JPS6323922A - Epoxy resin composition for sealing - Google Patents
Epoxy resin composition for sealingInfo
- Publication number
- JPS6323922A JPS6323922A JP16931486A JP16931486A JPS6323922A JP S6323922 A JPS6323922 A JP S6323922A JP 16931486 A JP16931486 A JP 16931486A JP 16931486 A JP16931486 A JP 16931486A JP S6323922 A JPS6323922 A JP S6323922A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- weight
- filler
- curing agent
- resin composition
- 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.)
- Granted
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 53
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 53
- 239000000203 mixture Substances 0.000 title claims abstract description 50
- 238000007789 sealing Methods 0.000 title claims abstract description 15
- 239000000945 filler Substances 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004094 surface-active agent Substances 0.000 claims abstract description 17
- 239000007822 coupling agent Substances 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 6
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims abstract description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims 2
- 125000002883 imidazolyl group Chemical group 0.000 claims 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 abstract description 11
- 239000007787 solid Substances 0.000 abstract description 9
- -1 R<4> is H Chemical group 0.000 abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 6
- 239000004065 semiconductor Substances 0.000 abstract description 5
- XMQYIPNJVLNWOE-UHFFFAOYSA-N dioctyl hydrogen phosphite Chemical compound CCCCCCCCOP(O)OCCCCCCCC XMQYIPNJVLNWOE-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052731 fluorine Inorganic materials 0.000 abstract description 3
- 239000011737 fluorine Substances 0.000 abstract description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 2
- 229910002026 crystalline silica Inorganic materials 0.000 abstract description 2
- 150000002460 imidazoles Chemical class 0.000 abstract description 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 12
- 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 8
- 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
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 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 3
- 230000007423 decrease Effects 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-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
- 238000005520 cutting process Methods 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 239000005350 fused silica glass Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- AXJZCJSXNZZMDU-UHFFFAOYSA-N (5-methyl-1h-imidazol-4-yl)methanol Chemical compound CC=1N=CNC=1CO AXJZCJSXNZZMDU-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
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 1
- RBHIUNHSNSQJNG-UHFFFAOYSA-N 6-methyl-3-(2-methyloxiran-2-yl)-7-oxabicyclo[4.1.0]heptane Chemical compound C1CC2(C)OC2CC1C1(C)CO1 RBHIUNHSNSQJNG-UHFFFAOYSA-N 0.000 description 1
- RXSZJZHDKKQGMT-UHFFFAOYSA-N CCCCCCCCOP(CCCCCCCC)(CCCCCCCC)(O)OCCCCCCCC.CCCCCCCCOP(CCCCCCCC)(CCCCCCCC)(O)OCCCCCCCC Chemical compound CCCCCCCCOP(CCCCCCCC)(CCCCCCCC)(O)OCCCCCCCC.CCCCCCCCOP(CCCCCCCC)(CCCCCCCC)(O)OCCCCCCCC RXSZJZHDKKQGMT-UHFFFAOYSA-N 0.000 description 1
- 241001062872 Cleyera japonica Species 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 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
- UMHKOAYRTRADAT-UHFFFAOYSA-N [hydroxy(octoxy)phosphoryl] octyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OP(O)(=O)OCCCCCCCC UMHKOAYRTRADAT-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- XHWQYYPUYFYELO-UHFFFAOYSA-N ditridecyl phosphite Chemical compound CCCCCCCCCCCCCOP([O-])OCCCCCCCCCCCCC XHWQYYPUYFYELO-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000006355 external stress Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、温度、湿度、衝撃等の外的ストレスから半導
体素子等を保護する為の樹脂封止材料に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a resin encapsulation material for protecting semiconductor elements and the like from external stresses such as temperature, humidity, and impact.
［従来の技術］
半導体素子等の樹脂封止材料としては、エポキシ系樹脂
が一般的に使用されている。この半導体素子封止用エポ
キシ樹脂組成物は、固形エポキシ樹脂組成物と液性エポ
キシ樹脂組成物とに大別される。後者は、ざらに二液性
エポキシ樹脂組成物と一液性エボキシ樹脂組成物とに分
けられる。[Prior Art] Epoxy resins are generally used as resin sealing materials for semiconductor devices and the like. This epoxy resin composition for encapsulating semiconductor elements is broadly classified into solid epoxy resin compositions and liquid epoxy resin compositions. The latter can be roughly divided into two-component epoxy resin compositions and one-component epoxy resin compositions.
固形エポキシ樹脂組成物は、少品種大量生産に用いられ
、その耐湿信頼性が良い反面、多品種少量生産には、コ
スト的に高くなり、製品により樹脂組成物量を変えづら
く１作業効率が悪い欠点がある。Solid epoxy resin compositions are used for mass production of a small number of products, and have good moisture resistance and reliability. However, they are expensive for high variety, small volume production, and have the disadvantage of being difficult to change the amount of resin composition depending on the product, resulting in poor work efficiency. There is.
これに対して、液性エポキシ樹脂組成物は、専用ＩＣ等
の多品種少量生産を中心に用いられ、ディスペンサーを
用いた自動化ラインに組み込まれて使用されている。On the other hand, liquid epoxy resin compositions are mainly used for high-mix, low-volume production of dedicated ICs and the like, and are used by being incorporated into automated lines using dispensers.
このうち、二液性エポキシ樹脂組成物は、粘度が低く、
流動性が良いため、半導体素子の封止作業効率が良く、
広く用いられている。しかしながら、エポキシ樹脂と硬
化剤とを使用する前に混合する必要があること、混合し
た組成物の貯蔵安定性が悪いこと、更に、耐湿信頼性に
劣ることなどの欠点があり、高い信頼性が要求される分
野では使用することができない。Among these, two-component epoxy resin compositions have low viscosity,
Due to its good fluidity, the efficiency of sealing semiconductor devices is high.
Widely used. However, there are drawbacks such as the need to mix the epoxy resin and curing agent before use, poor storage stability of the mixed composition, and poor moisture resistance reliability. It cannot be used in the field where it is required.
他方、−液性エポキシ樹脂ｌｊｉ放物は、耐湿及び耐熱
信頼性において固形エポキシ樹脂組成物と同等の性能を
有しており、その用途を広げつつある。しかしながら、
−液性エポキシ樹脂組成物は粘度が高く流動性が悪いた
め、前述の二液性エポキシ樹脂組成物と比較すると封止
作業効率が大きく劣るという欠点が指摘されている。こ
れに対して１反応性希釈剤等を添加することにより、組
成物の粘度を下げ流動性を高めることが提案されている
が、耐湿及び耐熱信頼性が大きく低下し、−液性エポキ
シ樹脂組成物の特性を失ってしまう。On the other hand, -liquid epoxy resin lji parabolic has performance equivalent to that of solid epoxy resin compositions in moisture resistance and heat resistance reliability, and its uses are expanding. however,
- Since liquid epoxy resin compositions have high viscosity and poor fluidity, it has been pointed out that they have a drawback of being significantly inferior in sealing efficiency compared to the two-component epoxy resin compositions described above. On the other hand, it has been proposed to reduce the viscosity of the composition and increase its fluidity by adding a reactive diluent, etc., but this greatly reduces the moisture resistance and heat resistance reliability. Things lose their properties.
［［明が解決しようとする問題点］
本発明は、前述の実情に鑑みてなされたものであり、そ
の解決しようとする問題点は前述の従来の技術の欠点で
あり、その目的は半導体素子の封止後の信頼性が固形エ
ポキシ樹脂組成物と同等であり、かつ、刃出作業性が二
液性エポキシ樹脂組成物と同程度である、−液性エポキ
シ樹脂組成物を提供することにある。[[Problems to be Solved by Ming] The present invention has been made in view of the above-mentioned circumstances, and the problems to be solved by the present invention are the drawbacks of the above-mentioned conventional techniques. To provide a liquid-based epoxy resin composition, which has the same reliability after sealing as a solid epoxy resin composition, and has the same level of cutting workability as a two-part epoxy resin composition. be.
ｃ問題点を解決するための手段］
上記の問題点を解決するために、本発明者らが鋭意検討
した結果。c. Means for Solving the Problems] The results of intensive studies by the present inventors to solve the above problems.
エポキシ樹脂、硬化剤、界面活性剤及び充填剤を含む組
成物であって、
（イ）前記硬化剤が下記一般式（Ａ）又は（Ｂ）で示さ
れるイミダゾール化合物より選ばれる少なくとも一種を
含む硬化剤であり、エポキシ樹脂１００重量部に対し、
１〜８重量部の割合で配合され。A composition containing an epoxy resin, a curing agent, a surfactant, and a filler, wherein (a) the curing agent contains at least one type of imidazole compound represented by the following general formula (A) or (B); agent, per 100 parts by weight of epoxy resin,
It is blended in a proportion of 1 to 8 parts by weight.
（Ａ）
（式中１ｍは１〜１４の、ｎはＯ〜２の整数、Ｒ１，Ｆ
ｔｆｆｉおよびＲｉは水素原子、アルキル基又はフェニ
ル基を示す、）
（以下余白、）
（Ｂ）
！
（式中、Ｒ４は水素原子、メチル基又は、ヒドロキシメ
チル基を、Ｒ５はアルキル基又はフェニル基を示す、）
（ロ）前記界面活性剤かフッ素系界面活性剤であり、エ
ポキシ樹脂１００重量部に対し、０．００１〜１重量部
の割合て配合され、
かつ、
（い）前記充填剤がチタネート系カップリング剤により
処理された充填材であり、全組成物に対し、５０〜８０
重量％配合されていることを特徴とする封止用エポキシ
樹脂組成物が、封止後の信頼性と封止作業性との両方を
満足することを見い出し、本発明を完成するに至った。(A) (In the formula, 1m is an integer of 1 to 14, n is an integer of O to 2, R1, F
tffi and Ri represent a hydrogen atom, an alkyl group, or a phenyl group.) (Hereinafter referred to as the margin) (B)! (In the formula, R4 represents a hydrogen atom, a methyl group, or a hydroxymethyl group, and R5 represents an alkyl group or a phenyl group.) (b) The above surfactant is a fluorine-based surfactant, and 100 parts by weight of an epoxy resin (b) The filler is a filler treated with a titanate coupling agent, and the filler is blended in an amount of 0.001 to 1 part by weight based on the total composition.
The present inventors have discovered that an epoxy resin composition for sealing, which is characterized in that the epoxy resin composition contains 1% by weight, satisfies both the reliability after sealing and the workability of sealing, and has completed the present invention.
すなわち、エポキシ樹脂とイミダゾール化合物を硬化剤
とする耐熱及び耐湿性に優れたー液性のエポキシ樹脂硬
化系と、フッ素系界面活性剤によるエポキシ樹脂組成物
の表面張力の低下及びチタネート系カップリング剤によ
り処理された充填材を使用することによるエポキシ樹脂
組成物の低粘度化の相乗効果により封止作業性が大幅に
向上した充填材添加エポキシ樹脂系とを、効果的に組み
合わせたものである。In other words, a liquid epoxy resin curing system with excellent heat and moisture resistance using an epoxy resin and an imidazole compound as a curing agent, a fluorosurfactant to lower the surface tension of the epoxy resin composition, and a titanate coupling agent. This is an effective combination of a filler-added epoxy resin system in which sealing workability has been greatly improved due to the synergistic effect of lowering the viscosity of the epoxy resin composition by using fillers treated with .
以下１本発明の封止用エポキシ樹脂組成物について、更
に詳しく説明する。The epoxy resin composition for sealing of the present invention will be explained in more detail below.
本発明に３いて用いられるエポキシ樹脂は、ビスフェノ
ールＡ型の液状エポキシ樹脂、ビスフェノールＦ型の液
状エポキシ樹脂、ｌ、１−ビス（４−ヒドロキシフェニ
ル）エタンのグリシジルエーテルより選ばれる液状エポ
キシ樹脂を主成分とするものである。The epoxy resin used in the present invention is mainly a liquid epoxy resin selected from bisphenol A type liquid epoxy resin, bisphenol F type liquid epoxy resin, and glycidyl ether of l,1-bis(4-hydroxyphenyl)ethane. It is an ingredient.
本発明においては、これら液状エポキシ樹脂と共に、公
知の固体エポキシ樹脂、たとえばビスフェノールＡ型の
固体エポキシ樹脂、フェノールノボラック型のエポキシ
樹脂等の固体のエポキシ樹脂、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、ジシクロペンタジェンオキサイド、リモネンジオ
キサイド等を全体が液状を保つ範囲内において用いても
良い。In the present invention, in addition to these liquid epoxy resins, known solid epoxy resins, such as solid epoxy resins such as bisphenol A type solid epoxy resins and phenol novolac type epoxy resins, and diglycidyl derived from polybasic acids and epichlorohydrin are used. Ester and its derivatives, dicyclopentadiene oxide, limonene dioxide, etc. may be used within the range where the whole remains liquid.
本発明において用いられる硬化剤は前記一般式（Ａ）又
は（Ｂ）て示される化合物のうちから選ばれる少なくと
も１種のイミダゾール化合物を含むものである。The curing agent used in the present invention contains at least one imidazole compound selected from the compounds represented by the general formula (A) or (B).
一般式（Ａ）で表わされるイミダゾール化合物としては
、例えば、２，４−ジアミノ−６（２′−メチルイミダ
ゾリル−（１） ′）エチル−８−トソアジンとイソシ
アヌル酸との付加物（結品水を含む）、又、一般式（Ｂ
）で示されるイミダゾール化合物としては、２−フェニ
ル−４−メチル−５−ヒドロキシメチルイミダゾール、
２−フェニル−４，５−ジヒドロキシメチルイミダゾー
ル等が挙げられる。Examples of the imidazole compound represented by the general formula (A) include an adduct of 2,4-diamino-6(2'-methylimidazolyl-(1)')ethyl-8-tosoazine and isocyanuric acid ), and the general formula (B
) Examples of the imidazole compounds include 2-phenyl-4-methyl-5-hydroxymethylimidazole,
Examples include 2-phenyl-4,5-dihydroxymethylimidazole.
硬化剤量はエポキシ樹脂１００重量部に対し１〜８重量
部の割合で配合される。硬化剤量が１重量部より少ない
場合は硬化性に劣り、硬化剤量か８重量部より多い場合
は、貯蔵安定性が低下し、組成物の粘度が上昇し、耐湿
性も低下する為好ましくない。The curing agent is blended in an amount of 1 to 8 parts by weight per 100 parts by weight of the epoxy resin. If the amount of the curing agent is less than 1 part by weight, the curability will be poor, and if the amount of the curing agent is more than 8 parts by weight, the storage stability will decrease, the viscosity of the composition will increase, and the moisture resistance will decrease, so it is preferable. do not have.
また前記硬化剤が微粉末状に粉砕され、その粒径か１ｐ
ｍＬＪ下であることかより一層望ましい。In addition, the hardening agent is pulverized into a fine powder, and the particle size is 1 p.
It is even more desirable that it be below mLJ.
これは粉砕により硬化剤の分散度か良くなり、粉砕され
ていない硬化剤より少ない量で同し硬化物特性か得られ
るからである。This is because pulverization improves the degree of dispersion of the curing agent, and the same properties of the cured product can be obtained with a smaller amount of curing agent that is not pulverized.
未発１１において用いられる界面活性剤は、フッ素系界
面活性剤であり、フッ素化アルキルエステル等が挙げら
れる。４゜
界面活性剤量はエポキシ樹脂１００重量部に対し、（１
，００１〜１重量部の割合で配合される。界面活性剤量
がｏ、ｏｎｔ重量部より少ない場合は流動性に劣り、界
面活性剤量か１重量部より多い場合は、接着性が低下し
たり、硬化時に樹脂表面ににじみ出して汚染の原因とな
るなど好ましくない。The surfactant used in Misaki No. 11 is a fluorine-based surfactant, and examples thereof include fluorinated alkyl esters. 4゜The amount of surfactant is (1) per 100 parts by weight of epoxy resin.
,001 to 1 part by weight. If the amount of surfactant is less than 1 part by weight, the fluidity will be poor, and if the amount of surfactant is more than 1 part by weight, it may cause poor adhesion or ooze out onto the resin surface during curing, causing contamination. This is not desirable.
特に接着性を低下させずに流動性の良い組を物を得たい
場合は、前記界面活性剤をエポキシ樹脂１００重量部に
対し、０．０１〜０．５重量部の割合で配合することが
望ましい。In particular, if you want to obtain a material with good fluidity without reducing adhesiveness, the surfactant may be blended at a ratio of 0.01 to 0.5 parts by weight to 100 parts by weight of the epoxy resin. desirable.
本発明において用いられる充填材は全組成物に対し５０
〜８０重量％の割合で用いられる。５０重量％より少な
い場合は硬化した組成物の線膨張係数。The filler used in the present invention is 50% of the total composition.
It is used in a proportion of ~80% by weight. If it is less than 50% by weight, it is the linear expansion coefficient of the cured composition.
吸水率等が高く好ましくない、又、８０重量％より多い
場合は、系の粘度か上昇し、作業性が低下し実際的でな
い、充填材としては粉枠又は未粉枠の溶融シリカ、結晶
シリカ、水溜化アルミニウム、アルミナ、酸化ジルコニ
ウム、ケイ酸ジルコニウム、三酸化アンチモン、ガラス
粒、炭霞カルシウム等が挙げられる。The water absorption rate is high and undesirable, and if it exceeds 80% by weight, the viscosity of the system increases and workability decreases, making it impractical.As a filler, use powdered or unpowdered fused silica or crystalline silica. , hydrated aluminum, alumina, zirconium oxide, zirconium silicate, antimony trioxide, glass particles, calcium carbonate, and the like.
尚、本発明で用いられる充填材は、カップリング剤のう
ち、チタネート系カップリング剤で表面処理を行なった
充填材であり、チタネート系カップリング剤としては、
テトライソプロピルビス（ジオクチルホスファイト）チ
タネート、イソプロピルトッドデシルベンゼンスルホニ
ルチタネート、テトラトオクチルビス（ジトリデシルホ
スファイト）チタネート、ビス（ジオクチルパイロホス
フェート）オキシアセテートチタネート等が挙げられる
。The filler used in the present invention is a filler that has been surface-treated with a titanate coupling agent among coupling agents, and the titanate coupling agent includes:
Examples include tetraisopropyl bis(dioctyl phosphite) titanate, isopropyl toddecylbenzenesulfonyl titanate, tetratooctyl bis(ditridecyl phosphite) titanate, bis(dioctyl pyrophosphate) oxyacetate titanate, and the like.
チタネート系カップリング剤による充填材の表面処理は
、乾式法、湿式法などいかなる方法で行なったものであ
っても差し支えない。The surface treatment of the filler with the titanate coupling agent may be carried out by any method such as a dry method or a wet method.
更に本発明の組成物には、上記エポキシ樹脂、硬化剤、
界面活性剤及び充填材の外に、必要に応じて、硬化促進
剤、難燃剤１着色剤、防錆剤、腐食防止剤等を加えるこ
とかできる。Furthermore, the composition of the present invention includes the above-mentioned epoxy resin, a curing agent,
In addition to the surfactant and filler, a curing accelerator, a flame retardant, a coloring agent, a rust preventive, a corrosion inhibitor, etc. can be added as necessary.
本発明の封止用エポキシ樹脂組成物は、前記のエポキシ
樹脂、硬化剤、界面活性剤及び充填材を含む組成物であ
るが、これらの組成物は、例えばミキサー、ニーター、
ロール等による混合・混練により得ることかできる。さ
らに、この混合・混線中あるいは混合・混線後に非加熱
下で真空脱気することが好ましい。The epoxy resin composition for sealing of the present invention is a composition containing the above-mentioned epoxy resin, a curing agent, a surfactant, and a filler, and these compositions can be mixed, for example, with a mixer, a kneader, or a filler.
It can be obtained by mixing and kneading using a roll or the like. Furthermore, it is preferable to perform vacuum degassing without heating during or after this mixing/crossing.
このようにして得られる本発明の封止用エポキシ樹脂組
成物は、エポキシ樹脂とイミダゾール化合物とから形成
される耐熱及び耐湿性に優れた特性と、フッ素系界面活
性剤とチタネート系カップリング剤により処理された充
填材との相乗効果により得られる優れた作業性との両方
を合わせ備えたー液性エポキシ樹脂組成物を提供するも
のである。The epoxy resin composition for sealing of the present invention obtained in this way has excellent heat and moisture resistance properties formed from an epoxy resin and an imidazole compound, and a fluorosurfactant and a titanate coupling agent. The object of the present invention is to provide a liquid epoxy resin composition that has both excellent workability obtained through a synergistic effect with treated fillers.
［実施例］ 次に実施例及び比較例について説明する。[Example] Next, Examples and Comparative Examples will be described.
実施例１
ビスフェノールＡ型エポキシ樹脂（エポキシ当量１９０
）１００重量部、２−フェニル−４−メチル−５−ヒド
ロキシメチルイミダゾール（四国化成社２Ｐ４ＭＨ２）
を１ｇｍ以下の粒径に粉枠し４重量部、充填材として、
チタネート系カップリング剤：テトライソプロピルビス
（ジオクチルホスファイト）チタネート（味の素社 Ｋ
Ｒ−４１Ｂ）を０．３重量部の割合で処理した、平均粒
径１５ルｍの溶融シリカ（龍森社ヒユーズレックスＲＤ
−８）１８０重量部、フッ素系界面活性剤としてＦＣ−
４３０（住友スリーエム社商品名） Ｏ，ＯＳ重量部加
え３子４！Ｒ混合した後に３本ロールで混練し１次いで
減圧下に脱気して＃？成放物料を調整した。Example 1 Bisphenol A type epoxy resin (epoxy equivalent: 190
) 100 parts by weight, 2-phenyl-4-methyl-5-hydroxymethylimidazole (Shikoku Kasei 2P4MH2)
powder to a particle size of 1 gm or less, 4 parts by weight, as a filler,
Titanate coupling agent: Tetraisopropyl bis(dioctyl phosphite) titanate (Ajinomoto Co., Ltd. K)
Fused silica with an average particle size of 15 lm (R-41B) treated at a ratio of 0.3 parts by weight (Tatsumorisha Fuse Rex RD)
-8) 180 parts by weight, FC- as a fluorosurfactant
430 (Sumitomo 3M product name) O, OS weight part plus 3 children 4! After R mixing, knead with three rolls, then degas under reduced pressure and #? Adjusted the release charge.
実」１１ス
実施例１において、硬化剤に、粉枠していない２−フェ
ニル−４−メチル−５−ヒドロキシメチルイミダゾール
を４重量部用い、カップリンク剤に、テトラオクチルビ
ス（ジオクチルホスファイト）チタネートを０．３重量
部用いる他は実施例１と同様にして試料を調整した。In Example 1, 4 parts by weight of unpowdered 2-phenyl-4-methyl-5-hydroxymethylimidazole was used as the curing agent, and tetraoctyl bis(dioctyl phosphite) was used as the coupling agent. A sample was prepared in the same manner as in Example 1, except that 0.3 parts by weight of titanate was used.
実施例３
実施例１において、界面活性剤として、ＦＣ−４３０を
ｏ、ｏｏｓ重量部用いる他は実施例１と同様にして試料
を調整した。Example 3 A sample was prepared in the same manner as in Example 1 except that o, oos parts by weight of FC-430 were used as the surfactant.
比較例１
実施例１において、界面活性剤を使用しない以外は実施
例１と同様にして試料を調整した。Comparative Example 1 A sample was prepared in the same manner as in Example 1 except that no surfactant was used.
比較例２
実施例１において、カップリング剤にシランカップリン
グ剤として、γ−グリシドオキシプロビルトリメトキシ
シラン（Ｂ本ユニカー２１Ａ−１８７）を用いる他は実
施例１と同様にして試料を調整した。Comparative Example 2 A sample was prepared in the same manner as in Example 1, except that γ-glycidoxypropyltrimethoxysilane (B Hon Unicar 21A-187) was used as the silane coupling agent. did.
ルオむ１１
ビスフェノールＡ型エポキシ樹脂（エポキシ当９．１９
０）９０重量部、反応性希釈剤としてメタ・パラクレジ
ールグリシジルエーテル（阪木薬品社ｍ。Luom 11 Bisphenol A type epoxy resin (epoxy weight 9.19
0) 90 parts by weight, meta-paracresyl glycidyl ether (Sakaki Pharmaceutical Co., Ltd.) as a reactive diluent.
ｐ−ＣＧＥ）１０重？部、硬化剤として２−フェニル−
４−メチル−５−ヒドロキシメチルイミダゾールを４重
量部、充填材として実施例１と同様のシリカを１８０重
量部、カップリング剤としてテトライソプロピルビス（
ジオクチルホスファイト）チタネートを０．３重ｒ部の
割合て処理し、実施例１と同様にして試料を調整した。p-CGE) 10 layers? part, 2-phenyl- as a curing agent
4 parts by weight of 4-methyl-5-hydroxymethylimidazole, 180 parts by weight of the same silica as in Example 1 as a filler, and tetraisopropyl bis(
A sample was prepared in the same manner as in Example 1 by treating the sample with 0.3 parts by weight of dioctyl phosphite (dioctyl phosphite) titanate.
このようにして得られた試料を、以下に示す方法で評価
し、その結果を表に示す。The samples thus obtained were evaluated by the method shown below, and the results are shown in the table.
（以下余白）
（１）流動性ニ
ガラス上に０．２ｇの試料を滴下し、硬化条件１００”
Ｃｘ２Ｈｒ＋１５０℃Ｘ２Ｈｒで硬化させた後の広がり
面積を測定する。(Left below) (1) Drop 0.2g of sample onto fluid glass and cure under 100”
The spreading area after curing at Cx2Hr+150°C x2Hr is measured.
（２）耐湿性：
小型パターンを有する湿度センサーを樹脂組成物中に埋
め込み、１００℃ｘ２Ｈｒ＋１５０℃Ｘ２Ｈｒの条件で
硬化させて得られた成型物を１２１”Ｃ・２気圧の蒸気
釜中に入れ、湿度センサーまで湿気が達するまでの時間
を測定する。(2) Moisture resistance: A humidity sensor with a small pattern was embedded in a resin composition, and the molded product obtained by curing under the conditions of 100°C x 2 hours + 150°C x 2 hours was placed in a steam pot at 121"C and 2 atm. Measures the time it takes for moisture to reach the humidity sensor.
（３）耐熱性：
１００℃ｘ２Ｈｒ＋１５０ ＠Ｃｘ２Ｈｒの条件で硬化
させて得られた成型物を熱ｌ！１ｒＳ分析（ＴＭＡ）に
より熱線膨張係数及びガラス転移点を測定する。(3) Heat resistance: The molded product obtained by curing under the conditions of 100℃ x 2Hr + 150 @Cx2Hr is heated to 1! The linear thermal expansion coefficient and glass transition point are measured by 1rS analysis (TMA).
表に示す結果から分かるように１本発明の対重用エポキ
シ樹脂組成物は、流動性において比較例に示す従来品と
格段の差異がある。すなわち。As can be seen from the results shown in the table, the epoxy resin composition for heavy duty use of the present invention is significantly different from the conventional product shown in the comparative example in fluidity. Namely.
フッ素系界面活性剤あるいはチタネート系カップリング
剤により処理された充填材のいずれか一方だけては、エ
ポキシ樹脂組成物の流動性は殆ど改善されないが、この
両方を組み合わせることにより、その相乗効果により流
動性が大幅に向上するものである。The fluidity of the epoxy resin composition is hardly improved by using either a fluorosurfactant or a filler treated with a titanate coupling agent alone, but by combining both, the fluidity is improved due to their synergistic effect. This greatly improves performance.
更に本発明の刃出用エポキシ樹脂組成物の骨格構造は、
エポキシ樹脂とイミダゾール化合物とから形成されるも
のであるから、高い耐湿性及び高い耐熱性を保持してい
る。これは１反応性希釈剤を使用して高Ｍ！、動化する
従来例と比較すると５本発明の組成物の耐湿性及び耐熱
性の高いことが明確である。Furthermore, the skeletal structure of the epoxy resin composition for cutting edge of the present invention is as follows:
Since it is formed from an epoxy resin and an imidazole compound, it maintains high moisture resistance and high heat resistance. This is high M using 1 reactive diluent! It is clear that the composition of the present invention has high moisture resistance and heat resistance when compared with conventional examples.
［発明の効果］
本発明の封止用エポキシ樹脂組成物は、固形エポキシ樹
脂組成物と同等の高い耐湿及び耐熱特性と、二液性エポ
キシ樹脂組成物と同等の優れた封止作業性能との両方の
長所を合わせ持つ一液性の組成物であり、専用ＩＣ等の
多品種少量生産に適合したものであり、産業−Ｅ極めて
有用なものである。[Effects of the Invention] The epoxy resin composition for sealing of the present invention has high moisture resistance and heat resistance properties equivalent to solid epoxy resin compositions, and excellent sealing work performance equivalent to two-component epoxy resin compositions. It is a one-component composition that combines the advantages of both, and is suitable for high-mix, low-volume production of dedicated ICs, etc., and is extremely useful for industry-E.
Claims (1)
組成物であって、 （イ）前記硬化剤が下記一般式（Ａ）又は（Ｂ）で示さ
れるイミダゾール化合物より選ばれる少なくとも一種を
含む硬化剤であり、エポキシ樹脂１００重量部に対し、
１〜８重量部の割合で配合され、 （Ａ） ▲数式、化学式、表等があります▼ （式中、ｍは１〜１４の、ｎは０〜２の整数、Ｒ＾１、
Ｒ＾２およびＲ＾３は水素原子、アルキル基又はフェニ
ル基を示す。） （Ｂ） ▲数式、化学式、表等があります▼ （式中、Ｒ＾４は水素原子、メチル基又はヒドロキシメ
チル基を、Ｒ＾５はアルキル基又はフェニル基を示す。 ） （ロ）前記界面活性剤がフッ素系界面活性剤であり、エ
ポキシ樹脂１００重量部に対し、０．００１〜１重量部
の割合で配合され、 かつ、 （ハ）前記充填材がチタネート系カップリング剤により
処理された充填材であり、全組成物に対し、５０〜８０
重量％配合されていることを特徴とする封止用エポキシ
樹脂組成物。[Scope of Claims] A composition comprising an epoxy resin, a curing agent, a surfactant, and a filler, wherein (a) the curing agent is selected from imidazole compounds represented by the following general formula (A) or (B). A curing agent containing at least one type of epoxy resin,
It is blended at a ratio of 1 to 8 parts by weight, (A) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, m is an integer from 1 to 14, n is an integer from 0 to 2, R^1,
R^2 and R^3 represent a hydrogen atom, an alkyl group or a phenyl group. ) (B) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^4 represents a hydrogen atom, a methyl group, or a hydroxymethyl group, and R^5 represents an alkyl group or a phenyl group.) (B) The above the surfactant is a fluorosurfactant, and is blended in a proportion of 0.001 to 1 part by weight per 100 parts by weight of the epoxy resin; and (c) the filler is treated with a titanate coupling agent. It is a filler with 50 to 80% of the total composition.
An epoxy resin composition for sealing, characterized in that it contains % by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16931486A JPH0621156B2 (en) | 1986-07-17 | 1986-07-17 | Epoxy resin composition for encapsulation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16931486A JPH0621156B2 (en) | 1986-07-17 | 1986-07-17 | Epoxy resin composition for encapsulation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6323922A true JPS6323922A (en) | 1988-02-01 |
| JPH0621156B2 JPH0621156B2 (en) | 1994-03-23 |
Family
ID=15884237
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16931486A Expired - Lifetime JPH0621156B2 (en) | 1986-07-17 | 1986-07-17 | Epoxy resin composition for encapsulation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0621156B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07268187A (en) * | 1994-04-04 | 1995-10-17 | Sumitomo Bakelite Co Ltd | Epoxy resin composition for sealing semiconductor |
| WO2001074798A1 (en) * | 2000-03-31 | 2001-10-11 | Loctite Corporation | Reworkable composition of oxirane(s) or thiirane(s)-containing resin and curing agent |
| US7012120B2 (en) | 2000-03-31 | 2006-03-14 | Henkel Corporation | Reworkable compositions of oxirane(s) or thirane(s)-containing resin and curing agent |
| US8053587B2 (en) | 2000-03-31 | 2011-11-08 | Henkel Corporation | Reworkable thermosetting resin composition |
| JP2019006972A (en) * | 2017-06-23 | 2019-01-17 | 住友ベークライト株式会社 | Production method of resin composition for encapsulation and method for manufacturing electronic device |
| CN116694275A (en) * | 2023-04-26 | 2023-09-05 | 湖北三选科技有限公司 | Liquid epoxy plastic package material and preparation method thereof |
-
1986
- 1986-07-17 JP JP16931486A patent/JPH0621156B2/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07268187A (en) * | 1994-04-04 | 1995-10-17 | Sumitomo Bakelite Co Ltd | Epoxy resin composition for sealing semiconductor |
| WO2001074798A1 (en) * | 2000-03-31 | 2001-10-11 | Loctite Corporation | Reworkable composition of oxirane(s) or thiirane(s)-containing resin and curing agent |
| US7012120B2 (en) | 2000-03-31 | 2006-03-14 | Henkel Corporation | Reworkable compositions of oxirane(s) or thirane(s)-containing resin and curing agent |
| US8053587B2 (en) | 2000-03-31 | 2011-11-08 | Henkel Corporation | Reworkable thermosetting resin composition |
| JP2019006972A (en) * | 2017-06-23 | 2019-01-17 | 住友ベークライト株式会社 | Production method of resin composition for encapsulation and method for manufacturing electronic device |
| CN116694275A (en) * | 2023-04-26 | 2023-09-05 | 湖北三选科技有限公司 | Liquid epoxy plastic package material and preparation method thereof |
| CN116694275B (en) * | 2023-04-26 | 2024-03-08 | 湖北三选科技有限公司 | Liquid epoxy plastic package material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0621156B2 (en) | 1994-03-23 |
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Free format text: JAPANESE INTERMEDIATE CODE: R250 |
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| EXPY | Cancellation because of completion of term |