JP2002302533A - Epoxy resin composition for sealing photo-semiconductor and photo-semiconductor device - Google Patents
Epoxy resin composition for sealing photo-semiconductor and photo-semiconductor deviceInfo
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- JP2002302533A JP2002302533A JP2002016225A JP2002016225A JP2002302533A JP 2002302533 A JP2002302533 A JP 2002302533A JP 2002016225 A JP2002016225 A JP 2002016225A JP 2002016225 A JP2002016225 A JP 2002016225A JP 2002302533 A JP2002302533 A JP 2002302533A
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- Prior art keywords
- epoxy resin
- resin composition
- optical semiconductor
- less
- semiconductor encapsulation
- 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.)
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- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、透明性、耐半田性
及び離型性に優れた光半導体封止用エポキシ樹脂組成物
及びその製法、その硬化物で封止された光半導体装置に
関するのものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin composition for encapsulating an optical semiconductor having excellent transparency, solder resistance and mold release properties, a method for producing the same, and an optical semiconductor device encapsulated with a cured product thereof. Things.
【0002】[0002]
【従来の技術】近年、通信情報機器の小型化、集積密度
の向上及び製造プロセスの簡略化をねらい、半導体産業
において従来の実装方法にかわり、表面実装方法の要求
が急速に高まっている。さらにオプトエレクトロニクス
の分野に着目すると、従来の半導体封止樹脂の機能に加
えて、透明性が非常に重要な要因となっている。すなわ
ち、フォトセンサー、LED、発光素子等のオプトデバ
イスにおいては、表面実装におけるIRリフロー等の実
装方式を行っても、透明性が損なわれることなく、その
上、熱衝撃によるパッケージクラックの発生や、チップ
やリードフレームと樹脂間に剥離を生じず、高い信頼性
のある封止用樹脂が求められている。2. Description of the Related Art In recent years, in order to reduce the size of communication information equipment, improve the integration density, and simplify the manufacturing process, the semiconductor industry has rapidly increased the demand for a surface mounting method instead of the conventional mounting method. Further focusing on the field of optoelectronics, transparency is a very important factor in addition to the function of the conventional semiconductor sealing resin. That is, in an opto-device such as a photosensor, an LED, and a light-emitting element, even if a mounting method such as IR reflow in surface mounting is performed, transparency is not impaired, and furthermore, package cracking due to thermal shock, There is a demand for a highly reliable sealing resin which does not cause separation between the resin and the chip or the lead frame.
【0003】また、このような光半導体素子の生産効率
を高めるべく、従来用いられてきたような液状封止材に
よる封止は次第にマルチ成形機によるトランスファー成
形へと移りつつある。この場合、樹脂組成物は必然的に
常温で固体である必要があり、流動時のムラや速硬化に
よる着色の問題などの新たな問題を解決しなくてはなら
ない。特に着色は、低波長な光線の発光を妨げ、特に青
色や、白色の発光素子の発光効率や色合いに悪影響を及
ぼすことがある。Further, in order to increase the production efficiency of such an optical semiconductor device, sealing using a liquid sealing material, which has been conventionally used, is gradually shifting to transfer molding using a multi-molding machine. In this case, the resin composition must necessarily be solid at room temperature, and new problems such as unevenness in flowing and coloring due to rapid curing must be solved. In particular, coloring may hinder emission of low-wavelength light, and may particularly adversely affect the luminous efficiency and color of a blue or white light-emitting element.
【0004】トランスファー成形に用いる、常温で固体
のエポキシ樹脂組成物の製法としては、一般的に常温で
固体のエポキシ樹脂と、常温で固体の硬化剤を、加熱ニ
ーダー等の装置を用いて溶融混練して得る手法が一般的
に知られているが、溶融混練という操作において、加熱
が不十分である場合、材料のムラが原因となり特性が低
下することが問題であった。[0004] As a method for producing an epoxy resin composition which is solid at ordinary temperature used in transfer molding, generally, an epoxy resin which is solid at ordinary temperature and a curing agent which is solid at ordinary temperature are melt-kneaded using a device such as a heating kneader. Although the technique obtained by the above method is generally known, when the heating is insufficient in the operation of melt-kneading, there is a problem that the properties are deteriorated due to unevenness of the material.
【0005】この問題に対し、特許第2970214号
公報では、特定の分子量範囲に含まれるビスフェノール
A型エポキシ樹脂に対し、一定割合で脂環式エポキシ樹
脂もしくは含複素環エポキシ樹脂を組み合わせることで
耐熱性と透明性が得られ、かつムラの発生を抑えること
ができると示されている。しかし、この場合硬化剤とし
ては、主に固体の硬化剤を使用することが条件となる。
固体の酸無水物硬化剤は、不飽和結合などの、光透過性
を低下させる要因を含むものが多く、硬化物の透過率が
低波長領域において低下する傾向にあった。[0005] To solve this problem, Japanese Patent No. 2970214 discloses that a heat-resistant bisphenol A type epoxy resin in a specific molecular weight range is combined with an alicyclic epoxy resin or a heterocyclic epoxy resin at a fixed ratio. And that transparency can be obtained and the occurrence of unevenness can be suppressed. However, in this case, the condition is that a solid curing agent is mainly used as the curing agent.
Many solid acid anhydride curing agents contain factors such as unsaturated bonds that reduce light transmittance, and the transmittance of the cured product tends to decrease in a low wavelength region.
【0006】また、ムラを無くす技術として、特許26
56336号広報には、溶剤にエポキシ樹脂組成物を溶
解し、均一に混合した後に、溶剤を除去してムラの無い
組成物を得る技術が述べられているが、この場合も同様
に、トランスファー成形に供するためには、硬化剤の種
類は常温で固体のものを主としなくてはならないという
制約がある。As a technique for eliminating unevenness, Japanese Patent No.
No. 56336 discloses a technique in which an epoxy resin composition is dissolved in a solvent, mixed uniformly, and then the solvent is removed to obtain a composition having no unevenness. However, there is a restriction that the type of the curing agent must be a solid at room temperature.
【0007】一方、硬化物の表面実装信頼性として、吸
水率を低くすることが求められており、吸水率を低減す
るために充填剤を添加することが代表的な手法であるこ
とは当業者間では公知のことである。これは、シリカな
どの無機質充填材を、樹脂組成物中に高い比率で充填す
ることで、封止樹脂組成物の吸水率、線膨張係数を低下
させ、高温時の変形やクラックなどを抑止できるもので
あるが、このようにして得た樹脂組成物は、シリカ粒子
と樹脂の界面で起こる光の反射や屈折の影響により、樹
脂硬化物の光透過性は極端に低いものとなる。樹脂組成
物の硬化物中を光線が透過する際、樹脂と充填材との界
面において反射・屈折される光線の量は、界面前後での
屈折率の差に比例する事が知られており、一般的なシリ
カ粒子の屈折率は、1.4前後であるのに対し、エポキ
シ樹脂の硬化体は、1.5前後であり、充填材種を変え
ない限り、この点を解消することは難しい。On the other hand, it is required to lower the water absorption as the surface mounting reliability of the cured product, and it is known by those skilled in the art that adding a filler to reduce the water absorption is a typical method. It is well known in between. This means that by filling an inorganic filler such as silica into the resin composition at a high ratio, the water absorption of the sealing resin composition, the coefficient of linear expansion can be reduced, and deformation and cracks at high temperatures can be suppressed. However, in the resin composition thus obtained, the light transmittance of the cured resin becomes extremely low due to the influence of light reflection and refraction occurring at the interface between the silica particles and the resin. It is known that the amount of light reflected and refracted at the interface between the resin and the filler when the light passes through the cured product of the resin composition is proportional to the difference in the refractive index before and after the interface. The refractive index of general silica particles is around 1.4, whereas the cured body of epoxy resin is around 1.5, and it is difficult to eliminate this point unless the type of filler is changed. .
【0008】これを解消するために、特開平6−654
73号公報では、シリカ以外の充填材として、Si
O2、CaOおよびAl2O3を主成分とするガラス粒子
を、光半導体封止用樹脂組成物の充填材として用いる技
術が述べられている。この技術によれば、各成分の組成
を変化させることや、金属元素類を添加することで、充
填材の屈折率を容易に変化させることができる。しか
し、本発明者らが光半導体封止用樹脂組成物の充填材と
して、該技術によるガラス充填材を用いたところ、確か
に透明性は高くなり、吸水率および線膨張係数も低減さ
れるが、不十分であり、透明性と表面実装の能力を両立
することは難しい。これより、本発明者らは、表面実装
能力と透明性を両立するには、充填剤の添加のみだけで
はなく樹脂そのものの特性も高める必要があるとの結論
に至った。To solve this problem, Japanese Patent Laid-Open Publication No.
No. 73 discloses that as a filler other than silica, Si
A technique is described in which glass particles containing O 2 , CaO, and Al 2 O 3 as main components are used as a filler of a resin composition for encapsulating an optical semiconductor. According to this technique, the refractive index of the filler can be easily changed by changing the composition of each component or adding a metal element. However, when the present inventors used a glass filler according to the technology as a filler for an optical semiconductor encapsulating resin composition, the transparency certainly increased, and the water absorption and the linear expansion coefficient were reduced. Insufficient, it is difficult to achieve both transparency and surface mounting capability. From this, the present inventors have concluded that in order to achieve both surface mounting capability and transparency, it is necessary not only to add a filler but also to enhance the properties of the resin itself.
【0009】更に、光半導体封止用材料は、可視光を透
過することが必須であるが、同時に金型からの離型性も
重要な項目である。従来は離型性を良くするために、定
期的に離型剤成分を含んだ材料を成形したり、フッ素系
やシリコーン系などの離型剤を金型に直接噴霧する手法
がとられているが、その場合連続成形の生産効率を下げ
るのみでなく、金型に離型剤が残り汚染される問題があ
る。そこで、これまでに封止材料中に離型剤を予め添加
混合する検討が行われている。従来公知の離型剤を添加
した場合、離型剤の種類によっては、その添加量を増や
すと離型性は向上するが、樹脂硬化物に曇りが生じ、光
透過率が低下する。添加量を減らすと離型性が悪くな
り、金型からパッケージが離型する際に、パッケージに
クラックが生じたり、リードフレームの曲がりが光半導
体装置の変形が発生する。すなわち、透明性と離型性の
面で両方の特性を満たす樹脂組成物は、未だ開発がなさ
れていない。Further, the optical semiconductor encapsulating material is required to transmit visible light, but at the same time, the releasability from the mold is also an important item. Conventionally, in order to improve the releasability, a method of periodically molding a material containing a release agent component or directly spraying a mold release agent such as a fluorine-based or silicone-based release agent on a mold has been adopted. However, in this case, not only does the production efficiency of continuous molding decrease, but also there is a problem that the release agent remains in the mold and is contaminated. Therefore, studies have been made on adding and mixing a release agent in advance in the sealing material. When a conventionally known release agent is added, depending on the type of the release agent, an increase in the amount of the release agent improves the releasability, but causes clouding of the cured resin and lowers the light transmittance. If the amount of addition is reduced, the releasability deteriorates, and when the package is released from the mold, cracks are generated in the package, and bending of the lead frame causes deformation of the optical semiconductor device. That is, a resin composition that satisfies both properties in terms of transparency and release properties has not yet been developed.
【0010】特許2781279号公報には、ポリエー
テル構造と長鎖アルキル基からなる構造の界面活性剤を
離型剤として、光半導体封止用の材料に予め添加するこ
とが記載されているが、本発明者らが光半導体封止用の
材料に添加したところ、金型からの離型性は優れるが、
高温での硬化時に樹脂硬化物に曇りが生じ、光半導体封
止用樹脂組成物としては、未だ不十分な透明性である。Japanese Patent No. 2781279 describes that a surfactant having a structure comprising a polyether structure and a long-chain alkyl group is previously added as a release agent to a material for encapsulating an optical semiconductor. When the present inventors added to the material for optical semiconductor encapsulation, the releasability from the mold is excellent,
When cured at a high temperature, the cured resin becomes cloudy, and the resin composition for encapsulating an optical semiconductor still has insufficient transparency.
【0011】[0011]
【発明が解決しようとする課題】本発明は、透明性、耐
半田性及び離型性に優れた光半導体封止用エポキシ樹脂
組成物、及びその硬化物で封止された光半導体装置を提
供することにある。SUMMARY OF THE INVENTION The present invention provides an epoxy resin composition for encapsulating an optical semiconductor, which is excellent in transparency, solder resistance and mold release properties, and an optical semiconductor device encapsulated with a cured product thereof. Is to do.
【0012】[0012]
【課題を解決するための手段】本発明らは、樹脂組成物
の硬化時に発生する曇りが、樹脂硬化後に溶解度が変化
し、樹脂硬化物中で非相溶となった離型剤が大きな領域
を形成することに起因すると考え、鋭意検討の結果、特
定構造の離型剤の、樹脂に対する相溶性が異なる部分ど
うしの結合部に、中間的な相溶性の部分を導入すること
で、光損失の大きな領域の発生を低減できることを見出
すとともに、特定の組み合わせのエポキシ樹脂及び凝固
点が50℃以下の酸無水物硬化剤の、中間反応物を用い
た、吸水率及び透明性に適した特性を発現する組成物
に、さらに特定の無機充填剤及び離型剤を用いること
で、より吸水率を低減し、かつ高い光透過率を維持し、
耐半田性及び離型性にも優れた特性を発現する光半導体
封止用組成物を得るに至った。Means for Solving the Problems The present invention relates to a method for producing a resin composition in which the haze generated during the curing of the resin composition changes in solubility after the curing of the resin, and the release agent becomes incompatible in the cured resin. As a result of diligent studies, the introduction of an intermediate compatible part into the joint between parts of the mold release agent with a specific structure that differ in compatibility with the resin results in light loss. Of the specific area of the epoxy resin and acid anhydride curing agent with a freezing point of 50 ° C or less, using the intermediate reactant, and exhibiting characteristics suitable for water absorption and transparency. The composition to be used, by further using a specific inorganic filler and a release agent, to further reduce the water absorption, and maintain a high light transmittance,
Thus, an optical semiconductor encapsulating composition that exhibits excellent properties in terms of solder resistance and release properties has been obtained.
【0013】即ち、本発明は、(1)〜(8)項に記載
の光半導体封止用エポキシ樹脂組成物である。 (1)エポキシ樹脂と硬化剤の中間反応物(A)、硬化
促進剤(B)、無機充填剤(C)、離型剤(D)を必須
成分とする光半導体封止用エポキシ樹脂組成物におい
て、中間反応物(A)が下記成分(a)、及び成分
(b)を含んでなり、且つ無溶媒下、80℃以上150
℃以下の温度で、溶融混合して得られたものであること
を特徴とする光半導体封止用エポキシ樹脂組成物であ
る。 (a)トリグリシジルイソシアヌレート、及びビスフェ
ノール型エポキシ樹脂からなり、成分(a)全体の平均
エポキシ当量が200以上400以下のエポキシ樹脂。 (b)凝固点50℃以下の酸無水物硬化剤。That is, the present invention is the epoxy resin composition for encapsulating an optical semiconductor according to the above (1) to (8). (1) An epoxy resin composition for encapsulating an optical semiconductor comprising an intermediate reaction product (A) of an epoxy resin and a curing agent, a curing accelerator (B), an inorganic filler (C), and a release agent (D) as essential components. Wherein the intermediate reactant (A) comprises the following component (a) and component (b), and is free from solvent at 80 ° C.
An epoxy resin composition for encapsulating an optical semiconductor, which is obtained by melting and mixing at a temperature of not more than ℃. (A) An epoxy resin comprising triglycidyl isocyanurate and a bisphenol-type epoxy resin, and having an average epoxy equivalent of 200 to 400 in the entire component (a). (B) An acid anhydride curing agent having a freezing point of 50 ° C. or less.
【0014】(2)ビスフェノール型エポキシ樹脂が、
210以上1100以下の平均エポキシ当量を有し、ト
リグリシジルイソシアヌレートが、(a)成分中に5%
以上45%以下で含まれることを特徴とする前記(1)
項に記載の光半導体封止用エポキシ樹脂組成物である。(2) Bisphenol type epoxy resin is
It has an average epoxy equivalent of 210 or more and 1100 or less, and triglycidyl isocyanurate contains 5% in the component (a).
(1) characterized in that it is contained in an amount of not less than 45% or less.
It is an epoxy resin composition for optical semiconductor encapsulation described in item.
【0015】(3)ビスフェノール型エポキシ樹脂が、
更に好ましくは、一般式(1)で表されるエポキシ樹脂
であることを特徴とする前記(2)項に記載の光半導体
封止用エポキシ樹脂組成物である。(3) Bisphenol type epoxy resin is
More preferably, the epoxy resin composition for optical semiconductor encapsulation according to the above item (2) is an epoxy resin represented by the general formula (1).
【0016】[0016]
【化3】 (但し、式(1)中、nの値が1〜7であり、RはC
(CH3)2及びCH2を示し、1分子中それぞれ少なく
とも1個以上有する。)Embedded image (However, in the formula (1), the value of n is 1 to 7, and R is C
(CH 3 ) 2 and CH 2 , each having at least one or more in one molecule. )
【0017】(4)凝固点50℃以下の酸無水物硬化剤
(b)が、好ましくは、ヘキサヒドロ無水フタル酸及び
4−メチルヘキサヒドロ無水フタル酸からなる群より選
ばれる少なくとも1つであることを特徴とする前記
(1)項に記載の光半導体封止用エポキシ樹脂組成物で
ある。(4) The acid anhydride curing agent (b) having a freezing point of 50 ° C. or lower is preferably at least one selected from the group consisting of hexahydrophthalic anhydride and 4-methylhexahydrophthalic anhydride. An epoxy resin composition for encapsulating an optical semiconductor as described in the above item (1).
【0018】(5)硬化促進剤(B)が、イミダゾール
類、イミダゾール塩類、双環式アミジン類、双環式アミ
ジンのカルボン酸類、及びホスホニウム塩類からなる群
より少なくとも1つ選ばれることを特徴とする前記
(1)項に記載の光半導体封止用エポキシ樹脂組成物で
ある。(5) The curing accelerator (B) is at least one selected from the group consisting of imidazoles, imidazole salts, bicyclic amidines, carboxylic acids of bicyclic amidines, and phosphonium salts. The epoxy resin composition for optical semiconductor encapsulation according to the above item (1).
【0019】(6)無機充填材(C)の屈折率と、無機
充填材(C)以外の成分の硬化物の屈折率との差が、
0.01以下である前記(1)項に記載の光半導体封止
用エポキシ樹脂組成物である。(6) The difference between the refractive index of the inorganic filler (C) and the refractive index of the cured product of the component other than the inorganic filler (C) is as follows:
The epoxy resin composition for optical semiconductor encapsulation according to the above item (1), which has a value of 0.01 or less.
【0020】(7)無機充填剤(C)が、SiO2、C
aO、およびAl2O3からなる、平均粒径5μm以上1
00μm以下の球状ガラス粒子であり、光半導体封止用
エポキシ樹脂組成物中に5重量%以上、70重量%以下
の割合で配合されてなることを特徴とする前記(1)項
に記載の光半導体封止用エポキシ樹脂組成物である。(7) When the inorganic filler (C) is SiO 2 , C
aO and Al 2 O 3 , average particle size of 5 μm or more 1
The light according to the above (1), wherein the light is spherical glass particles having a diameter of not more than 00 μm, and is blended in the epoxy resin composition for encapsulating an optical semiconductor at a ratio of 5% by weight or more and 70% by weight or less. It is an epoxy resin composition for semiconductor encapsulation.
【0021】(8)離型剤(D)が、一般式(2)で表
される化合物であり、光半導体封止用エポキシ樹脂組成
物中に0.01重量%以上、5重量%以下の割合で配合
されてなることを特徴とする前記(1)項に記載の光半
導体封止用エポキシ樹脂組成物である。(8) The release agent (D) is a compound represented by the general formula (2) and is contained in the epoxy resin composition for encapsulating an optical semiconductor in an amount of 0.01% by weight or more and 5% by weight or less. The epoxy resin composition for optical semiconductor encapsulation according to the above item (1), which is blended in a ratio.
【0022】[0022]
【化4】 (但し、式(2)中、kの値が40〜60であり、mの
値は1〜5であり、nの値は15〜45である。R1、
R2は水素原子もしくは一価のアルキル基であり、少な
くとも一方が一価のアルキル基である。)Embedded image (However, in the formula (2), the value of k is 40 to 60, the value of m is 1 to 5, and the value of n is 15 to 45. R 1 ,
R 2 is a hydrogen atom or a monovalent alkyl group, at least one of which is a monovalent alkyl group. )
【0023】更に本発明は、前記(1)〜(8)項のい
ずれかに記載の光半導体封止用エポキシ樹脂組成物の硬
化物で封止された光半導体装置である。The present invention further provides an optical semiconductor device sealed with a cured product of the epoxy resin composition for optical semiconductor encapsulation according to any one of the above items (1) to (8).
【0024】[0024]
【発明の実施の形態】本発明に用いる、エポキシ樹脂と
硬化剤の中間反応物(A)は、成分(a)のトリグリシ
ジルイソシアヌレート、及びビスフェノール型エポキシ
樹脂からなり、成分(a)全体の平均エポキシ当量が2
00以上400以下のエポキシ樹脂成分と、成分(b)
の凝固点50℃以下の酸無水物硬化剤成分を含み、80
℃以上150℃以下の温度で、且つ無溶媒で、溶融混合
して得られる化合物であり、従来の加熱ニーダーやロー
ル混練機を用い、他添加剤も加えた上で一括して溶融混
合する手法に比べ、軟化点もしくは凝固点の低い原料が
多量に含まれていても、Bステージ化反応をより促進で
きるため、反応後には常温で固体の中間反応物とするこ
とができることを特徴とする。BEST MODE FOR CARRYING OUT THE INVENTION The intermediate product (A) of the epoxy resin and the curing agent used in the present invention comprises the triglycidyl isocyanurate of the component (a) and the bisphenol type epoxy resin. Average epoxy equivalent of 2
An epoxy resin component of at least 00 and at most 400, and component (b)
Containing an acid anhydride curing agent component having a freezing point of 50 ° C. or lower;
A compound obtained by melting and mixing at a temperature of 150 ° C or higher and 150 ° C or lower, and without solvent, using a conventional heating kneader or roll kneader, adding other additives, and melt-mixing all at once. Compared with the above, even if a large amount of a raw material having a low softening point or freezing point is contained, the B-stage formation reaction can be further promoted, so that it is possible to obtain a solid intermediate reactant at room temperature after the reaction.
【0025】本発明で、中間反応物(A)を得る工程と
しては、加熱反応釜などの一般的な加熱反応装置を用い
ることができる。具体的な方法としては、成分(a)、
及び成分(b)を、反応釜で、無溶剤で、上記温度で、
60〜240分間加熱混合し、使用に好ましい軟化点、
具体的には常温での取り扱いに問題を生じない50℃以
上、が得られた時点で、反応物を取り出し、冷却粉砕し
て中間反応物を得る方法が挙げられる。In the present invention, as the step of obtaining the intermediate reactant (A), a general heating reactor such as a heating reactor can be used. As a specific method, component (a),
And component (b) in a reaction vessel, without solvent, at the above temperature,
Heat-mix for 60-240 minutes, softening point suitable for use,
Specifically, there is a method in which, when a temperature of 50 ° C. or higher, at which no problem occurs in handling at normal temperature, is obtained, the reactant is taken out, cooled and pulverized to obtain an intermediate reactant.
【0026】中間反応物(A)に用いる、トリグリシジ
ルイソシアヌレート及びビスフェノール型エポキシ樹脂
からなる、全体の平均エポキシ当量が200以上400
以下のエポキシ樹脂(a)において、平均エポキシ当量
が200より下回る場合で、トリグリシジルイソシアヌ
レートの配合比率が高い場合は、エポキシ樹脂の反応性
が著しく高まり、前述の中間反応時に、増粘や材料のゲ
ル化を生じ易くなるのに加え、得られる硬化物が、非常
にもろくなるために本発明の目的には適さず、また、ビ
スフェノール型エポキシ樹脂のエポキシ当量が小さい場
合、ビスフェノール型エポキシ樹脂が液状であったり、
軟化点が低いために、中間反応を行っても、常温で固体
の中間反応物とするのが難しい。平均エポキシ当量が4
00を越える場合で、トリグリシジルイソシアヌレート
の比率が低い場合、多官能な成分が減少することによ
り、期待した耐熱性が得られず、また、ビスフェノール
型エポキシ樹脂のエポキシ当量が大きい場合、エポキシ
樹脂の粘度が非常に高いものとなり、金型未充填などの
成形不良を発生するため不適である。The total average epoxy equivalent of triglycidyl isocyanurate and bisphenol type epoxy resin used for the intermediate reactant (A) is 200 to 400.
In the following epoxy resin (a), when the average epoxy equivalent is less than 200, and when the blending ratio of triglycidyl isocyanurate is high, the reactivity of the epoxy resin is significantly increased, and during the above-mentioned intermediate reaction, viscosity increase and material In addition to the fact that the resulting cured product is very brittle, it is not suitable for the purpose of the present invention, and when the epoxy equivalent of the bisphenol-type epoxy resin is small, the bisphenol-type epoxy resin is Liquid,
Since the softening point is low, it is difficult to obtain a solid intermediate reactant at room temperature even if an intermediate reaction is performed. Average epoxy equivalent of 4
When the ratio of triglycidyl isocyanurate is lower than 00, the expected heat resistance cannot be obtained due to the decrease in the number of polyfunctional components, and when the epoxy equivalent of the bisphenol type epoxy resin is large, the epoxy resin Has an extremely high viscosity and is not suitable because molding defects such as unfilled molds occur.
【0027】本発明に用いるエポキシ樹脂(a)におい
て、前記平均エポキシ当量を得るにあたり、ビスフェノ
ール型エポキシ樹脂の平均エポキシ当量が210以上1
100以下であり、エポキシ樹脂(a)中に含まれるト
リグリシジルイソシアヌレートの配合比率が、5重量%
以上45重量%以下であることが好ましい。In the epoxy resin (a) used in the present invention, in order to obtain the above average epoxy equivalent, the average epoxy equivalent of the bisphenol type epoxy resin is not less than 210 and not more than 1
100 or less, and the mixing ratio of triglycidyl isocyanurate contained in the epoxy resin (a) is 5% by weight.
It is preferably at least 45% by weight.
【0028】本発明に用いるビスフェノール型エポキシ
樹脂としては、ビスフェノール骨格を有するものであれ
ば、何ら制限されるものではないが、透明性の観点から
着色の少ないエポキシ樹脂を用いることがより好まし
い。具体的には、ビスフェノールA型エポキシ樹脂、ビ
スフェノールF型エポキシ樹脂などが挙げられるが、一
般式(1)で表される構造のビスフェノール型エポキシ
樹脂はビスフェノールA型エポキシ樹脂の色調安定性と
ビスフェノールF型エポキシ樹脂の低粘度の性質を兼ね
備えるため、特性上より好ましい。The bisphenol type epoxy resin used in the present invention is not particularly limited as long as it has a bisphenol skeleton. From the viewpoint of transparency, it is more preferable to use a less colored epoxy resin. Specific examples include bisphenol A type epoxy resin and bisphenol F type epoxy resin. The bisphenol type epoxy resin having the structure represented by the general formula (1) is based on the color stability of bisphenol A type epoxy resin and bisphenol F type. Since the epoxy resin also has the property of low viscosity, it is more preferable in terms of characteristics.
【0029】本発明に用いる、凝固点が50℃以下の酸
無水物硬化剤(b)としては、従来公知のものが使用で
きる。具体的には、ヘキサヒドロ無水フタル酸、4−メ
チル−ヘキサヒドロ無水フタル酸、3−メチル−ヘキサ
ヒドロ無水フタル酸と4−メチル−ヘキサヒドロ無水フ
タル酸との混合物、及びエンドメチレンテトラヒドロ無
水フタル酸などが例示されるが、特にこれらに限定され
るものではなく、これらの単独もしくは2種以上用いる
ことができる。これらの酸無水物のうち、ヘキサヒドロ
無水フタル酸および4−メチルヘキサヒドロ無水フタル
酸が透明性およびBステージ化中間反応物の溶融粘度が
低い点に加え、透明性に優れる硬化物を得られるという
点で非常に優れ、より好ましい。As the acid anhydride curing agent (b) having a freezing point of 50 ° C. or lower used in the present invention, conventionally known ones can be used. Specific examples include hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, a mixture of 3-methyl-hexahydrophthalic anhydride and 4-methyl-hexahydrophthalic anhydride, and endmethylenetetrahydrophthalic anhydride. However, the present invention is not particularly limited thereto, and these can be used alone or in combination of two or more. Among these acid anhydrides, hexahydrophthalic anhydride and 4-methylhexahydrophthalic anhydride can obtain a cured product excellent in transparency in addition to the fact that the transparency and the melt viscosity of the B-staged intermediate reactant are low. Very excellent in point, more preferable.
【0030】これらの凝固点が50℃以下の酸無水物硬
化剤(b)は、エポキシ樹脂(a)との中間反応の際
に、その反応物の溶融粘度を低減し、反応が均一に進行
させることを可能とし、低い温度でも容易に液化するた
め、反応温度を低く保つことが可能であり、結果として
中間反応時のゲル化による反応の暴走を抑えることがで
きる。The acid anhydride curing agent (b) having a freezing point of 50 ° C. or lower reduces the melt viscosity of the reaction product during the intermediate reaction with the epoxy resin (a), and the reaction proceeds uniformly. This makes it possible to liquefy easily even at a low temperature, so that the reaction temperature can be kept low, and as a result, runaway of the reaction due to gelation during the intermediate reaction can be suppressed.
【0031】本発明の中間反応物(A)において、エポ
キシ樹脂(a)と硬化剤(b)の配合比は、酸無水物硬
化剤の酸無水物基に対する、エポキシ樹脂のエポキシ基
のモル比が、0.8〜1.4が好ましく、より好ましく
は1.0〜1.2である。In the intermediate product (A) of the present invention, the mixing ratio of the epoxy resin (a) and the curing agent (b) is determined by the molar ratio of the epoxy group of the epoxy resin to the acid anhydride group of the acid anhydride curing agent. However, it is preferably 0.8 to 1.4, more preferably 1.0 to 1.2.
【0032】本発明に用いる硬化促進剤(B)として
は、通常、エポキシ樹脂のアニオン硬化に用いられるも
のは、すべて使用可能であり、具体的にはイミダゾール
類、4級アンモニウム塩類、アミン類、ホスフィン類、
ホスホニウム塩類、双環式アミジン類およびそれらの塩
類などがあげられる。これらは、単独でも2種以上用い
ても差し支えない。これらのうち、2−メチルイミダゾ
ール、2−フェニル−4−イミダゾールなどのイミダゾ
ール類、2−フェニルイミダゾール イソシアヌル酸付
加物などのイミダゾール塩類、1,8−ジアザビシクロ
(5,4,0)ウンデセン−7などの双環式アミジン
類、1,8−ジアザビシクロ(5,4,0)ウンデセン
−7のオクチル酸塩などの双環式アミジンのカルボン酸
塩類、およびテトラフェニルホスホニウムブロマイドな
どのホスホニウム塩類を用いると、硬化性がよく、着色
がなくより好ましい。硬化促進剤の添加量は、中間反応
物(A)100重量部に対して、0.5〜2重量部が好
ましい。As the curing accelerator (B) used in the present invention, all of those usually used for anionic curing of an epoxy resin can be used, and specific examples thereof include imidazoles, quaternary ammonium salts, amines, and the like. Phosphines,
Examples include phosphonium salts, bicyclic amidines, and salts thereof. These may be used alone or in combination of two or more. Among them, imidazoles such as 2-methylimidazole and 2-phenyl-4-imidazole, imidazole salts such as 2-phenylimidazole isocyanuric acid adduct, 1,8-diazabicyclo (5,4,0) undecene-7 and the like With the use of bicyclic amidines, carboxylate salts of a bicyclic amidine such as octylate of 1,8-diazabicyclo (5,4,0) undecene-7, and phosphonium salts such as tetraphenylphosphonium bromide, Good curability, no coloring, more preferable. The addition amount of the curing accelerator is preferably 0.5 to 2 parts by weight based on 100 parts by weight of the intermediate reactant (A).
【0033】本発明に用いる無機充填材(C)は、透明
性を損なわないために、エポキシ樹脂組成物において、
無機充填材の屈折率と無機充填材以外の成分の屈折率と
を整合する必要がある。具体的には、無機充填材とそれ
以外の樹脂成分の硬化物の屈折率の差が、適用する製品
の透過すべき光波長において計測した屈折率の差が0.
01以下であることが、特に好ましい。屈折率を測定す
る波長としては、適用する光半導体用製品の発光ピー
ク、もしくは受光する光線の波長ピークを用いればよ
い。このような条件を満たす充填材であれば、従来公知
のものが使用できる。具体的には、シリカ粉末、タル
ク、カオリンクレー、マイカ等の天然化合物、ガラス等
の合成化合物が使用できるが、天然化合物は屈折率が一
義的に決定されているものが多く、樹脂成分に整合する
ものは、おのずと限られてくる。そのため、本発明に用
いる無機充填材としては、SiO2、CaO、およびA
l2O3からなる、球状ガラス粒子が、任意の屈折率のも
のが容易に得られるという点でより好ましい。本発明の
樹脂組成物における(C)成分以外の成分の硬化物に、
前述組成のガラス粒子の屈折率を整合するためには、S
iO2を40〜70重量%、CaOを1〜40重量%、
Al2O3を5〜30重量%、合計で100重量%となる
ような組成が好ましい。ただし、必要に応じて、他成分
として金属元素類、金属酸化物類などを添加することは
差し支えない。The inorganic filler (C) used in the present invention is used in an epoxy resin composition so as not to impair the transparency.
It is necessary to match the refractive index of the inorganic filler with the refractive index of components other than the inorganic filler. Specifically, the difference in the refractive index between the inorganic filler and the cured product of the other resin component is 0.
It is particularly preferred that the value be 01 or less. The wavelength at which the refractive index is measured may be the emission peak of the applied optical semiconductor product or the wavelength peak of the received light beam. As long as the filler satisfies such conditions, a conventionally known filler can be used. Specifically, natural compounds such as silica powder, talc, kaolin clay, and mica, and synthetic compounds such as glass can be used. What you do is naturally limited. Therefore, as the inorganic filler used in the present invention, SiO 2 , CaO, and A
Spherical glass particles composed of l 2 O 3 are more preferable in that those having an arbitrary refractive index can be easily obtained. A cured product of a component other than the component (C) in the resin composition of the present invention,
In order to match the refractive index of the glass particles having the above composition, S
iO 2 40 to 70% by weight, the CaO 1~40% by weight,
A composition in which Al 2 O 3 is 5 to 30% by weight, that is, 100% by weight in total is preferable. However, if necessary, a metal element, a metal oxide, or the like may be added as another component.
【0034】また、前述ガラス粒子は、球状であり、平
均粒径が5μm以上、100μm以下であると良い。形
状を球状とすることにより、光の散乱損失を小さく抑え
ることができる。また平均粒径が5μm未満の場合、ガ
ラス粒子が凝集して透明性を低下させる。一方、平均粒
径が100μmを越える場合、樹脂組成物成形時に金型
のゲート部で樹脂詰まりがおこり、未充填となる場合が
ある。The glass particles are preferably spherical and have an average particle size of 5 μm or more and 100 μm or less. By making the shape spherical, light scattering loss can be reduced. When the average particle size is less than 5 μm, the glass particles aggregate to lower the transparency. On the other hand, if the average particle size exceeds 100 μm, the resin may be clogged at the gate of the mold during molding of the resin composition, and the resin composition may not be filled.
【0035】無機充填剤の配合量としては、エポキシ樹
脂組成物中に5重量パーセント以上、70重量パーセン
ト以下であることがより好ましい。配合量が、5重量パ
ーセント未満の場合、吸水率の低減効果が僅かであり、
耐半田性が向上しない場合がある。一方、70重量パー
セントを超える場合、成形時に前述の未充填のような成
形不良が生じる場合がある。The amount of the inorganic filler is more preferably from 5% by weight to 70% by weight in the epoxy resin composition. When the blending amount is less than 5% by weight, the effect of reducing the water absorption is small,
The solder resistance may not be improved. On the other hand, when it exceeds 70% by weight, molding failure such as the above-mentioned unfilling may occur during molding.
【0036】本発明で用いる離型剤(D)は、一般式
(2)で表される化合物である。一般式(2)で表され
る化合物は、1分子内にエポキシ樹脂に相溶する性質と
相溶しない性質の両者の性質を有しているため、従来の
離型剤とは異なり、透明性と離型性を両立することがで
きる。The release agent (D) used in the present invention is a compound represented by the general formula (2). Since the compound represented by the general formula (2) has both a property of being compatible with the epoxy resin and a property of being incompatible in one molecule, unlike a conventional release agent, the compound has transparency. And releasability can be compatible.
【0037】離型剤(D)の配合量としては、全エポキ
シ樹脂組成物中に0.01重量%以上、5重量%以下が
好ましい。0.01重量%を下まわるとパッケージの離
型性が悪くなる恐れがあり、また、5重量%を越えると
樹脂硬化物に曇りが生じ、透明性が低下する恐れがあ
る。The compounding amount of the release agent (D) is preferably 0.01% by weight or more and 5% by weight or less in the whole epoxy resin composition. If the amount is less than 0.01% by weight, the releasability of the package may be deteriorated. If the amount is more than 5% by weight, the cured resin may become cloudy and the transparency may be reduced.
【0038】本発明の光半導体封止用エポキシ樹脂組成
物には、上記成分以外に、必要に応じて、従来公知の酸
化防止剤、離型剤、カップリング剤、充填剤、着色剤、
紫外線吸収剤等の当業者にて公知の添加剤、副資材を組
み合わせることは何らさしつかえない。In addition to the above components, the epoxy resin composition for encapsulating an optical semiconductor of the present invention may further comprise, if necessary, a conventionally known antioxidant, release agent, coupling agent, filler, colorant,
Combining additives and auxiliary materials known to those skilled in the art, such as ultraviolet absorbers, can be used at all.
【0039】本発明の樹脂組成物は、(A)〜(D)成
分、及びその他の添加剤を、ミキサー等を用いて混合
後、加熱ニーダや加熱ロール、押し出し機等を用いて加
熱混練し、続いて冷却、粉砕することで得られる。The resin composition of the present invention is obtained by mixing the components (A) to (D) and other additives using a mixer or the like, and then kneading the mixture using a heating kneader, a heating roll, an extruder or the like. , Followed by cooling and pulverization.
【0040】このようにして得られた光半導体封止用エ
ポキシ樹脂組成物を用いての封止は、一般的な方法でで
きるが、例えば、トランスファー成形法等により、光半
導体素子を封止して、エポキシ樹脂組成物の硬化物で封
止された光半導体装置を得ることができる。The encapsulation using the optical resin encapsulating epoxy resin composition thus obtained can be performed by a general method. For example, the optical semiconductor element is encapsulated by a transfer molding method or the like. Thus, an optical semiconductor device sealed with a cured product of the epoxy resin composition can be obtained.
【0041】[0041]
【実施例】以下に、本発明について更に詳細に説明する
ため実施例を示すが、これらに本発明が限定されるもの
ではない。EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.
【0042】(実施例1〜7)成分(a)、及び成分
(b)に相当する成分を、表1に示した配合割合で、1
00℃の反応釜で130〜220分加熱反応させて得た
中間反応物に、成分(B)〜(D)に相当する成分、及
び各種添加剤等を表1に示した配合割合で混合し、2本
ロールを用いて、50〜90℃で5分間混練し、得られ
た混練物シートを、冷却後粉砕して、樹脂組成物を得
た。評価方法は以下の通り。結果は表1にまとめて示
す。(Examples 1 to 7) The components corresponding to the components (a) and (b) were mixed in the proportions shown in Table 1 to obtain 1
The components corresponding to components (B) to (D) and various additives were mixed in the mixing ratio shown in Table 1 with an intermediate reaction product obtained by heating and reacting in a reaction vessel at 00 ° C. for 130 to 220 minutes. Using a two-roll mill, the mixture was kneaded at 50 to 90 ° C. for 5 minutes, and the obtained kneaded material sheet was cooled and pulverized to obtain a resin composition. The evaluation method is as follows. The results are summarized in Table 1.
【0043】(比較例1)成分(a)に該当するエポキ
シ樹脂、成分(b)に相当する酸無水物に、本発明の中
間反応を経ずに、成分(B)〜(D)に相当する成分、
及び各種添加剤等を表2に示した配合割合で混合し、加
熱ニーダーを用いて、90℃で20分間混練し、得られ
た混練物シートを冷却したが、混練物の軟化点が十分に
得られず、成形可能な材料を得ることができなかった。(Comparative Example 1) The epoxy resin corresponding to the component (a) and the acid anhydride corresponding to the component (b) correspond to the components (B) to (D) without undergoing the intermediate reaction of the present invention. Ingredients,
And various additives were mixed in the mixing ratio shown in Table 2 and kneaded at 90 ° C. for 20 minutes using a heating kneader, and the obtained kneaded material sheet was cooled, but the softening point of the kneaded material was sufficient. No moldable material could be obtained.
【0044】(比較例2)特許2656336号公報に
開示されている技術に基づき、成分(a)に該当するエ
ポキシ樹脂、成分(b)に相当する酸無水物、及び成分
(B)〜(D)に相当する成分の合計量100重量部
を、500重量部のジクロルメタンに加温しながら完全
に溶解した後、還流させながら温度39〜41℃の状態
で50時間混合を継続し、150℃のゲル化時間が60
秒の溶液を作成した。この溶液を45℃に加温しながら
減圧し、その後加温して、トランスファー成形に供する
ことができる軟化点が得られるまで反応を進行させた
が、軟化点が十分に得られずにゲル化が進行して、成形
可能な材料を得ることができなかった。Comparative Example 2 An epoxy resin corresponding to the component (a), an acid anhydride corresponding to the component (b), and components (B) to (D) based on the technology disclosed in Japanese Patent No. 2656336. After 100 parts by weight of the total amount of the components corresponding to the above) were completely dissolved in 500 parts by weight of dichloromethane while heating, mixing was continued for 50 hours at a temperature of 39 to 41 ° C. while refluxing, and the mixture was heated to 150 ° C. Gel time 60
A second solution was made. The solution was decompressed while being heated to 45 ° C., and then heated, and the reaction was allowed to proceed until a softening point that could be used for transfer molding was obtained. Progressed, and a moldable material could not be obtained.
【0045】(比較例3)特許2970214号公報に
開示されている技術に基づき、成分(a)に該当するエ
ポキシ樹脂、成分(b)に相当する酸無水物に、本発明
の中間反応を経ずに、成分(B)〜(D)に相当する成
分、及び各種添加剤等を表2に示した配合割合で混合
し、90℃の熱ロールで15分間混練し、得られた混練
物シートを冷却粉砕し、樹脂組成物を得た。評価方法は
以下の通り。結果は表2にまとめて示す。(Comparative Example 3) Based on the technology disclosed in Japanese Patent No. 2970214, an epoxy resin corresponding to the component (a) and an acid anhydride corresponding to the component (b) were subjected to the intermediate reaction of the present invention. Instead, the components corresponding to components (B) to (D), various additives, and the like were mixed at the mixing ratio shown in Table 2, and kneaded with a hot roll at 90 ° C. for 15 minutes to obtain a kneaded material sheet. Was cooled and pulverized to obtain a resin composition. The evaluation method is as follows. The results are summarized in Table 2.
【0046】(比較例4〜8)成分(a)、成分(b)
に相当する成分を、表2に示した配合割合で、100℃
の反応釜で110〜200分加熱反応させて得た中間反
応物に、成分(B)〜(D)に相当する成分、及び各種
添加剤等を表2に示した配合割合で混合し、2本ロール
を用いて、50〜90℃で5分間混練し、得られた混練
物シートを、冷却後粉砕して、樹脂組成物を得た。評価
方法は以下の通り。結果は表2にまとめて示す。(Comparative Examples 4 to 8) Component (a), Component (b)
At a blending ratio shown in Table 2 at 100 ° C.
The components corresponding to components (B) to (D) and various additives were mixed in the mixing ratio shown in Table 2 with the intermediate reaction product obtained by performing a heating reaction in the reaction vessel for 110 to 200 minutes. Using this roll, the mixture was kneaded at 50 to 90 ° C. for 5 minutes, and the obtained kneaded material sheet was cooled and pulverized to obtain a resin composition. The evaluation method is as follows. The results are summarized in Table 2.
【0047】[軟化点の測定]合成した成分(A)の、
中間反応物の軟化点は、室温から250℃の温度傾斜を
持たせた銅棒上に、粉砕した成分(A)を散布し、10
秒後に刷毛を用いて、はきとることの可否の境界温度を
もって軟化点とした。この際、50℃未満で測定不可能
な軟化点のものを×と表記した。[Measurement of softening point]
The softening point of the intermediate reactant was determined by spraying the pulverized component (A) on a copper rod having a temperature gradient from room temperature to 250 ° C.
After a second, using a brush, the softening point was determined based on the boundary temperature at which removal was possible. At this time, those having a softening point which cannot be measured at a temperature lower than 50 ° C. were indicated by x.
【0048】[光透過率の測定]上記の樹脂組成物タブ
レットを、金型温度150℃、注入圧力6.86MP
a、硬化時間90秒の条件でトランスファー成形し、3
0×10×1mmの成形品を得た。この成形品を、積分
球を搭載した分光光度計(島津製作所製自記分光光度計
UV−3100)を用いて、波長400nm、厚み1m
mの光透過率を測定した。[Measurement of Light Transmittance] The above resin composition tablet was placed at a mold temperature of 150 ° C. and an injection pressure of 6.86 MP.
a, transfer molding under the condition of curing time 90 seconds, 3
A molded product of 0 × 10 × 1 mm was obtained. Using a spectrophotometer equipped with an integrating sphere (Shimazu Seisakusho's self-recording spectrophotometer UV-3100), the molded article was subjected to a wavelength of 400 nm and a thickness of 1 m.
m was measured.
【0049】[流動性の評価]成形前の樹脂組成物を、
EMMI−I−66に準じたスパイラルフロー測定用の
金型を用い、成形温度175℃、注入圧力6.86MP
a、硬化時間5分の条件で成形し、充填した長さを測定
し、この長さが60cm以上得られたものを流動性○、
そうでないものを×とした。[Evaluation of fluidity] The resin composition before molding was
Using a mold for spiral flow measurement according to EMMI-I-66, molding temperature 175 ° C, injection pressure 6.86MP
a, molded under the condition of 5 minutes curing time, the filled length was measured, and those having a length of 60 cm or more were measured for fluidity ○,
Those that are not are marked as x.
【0050】[ガラス転移温度の測定]上記の樹脂組成
物タブレットを、金型温度150℃、注入圧力6.86
MPa、硬化時間90秒の条件でトランスファー成形
し、この成形品を、温度150℃の熱風オーブンで2時
間ポストキュアした後、熱膨張計(セイコー電子社製T
MA120)を用い、5℃/分の昇温速度で昇温して、
前記成形品の伸び率が急激に変化する温度をガラス転移
点として測定した。[Measurement of glass transition temperature] The above resin composition tablet was molded at a mold temperature of 150 ° C and an injection pressure of 6.86.
After transfer molding under the conditions of 90 MPa and a curing time of 90 seconds, the molded article was post-cured in a hot air oven at a temperature of 150 ° C. for 2 hours, and then subjected to a thermal dilatometer (T-Seiko Electronics Co., Ltd.).
MA120) at a heating rate of 5 ° C./min.
The temperature at which the elongation rate of the molded article rapidly changed was measured as the glass transition point.
【0051】[離型性の評価]上記の樹脂組成物タブレ
ットを、メラミン樹脂クリーニング材によりクリーニン
グ済みの表面実装用パッケージ(12ピンSOP、4×
5mm、厚み1.2mm、チップサイズは1.5mm×
2.0mm、リードフレームは42アロイ製)金型を用
いて、金型温度150℃、注入圧力6.86MPa、硬
化時間90秒でトランスファー成形した。評価はパッケ
ージがイジェクトピンによって金型から離型する場合を
○、パッケージの変形やクラックが発生する場合を×と
した。[Evaluation of Releasability] The above-mentioned resin composition tablet was cleaned with a melamine resin cleaning material and then packaged for surface mounting (12-pin SOP, 4 ×
5mm, thickness 1.2mm, chip size is 1.5mm ×
Transfer molding was performed using a mold having a mold temperature of 150 ° C., an injection pressure of 6.86 MPa, and a curing time of 90 seconds using a mold of 2.0 mm and a lead frame made of 42 alloy. The evaluation was evaluated as ○ when the package was released from the mold by the eject pin, and as X when the package was deformed or cracked.
【0052】[耐半田性の評価]上記の樹脂組成物タブ
レットを、メラミン樹脂クリーニング材によりクリーニ
ング済みの表面実装用パッケージ(12ピンSOP、4
×5mm、厚み1.2mm、チップサイズは1.5mm
×2.0mm、リードフレームは42アロイ製)金型を
用いて、金型温度150℃、注入圧力6.86MPa、
硬化時間90秒でトランスファー成形し、温度150℃
の熱風オーブンで、2時間後硬化させた。得られた光半
導体パッケージを、温度85℃、相対湿度60%の環境
下で、168時間放置し、その後240℃のIRリフロ
ー処理を行った。処理したパッケージを顕微鏡及び超音
波探傷装置で観察し、クラック、チップと樹脂との剥離
の有無を確認した。[Evaluation of Solder Resistance] A surface mounting package (12-pin SOP, 4
× 5mm, thickness 1.2mm, chip size 1.5mm
× 2.0 mm, lead frame made of 42 alloy) Using a mold, mold temperature 150 ° C., injection pressure 6.86 MPa,
Transfer molding with curing time 90 seconds, temperature 150 ° C
In a hot air oven for 2 hours. The obtained optical semiconductor package was left in an environment of a temperature of 85 ° C. and a relative humidity of 60% for 168 hours, and then subjected to an IR reflow treatment at 240 ° C. The processed package was observed with a microscope and an ultrasonic flaw detector to confirm the presence of cracks and separation between the chip and the resin.
【0053】[0053]
【表1】 [Table 1]
【0054】表1中、注1:油化シェルエポキシ製ビス
フェノールA型エポキシ樹脂(エポキシ当量475)、
注2:三井化学製ビスフェノール型エポキシ樹脂(エ
ポキシ当量500、 一般式(2)で表されるエポキシ
樹脂で、C(CH3)2が70%、CH2が30%含み、
n=2)、 注3:三井化学製ビスフェノール型エポキ
シ樹脂(エポキシ当量980、 一般式(2)で表され
るエポキシ樹脂で、C(CH3)2が70%、CH2が3
0%含み、n=4)、 注4:日産化学製 トリグリシ
ジルイソシアヌレート(エポキシ当量100)、 注
5:新日本理化製ヘキサヒドロ無水フタル酸とメチルヘ
キサヒドロ無水フタル酸との混合物(凝固点−15
℃)、 注6:新日本理化製ヘキサヒドロ無水フタル酸
(凝固点37℃)、 注7:サンアプロ製ジアザビシク
ロウンデセンとオクチル酸との塩、 注8:四国化成製
イミダゾール、 注9:北興化学製テトラフェニルホス
ホニウムブロマイド、 注10:北興化学製トリフェニ
ルホスフィン、 注11:SiO2、CaO、およびA
l2O3からなり、平均粒径25μmで、表1の屈折率差
に調整した球状ガラス、 注12:SiO2、CaO、
およびAl2O3からなり、平均粒径40μmで、表1の
屈折率差に調整した球状ガラス、 注13:SiO2、
CaO、およびAl2O3からなり、平均粒径25μm
で、表1の屈折率差に調整した球状ガラス、 注14:
平均粒径20μmの平板状タルク、 注15:一般式
(1)で表される離型剤である化合物A(式中k=4
8、m=2、n=21、R1=H、R2=CH3)、 注
16:一般式(1)で表される離型剤である化合物B
(式中k=54、m=4、n=18、R1=H、R2=C
H3CH2CH2)、 注17:住友化学製リン系酸化防
止剤、 注18:住友化学製フェノール系酸化防止剤。In Table 1, Note 1: Bisphenol A type epoxy resin (epoxy equivalent: 475) manufactured by Yuka Shell Epoxy,
Note 2: Bisphenol type epoxy resin manufactured by Mitsui Chemicals (epoxy equivalent: 500, epoxy resin represented by the general formula (2), containing 70% of C (CH 3 ) 2 and 30% of CH 2 ,
n = 2), Note 3: Bisphenol-type epoxy resin manufactured by Mitsui Chemicals (epoxy equivalent: 980, epoxy resin represented by the general formula (2), C (CH 3 ) 2 is 70%, CH 2 is 3
0%, n = 4) Note 4: Triglycidyl isocyanurate manufactured by Nissan Chemical Co., Ltd. (epoxy equivalent: 100) Note 5: Mixture of hexahydrophthalic anhydride and methylhexahydrophthalic anhydride manufactured by Shin Nippon Rika (freezing point −15)
℃), Note 6: Hexahydrophthalic anhydride (freezing point 37 ° C) manufactured by Shin Nippon Rika, Note 7: Salt of diazabicycloundecene and octylic acid manufactured by San Apro, Note 8: Imidazole manufactured by Shikoku Chemicals, Note 9: Hokuko Chemical Note 10: Triphenylphosphine manufactured by Hokuko Chemical, Note 11: SiO 2 , CaO, and A
Spherical glass composed of l 2 O 3 and having an average particle size of 25 μm and adjusted to the refractive index difference shown in Table 1. Note 12: SiO 2 , CaO,
And spherical glass composed of Al 2 O 3 and having an average particle size of 40 μm and adjusted to the refractive index difference shown in Table 1. Note 13: SiO 2 ,
It consists of CaO and Al 2 O 3 and has an average particle size of 25 μm
Spherical glass adjusted to the refractive index difference shown in Table 1,
Tabular talc having an average particle size of 20 μm. Note 15: Compound A, a release agent represented by the general formula (1) (where k = 4
8, m = 2, n = 21, R 1 = H, R 2 = CH 3 ), Note 16: Compound B which is a release agent represented by the general formula (1)
(Where k = 54, m = 4, n = 18, R 1 = H, R 2 = C
H 3 CH 2 CH 2 ), Note 17: Phosphorus antioxidant manufactured by Sumitomo Chemical, Note 18: Phenolic antioxidant manufactured by Sumitomo Chemical.
【0055】[0055]
【表2】 [Table 2]
【0056】表1中、注1:油化シェルエポキシ製ビス
フェノールA型エポキシ樹脂(エポキシ当量475)、
注2:三井化学製ビスフェノールF型エポキシ樹脂
(エポキシ当量950)、 注3:三井化学製ビスフェ
ノール型エポキシ樹脂(エポキシ当量500、 一般式
(2)で表されるエポキシ樹脂で、C(CH3)2が70
%、CH2が30%含み、n=2)、 注4:三井化学
製ビスフェノール型エポキシ樹脂(エポキシ当量98
0、 一般式(2)で表されるエポキシ樹脂で、C(C
H3)2が70%、CH2が30%含み、n=4)、 注
5:日産化学製 トリグリシジルイソシアヌレート(エ
ポキシ当量100)、 注6:三井化学製3官能エポキ
シ樹脂(エポキシ当量210)、 注7:新日本理化製
ヘキサヒドロ無水フタル酸とメチルヘキサヒドロ無水フ
タル酸との混合物(凝固点−15℃)、注8:新日本理
化製ヘキサヒドロ無水フタル酸(凝固点37℃)、 注
9:新日本理化製テトラヒドロ無水フタル酸(凝固点1
00℃)、 注10:サンアプロ製ジアザビシクロウン
デセンとオクチル酸との塩、 注11:四国化成製イミ
ダゾール類、 注12:北興化学製テトラフェニルホス
ホニウムブロマイド、13:SiO2、CaO、および
Al2O3からなり、平均粒径25μmで、表2の屈折率
差に調整した球状ガラス、 注14:SiO2、Ca
O、およびAl2O 3からなり、平均粒径40μmで、表
2の屈折率差に調整した球状ガラス、 注15:平均粒
径15μmの、屈折率を調整した球状ガラス、 注1
6:SiO2、CaO、およびAl2O3からなり、平均
粒径5μmで、表2の屈折率差に調整した球状ガラス、
注17:一般式(1)で表される離型剤である化合物
A(式中k=48、m=2、n=21、R1=H、R2=
CH3)、 注18:一般式(1)で表される離型剤で
ある化合物B(式中k=54、m=4、n=18、R1
=H、R2=CH3CH2CH2)、 注19:クラリアン
トジャパン製離型剤、注20:住友化学製フェノール系
酸化防止剤、 注21:住友化学製リン系酸化防止剤、
注22:中間反応の溶融混合において、ゲル化が進行
した。In Table 1, Note 1: Oil-made shell epoxy screws
Phenol A type epoxy resin (epoxy equivalent 475),
Note 2: Bisphenol F type epoxy resin manufactured by Mitsui Chemicals
(Epoxy equivalent 950), Note 3: Bisphe manufactured by Mitsui Chemicals, Inc.
Knol type epoxy resin (epoxy equivalent 500, general formula
An epoxy resin represented by (2), wherein C (CHThree)TwoIs 70
%, CHTwo30%, n = 2), Note 4: Mitsui Chemicals
Bisphenol epoxy resin (epoxy equivalent 98
0, an epoxy resin represented by the general formula (2)
HThree)TwoIs 70%, CHTwoContains 30%, n = 4)
5: Triglycidyl isocyanurate (Nissan Chemical)
Poxy equivalent 100), Note 6: Mitsui Chemicals trifunctional epoxy
Resin (epoxy equivalent 210), Note 7: manufactured by Shin Nippon Rika
Hexahydrophthalic anhydride and methylhexahydrophthalic anhydride
Mixture with tallic acid (freezing point -15 ℃), Note 8: Shin Nihon
Hexahydrophthalic anhydride (freezing point 37 ° C)
9: Nippon Rika's tetrahydrophthalic anhydride (freezing point 1
00 ° C), Note 10: San-Apro diazabicycloun
Salt of decene and octylic acid, Note 11: Shikoku Kasei Imi
Dazoles, Note 12: Tetraphenylphos manufactured by Hokuko Chemical
Honium bromide, 13: SiOTwo, CaO, and
AlTwoOThreeHaving an average particle size of 25 μm and a refractive index of Table 2.
Spherical glass adjusted to the difference, Note 14: SiOTwo, Ca
O, and AlTwoO ThreeAnd an average particle size of 40 μm.
Spherical glass adjusted to a refractive index difference of 2, Note 15: Average grain
Spherical glass with a refractive index of 15 μm, Note 1
6: SiOTwo, CaO, and AlTwoOThreeConsisting of
A spherical glass having a particle diameter of 5 μm and adjusted to the refractive index difference shown in Table 2;
Note 17: Compound which is a release agent represented by the general formula (1)
A (where k = 48, m = 2, n = 21, R1= H, RTwo=
CHThree), Note 18: Release agent represented by general formula (1)
A compound B (where k = 54, m = 4, n = 18, R1
= H, RTwo= CHThreeCHTwoCHTwo), Note 19: Clarian
Release agent manufactured by Tojapan, Note 20: Phenol type manufactured by Sumitomo Chemical
Antioxidant, Note 21: Phosphorus antioxidant manufactured by Sumitomo Chemical,
Note 22: Gelation progresses during melt mixing of the intermediate reaction
did.
【0057】表の結果から明らかなように、本発明の樹
脂組成物は耐半田性、離型性に優れるとともに、80%
以上の良好な光透過率を両立していることがわかる。As is evident from the results in the table, the resin composition of the present invention has excellent solder resistance and releasability, and has a 80%
It can be seen that both of the above excellent light transmittances are satisfied.
【0058】[0058]
【発明の効果】本発明、透明性、耐半田性及び離型性に
優れた光半導体封止用エポキシ樹脂組成物が得られ、こ
れを用いて、高い信頼性を有したオプトデバイスを提供
することができる。Industrial Applicability According to the present invention, an epoxy resin composition for encapsulating an optical semiconductor having excellent transparency, solder resistance and mold release properties is obtained, and by using this, an optical device having high reliability is provided. be able to.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 FI テーマコート゛(参考) C08L 71/02 C08L 71/02 H01L 23/29 H01L 23/30 R 23/31 Fターム(参考) 4J002 CD051 CD141 CH002 CH012 DJ017 DJ037 DJ047 DL007 EN006 EN136 EU116 EW136 EW176 FD017 FD146 FD162 GQ01 GQ05 4J036 AA02 AB17 AD01 DB15 DB22 DC41 DC48 GA22 JA07 4M109 AA01 BA01 CA21 EA02 EB04 EB12 EC11 GA01 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C08L 71/02 C08L 71/02 H01L 23/29 H01L 23/30 R 23/31 F term (reference) 4J002 CD051 CD141 CH002 CH012 DJ017 DJ037 DJ047 DL007 EN006 EN136 EU116 EW136 EW176 FD017 FD146 FD162 GQ01 GQ05 4J036 AA02 AB17 AD01 DB15 DB22 DC41 DC48 GA22 JA07 4M109 AA01 BA01 CA21 EA02 EB04 EB12 EC11 GA01
Claims (9)
(A)、硬化促進剤(B)、無機充填剤(C)、離型剤
(D)を必須成分とする光半導体封止用エポキシ樹脂組
成物において、中間反応物(A)が下記成分(a)、及
び成分(b)を含んでなり、且つ無溶媒下、80℃以上
150℃以下の温度で、溶融混合して得られたものであ
ることを特徴とする光半導体封止用エポキシ樹脂組成
物。 (a)トリグリシジルイソシアヌレート、及びビスフェ
ノール型エポキシ樹脂からなり、成分(a)全体の平均
エポキシ当量が200以上400以下のエポキシ樹脂。 (b)凝固点50℃以下の酸無水物硬化剤。1. An epoxy resin for optical semiconductor encapsulation containing an intermediate reaction product (A) of an epoxy resin and a curing agent, a curing accelerator (B), an inorganic filler (C), and a release agent (D) as essential components. In the composition, the intermediate reactant (A) comprises the following components (a) and (b), and is obtained by melt-mixing at 80 ° C. or more and 150 ° C. or less in the absence of a solvent. An epoxy resin composition for encapsulating an optical semiconductor, characterized in that: (A) An epoxy resin comprising triglycidyl isocyanurate and a bisphenol-type epoxy resin, and having an average epoxy equivalent of 200 to 400 in the entire component (a). (B) An acid anhydride curing agent having a freezing point of 50 ° C. or less.
0以上1100以下の平均エポキシ当量を有し、トリグ
リシジルイソシアヌレートが、(a)成分中に5%以上
45%以下で含まれることを特徴とする請求項1記載の
光半導体封止用エポキシ樹脂組成物。2. A bisphenol type epoxy resin comprising 21
The epoxy resin for optical semiconductor encapsulation according to claim 1, wherein the epoxy resin has an average epoxy equivalent of 0 or more and 1100 or less, and triglycidyl isocyanurate is contained in the component (a) in an amount of 5% or more and 45% or less. Composition.
式(1)で表されるエポキシ樹脂であることを特徴とす
る請求項2記載の光半導体封止用エポキシ樹脂組成物。 【化1】 (但し、式(1)中、nの値が1〜7であり、RはC
(CH3)2及びCH2を示し、1分子中それぞれ少なく
とも1個以上有する。)3. The epoxy resin composition for optical semiconductor encapsulation according to claim 2, wherein the bisphenol type epoxy resin is an epoxy resin represented by the general formula (1). Embedded image (However, in the formula (1), the value of n is 1 to 7, and R is C
(CH 3 ) 2 and CH 2 , each having at least one or more in one molecule. )
(b)が、ヘキサヒドロ無水フタル酸及び4−メチルヘ
キサヒドロ無水フタル酸からなる群より選ばれる少なく
とも1つであることを特徴とする請求項1記載の光半導
体封止用エポキシ樹脂組成物。4. The acid anhydride curing agent (b) having a freezing point of 50 ° C. or lower is at least one selected from the group consisting of hexahydrophthalic anhydride and 4-methylhexahydrophthalic anhydride. Item 4. The epoxy resin composition for optical semiconductor encapsulation according to Item 1.
イミダゾール塩類、双環式アミジン類、双環式アミジン
のカルボン酸類、及びホスホニウム塩類からなる群より
少なくとも1つ選ばれることを特徴とする請求項1記載
の光半導体封止用エポキシ樹脂組成物。5. The curing accelerator (B) comprises an imidazole,
The epoxy resin composition for optical semiconductor encapsulation according to claim 1, wherein at least one selected from the group consisting of imidazole salts, bicyclic amidines, carboxylic acids of bicyclic amidines, and phosphonium salts.
材(C)以外の成分の硬化物の屈折率との差が、0.0
1以下である請求項1記載の光半導体封止用エポキシ樹
脂組成物。6. The difference between the refractive index of the inorganic filler (C) and the refractive index of a cured product of a component other than the inorganic filler (C) is 0.0
The epoxy resin composition for encapsulating an optical semiconductor according to claim 1, which is 1 or less.
O、およびAl2O3からなる、平均粒径5μm以上10
0μm以下の球状ガラス粒子であり、光半導体封止用エ
ポキシ樹脂組成物中に5重量%以上、70重量%以下の
割合で配合されてなることを特徴とする請求項1記載の
光半導体封止用エポキシ樹脂組成物。7. An inorganic filler (C) comprising SiO 2 , Ca
O and Al 2 O 3 , having an average particle size of 5 μm or more and 10 or more
2. The optical semiconductor encapsulation according to claim 1, wherein the optical glass encapsulation is spherical glass particles having a particle size of 0 [mu] m or less, and is blended in the epoxy resin composition for optical semiconductor encapsulation at a ratio of 5% by weight to 70% by weight. Epoxy resin composition for use.
る化合物であり、光半導体封止用エポキシ樹脂組成物中
に0.01重量%以上、5重量%以下の割合で配合され
てなることを特徴とする請求項1記載の光半導体封止用
エポキシ樹脂組成物。 【化2】 (但し、式(2)中、kの値が40〜60であり、mの
値は1〜5であり、nの値は15〜45である。R1、
R2は水素原子もしくは一価のアルキル基であり、少な
くとも一方が一価のアルキル基である。)8. The release agent (D) is a compound represented by the general formula (2), and has a ratio of 0.01% by weight or more and 5% by weight or less in the epoxy resin composition for encapsulating an optical semiconductor. 2. The epoxy resin composition for optical semiconductor encapsulation according to claim 1, wherein the epoxy resin composition is blended. Embedded image (However, in the formula (2), the value of k is 40 to 60, the value of m is 1 to 5, and the value of n is 15 to 45. R 1 ,
R 2 is a hydrogen atom or a monovalent alkyl group, at least one of which is a monovalent alkyl group. )
体封止用エポキシ樹脂組成物の硬化物で封止された光半
導体装置。9. An optical semiconductor device encapsulated with a cured product of the epoxy resin composition for optical semiconductor encapsulation according to claim 1. Description:
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