JPS6154326B2 - - Google Patents

Info

Publication number
JPS6154326B2
JPS6154326B2 JP55176107A JP17610780A JPS6154326B2 JP S6154326 B2 JPS6154326 B2 JP S6154326B2 JP 55176107 A JP55176107 A JP 55176107A JP 17610780 A JP17610780 A JP 17610780A JP S6154326 B2 JPS6154326 B2 JP S6154326B2
Authority
JP
Japan
Prior art keywords
epoxy resin
parts
curing
resin composition
methylimidazole
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.)
Expired
Application number
JP55176107A
Other languages
Japanese (ja)
Other versions
JPS57100128A (en
Inventor
Masahiro Matsumura
Masaaki Ootsu
Yoshihiro Kitsuta
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Panasonic Electric Works Co Ltd
Original Assignee
Matsushita Electric Works Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Matsushita Electric Works Ltd filed Critical Matsushita Electric Works Ltd
Priority to JP17610780A priority Critical patent/JPS57100128A/en
Publication of JPS57100128A publication Critical patent/JPS57100128A/en
Publication of JPS6154326B2 publication Critical patent/JPS6154326B2/ja
Granted legal-status Critical Current

Links

Description

【発明の詳細な説明】[Detailed description of the invention]

この発明は、成形性(低圧充填性)の優れたエ
ポキシ樹脂組成物、特にIC,LSI封止用として最
適なエポキシ樹脂組成物に関するものである。 トランジスター,IC,LSI等の半導体装置は、
一般に、大量生産可能なトランスフアー成形で樹
脂封止されているが、トランスフアー成形を行う
場合、低圧で充分流動性のある封止材料を用いな
いと、IC,LSI等の素子の断線が起こり、高価な
半導体装置が不良品になつてしまう。しかし、従
来の市販品を含む材料には、低圧流動性を満足さ
せるものはほとんどないのが現状である。 この発明者らは、このような情況に鑑み、低圧
流動性に優れ、しかも速硬化かつ貯蔵安定性に優
れた半導体装置封止用エポキシ樹脂組成物を得る
ために鋭意研究した結果、多官能エポキシ樹脂
に、硬化剤としてノボラツク系化合物を配合する
とともに、硬化助剤として2―メチルイミダゾー
ル・無水ピロメツト酸塩を配合すると、所期の目
的を達成しうることを見いだしこの発明を完成す
るに到つた。 すなわち、この発明は、多官能エポキシ樹脂、
硬化剤としてのノボラツク系化合物および硬化助
剤としての2―メチルイミダゾール・無水ピロメ
リツト酸塩が配合されているエポキシ樹脂組成物
をその要旨とするものである。 この発明で用いるエポキシ樹脂は、分子内に少
なくとも2個のエポキシ基を有する化合物であれ
ば特に限定しない。しかし一般的には、エポキシ
当量100〜4000の通常のエポキシ樹脂が用いられ
る。例えば、ビスフエノール系エポキシ樹脂、脂
環式エポキシ樹脂、ノボラツク系エポキシ樹脂、
含窒素エポキシ樹脂ならびにブロム化エポキシ樹
脂のようなハロゲン化エポキシ樹脂があげられ
る。 また硬化剤として用いるノボラツク系化合物と
しては、フエノール、クレゾール、キシレノー
ル、レゾルシン等のフエノール類とホルムアルデ
ヒドのようなアルデヒド類とを酸性触媒下で反応
させて得られるものがあげられる。このようなノ
ボラツク系化合物の配合量は、エポキシ樹脂100
重量部(以下「部」と略す)に対して、10〜100
部が好ましい。この範囲をはずれると、いずれの
場合も硬化不足となり、硬化物の耐熱性、耐薬品
性が劣るようになるからである。 この発明では、硬化促進剤として、2―メチル
イミダゾール・無水ピロメリツト酸塩を用いる。
このように、硬化促進剤として2―メチルイミダ
ゾール・無水ピロメリツト酸塩を用いることがこ
の発明の特徴である。他のイミダゾール誘導体お
よび有機酸の錯塩を用いても、この発明のような
低圧流動性に優れたエポキシ樹脂組成物は得られ
ないのである。硬化促進剤の量は、エポキシ樹脂
100部に対して1〜10部が好ましい。1部未満で
は硬化が遅く、また10部を超えると貯蔵安定性が
悪くなる欠点が生じてくるからである。 なお、本発明のエポキシ樹脂組成物には、半導
体装置封止剤として各種の充填剤を配合すること
が好ましい。例えば、シリカ、溶融シリカ、石英
ガラス粉、炭酸カルシウム、クレー、タルク、け
いそう土、マイカ、ケイ酸ジルコニウムなどがあ
げられ、全材料に対して30〜80重量%(以下
「%」と略す)用いることができる。 離型剤としては、モンタナワツクス、カルナウ
バワツクス、ステアリン酸、ステアリン酸金属塩
などが用いられる。さらに必要に応じて難燃化
剤、表面処理剤、染顔料などを用いることもでき
るのである。 この発明のエポキシ樹脂組成物を用いて成形材
料をつくる場合は、つぎのようにして行われる。
すなわち、この発明のエポキシ樹脂組成物および
その他の充填材等を混合する。混合は、ミキシン
グロールや加圧ニーダー等の汎用の混合機械を使
用して行えばよい。ついで混合物を微粉砕し必要
に応じてタブレツト化してトランスフアー成形材
料とする。 この発明の樹脂組成物からつくられた成形材料
は、低圧流動性に優れ、速硬化性、かつ材料の保
存安定性が良好であるため、IC、LSIの封止用と
して最適であり、封止される半導体装置の成形時
の不良率の低減を実現しうるようになるのであ
る。 つぎに実施例について比較例と併せて説明す
る。 まず、つぎのようにして硬化助剤および硬化剤
を合成した。 (硬化助剤の合成) 無水ピロメリツト酸109部をTHF109部に溶解
させた液をフラスコに入れた。他方、滴下ロート
中に、2―メチルイミダゾール82部をTHF82部
に溶解させた液を入れた。常温で2―メチルイミ
ダゾール液をフラスコ中に滴下していくと、すぐ
に淡黄色の沈澱が生じ、この沈澱を過し、乾燥
させて2―メチルイミダゾール・無水ピロメリツ
ト酸塩を得た。実施例はもとより、比較例に用い
る硬化助剤もこの方法と同様にして得られたもの
である。 (硬化剤の合成) フエノール94部、37%ホルマリン64.9部、蓚酸
0.27部を撹拌器、冷却器、温度計を備えたフラス
コに入れ、100℃で100分間反応させた。その後、
薄膜乾燥脱水で水を取り除き、最終160℃で60分
間反応させ脱蓚酸を行なつてフエノールノボラツ
クを得た。このノボラツクは、遊離フエノール
0.2%で数平均分子量700であつた。またOH当量
は104.2であつた。 つぎに、上記の硬化助剤および硬化剤を用いて
つぎのようにして成形材料を得た。 〔実施例1〜3、比較例1〜5〕 各原料を下記のように配合した。 クレゾールノボラツク型エポキシ樹脂(エポキ
シ当量207.9,YDCN 220L,東都化成社製)
:100部 フエノールノボラツク(OH当量104.2)
:50.1部 硬化促進剤:次表に示すものを同表に示す量用
いた。 溶融シリカ(S―1,電気化学工業社製)
:360部 ステアリン酸亜鉛 : 3部 カーボンブラツク : 1部 エポキシシラン(KBM403,信越化学社製)
: 1部 上記配合物を100〜12℃においてミキシングロ
ールで20〜30分間混練し、円板延び(測定条件は
次表の*3の保存安定性の場合と同じ)で150〜
170mmになつた時、混練をやめ、シート状材料を
とり出し、冷却粉砕してエポキシ樹脂成形材料を
得た。 〔実施例4,5〕 エポキシ樹脂として、エポキシ当量190のもの
(N―740、大日本インキ社製)を100部用い、フ
エノールノボラツク(OH当量104.2)の量を54.8
部にした。それ以外は上記と同様にしてエポキシ
樹脂成形材料を得た。 以上の実施例および比較例で得られたエポキシ
樹脂成形材料の特性およびそれを用いて製造した
成形品の不良数を求めて次表に示した。実施例の
ものは、ふくれおよび断線がなく極めて優れてい
ることがわかる。
The present invention relates to an epoxy resin composition with excellent moldability (low-pressure filling properties), and particularly to an epoxy resin composition optimal for encapsulating ICs and LSIs. Semiconductor devices such as transistors, ICs, and LSIs are
Generally, resin sealing is performed using transfer molding, which can be mass-produced, but when performing transfer molding, unless a sealing material with sufficient fluidity is used at low pressure, disconnection of IC, LSI, etc. elements may occur. , expensive semiconductor devices end up being defective. However, at present, there are almost no materials, including conventional commercial products, that satisfy low-pressure fluidity. In view of these circumstances, the inventors conducted intensive research to obtain an epoxy resin composition for encapsulating semiconductor devices that has excellent low-pressure fluidity, fast curing, and excellent storage stability. The inventors discovered that the desired objective could be achieved by blending a novolak-based compound as a curing agent with the resin and 2-methylimidazole/pyrometh anhydride as a curing aid, leading to the completion of this invention. . That is, this invention provides a polyfunctional epoxy resin,
The gist thereof is an epoxy resin composition containing a novolac type compound as a curing agent and 2-methylimidazole/pyromellitic anhydride as a curing aid. The epoxy resin used in this invention is not particularly limited as long as it is a compound having at least two epoxy groups in the molecule. However, in general, ordinary epoxy resins having an epoxy equivalent weight of 100 to 4000 are used. For example, bisphenol epoxy resin, alicyclic epoxy resin, novolak epoxy resin,
Mention may be made of nitrogen-containing epoxy resins and halogenated epoxy resins such as brominated epoxy resins. Examples of novolac compounds used as curing agents include those obtained by reacting phenols such as phenol, cresol, xylenol, and resorcin with aldehydes such as formaldehyde under an acidic catalyst. The blending amount of such novolak-based compounds is 100% of the epoxy resin.
10 to 100 parts by weight (hereinafter referred to as "parts")
part is preferred. If it is outside this range, curing will be insufficient in any case, and the cured product will have poor heat resistance and chemical resistance. In this invention, 2-methylimidazole anhydrous pyromellistate is used as a curing accelerator.
As described above, it is a feature of the present invention that 2-methylimidazole/pyromellitic anhydride is used as a curing accelerator. Even if other imidazole derivatives and organic acid complex salts are used, an epoxy resin composition with excellent low-pressure fluidity as in the present invention cannot be obtained. The amount of curing accelerator depends on the epoxy resin
1 to 10 parts per 100 parts is preferred. If it is less than 1 part, curing will be slow, and if it exceeds 10 parts, storage stability will be poor. In addition, it is preferable that various fillers are blended into the epoxy resin composition of the present invention as a semiconductor device encapsulant. Examples include silica, fused silica, quartz glass powder, calcium carbonate, clay, talc, diatomaceous earth, mica, zirconium silicate, etc., and 30 to 80% by weight of the total material (hereinafter abbreviated as "%") Can be used. As the mold release agent, montana wax, carnauba wax, stearic acid, stearic acid metal salt, etc. are used. Furthermore, flame retardants, surface treatment agents, dyes and pigments, etc. can also be used as necessary. When producing a molding material using the epoxy resin composition of the present invention, it is carried out as follows.
That is, the epoxy resin composition of the present invention and other fillers are mixed. Mixing may be performed using a general-purpose mixing machine such as a mixing roll or a pressure kneader. The mixture is then finely ground and, if necessary, made into tablets to provide a transfer molding material. The molding material made from the resin composition of this invention has excellent low-pressure fluidity, fast curing properties, and good storage stability, making it ideal for encapsulating ICs and LSIs. This makes it possible to reduce the defect rate during molding of semiconductor devices. Next, examples will be described together with comparative examples. First, a curing aid and a curing agent were synthesized as follows. (Synthesis of hardening aid) A solution prepared by dissolving 109 parts of pyromellitic anhydride in 109 parts of THF was placed in a flask. On the other hand, a solution of 82 parts of 2-methylimidazole dissolved in 82 parts of THF was placed in the dropping funnel. When the 2-methylimidazole solution was dropped into the flask at room temperature, a pale yellow precipitate was immediately formed, and this precipitate was filtered and dried to obtain 2-methylimidazole anhydrous pyromellistate. The curing aids used not only in the Examples but also in the Comparative Examples were obtained in the same manner as this method. (Synthesis of hardening agent) 94 parts of phenol, 64.9 parts of 37% formalin, oxalic acid
0.27 part was placed in a flask equipped with a stirrer, a condenser, and a thermometer, and the mixture was reacted at 100°C for 100 minutes. after that,
Water was removed by thin film drying and dehydration, and a final reaction was carried out at 160°C for 60 minutes to remove oxalate and obtain a phenol novolak. This novolac is free phenol
At 0.2%, the number average molecular weight was 700. Moreover, the OH equivalent was 104.2. Next, a molding material was obtained in the following manner using the above curing aid and curing agent. [Examples 1 to 3, Comparative Examples 1 to 5] Each raw material was blended as follows. Cresol novolak type epoxy resin (epoxy equivalent 207.9, YDCN 220L, manufactured by Toto Kasei Co., Ltd.)
: 100 parts phenol novolac (OH equivalent 104.2)
: 50.1 parts Curing accelerator: The materials shown in the following table were used in the amounts shown in the same table. Fused silica (S-1, manufactured by Denki Kagaku Kogyo Co., Ltd.)
: 360 parts Zinc stearate : 3 parts Carbon black : 1 part Epoxy silane (KBM403, manufactured by Shin-Etsu Chemical)
: 1 part The above compound was kneaded for 20 to 30 minutes with a mixing roll at 100 to 12°C, and the disc elongation (measurement conditions are the same as for storage stability in *3 in the following table) was 150 to 100.
When it reached 170 mm, kneading was stopped, the sheet material was taken out, cooled and ground to obtain an epoxy resin molding material. [Examples 4 and 5] As the epoxy resin, 100 parts of an epoxy equivalent of 190 (N-740, manufactured by Dainippon Ink Co., Ltd.) was used, and the amount of phenol novolak (OH equivalent: 104.2) was 54.8 parts.
I made it into a department. An epoxy resin molding material was obtained in the same manner as above except that. The characteristics of the epoxy resin molding materials obtained in the above Examples and Comparative Examples and the number of defective molded products manufactured using the same were determined and are shown in the following table. It can be seen that the samples of Examples are extremely excellent with no blisters or disconnections.

【表】【table】

【表】【table】 【図面の簡単な説明】[Brief explanation of the drawing]

図面は流動性試験の説明図である。 The drawing is an explanatory diagram of the fluidity test.

Claims (1)

【特許請求の範囲】 1 多官能エポキシ樹脂、硬化剤としてのノボラ
ツク系化合物および硬化助剤としての2―メチル
イミダゾール・無水ピロメリツト酸塩が配合され
ているエポキシ樹脂組成物。 2 多官能エポキシ樹脂100重量部に対して2―
メチルイミダゾール・無水ピロメリツト酸塩が1
〜10重量部配合されている特許請求の範囲第1項
記載のエポキシ樹脂組成物。
[Scope of Claims] 1. An epoxy resin composition containing a polyfunctional epoxy resin, a novolac compound as a curing agent, and 2-methylimidazole/pyromellitic anhydride as a curing aid. 2 2- for 100 parts by weight of polyfunctional epoxy resin
Methylimidazole/pyromellitic anhydride is 1
The epoxy resin composition according to claim 1, wherein the epoxy resin composition is blended in an amount of 10 parts by weight.
JP17610780A 1980-12-13 1980-12-13 Epoxy resin composition Granted JPS57100128A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP17610780A JPS57100128A (en) 1980-12-13 1980-12-13 Epoxy resin composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP17610780A JPS57100128A (en) 1980-12-13 1980-12-13 Epoxy resin composition

Publications (2)

Publication Number Publication Date
JPS57100128A JPS57100128A (en) 1982-06-22
JPS6154326B2 true JPS6154326B2 (en) 1986-11-21

Family

ID=16007808

Family Applications (1)

Application Number Title Priority Date Filing Date
JP17610780A Granted JPS57100128A (en) 1980-12-13 1980-12-13 Epoxy resin composition

Country Status (1)

Country Link
JP (1) JPS57100128A (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4594291A (en) * 1984-07-17 1986-06-10 The Dow Chemical Company Curable, partially advanced epoxy resins
JPH0618853B2 (en) * 1987-04-03 1994-03-16 信越化学工業株式会社 Epoxy resin composition
JPH10176036A (en) * 1996-12-19 1998-06-30 Shin Etsu Chem Co Ltd Epoxy resin composition and semiconductor device
JP6836740B2 (en) * 2016-10-13 2021-03-03 三菱瓦斯化学株式会社 Resin composition, resin sheet, printed wiring board and semiconductor device

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3493630A (en) * 1964-09-22 1970-02-03 Union Carbide Corp Epoxy resins cured with phenolic novolacs and imidazoles
US3746686A (en) * 1971-07-12 1973-07-17 Shell Oil Co Process for curing polyepoxides with polycarboxylic acid salts of an imidazole compound and compositions thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3493630A (en) * 1964-09-22 1970-02-03 Union Carbide Corp Epoxy resins cured with phenolic novolacs and imidazoles
US3746686A (en) * 1971-07-12 1973-07-17 Shell Oil Co Process for curing polyepoxides with polycarboxylic acid salts of an imidazole compound and compositions thereof

Also Published As

Publication number Publication date
JPS57100128A (en) 1982-06-22

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