JPH0562899B2 - - Google Patents
Info
- Publication number
- JPH0562899B2 JPH0562899B2 JP2396486A JP2396486A JPH0562899B2 JP H0562899 B2 JPH0562899 B2 JP H0562899B2 JP 2396486 A JP2396486 A JP 2396486A JP 2396486 A JP2396486 A JP 2396486A JP H0562899 B2 JPH0562899 B2 JP H0562899B2
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- brominated
- encapsulation
- flame
- zco
- 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 - Fee Related
Links
- 239000003822 epoxy resin Substances 0.000 claims description 28
- 229920000647 polyepoxide Polymers 0.000 claims description 28
- 239000003063 flame retardant Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 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 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000011256 inorganic filler Substances 0.000 claims description 3
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 2
- 238000004898 kneading Methods 0.000 claims description 2
- 238000005538 encapsulation Methods 0.000 description 9
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 229920003986 novolac Polymers 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- 239000012778 molding material Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 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 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 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
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229920001342 Bakelite® Polymers 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 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
- 150000001412 amines Chemical class 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- -1 curing accelerator Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012803 melt mixture Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Description
〔産業上の利用分野〕
本発明は、耐湿性に優れる難燃性エポキシ樹脂
組成物の製造方法に関するものである。
〔従来技術〕
近年、IC、LSIなどの半導体素子を安価に封止
するために、セラミツク封止や金属封止に代り熱
硬化性樹脂成形材料を用いて、樹脂封止する方法
が行なわれるようになつた。また、封止用成形材
料としては、低圧成形用エポキシ樹脂成形材料が
最も一般的に用いられている。この樹脂封止化に
伴ない、封止樹脂の信頼性特に耐湿性の向上は、
強く要求されている。樹脂封止の耐湿性はその配
合組成に依るところが大きく、バルク透湿、界面
よりの水侵入、不純物レベル、電気特性等が支配
要因と考えられるが、この中で不純物の影響は非
常に大きい。
封止樹脂の耐湿性試験にて、Al配線腐食の要
因となる不純物としては、ナトリウム、塩素、臭
素等があげられる。この中で、ナトリウムや塩素
は原料の製造方法及び精製により、耐湿性にほぼ
問題の無いレベルにまで低減している。これに対
し、臭素に関しては、この発生源が難燃剤として
使用している臭素化エポキシ樹脂で有る為にその
低減化は難しい。臭素系以外の難燃方法も数種提
案されているが、成形性・信頼性・価格面でバラ
ンスより、現在の半導体封止用エポキシ樹脂の難
燃剤としては、臭素化エポキシ樹脂／三酸化アン
チモン系が最も一般的である。
また、ハロゲンを低減化するために、単純に
MgxAly（OH）zCO3・XH2Ｏを組成物中に添加
する方法もあるが、この方法では、ハロゲンを捕
捉するには、かなりの添加量を必要とし、成形性
及び耐湿性以外の信頼性、又、価格面より実用的
でない。
〔発明の目的〕
そこで、本発明者らは、MgxAly（OH）
zCO3・XH2Ｏで示される化合物を臭素化エポキ
シ樹脂と予め溶融混合することに着目し検討した
結果、本製造方法により得られる難燃性エポキシ
樹脂組成物は、耐湿性に極めて優れ且つ成形性・
信頼性・難燃性等の他特性も従来と同等で有るこ
とを見出し、本発明を完成するに至つたものであ
る。
〔発明の構成〕
本発明は、一般式MgxAly（OH）zCO3・XH2
Ｏ〔式中、ｘ、ｙ、ｚ、Ｘは0.1以上の正数を表わ
す〕で示される化合物を臭素化エポキシ樹脂と予
め溶融混合した後、これにエポキシ樹脂、硬化
剤、無機質充填材及び他の添加剤を加え混練する
ことを特徴とする難燃性エポキシ樹脂組成物の製
造方法である。
エポキシ樹脂とは、ビスフエノール型エポキシ
樹脂、フエノールノボラツク型エポキシ樹脂、ク
レゾールノボラツク型エポキシ樹脂等エポキシを
有するもの全般をいい、硬化剤とはフエノールノ
ボラツク類、酸無水物類、アミン類等エポキシ樹
脂と架橋反応するもの全般をいい、無機質充填材
とは、シリカ、アルミナ、クレー、マイカ、ガラ
ス、アスベスト等のことをいう。
但し、半導体封止用としては、特に、エポキシ
樹脂はクレゾールノボラツク型エポキシ樹脂、硬
化剤はフエノールノボラツク、充填材はシリカを
使用することが望ましいが、これら原料中に含ま
れるアルカリ金属及びハロゲン等の不純物は、極
めて少ないことが必須である。
又、本発明で用いる臭素化エポキシ樹脂とは、
臭素化ビスフエノール型エポキシ樹脂、臭素化フ
エノールノボラツク型エポキシ樹脂等臭素を含有
するエポキシ樹脂全般をいうが、予め、MgxAly
（OH）zCO3・XH2Ｏと臭素化エポキシ樹脂を溶
融混合した後に、他原料と混練することが必須で
ある。
〔発明の効果〕
本発明方法に従うと、臭素化エポキシ樹脂より
発生する遊離臭素を効果的に抑制できる、即ち、
耐湿性の極めて優れる難燃性エポキシ樹脂組成物
を得ることができる。
本発明は、IC、LSIのプラスチツク化をさらに
促進させるものであり、IC、LSIの汎用化に寄与
する効果は非常に大きいものである。
〔実施例〕
以下低圧封入成形材料での実施例を用い説明す
る。
実施例で用いた原料は次の通りである。又、配
合における部は全て重量部である。
エポキシ樹脂 住友化学工業(株) ESCN−195L
硬化剤 住友ベークライト(株)
硬化促進剤 住友化学工業(株) スミキユアーＤ
臭素化エポキシ樹脂 日本化薬(株) BREN
三酸化アンチモン 住友金属鉱山(株)
充填材 龍森(株) RD−８
表面処理材 日本ユニカー(株) Ａ−186
顔料 三菱化成(株) カーボン
離型材 野田ワツクス(株)
Mg4.5Al2（OH）13CO3・3.5H2Ｏ協和化学工業(株)
臭素化エポキシ樹脂、Mg4.5Al2（OH）13CO3・
3.5H2Ｏの溶融混合品
臭素化エポキシ樹脂ａ部とMg4.5Al2（OH）13
CO3・3.5H2Ｏ ｂ部とを表１の様に150℃、30分
（樹脂溶融後の正味時間）溶融混合後冷却しハン
マーミルで粉砕した。
[Industrial Application Field] The present invention relates to a method for producing a flame-retardant epoxy resin composition having excellent moisture resistance. [Prior art] In recent years, in order to encapsulate semiconductor devices such as ICs and LSIs at low cost, resin encapsulation methods using thermosetting resin molding materials have been used instead of ceramic encapsulation and metal encapsulation. It became. Moreover, as a molding material for sealing, an epoxy resin molding material for low pressure molding is most commonly used. Along with this shift to resin encapsulation, the reliability of the encapsulation resin, especially the moisture resistance, has improved.
strongly requested. The moisture resistance of resin sealing largely depends on its compounding composition, and the controlling factors are considered to be bulk moisture permeability, water intrusion from the interface, impurity level, electrical properties, etc. Among these, the influence of impurities is extremely large. In moisture resistance tests of sealing resins, impurities that cause corrosion of Al wiring include sodium, chlorine, and bromine. Among these, sodium and chlorine are reduced to a level that causes almost no problem with moisture resistance due to the manufacturing method and purification of the raw materials. On the other hand, it is difficult to reduce bromine because the source of bromine is the brominated epoxy resin used as a flame retardant. Although several types of flame retardant methods other than brominated ones have been proposed, due to the balance of moldability, reliability, and price, the current flame retardants for epoxy resins for semiconductor encapsulation are brominated epoxy resins/antimony trioxide. system is the most common. In addition, in order to reduce halogen, simply
There is also a method of adding MgxAly( OH )zCO 3 . , Also, it is not practical due to the price. [Object of the invention] Therefore, the present inventors discovered that MgxAly(OH)
As a result of a study focusing on melt- mixing a compound represented by zCO 3 . sex·
It was discovered that other properties such as reliability and flame retardancy were also the same as conventional ones, leading to the completion of the present invention. [Structure of the Invention] The present invention is based on the general formula MgxAly(OH)zCO 3・XH 2
After melt-mixing the compound represented by O [wherein x, y, z, and This is a method for producing a flame-retardant epoxy resin composition, which is characterized by adding and kneading additives. Epoxy resin refers to all products containing epoxy, such as bisphenol type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, etc., and curing agents include phenol novolacs, acid anhydrides, amines, etc. Inorganic fillers refer to all materials that crosslink with epoxy resins, and inorganic fillers include silica, alumina, clay, mica, glass, and asbestos. However, for semiconductor encapsulation, it is particularly desirable to use a cresol novolac type epoxy resin, a phenol novolac as a curing agent, and silica as a filler, but the alkali metals and halogens contained in these raw materials It is essential that impurities such as, etc., be extremely small. Moreover, the brominated epoxy resin used in the present invention is
This refers to all epoxy resins containing bromine, such as brominated bisphenol type epoxy resins and brominated phenol novolac type epoxy resins.
After melt-mixing (OH)zCO 3 .XH 2 O and the brominated epoxy resin, it is essential to knead them with other raw materials. [Effects of the Invention] According to the method of the present invention, free bromine generated from brominated epoxy resin can be effectively suppressed, that is,
A flame-retardant epoxy resin composition with extremely excellent moisture resistance can be obtained. The present invention further promotes the use of plastics for ICs and LSIs, and has a very large effect in contributing to the generalization of ICs and LSIs. [Example] The following will describe an example using a low-pressure encapsulation molding material. The raw materials used in the examples are as follows. Also, all parts in the formulation are parts by weight. Epoxy resin Sumitomo Chemical Co., Ltd. ESCN-195L Curing agent Sumitomo Bakelite Co., Ltd. Curing accelerator Sumitomo Chemical Co., Ltd. Sumikiure D Brominated epoxy resin Nippon Kayaku Co., Ltd. BREN Antimony trioxide Sumitomo Metal Mining Co., Ltd. Filling Material Ryumori Co., Ltd. RD-8 Surface treatment material Nippon Unicar Co., Ltd. A-186 Pigment Mitsubishi Kasei Co., Ltd. Carbon mold release agent Noda Wax Co., Ltd. Mg4.5Al 2 (OH) 13 CO 3・3.5H 2 O Kyowa Kagaku Kogyo Co., Ltd. Brominated epoxy resin, Mg4.5Al 2 (OH) 13 CO 3・
Melt mixture of 3.5H 2 O Brominated epoxy resin part a and Mg4.5Al 2 (OH) 13
Part B of CO 3 .3.5H 2 O was melt-mixed at 150° C. for 30 minutes (net time after melting the resin) as shown in Table 1, then cooled and pulverized with a hammer mill.
【表】
実施例
エポキシ樹脂、硬化剤、硬化促進剤、充填材、
三酸化アンチモン、臭素化エポキシ樹脂、表面処
理剤、顔料、離型剤、臭素化エポキシ樹脂と
Mg4.5Al2（OH）13CO3・3.5H2Ｏの溶融混合品、
を表２のように配合しヘンシエルミキサーにて
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を得た。これら材料の成
形性、信頼性を評価した結果、表２に示す様に、
本発明によると、従来品及びMgxAly（OH）
zCO3・XH2Ｏの単純添加品に比べ成形性、耐燃
性等を損なうことなく、極めて優れた耐湿性を示
すことが判つた。[Table] Examples Epoxy resin, curing agent, curing accelerator, filler,
Antimony trioxide, brominated epoxy resin, surface treatment agent, pigment, mold release agent, brominated epoxy resin and
Mg4.5Al 2 (OH) 13 molten mixture of CO 3 and 3.5H 2 O,
were blended as shown in Table 2 and mixed in a Henschel mixer, then kneaded for 3 minutes with heated rolls at 100°C.
Several types of low-pressure encapsulation molding materials were obtained. As a result of evaluating the formability and reliability of these materials, as shown in Table 2,
According to the present invention, conventional products and MgxAly(OH)
It was found that compared to products with simple addition of zCO 3 .
Claims (1)
ｘ、ｙ、ｚ、Ｘは0.1以上の正数を表わす〕で示
される化合物を臭素化エポキシ樹脂と予め溶融混
合した後、これにエポキシ樹脂、硬化剤、無機質
充填材及び他の添加剤を加え混練することを特徴
とする難燃性エポキシ樹脂組成物の製造方法。[Claims] 1 General formula MgxAly(OH)zCO 3 .XH 2 O [in the formula,
x, y, z, X represent positive numbers of 0.1 or more] is melt-mixed with a brominated epoxy resin in advance, and then the epoxy resin, curing agent, inorganic filler and other additives are added thereto. A method for producing a flame-retardant epoxy resin composition, which comprises kneading.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2396486A JPS62184050A (en) | 1986-02-07 | 1986-02-07 | Production of flame-retardant epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2396486A JPS62184050A (en) | 1986-02-07 | 1986-02-07 | Production of flame-retardant epoxy resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62184050A JPS62184050A (en) | 1987-08-12 |
| JPH0562899B2 true JPH0562899B2 (en) | 1993-09-09 |
Family
ID=12125230
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2396486A Granted JPS62184050A (en) | 1986-02-07 | 1986-02-07 | Production of flame-retardant epoxy resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62184050A (en) |
-
1986
- 1986-02-07 JP JP2396486A patent/JPS62184050A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62184050A (en) | 1987-08-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2712898B2 (en) | Epoxy composition for semiconductor encapsulation | |
| JPH09241483A (en) | Epoxy resin composition | |
| JPH09255812A (en) | Resin composition | |
| JPH0977958A (en) | Epoxy resin composition and semiconductor device | |
| JPH0562899B2 (en) | ||
| JPH07242799A (en) | Epoxy resin composition for semiconductor encapsulation | |
| JP2002003577A (en) | Epoxy resin composition for semiconductor encapsulation and semiconductor device | |
| JP2867471B2 (en) | Resin composition | |
| JPH09235452A (en) | Epoxy resin composition for semiconductor encapsulation | |
| JP2560469B2 (en) | Epoxy resin composition | |
| JP2501149B2 (en) | Epoxy resin composition for semiconductor encapsulation | |
| JP2001114994A (en) | Epoxy resin composition and semiconductor device | |
| JPH0782343A (en) | Epoxy resin composition for semiconductor encapsulation and semiconductor device | |
| JPH0558444B2 (en) | ||
| JPS6042418A (en) | Sealing resin composition | |
| JP3889206B2 (en) | Resin composition for sealing and semiconductor sealing device | |
| JPH01190748A (en) | Epoxy resin composition for semiconductor encapsulation | |
| JPH0528243B2 (en) | ||
| JPH06102750B2 (en) | Epoxy resin composition and cured product thereof | |
| JPH10237160A (en) | Epoxy resin composition and semiconductor device | |
| JP2906599B2 (en) | Resin composition for semiconductor encapsulation | |
| JPH0730236B2 (en) | Epoxy resin composition for semiconductor encapsulation | |
| JP3413923B2 (en) | Epoxy resin composition for semiconductor encapsulation and resin-encapsulated semiconductor device | |
| JPH03119051A (en) | Epoxy resin composition | |
| JPH08245753A (en) | Epoxy resin composition for semiconductor encapsulation and semiconductor device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |