JP5358240B2 - Adhesive for semiconductor - Google Patents
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- JP5358240B2 JP5358240B2 JP2009075060A JP2009075060A JP5358240B2 JP 5358240 B2 JP5358240 B2 JP 5358240B2 JP 2009075060 A JP2009075060 A JP 2009075060A JP 2009075060 A JP2009075060 A JP 2009075060A JP 5358240 B2 JP5358240 B2 JP 5358240B2
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本発明は、硬化物の柔軟性が高く、かつ、吸水性が低く耐リフロー性に優れた半導体用接着剤に関する。 The present invention relates to a semiconductor adhesive having high flexibility of a cured product, low water absorption and excellent reflow resistance.
半導体装置の製造方法において、半導体チップを基板等に接着固定（ダイボンディング）する際には、例えば、液状エポキシ等の接着剤が用いられる。ダイボンディング工程において用いられる接着剤に求められる性質として、例えば、吸水性の低さが挙げられる。半導体装置の製造方法においては、ダイボンディング工程の後に２００〜２６０℃の高温に達するリフロー工程を行う必要があり、このとき、接着剤が多くの水分を含んでいると、水分の急激な膨張及び気化により半導体装置にクラック等の不具合が生じやすいためである。 In the manufacturing method of a semiconductor device, when a semiconductor chip is bonded and fixed to a substrate or the like (die bonding), for example, an adhesive such as liquid epoxy is used. Examples of properties required for the adhesive used in the die bonding step include low water absorption. In the manufacturing method of a semiconductor device, it is necessary to perform a reflow process that reaches a high temperature of 200 to 260 ° C. after the die bonding process. If the adhesive contains a large amount of moisture, rapid expansion of moisture and This is because defects such as cracks are likely to occur in the semiconductor device due to vaporization.
従来、接着剤の吸水性を低下させ、耐リフロー性を向上させるために、接着剤に無機充填材を添加する方法が用いられてきた。例えば、特許文献１には、接着強度、硬化性に優れ、特に銅リードフレームと半導体素子との接着に用いた場合に耐リフロー性に優れる半導体装置を得ることのできる半導体用ダイアタッチペーストが開示されており、特許文献１の半導体用ダイアタッチペーストは、必須成分として銀粉、シリカ等の充填材を含有している。 Conventionally, a method of adding an inorganic filler to an adhesive has been used to reduce the water absorption of the adhesive and improve the reflow resistance. For example, Patent Document 1 discloses a die attach paste for a semiconductor that is excellent in adhesive strength and curability, and that can obtain a semiconductor device that is particularly excellent in reflow resistance when used for bonding a copper lead frame and a semiconductor element. The die attach paste for semiconductor of Patent Document 1 contains a filler such as silver powder or silica as an essential component.
しかし、無機充填材の添加量が増加すると、接着剤を硬化して得られる硬化物の柔軟性が低下し、硬くて脆い硬化物となり、得られる半導体装置の信頼性が低下するという問題があった。従って、硬化物が柔軟性を失うことなく、かつ、吸水性が低く耐リフロー性に優れた接着剤を得ることは困難であった。 However, as the amount of the inorganic filler added increases, the flexibility of the cured product obtained by curing the adhesive decreases, resulting in a hard and brittle cured product, and the reliability of the resulting semiconductor device decreases. It was. Therefore, it has been difficult to obtain an adhesive that does not lose flexibility in the cured product and has low water absorption and excellent reflow resistance.
本発明は、硬化物の柔軟性が高く、かつ、吸水性が低く耐リフロー性に優れた半導体用接着剤を提供することを目的とする。 An object of this invention is to provide the adhesive agent for semiconductors with the high softness | flexibility of hardened | cured material, low water absorption, and excellent reflow resistance.
本発明は、下記式（１）で表されるエポキシ樹脂及び硬化剤を含有する半導体用接着剤である。 The present invention is an adhesive for a semiconductor containing an epoxy resin represented by the following formula (1) and a curing agent.
式（１）中、Ｒは水素原子又は炭素数１〜４のアルキル基を表し、ｎは１５０〜１７５の整数を表す。
以下、本発明を詳述する。
In formula (1), R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 150 to 175.
The present invention is described in detail below.
一般に、柔軟性の高いエポキシ樹脂硬化物を得るためには、例えば、ブタジエン骨格を有するエポキシ樹脂を用いることが考えられる。しかし、従来公知のブタジエン骨格を有するエポキシ樹脂は、耐リフロー性に劣っていた。これは、従来公知のブタジエン骨格を有するエポキシ樹脂は、その製法上、一般にニトリル基を有しており、比較的高極性であって吸水性が高いことが原因であると考えられる。
そこで、本発明者らは、従来公知のブタジエン骨格を有するエポキシ樹脂とは異なり、ニトリル基を有さず比較的低極性の上記式（１）で表されるエポキシ樹脂を製造する方法を見出した。更に、本発明者らは、上記式（１）で表されるエポキシ樹脂と硬化剤とを含有する半導体用接着剤は、吸水性が低く耐リフロー性に優れ、かつ、高い柔軟性を有する硬化物を形成することができることを見出し、本発明を完成させるに至った。
In general, in order to obtain a cured epoxy resin with high flexibility, for example, it is conceivable to use an epoxy resin having a butadiene skeleton. However, conventionally known epoxy resins having a butadiene skeleton have poor reflow resistance. This is presumably because epoxy resins having a conventionally known butadiene skeleton generally have a nitrile group because of their production methods, are relatively high in polarity, and have high water absorption.
Therefore, the present inventors have found a method for producing an epoxy resin represented by the above formula (1) having no nitrile group and having a relatively low polarity, unlike an epoxy resin having a conventionally known butadiene skeleton. . Furthermore, the present inventors have found that a semiconductor adhesive containing the epoxy resin represented by the above formula (1) and a curing agent has a low water absorption, excellent reflow resistance, and high flexibility. The present inventors have found that an object can be formed and have completed the present invention.
本発明の半導体用接着剤は、下記式（１）で表されるエポキシ樹脂を含有する。 The adhesive for semiconductors of this invention contains the epoxy resin represented by following formula (1).
上記式（１）中、Ｒは水素原子又は炭素数１〜４のアルキル基を表し、ｎは１５０〜１７５の整数を表す。 In said formula (1), R represents a hydrogen atom or a C1-C4 alkyl group, and n represents the integer of 150-175.
上記式（１）で表されるエポキシ樹脂は、ブタジエン骨格を有する。上記式（１）で表されるエポキシ樹脂がブタジエン骨格を有することにより、得られる半導体用接着剤の硬化物は、高い柔軟性を有することができる。
また、従来公知のブタジエン骨格を有するエポキシ樹脂は、一般にニトリル基を有し比較的高極性であるため、吸水性が高く、耐リフロー性に劣っていた。これに対し、上記式（１）で表されるエポキシ樹脂は、ニトリル基を有さず比較的低極性であるため、得られる半導体用接着剤の吸水性を低下させることができ、耐リフロー性を向上させることができる。
The epoxy resin represented by the above formula (1) has a butadiene skeleton. When the epoxy resin represented by the above formula (1) has a butadiene skeleton, the obtained cured product of the adhesive for semiconductor can have high flexibility.
Moreover, conventionally known epoxy resins having a butadiene skeleton generally have a nitrile group and have a relatively high polarity, and therefore have high water absorption and poor reflow resistance. On the other hand, the epoxy resin represented by the above formula (1) does not have a nitrile group and has a relatively low polarity. Therefore, the water absorption of the obtained adhesive for semiconductors can be reduced, and reflow resistance can be reduced. Can be improved.
上記式（１）で表されるエポキシ樹脂において、上記ブタジエン骨格の繰り返し数の下限は１５０、上限は１７５である。上記ブタジエン骨格の繰り返し数が１５０未満であると、得られる半導体用接着剤の硬化物は、充分に高い柔軟性を有することができない。上記ブタジエン骨格の繰り返し数が１７５を超えると、得られる半導体用接着剤が吸水性に劣ったり、硬化物が充分に高い柔軟性を有することができなかったりする。上記式（１）で表されるエポキシ樹脂において、上記ブタジエン骨格の繰り返し数の好ましい下限は１５５、好ましい上限は１６０である。
なお、上記式（１）中、ｎは上記ブタジエン骨格の繰り返し数を表す。従って、上記式（１）中、ｎは１５０〜１７５の整数を表す。
In the epoxy resin represented by the above formula (1), the lower limit of the number of repetitions of the butadiene skeleton is 150, and the upper limit is 175. When the repeating number of the butadiene skeleton is less than 150, the obtained cured product of the adhesive for semiconductor cannot have a sufficiently high flexibility. If the number of repeating butadiene skeletons exceeds 175, the resulting semiconductor adhesive may have poor water absorption or the cured product may not have sufficiently high flexibility. In the epoxy resin represented by the formula (1), the preferable lower limit of the number of repeating butadiene skeletons is 155, and the preferable upper limit is 160.
In the above formula (1), n represents the number of repetitions of the butadiene skeleton. Therefore, in said formula (1), n represents the integer of 150-175.
上記式（１）中、Ｒは水素原子又は炭素数１〜４のアルキル基を表す。
上記炭素数１〜４のアルキル基は特に限定されず、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ｎ−ブチル基等が挙げられる。
In said formula (1), R represents a hydrogen atom or a C1-C4 alkyl group.
The alkyl group having 1 to 4 carbon atoms is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, and an n-butyl group.
上記式（１）で表されるエポキシ樹脂を製造する方法は特に限定されず、例えば、下記式（２）で表されるジシクロペンタジエン型エポキシ樹脂と下記式（３）で表されるブタジエン骨格を有するカルボン酸とを反応させて上記式（１）で表されるエポキシ樹脂を得る方法が挙げられる。 The method for producing the epoxy resin represented by the above formula (1) is not particularly limited. For example, a dicyclopentadiene type epoxy resin represented by the following formula (2) and a butadiene skeleton represented by the following formula (3): And a method of obtaining an epoxy resin represented by the above formula (1) by reacting with a carboxylic acid having the above formula.
上記式（３）中、Ｒは水素原子又は炭素数１〜４のアルキル基を表し、ｎは１５０〜１７５の整数を表す。 In said formula (3), R represents a hydrogen atom or a C1-C4 alkyl group, and n represents the integer of 150-175.
上記反応方法は特に限定されず、例えば、上記式（２）で表されるジシクロペンタジエン型エポキシ樹脂と上記式（３）で表されるブタジエン骨格を有するカルボン酸とを混合し、加熱溶解する方法が挙げられる。上記式（２）で表されるジシクロペンタジエン型エポキシ樹脂は、従来公知の他のエポキシ樹脂と比べて上記式（３）で表されるブタジエン骨格を有するカルボン酸との相溶性が高いことから、加熱溶融によって反応させることができる。
なお、上記式（３）で表されるブタジエン骨格を有するカルボン酸に対して、過剰当量の上記式（２）で表されるジシクロペンタジエン型エポキシ樹脂を用いることが好ましい。
The reaction method is not particularly limited. For example, a dicyclopentadiene type epoxy resin represented by the above formula (2) and a carboxylic acid having a butadiene skeleton represented by the above formula (3) are mixed and dissolved by heating. A method is mentioned. The dicyclopentadiene type epoxy resin represented by the above formula (2) has higher compatibility with the carboxylic acid having the butadiene skeleton represented by the above formula (3) than other conventionally known epoxy resins. , And can be reacted by heating and melting.
In addition, it is preferable to use an excess equivalent dicyclopentadiene type epoxy resin represented by the above formula (2) with respect to the carboxylic acid having a butadiene skeleton represented by the above formula (3).
上記反応方法においては溶媒を用いてもよいが、環境に与える影響等の観点から、溶媒を用いないことが好ましい。 In the above reaction method, a solvent may be used, but it is preferable not to use a solvent from the viewpoint of influence on the environment.
本発明の半導体用接着剤は、本発明の効果を妨げない範囲内で、上記式（１）で表されるエポキシ樹脂以外の他のエポキシ樹脂（以下、他のエポキシ樹脂ともいう）を含有してもよい。
上記他のエポキシ樹脂は特に限定されず、例えば、ビスフェノールＡ型、ビスフェノールＦ型、ビスフェノールＡＤ型、ビスフェノールＳ型等のビスフェノール型エポキシ樹脂、フェノールノボラック型、クレゾールノボラック型等のノボラック型エポキシ樹脂、トリスフェノールメタントリグリシジルエーテル等の芳香族エポキシ樹脂、ナフタレン型エポキシ樹脂、フルオレン型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、及び、これらの変性物、水添化物等が挙げられる。これらのエポキシ樹脂は、単独で用いられてもよく、二種以上が併用されてもよい。
The adhesive for semiconductors of the present invention contains an epoxy resin other than the epoxy resin represented by the above formula (1) (hereinafter also referred to as other epoxy resin) within a range not impeding the effects of the present invention. May be.
The other epoxy resins are not particularly limited. For example, bisphenol A type, bisphenol F type, bisphenol AD type, bisphenol S type and other bisphenol type epoxy resins, phenol novolak type, cresol novolak type and other novolak type epoxy resins, tris Aromatic epoxy resins such as phenol methane triglycidyl ether, naphthalene type epoxy resins, fluorene type epoxy resins, dicyclopentadiene type epoxy resins, modified products thereof, hydrogenated products and the like can be mentioned. These epoxy resins may be used independently and 2 or more types may be used together.
本発明の半導体用接着剤が上記他のエポキシ樹脂を含有する場合、上記式（１）で表されるエポキシ樹脂と上記他のエポキシ樹脂との合計に占める上記他のエポキシ樹脂の含有量は特に限定されないが、好ましい上限は３０重量％である。上記他のエポキシ樹脂の含有量が３０重量％を超えると、得られる半導体用接着剤は、硬化物が充分に高い柔軟性を有することができなかったり、吸水性が高くなって耐リフロー性が低下したりすることがある。上記他のエポキシ樹脂の含有量のより好ましい上限は、２０重量％である。 When the semiconductor adhesive of the present invention contains the other epoxy resin, the content of the other epoxy resin in the total of the epoxy resin represented by the formula (1) and the other epoxy resin is particularly Although not limited, a preferable upper limit is 30% by weight. When the content of the other epoxy resin exceeds 30% by weight, the resulting adhesive for a semiconductor cannot have a sufficiently high flexibility in the cured product, or has high water absorption and reflow resistance. It may decrease. The upper limit with more preferable content of said other epoxy resin is 20 weight%.
本発明の半導体用接着剤は、硬化剤を含有する。
上記硬化剤は特に限定されず、例えば、アミン系硬化剤、酸無水物硬化剤、フェノール系硬化剤等が挙げられる。なかでも、酸無水物硬化剤が好ましい。
The adhesive for semiconductors of the present invention contains a curing agent.
The said hardening | curing agent is not specifically limited, For example, an amine type hardening | curing agent, an acid anhydride hardening | curing agent, a phenol type hardening | curing agent etc. are mentioned. Of these, acid anhydride curing agents are preferred.
上記酸無水物硬化剤は特に限定されないが、２官能酸無水物硬化剤が好ましい。上記２官能酸無水物硬化剤は特に限定されず、例えば、無水フタル酸、ヘキサヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、エンドメチレンテトラヒドロ無水フタル酸、メチルエンドメチレンテトラヒドロ無水フタル酸、無水マレイン酸等が挙げられる。 The acid anhydride curing agent is not particularly limited, but a bifunctional acid anhydride curing agent is preferable. The bifunctional acid anhydride curing agent is not particularly limited. For example, phthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydroanhydride. Examples include phthalic acid and maleic anhydride.
また、上記硬化剤として、３官能以上の酸無水物硬化剤粒子を用いてもよい。上記３官能以上の酸無水物硬化剤粒子は特に限定されず、例えば、酸無水物無水トリメリット酸等の３官能の酸無水物からなる粒子、無水ピロメリット酸、無水ベンゾフェノンテトラカルボン酸、メチルシクロヘキセンテトラカルボン酸無水物、ポリアゼライン酸無水物等の４官能以上の酸無水物からなる粒子等が挙げられる。 In addition, trifunctional or higher functional acid anhydride curing agent particles may be used as the curing agent. The trifunctional or higher functional acid anhydride curing agent particles are not particularly limited. For example, particles composed of trifunctional acid anhydrides such as acid anhydride trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, methyl Examples thereof include particles composed of tetrafunctional or higher functional acid anhydrides such as cyclohexene tetracarboxylic acid anhydride and polyazeline acid anhydride.
上記３官能以上の酸無水物硬化剤粒子の平均粒子径は特に限定されないが、好ましい下限が０．１μｍ、好ましい上限が２０μｍである。上記３官能以上の酸無水物硬化剤粒子の平均粒子径が０．１μｍ未満であると、硬化剤の凝集が生じ、得られる半導体用接着剤が増粘することがある。上記３官能以上の酸無水物硬化剤粒子の平均粒子径が２０μｍを超えると、硬化時に硬化剤粒子が充分に拡散することができず、硬化不良となることがある。 The average particle diameter of the trifunctional or higher functional acid anhydride curing agent particles is not particularly limited, but a preferable lower limit is 0.1 μm and a preferable upper limit is 20 μm. If the average particle diameter of the trifunctional or higher functional acid anhydride curing agent particles is less than 0.1 μm, aggregation of the curing agent may occur, and the resulting adhesive for semiconductor may be thickened. If the average particle diameter of the trifunctional or higher functional acid anhydride curing agent particles exceeds 20 μm, the curing agent particles cannot be sufficiently diffused during curing, resulting in poor curing.
上記硬化剤の含有量は特に限定されないが、上記式（１）で表されるエポキシ樹脂と上記他のエポキシ樹脂との合計１００重量部に対する好ましい下限が５重量部、好ましい上限が１５０重量部である。上記硬化剤の含有量が５重量部未満であると、得られる半導体用接着剤が充分に硬化しないことがある。上記硬化剤の含有量が１５０重量部を超えると、得られる半導体用接着剤の接続信頼性が低下することがある。上記硬化剤の含有量は、上記式（１）で表されるエポキシ樹脂と上記他のエポキシ樹脂との合計１００重量部に対するより好ましい下限が１０重量部、より好ましい上限が１４０重量部、更に好ましい下限が３０重量部、更に好ましい上限が７０重量部である。 Although content of the said hardening | curing agent is not specifically limited, The preferable minimum with respect to a total of 100 weight part of the epoxy resin represented by the said Formula (1) and said other epoxy resin is 5 weight part, A preferable upper limit is 150 weight part. is there. If the content of the curing agent is less than 5 parts by weight, the resulting semiconductor adhesive may not be sufficiently cured. When content of the said hardening | curing agent exceeds 150 weight part, the connection reliability of the adhesive agent for semiconductors obtained may fall. The content of the curing agent is more preferably 10 parts by weight with respect to a total of 100 parts by weight of the epoxy resin represented by the formula (1) and the other epoxy resin, and more preferably 140 parts by weight. The lower limit is 30 parts by weight, and the more preferable upper limit is 70 parts by weight.
また、上記硬化剤が、上記２官能酸無水物硬化剤と上記３官能以上の酸無水物硬化剤粒子とを含有する場合、これらの配合比は特に限定されないが、上記３官能以上の酸無水物硬化剤粒子の含有量（重量）を上記２官能酸無水物硬化剤の含有量（重量）で除した値［＝（３官能以上の酸無水物硬化剤粒子の含有量）／（２官能酸無水物硬化剤の含有量）］の好ましい下限が０．１、好ましい上限が１０である。上記値が０．１未満であると、上記３官能以上の酸無水物硬化剤粒子を添加する効果が充分に得られないことがある。上記値が１０を超えると、得られる半導体用接着剤の硬化物が脆くなり、充分な接着信頼性が得られないことがある。上記値のより好ましい下限は０．２、より好ましい上限は８である。 Moreover, when the said hardening | curing agent contains the said bifunctional acid anhydride hardening | curing agent and the said trifunctional or more acid anhydride hardening | curing agent particle | grain, these compounding ratios are not specifically limited, The said trifunctional or more acid anhydride Value obtained by dividing content (weight) of product curing agent particle by content (weight) of bifunctional acid anhydride curing agent [= (content of trifunctional or higher functional acid anhydride curing agent particles) / (bifunctional The preferred lower limit of the content of the acid anhydride curing agent)] is 0.1, and the preferred upper limit is 10. When the value is less than 0.1, the effect of adding the trifunctional or higher functional acid anhydride curing agent particles may not be sufficiently obtained. If the above value exceeds 10, the resulting cured product of the semiconductor adhesive may become brittle, and sufficient adhesion reliability may not be obtained. A more preferred lower limit of the above value is 0.2, and a more preferred upper limit is 8.
また、上記硬化剤として立体障害の小さい硬化剤を用いることで、得られる半導体用接着剤の吸水性をより低下させることができ、耐リフロー性を向上させることができる。上述した硬化剤のうち立体障害の小さい硬化剤の市販品として、例えば、ＹＨ３０６、ＹＨ３０７、ＹＨ３０９（以上、ジャパンエポキシレジン社製）、ＨＮＡ−１００（新日本理化社製）が挙げられる。 Further, by using a curing agent having a small steric hindrance as the curing agent, the water absorption of the obtained adhesive for semiconductor can be further reduced, and the reflow resistance can be improved. Examples of commercially available curing agents having small steric hindrance among the above-described curing agents include YH306, YH307, YH309 (manufactured by Japan Epoxy Resin Co., Ltd.) and HNA-100 (manufactured by Shin Nippon Rika Co., Ltd.).
本発明の半導体用接着剤は、硬化促進剤を含有することが好ましい。
上記硬化促進剤は特に限定されず、例えば、イミダゾール系硬化促進剤、３級アミン系硬化促進剤等が挙げられる。なかでも、硬化速度や硬化物の物性等の調整をするための反応系の制御をしやすいことから、イミダゾール系硬化促進剤が好ましい。これらの硬化促進剤は、単独で用いられてもよく、二種以上が併用されてもよい。
The adhesive for semiconductor of the present invention preferably contains a curing accelerator.
The said hardening accelerator is not specifically limited, For example, an imidazole series hardening accelerator, a tertiary amine type hardening accelerator, etc. are mentioned. Of these, an imidazole-based curing accelerator is preferred because it is easy to control the reaction system for adjusting the curing speed and the physical properties of the cured product. These hardening accelerators may be used independently and 2 or more types may be used together.
上記イミダゾール系硬化促進剤は特に限定されず、例えば、イミダゾールの１位をシアノエチル基で保護した１−シアノエチル−２−フェニルイミダゾールや、イソシアヌル酸で塩基性を保護したイミダゾール系硬化促進剤（商品名「２ＭＡ−ＯＫ」、四国化成工業社製）等が挙げられる。これらのイミダゾール系硬化促進剤は、単独で用いられてもよく、二種以上が併用されてもよい。 The imidazole curing accelerator is not particularly limited. For example, 1-cyanoethyl-2-phenylimidazole in which the 1-position of imidazole is protected with a cyanoethyl group, or an imidazole curing accelerator with a basicity protected with isocyanuric acid (trade name) “2MA-OK”, manufactured by Shikoku Kasei Kogyo Co., Ltd.). These imidazole type hardening accelerators may be used independently and 2 or more types may be used together.
本発明の半導体用接着剤が上記硬化促進剤を含有する場合、上記硬化促進剤の含有量は特に限定されないが、上記式（１）で表されるエポキシ樹脂と上記他のエポキシ樹脂との合計１００重量部に対する好ましい下限が１重量部、好ましい上限が２０重量部である。上記硬化促進剤の含有量が１重量部未満であると、得られる半導体用接着剤が充分に硬化しないことがある。上記硬化促進剤の含有量が２０重量部を超えると、得られる半導体用接着剤は、硬化物が充分に高い柔軟性を有することができなかったり、接着信頼性が低下したりすることがある。 When the semiconductor adhesive of the present invention contains the curing accelerator, the content of the curing accelerator is not particularly limited, but is the total of the epoxy resin represented by the formula (1) and the other epoxy resin. A preferred lower limit for 100 parts by weight is 1 part by weight, and a preferred upper limit is 20 parts by weight. When the content of the curing accelerator is less than 1 part by weight, the resulting semiconductor adhesive may not be sufficiently cured. When the content of the curing accelerator exceeds 20 parts by weight, the resulting semiconductor adhesive may not have a sufficiently high flexibility in the cured product, or the adhesion reliability may be lowered. .
本発明の半導体用接着剤は、本発明の効果を妨げない範囲内で、無機充填材を含有してもよい。上記無機充填材を含有することにより、得られる半導体用接着剤の吸水性をより低下させることができ、耐リフロー性を向上させることができる。
上記無機充填材は特に限定されず、例えば、ヒュームドシリカ、コロイダルシリカ等のシリカ、ガラス繊維、アルミナ微粒子等の無機微粒子等が挙げられる。
The adhesive for semiconductors of the present invention may contain an inorganic filler as long as the effects of the present invention are not hindered. By containing the said inorganic filler, the water absorption of the adhesive for semiconductors obtained can be reduced more, and reflow resistance can be improved.
The inorganic filler is not particularly limited, and examples thereof include silica such as fumed silica and colloidal silica, inorganic fine particles such as glass fibers and alumina fine particles, and the like.
上記無機充填材として粒子状の無機充填材を用いる場合、平均粒子径の好ましい下限は０．１ｎｍ、好ましい上限は５０μｍである。上記粒子状の無機充填材の平均粒子径が０．１ｎｍ未満であると、無機充填材としての機能が発現できないことがある。上記粒子状の無機充填材の平均粒子径が５０μｍを超えると、充填量を多くすることができないことがある。上記粒子状の無機充填材の平均粒子径は、より好ましい下限は１μｍ、より好ましい上限は３０μｍである。 When a particulate inorganic filler is used as the inorganic filler, the preferred lower limit of the average particle diameter is 0.1 nm, and the preferred upper limit is 50 μm. When the average particle size of the particulate inorganic filler is less than 0.1 nm, the function as an inorganic filler may not be exhibited. When the average particle diameter of the particulate inorganic filler exceeds 50 μm, the filling amount may not be increased. The average particle diameter of the particulate inorganic filler is more preferably a lower limit of 1 μm and a more preferable upper limit of 30 μm.
本発明の半導体用接着剤が上記無機充填材を含有する場合、上記無機充填材の含有量は特に限定されないが、上記式（１）で表されるエポキシ樹脂と上記他のエポキシ樹脂との合計１００重量部に対する好ましい下限は５重量部、好ましい上限は１００重量部である。上記無機充填材の含有量が５重量部未満であると、上記無機充填材を添加する効果をほとんど得ることができないことがある。上記無機充填材の含有量が１００重量部を超えると、得られる半導体用接着剤の硬化物は、充分に高い柔軟性を有することができないことがある。上記無機充填材の含有量は、上記式（１）で表されるエポキシ樹脂と上記他のエポキシ樹脂との合計１００重量部に対するより好ましい下限は３０重量部、より好ましい上限は６０重量部である。 When the semiconductor adhesive of the present invention contains the inorganic filler, the content of the inorganic filler is not particularly limited, but is the sum of the epoxy resin represented by the above formula (1) and the other epoxy resin. A preferred lower limit for 100 parts by weight is 5 parts by weight, and a preferred upper limit is 100 parts by weight. If the content of the inorganic filler is less than 5 parts by weight, the effect of adding the inorganic filler may be hardly obtained. When content of the said inorganic filler exceeds 100 weight part, the hardened | cured material of the adhesive agent for semiconductors obtained may not have a sufficiently high softness | flexibility. The content of the inorganic filler is preferably 30 parts by weight and more preferably 60 parts by weight with respect to a total of 100 parts by weight of the epoxy resin represented by the formula (1) and the other epoxy resin. .
本発明の半導体用接着剤は、本発明の効果を阻害しない範囲内で希釈剤を含有してもよい。
上記希釈剤は特に限定されないが、半導体用接着剤の加熱硬化時に硬化物に取り込まれる反応性希釈剤が好ましい。なかでも、得られる半導体用接着剤の接着信頼性を悪化させないために、１分子中に２以上の官能基を有する反応性希釈剤がより好ましい。
上記１分子中に２以上の官能基を有する反応性希釈剤として、例えば、脂肪族型エポキシ、エチレンオキサイド変性エポキシ、プロピレンオキサイド変性エポキシ、シクロヘキサン型エポキシ、ジシクロペンタジエン型エポキシ、フェノール型エポキシが挙げられる。
The adhesive for semiconductors of the present invention may contain a diluent as long as the effects of the present invention are not impaired.
Although the said diluent is not specifically limited, The reactive diluent taken in into hardened | cured material at the time of heat-hardening of the adhesive agent for semiconductors is preferable. Among these, a reactive diluent having two or more functional groups in one molecule is more preferable in order not to deteriorate the adhesion reliability of the obtained adhesive for semiconductor.
Examples of the reactive diluent having two or more functional groups in one molecule include aliphatic epoxy, ethylene oxide modified epoxy, propylene oxide modified epoxy, cyclohexane epoxy, dicyclopentadiene epoxy, and phenol epoxy. It is done.
本発明の半導体用接着剤が上記希釈剤を含有する場合、上記希釈剤の含有量は特に限定されないが、上記式（１）で表されるエポキシ樹脂と上記他のエポキシ樹脂との合計１００重量部に対する好ましい下限は１重量部、好ましい上限は５０重量部である。上記希釈剤の含有量が１重量部未満であると、上記希釈剤を添加する効果をほとんど得ることができないことがある。上記希釈剤の含有量が５０重量部を超えると、得られる半導体用接着剤の接着信頼性が劣ったり、必要な粘度特性が得られなかったりすることがある。上記希釈剤の含有量は、上記式（１）で表されるエポキシ樹脂と上記他のエポキシ樹脂との合計１００重量部に対するより好ましい下限が５重量部、より好ましい上限が２０重量部である。 When the semiconductor adhesive of the present invention contains the diluent, the content of the diluent is not particularly limited, but the total weight of the epoxy resin represented by the formula (1) and the other epoxy resin is 100 weights. The preferred lower limit for parts is 1 part by weight, and the preferred upper limit is 50 parts by weight. If the content of the diluent is less than 1 part by weight, the effect of adding the diluent may be hardly obtained. When content of the said diluent exceeds 50 weight part, the adhesive reliability of the adhesive agent for semiconductors obtained may be inferior, or a required viscosity characteristic may not be acquired. The content of the diluent is more preferably 5 parts by weight and more preferably 20 parts by weight based on a total of 100 parts by weight of the epoxy resin represented by the formula (1) and the other epoxy resin.
本発明の半導体用接着剤は、必要に応じて、溶媒を含有してもよい。
上記溶媒は特に限定されず、例えば、芳香族炭化水素類、塩化芳香族炭化水素類、塩化脂肪族炭化水素類、アルコール類、エステル類、エーテル類、ケトン類、グリコールエーテル（セロソルブ）類、脂環式炭化水素類、脂肪族炭化水素類が挙げられる。
The semiconductor adhesive of the present invention may contain a solvent, if necessary.
The solvent is not particularly limited, and examples thereof include aromatic hydrocarbons, chlorinated aromatic hydrocarbons, chlorinated aliphatic hydrocarbons, alcohols, esters, ethers, ketones, glycol ethers (cellosolves), and fats. Examples thereof include cyclic hydrocarbons and aliphatic hydrocarbons.
本発明の半導体用接着剤は、必要に応じて、無機イオン交換体を含有してもよい。上記無機イオン交換体のうち、市販品としては、例えば、ＩＸＥシリーズ（東亞合成社製）等が挙げられる。
上記無機イオン交換体の含有量は特に限定されないが、好ましい下限が１重量％、好ましい上限が１０重量％である。
The adhesive for semiconductors of this invention may contain an inorganic ion exchanger as needed. Among the inorganic ion exchangers, examples of commercially available products include IXE series (manufactured by Toagosei Co., Ltd.).
Although content of the said inorganic ion exchanger is not specifically limited, A preferable minimum is 1 weight% and a preferable upper limit is 10 weight%.
本発明の半導体用接着剤は、その他必要に応じて、ブリード防止剤、イミダゾールシランカップリング剤等の接着性付与剤等の添加剤を含有してもよい。 The semiconductor adhesive of the present invention may contain additives such as an anti-bleeding agent and an adhesion-imparting agent such as an imidazole silane coupling agent, if necessary.
本発明の半導体用接着剤を製造する方法は特に限定されず、例えば、上記式（１）で表されるエポキシ樹脂、上記硬化剤、及び、必要に応じて他の添加剤等を所定量配合して混合することにより半導体用接着剤を得る方法が挙げられる。
上記混合する方法は特に限定されず、例えば、ホモディスパー、万能ミキサー、バンバリーミキサー、ニーダー等を用いて混合する方法が挙げられる。
The method for producing the semiconductor adhesive of the present invention is not particularly limited. For example, a predetermined amount of the epoxy resin represented by the above formula (1), the curing agent, and other additives as necessary is blended. And a method of obtaining an adhesive for semiconductors by mixing them.
The method of mixing is not particularly limited, and examples thereof include a method of mixing using a homodisper, a universal mixer, a Banbury mixer, a kneader and the like.
本発明の半導体用接着剤の用途は特に限定されないが、例えば、半導体装置の製造において、半導体チップを基板又は他の半導体チップに接着固定するために用いることができる。 The application of the adhesive for semiconductors of the present invention is not particularly limited. For example, in the manufacture of a semiconductor device, it can be used for bonding and fixing a semiconductor chip to a substrate or another semiconductor chip.
本発明によれば、硬化物の柔軟性が高く、かつ、吸水性が低く耐リフロー性に優れた半導体用接着剤を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the adhesive agent for semiconductors with which the softness | flexibility of hardened | cured material is high, water absorption is low, and it was excellent in reflow resistance can be provided.
以下に実施例を挙げて本発明を更に詳しく説明するが、本発明はこれら実施例のみに限定されない。 EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.
（実施例１）
（１）式（１）で表されるエポキシ樹脂の合成
フラスコ中で、ブタジエン骨格を有するカルボン酸（宇部興産社製、ＣＴＢ）とジシクロペンタジエン型エポキシ樹脂（アデカ社製、アデカレジンＥＰ−４０８８Ｓ）とを表１に示す組成に従って混合し、１７０度で６０分、加熱溶解させることにより、エポキシ樹脂を得た。得られたエポキシ樹脂はＮＭＲにより構造を解析し、式（１）で表されるエポキシ樹脂であることを確認した。
Example 1
(1) In a synthetic flask of an epoxy resin represented by the formula (1), a carboxylic acid having a butadiene skeleton (CTB manufactured by Ube Industries, Ltd.) and a dicyclopentadiene type epoxy resin (manufactured by Adeka, Adeka Resin EP-4088S) Were mixed according to the composition shown in Table 1, and dissolved by heating at 170 degrees for 60 minutes to obtain an epoxy resin. The obtained epoxy resin was analyzed for structure by NMR and confirmed to be an epoxy resin represented by the formula (1).
（２）半導体用接着剤の製造
得られた式（１）で表されるエポキシ樹脂、酸無水物硬化剤（ジャパンエポキシレジン社製、ＹＨ３０６）、イミダゾール系硬化促進剤（四国化成工業社製、２ＭＡＯＫ−ＰＷ）、無機充填材（トクヤマ社製、ＳＥ−８）及びカップリング剤（日鉱金属社製、ＳＰ−１０００）を表１に示す組成に従って混合し、遊星攪拌機を用いて、攪拌、脱泡及びろ過（開口径２０μｍのポリエステルメッシュ、ＮＢＣ社製「Ｔ−ＮＯ５０８Ｔ」）を行うことにより、半導体用接着剤を得た。
(2) Manufacture of adhesive for semiconductor Epoxy resin represented by formula (1), acid anhydride curing agent (manufactured by Japan Epoxy Resin, YH306), imidazole curing accelerator (manufactured by Shikoku Kasei Kogyo Co., Ltd., 2MAOK-PW), an inorganic filler (manufactured by Tokuyama, SE-8) and a coupling agent (manufactured by Nikko Metals, SP-1000) are mixed in accordance with the composition shown in Table 1, and are stirred and removed using a planetary stirrer. By performing foaming and filtration (polyester mesh having an opening diameter of 20 μm, “T-NO508T” manufactured by NBC), an adhesive for semiconductor was obtained.
（実施例２〜７）
表１に示す組成に従って添加物の配合量を変えたこと以外は実施例１と同様にして、半導体用接着剤を得た。
なお、酸無水物硬化剤として、実施例１で用いたＹＨ３０６（ジャパンエポキシレジン社製）に加えて、ＹＨ３０７、ＹＨ３０９（以上、ジャパンエポキシレジン社製）、ＨＮＡ−１００（新日本理化社製）を、イミダゾール系硬化促進剤として、実施例１で用いた２ＭＡＯＫ−ＰＷ（四国化成工業社製）に加えて、２ＭＺＡ（四国化成工業社製）、Ｐ−０５０５（四国化成工業社製）を表１に示すように用いた。
(Examples 2 to 7)
A semiconductor adhesive was obtained in the same manner as in Example 1 except that the amount of additive was changed according to the composition shown in Table 1.
In addition to YH306 (manufactured by Japan Epoxy Resin Co., Ltd.) used in Example 1, as acid anhydride curing agents, YH307, YH309 (manufactured by Japan Epoxy Resin Co., Ltd.), HNA-100 (manufactured by Nippon Nippon Chemical Co., Ltd.) As an imidazole-based curing accelerator, in addition to 2MAOK-PW (manufactured by Shikoku Kasei Kogyo Co., Ltd.) used in Example 1, 2MZA (manufactured by Shikoku Kasei Kogyo Co., Ltd.), P-0505 (manufactured by Shikoku Kasei Kogyo Co., Ltd.) 1 was used.
（比較例１）
式（１）で表されるエポキシ樹脂の代わりに、ジシクロペンタジエン型エポキシ樹脂（アデカ社製、アデカレジンＥＰ−４０８８Ｓ）とＮＢＲ変性エポキシ樹脂（アデカ社製、ＥＰＲ−４０３３）とを用い、表１に示す組成に従って添加物の配合量を変えたこと以外は実施例１と同様にして、半導体用接着剤を得た。
(Comparative Example 1)
Instead of the epoxy resin represented by the formula (1), dicyclopentadiene type epoxy resin (manufactured by Adeka, Adeka Resin EP-4088S) and NBR modified epoxy resin (manufactured by Adeka, EPR-4033) were used. A semiconductor adhesive was obtained in the same manner as in Example 1 except that the blending amount of the additive was changed according to the composition shown in FIG.
（比較例２）
式（１）で表されるエポキシ樹脂の代わりに、ＮＢＲ変性エポキシ樹脂（アデカ社製、ＥＰＲ−４０３３）を用い、表１に示す組成に従って添加物の配合量を変えたこと以外は実施例１と同様にして、半導体用接着剤を得た。
(Comparative Example 2)
Example 1 except that an NBR-modified epoxy resin (manufactured by Adeka Co., EPR-4033) was used instead of the epoxy resin represented by the formula (1), and the amount of additive was changed according to the composition shown in Table 1. In the same manner, an adhesive for semiconductor was obtained.
（比較例３）
式（１）で表されるエポキシ樹脂の代わりに、ビスフェノールＡ型エポキシ樹脂（ジャパンエポキシレジン社製、ＹＬ９８０）を用い、表１に示す組成に従って添加物の配合量を変えたこと以外は実施例１と同様にして、半導体用接着剤を得た。
(Comparative Example 3)
Example except that bisphenol A type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., YL980) was used instead of the epoxy resin represented by the formula (1), and the amount of additives was changed according to the composition shown in Table 1. In the same manner as in Example 1, a semiconductor adhesive was obtained.
＜評価＞
実施例及び比較例で得られた半導体用接着剤について、以下の評価を行った。結果を表１に示す。
<Evaluation>
The following evaluation was performed about the adhesive agent for semiconductors obtained by the Example and the comparative example. The results are shown in Table 1.
（１）吸水率
得られた半導体用接着剤からなるペースト約１ｇを、ＰＥＴフィルムの裏面上に約５ｍｍの高さとなるように塗布し、１１０度で０．５時間、次いで、１７０度で１時間硬化させた。得られた硬化物を温度摂氏８５度、湿度８５％の環境下に２４時間置いて吸水させ、吸水前後の硬化物の重量変化から下記式（Ａ）を用いて吸水率を算出した。
吸水率［％］＝｛（吸水後の硬化物重量［ｇ］）−（吸水前の硬化物重量［ｇ］）｝／ （吸水前の硬化物重量［ｇ］）×１００ （Ａ）
(1) Water absorption rate About 1 g of the paste composed of the obtained adhesive for semiconductor is applied on the back surface of the PET film so as to have a height of about 5 mm, 1 hour at 110 degrees and then 0.5 hours. Cured for hours. The obtained cured product was placed in an environment of 85 degrees Celsius and 85% humidity for 24 hours to absorb water, and the water absorption was calculated from the change in weight of the cured product before and after water absorption using the following formula (A).
Water absorption [%] = {(cured material weight [g] after water absorption) − (cured material weight [g] before water absorption)} / (cured material weight [g] before water absorption) × 100 (A)
（２）柔軟性
ＰＥＴフィルムの裏面上に耐熱テープで長さ約５ｃｍ、幅約３ｍｍ、高さ約０．６ｍｍの型を作製し、この型に、得られた半導体用接着剤からなるペーストを流し込み、流し込んだ面を水平にした後、１１０度で０．５時間、次いで、１７０度で１時間硬化させた。
得られた硬化物について、粘弾性測定装置（アイティー計測制御社製、商品名「ＤＶＡ−２００」）を用いて、昇温速度１０℃／分、引っ張り、つかみ幅２４ｍｍ、１０Ｈｚで２７０℃まで昇温させて、２５℃及び２７０℃にて動的粘弾性測定を行うことにより、柔軟性を評価した。
(2) A mold having a length of about 5 cm, a width of about 3 mm, and a height of about 0.6 mm is prepared on the back surface of the flexible PET film with a heat-resistant tape, and the obtained paste made of an adhesive for semiconductor is applied to the mold. After pouring and leveling the poured surface, it was cured at 110 degrees for 0.5 hours and then at 170 degrees for 1 hour.
About the obtained hardened | cured material using a viscoelasticity measuring apparatus (The product made from IT measurement control company, brand name "DVA-200"), temperature rising rate 10 degree-C / min, tension | pulling, grip width 24mm, 270 degreeC at 10 Hz The temperature was raised and the dynamic viscoelasticity measurement was performed at 25 ° C. and 270 ° C. to evaluate the flexibility.
（３）耐リフロー性
ＦＲ−４のガラスエポキシ基板（１０ｍｍ×１０ｍｍ×０．２ｍｍ厚）とガラスチップ（松浪硝子工業社製、１０ｍｍ×１０ｍｍ）とを、得られた半導体用接着剤を用いて１１０度で０．５時間、次いで、１７０度で１時間硬化させることにより接着した。
得られた硬化物を温度摂氏８５度、湿度８５％の環境下に２４時間置いて吸水させた後、リフロー装置（日本ＡＮＴＯＭ社製、「ＵＮＩ−５０１６Ｆ」）を用いて、最高温度２７０度のリフロー工程（１８５℃１分、１８０℃２分、２７０℃１分、及び、１４０℃１分のサイクル）を３回行った。この操作を、合計６つのサンプルについて行った。
リフロー工程後、チップ−接着剤−基板の剥離やボイドの発生を目視により観察し、６つのサンプル全てにおいてリフロー工程後に剥離やボイドが観察されなかった場合を「○」と、少なくとも１つのサンプルにリフロー工程後に剥離やボイドが観察された場合を「×」として耐リフロー性を評価した。
(3) Reflow resistant FR-4 glass epoxy substrate (10 mm × 10 mm × 0.2 mm thickness) and glass chip (manufactured by Matsunami Glass Industrial Co., Ltd., 10 mm × 10 mm) using the obtained adhesive for semiconductor Adhesion was achieved by curing at 110 degrees for 0.5 hour and then at 170 degrees for 1 hour.
The obtained cured product was placed in an environment having a temperature of 85 degrees Celsius and a humidity of 85% for 24 hours to absorb water, and then using a reflow apparatus (“UNI-5016F” manufactured by ANTOM, Japan) with a maximum temperature of 270 degrees. The reflow process (a cycle of 185 ° C. for 1 minute, 180 ° C. for 2 minutes, 270 ° C. for 1 minute, and 140 ° C. for 1 minute) was performed three times. This operation was performed for a total of six samples.
After the reflow process, the chip-adhesive-substrate peeling and voids were observed visually. In all six samples, no peeling or voids were observed after the reflow process. The case where peeling and voids were observed after the reflow process was evaluated as “×” to evaluate the reflow resistance.
本発明によれば、硬化物の柔軟性が高く、かつ、吸水性が低く耐リフロー性に優れた半導体用接着剤を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the adhesive agent for semiconductors with which the softness | flexibility of hardened | cured material is high, water absorption is low, and it was excellent in reflow resistance can be provided.
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