JP3681020B2 - Epoxy resin mixture, epoxy resin composition and cured product thereof - Google Patents
Epoxy resin mixture, epoxy resin composition and cured product thereof Download PDFInfo
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Description
【０００１】
【発明の属する技術分野】
本発明は高信頼性半導体封止用を始めとする電気・電子部品絶縁材料用、及び積層板（プリント配線板）やＣＦＲＰ（炭素繊維強化プラスチック）を始めとする各種複合材料用、接着剤、塗料等に有用なエポキシ樹脂混合物、エポキシ樹脂組成物及びその硬化物に関する。
【０００２】
【従来の技術】
エポキシ樹脂は作業性及びその硬化物の優れた電気特性、耐熱性、接着性、耐湿性（耐水性）等により電気・電子部品、構造用材料、接着剤、塗料等の分野で幅広く用いられている。
【０００３】
【発明が解決しようとする課題】
しかし、近年電気・電子分野においてはその発展に伴い、エポキシ樹脂に対して耐熱性、耐湿性、密着性、フィラー高充填のための低粘度化等の諸特性の一層の向上が求められている。また、構造材としては航空宇宙材料、レジャー・スポーツ器具用途などにおいて軽量で機械物性の優れた材料であるのと同時に、作業性の向上のために低粘度のエポキシ樹脂が求められている。これらの要求に対しエポキシ樹脂組成物について多くの提案がなされてはいるが、未だ充分とはいえない。
【０００４】
【課題を解決するための手段】
本発明者らは前記のような特性を持つエポキシ樹脂組成物について鋭意研究の結果、本発明を完成した。
即ち、本発明は、
【０００５】
（１）下記式（１）
【０００６】
【化３】
（式中、Ｐは水素原子または炭素数１〜５のアルキル基を表し、ｎは平均値で１〜１５の正数を示す。Ｇはグリシジル基を表す。）
【０００８】
で表されるエポキシ樹脂（Ａ）と下記式（２）
【０００９】
【化４】
（式中、Ｒ、ｎ及びＧはそれぞれ式（１）におけるのと同じ意味を表す。）
【００１１】
で表されるエポキシ樹脂（Ｂ）とを混合して得られるエポキシ樹脂混合物、
（２）上記（１）記載のエポキシ樹脂混合物及び硬化剤を含有するエポキシ樹脂組成物、
（３）無機充填材を含有する上記（２）記載のエポキシ樹脂組成物、
（４）上記（２）または（３）記載のエポキシ樹脂組成物を硬化してなる硬化物に関する。
【００１２】
本発明のエポキシ樹脂混合物におけるエポキシ樹脂（Ａ）としては、例えば下記式（３）
【００１３】
【化５】
で表されるＮＣ−７０００（日本化薬（株）製）が挙げられる。
【００１５】
また、エポキシ樹脂（Ｂ）の具体例としては、例えば下記式（４）
【００１６】
【化６】
で表されるＥＰＰＮ−５０１或はＥＰＰＮ−５０２（日本化薬（株）製）、下記式（５）
【００１８】
【化７】
（式（３）、（４）及び（５）中、ｎ及びＧは式（１）におけるのと同じ意味を表す。また、式（５）中、Ｍｅはメチル基を、ｔ−Ｂｕはターシャリーブチル基をそれぞれ表す。）
で表されるＦＡＥ−２５００（日本化薬（株）製）等が挙げられる。
【００２０】
前記（１）記載のエポキシ樹脂混合物においてエポキシ樹脂（Ｂ）の占める割合は通常１０〜９０重量％、好ましくは２０〜８０重量％、特に好ましくは４０〜６０重量％である。
【００２１】
以下本発明のエポキシ樹脂組成物につき説明する。
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混合物は単独でまたは他のエポキシ樹脂と併用して使用することが出来る。併用する場合、本発明のエポキシ樹脂混合物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。
【００２２】
本発明のエポキシ樹脂混合物と併用しうる他のエポキシ樹脂の具体例としては、ビスフェノール類、フェノール類（フェノール、アルキル置換フェノール、ナフトール、アルキル置換ナフトール、ジヒドロキシベンゼン、ジヒドロキシナフタレン等）と各種アルデヒドとの重縮合物、フェノール類と各種ジエン化合物との重合物、フェノール類と芳香族ジメチロールとの重縮合物、ビフェノール類、アルコール類等をグリシジル化したグリシジルエーテル系エポキシ樹脂、脂環式エポキシ樹脂、グリシジルアミン系エポキシ樹脂、グリシジルエステル系エポキシ樹脂等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種以上を用いてもよい。
【００２３】
本発明のエポキシ樹脂組成物は、硬化剤を含有する。硬化剤としてはアミン系化合物、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。用いう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、ビスフェノール類、フェノール類（フェノール、アルキル置換フェノール、ナフトール、アルキル置換ナフトール、ジヒドロキシベンゼン、ジヒドロキシナフタレン等）と各種アルデヒドとの重縮合物、フェノール類と各種ジエン化合物との重合物、フェノール類と芳香族ジメチロールとの重縮合物、ビフェノール類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。前記においてフェノール類と各種アルデヒドとの重縮合物を硬化剤として用いる場合、２核体の割合が２０％重量以下、好ましくは１５％重量以下のものがエポキシ樹脂組成物のゲルタイムが短縮できるなど硬化速度を速める上において、効果的である。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０．５〜１．５当量が好ましく、０．６〜１．２当量が特に好ましい。エポキシ基１当量に対して、０．５当量に満たない場合、あるいは１．５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。
【００２４】
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、オクチル酸スズなどの金属化合物などが挙げられる。硬化促進剤はエポキシ樹脂１００重量部に対して０．０１〜１５重量部が必要に応じ用いられる。
さらに、本発明のエポキシ樹脂組成物には、必要に応じてシリカ、アルミナ、タルク等の充填材やシランカップリング剤、離型剤、顔料等の種々の配合剤を添加することができる。
【００２５】
本発明のエポキシ樹脂組成物は、上記各成分を所定の割合で均一に混合することにより得られ、半導体封止用として用いるのが特に好ましい。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、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本発明のエポキシ樹脂組成物を得、そのエポキシ樹脂組成物を、溶融注型法あるいはトランスファ−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形し、必要により８０〜２００℃で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。
【００２６】
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本発明の硬化物を得ることもできる。
【００２７】
その際溶剤は本発明のエポキシ樹脂組成物と溶剤の合計重量に対し溶剤の占める割合が、通常１０〜７０重量％、好ましくは１５〜６５重量％となる量使用する。
【００２８】
【実施例】
以下本発明を実施例により更に詳細に説明する。尚、本発明はこれら実施例に限定されるものではない。また実施例において、エポキシ当量、軟化点測定の分析条件は以下の通りである。
エポキシ当量
ＪＩＳ Ｋ−７２３６に準じた方法で測定し、単位はｇ／ｅｑである。
軟化点
ＪＩＳ Ｋ−７２３４に準じた方法で測定
【００２９】
実施例１〜３、比較例１
エポキシ樹脂（Ａ）として前記式（３）で表されるＮＣ−７０００（日本化薬（株）製、エポキシ当量２３３ｇ／ｅｑ、軟化点９２℃）をエポキシ樹脂（Ｂ）として前記式（４）で表されるＥＰＰＮ−５０１Ｈ（日本化薬（株）、エポキシ当量１６４ｇ／ｅｑ、軟化点５３℃）を、また比較例としてＮＣ−７０００のみを、硬化剤（フェノールノボラック樹脂（日本化薬（株）製、ＰＮ−８０、軟化点８３℃、水酸基当量１０６ｇ／ｅｑ）を、更に硬化促進剤（トリフェニルフォスフィン）を表１の配合物の組成の欄に示した量配合し、７０〜８０℃で１５分間ロール混練、冷却、粉砕しゲルタイムを測定した。また、更にこの粉砕物をタブレット化し、トランスファー成型機により樹脂成形体を調製し、１６０℃で２時間、更に１８０℃で８時間で硬化させた。
【００３０】
このようにして得られた硬化物の物性を測定した結果を表１の硬化物の物性の欄に示す。尚、表１の配合物の組成の欄の数値は重量部を表す。
また、物性値の測定及びトランスファー成型は以下の方法で行った。
トランスファー成型条件
温度：１５０℃
成形圧力：５０ｋｇ／ｃｍ2
時間：３分
ガラス転移温度（ＴＭＡ）
真空理工（株）製 ＴＭ−７０００
昇温度速度 ２℃／ｍｉｎ．
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（％）
【００３１】
【表１】
表１より明らかなように本発明のエポキシ樹脂混合物は低い溶融粘度を示し、該エポキシ樹脂混合物を用いた本発明のエポキシ樹脂組成物は、その硬化物において高い耐熱性及び低い吸水率を示した。
【００３３】
【発明の効果】
本発明のエポキシ樹脂混合物は低い溶融粘度を示し、該エポキシ樹脂混合物を含有してなるエポキシ樹脂組成物は、高い耐熱性及び低い吸水性を示す。従って、本発明のエポキシ樹脂は、電気電子部品用絶縁材料（高信頼性半導体封止材料など）及び積層板（プリント配線板など）やＣＦＲＰを始めとする各種複合材料、接着剤、塗料等に極めて有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention is used for insulating materials for electrical and electronic parts including those for highly reliable semiconductor sealing, and for various composite materials including laminated boards (printed wiring boards) and CFRP (carbon fiber reinforced plastics), adhesives, The present invention relates to an epoxy resin mixture, an epoxy resin composition, and a cured product thereof useful for paints and the like.
[0002]
[Prior art]
Epoxy resins are widely used in the fields of electrical and electronic parts, structural materials, adhesives, paints, etc. due to their workability and excellent electrical properties, heat resistance, adhesion, moisture resistance (water resistance), etc. Yes.
[0003]
[Problems to be solved by the invention]
However, in recent years, with the development in the electric / electronic field, further improvements in various properties such as heat resistance, moisture resistance, adhesion, and low viscosity for high filler filling are required for epoxy resins. . In addition, as a structural material, it is a lightweight material with excellent mechanical properties for use in aerospace materials, leisure and sports equipment, and at the same time, a low-viscosity epoxy resin is required to improve workability. Many proposals for epoxy resin compositions have been made to meet these requirements, but they are still not sufficient.
[0004]
[Means for Solving the Problems]
The inventors of the present invention have completed the present invention as a result of intensive studies on the epoxy resin composition having the above-mentioned characteristics.
That is, the present invention
[0005]
(1) The following formula (1)
[0006]
[Chemical 3]
(In the formula, P represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, n represents an average value and represents a positive number of 1 to 15. G represents a glycidyl group.)
[0008]
The epoxy resin (A) represented by the following formula (2)
[0009]
[Formula 4]
(In the formula, R, n and G each have the same meaning as in formula (1).)
[0011]
An epoxy resin mixture obtained by mixing with an epoxy resin (B) represented by
(2) An epoxy resin composition containing the epoxy resin mixture and a curing agent according to (1) above,
(3) The epoxy resin composition according to the above (2), which contains an inorganic filler,
(4) The present invention relates to a cured product obtained by curing the epoxy resin composition described in (2) or (3).
[0012]
As an epoxy resin (A) in the epoxy resin mixture of the present invention, for example, the following formula (3)
[0013]
[Chemical formula 5]
NC-7000 (made by Nippon Kayaku Co., Ltd.) is mentioned.
[0015]
Moreover, as a specific example of an epoxy resin (B), for example, the following formula (4)
[0016]
[Chemical 6]
EPPN-501 or EPPN-502 (manufactured by Nippon Kayaku Co., Ltd.) represented by the following formula (5)
[0018]
[Chemical 7]
(In the formulas (3), (4) and (5), n and G have the same meaning as in the formula (1). In the formula (5), Me represents a methyl group, t-Bu represents tarsia. Each represents a butyl group.)
And FAE-2500 (manufactured by Nippon Kayaku Co., Ltd.).
[0020]
The proportion of the epoxy resin (B) in the epoxy resin mixture described in (1) is usually 10 to 90% by weight, preferably 20 to 80% by weight, and particularly preferably 40 to 60% by weight.
[0021]
Hereinafter, the epoxy resin composition of the present invention will be described.
In the epoxy resin composition of the present invention, the epoxy resin mixture of the present invention can be used alone or in combination with other epoxy resins. When used together, the proportion of the epoxy resin mixture of the present invention in the total epoxy resin is preferably 30% by weight or more, particularly preferably 40% by weight or more.
[0022]
Specific examples of other epoxy resins that can be used in combination with the epoxy resin mixture of the present invention include bisphenols, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes. Polycondensates, polymers of phenols and various diene compounds, polycondensates of phenols and aromatic dimethylol, glycidyl ether epoxy resins, alicyclic epoxy resins, glycidyls obtained by glycidylation of biphenols, alcohols, etc. Examples thereof include, but are not limited to, amine-based epoxy resins and glycidyl ester-based epoxy resins. These may be used alone or in combination of two or more.
[0023]
The epoxy resin composition of the present invention contains a curing agent. As the curing agent, an amine compound, an acid anhydride compound, an amide compound, a phenol compound, or the like can be used. Specific examples of the curing agent that can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, polyamide resin synthesized from linolenic acid and ethylenediamine, phthalic anhydride, triethylene anhydride. Mellitic acid, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic acid anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, bisphenols, phenols (phenol, alkyl substituted) Polymerization of phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) with various aldehydes, phenols and various diene compounds , Polycondensates of phenols with aromatic dimethylol, biphenols and modified products thereof, imidazo - Le, BF 3 - amine complex, guanidine derivatives. In the above, when a polycondensate of phenols and various aldehydes is used as a curing agent, a binuclear ratio of 20% by weight or less, preferably 15% by weight or less can be cured such that the gel time of the epoxy resin composition can be shortened. It is effective in increasing the speed. 0.5-1.5 equivalent is preferable with respect to 1 equivalent of epoxy groups of an epoxy resin, and, as for the usage-amount of a hardening | curing agent, 0.6-1.2 equivalent is especially preferable. When less than 0.5 equivalent or more than 1.5 equivalent with respect to 1 equivalent of epoxy group, curing may be incomplete and good cured properties may not be obtained.
[0024]
Moreover, when using the said hardening | curing agent, a hardening accelerator may be used together. Specific examples of the curing accelerator that can be used include, 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. If necessary, the curing accelerator is used in an amount of 0.01 to 15 parts by weight based on 100 parts by weight of the epoxy resin.
Furthermore, various compounding agents, such as fillers, such as a silica, an alumina, and a talc, a silane coupling agent, a mold release agent, and a pigment, can be added to the epoxy resin composition of this invention as needed.
[0025]
The epoxy resin composition of the present invention is obtained by uniformly mixing the above components at a predetermined ratio, and is particularly preferably used for semiconductor encapsulation. 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 and a curing agent, and if necessary, a curing accelerator, a filler, and a compounding agent are sufficiently mixed using an extruder, a kneader, a roll, or the like as necessary until uniform. The epoxy resin composition of the present invention is obtained, and the epoxy resin composition is molded by a melt casting method, a transfer molding method, an injection molding method, a compression molding method, or the like, and heated at 80 to 200 ° C. as necessary. Thus, the cured product of the present invention can be obtained.
[0026]
In addition, the epoxy resin composition of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc., and is applied to a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. The cured product of the present invention can also be obtained by hot press molding a prepreg obtained by impregnation and heat drying.
[0027]
At that time, the solvent is used in such an amount that the ratio of the solvent to the total weight of the epoxy resin composition of the present invention and the solvent is usually 10 to 70% by weight, preferably 15 to 65% by weight.
[0028]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to these examples. Moreover, in an Example, the analysis conditions of an epoxy equivalent and a softening point measurement are as follows.
Epoxy equivalent Measured by a method according to JIS K-7236, and the unit is g / eq.
Softening point Measured by a method according to JIS K-7234.
Examples 1-3, Comparative Example 1
NC-7000 (Nippon Kayaku Co., Ltd., epoxy equivalent 233 g / eq, softening point 92 ° C.) represented by the formula (3) as the epoxy resin (A) is used as the epoxy resin (B) and the formula (4). EPPN-501H (Nippon Kayaku Co., Ltd., epoxy equivalent 164 g / eq, softening point 53 ° C.) and, as a comparative example, only NC-7000, a curing agent (phenol novolac resin (Nippon Kayaku Co., Ltd.) ), PN-80, softening point 83 ° C., hydroxyl group equivalent 106 g / eq), and further a curing accelerator (triphenylphosphine) in an amount shown in the column of the composition of the composition in Table 1, 70-80 The gel time was measured by roll kneading, cooling and pulverization at 15 ° C. for 15 minutes, and the pulverized product was further tableted, and a resin molded product was prepared by a transfer molding machine at 160 ° C. for 2 hours and further at 180 ° C. It was cured in time.
[0030]
The result of measuring the physical properties of the cured product thus obtained is shown in the column of physical properties of the cured product in Table 1. In addition, the numerical value of the column of the composition of the compound of Table 1 represents a weight part.
Moreover, the measurement of physical property values and transfer molding were performed by the following methods.
Transfer molding temperature: 150 ° C
Molding pressure: 50 kg / cm 2
Time: 3 minutes Glass transition temperature (TMA)
TM-7000 manufactured by Vacuum Riko Co., Ltd.
Temperature increase rate 2 ° C / min.
Weight increase rate (%) after boiling a disk-shaped test piece having a water absorption diameter of 5 cm × thickness of 4 mm in water at 100 ° C. for 24 hours
[0031]
[Table 1]
As is clear from Table 1, the epoxy resin mixture of the present invention exhibited a low melt viscosity, and the epoxy resin composition of the present invention using the epoxy resin mixture exhibited high heat resistance and low water absorption in the cured product. .
[0033]
【The invention's effect】
The epoxy resin mixture of the present invention exhibits a low melt viscosity, and an epoxy resin composition containing the epoxy resin mixture exhibits high heat resistance and low water absorption. Therefore, the epoxy resin of the present invention can be used for insulating materials for electrical and electronic parts (high reliability semiconductor encapsulating materials, etc.), laminated boards (printed wiring boards, etc.), various composite materials including CFRP, adhesives, paints, etc. Very useful.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19275496A JP3681020B2 (en) | 1996-07-04 | 1996-07-04 | Epoxy resin mixture, epoxy resin composition and cured product thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19275496A JP3681020B2 (en) | 1996-07-04 | 1996-07-04 | Epoxy resin mixture, epoxy resin composition and cured product thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1017643A JPH1017643A (en) | 1998-01-20 |
| JP3681020B2 true JP3681020B2 (en) | 2005-08-10 |
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| JP19275496A Expired - Fee Related JP3681020B2 (en) | 1996-07-04 | 1996-07-04 | Epoxy resin mixture, epoxy resin composition and cured product thereof |
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| JP (1) | JP3681020B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003096310A (en) * | 2001-09-26 | 2003-04-03 | Shigeru Koshibe | Infrared light transparent resin composition |
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1996
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| Publication number | Publication date |
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| JPH1017643A (en) | 1998-01-20 |
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