JP2001055425A - Resorcinol novolak resin, epoxy resin composition and its cured material - Google Patents
Resorcinol novolak resin, epoxy resin composition and its cured materialInfo
- Publication number
- JP2001055425A JP2001055425A JP2000154446A JP2000154446A JP2001055425A JP 2001055425 A JP2001055425 A JP 2001055425A JP 2000154446 A JP2000154446 A JP 2000154446A JP 2000154446 A JP2000154446 A JP 2000154446A JP 2001055425 A JP2001055425 A JP 2001055425A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- formula
- resin composition
- curing agent
- epoxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はエポキシ樹脂用硬化
剤として好適に使用できるレゾルシンノボラック樹脂及
び、該レゾルシンノボラック樹脂を含有し、耐熱性に優
れる硬化物を与え、しかも粘度の低いエポキシ樹脂組成
物およびその硬化物に関する。The present invention relates to a resorcinol novolak resin which can be suitably used as a curing agent for an epoxy resin, and an epoxy resin composition containing the resorcinol novolak resin to give a cured product having excellent heat resistance and having a low viscosity. And a cured product thereof.
【０００２】[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、特に半導体封止材等の用
途においてはオルソクレゾールノボラックエポキシ樹脂
とその硬化剤としてフェノールノボラック樹脂との組合
せが一般的に使用されている。更に高耐熱性が要求され
る場合においては、トリフェニルメタン型エポキシ樹脂
とトリフェニルメタン型硬化剤との組合せが知られてい
る2. Description of the Related Art Epoxy resins can be cured with various curing agents to give cured products having generally excellent mechanical properties, water resistance, chemical resistance, heat resistance, and electrical properties. It is used in a wide range of fields, such as laminates, molding materials, and casting materials. Conventionally, a combination of an ortho-cresol novolak epoxy resin and a phenol novolak resin as a curing agent thereof has been generally used, particularly for applications such as semiconductor encapsulants. Further, when high heat resistance is required, a combination of a triphenylmethane type epoxy resin and a triphenylmethane type curing agent is known.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、前記し
たようなトリフェニルメタン型エポキシ樹脂とトリフェ
ニルメタン型硬化剤との組合せにおいて得られる硬化物
は耐熱性は非常に高くなるものの、吸水率が上昇すると
いう欠点がある。また近年半導体封止材などの用途にお
いては、半導体装置が従来のピン挿入の方法から、いわ
ゆる表面実装法に実装方法が変わりつつある。この表面
実装方法では実装時に半導体装置そのものが半田浴の高
温に晒されることによりパッケージにクラックが生じる
などの問題が指摘されている。このような問題を解決す
るためにはフィラーなどの無機充填材の充填量を増加さ
せることにより硬化物全体の吸水率を低下させることが
有効な手段として提案されているが、高フィラー充填を
実現させるためには樹脂の粘度は十分低くなければなら
ない。しかしながら前記した様なトリフェニルメタン型
硬化剤は１５０℃における溶融粘度が通常６ポイズ以上
と非常に高く高フィラー充填には適していない。最近の
半導体産業などの目ざましい発達にともない、これらに
使用される電気絶縁材料などに要求される耐熱性、耐水
性即ち低粘性は益々厳しくなっており、これらの特性に
優れたエポキシ樹脂用硬化剤の出現が待ち望まれてい
る。However, the cured product obtained by the combination of the triphenylmethane type epoxy resin and the triphenylmethane type curing agent as described above has a very high heat resistance but an increased water absorption. There is a disadvantage of doing so. In recent years, in applications such as a semiconductor sealing material, the mounting method of a semiconductor device has been changing from a conventional pin insertion method to a so-called surface mounting method. In this surface mounting method, a problem has been pointed out that the semiconductor device itself is exposed to the high temperature of the solder bath during mounting, so that cracks are generated in the package. In order to solve such a problem, it has been proposed as an effective means to decrease the water absorption of the entire cured product by increasing the filling amount of an inorganic filler such as a filler. To achieve this, the viscosity of the resin must be sufficiently low. However, the triphenylmethane-type curing agent as described above has a very high melt viscosity at 150 ° C. of usually 6 poise or more, and is not suitable for filling with a high filler. With the remarkable development of the semiconductor industry in recent years, the heat resistance, water resistance, that is, low viscosity required for electrical insulating materials used for these materials are becoming increasingly severe, and curing agents for epoxy resins excellent in these characteristics The appearance of is expected.
【０００４】[0004]
【課題を解決するための手段】本発明者らはこうした実
状に鑑み、耐熱性に優れた硬化物を与え粘度の低いエポ
キシ樹脂組成物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。Means for Solving the Problems In view of these circumstances, the present inventors have conducted intensive studies for an epoxy resin composition which gives a cured product having excellent heat resistance and has a low viscosity. As a result, the present invention has been completed. Was.
【０００５】すなわち本発明は（１）下記式（１）That is, the present invention provides (1) the following formula (1)
【０００６】[0006]
【化３】 Embedded image
【０００７】（式中、ｎは平均値であり０．０１〜２０
の正数を表し、Ｒは独立して水素原子あるいは炭素数１
〜４のアルキル基を表す。）で表され、軟化点が５０〜
１００℃であるレゾルシンノボラック樹脂、（２）
（ａ）１分子中にエポキシ基を２個以上有するエポキシ
樹脂 （ｂ）エポキシ樹脂の硬化剤として請求項１記載のレゾ
ルシンノボラック樹脂を含有するエポキシ樹脂組成物、
（３）（ａ）成分が下記式（２）(Where n is an average value and is 0.01 to 20)
R is independently a hydrogen atom or a carbon atom
Represents an alkyl group of 4 to 4. ) And has a softening point of 50 to
Resorcinol novolak resin at 100 ° C., (2)
(A) an epoxy resin having two or more epoxy groups in one molecule; and (b) an epoxy resin composition containing the resorcinol novolak resin according to claim 1 as a curing agent for the epoxy resin.
(3) The component (a) is represented by the following formula (2)
【０００８】[0008]
【化４】 Embedded image
【０００９】（式中、ｍは平均値であり正数を、Ｌは独
立して水素原子あるいは炭素数１〜４のアルキル基を、
Ｇはグリシジル基をそれぞれ表す。）で表される化合物
である上記（２）記載のエポキシ樹脂組成物、（４）硬
化促進剤を含有する上記（２）または（３）記載のエポ
キシ樹脂組成物、（５）上記（２）、（３）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。(Wherein m is an average value and a positive number, L is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
G represents a glycidyl group. The epoxy resin composition according to the above (2), which is a compound represented by (2), (4) the epoxy resin composition according to the above (2) or (3), which contains a curing accelerator, and (5) the above (2). , (3) and (4)
A cured product obtained by curing the epoxy resin composition according to any one of the above.
【００１０】[0010]
【発明の実施の形態】式（１）で表される化合物は例え
ば、式（３）BEST MODE FOR CARRYING OUT THE INVENTION The compound represented by the formula (1) is, for example, a compound represented by the formula (3)
【００１１】[0011]
【化５】 Embedded image
【００１２】（式中、Ｒは式（１）におけるのと同じ意
味を表す。）で表される化合物とホルマリンとの脱水縮
合反応を酸性触媒の存在下で行うことにより得ることが
できる。(Wherein R has the same meaning as in formula (1)). The compound can be obtained by performing a dehydration condensation reaction between the compound represented by formula (1) and formalin in the presence of an acidic catalyst.
【００１３】式（３）におけるＲがアルキル基である場
合、Ｒとしてはメチル基、エチル基、プロピル基、ブチ
ル基等が挙げられる。式（３）で表される化合物の具体
例としては、ハイドロキノン、レゾルシン、カテコー
ル、メチルハイドロキノンなどが挙げられる。これらは
単独で使用してもよく、２種以上を併用してもよい。When R in the formula (3) is an alkyl group, examples of R include a methyl group, an ethyl group, a propyl group and a butyl group. Specific examples of the compound represented by the formula (3) include hydroquinone, resorcin, catechol, methylhydroquinone, and the like. These may be used alone or in combination of two or more.
【００１４】ホルマリンの形状としてはその水溶液を用
いてもよく、固形のパラホルムアルデヒドでもよい。ホ
ルマリンの使用量としては、式（３）で表される化合物
１モルに対して通常０．０１〜０．９５モル、好ましく
は０．０５〜０．９モル、より好ましくは０．１〜０．
８５モルである。Formalin may be in the form of an aqueous solution or solid paraformaldehyde. The amount of formalin to be used is generally 0.01 to 0.95 mol, preferably 0.05 to 0.9 mol, more preferably 0.1 to 0 mol, per 1 mol of the compound represented by the formula (3). .
85 moles.
【００１５】酸触媒としては、塩酸、硫酸、パラトルエ
ンスルホン酸、シュウ酸、酢酸等が挙げられるが、特に
パラトルエンスルホン酸又はシュウ酸が好ましい。酸触
媒の使用量は、通常、式（３）で表される化合物の使用
量の０．０１〜１０重量％、好ましくは、０．０２〜５
重量％である。Examples of the acid catalyst include hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, oxalic acid, acetic acid and the like, and particularly preferred is p-toluenesulfonic acid or oxalic acid. The amount of the acid catalyst used is usually 0.01 to 10% by weight, preferably 0.02 to 5% by weight of the amount of the compound represented by the formula (3).
% By weight.
【００１６】上記縮合反応は無溶剤下で、あるいは有機
溶剤の存在下で行うことができる。有機溶剤を使用する
場合の具体例としてはメチルイソブチルケトン、トルエ
ン、キシレンなどが挙げられる。有機溶剤を使用する場
合の使用量は仕込んだ原料の総重量に対して通常３０〜
５０重量％、好ましくは５０〜３００重量％、特に好ま
しくは１００〜２５０重量％である。反応を円滑に進行
させる上で、生成した水分を分留管などを用いて反応系
外へ留去することは好ましい。反応温度は通常５０〜１
５０℃、好ましくは６０〜１４０℃である。反応時間は
通常０．５〜１５時間、好ましくは１〜１０時間であ
る。The above condensation reaction can be carried out without a solvent or in the presence of an organic solvent. Specific examples when using an organic solvent include methyl isobutyl ketone, toluene, xylene and the like. When using an organic solvent, the amount used is usually 30 to the total weight of the raw materials charged.
It is 50% by weight, preferably 50 to 300% by weight, particularly preferably 100 to 250% by weight. In order for the reaction to proceed smoothly, it is preferable to distill off the generated water out of the reaction system using a fractionating tube or the like. The reaction temperature is usually 50 to 1
The temperature is 50 ° C, preferably 60 to 140 ° C. The reaction time is generally 0.5-15 hours, preferably 1-10 hours.
【００１７】反応終了後、水洗処理を行って未反応の式
（３）で表される化合物を除去する。水洗処理を行う場
合は水酸化ナトリウム、水酸化カリウムなどのアルカリ
金属水酸化物、水酸化カルシウム、水酸化マグネシウム
などのアルカリ土類金属水酸化物、アンモニア、リン酸
二水素ナトリウム、さらにはジエチレントリアミン、ト
リエチレンテトラミン、アニリン、フェニレンジアミン
などの有機アミンなど様々な塩基性物質などを用いて水
層のｐＨを中性にする。After the completion of the reaction, a water washing treatment is performed to remove unreacted compound represented by the formula (3). When performing water washing treatment, sodium hydroxide, alkali metal hydroxides such as potassium hydroxide, calcium hydroxide, alkaline earth metal hydroxides such as magnesium hydroxide, ammonia, sodium dihydrogen phosphate, and further diethylene triamine, The pH of the aqueous layer is made neutral using various basic substances such as organic amines such as triethylenetetramine, aniline, and phenylenediamine.
【００１８】中和処理を行った後、加熱減圧下で未反応
の式（３）で表される化合物及び溶剤を留去し、生成物
の濃縮を行い、式（１）で表される本発明のレゾルシン
ノボラック樹脂を得ることができる。こうして得られる
本発明のレゾルシンノボラック樹脂は、未反応の式
（３）の含有量が通常１０〜３０重量％、好ましい条件
下で得られたものは１２〜２８重量％である。尚、式
（１）においてｎは平均値であり、正数を表すが通常
０．０１〜２０、好ましくは０．１〜１５であり、例え
ばゲルパーミエーションクロマトグラフィー等で測定す
ることができる。また得られた化合物の好ましい軟化点
は通常５０〜１００℃であり、好ましくは６０〜９５℃
である。更に１５０℃における溶融粘度は通常０．１〜
１０ポイズであり、好ましくは０．２〜８ポイズであ
る。After the neutralization treatment, the unreacted compound of the formula (3) and the solvent are distilled off under reduced pressure under heating, the product is concentrated, and the product of the formula (1) is concentrated. The resorcinol novolak resin of the invention can be obtained. The thus-obtained resorcinol novolak resin of the present invention has an unreacted content of the formula (3) of usually 10 to 30% by weight, and the one obtained under preferable conditions is 12 to 28% by weight. In the formula (1), n is an average value and represents a positive number, but is usually 0.01 to 20, preferably 0.1 to 15, and can be measured by, for example, gel permeation chromatography or the like. The obtained compound preferably has a softening point of usually from 50 to 100 ° C, preferably from 60 to 95 ° C.
It is. Further, the melt viscosity at 150 ° C. is usually 0.1 to
It is 10 poise, preferably 0.2 to 8 poise.
【００１９】本発明のエポキシ樹脂組成物は、上記のよ
うにして得られた本発明のレゾルシンノボラック樹脂及
びエポキシ樹脂を含有する。本発明のエポキシ樹脂組成
物に使用し得るエポキシ樹脂としては１分子中にエポキ
シ基を２個以上有するものであれば特に制限はない。具
体的にはノボラック型エポキシ樹脂、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縮
合型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、
ビスフェノールＦ型エポキシ樹脂、ビフェニル型エポキ
シ樹脂などが挙げられるがこれらは単独で用いてもよ
く、２種以上併用してもよい。The epoxy resin composition of the present invention contains the resorcinol novolak resin of the present invention obtained as described above and an epoxy resin. The epoxy resin that can be used in the epoxy resin composition of the present invention is not particularly limited as long as it has two or more epoxy groups in one molecule. Specifically, novolak type epoxy resin, triphenylmethane type epoxy resin, dicyclopentadiene phenol condensation type epoxy resin, bisphenol A type epoxy resin,
Bisphenol F type epoxy resin, biphenyl type epoxy resin and the like may be mentioned, but these may be used alone or in combination of two or more.
【００２０】本発明のエポキシ樹脂組成物において好ま
しいエポキシ樹脂としては、前記式（２）で表されるト
リフェニルメタン型エポキシ樹脂が挙げられる。具体的
には下記式（４）As a preferred epoxy resin in the epoxy resin composition of the present invention, a triphenylmethane type epoxy resin represented by the above formula (2) can be mentioned. Specifically, the following equation (4)
【００２１】[0021]
【化６】 Embedded image
【００２２】（式中、ｍ及びＧは式（２）におけるのと
同じ意味を表す。）で表されるＥＰＰＮ−５００シリー
ズ（日本化薬（株）製）や下記式（５）(Wherein m and G have the same meanings as in the formula (2)) and the EPPN-500 series (manufactured by Nippon Kayaku Co., Ltd.) or the following formula (5)
【００２３】[0023]
【化７】 Embedded image
【００２４】（式中、ｍ及びＧは式（２）におけるのと
同じ意味を、ｔ−Ｂｕはターシャリーブチル基を、又、
Ｍｅはメチル基をそれぞれ表す。）で表されるＦＡＥ−
２５００（日本化薬（株）製）などが使用できる。(Wherein m and G have the same meanings as in formula (2), t-Bu represents a tertiary butyl group, and
Me represents a methyl group. FAE- represented by)
2500 (manufactured by Nippon Kayaku Co., Ltd.) and the like can be used.
【００２５】尚、式（２）で表されるトリフェニルメタ
ン型エポキシ樹脂は、これら市販のものの他、ホルミル
基を有する置換又は非置換のフェノール類とそれら以外
の置換又は非置換のフェノール類とを酸触媒の存在下に
反応させ得られる化合物とエピクロルヒドリンとをアル
カリ金属水酸化物の存在下に反応させ得ることができ
る。式（２）におけるＬはこれら置換フェノールの置換
基であり、具体的にはメチル基、エチル基、プロピル
基、ブチル基等が挙げられる。尚、式（２）においてｍ
は平均値であり、正数を表すが通常０．０１〜１０、好
ましくは０．１〜５であり、例えばゲルパーミエーショ
ンクロマトグラフィー等で測定することができる。The triphenylmethane type epoxy resins represented by the formula (2) include, besides these commercially available products, substituted or unsubstituted phenols having a formyl group and other substituted or unsubstituted phenols. Can be reacted in the presence of an acid catalyst to react the resulting compound with epichlorohydrin in the presence of an alkali metal hydroxide. L in the formula (2) is a substituent of these substituted phenols, and specific examples include a methyl group, an ethyl group, a propyl group, and a butyl group. Note that in equation (2), m
Is an average value and represents a positive number, and is usually from 0.01 to 10, preferably from 0.1 to 5, and can be measured by, for example, gel permeation chromatography or the like.
【００２６】本発明のエポキシ樹脂組成物において硬化
剤としては、式（１）で表される化合物の他に他の硬化
剤を併用して用いても良い。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−ル系化合物などが使用できる。併用し得る硬化剤
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、トリフェニルメタン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
らを併用する場合、式（１）で表される化合物が全硬化
剤中に占める割合としては通常２０重量％以上、好まし
くは３０重量％以上である。As the curing agent in the epoxy resin composition of the present invention, other curing agents may be used in combination with the compound represented by the formula (1). As the curing agent, for example, amine compounds, acid anhydride compounds, amide compounds, phenol compounds and the like can be used. Specific examples of the curing agent that can be used in combination include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, a polyamide resin synthesized from a dimer of linolenic acid and ethylenediamine, phthalic anhydride, and anhydride. Trimellitic acid, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, phenol-novolak, triphenylmethane and the like , Imidazole, BF 3 -amine complex, guanidine derivative and the like, but are not limited thereto. When these are used in combination, the proportion of the compound represented by the formula (1) in the total curing agent is usually 20% by weight or more, preferably 30% by weight or more.
【００２７】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。The amount of the curing agent used in the epoxy resin composition of the present invention is preferably 0.7 to 1.2 equivalents per equivalent of the epoxy group of the epoxy resin. If the amount is less than 0.7 equivalents or more than 1.2 equivalents with respect to 1 equivalent of epoxy group, curing may be incomplete and good cured physical properties may not be obtained.
【００２８】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。When the above curing agent is used, a curing accelerator may be used in combination. Specific examples of the curing accelerator that can be used include, for example, imidazoles such as 2-methylimidazole, 2-ethylimidazole, 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 in an amount of 0.1 to 5.0 parts by weight based on 100 parts by weight of the epoxy resin as required.
【００２９】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０〜９
０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 if necessary. Specific examples of the inorganic filler that can be used include silica, alumina, and talc. The inorganic filler is used in the epoxy resin composition of the present invention in an amount of from 0 to 9;
An amount occupying 0% by weight is used. Further, to the epoxy resin composition of the present invention, 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.
【００３０】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並びに必要
により硬化促進剤、無機充填材及び配合剤とを必要に応
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硬化物を得ることができる。The epoxy resin composition of the present invention can be easily made into a cured product by a method similar to a conventionally known method. For example, the epoxy resin of the present invention, a curing agent, and if necessary, a curing accelerator, an inorganic filler, and a compounding agent are sufficiently mixed by using an extruder, a kneader, a roll, or the like, if necessary, until they become uniform. To obtain an epoxy resin composition, and then melt the epoxy resin composition and mold it using a casting or transfer molding machine.
By heating for a time, a cured product can be obtained.
【００３１】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１０〜７０重量％、好ましくは１
５〜７０重量％を占める量を用いる。Further, the epoxy resin composition of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, and the like, and is used to prepare glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. A prepreg obtained by impregnating a substrate and drying by heating may be subjected to hot press molding to obtain a cured product. The solvent in this case is usually 10 to 70% by weight, preferably 1% by weight in the mixture of the epoxy resin composition of the present invention and the solvent.
An amount occupying 5 to 70% by weight is used.
【００３２】[0032]
【実施例】次に本発明を更に実施例、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。Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. In the following, parts are by weight unless otherwise specified.
【００３３】実施例１ 温度計、滴下ロート、冷却管、分留管、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レゾルシン
２２０部及びパラトルエンスルホン酸１．１部をメチル
イソブチルケトン４４０部に溶解させた。更に還流温度
まで加熱し撹拌しながら３５％のホルマリン水溶液５
１．４部を１時間かけて滴下し、生成した水分を分留管
を用いて系外に除去した。３時間反応を行い、反応終了
後、７０℃に冷却し２０％リン酸二水素ナトリウム水溶
液４０部を加え撹拌し、水２００部で３回水洗を繰り返
した。Example 1 220 parts of resorcinol and 1.1 parts of paratoluenesulfonic acid were added to 440 parts of methyl isobutyl ketone while purging with nitrogen gas to a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer. Dissolved. Further, while heating to the reflux temperature and stirring, a 35% formalin aqueous solution 5
1.4 parts were added dropwise over 1 hour, and the generated water was removed from the system using a fractionating tube. The reaction was carried out for 3 hours, and after completion of the reaction, the mixture was cooled to 70 ° C., added with 40 parts of a 20% aqueous solution of sodium dihydrogen phosphate, stirred, and repeatedly washed with 200 parts of water three times.
【００３４】次いで、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及び未反
応のレゾルシンを留去し、下記式（６）Next, methyl isobutyl ketone and unreacted resorcinol were distilled off from the oil layer under reduced pressure by heating using a rotary evaporator, and the following formula (6) was obtained.
【００３５】[0035]
【化８】 Embedded image
【００３６】で表される化合物（Ａ）（本発明のレゾル
シンノボラック樹脂；式（６）中、ｎ＝１．３（平均
値））１３２部を得た。得られた化合物（Ａ）は１５０
℃での溶融粘度が１．６ポイズ、軟化点６７．４℃、水
酸基当量は５８ｇ／ｅｑであった。また化合物（Ａ）中
の未反応のレゾルシンの含有量は２１．５重量％であっ
た。132 parts of the compound (A) represented by the formula (resorcinol novolak resin of the present invention; n = 1.3 (average value) in the formula (6)) was obtained. The compound (A) obtained was 150
The melt viscosity at 1.6 ° C. was 1.6 poise, the softening point was 67.4 ° C., and the hydroxyl equivalent was 58 g / eq. Further, the content of unreacted resorcin in compound (A) was 21.5% by weight.
【００３７】実施例２〜３ エポキシ樹脂に前記式（４）で表されるＥＰＰＮ−５０
２Ｈ（日本化薬（株）製、エポキシ当量１７０ｇ／ｅ
ｑ、１５０℃での溶融粘度１．８ポイズ、軟化点６５
℃）を用い、実施例２として硬化剤に化合物（Ａ）のみ
を、実施例３として硬化剤に化合物（Ａ）と下記式
（７）Examples 2-3 An EPPN-50 represented by the above formula (4) was added to an epoxy resin.
2H (Nippon Kayaku Co., Ltd., epoxy equivalent 170g / e
q, melt viscosity at 150 ° C. 1.8 poise, softening point 65
° C), as Example 2, only the compound (A) was used as the curing agent, and as Example 3, the compound (A) was used as the curing agent and the following formula (7)
【００３８】[0038]
【化９】 Embedded image
【００３９】で表されるトリフェニルメタン型樹脂（１
５０℃での溶融粘度９．０ポイズ、水酸基当量９７ｇ／
ｅｑ、軟化点１１５℃）の混合物を、比較例１として前
記式（７）で表される化合物のみを用い、硬化促進剤と
してトリフェニルホスフィン（ＴＰＰ）、充填剤として
球状シリカ（平均粒径３０ミクロン）及び破砕シリカ
（平均粒径５ミクロン）を用いて表１に示す組成及び重
量比で配合し、７０℃で１５分ロールで混練し、１７５
℃、成形圧力７０ｋｇ／ｃｍ２でスパイラルフローの測
定、及び１８０秒間トランスファー成形してその後１６
０℃で２時間、更に１８０℃で８時間硬化せしめて試験
片を作製し、ガラス転移点（下記条件）を測定した。The triphenylmethane type resin (1)
Melt viscosity at 50 ° C. 9.0 poise, hydroxyl equivalent 97 g /
eq, a softening point of 115 ° C.) using only the compound represented by the formula (7) as Comparative Example 1, triphenylphosphine (TPP) as a hardening accelerator, and spherical silica (average particle size of 30) as a filler. Micron) and crushed silica (average particle size 5 micron) at the composition and weight ratio shown in Table 1, kneading with a roll at 70 ° C. for 15 minutes, and 175
Spiral flow measurement at a molding pressure of 70 kg / cm 2 , and transfer molding for 180 seconds.
The test piece was prepared by curing at 0 ° C. for 2 hours and further at 180 ° C. for 8 hours, and the glass transition point (the following conditions) was measured.
【００４０】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 analyzer (TMA): TM- manufactured by Vacuum Riko Co., Ltd.
7000 Heating rate: 2 ° C./min.
【００４１】 表１ 実施例 実施例 比較例 ２ ３ １ 配合物の組成 ＥＰＰＮ−５０２Ｈ 22.2 20.8 19.0 化合物（Ａ） 7.6 4.5 トリフェニルメタン型樹脂 4.5 10.8 ＴＰＰ 0.2 0.2 0.2 球状シリカ 49 49 49 破砕シリカ 21 21 21 硬化物の物性 ガラス転移点（℃） 215 214 212 スパイラルフロー（ｃｍ） 85 78 62Table 1 Example Example Comparative Example 2 3 1 Composition of Formulation EPPN-502H 22.2 20.8 19.0 Compound (A) 7.6 4.5 Triphenylmethane type resin 4.5 10.8 TPP 0.2 0.2 0.2 Spherical silica 49 49 49 Fragmented silica 21 21 21 Physical properties of cured product Glass transition point (℃) 215 214 212 Spiral flow (cm) 85 78 62
【００４２】このように本発明のエポキシ樹脂組成物は
溶融粘度が低く（スパイラルフローが大きいことから判
断される）高フィラー充填が可能であり、しかも表１に
示されるようにその硬化物は、極めて高いガラス転移点
を示した。As described above, the epoxy resin composition of the present invention has a low melt viscosity (determined from a large spiral flow) and can be filled with a high filler. Further, as shown in Table 1, the cured product is It showed a very high glass transition point.
【００４３】[0043]
【発明の効果】本発明のレゾルシンノボラック樹脂は、
エポキシ樹脂の硬化剤として使用した場合、従来一般的
に使用されてきたエポキシ樹脂組成物と比較して、低粘
度で高フィラー充填が可能でありありしかも耐熱性に優
れた硬化物を与えることができ、本発明のエポキシ樹脂
組成物は、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。The resorcinol novolak resin of the present invention comprises:
When used as a curing agent for epoxy resins, compared to epoxy resin compositions that have been commonly used in the past, low viscosity, high filler filling is possible, and it is possible to give cured products with excellent heat resistance. The epoxy resin composition of the present invention is extremely useful for a wide range of applications such as molding materials, casting materials, laminate materials, paints, adhesives, and resists.
Claims (5)
し、Ｒは独立して水素原子あるいは炭素数１〜４のアル
キル基を表す。）で表され、軟化点が５０〜１００℃で
あるレゾルシンノボラック樹脂。(1) The following formula (1): (In the formula, n is an average value and represents a positive number of 0.01 to 20, and R independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) A resorcinol novolak resin at 100 ° C.
するエポキシ樹脂（ｂ）エポキシ樹脂の硬化剤として請
求項１記載のレゾルシンノボラック樹脂を含有するエポ
キシ樹脂組成物。2. An epoxy resin composition comprising (a) an epoxy resin having two or more epoxy groups in one molecule, and (b) a resorcinol novolak resin according to claim 1 as a curing agent for the epoxy resin.
子あるいは炭素数１〜４のアルキル基を、Ｇはグリシジ
ル基をそれぞれ表す。）で表される化合物である請求項
２記載のエポキシ樹脂組成物。3. Component (a) is represented by the following formula (2): ## STR2 ## (Wherein m is an average and a positive number, L is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and G is a glycidyl group). 3. The epoxy resin composition according to 2.
載のエポキシ樹脂組成物。4. The epoxy resin composition according to claim 2, further comprising a curing accelerator.
載のエポキシ樹脂組成物を硬化してなる硬化物。5. A cured product obtained by curing the epoxy resin composition according to any one of claims 2, 3 and 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000154446A JP2001055425A (en) | 1999-06-10 | 2000-05-25 | Resorcinol novolak resin, epoxy resin composition and its cured material |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16410799 | 1999-06-10 | ||
| JP11-164107 | 1999-06-10 | ||
| JP2000154446A JP2001055425A (en) | 1999-06-10 | 2000-05-25 | Resorcinol novolak resin, epoxy resin composition and its cured material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001055425A true JP2001055425A (en) | 2001-02-27 |
Family
ID=26489331
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000154446A Pending JP2001055425A (en) | 1999-06-10 | 2000-05-25 | Resorcinol novolak resin, epoxy resin composition and its cured material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001055425A (en) |
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| WO2014208694A1 (en) | 2013-06-27 | 2014-12-31 | 日立化成株式会社 | Resin composition, resin sheet, cured resin sheet, resin sheet structure, cured resin sheet structure, method for producing cured resin sheet structure, semiconductor device, and led device |
| US9745411B2 (en) | 2013-06-27 | 2017-08-29 | Hitachi Chemical Company, Ltd. | Resin composition, resin sheet, cured resin sheet, resin sheet structure, cured resin sheet structure, method for producing cured resin sheet structure, semiconductor device, and LED device |
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| WO2021020081A1 (en) * | 2019-07-26 | 2021-02-04 | 富士フイルム株式会社 | Composition for forming heat-conducting material, heat-conducting material, heat-conducting sheet, and device with heat-conducting layer |
| JPWO2021020081A1 (en) * | 2019-07-26 | 2021-02-04 | ||
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| CN114478427A (en) * | 2022-02-18 | 2022-05-13 | 四川金象赛瑞化工股份有限公司 | High-performance thermosetting resin curing agent/diluent and preparation method thereof |
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