JPS6317928A - Epoxy resin composition - Google Patents
Epoxy resin compositionInfo
- Publication number
- JPS6317928A JPS6317928A JP61160806A JP16080686A JPS6317928A JP S6317928 A JPS6317928 A JP S6317928A JP 61160806 A JP61160806 A JP 61160806A JP 16080686 A JP16080686 A JP 16080686A JP S6317928 A JPS6317928 A JP S6317928A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- silicone oil
- resin
- modified
- 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.)
- Pending
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 29
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 29
- 239000000203 mixture Substances 0.000 title claims abstract description 17
- 229920002545 silicone oil Polymers 0.000 claims abstract description 16
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 9
- 125000003282 alkyl amino group Chemical group 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims abstract description 5
- 239000011256 inorganic filler Substances 0.000 claims abstract description 5
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 4
- 239000005011 phenolic resin Substances 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000843 powder Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 2
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- 150000003512 tertiary amines Chemical class 0.000 abstract description 2
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- 125000002947 alkylene group Chemical group 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 17
- 239000011347 resin Substances 0.000 description 17
- 239000000463 material Substances 0.000 description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
- 229920003986 novolac Polymers 0.000 description 9
- 238000007789 sealing Methods 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- 125000003277 amino group Chemical group 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 239000006082 mold release agent Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229920013822 aminosilicone Polymers 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 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 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-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
- 239000000919 ceramic Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ODNBVEIAQAZNNM-UHFFFAOYSA-N 1-(6-chloroimidazo[1,2-b]pyridazin-3-yl)ethanone Chemical compound C1=CC(Cl)=NN2C(C(=O)C)=CN=C21 ODNBVEIAQAZNNM-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
- GUNJVIDCYZYFGV-UHFFFAOYSA-K Antimony trifluoride Inorganic materials F[Sb](F)F GUNJVIDCYZYFGV-UHFFFAOYSA-K 0.000 description 1
- 229920001342 Bakelite® Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000004637 bakelite Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Landscapes
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は成形性に優れかつ熱衝撃を受けた場合の耐クラ
ツク性、耐湿性に優れた特長を持つ低応カエボキシ樹脂
組成物に関するものである。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a low-resistance carboxy resin composition that has excellent moldability and excellent crack resistance and moisture resistance when subjected to thermal shock. be.
コンデンサーダイオード、トランジスターなどの個別半
導体またはＩＣ，ＬＳＩなどの集積回路に用いられてい
る半導体素子を機械的・電気的な外的環境から保獲する
ための封止技術として、気密封止、セラミック封止、プ
ラスチック封止などがある。しかし、封止技術としては
安価で量産性にすぐれ経済的に有利な、プラスチック封
止（中でもエポキシ樹脂）が主流である。ところが、エ
ポキシ樹脂は耐湿性、応力特性等に問題があ）、信頼性
において気密封止、セラミック封止などに劣っている。Hermetic sealing and ceramic sealing are used as sealing technologies to protect individual semiconductors such as capacitor diodes and transistors, or semiconductor elements used in integrated circuits such as ICs and LSIs from external mechanical and electrical environments. There are plastic seals, plastic seals, etc. However, as a sealing technology, plastic sealing (especially epoxy resin) is the mainstream, as it is inexpensive, easy to mass produce, and economically advantageous. However, epoxy resins have problems with moisture resistance, stress characteristics, etc., and are inferior to hermetic sealing, ceramic sealing, etc. in terms of reliability.
さらにシリコーンチップとの膨張係数の差が大きいため
、硬化後、内部応力が発生する。Furthermore, since there is a large difference in expansion coefficient from the silicone chip, internal stress is generated after curing.
温度サイクル試験、半田耐熱試験において内部応力の増
大によシ半導体素子中の配線や半導体素子保！膜にずれ
やキレンが生じたシ、半導体素子のボンディング線が切
断されるという問題点を有している。一方、近来、半導
体素子の大型化に伴ない、半導体素子に対する封止用樹
脂の内部応力を小さくすることが望まれている。During temperature cycle tests and solder heat resistance tests, wiring inside semiconductor devices and semiconductor devices are protected due to increased internal stress! There are problems in that the film is misaligned or cracked, and the bonding lines of the semiconductor element are cut. On the other hand, in recent years, as semiconductor devices have become larger, it has been desired to reduce the internal stress of a sealing resin for semiconductor devices.
一般に内部応力を低下されるには、次のいずれかによっ
て達成できる。すなわち（ａ）線膨長係数を下げる。（
ｂ）曲げ弾性率を下げる。（ｃ）ガラス転移温度を上げ
るかである。しかし、以下の問題を有している。（ｄ）
線膨長係数を下げるためには、無機充填材を添加するこ
とが行われるが多量に添加して線膨長係数を下げすぎる
と曲げ弾性率が大きくなる。（ｅ）曲げ弾性率を下げる
ためには可塑性付与剤（例えばシリコーンオイル）を添
加することが行われるが、大量に添加すると成形時に流
出が起こる。また、架橋密度の低い樹脂を用いるとガラ
ス転移温度の低下や線膨長係数の増加が起こる。（ｆ）
ガラス転移温度を上げ過ぎると曲げ弾性率が大きくなる
。Generally, internal stress can be reduced by one of the following methods: That is, (a) lowering the linear expansion coefficient. (
b) Decrease the flexural modulus. (c) Increase the glass transition temperature. However, it has the following problems. (d)
In order to lower the coefficient of linear expansion, an inorganic filler is added. However, if a large amount is added to lower the coefficient of linear expansion too much, the flexural modulus increases. (e) In order to lower the flexural modulus, a plasticizer (for example, silicone oil) is added, but if a large amount is added, outflow occurs during molding. Furthermore, when a resin with a low crosslinking density is used, the glass transition temperature decreases and the linear expansion coefficient increases. (f)
If the glass transition temperature is raised too much, the flexural modulus increases.
したがって、低応力を達成するためには、これらの諸問
題を解決しなければならない。Therefore, in order to achieve low stress, these problems must be solved.
本発明は、従来成形性に問題があシ市場レベルでの適用
ができなかったシリコーンオイルによる低応力化エポキ
シ樹脂組成物を抜本的に改良し、産業レベルでの適用す
なわち実用的製品の開発を目的として研究した結果、プ
ロトン供与剤をシリコーンオイル変性するときの触媒と
することによシ成形性に優れた低応力エポキシ樹脂組成
物が得られることを見出したものである。The present invention fundamentally improves the stress-reducing epoxy resin composition using silicone oil, which conventionally had problems with moldability and could not be applied at the market level, and aims to be applied at the industrial level, that is, to develop practical products. As a result of research aimed at this purpose, it was discovered that a low stress epoxy resin composition with excellent moldability could be obtained by using a proton donor as a catalyst for modifying silicone oil.
本発明は、（ａ）工ｆキシ樹脂、（ｂ）フェノール樹脂
硬化剤、（ｃ）硬化促進剤および（ｄ）無機充填剤より
なる構成においてエポキシ樹脂として末端にアルキルア
ミノ基又はフェニルアミノ基を有するシリコーンオイル
でプロトン供与剤を触媒として反応させてなるシリコー
ンオイル変性エビキシ樹脂を全量もしくは一部用いるこ
とを特徴とするエポキシ樹脂組成物である。The present invention provides an epoxy resin having a structure consisting of (a) a synthetic resin, (b) a phenolic resin curing agent, (c) a curing accelerator, and (d) an inorganic filler. This epoxy resin composition is characterized in that it uses all or part of a silicone oil-modified Ebixi resin obtained by reacting silicone oil with a proton donor as a catalyst.
ここで言うプロトン供与剤とは、フェノール、酢酸、水
、アルコール類（メチル、エチル、プロピル、ブチル、
ｔ−ブチル、ｉ−ブチルアルコール）、アセトニトリル
、ニトロベンゼン、ジオキサン、トルエン、ジプロピル
エーテル等である。The proton donors mentioned here include phenol, acetic acid, water, alcohols (methyl, ethyl, propyl, butyl,
t-butyl, i-butyl alcohol), acetonitrile, nitrobenzene, dioxane, toluene, dipropyl ether, etc.
ここで、プロトン供与剤を触媒として使用するのは、エ
ポキシ基を開環させ、アミノ基の攻撃を受けやすくする
ためである。Here, the reason why a proton donor is used as a catalyst is to open the epoxy group and make it more susceptible to attack by the amino group.
末端にアルキルアミノ基又はフェニルアミノ基を有する
シリコーンオイルとは
である。What is a silicone oil having an alkylamino group or a phenylamino group at the end?
変性されるエポキシ樹脂とはノボラック型又はビスフェ
ノールＡ型エポキシ樹脂である。The epoxy resin to be modified is a novolac type or bisphenol A type epoxy resin.
エポキシ樹脂組成物とは、前記シリコーンオイル変性エ
ポキシ樹脂（以下変性樹脂）を必須要件とし、更に他の
エポキシ樹脂及び硬化剤、硬化促進剤、充填基材、離型
剤、着色剤、難燃剤である。An epoxy resin composition includes the silicone oil-modified epoxy resin (hereinafter referred to as modified resin) as an essential requirement, and further contains other epoxy resins, a curing agent, a curing accelerator, a filling base material, a mold release agent, a coloring agent, and a flame retardant. be.
他のエポキシ樹脂はフェノールノボラック型エゴキシ樹
脂、クレゾールノボラック型エゼキシ樹脂である。Other epoxy resins are phenol novolac type egoxy resin and cresol novolac type epoxy resin.
硬化剤はフェノールノボラック、芳香族アミン、酸無水
物である。Hardeners are phenolic novolaks, aromatic amines, and acid anhydrides.
硬化促進剤は第３級アミン類である。Curing accelerators are tertiary amines.
充填基材はシリカ粉、アルミナ粉、ガラス繊維である。The filling base materials are silica powder, alumina powder, and glass fiber.
離型材はステアリン酸、天然ワックス、合成ワックスで
ある。The mold release agent is stearic acid, natural wax, or synthetic wax.
着色材はカーボンブラック、金属酸化物、有機染料であ
る。Colorants are carbon black, metal oxides, and organic dyes.
難燃材はＢｒ含含有エキキシ三酸化アンチモン、水利ア
ルミナである。The flame retardant materials are Br-containing excoxyantimony trioxide and water-containing alumina.
本発明に使用する変性樹脂はプロトン供与剤を触媒とし
て末端にアルキルアミノ基またはフェニルアミノ基を有
するシリコーンオイルを反応させたものであシ、反応は
加熱等を行うことによシ促進でき例えば加熱条件として
は７０〜１８０℃、１〜４時間を上げることが出来る。The modified resin used in the present invention is one obtained by reacting a silicone oil having an alkylamino group or a phenylamino group at the end using a proton donor as a catalyst.The reaction can be accelerated by heating, etc. The conditions may be 70 to 180°C for 1 to 4 hours.
ここで変性するシリコーンオイルは重合度が５０〜３０
０のものが望ましい５０未満になると耐湿性の低下や硬
化挙動の制御がむずかしい。３００を越えるようになる
と成形品表面にむらが発生しやすく、シリコーンオイル
かにじみでるためＩＣ。The silicone oil modified here has a degree of polymerization of 50 to 30.
When it is less than 50, which is preferably 0, moisture resistance decreases and it is difficult to control curing behavior. If it exceeds 300, unevenness tends to occur on the surface of the molded product and silicone oil oozes out, so IC.
ＬＳＩ等の集積回路に使用できない。Cannot be used for integrated circuits such as LSI.
末端にアミノ基を有するシリコーンオイルの使用蓋とし
ては、組成物全量に対して、１０重量％以下しか使用す
ることができない。１０重量％を越えると変性樹脂中に
ゲル化物が発生し成形性が問題となる。一方、末端にア
ルキルアミノ基を有するシリコーンオイルを用いた場合
、組成物全量に対して２０重量％まで成形性に問題なく
使用することが出来る。Silicone oil having an amino group at its terminal can only be used in an amount of 10% by weight or less based on the total amount of the composition. If it exceeds 10% by weight, gelled products will occur in the modified resin, causing problems in moldability. On the other hand, when a silicone oil having an alkylamino group at the end is used, it can be used up to 20% by weight based on the total amount of the composition without any problem in moldability.
末端にアミノ基を有するシリコーンオイルを用いて変性
を行ったものは、樹脂の安定性が悪く、保存性に問題が
ある。一方末端にアルキルアミノ基を有するオイルを用
いて変性を行ったものは、樹脂の安定性が良く、長期保
存が可能である。When modified using silicone oil having an amino group at the end, the resin has poor stability and there are problems with storage stability. On the other hand, resins modified using an oil having an alkylamino group at the end have good stability and can be stored for a long period of time.
このように本発明において末端にアルキルアミノ基を有
するシリコーンオイルをプロトン供与剤で変・性させた
エポキシ樹脂を用いることによシ、末端にアミン基を有
するシリコーンオイルをプロトン供与剤で変性した場合
に比べ樹脂封止型半導体装置の成形性、耐クラツク性、
耐湿性などの信頼性をよシー層改善することが出来る。In this way, in the present invention, by using an epoxy resin in which a silicone oil having an alkylamino group at the end is modified and modified with a proton donor, a silicone oil having an amine group at the end is modified with a proton donor. The moldability, crack resistance, and
It is possible to improve reliability such as moisture resistance.
以下、樹脂封止型半導体装置の検討例で説明する。 A study example of a resin-sealed semiconductor device will be explained below.
本発明による実施例往、従来の技術にくらべて成形性、
耐湿性、耐クラツク性の点で優れてお９工業的に利用で
きる高付加価値を有している。Examples of the present invention have better moldability than conventional techniques.
It has excellent moisture resistance and crack resistance, and has high added value that can be used industrially.
実施例で用いた原料は次の通シでおる。又、配合におけ
る部は全て重量部である。The raw materials used in the examples are as follows. Also, all parts in the formulation are parts by weight.
フェノールノボ 硬 化 剤 住人ベークライト■ ２ツ。phenol novo Hardening agent Resident Bakelite■ 2 pieces.
硬化促進剤 住人化学工業■ スミキ
ュアーＤ臭素化エポキシ樹脂 日本化薬■
ＢＲＥＮ三酸化アンチモン 住人金属鉱山■充
填基材 無疵■ ＲＤ−８表面処理材
日本ユニカー■ Ａ−１８６１１１型
材 野田ワックス−プロトン供与剤
エタノール
末端シリコーンジアミン 信越化学工業■ Ｘ２２
−１６１実施例
シリコーンオイル変性エポキシ樹脂（変性樹脂）の合成
品
フェノールノボラック型エポキシ樹脂８部と末端にメチ
ルアミンシリコーンオイル（シリコーンジアミンの重合
度の異なるもの）ｂ部とエタノール０．２ｓを表１の様
に８０℃、４時間（樹脂溶融後の正味時間）溶融混合、
冷却後粉砕し３種のシリコーンオイル変性エポキシ樹脂
を得た。Curing accelerator Sumikure D brominated epoxy resin Nippon Kayaku■
BREN Antimony Trioxide Resident Metal Mine ■ Filling base material No defects ■ RD-8 surface treatment material
Nippon Unicar■ A-186111 type Material Noda wax - proton donor
Ethanol-terminated silicone diamine Shin-Etsu Chemical ■ X22
-161 Example Synthesis of silicone oil-modified epoxy resin (modified resin) 8 parts of phenol novolac type epoxy resin, b part of methylamine silicone oil (with different degree of polymerization of silicone diamine) and 0.2 s of ethanol Table 1 Melt mixing at 80℃ for 4 hours (net time after resin melting),
After cooling, the mixture was pulverized to obtain three types of silicone oil-modified epoxy resins.
表 １
フェノールノボラック型エデキシ樹脂、硬化剤、硬化促
進剤、充填基材、三醗化アンチモン、臭素化エポキシ樹
脂、表面処理材、顔料、離型剤、フェノールノボラック
型エポキシ樹脂と末端にＮ−メチルアミノシリコーンオ
イルの混融混合品（変性樹脂）Ａ、８１Ｃを表２のよう
に配合しヘンシェルミキサーにて混合した後、１００℃
の加熱ロールで３分間混練し、数種の低圧封入成形材料
（１，２，３）を得た。これらの材料の成形性、信頼性
を評価した結果、表２に示すように本発明によると比較
例にくらべ成形性、耐クラツク性等が極めて優れている
ことが判明した。Table 1 Phenol novolac type edexy resin, curing agent, curing accelerator, filling base material, antimony trifluoride, brominated epoxy resin, surface treatment material, pigment, mold release agent, phenol novolac type epoxy resin and N-methyl terminal Amino silicone oil mixture (modified resin) A and 81C were blended as shown in Table 2, mixed in a Henschel mixer, and then heated at 100°C.
The mixture was kneaded for 3 minutes using heated rolls to obtain several types of low-pressure encapsulated molding materials (1, 2, 3). As a result of evaluating the moldability and reliability of these materials, as shown in Table 2, it was found that the present invention was extremely superior in moldability, crack resistance, etc. compared to the comparative example.
比較例
実施例と同様にフェノールノボラック型エデキシ樹脂、
硬化剤、硬化促進剤、充填基材、三酸化アンチモン、臭
素化ニブキシ樹脂、表面処理材、顔料、離型剤、フェノ
ールノボラック型エダキシ樹脂と末端アミノシリコーン
オイルの混融混合品（変性樹脂−１）（Ｄ、Ｅ、Ｆ）お
よび末端アミノシリコーンオイルの単純混融混合品（単
純変性）樹脂）（Ｅ、Ｆ、Ｇ）オ表。。ようよ配合１、
ヘンシェルミキサーにて混合した後、１００℃の加熱ロ
ールで３分間混練し、数種の低圧封入成形材料（４〜９
）を得た。Comparative Example Similar to the example, phenol novolac type edexy resin,
Curing agent, curing accelerator, filling base material, antimony trioxide, brominated niboxy resin, surface treatment material, pigment, mold release agent, blended mixture of phenol novolak type edoxy resin and terminal amino silicone oil (modified resin-1) ) (D, E, F) and a simple blend mixture (simple modified) resin of terminal amino silicone oil) (E, F, G). . Yoyo combination 1,
After mixing with a Henschel mixer, kneading with a heating roll at 100°C for 3 minutes, several types of low-pressure encapsulated molding materials (4 to 9
) was obtained.
＊１ １６ ｐｉｎ ＤＩＦを成形した時のリードピン
上のパリ発生程度で判定タイバ一部までの距離の一以下
の時Ａ、１６−局の時Ｂ、Ｘ／２〜％の時Ｃ１％以上（
タイバーを超えた）Ｄ
＊２ ＴＣＴ、４ ｗ Ｘ ９ ｍの大きさの模擬素子
を封止した１ ６ ｐｉｎ ＤＩＰに一６５℃（３０分
）；室温（５分）、１５０℃（３０分）なる熱衝撃を３
００サイクル与えクラック発生数／総数で判定。*1 Judgment based on the degree of occurrence of paris on the lead pin when molding 16 pin DIF: A when the distance to a part of the tie bar is less than 1, B when 16-station, C 1% or more when X/2~% (
(beyond the tie bar) D *2 TCT, 1 6 pin DIP sealed with a simulated element of size 4 w x 9 m - 65°C (30 minutes); room temperature (5 minutes), 150°C (30 minutes) thermal shock 3
Judging by the number of cracks generated/total number given 00 cycles.
＊３ＴＳＴ、 ４ ｗｘ Ｘ ６■の大きさの模擬素子
を封止した１ ６ ｐｉｎ ＤＩＰに一１９５℃（２分
） 、１５０’Ｃ（２分）なる熱衝撃を３００サイクル
与えクラック発生数／総数で判定。*3TST, 300 cycles of thermal shock of -195°C (2 minutes) and 150'C (2 minutes) were applied to a 16 pin DIP sealed with a simulated element of size 4 w x 6 cm, and the number of cracks generated/total number. Judgment.
＊４耐湿性、アルミ模擬素子を封止した１ ６ ｐｉｎ
ＤＩＰを１３５℃、１００チの条件で
１５・００ｈｒ保管しアルミ腐食による不良率／総数で
判定。*4 Moisture resistant, 16 pin sealed aluminum simulated element
DIP was stored for 15.00 hours at 135℃ and 100cm, and judged based on the percentage defective due to aluminum corrosion/total number.
Claims (1)
硬化促進剤および（ｄ）無機充填剤よりなる構成におい
てエポキシ樹脂として、末端にアルキルアミノ基または
フェニルアミノ基を有するシリコーンオイルでプロトン
供与剤を触媒として反応させてなるシリコーンオイル変
性エポキシ樹脂を全量もしくは一部用いることを特徴と
するエポキシ樹脂組成物。(a) Epoxy resin (b) Phenolic resin curing agent (c)
In a structure consisting of a curing accelerator and (d) an inorganic filler, the epoxy resin is a silicone oil-modified epoxy resin obtained by reacting a silicone oil having an alkylamino group or a phenylamino group at the end with a proton donor as a catalyst. An epoxy resin composition characterized in that it is partially used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61160806A JPS6317928A (en) | 1986-07-10 | 1986-07-10 | Epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61160806A JPS6317928A (en) | 1986-07-10 | 1986-07-10 | Epoxy resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6317928A true JPS6317928A (en) | 1988-01-25 |
Family
ID=15722838
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61160806A Pending JPS6317928A (en) | 1986-07-10 | 1986-07-10 | Epoxy resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6317928A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6317927A (en) * | 1986-07-09 | 1988-01-25 | Sumitomo Bakelite Co Ltd | Epoxy resin composition |
| JPS63164451A (en) * | 1986-12-26 | 1988-07-07 | Nitto Electric Ind Co Ltd | Semiconductor device |
| JPS649215A (en) * | 1987-07-02 | 1989-01-12 | Shinetsu Chemical Co | Epoxy resin composition |
| JPH01268721A (en) * | 1988-07-09 | 1989-10-26 | Sunstar Eng Inc | Modified polysiloxane |
| JPH0291966A (en) * | 1988-09-29 | 1990-03-30 | Nitto Denko Corp | Semiconductor device |
| JPH02269159A (en) * | 1987-09-24 | 1990-11-02 | Basf Corp | Thermosetting resin system containing modifier comprising siloxane having terminal secondary amine group |
| JPH0362844A (en) * | 1989-02-27 | 1991-03-18 | Shin Etsu Chem Co Ltd | Epoxy resin composition for sealing semiconductor and semiconductor device |
| EP0435427A2 (en) * | 1989-12-28 | 1991-07-03 | Kureha Kagaku Kogyo Kabushiki Kaisha | Electronic device sealing resin compositions and sealed electronic devices |
| JPH0885718A (en) * | 1995-03-16 | 1996-04-02 | Nitto Denko Corp | Semiconductor device |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62260817A (en) * | 1986-05-08 | 1987-11-13 | Sumitomo Bakelite Co Ltd | Epoxy resin composition and sealed semiconductor device |
| JPS6317927A (en) * | 1986-07-09 | 1988-01-25 | Sumitomo Bakelite Co Ltd | Epoxy resin composition |
-
1986
- 1986-07-10 JP JP61160806A patent/JPS6317928A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62260817A (en) * | 1986-05-08 | 1987-11-13 | Sumitomo Bakelite Co Ltd | Epoxy resin composition and sealed semiconductor device |
| JPS6317927A (en) * | 1986-07-09 | 1988-01-25 | Sumitomo Bakelite Co Ltd | Epoxy resin composition |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6317927A (en) * | 1986-07-09 | 1988-01-25 | Sumitomo Bakelite Co Ltd | Epoxy resin composition |
| JPS63164451A (en) * | 1986-12-26 | 1988-07-07 | Nitto Electric Ind Co Ltd | Semiconductor device |
| JPS649215A (en) * | 1987-07-02 | 1989-01-12 | Shinetsu Chemical Co | Epoxy resin composition |
| JPH02269159A (en) * | 1987-09-24 | 1990-11-02 | Basf Corp | Thermosetting resin system containing modifier comprising siloxane having terminal secondary amine group |
| JPH01268721A (en) * | 1988-07-09 | 1989-10-26 | Sunstar Eng Inc | Modified polysiloxane |
| JPH0291966A (en) * | 1988-09-29 | 1990-03-30 | Nitto Denko Corp | Semiconductor device |
| JPH0362844A (en) * | 1989-02-27 | 1991-03-18 | Shin Etsu Chem Co Ltd | Epoxy resin composition for sealing semiconductor and semiconductor device |
| EP0435427A2 (en) * | 1989-12-28 | 1991-07-03 | Kureha Kagaku Kogyo Kabushiki Kaisha | Electronic device sealing resin compositions and sealed electronic devices |
| US5223557A (en) * | 1989-12-28 | 1993-06-29 | Kureha Kagaku Kogyo K.K. | Electronic device sealing resin compositions and sealed electronic devices |
| JPH0885718A (en) * | 1995-03-16 | 1996-04-02 | Nitto Denko Corp | Semiconductor device |
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