JPS6210571B2 - - Google Patents
Info
- Publication number
- JPS6210571B2 JPS6210571B2 JP15989982A JP15989982A JPS6210571B2 JP S6210571 B2 JPS6210571 B2 JP S6210571B2 JP 15989982 A JP15989982 A JP 15989982A JP 15989982 A JP15989982 A JP 15989982A JP S6210571 B2 JPS6210571 B2 JP S6210571B2
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- moles
- mol
- epoxy
- group
- 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
Links
- 239000003822 epoxy resin Substances 0.000 claims description 32
- 229920000647 polyepoxide Polymers 0.000 claims description 32
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- -1 imidazole compound Chemical class 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 125000003700 epoxy group Chemical group 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- RUEBPOOTFCZRBC-UHFFFAOYSA-N (5-methyl-2-phenyl-1h-imidazol-4-yl)methanol Chemical compound OCC1=C(C)NC(C=2C=CC=CC=2)=N1 RUEBPOOTFCZRBC-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 5
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 5
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229910015900 BF3 Inorganic materials 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- NRCVBBCKYNCMEV-UHFFFAOYSA-N (2-ethyl-5-methyl-1h-imidazol-4-yl)methanol Chemical compound CCC1=NC(C)=C(CO)N1 NRCVBBCKYNCMEV-UHFFFAOYSA-N 0.000 description 1
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- NWOMMWVCNAOLOG-UHFFFAOYSA-N 1h-imidazol-5-ylmethanediol Chemical compound OC(O)C1=CN=CN1 NWOMMWVCNAOLOG-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- ZXTHWIZHGLNEPG-UHFFFAOYSA-N 2-phenyl-4,5-dihydro-1,3-oxazole Chemical compound O1CCN=C1C1=CC=CC=C1 ZXTHWIZHGLNEPG-UHFFFAOYSA-N 0.000 description 1
- GRWFFFOEIHGUBG-UHFFFAOYSA-N 3,4-Epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclo-hexanecarboxylate Chemical group C1C2OC2CC(C)C1C(=O)OCC1CC2OC2CC1C GRWFFFOEIHGUBG-UHFFFAOYSA-N 0.000 description 1
- RBHIUNHSNSQJNG-UHFFFAOYSA-N 6-methyl-3-(2-methyloxiran-2-yl)-7-oxabicyclo[4.1.0]heptane Chemical group C1CC2(C)OC2CC1C1(C)CO1 RBHIUNHSNSQJNG-UHFFFAOYSA-N 0.000 description 1
- 102100029647 Apoptosis-associated speck-like protein containing a CARD Human genes 0.000 description 1
- 101000728679 Homo sapiens Apoptosis-associated speck-like protein containing a CARD Proteins 0.000 description 1
- 101000707471 Homo sapiens Serine incorporator 3 Proteins 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- MGJKQDOBUOMPEZ-UHFFFAOYSA-N N,N'-dimethylurea Chemical compound CNC(=O)NC MGJKQDOBUOMPEZ-UHFFFAOYSA-N 0.000 description 1
- QSBINWBNXWAVAK-PSXMRANNSA-N PE-NMe(16:0/16:0) Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP(O)(=O)OCCNC)OC(=O)CCCCCCCCCCCCCCC QSBINWBNXWAVAK-PSXMRANNSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- UUQQGGWZVKUCBD-UHFFFAOYSA-N [4-(hydroxymethyl)-2-phenyl-1h-imidazol-5-yl]methanol Chemical compound N1C(CO)=C(CO)N=C1C1=CC=CC=C1 UUQQGGWZVKUCBD-UHFFFAOYSA-N 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- UTTHLMXOSUFZCQ-UHFFFAOYSA-N benzene-1,3-dicarbohydrazide Chemical compound NNC(=O)C1=CC=CC(C(=O)NN)=C1 UTTHLMXOSUFZCQ-UHFFFAOYSA-N 0.000 description 1
- HCOMFAYPHBFMKU-UHFFFAOYSA-N butanedihydrazide Chemical compound NNC(=O)CCC(=O)NN HCOMFAYPHBFMKU-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- GRGBENNNGZARRZ-UHFFFAOYSA-N dodecanedihydrazide Chemical compound NNC(=O)CCCCCCCCCCC(=O)NN GRGBENNNGZARRZ-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000005464 sample preparation method Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Landscapes
- Organic Insulating Materials (AREA)
- Epoxy Resins (AREA)
Description
本発明は、室温付近で極めて優れた貯蔵安定性
を有し、且つ100〜150℃の温度ですみやかに硬化
可能な一液性エポキシ樹脂組成物に関するもので
あり、この組成物は特に電気、電子部品の注型に
適するものである。
エポキシ樹脂は電気絶縁性、接着性、耐湿性に
優れており、しかも硬化時の収縮が小さいという
特長があり、電気部品や半導体素子、集積回路の
絶縁封止用として使用されている。
エポキシ樹脂の硬化剤としては(1)ポリアミン
類、(2)有機二塩基酸無水物、(3)フエノール樹脂、
(4)イミダゾール類、(5)三フツ化ほう素のアミン錯
体等があげられるが、これらの多くはエポキシ樹
脂と混合した場合の可使時間が数分〜数日と短い
ため、エポキシ樹脂と硬化剤を別々に保管してお
き、使用直前に混合し使用するのが一般的で多液
型であり、予備分散、秤量、混合が必要とされ
る。
三フツ化ほう素のアミン錯体は優れた潜在性を
有し、しかも120〜130℃で速やかに硬化可能な硬
化剤であるが硬化時にアミンガスを発生しやす
く、半導体素子を含む電子部品の封止剤としては
素子の汚染の点から好ましくない。
一方、ジシアンジアミドは古くから知られてい
る潜在性硬化剤であるが、単独で使用する場合
170℃以上の硬化温度が必要である。ジシアンジ
アミドの硬化促進剤としてイミダゾール化合物
（特開昭55―165916号公報）、（クロルフエニル）
―１，１―Ｎジメチル尿素（特開昭50―25700号
公報）等が紹介されているが、いずれの場合も厚
膜で硬化する際に極めて発熱が高く上記硬化促進
剤を分解せしめ、ガスを発生し、薄膜の場合は硬
化の進行が極めて遅いという欠点を有しており、
電子部品の封止には適さない。
本発明はこれらの欠点を改良したものであり、
室温では優れた潜在性、具体的には４ケ月以上の
可使時間を有し、しかも100〜150℃の温度で速や
かに硬化可能な樹脂組成物であり、詳しくは、
(1) 分子内にエポキシ基を有するエポキシ樹脂
(2) 有機二塩基酸ジヒドラジドを上記エポキシ樹
脂100モルに対し３〜15モル
(3) 一般式（）
The present invention relates to a one-component epoxy resin composition that has extremely excellent storage stability near room temperature and can be rapidly cured at a temperature of 100 to 150°C. It is suitable for casting parts. Epoxy resin has excellent electrical insulation, adhesive properties, and moisture resistance, and also has the advantage of low shrinkage when cured, and is used for insulating and sealing electrical parts, semiconductor devices, and integrated circuits. As curing agents for epoxy resins, (1) polyamines, (2) organic dibasic acid anhydrides, (3) phenolic resins,
Examples include (4) imidazoles and (5) amine complexes of boron trifluoride, but many of these have a short pot life of several minutes to several days when mixed with epoxy resins, so they are not compatible with epoxy resins. Generally, the curing agent is stored separately and mixed immediately before use. It is a multi-component type, and requires preliminary dispersion, weighing, and mixing. Amine complexes of boron trifluoride are curing agents that have excellent latent properties and can be cured quickly at 120 to 130°C, but they tend to generate amine gas during curing, making them difficult to encapsulate electronic components including semiconductor devices. It is not preferred as an agent in terms of contamination of the device. On the other hand, dicyandiamide is a latent curing agent that has been known for a long time, but when used alone
A curing temperature of 170°C or higher is required. Imidazole compound (Japanese Unexamined Patent Publication No. 165916/1983), (chlorphenyl) as a curing accelerator for dicyandiamide
-1,1-N dimethylurea (Japanese Unexamined Patent Publication No. 50-25700) has been introduced, but in either case, when curing a thick film, it generates extremely high heat and decomposes the curing accelerator, causing gas The problem is that the curing process is extremely slow in the case of thin films.
Not suitable for sealing electronic components. The present invention improves these drawbacks,
It is a resin composition that has excellent latent properties at room temperature, specifically a pot life of 4 months or more, and can be rapidly cured at temperatures of 100 to 150°C. Epoxy resin having an epoxy group (2) 3 to 15 mol of organic dibasic acid dihydrazide per 100 mol of the above epoxy resin (3) General formula ()
【式】
（R1はメチル基、水素又はヒドロキシメチ
ル基をR2はアルキル基を示す。
で表わされるイミダゾール化合物を上記エポ
キシ樹脂100モルに対し２〜７モル含有してな
る一液性エポキシ樹脂組成物に関する。
本発明に使用する分子内にエポキシ基を有する
エポキシ樹脂としては、ビスフエノールＡ、ビス
フエノールＦ、フエノールノボラツク樹脂、クレ
ゾールノボラツク樹脂等の多価フエノールとエピ
クロルヒドリンから誘導される多価フエノールの
ポリグリシジルエーテル型エポキシ樹脂、多塩基
酸とエピクロルヒドリンから誘導されるジグリシ
ジルエステル及びその誘導体、ジシクロペンタジ
エンオキサイド、３，４―エポキシ―６―メチル
シクロヘキシルメチル―３，４―エポキシ―６―
メチルシクロヘキサンカルボキシレート、リモネ
ンジオキサイド、イソブチレンから誘導されるメ
チル置換型エポキシ等が用いられる。分子内にエ
ポキシ基を１個より多く含むエポキシ樹脂が好ま
しい。耐熱性の点から多価フエノールのポリグリ
シジルエーテル型エポキシ樹脂が好ましい。
本発明に使用される有機二塩基酸ジヒドラジド
としてはシユウ酸、マロン酸、コハク酸、アジピ
ン酸、セバシン酸、ドデカン酸、ヘキサデカン
酸、イソフタル酸等のジヒドラジドがこれに属す
る。アジピン酸ジヒドラジド、イソフタル酸ジヒ
ドラジド及びこれらの混合物が好ましい。有機二
塩基酸ジヒドラジドの配合量はエポキシ樹脂100
モルに対して３〜15モルの範囲とされ、６〜12モ
ルの範囲が好ましい。有機二塩基酸ジヒドラジド
が３モルより少ない場合は硬化性に劣り、しかも
硬化物のガラス転移温度が低く耐熱性に乏しい。
また15モルより多い場合は可使時間が短くなり貯
蔵安定性に劣る。
本発明において用いられる上記の一般式（）
で表わされるイミダゾール化合物としては、２―
エチル―４―メチル―５―ヒドロキシメチルイミ
ダゾール、２―フエニル―４―メチル―５―ヒド
ロキシメチルイミダゾール、２―フエニル―４，
５―ジヒドロキシメチルイミダゾールなどがこれ
に属し、その添加量は前記エポキシ樹脂100モル
に対し２〜７モルの範囲とされ、硬化性と可使時
間のバランスから３〜５モルが好ましい。イミダ
ゾール化合物が２モルより少ない場合は硬化性に
劣り、ゲル化するまで極めて長時間を要する。ま
た７モルを超える添加量ではイミダゾールが硬化
剤として作用し、貯蔵安定性が著しく低下するば
かりでなく硬化物のガラス転移温度も低下する。
本発明の組成物には必要に応じて充てん剤、着
色剤、カツプリング剤を添加することもできる。
本発明を実施例及び比較例によつて説明する。
実施例及び比較例の試料の作成方法及び特性の評
価方法を以下に示す。
(1) 試料の作成方法
エポキシ樹脂、有機二塩基酸ジヒドラジド及び
イミダゾール化合物をラポスターラーで撹拌後、
小型三本ロールで十分に混練した後、真空らいか
い器により5Torrの減圧下で真空混合脱気した。
この後金属シヤーレに0.3〜0.7mmの膜厚状に塗布
し、120℃で２時間、ついで150℃で４時間硬化し
た。
(2) ゲル化時間の測定
所定の温度に保温したホツトプレート上に上記
混練試料を１ｇ採取しミクロスパチユラで撹拌
し、樹脂の流動性がなくなるまでの時間をゲル化
時間とした。
(3) ガラス転移温度の測定
0.3〜0.7mmの膜厚で120℃で２時間、ついで150
℃で４時間硬化した試料をPerkin Elmer社製熱
物理試験器TMS―１を用いて線膨張率を測定
し、その変曲点をガラス転移温度とした。
(4) 可使時間の測定
(1)で混練した試料200ｇを密閉容器に入れ所定
温度に放置し、１日毎に25℃における粘度を測定
した。粘度が初期粘度の1.5倍に達した時間を可
使時間とした。
実施例 １
エポキシ当量190のエピービス型エポキシ樹脂
（油化シエル社製エピコート828）１モル、アジピ
ン酸ジヒドラジド0.05モル、２―フエニル―４―
メチル―５―ヒドロキシメチルイミダゾール0.04
モルを混合し試料を作成した。
実施例 ２
エポキシ当量190のエピービス型エポキシ樹脂
（油化シエル社製エピコート828）１モル、ドデカ
ン二酸ジヒドラジド0.07モル、２―フエニル―４
―メチル５―ヒドロキシメチルイミダゾール0.03
モルを混合し試料を作成した。
実施例 ３
エポキシ当量190のエピービス型エポキシ樹脂
（油化シエル社製エピコート828）0.5モル、エポ
キシ当量175のフエノールノボラツク型エポキシ
樹脂（ダウケミカル社製DEN431）0.5モル、コハ
ク酸ジヒドラジド0.1モル、２―フエニル―４―
メチル―５―ヒドロキシメチルイミダゾール0.03
モルを混合して試料を作成した。
実施例 ４
エポキシ当量190のエピービス型エポキシ樹脂
（油化シエル社製エピコート828）１モル、イソフ
タル酸ジヒドラジド0.1モル、２―フエニル４，
５―ジヒドロキシメチルイミダゾール0.04モルを
混合して試料を作成した。
比較例 １
エポキシ当量190のエピービス型エポキシ樹脂
（油化シエル社製エピコート828）１モル、アジピ
ン酸ジヒドラジド0.2モル，２―フエニル４―メ
チル５―ヒドロキシメチルイミダゾール0.03モル
を混合して試料を作成した。
比較例 ２
エポキシ当量190のエピービス型エポキシ樹脂
（油化シエル社製エピコート828）１モル、アジピ
ン酸ジヒドラジド0.1モル、２―フエニル４―メ
チル５―ヒドロキシメチルイミダゾール0.1モル
を混合して試料を作成した。
比較例 ３
エポキシ当量175のフエノールノボラツク型エ
ポキシ樹脂（ダウケミカル社製DEN431）１モ
ル、ジシアンジアミド0.1モル、２―フエニル４
―メチル５―ヒドロキシメチルイミダゾール0.04
モルを混合して試料を作成した。
表１に実施例１〜４及び比較例１〜３の評価結
果をまとめて示す。[Formula] (R 1 is a methyl group, hydrogen or hydroxymethyl group, and R 2 is an alkyl group.) A one-component epoxy resin containing 2 to 7 moles of an imidazole compound represented by the above formula per 100 moles of the above epoxy resin. Regarding the composition.Epoxy resins having an epoxy group in the molecule used in the present invention include polyhydric phenols such as bisphenol A, bisphenol F, phenol novolac resins, and cresol novolak resins, and polyphenols derived from epichlorohydrin. Polyglycidyl ether type epoxy resin of polyhydric phenol, diglycidyl ester derived from polybasic acid and epichlorohydrin and its derivatives, dicyclopentadiene oxide, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6 ―
Methyl cyclohexane carboxylate, limonene dioxide, methyl substituted epoxy derived from isobutylene, and the like are used. Epoxy resins containing more than one epoxy group in the molecule are preferred. From the viewpoint of heat resistance, a polyglycidyl ether type epoxy resin of polyhydric phenol is preferred. The organic dibasic acid dihydrazides used in the present invention include dihydrazides such as oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, dodecanoic acid, hexadecanoic acid, and isophthalic acid. Adipic dihydrazide, isophthalic dihydrazide and mixtures thereof are preferred. The amount of organic dibasic acid dihydrazide is 100% of the epoxy resin.
It ranges from 3 to 15 moles, preferably from 6 to 12 moles. When the amount of organic dibasic acid dihydrazide is less than 3 moles, the curability is poor, and the cured product has a low glass transition temperature and poor heat resistance.
If the amount is more than 15 moles, the pot life will be shortened and the storage stability will be poor. The above general formula () used in the present invention
The imidazole compound represented by 2-
Ethyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,
5-dihydroxymethylimidazole and the like belong to this category, and the amount added is in the range of 2 to 7 moles per 100 moles of the epoxy resin, preferably 3 to 5 moles in view of the balance between curability and pot life. When the amount of imidazole compound is less than 2 moles, the curability is poor and it takes a very long time to gel. Further, if the amount added exceeds 7 mol, imidazole acts as a curing agent, and not only the storage stability is significantly lowered but also the glass transition temperature of the cured product is lowered. Fillers, colorants, and coupling agents can also be added to the composition of the present invention, if necessary. The present invention will be explained with reference to Examples and Comparative Examples.
A method for preparing samples and a method for evaluating characteristics of Examples and Comparative Examples are shown below. (1) Sample preparation method After stirring the epoxy resin, organic dibasic acid dihydrazide, and imidazole compound with a lap posterer,
After thorough kneading with a small three-roller, the mixture was vacuum mixed and degassed under a reduced pressure of 5 Torr using a vacuum sieve.
Thereafter, it was applied to a metal shear coat to a thickness of 0.3 to 0.7 mm, and cured at 120°C for 2 hours and then at 150°C for 4 hours. (2) Measurement of gelation time 1 g of the above-mentioned kneaded sample was collected on a hot plate kept at a predetermined temperature and stirred with a microspatula, and the time until the resin lost its fluidity was defined as the gelation time. (3) Measurement of glass transition temperature: 2 hours at 120℃ with a film thickness of 0.3 to 0.7mm, then 150℃
The coefficient of linear expansion of the sample cured at ℃ for 4 hours was measured using a thermophysical tester TMS-1 manufactured by Perkin Elmer, and the inflection point was defined as the glass transition temperature. (4) Measurement of pot life 200 g of the sample kneaded in (1) was placed in a sealed container and left at a predetermined temperature, and the viscosity at 25°C was measured every day. The time when the viscosity reached 1.5 times the initial viscosity was defined as the pot life. Example 1 1 mol of Epibis type epoxy resin (Epicote 828 manufactured by Yuka Ciel Co., Ltd.) with an epoxy equivalent of 190, 0.05 mol of adipic acid dihydrazide, 2-phenyl-4-
Methyl-5-hydroxymethylimidazole 0.04
A sample was prepared by mixing the moles. Example 2 1 mol of Epibis type epoxy resin with an epoxy equivalent of 190 (Epicote 828 manufactured by Yuka Ciel Co., Ltd.), 0.07 mol of dodecanedioic acid dihydrazide, 2-phenyl-4
-Methyl 5-hydroxymethylimidazole 0.03
A sample was prepared by mixing the moles. Example 3 0.5 mol of Epibis type epoxy resin with epoxy equivalent of 190 (Epicote 828, manufactured by Yuka Shell Co., Ltd.), 0.5 mol of phenol novolac type epoxy resin (DEN431, manufactured by Dow Chemical Company) with epoxy equivalent of 175, 0.1 mol of succinic acid dihydrazide, 2 -Phenyl-4-
Methyl-5-hydroxymethylimidazole 0.03
Samples were prepared by mixing moles. Example 4 1 mol of Epibis type epoxy resin (Epicote 828 manufactured by Yuka Ciel Co., Ltd.) with an epoxy equivalent of 190, 0.1 mol of isophthalic acid dihydrazide, 2-phenyl 4,
A sample was prepared by mixing 0.04 mol of 5-dihydroxymethylimidazole. Comparative Example 1 A sample was prepared by mixing 1 mol of Epibis type epoxy resin (Epicote 828 manufactured by Yuka Ciel Co., Ltd.) with an epoxy equivalent of 190, 0.2 mol of adipic acid dihydrazide, and 0.03 mol of 2-phenyl 4-methyl 5-hydroxymethylimidazole. . Comparative Example 2 A sample was prepared by mixing 1 mol of Epibis type epoxy resin (Epicote 828 manufactured by Yuka Ciel Co., Ltd.) with an epoxy equivalent of 190, 0.1 mol of adipic acid dihydrazide, and 0.1 mol of 2-phenyl 4-methyl 5-hydroxymethylimidazole. . Comparative Example 3 1 mol of phenol novolak type epoxy resin (DOW Chemical Company DEN431) with epoxy equivalent weight 175, 0.1 mol of dicyandiamide, 2-phenyl 4
-Methyl 5-hydroxymethylimidazole 0.04
Samples were prepared by mixing moles. Table 1 summarizes the evaluation results of Examples 1 to 4 and Comparative Examples 1 to 3.
【表】
本発明になるエポキシ樹脂組成物は従来の多液
型と異なり、秤量、混合の必要がなく作業性に優
れている。しかも室温付近の温度で長期間の可使
時間を有し、しかも100〜150℃で分解ガスを発生
することなしに速やかに硬化する。硬化物は高い
ガラス転移温度を有するため作業時に温度上昇を
伴う電気、電子部品の絶縁封止材料に適し特に半
導体素子を封止する場合、その素子の信頼性を向
上できるものと考える。[Table] Unlike the conventional multi-component type, the epoxy resin composition of the present invention does not require weighing or mixing, and has excellent workability. In addition, it has a long pot life at temperatures around room temperature, and hardens quickly at 100 to 150°C without generating decomposition gas. Since the cured product has a high glass transition temperature, it is suitable as an insulating sealing material for electrical and electronic components that are subject to temperature increases during operation, and is believed to improve the reliability of semiconductor devices, especially when sealing semiconductor devices.
Claims (1)
脂 (ii) 有機二塩基酸ジヒドラジドを上記エポキシ樹
脂100モルに対し３〜15モル (iii) 一般式（） 【式】 （R1はメチル基、水素又はヒドロキシメチ
ル基をR2はアルキル基を示す。） で表わされるイミダゾール化合物を上記のエ
ポキシ樹脂100モルに対し２〜７モル含有して
なる一液性エポキシ樹脂組成物。 ２ 分子内にエポキシ基を有するエポキシ樹脂
が、多価フエノールのポリグリシジルエーテル型
エポキシ樹脂である特許請求の範囲第１項記載の
一液性エポキシ樹脂組成物。[Scope of Claims] 1 (i) Epoxy resin having an epoxy group in the molecule (ii) 3 to 15 moles of organic dibasic acid dihydrazide per 100 moles of the above epoxy resin (iii) General formula () [Formula] ( A one-component epoxy resin composition containing 2 to 7 moles of an imidazole compound represented by (R 1 is a methyl group, hydrogen, or hydroxymethyl group, and R 2 is an alkyl group) per 100 moles of the above epoxy resin. . 2. The one-component epoxy resin composition according to claim 1, wherein the epoxy resin having an epoxy group in the molecule is a polyglycidyl ether type epoxy resin of polyhydric phenol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15989982A JPS5949224A (en) | 1982-09-14 | 1982-09-14 | Epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15989982A JPS5949224A (en) | 1982-09-14 | 1982-09-14 | Epoxy resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5949224A JPS5949224A (en) | 1984-03-21 |
| JPS6210571B2 true JPS6210571B2 (en) | 1987-03-06 |
Family
ID=15703601
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15989982A Granted JPS5949224A (en) | 1982-09-14 | 1982-09-14 | Epoxy resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5949224A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013031519A1 (en) * | 2011-08-26 | 2013-03-07 | デクセリアルズ株式会社 | Solar cell conductive adhesive and connection method using same, solar cell module, and method for producing solar cell module |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6136318A (en) * | 1984-07-30 | 1986-02-21 | Hitachi Chem Co Ltd | Epoxy resin composition |
| JPS61192721A (en) * | 1985-02-22 | 1986-08-27 | Ajinomoto Co Inc | One-pack epoxy resin composition |
| JPS62129309A (en) * | 1985-12-02 | 1987-06-11 | Toray Ind Inc | Epoxy resin composition |
| JPH0791506B2 (en) * | 1990-10-09 | 1995-10-04 | 松下電器産業株式会社 | Coating composition for electronic parts |
| GB0412196D0 (en) * | 2004-06-02 | 2004-07-07 | Hexcel Composites Ltd | Cure accelerators |
-
1982
- 1982-09-14 JP JP15989982A patent/JPS5949224A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013031519A1 (en) * | 2011-08-26 | 2013-03-07 | デクセリアルズ株式会社 | Solar cell conductive adhesive and connection method using same, solar cell module, and method for producing solar cell module |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5949224A (en) | 1984-03-21 |
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