JPH0558444B2 - - Google Patents
Info
- Publication number
- JPH0558444B2 JPH0558444B2 JP4742986A JP4742986A JPH0558444B2 JP H0558444 B2 JPH0558444 B2 JP H0558444B2 JP 4742986 A JP4742986 A JP 4742986A JP 4742986 A JP4742986 A JP 4742986A JP H0558444 B2 JPH0558444 B2 JP H0558444B2
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- brominated
- bismuth
- flame
- moisture resistance
- 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 29
- 229920000647 polyepoxide Polymers 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 10
- 229910052797 bismuth Inorganic materials 0.000 claims description 8
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 8
- 239000003063 flame retardant Substances 0.000 claims description 8
- 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 7
- 229910001410 inorganic ion Inorganic materials 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000011256 inorganic filler Substances 0.000 claims description 4
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 2
- 238000005538 encapsulation Methods 0.000 description 9
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 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 6
- 238000000034 method Methods 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
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012778 molding material Substances 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000002994 raw material Substances 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
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-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
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 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
- 239000012803 melt mixture 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
- 229930185605 Bisphenol Natural products 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
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000010425 asbestos Substances 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
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000006082 mold release agent Substances 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
- 239000000049 pigment Substances 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
- 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・価格面での
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、単純にビスマス系無機イ
オン交換体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、ビスマス系無機イオン
交換体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
も従来と同等であることを見出し、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、ビスマス系無機イオン交換体を臭素
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、ビスマス
系無機イオン交換体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。
ビスマス系無機イオン交換体には、ビスマスの
含水酸化物、水酸化物などがある。
〔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。
[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/trioxides. The antimony family is the most common. In addition, there is a method of simply adding a bismuth-based inorganic ion exchanger to the composition in order to reduce the amount of halogen.
This method requires a considerable amount of addition to capture the halogen, and is not practical due to reliability issues other than moldability and moisture resistance, as well as cost. [Object of the Invention] Therefore, the present inventors focused on and studied the method of melt-mixing a bismuth-based inorganic ion exchanger with a brominated epoxy resin in advance, and as a result, a flame-retardant epoxy resin composition obtained by the present production method was developed. discovered that it has extremely excellent moisture resistance and other properties such as moldability, reliability, flame retardancy, etc. are equivalent to conventional ones, and have completed the present invention. [Structure of the Invention] The present invention is characterized in that after a bismuth-based inorganic ion exchanger is melt-mixed with a brominated epoxy resin in advance, the epoxy resin, a curing agent, an inorganic filler, and other additives are added thereto and kneaded. This is a method for producing a flame-retardant epoxy resin composition. 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. It is essential to knead. Bismuth-based inorganic ion exchangers include hydrous oxides and hydroxides of bismuth. [Effects of the Invention] According to the method of the present invention, free bromine generated from a 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. or,
All parts in the formulations are parts by weight.
【表】
シ樹脂
[Table] Resin
【表】
物
臭素化エポキシ樹脂とビスマス系無機イオン交
換体の溶融混合品
臭素化エポキシ樹脂ａ部とHK−500b部を表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。[Table] Item Melt mixture of brominated epoxy resin and bismuth-based inorganic ion exchanger Table 1 shows part a of brominated epoxy resin and part HK-500b.
After melt-mixing at 150°C for 30 minutes (net time after resin melting), the mixture was cooled and pulverized with a hammer mill.
【表】
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
理材、顔料、離型剤、臭素化エポキシ樹脂とHK
−500の溶融混合品、を表２の様に配合し、
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
ビスマス系無機イオン交換体の単純添加品に比べ
極めて優れた耐湿性を示すことが判つた。[Table] Epoxy resin, curing agent, curing accelerator, filler,
Antimony trioxide, brominated epoxy resin, surface treatment material, pigment, mold release agent, brominated epoxy resin and HK
-500 melt mixture product is blended as shown in Table 2,
After mixing in a Henschel mixer, the mixture was kneaded for 3 minutes with a heated roll at 100°C to obtain several types of low-pressure encapsulation materials. As a result of evaluating the moldability and reliability of these materials, as shown in Table 2, it was found that the present invention exhibited extremely superior moisture resistance compared to conventional products and products with the simple addition of a bismuth-based inorganic ion exchanger. .
Claims (1)
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。1. A flame-retardant epoxy resin composition characterized in that a bismuth-based inorganic ion exchanger is melt-mixed with a brominated epoxy resin in advance, and then the epoxy resin, curing agent, inorganic filler, and other additives are added and kneaded. How things are manufactured.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4742986A JPS62207319A (en) | 1986-03-06 | 1986-03-06 | Production of flame-retarding epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4742986A JPS62207319A (en) | 1986-03-06 | 1986-03-06 | Production of flame-retarding epoxy resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62207319A JPS62207319A (en) | 1987-09-11 |
| JPH0558444B2 true JPH0558444B2 (en) | 1993-08-26 |
Family
ID=12774906
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4742986A Granted JPS62207319A (en) | 1986-03-06 | 1986-03-06 | Production of flame-retarding epoxy resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62207319A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03157448A (en) * | 1989-11-15 | 1991-07-05 | Mitsubishi Electric Corp | Epoxy resin composition for sealing semiconductor |
| JPH10152599A (en) * | 1996-11-21 | 1998-06-09 | Sumitomo Bakelite Co Ltd | Epoxy resin composition |
-
1986
- 1986-03-06 JP JP4742986A patent/JPS62207319A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62207319A (en) | 1987-09-11 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |