JP4936353B2 - Epoxy resin composition for sealing - Google Patents

Epoxy resin composition for sealing Download PDF

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JP4936353B2
JP4936353B2 JP2005310540A JP2005310540A JP4936353B2 JP 4936353 B2 JP4936353 B2 JP 4936353B2 JP 2005310540 A JP2005310540 A JP 2005310540A JP 2005310540 A JP2005310540 A JP 2005310540A JP 4936353 B2 JP4936353 B2 JP 4936353B2
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epoxy resin
resin composition
sealing
ion exchanger
inorganic
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JP2007119536A (en
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貴之 市川
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Panasonic Corp
Panasonic Holdings Corp
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Panasonic Corp
Matsushita Electric Industrial Co Ltd
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本発明は、電子部品、半導体等の封止用エポキシ樹脂組成物とこれにより封止された電子部品または半導体装置に関するものである。   The present invention relates to an epoxy resin composition for sealing electronic parts, semiconductors, and the like, and an electronic part or a semiconductor device sealed thereby.

従来より、電子部品や半導体装置等に対して使用する封止用樹脂については、難燃性を付与するためにハロゲン系難燃化合物やアンチモン化合物を配合するとともに、高温雰囲気下での電気特性の信頼性、すなわち高温放置特性を向上させるために、酸化ビスマス水和物等の金属水和物と、ハイドロタルサイト系等の無機イオン交換体を添加したものが知られている(たとえば特許文献1〜3)。   Conventionally, for sealing resins used for electronic parts and semiconductor devices, halogen-based flame retardant compounds and antimony compounds are blended in order to impart flame retardancy, and electrical properties under high temperature atmospheres are also included. In order to improve the reliability, that is, the property of standing at high temperature, a metal hydrate such as bismuth oxide hydrate and an inorganic ion exchanger such as hydrotalcite are added (for example, Patent Document 1). ~ 3).

しかしながら、このような従来の封止用樹脂組成物の場合には、ハロゲン系難燃化合物として代表的な臭素化エポキシ樹脂やアンチモン化合物は、半導体装置の高温放置特性を低下させるという欠点があった。また、近年では、環境への配慮から、臭素化合物やアンチモン化合物を含まない封止用樹脂への転換が求められていた。   However, in the case of such a conventional sealing resin composition, brominated epoxy resins and antimony compounds, which are typical halogen-based flame retardant compounds, have the drawback of reducing the high temperature storage characteristics of semiconductor devices. . In recent years, in consideration of the environment, conversion to a sealing resin containing no bromine compound or antimony compound has been required.

そこで、これら従来の難燃化合物の代替材としてリン系難燃剤の使用や、金属水和物、イオン交換体の選択等が試みられている(たとえば特許文献4〜5)が、たとえば自動車に搭載される電子機器175℃の場合のように高度な高温放置特性を満足できる封止用樹脂はこれまでのところ実現されていない。
特開平10−158360号公報 特開平11−181238号公報 特開2001−234035号公報 特開2002−371194号公報 特開2002−371195号公報
Therefore, attempts have been made to use phosphorus-based flame retardants as alternatives to these conventional flame retardant compounds, and to select metal hydrates and ion exchangers (for example, Patent Documents 4 to 5). So far, no sealing resin that can satisfy a high temperature storage property as in the case of 175 ° C. of electronic equipment has been realized.
JP-A-10-158360 Japanese Patent Laid-Open No. 11-181238 JP 2001-234035 A JP 2002-371194 A JP 2002-371195 A

本発明は、上記のとおりの背景から、従来の問題点を解消し、難燃性を有しているとともに、さらに一層の高温放置特性にも優れた新しい封止用の樹脂組成物と、これを用いて封止した電子部品、半導体装置を提供することを課題としている。   In view of the background as described above, the present invention solves the conventional problems, has a flame retardancy, and further has a high temperature storage property, and a new sealing resin composition, It is an object of the present invention to provide an electronic component and a semiconductor device that are sealed using a metal.

本発明は、上記の課題を解決するための手段として封止用エポキシ樹脂組成物を提供するものであって、このものは以下のことを特徴としている。   This invention provides the epoxy resin composition for sealing as a means for solving said subject, Comprising: This thing is characterized by the following.

第1:電子部品または半導体装置向けの封止用エポキシ樹脂組成物であって、(A)エポキシ樹脂、(B)硬化剤、(C)無機充填材とともに、(D)金属水和物並びに(E)無機イオン交換体を必須成分として含有し、(C)無機充填材は溶融シリカ、結晶シリカおよび窒化ケイ素のうちの1種以上のものであり、(E)無機イオン交換体はジルコニウム系イオン交換体とマグネシウム系イオン交換体である。 First: An epoxy resin composition for sealing for electronic components or semiconductor devices, comprising (A) an epoxy resin, (B) a curing agent, (C) an inorganic filler, (D) a metal hydrate, and ( E) containing an inorganic ion exchanger as an essential component, (C) the inorganic filler is one or more of fused silica, crystalline silica, and silicon nitride, and (E) the inorganic ion exchanger is a zirconium-based ion An exchanger and a magnesium-based ion exchanger.

第2:(E)無機イオン交換体は、組成物全体量に対しての0.05〜5wt%の範囲で含有されている。   Second: (E) The inorganic ion exchanger is contained in the range of 0.05 to 5 wt% with respect to the total amount of the composition.

第3:(E)無機イオン交換体としてのジルコニウム系イオン交換体とマグネシウム系イオン交換体との比率は、重量比で1:5〜5:1の範囲内である。   Third: (E) The ratio of the zirconium-based ion exchanger as the inorganic ion exchanger and the magnesium-based ion exchanger is in the range of 1: 5 to 5: 1 by weight.

第4:組成物全体量に対して、(A)エポキシ樹脂 5〜10wt%、(B)硬化剤 3〜5wt%、(C)無機充填材 60〜90wt%、(D)金属水和物 5〜20wt%の範囲で含有されている
第5:(D)金属水和物が、酸化ビスマス水和物である。
そして、本発明は、以上いずれかの封止用エポキシ樹脂組成物の硬化物によって封止された電子部品または半導体装置を提供する。
Fourth: (A) Epoxy resin 5 to 10 wt%, (B) Curing agent 3 to 5 wt%, (C) Inorganic filler 60 to 90 wt%, (D) Metal hydrate 5 with respect to the total amount of the composition 5 It is contained in a range of ˜20 wt% .
Fifth: (D) The metal hydrate is bismuth oxide hydrate.
And this invention provides the electronic component or semiconductor device sealed with the hardened | cured material of the epoxy resin composition for sealing in any one of the above.

上記のとおりの第1の発明によるエポキシ樹脂組成物によれば、エポキシ樹脂において、金属水和物とともに、ジルコニウム系、そしてマグネシウム系の、少くとも特定の2種の無機イオン交換体を配合することによって、従来のような臭素樹脂やアンチモン化合物という難燃化合物を使用することなく、難燃性とともに、優れた高温放置特性を有する封止用樹脂を実現可能としている。   According to the epoxy resin composition of the first invention as described above, in the epoxy resin, together with the metal hydrate, at least two specific inorganic ion exchangers of zirconium type and magnesium type are blended. Thus, without using a conventional flame retardant compound such as a bromine resin or an antimony compound, it is possible to realize a sealing resin having flame retardancy and excellent high temperature storage characteristics.

そして、第2から第5の発明の特定の配合割合からなる本発明の封止用エポキシ樹脂組成物によれば、上記のとおりの効果は、より確実に、より一層顕著なものとなる。 And according to the epoxy resin composition for sealing of the present invention comprising the specific blending ratios of the second to fifth inventions, the effects as described above are more reliably and more prominent.

上記第6の発明では、このような優れた効果を体現した電子部品や半導体装置が提供されることになる。 In the sixth aspect of the invention, an electronic component or a semiconductor device that embodies such excellent effects is provided.

本発明の封止用エポキシ樹脂組成物における必須成分の一つとしての(A)エポキシ樹脂については、従来より知られている非ハロゲン系エポキシ樹脂の各種のものであってよく、たとえば、O−クレゾールノボラック型エポキシ樹脂、ビフェニル型エポキシ樹脂、トリフェニルメタン型エポキシ樹脂、ナフタレン環を有するエポキシ樹脂等が好適なものとして挙げられる。   The (A) epoxy resin as one of the essential components in the epoxy resin composition for sealing of the present invention may be various types of conventionally known non-halogen epoxy resins. Preferred examples include a cresol novolac type epoxy resin, a biphenyl type epoxy resin, a triphenylmethane type epoxy resin, and an epoxy resin having a naphthalene ring.

なかでも、O−クレゾールノボラック型エポキシ樹脂は特に好適なものとして例示される。   Especially, an O-cresol novolak type epoxy resin is illustrated as a particularly suitable thing.

また、(B)硬化剤についても同様に従来より知られている各種のものであってよく、たとえばフェノール樹脂、フェノールノボラック樹脂、アミン類、イミダゾール類、トリフェニルホスフィン等のリン系硬化剤等が例示される。なかでも、硬化剤としては、1分子中に2個以上のフェノール性水酸基を有するフェノール樹脂、フェノールノボラック樹脂の1種以上のものが好適に考慮される。   Similarly, the (B) curing agent may be various conventionally known ones, such as phosphorus curing agents such as phenol resins, phenol novolac resins, amines, imidazoles, and triphenylphosphine. Illustrated. Especially, as a hardening | curing agent, the phenol resin which has a 2 or more phenolic hydroxyl group in 1 molecule, and 1 or more types of a phenol novolak resin are considered suitably.

(C)無機充填材については、シリカ、アルミナ、窒化アルミニウム、窒化ケイ素、タルク、炭酸カルシウム、ガラス粉、酸化チタン等の従来より知られている各種のものの1種以上であってよく、なかでも、溶融シリカ、結晶シリカ、窒化ケイ素がより好適なものとして考慮される。   (C) The inorganic filler may be one or more of various conventionally known materials such as silica, alumina, aluminum nitride, silicon nitride, talc, calcium carbonate, glass powder, titanium oxide, among others. Fused silica, crystalline silica, silicon nitride are considered more suitable.

(D)金属水和物については、従来より知られている酸化ビスマス水和物のような、市販品をはじめとする各種の金属化合物の水和物の1種以上であってよい。そして、この(D)金属水和物とともに必須成分として、本発明の封止用エポキシ樹脂組成物には、(E)無機イオン交換体として、市販品等としての、イオン交換能を有するジルコニウム(Zr)系イオン交換体とマグネシウム(Mg)系イオン交換体とが共に添加配合される。これらの成分の配合なしには難燃性、そして優れた高温放置特性は得られない。また、(E)無機イオン交換体としてジルコニウム系およびマグネシウム系とを併用することなしに一方のみの配合においても、優れた高温放置特性は得られない。   The metal hydrate (D) may be one or more hydrates of various metal compounds including commercially available products such as bismuth oxide hydrate which has been conventionally known. And as an essential component with this (D) metal hydrate, the epoxy resin composition for sealing of the present invention includes (E) an inorganic ion exchanger, zirconium having ion exchange capacity as a commercially available product ( A Zr) ion exchanger and a magnesium (Mg) ion exchanger are both added and blended. Without blending these components, flame retardancy and excellent high temperature storage characteristics cannot be obtained. In addition, (E) excellent high temperature storage characteristics cannot be obtained even when only one of the inorganic ion exchangers is used in combination without zirconium and magnesium.

なお、本発明における高温放置特性としては、たとえば自動車向けの車載用特性としての175℃以上の温度での電気的特性の優れた信頼性の実現を目安としている。   Note that, as the high temperature storage characteristics in the present invention, for example, realization of excellent reliability of electrical characteristics at a temperature of 175 ° C. or more as in-vehicle characteristics for automobiles is used as a guide.

本発明においては、必須成分としての上記の(E)無機イオン交換体については、樹脂組成物全体量において、0.05〜5wt%の範囲で配合することが、好ましく、さらに好ましくは、0.1〜3.5wt%の範囲とすることが考慮される。また、ジルコニウム系イオン交換体とマグネシウム系イオン交換体との相互の比率については、重量比で、1:5〜5:1の範囲内、さらに好ましくは、1:2〜2:1の範囲内とすることが考慮される。   In the present invention, the above-mentioned (E) inorganic ion exchanger as an essential component is preferably blended in the range of 0.05 to 5 wt% in the total amount of the resin composition, and more preferably 0. Considering a range of 1 to 3.5 wt%. The ratio of the zirconium ion exchanger to the magnesium ion exchanger is, by weight, in the range of 1: 5 to 5: 1, more preferably in the range of 1: 2 to 2: 1. Is considered.

エポキシ樹脂組成物における(E)無機イオン交換体以外の成分としては、(A)エポキシ樹脂が5〜10wt%、(B)硬化剤が3〜5wt%、(C)無機充填材が60〜90wt%、(D)金属水和物が5〜20wt%の範囲が一般的に好適に考慮される。   Components other than the (E) inorganic ion exchanger in the epoxy resin composition include (A) an epoxy resin of 5 to 10 wt%, (B) a curing agent of 3 to 5 wt%, and (C) an inorganic filler of 60 to 90 wt%. %, (D) a range of 5 to 20 wt% metal hydrate is generally suitably considered.

そして、本発明の組成物の効果を阻害しない範囲において、あるいはまた必要に応じて、天然ワックス、合成ワックス、ステアリン酸、モンタン酸、モンタン酸エステル、リン酸エステル等の従来より知られている離型剤をはじめとして、エラストマー等の低応力化成分、着色剤、シランカップリング剤等の無機充填材用の処理剤、硬化促進剤等を適宜に添加配合してもよい。   In addition, as long as the effect of the composition of the present invention is not hindered or necessary, a conventionally known release agent such as natural wax, synthetic wax, stearic acid, montanic acid, montanic acid ester, phosphoric acid ester, etc. In addition to a mold agent, a low stress component such as an elastomer, a colorant, a treatment agent for an inorganic filler such as a silane coupling agent, a curing accelerator, and the like may be appropriately added and blended.

そして、本発明の上記のエポキシ樹脂組成物は、以上のとおりの各種の成分を配合し、ミキサー等で均一に混合した後にロール等で加熱混練することで調製することができる。   And said epoxy resin composition of this invention can be prepared by mix | blending the various components as mentioned above, mixing uniformly with a mixer etc., and then heat-kneading with a roll etc. now.

また、得られた樹脂組成物を用いて電子部品や半導体装置を封止するための方法としては、代表的には低圧トランスファー成形法があるが、射出成形、圧縮成形、あるいは注型等による封止も可能である。封止の際の加熱によって樹脂組成物を硬化させることで、電子部品や半導体装置の封止品が得られることになる。これにより、たとえば、ILS、トランジスター、サイリスタ、ダイオード等の封止品が得られる。   Moreover, as a method for sealing electronic parts and semiconductor devices using the obtained resin composition, there is typically a low-pressure transfer molding method, but sealing by injection molding, compression molding, casting or the like. It can also be stopped. By curing the resin composition by heating at the time of sealing, a sealed product of an electronic component or a semiconductor device can be obtained. Thereby, for example, a sealed product such as an ILS, a transistor, a thyristor, or a diode is obtained.

そこで以下に実施例を示し、さらに詳しく説明する。もちろん、以下の例によって発明が限定されることはない。   Therefore, an example will be shown below and will be described in more detail. Of course, the invention is not limited by the following examples.

表1に示した各種の組成配合(重量部)のエポキシ樹脂組成物を上記方法によって調製した。   Epoxy resin compositions having various compositions (parts by weight) shown in Table 1 were prepared by the above method.

表1のエポキシ樹脂組成物の各々について、以下の方法によって難燃性と高温放置特性とを評価した。なお、エポキシ樹脂組成物の成形条件は、金型温度175℃、注入圧力6.9MPa、90sキュアである。
(評価)
1 難燃性
175℃で成形し得られた成形品(厚み0.8mm)をUL耐炎性規格に基づき燃焼性の試験を実施した。
2 高温放置特性
16DIP(3μmのアルミ配線TEG:試験用半導体素子)を200℃の条件下で、TEGアルミ配線の抵抗変化率を測定し、変化率が50%越えたものを不良とし、不良数が50%を超えた時間を表す。
About each of the epoxy resin composition of Table 1, the flame retardance and high temperature leaving property were evaluated with the following method. The molding conditions of the epoxy resin composition are a mold temperature of 175 ° C., an injection pressure of 6.9 MPa, and a 90 s cure.
(Evaluation)
1 Flame retardance A molded product obtained by molding at 175 ° C. (thickness 0.8 mm) was subjected to a flammability test based on the UL flame resistance standard.
2 High-temperature storage characteristics The resistance change rate of TEG aluminum wiring is measured under the condition of 16 DIP (3 μm aluminum wiring TEG: test semiconductor element) at 200 ° C. Represents the time over 50%.

表1のように、本発明の実施例1−5においては、難燃性とともに、優れた高温放置特性が得られることが確認された。   As shown in Table 1, in Example 1-5 of the present invention, it was confirmed that excellent high temperature storage characteristics were obtained along with flame retardancy.

Figure 0004936353
Figure 0004936353

Claims (6)

電子部品または半導体装置向けの封止用エポキシ樹脂組成物であって、(A)エポキシ樹脂、(B)硬化剤、(C)無機充填材とともに、(D)金属水和物並びに(E)無機イオン交換体を必須成分として含有し、(C)無機充填材は溶融シリカ、結晶シリカおよび窒化ケイ素のうちの1種以上のものであり、(E)無機イオン交換体はジルコニウム系イオン交換体とマグネシウム系イオン交換体であることを特徴とする封止用エポキシ樹脂組成物。 An epoxy resin composition for sealing for electronic parts or semiconductor devices, comprising (A) an epoxy resin, (B) a curing agent, (C) an inorganic filler, (D) a metal hydrate, and (E) an inorganic An ion exchanger as an essential component; (C) the inorganic filler is one or more of fused silica, crystalline silica and silicon nitride; and (E) the inorganic ion exchanger is a zirconium ion exchanger and An epoxy resin composition for sealing, which is a magnesium-based ion exchanger. (E)無機イオン交換体は、組成物全体量の0.05〜5wt%の範囲で含有されていることを特徴とする請求項1の封止用エポキシ樹脂組成物。   The epoxy resin composition for sealing according to claim 1, wherein (E) the inorganic ion exchanger is contained in a range of 0.05 to 5 wt% of the total amount of the composition. (E)無機イオン交換体としてのジルコニウム系イオン交換体とマグネシウム系イオン交換体との比率は、重量比で1:5〜5:1の範囲内であることを特徴とする請求項1または2の封止用エポキシ樹脂組成物。   (E) The ratio of the zirconium-based ion exchanger as the inorganic ion exchanger to the magnesium-based ion exchanger is in the range of 1: 5 to 5: 1 by weight. An epoxy resin composition for sealing. 組成物全体量に対して、(A)エポキシ樹脂 5〜10wt%、(B)硬化剤 3〜5wt%、(C)無機充填材 60〜90wt%、(D)金属水和物 5〜20wt%の範囲で含有されていることを特徴とする請求項1から3のうちのいずれかの封止用エポキシ樹脂組成物。   (A) Epoxy resin 5 to 10 wt%, (B) Curing agent 3 to 5 wt%, (C) Inorganic filler 60 to 90 wt%, (D) Metal hydrate 5 to 20 wt% with respect to the total amount of the composition The epoxy resin composition for sealing according to any one of claims 1 to 3, which is contained in the range of (D)金属水和物が、酸化ビスマス水和物であることを特徴とする請求項1から4のうちのいずれかの封止用エポキシ樹脂組成物。(D) The epoxy resin composition for sealing according to any one of claims 1 to 4, wherein the metal hydrate is bismuth oxide hydrate. 請求項1から5のうちのいずれかの封止用エポキシ樹脂組成物の硬化物によって封止されていることを特徴とする電子部品または半導体装置。An electronic component or a semiconductor device, which is sealed with a cured product of the sealing epoxy resin composition according to claim 1.
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JP2712898B2 (en) * 1991-07-17 1998-02-16 東レ株式会社 Epoxy composition for semiconductor encapsulation
JPH09188866A (en) * 1995-12-29 1997-07-22 Toagosei Co Ltd Adhesive composition for surface mounting
JP2003192912A (en) * 2001-12-27 2003-07-09 Kyocera Chemical Corp Sealing resin composition and semiconductor device sealed therewith
JP4337411B2 (en) * 2003-06-09 2009-09-30 東亞合成株式会社 Inorganic anion exchanger and epoxy resin composition for sealing electronic parts using the same
US20070029682A1 (en) * 2005-08-05 2007-02-08 Shin-Etsu Chemical Co., Ltd. Epoxy resin composition and semiconductor device

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