式会社製、エポキシ当量１７０ｇ／ｅｑ)１００部に対し硬化剤として実施例１で得られた化合物（Ａ）２６部を、硬化促進剤として２−エチル−４−メチルイミダゾール（２Ｅ４ＭＺ）１部を配合し、均一に混合し、本発明のエポキシ樹脂組成物を得た。得られたエポキシ樹脂組成物は常温において液状であった。これらを金型に注型し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た。結果を表１に示した。ガラス転移温度の測定は下記の機器、条件で行った。
Example 3
26 parts of the compound (A) obtained in Example 1 as a curing agent with respect to 100 parts of RE-304S (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 170 g / eq) as an epoxy resin and 2-ethyl- as a curing accelerator 4-methylimidazole (2E4MZ) 1 part was mix | blended and mixed uniformly, and the epoxy resin composition of this invention was obtained. The obtained epoxy resin composition was liquid at normal temperature. These were cast into a mold and cured at 80 ° C. for 2 hours, 120 ° C. for 2 hours, and 180 ° C. for 4 hours to prepare test pieces, and the glass transition temperature was measured under the following conditions. The results are shown in Table 1. The glass transition temperature was measured with the following equipment and conditions.
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.
実施例４
硬化剤として実施例１で得られた化合物（Ａ）２６部の代わりに実施例２で得られた化合物（Ｂ）２８部を用いる以外は実施例３と同様にして本発明のエポキシ樹脂組成物を得た。得られたエポキシ樹脂組成物は常温において液状であった。さらに実施例３と同様にして硬化せしめて試験片を作成し、硬化物の物性を測定した。結果を表１に示した。
Example 4
The epoxy resin composition of the present invention is the same as in Example 3 except that 28 parts of the compound (B) obtained in Example 2 is used instead of 26 parts of the compound (A) obtained in Example 1 as a curing agent. Got. The obtained epoxy resin composition was liquid at normal temperature. Furthermore, it hardened | cured similarly to Example 3, the test piece was created, and the physical property of hardened | cured material was measured. The results are shown in Table 1.
表１
実施例３ 実施例４
配合物の組成
ＲＥ−３０４Ｓ １００ １００
化合物（Ａ） ２６
化合物（Ｂ） ２８
２Ｅ４ＭＺ １ １
硬化物の物性
ガラス転移点（℃） １８７ １８１
Table 1
Example 3 Example 4
Composition of the formulation RE-304S 100 100
Compound (A) 26
Compound (B) 28
2E4MZ 1 1
Physical properties of cured product Glass transition point (° C) 187 181
表１の（硬化物の物性）により、本発明のエポキシ樹脂組成物のガラス転移点が１８０℃以上と高いことより、耐熱性が高いことがわかる。 From the (physical properties of the cured product) in Table 1, it can be seen that the glass transition point of the epoxy resin composition of the present invention is as high as 180 ° C. or higher, so that the heat resistance is high.
Claims (5)
及びエポキシ樹脂を含有するエポキシ樹脂組成物。
And an epoxy resin composition containing an epoxy resin.
下記式（３）
で表されるビスフェノール化合物とグリシドールとを、ビスフェノール化合物の水酸基１当量に対してグリシドール１．０５〜１．５モル反応させ得られたものである請求項１または２記載のエポキシ樹脂組成物。 Curing agent for epoxy resin
Following formula (3)
The epoxy resin composition according to claim 1 or 2, wherein the bisphenol compound and glycidol represented by the formula are obtained by reacting 1.05 to 1.5 mol of glycidol with respect to 1 equivalent of the hydroxyl group of the bisphenol compound.
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| WO2022138343A1 (en) * | 2020-12-22 | 2022-06-30 | 旭化成株式会社 | Epoxy resin composition, adhesive film, printed wiring board, semiconductor chip package, semiconductor device, and method for using adhesive film |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54106456A (en) * | 1978-02-08 | 1979-08-21 | Mitsubishi Petrochem Co Ltd | Novel hydroxyalkylation process of bisphenols |
| JPH01221342A (en) * | 1988-02-29 | 1989-09-04 | Mitsui Petrochem Ind Ltd | Novel hydroxy compound and production thereof |
| JP2003238661A (en) * | 2002-02-19 | 2003-08-27 | Taiyo Ink Mfg Ltd | Epoxy resin curing agent and resist composition containing the same |
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2003
- 2003-12-22 JP JP2003424916A patent/JP4565489B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54106456A (en) * | 1978-02-08 | 1979-08-21 | Mitsubishi Petrochem Co Ltd | Novel hydroxyalkylation process of bisphenols |
| JPH01221342A (en) * | 1988-02-29 | 1989-09-04 | Mitsui Petrochem Ind Ltd | Novel hydroxy compound and production thereof |
| JP2003238661A (en) * | 2002-02-19 | 2003-08-27 | Taiyo Ink Mfg Ltd | Epoxy resin curing agent and resist composition containing the same |
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