JP2005162826A - Sealing resin composition and resin-sealed semiconductor device - Google Patents

Sealing resin composition and resin-sealed semiconductor device Download PDF

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JP2005162826A
JP2005162826A JP2003401755A JP2003401755A JP2005162826A JP 2005162826 A JP2005162826 A JP 2005162826A JP 2003401755 A JP2003401755 A JP 2003401755A JP 2003401755 A JP2003401755 A JP 2003401755A JP 2005162826 A JP2005162826 A JP 2005162826A
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resin composition
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resin
epoxy resin
chemical formula
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Yuzuru Wada
譲 和田
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Kyocera Chemical Corp
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
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    • H01L2924/0002Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a sealing resin composition which has excellent flame retardancy without substantially using a halogen-based flame retardant and an antimony compound, and has a low contracting property and a low moisture-absorbing property. <P>SOLUTION: The sealing resin composition containing (a) an epoxy resin, (b) a phenolic resin curing agent, (c) a curing accelerator, (d) an inorganic filler, and (e) a coupling agent as essential components is characterized in that (a) the epoxy resin contains an epoxy resin represented by the formula (1) [(n) is an integer of ≥1] and an epoxy resin represented by formula (2) [(m) and (n) are each an integer of ≥1; R is an alkyl] and having a number-average mol. wt. of ≥1,500 as essential components and that (b) the phenolic resin curing agent contains a phenolic resin curing agent represented by formula (3) [(n) is an integer of ≥1] as an essential component. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

本発明は封止用樹脂組成物および樹脂封止型半導体装置に係り、特にハロゲン系難燃剤およびアンチモン化合物を使用せずに優れた難燃性を有し、低収縮かつ低吸湿の封止用樹脂組成物およびそれを利用した樹脂封止型半導体装置に関する。   The present invention relates to a sealing resin composition and a resin-encapsulated semiconductor device, and particularly has excellent flame retardancy without using a halogen-based flame retardant and an antimony compound, and has a low shrinkage and low moisture absorption. The present invention relates to a resin composition and a resin-encapsulated semiconductor device using the same.

電子機器の小型化、軽量化、高性能化により、半導体素子の高集積化及び小型化が進み、半導体装置の表面実装化が進んでいる。また、エリア実装型半導体装置が開発され、従来の表面実装型半導体装置からエリア実装型半導体装置への移行が進んでいる。   With the miniaturization, weight reduction, and performance enhancement of electronic devices, semiconductor elements have been highly integrated and miniaturized, and semiconductor devices have been surface-mounted. In addition, area mounting type semiconductor devices have been developed, and the transition from conventional surface mounting type semiconductor devices to area mounting type semiconductor devices is progressing.

エリア実装型半導体装置としてはBGA(BallGrid Array)、あるいは、さらに小型化されたCSP(Chip Scale Package)等が代表的なものとして挙げられる。これらは、従来のQFP(Quad Flat Package)、SOP(Small Outline Package)に代表される表面実装型半導体装置では限界に近づいている多ピン化・高速化への要求に対応するために開発されたものである。   Typical examples of the area mounting type semiconductor device include a BGA (Ball Grid Array) or a further downsized CSP (Chip Scale Package). These were developed to meet the demand for higher pin counts and higher speeds that are approaching the limits of conventional surface mount semiconductor devices such as QFP (Quad Flat Package) and SOP (Small Outline Package). Is.

エリア実装型半導体装置は、BT樹脂/銅箔回路基板(ビスマレイミド・トリアジン樹脂/ガラスクロス基板)に代表される硬質回路基板、あるいは、ポリイミド樹脂フィルム/銅箔回路基板に代表されるフレキシブル回路基板の片面上に半導体素子が搭載され、その半導体素子搭載面、すなわち基板の片面のみがエポキシ樹脂組成物等で成形・封止されている。   Area mounting type semiconductor devices are BT resin / copper foil circuit board (bismaleimide / triazine resin / glass cloth board) or a hard circuit board or polyimide resin film / copper foil circuit board. A semiconductor element is mounted on one side, and only the semiconductor element mounting surface, that is, one side of the substrate is molded and sealed with an epoxy resin composition or the like.

半導体素子を搭載する基板としては、上記有機基板以外にもリードフレーム等の金属基板を用いる構造も開発されている。また、基板の半導体素子搭載面の反対面には半田ボールが2次元的に並列して形成され、実装用回路基板との接合が可能となるように構成されている。   As a substrate for mounting a semiconductor element, a structure using a metal substrate such as a lead frame in addition to the organic substrate has been developed. Also, solder balls are two-dimensionally formed in parallel on the surface opposite to the semiconductor element mounting surface of the substrate so that it can be joined to the circuit board for mounting.

すなわち、エリア実装型半導体装置は基板の半導体素子搭載面側のみをエポキシ樹脂組成物で封止し、半田ボール形成面側は実質的に封止しないという片面封止構造となっている。なお、リードフレーム等の金属基板等においては半田ボール形成面に数十μm程度の封止樹脂層が存在することがあるが、半導体素子搭載面では数百μmから数mm程度の封止樹脂層が形成されるため、実質的に片面封止構造となっている。   That is, the area mounting type semiconductor device has a single-side sealing structure in which only the semiconductor element mounting surface side of the substrate is sealed with the epoxy resin composition, and the solder ball forming surface side is not substantially sealed. A metal substrate such as a lead frame may have a sealing resin layer of about several tens of μm on the solder ball forming surface, but a sealing resin layer of about several hundred μm to several mm on the semiconductor element mounting surface. Therefore, it has a substantially single-sided sealing structure.

エリア実装型半導体装置では片面封止構造となっていることから、有機基板、金属基板とエポキシ樹脂組成物の硬化物との間の熱膨張・熱収縮の不整合ならびにエポキシ樹脂組成物の成形硬化時の硬化収縮による影響を受けやすく、封止直後から反りが発生しやすくなっている。   Since the area mounting type semiconductor device has a single-sided sealing structure, thermal expansion / shrinkage mismatch between the organic substrate, metal substrate and the cured epoxy resin composition, and molding / curing of the epoxy resin composition It is easily affected by the curing shrinkage at the time, and warpage is likely to occur immediately after sealing.

特に、半導体装置を実装用回路基板上に半田接合で実装する際には200℃以上の加熱工程を経るため、この工程において半導体装置に反りが発生し、多数の半田ボールが平坦とならず、半導体装置の一部が実装用回路基板から浮き上がってしまい電気的接合の信頼性が低下するという課題がある。   In particular, when a semiconductor device is mounted on a circuit board for mounting by solder bonding, a heating process of 200 ° C. or higher is performed. Therefore, the semiconductor device is warped in this process, and a large number of solder balls are not flattened. There is a problem that a part of the semiconductor device is lifted from the circuit board for mounting and the reliability of electrical connection is lowered.

片面封止構造の半導体装置の反りを低減するものとして、例えば特定の多官能型エポキシ樹脂と多官能型フェノール樹脂とを組み合わせ、無機充填材の配合量を調整することにより反りを低減する方法が提案されている(例えば、特許文献1参照。)。また、片面封止構造の半導体装置の反りを低減するものとして、例えばトリフェノールメタン型エポキシ樹脂とトリフェノールメタン型フェノール樹脂を樹脂成分とするエポキシ樹脂組成物が提案されている(例えば、特許文献2参照。)。   As a method for reducing the warpage of a semiconductor device with a single-sided sealing structure, for example, there is a method of reducing warpage by combining a specific polyfunctional epoxy resin and a polyfunctional phenol resin and adjusting the blending amount of an inorganic filler. It has been proposed (see, for example, Patent Document 1). Moreover, as what reduces the curvature of the semiconductor device of a single-side sealing structure, the epoxy resin composition which uses a triphenolmethane type epoxy resin and a triphenolmethane type phenol resin as a resin component, for example is proposed (for example, patent documents) 2).

しかしながら、例えばトリフェノールメタン型エポキシ樹脂とトリフェノールメタン型フェノール樹脂を樹脂成分とするエポキシ樹脂組成物は、Tgが高く、硬化性、熱時曲げ強度は優れているが、エポキシ樹脂組成物の溶融粘度が比較的高いため無機充填材を高充填化することができず、低吸湿化が不十分となり、耐リフロー性に課題がある。   However, for example, an epoxy resin composition comprising a triphenolmethane type epoxy resin and a triphenolmethane type phenol resin as a resin component has a high Tg, excellent curability and bending strength when heated, but the epoxy resin composition is melted. Since the viscosity is relatively high, the inorganic filler cannot be highly filled, the moisture absorption is insufficient, and there is a problem in reflow resistance.

さらに、エポキシ樹脂組成物には低吸湿化に加えて、有機基板との良好な接着性も求められている。すなわち、半導体装置を赤外線リフロー、ベーパーフェイズソルダリング、半田浸漬等の手段により半田接合する場合、エポキシ樹脂組成物の硬化物ならびに有機基板からの吸湿により半導体装置内部に存在する水分が高温で急激に気化することによる応力で半導体装置にクラックが発生すると共に、半導体装置内部の有機基板の半導体素子搭載面とエポキシ樹脂組成物の硬化物との界面で剥離が発生することがある。   Furthermore, in addition to reducing moisture absorption, the epoxy resin composition is also required to have good adhesion to an organic substrate. That is, when a semiconductor device is soldered by means such as infrared reflow, vapor phase soldering, or solder dipping, the moisture present in the semiconductor device is rapidly increased at high temperatures due to moisture absorption from the cured epoxy resin composition and organic substrate. Cracks may occur in the semiconductor device due to the stress caused by vaporization, and peeling may occur at the interface between the semiconductor element mounting surface of the organic substrate inside the semiconductor device and the cured product of the epoxy resin composition.

また、エポキシ樹脂組成物中には、難燃性を確保するために難燃剤として塩素、臭素等のハロゲン元素を含むハロゲン系難燃剤やアンチモン化合物(通常、三酸化アンチモン)が含有されている(例えば、特許文献3参照。)。しかしながら、環境・衛生の点からハロゲン系難燃剤、アンチモン化合物を使用しない難燃性に優れたエポキシ樹脂組成物が求められている。   In addition, the epoxy resin composition contains a halogen-based flame retardant containing a halogen element such as chlorine or bromine or an antimony compound (usually antimony trioxide) as a flame retardant in order to ensure flame retardancy ( For example, see Patent Document 3.) However, an epoxy resin composition excellent in flame retardancy that does not use a halogen-based flame retardant or an antimony compound is required from the viewpoint of environment and hygiene.

このため、水酸化アルミニウムや水酸化マグネシウム等の水酸化物、硼素系化合物が検討されているが、多量に配合しないと難燃性の効果が発現せず、不純物も多く耐湿性に問題があることから実用化されていない。   For this reason, hydroxides such as aluminum hydroxide and magnesium hydroxide, and boron-based compounds have been studied. However, if not added in a large amount, the flame-retardant effect is not manifested, and there are many impurities and there is a problem with moisture resistance. It has not been put to practical use.

これに対し、赤燐系の難燃剤は少量の添加で効果があり、エポキシ樹脂組成物の難燃化に有用であるが、赤燐は水分と反応しホスフィンや腐食性の燐酸を生じるため耐湿性に問題があり、耐湿性に対する要求が極めて厳しい半導体封止用のエポキシ樹脂組成物には使用できない。   In contrast, red phosphorus-based flame retardants are effective when added in small amounts, and are useful for making flame retardant epoxy resin compositions. However, red phosphorus reacts with moisture to produce phosphine and corrosive phosphoric acid, so it is resistant to moisture. It cannot be used for an epoxy resin composition for semiconductor encapsulation, which has a problem in properties and has extremely strict requirements for moisture resistance.

このため、赤燐粒子を水酸化アルミニウム、金属酸化物、その他無機化合物、熱硬化性樹脂等の有機化合物で被膜し、赤燐の安定化を図っているが(例えば、特許文献4参照。)、依然耐湿性に問題があり、ハロゲン系難燃剤、アンチモン化合物を使用せずに難燃性、耐湿性を両立できるエポキシ樹脂組成物は得られていない。   For this reason, red phosphorus particles are coated with an organic compound such as aluminum hydroxide, metal oxide, other inorganic compounds, and a thermosetting resin to stabilize red phosphorus (see, for example, Patent Document 4). However, there is still a problem in moisture resistance, and an epoxy resin composition that can achieve both flame retardancy and moisture resistance without using a halogen flame retardant and an antimony compound has not been obtained.

環境・衛生の点以外でも、ハロゲン系難燃剤、アンチモン化合物を含むエポキシ樹脂組成物で封止した半導体装置を高温下で保管した場合、これらの難燃性成分から熱分解したハロゲン化物が遊離し、半導体素子の接合部を腐食し、半導体装置の信頼性を損なうという不具合が知られており、この様なことからもハロゲン系難燃剤、アンチモン化合物を使用しない難燃性に優れたエポキシ樹脂組成物が求められている。
特開2003−128878号公報 特開2000−031344号公報 特開平05−003269号公報 特開平11−279379号公報
In addition to environmental and sanitary points, when semiconductor devices sealed with epoxy resin compositions containing halogenated flame retardants and antimony compounds are stored at high temperatures, the thermally decomposed halides are released from these flame retardant components. The epoxy resin composition with excellent flame retardancy that does not use halogen flame retardants and antimony compounds is known to corrode the joints of semiconductor elements and impair the reliability of semiconductor devices. Things are sought.
JP 2003-128878 A JP 2000-031344 A JP 05-003269 A JP-A-11-279379

樹脂封止型半導体装置においては、実装時の反りやクラックの発生が抑制されていることが求められている。そして、このような樹脂封止型半導体装置の封止に用いられる封止用樹脂組成物においては、樹脂封止型半導体装置の反りやクラックの発生を抑制するために低収縮、低吸湿であることが求められ、また環境・衛生の面からハロゲン系難燃剤およびアンチモン化合物を使用しないことが求められている。しかしながら、従来の封止用樹脂組成物においては、これらの要求を満たすものは得られていない。   Resin-encapsulated semiconductor devices are required to suppress warping and cracking during mounting. And in the resin composition for sealing used for sealing of such a resin sealing type semiconductor device, in order to suppress generation | occurrence | production of the curvature and crack of a resin sealing type semiconductor device, it is low shrinkage and low moisture absorption. In view of environment and hygiene, it is required not to use halogenated flame retardants and antimony compounds. However, no conventional sealing resin composition has been obtained that satisfies these requirements.

本発明は上述したような課題を解決するためになされたものであって、低収縮、低吸湿であり、実質的にハロゲン系難燃剤およびアンチモン化合物を含まずに十分な難燃性を有する封止用樹脂組成物およびそれを利用した樹脂封止型半導体装置を提供することを目的としている。   The present invention has been made to solve the above-mentioned problems, and has a low shrinkage and a low moisture absorption, and has a sufficient flame retardancy substantially free from halogenated flame retardants and antimony compounds. An object of the present invention is to provide a stopping resin composition and a resin-encapsulated semiconductor device using the same.

本発明の封止用樹脂組成物は、(a)エポキシ樹脂、(b)フェノール樹脂硬化剤、(c)硬化促進剤、(d)無機充填材および(e)カップリング剤を必須成分とする封止用樹脂組成物であって、前記(a)エポキシ樹脂は下記化学式(1)で示されるエポキシ樹脂および下記化学式(2)で示される数平均分子量が1500以上のエポキシ樹脂を必須成分として含み、

Figure 2005162826
(但し、nは1以上の整数を表す)
Figure 2005162826
(但し、m、nは1以上の整数を、Rはアルキル基を表す)
前記(b)フェノール樹脂硬化剤は下記化学式(3)で示されるフェノール樹脂硬化剤を必須成分として含み、
Figure 2005162826
(但し、nは1以上の整数を表す)
実質的にハロゲン系難燃剤およびアンチモン化合物を含まないことを特徴とする。 The sealing resin composition of the present invention comprises (a) an epoxy resin, (b) a phenol resin curing agent, (c) a curing accelerator, (d) an inorganic filler, and (e) a coupling agent as essential components. A sealing resin composition, wherein the (a) epoxy resin includes an epoxy resin represented by the following chemical formula (1) and an epoxy resin having a number average molecular weight of 1,500 or more represented by the following chemical formula (2) as essential components: ,
Figure 2005162826
(However, n represents an integer of 1 or more)
Figure 2005162826
(However, m and n are integers of 1 or more, and R represents an alkyl group.)
The (b) phenol resin curing agent contains a phenol resin curing agent represented by the following chemical formula (3) as an essential component,
Figure 2005162826
(However, n represents an integer of 1 or more)
It is characterized by being substantially free of halogenated flame retardants and antimony compounds.

本発明の樹脂封止型半導体装置は、基板の片面に半導体素子が搭載され、前記半導体素子が搭載された前記基板の片面のみを樹脂組成物で封止してなる樹脂封止型半導体装置であって、前記樹脂組成物として上述した封止用樹脂組成物を用いたことを特徴とする。   The resin-encapsulated semiconductor device of the present invention is a resin-encapsulated semiconductor device in which a semiconductor element is mounted on one side of a substrate and only one side of the substrate on which the semiconductor element is mounted is sealed with a resin composition. In addition, the sealing resin composition described above is used as the resin composition.

本発明においては、封止用樹脂組成物に特定の(a)エポキシ樹脂および特定の(b)フェノール樹脂硬化剤を必須成分として含有させることにより、実質的にハロゲン系難燃剤およびアンチモン化合物を含まずにその硬化物に十分な難燃性を付与し、低収縮、低吸湿なものとすることができる。   In the present invention, the halogen-containing flame retardant and the antimony compound are substantially contained by including the specific (a) epoxy resin and the specific (b) phenol resin curing agent as essential components in the sealing resin composition. Therefore, sufficient flame retardancy can be imparted to the cured product, and low shrinkage and low moisture absorption can be achieved.

また、本発明の樹脂封止型半導体装置においては、上述したような封止用樹脂組成物により封止することにより耐リフロー性に優れ、反りが抑制され、特に片面封止構造の樹脂封止型半導体装置とした場合にその実装時等における反りを有効に抑制することができる。   Moreover, in the resin-encapsulated semiconductor device of the present invention, by sealing with the above-described encapsulating resin composition, it has excellent reflow resistance and warpage is suppressed. In the case of a type semiconductor device, it is possible to effectively suppress warping during mounting.

本発明の封止用樹脂組成物は、(a)エポキシ樹脂、(b)フェノール樹脂硬化剤、(c)硬化促進剤、(d)無機充填材および(e)カップリング剤を必須成分として含有するものである。以下、各成分について説明する。   The sealing resin composition of the present invention contains (a) an epoxy resin, (b) a phenol resin curing agent, (c) a curing accelerator, (d) an inorganic filler, and (e) a coupling agent as essential components. To do. Hereinafter, each component will be described.

本発明に用いられる(a)エポキシ樹脂は、少なくとも下記化学式(1)で示されるエポキシ樹脂および下記化学式(2)で示される数平均分子量が1500以上のエポキシ樹脂からなるものである。(a)エポキシ樹脂は、信頼性を確保するため樹脂中に含まれる塩素量が1000ppm以下であることが好ましい。   The (a) epoxy resin used in the present invention comprises at least an epoxy resin represented by the following chemical formula (1) and an epoxy resin having a number average molecular weight represented by the following chemical formula (2) of 1500 or more. (A) The epoxy resin preferably has a chlorine content of 1000 ppm or less in order to ensure reliability.

Figure 2005162826
(但し、nは1以上の整数を表す)
Figure 2005162826
(However, n represents an integer of 1 or more)

Figure 2005162826
(但し、m、nは1以上の整数を、Rはアルキル基を表す)
Figure 2005162826
(However, m and n are integers of 1 or more, and R represents an alkyl group.)

(a)エポキシ樹脂のうち、化学式(1)で示されるエポキシ樹脂は、エポキシ当量が200〜350の範囲のものが好ましく、250〜320の範囲のものがより好ましい。また、化学式(1)で示されるエポキシ樹脂は、軟化温度が40〜100℃の範囲のものが好ましく、軟化温度が50〜75℃の範囲のものがより好ましい。   (A) Among the epoxy resins, the epoxy resin represented by the chemical formula (1) preferably has an epoxy equivalent in the range of 200 to 350, and more preferably in the range of 250 to 320. The epoxy resin represented by the chemical formula (1) preferably has a softening temperature in the range of 40 to 100 ° C, and more preferably has a softening temperature in the range of 50 to 75 ° C.

さらに、化学式(1)で示されるエポキシ樹脂は、ICI粘度計(コーン&プレート型)により測定される溶融粘度(150℃)が0.01〜0.3Pa・sの範囲のものが好ましく、0.01〜0.15Pa・sの範囲のものがより好ましい。   Furthermore, the epoxy resin represented by the chemical formula (1) preferably has a melt viscosity (150 ° C.) measured by an ICI viscometer (cone & plate type) in the range of 0.01 to 0.3 Pa · s. A range of 0.01 to 0.15 Pa · s is more preferable.

このような化学式(1)で示されるエポキシ樹脂としては、例えばNC−3000P(日本化薬株式会社製、エポキシ当量273、軟化温度57℃、溶融粘度(150℃)0.07Pa・s)、NC−3000S(日本化薬株式会社製、エポキシ当量282、軟化温度59℃、溶融粘度(150℃)0.09Pa・s)等が挙げられる。   Examples of the epoxy resin represented by the chemical formula (1) include NC-3000P (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 273, softening temperature 57 ° C., melt viscosity (150 ° C.) 0.07 Pa · s), NC -3000S (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 282, softening temperature 59 ° C., melt viscosity (150 ° C.) 0.09 Pa · s) and the like.

(a)エポキシ樹脂のうち、化学式(2)で示されるエポキシ樹脂はブタジエンの繰り返し構造をもつ液状タイプのエポキシ樹脂であり、主として封止用樹脂組成物の収縮率を低減するために加えられるものである。   (A) Among the epoxy resins, the epoxy resin represented by the chemical formula (2) is a liquid type epoxy resin having a repeating structure of butadiene, and is mainly added to reduce the shrinkage rate of the sealing resin composition. It is.

化学式(2)で示されるエポキシ樹脂は、数平均分子量が1500以上であるものが好ましく、1700以上3000未満であればより好ましい。数平均分子量が1500未満であると成形後の収縮率が大きくなり、3000以上であると粘度が大きくなり成形性が低下するため好ましくない。   The epoxy resin represented by the chemical formula (2) preferably has a number average molecular weight of 1500 or more, more preferably 1700 or more and less than 3000. When the number average molecular weight is less than 1500, the shrinkage ratio after molding increases, and when it is 3000 or more, the viscosity increases and the moldability deteriorates.

また、化学式(2)で示されるエポキシ樹脂は、エポキシ当量が200〜280の範囲のものが好ましく、220〜260の範囲のものがより好ましい。また、化学式(2)で示されるエポキシ樹脂は、ICI粘度計(コーン&プレート型)により測定される溶融粘度(25℃)が10〜70Pa・sの範囲のものが好ましく、20〜50Pa・sの範囲のものがより好ましい。このようなものとしては、例えばE−1800−6.5(日本石油化学株式会社製、エポキシ当量240、溶融粘度(25℃)30Pa・s)が挙げられる。   The epoxy resin represented by the chemical formula (2) preferably has an epoxy equivalent in the range of 200 to 280, and more preferably in the range of 220 to 260. The epoxy resin represented by the chemical formula (2) preferably has a melt viscosity (25 ° C.) measured by an ICI viscometer (cone & plate type) in the range of 10 to 70 Pa · s, and 20 to 50 Pa · s. The thing of the range of is more preferable. As such a thing, E-1800-6.5 (The Nippon Petrochemical Co., Ltd. make, epoxy equivalent 240, melt viscosity (25 degreeC) 30 Pa.s) is mentioned, for example.

また、本発明においてはその趣旨に反しない範囲で、化学式(1)で示されるエポキシ樹脂および化学式(2)で示されるエポキシ樹脂以外の他のエポキシ樹脂を併用してもよい。   In the present invention, an epoxy resin represented by the chemical formula (1) and an epoxy resin other than the epoxy resin represented by the chemical formula (2) may be used in combination without departing from the spirit of the invention.

他のエポキシ樹脂としては1分子中に2個以上のエポキシ基を有するものであれば特に限定されるものではなく、例えばフェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ナフトールのノボラック型エポキシ樹脂、ビスフェノールAのノボラック型エポキシ樹脂、ビスフェノールAのグリシジルエーテル、テトラ(ヒドロキシフェニル)アルカンのエポキシ化物、ビスヒドロキシビフェニル系エポキシ樹脂等が挙げられる。   Other epoxy resins are not particularly limited as long as they have two or more epoxy groups in one molecule. For example, phenol novolac type epoxy resins, cresol novolak type epoxy resins, naphthol novolak type epoxy resins, Examples thereof include bisphenol A novolac type epoxy resins, bisphenol A glycidyl ethers, epoxidized tetra (hydroxyphenyl) alkanes, and bishydroxybiphenyl type epoxy resins.

(a)エポキシ樹脂の含有量は、封止用樹脂組成物全体に対して5〜15重量%とすることが好ましい。5重量%未満であると封止用樹脂組成物の流動性等が低下するため好ましくなく、15重量%を超えると封止用樹脂組成物の硬化物の難燃性および耐クラック性が低下するため好ましくない。   (A) It is preferable that content of an epoxy resin shall be 5-15 weight% with respect to the whole resin composition for sealing. If it is less than 5% by weight, the fluidity of the encapsulating resin composition is lowered, which is not preferable. If it exceeds 15% by weight, the flame retardancy and crack resistance of the cured product of the encapsulating resin composition are lowered. Therefore, it is not preferable.

化学式(1)で示されるエポキシ樹脂と化学式(2)で示されるエポキシ樹脂とは、化学式(1)で示されるエポキシ樹脂の含有量に対する化学式(2)で示されるエポキシ樹脂の含有量の比(=化学式(2)で示されるエポキシ樹脂の含有量/化学式(1)で示されるエポキシ樹脂の含有量)が0.05〜0.5であれば好ましく、0.1〜0.3であればより好ましい。上記比が0.05未満であると封止用樹脂組成物の収縮率が大きくなるため好ましくなく、0.5を超えると硬化物の難燃性が維持できなくなるため好ましくない。   The epoxy resin represented by the chemical formula (1) and the epoxy resin represented by the chemical formula (2) are the ratio of the content of the epoxy resin represented by the chemical formula (2) to the content of the epoxy resin represented by the chemical formula (1) ( The content of the epoxy resin represented by the chemical formula (2) / the content of the epoxy resin represented by the chemical formula (1) is preferably 0.05 to 0.5, and preferably 0.1 to 0.3. More preferred. If the ratio is less than 0.05, the shrinkage ratio of the encapsulating resin composition increases, which is not preferable. If the ratio exceeds 0.5, the flame retardancy of the cured product cannot be maintained, which is not preferable.

また、化学式(1)および化学式(2)で示されるエポキシ樹脂と共に、他のエポキシ樹脂を併用する場合、他のエポキシ樹脂の含有量は(a)エポキシ樹脂全体の20重量%以下が好ましく、10重量%以下であればより好ましい。他のエポキシ樹脂の含有量が20重量%を超えると封止用樹脂組成物の収縮率が大きくなり、また硬化物の難燃性も維持できなくなるため好ましくない。   When other epoxy resins are used in combination with the epoxy resins represented by the chemical formulas (1) and (2), the content of the other epoxy resins is preferably 20% by weight or less of the total epoxy resin (10). It is more preferable if it is not more than% by weight. If the content of the other epoxy resin exceeds 20% by weight, the shrinkage rate of the sealing resin composition increases, and the flame retardancy of the cured product cannot be maintained, which is not preferable.

本発明に用いられる(b)フェノール樹脂硬化剤は、少なくとも下記化学式(3)で示されるフェノール樹脂硬化剤を含むものである。(b)フェノール樹脂硬化剤は信頼性を確保するため、含まれるフリーのフェノール類の濃度が1重量%以下であることが好ましい。   The (b) phenol resin curing agent used in the present invention contains at least a phenol resin curing agent represented by the following chemical formula (3). (B) The phenol resin curing agent preferably has a concentration of free phenols of 1% by weight or less in order to ensure reliability.

Figure 2005162826
(但し、nは1以上の整数を表す)
Figure 2005162826
(However, n represents an integer of 1 or more)

化学式(3)で示されるフェノール樹脂硬化剤は、特にそのフェノール性水酸基当量が170〜230、好ましくは190〜220の範囲のもの、あるいは、軟化温度が40〜100℃、好ましくは55〜90℃の範囲のものが好ましい。   The phenol resin curing agent represented by the chemical formula (3) has a phenolic hydroxyl group equivalent of 170 to 230, preferably 190 to 220, or a softening temperature of 40 to 100 ° C, preferably 55 to 90 ° C. The thing of the range of is preferable.

このような化学式(3)で示されるフェノール樹脂硬化剤としては、例えばMEH−7851H(明和化成株式会社製、水酸基当量199、軟化温度82℃)、MEH−7851M(明和化成株式会社製、水酸基当量199、軟化温度76℃)、MEH−7851S(明和化成株式会社製、水酸基当量198、軟化温度74℃)、MEH−7851SS(明和化成株式会社製、水酸基当量198、軟化温度67℃)等が挙げられる。   Examples of the phenol resin curing agent represented by the chemical formula (3) include MEH-7851H (Maywa Kasei Co., Ltd., hydroxyl equivalent 199, softening temperature 82 ° C.), MEH-7851M (Maywa Kasei Co., Ltd., hydroxyl equivalent). 199, softening temperature 76 ° C.), MEH-7851S (Maywa Kasei Co., Ltd., hydroxyl equivalent 198, softening temperature 74 ° C.), MEH-7851SS (Maywa Kasei Co., Ltd., hydroxyl equivalent 198, softening temperature 67 ° C.) and the like. It is done.

(b)フェノール樹脂硬化剤においては、化学式(3)で示されるフェノール樹脂硬化剤と共に、他のフェノール樹脂硬化剤を併用してもよい。他のフェノール樹脂硬化剤としては、例えばフェノールノボラック樹脂、クレゾールノボラック樹脂、ジシクロペンタジエン変性フェノール樹脂、パラキシレン変性フェノール樹脂、フェノール類とベンズアルデヒド、ナフチルアルデヒド等との縮合物、トリフェノールメタン化合物、多官能型フェノール樹脂等が挙げられる。   (B) In the phenol resin curing agent, other phenol resin curing agents may be used in combination with the phenol resin curing agent represented by the chemical formula (3). Other phenol resin curing agents include, for example, phenol novolac resins, cresol novolac resins, dicyclopentadiene modified phenol resins, paraxylene modified phenol resins, condensates of phenols with benzaldehyde, naphthyl aldehyde, etc., triphenolmethane compounds, Examples thereof include functional phenol resins.

(b)フェノール樹脂硬化剤は、フェノール樹脂硬化剤のフェノール性水酸基数とエポキシ樹脂のエポキシ基数の比(=フェノール性水酸基数/エポキシ基数)が0.4〜1.5の範囲になるように添加量を調整することが好ましい。上記比が0.4未満では硬化反応が充分に起こりにくくなり、上記比が1.5を超えると硬化物の特性、特に耐湿性が劣化しやすくなる。   (B) The phenol resin curing agent is such that the ratio of the number of phenolic hydroxyl groups of the phenol resin curing agent to the number of epoxy groups of the epoxy resin (= phenolic hydroxyl group number / epoxy group number) is in the range of 0.4 to 1.5. It is preferable to adjust the addition amount. When the ratio is less than 0.4, the curing reaction is not likely to occur. When the ratio exceeds 1.5, the properties of the cured product, particularly moisture resistance, is likely to deteriorate.

また、(b)フェノール樹脂硬化剤として化学式(3)で示されるフェノール樹脂硬化剤と共に他のフェノール樹脂硬化剤を併用する場合、(b)フェノール樹脂硬化剤における他のフェノール樹脂硬化剤の含有量は30重量%以下とすることが好ましく、20重量%以下とすればより好ましい。他のフェノール樹脂硬化剤の含有量が30重量%を超えると硬化物の難燃性が維持できなくなるため好ましくない。   When (b) another phenol resin curing agent is used in combination with the phenol resin curing agent represented by the chemical formula (3) as the phenol resin curing agent, (b) the content of the other phenol resin curing agent in the phenol resin curing agent Is preferably 30% by weight or less, and more preferably 20% by weight or less. If the content of the other phenol resin curing agent exceeds 30% by weight, the flame retardancy of the cured product cannot be maintained, which is not preferable.

本発明に用いられる(c)硬化促進剤としては、フェノール樹脂を用いてエポキシ樹脂を硬化する際に硬化促進剤剤として使用されることが知られているものであれば特に制限されるものではない。   The (c) curing accelerator used in the present invention is not particularly limited as long as it is known to be used as a curing accelerator when a phenol resin is used to cure an epoxy resin. Absent.

このようなものとしては、例えばトリメチルホスフィン、トリエチルホスフィン、トリブチルホスフィン、トリフェニルホスフィン、トリ(P−メチルフェニル)ホスフィン、トリ(ノニルフェニルホスフィン)、メチルジフェニルホスフィン、ジブチルフェニルホスフィン、トリシクロヘキシルホスフィン、1,2−ビス(ジフェニルホスフィノ)エタン、ビス(ジフェニルホスフィノ)メタンなどの有機ホスフィン化合物、2−メチルイミダゾール、2,4−ジメチルイミダゾール、2−エチル−4−メチルイミダゾール、2−フェニルイミダゾール、2−フェニル−4−メチルイミダゾール、2−ヘプタデシルイミダゾール等のイミダゾール化合物またはその誘導体、DBU(1,8−ジアザビシクロ(5,4,0)ウンデセン−7)またはそのフェノール塩等が挙げられる。これらの硬化促進剤剤は必要に応じて組み合わせて用いてもよい。   Such as, for example, trimethylphosphine, triethylphosphine, tributylphosphine, triphenylphosphine, tri (P-methylphenyl) phosphine, tri (nonylphenylphosphine), methyldiphenylphosphine, dibutylphenylphosphine, tricyclohexylphosphine, 1 , 2-bis (diphenylphosphino) ethane, organic phosphine compounds such as bis (diphenylphosphino) methane, 2-methylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, Imidazole compounds such as 2-phenyl-4-methylimidazole and 2-heptadecylimidazole or derivatives thereof, DBU (1,8-diazabicyclo (5,4,0) undecene-7) Other its phenolic salts. These curing accelerator agents may be used in combination as necessary.

(c)硬化促進剤の含有量はそれぞれの触媒活性が異なるため一概にその好適量は決められないが、封止用樹脂組成物全体に対し0.1〜5重量%の範囲で含有させることが好ましい。硬化促進剤の含有量が0.1重量%未満では硬化性能が劣り、5重量%を超えると耐湿信頼性が低下する傾向があるため好ましくない。   (C) Since the content of the curing accelerator is different in each catalyst activity, its preferred amount cannot be determined in general, but it is contained in the range of 0.1 to 5% by weight with respect to the whole sealing resin composition. Is preferred. If the content of the curing accelerator is less than 0.1% by weight, the curing performance is inferior, and if it exceeds 5% by weight, the moisture resistance reliability tends to decrease, such being undesirable.

本発明に用いられる(d)無機充填材は封止用樹脂組成物の硬化物の収縮率、熱伝導率、吸湿性等の特性を改善、向上させる目的で配合されるものである。(d)無機充填材は最大粒径が100μm以下で平均粒径が1〜50μmの粉末状のものが適しており、最大粒径が75μm以下で平均粒径が5〜25μmであるとさらに好ましい。最大粒径が100μmを越えるか、あるいは平均粒径が50μmを超えると、狭部への充填が困難になるだけでなく、分散性が低下して成形品が不均一になる。また、平均粒径が1μm未満では、粘度が上昇し、成形性が不良となる。また、これらの粉末の形状は、できるだけ球状に近いものが、流動性、成形性、金型磨耗性などの観点からより好ましい。   The inorganic filler (d) used in the present invention is blended for the purpose of improving and improving properties such as shrinkage, thermal conductivity, hygroscopicity, etc. of the cured resin composition. (D) The inorganic filler is preferably in the form of a powder having a maximum particle size of 100 μm or less and an average particle size of 1 to 50 μm, more preferably a maximum particle size of 75 μm or less and an average particle size of 5 to 25 μm. . When the maximum particle size exceeds 100 μm or the average particle size exceeds 50 μm, not only is the filling of the narrow portion difficult, but the dispersibility is lowered and the molded product becomes non-uniform. On the other hand, when the average particle size is less than 1 μm, the viscosity increases and the moldability becomes poor. In addition, the shape of these powders is preferably as spherical as possible from the viewpoints of fluidity, moldability, mold wear, and the like.

このような(d)無機充填材としては、例えば溶融シリカ、結晶性シリカ、アルミナ、窒化ケイ素および窒化アルミウム等が挙げられ、これらは単独または2種以上混合して使用することができる。これらの中でも、コスト、特性の観点から、特に溶融シリカが好適に用いられる。   Examples of such (d) inorganic fillers include fused silica, crystalline silica, alumina, silicon nitride, and aluminum nitride, and these can be used alone or in combination of two or more. Among these, fused silica is particularly preferably used from the viewpoint of cost and characteristics.

(d)無機充填材の含有量は、封止用樹脂組成物全体に対し80〜90重量%とすることが好ましい。80重量%未満では封止用樹脂組成物の硬化物の難燃性および耐クラック性に劣り、90重量%を超えると封止用樹脂組成物の流動性が低下して成形性が低下するため好ましくない。   (D) It is preferable that content of an inorganic filler shall be 80 to 90 weight% with respect to the whole resin composition for sealing. If it is less than 80% by weight, the cured product of the encapsulating resin composition is inferior in flame retardancy and crack resistance, and if it exceeds 90% by weight, the fluidity of the encapsulating resin composition is lowered and moldability is lowered. It is not preferable.

本発明に用いられる(e)カップリング剤としては、無機充填材の表面処理に一般に使用されるものであれば特に制限されるものでないが、シリコン原子に結合したアルコキシ基を有するシラン化合物が好ましく、特に一級もしくは二級のアミンを有するシランカップリング剤が好ましい。これらのカップリング剤を用いることにより封止用樹脂組成物の成形性をより良好にすることができる。   The (e) coupling agent used in the present invention is not particularly limited as long as it is generally used for the surface treatment of inorganic fillers, but a silane compound having an alkoxy group bonded to a silicon atom is preferable. In particular, a silane coupling agent having a primary or secondary amine is preferred. By using these coupling agents, the moldability of the sealing resin composition can be further improved.

具体的には、γ−アミノプロピルトリエトキシシラン、γ−アミノプロピルトリメトキシシラン、N−β−(アミノエチル)−γ−アミノプロピルトリメトキシシラン、γ−ウレイドプロピルトリエトキシシラン、γ−N−フェニルアミノプロピルトリメトキシシラン等があけられる。これらのアミノシランは単独もしくは2種以上混合して使用することができ、さらにアミノシラン以外のカップリング剤を併用してもかまわない。   Specifically, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ-N- Phenylaminopropyltrimethoxysilane and the like are opened. These aminosilanes can be used alone or in combination of two or more, and a coupling agent other than aminosilane may be used in combination.

(e)カップリング剤の含有量は、封止用樹脂組成物の0.01〜5重量%であることが好ましい。0.01重量%未満では成形性の向上に効果がなく、5重量%を超えると信頼性に悪影響を与え好ましくない。   (E) It is preferable that content of a coupling agent is 0.01 to 5 weight% of the resin composition for sealing. If it is less than 0.01% by weight, there is no effect in improving moldability, and if it exceeds 5% by weight, the reliability is adversely affected, which is not preferable.

本発明の封止用樹脂組成物においては、上記(a)エポキシ樹脂、(b)フェノール樹脂硬化剤、(c)硬化促進剤、(d)無機充填材および(e)カップリング剤と共に、(f)シリコーン化合物および(g)密着付与剤を併用することが好ましい。   In the sealing resin composition of the present invention, together with the above (a) epoxy resin, (b) phenol resin curing agent, (c) curing accelerator, (d) inorganic filler and (e) coupling agent, It is preferable to use f) a silicone compound and (g) an adhesion-imparting agent in combination.

本発明に用いられる(f)シリコーン化合物は下記化学式(4)で示されるものであり、封止用樹脂組成物の成形性の向上、硬化物の接着性の向上、低応力化等のために加えられるものである。化学式(4)で示されるシリコーン化合物はシロキサン骨格の片末端、両末端または側鎖に反応基であるアミノ基、カルボキシル基、エポキシ基およびメチル基等を有するものである。反応基は、両末端または側鎖にあればより好ましい。   The silicone compound (f) used in the present invention is represented by the following chemical formula (4) for improving the moldability of the sealing resin composition, improving the adhesiveness of the cured product, reducing stress, etc. It is what is added. The silicone compound represented by the chemical formula (4) has a reactive group such as an amino group, a carboxyl group, an epoxy group, and a methyl group at one end, both ends, or side chains of the siloxane skeleton. It is more preferable that the reactive group is at both ends or side chains.

Figure 2005162826
(但し、l、m、nは0または1以上の整数を、Rはアルキル基を、Aはアミノ基、カルボキシル基、エポキシ基およびメチル基から選択される1価の官能基を表す)
Figure 2005162826
(However, l, m, and n are 0 or an integer of 1 or more, R is an alkyl group, and A is a monovalent functional group selected from an amino group, a carboxyl group, an epoxy group, and a methyl group)

化学式(4)で示されるシリコーン化合物のアミン当量は1000〜7000であることが好ましく、1500〜6500であるとより好ましい。アミン当量が1000未満では成形性の向上が不十分となり、逆にアミン当量が7000を超えると接着性が低下するようになるため好ましくない。   The amine equivalent of the silicone compound represented by the chemical formula (4) is preferably 1000 to 7000, and more preferably 1500 to 6500. If the amine equivalent is less than 1000, the moldability is not sufficiently improved. Conversely, if the amine equivalent exceeds 7000, the adhesiveness is lowered, which is not preferable.

(f)シリコーン化合物の含有量は、封止用樹脂組成物の0.01〜5重量%であることが好ましい。0.01重量%未満では成形性、接着性の向上に効果がなく、5重量%を超えると硬化物の信頼性に悪影響を与えるため好ましくない。   (F) It is preferable that content of a silicone compound is 0.01 to 5 weight% of the resin composition for sealing. If it is less than 0.01% by weight, there is no effect in improving moldability and adhesion, and if it exceeds 5% by weight, the reliability of the cured product is adversely affected.

本発明に用いられる(g)密着付与剤は、下記化学式(5)で示されるものである。この(g)密着付与剤は、上記(f)シリコーン化合物との組み合わせにより、基板上の金メッキされた部分との高い接着力を発現するものである。   The (g) adhesion-imparting agent used in the present invention is represented by the following chemical formula (5). This (g) adhesion-imparting agent expresses a high adhesive force with the gold-plated portion on the substrate in combination with the (f) silicone compound.

Figure 2005162826
Figure 2005162826

(g)密着付与剤の含有量は、(f)シリコーン合物の含有量に対する比(=(g)密着付与剤の含有量/(f)シリコーン合物の含有量)で0.05〜1.5となる範囲が好ましく、さらに好ましくは0.1〜1.0となる範囲が好ましい。上記比が0.05未満であると金メッキされた部分との接着力が低くなり、1.5を超えると硬化性が悪くなり、型離れ性も低下するため好ましくない。   The content of the (g) adhesion-imparting agent is 0.05 to 1 as a ratio to the content of (f) silicone compound (= (g) content of adhesion-imparting agent / (f) content of silicone compound). A range of 0.5 is preferable, and a range of 0.1 to 1.0 is more preferable. If the ratio is less than 0.05, the adhesive strength with the gold-plated portion is lowered, and if it exceeds 1.5, the curability is deteriorated and the mold releasability is also deteriorated.

本発明の封止用樹脂組成物には、上記(a)〜(g)成分の他に、天然ワックス類、合成ワックス類、直鎖脂肪酸やその金属塩、酸アミド類、エステル類、パラフィン類などの離型剤;カーボンブラック、二酸化チタンなどの顔料;シリコーンゴム、各種プラスチックス粉末、各種エンジニアリングプラスチックス粉末、ABS樹脂やMBS樹脂の粉末などの低応力化剤などを適宜添加することができる。このような(a)〜(g)成分以外の他の成分は、それらの含有量の合計が封止用樹脂組成物全体の5重量%以下となる範囲が好ましい。   In addition to the components (a) to (g), the sealing resin composition of the present invention includes natural waxes, synthetic waxes, linear fatty acids and metal salts thereof, acid amides, esters, paraffins. Release agents such as carbon black, pigments such as titanium dioxide; silicone rubber, various plastic powders, various engineering plastics powders, ABS resin and MBS resin powders and the like can be added as appropriate. . The components other than the components (a) to (g) are preferably within a range in which the total content thereof is 5% by weight or less of the whole encapsulating resin composition.

本発明の封止用樹脂組成物は上記(a)〜(e)成分を必須成分とし、必要に応じて(f)、(g)成分、その他添加剤を添加し、例えばヘンシェルミキサー等のミキサーによって充分混合し、さらに熱ロールによる溶融処理または二軸の押し出し機などによる溶融混合処理を加えた後、冷却、粉砕することにより調製することができる。   The sealing resin composition of the present invention comprises the above components (a) to (e) as essential components and, if necessary, added components (f) and (g) and other additives. For example, a mixer such as a Henschel mixer It is possible to prepare the mixture by cooling and pulverizing the mixture after further mixing by adding a melt process using a hot roll or a melt-mix process using a biaxial extruder.

本発明の樹脂封止型半導体装置は、上記封止用樹脂組成物により半導体素子を封止することにより製造することができる。この場合、最も一般的には、低圧トランスファ成形が用いられるが、コンプレッション成形、インジェクション成形、注型などによっても封止することができる。なお、本発明の封止用樹脂組成物によって封止される半導体素子は特に限定されるものではない。   The resin-encapsulated semiconductor device of the present invention can be manufactured by encapsulating a semiconductor element with the encapsulating resin composition. In this case, most commonly, low-pressure transfer molding is used, but sealing can also be performed by compression molding, injection molding, casting, or the like. In addition, the semiconductor element sealed with the resin composition for sealing of this invention is not specifically limited.

本発明の樹脂封止型半導体装置においては半導体素子の封止に収縮率が小さい封止用樹脂組成物を用いるため、特に反りが発生しやすい片面封止の樹脂封止型半導体装置、すなわち基板の片面に半導体素子が搭載され、この半導体素子が搭載された基板の片面のみを封止してなる樹脂封止型半導体装置においてその反りの発生が効果的に抑制される。   In the resin-encapsulated semiconductor device of the present invention, since a sealing resin composition having a small shrinkage rate is used for encapsulating a semiconductor element, a single-side encapsulated resin-encapsulated semiconductor device, that is, a substrate, which is particularly prone to warp In a resin-encapsulated semiconductor device in which a semiconductor element is mounted on one side of the substrate and only one side of the substrate on which the semiconductor element is mounted is sealed, the occurrence of warpage is effectively suppressed.

以下、本発明を実施例に基づいてさらに詳細に説明する。   Hereinafter, the present invention will be described in more detail based on examples.

(実施例1〜5および比較例1〜3)
表1に示す各成分が同表に示す割合で配合されてなる封止用樹脂組成物を、以下のようにして調製した(表中の配合量は重量部を示す)。すなわち、初めにヘンシェルミキサー中で無機充填剤をカップリング剤で処理し、次いで他の成分を配合混合して60〜130℃の加熱ロールで混練し、冷却した後、粉砕することにより、封止用樹脂組成物を得た。
(Examples 1-5 and Comparative Examples 1-3)
A sealing resin composition in which the components shown in Table 1 were blended in the proportions shown in the same table was prepared as follows (the blending amounts in the table indicate parts by weight). That is, the inorganic filler is first treated with a coupling agent in a Henschel mixer, then the other components are blended and mixed, kneaded with a heating roll at 60 to 130 ° C., cooled, and then pulverized, thereby sealing. A resin composition was obtained.

Figure 2005162826
Figure 2005162826

なお、表1に示した各成分としては、それぞれ以下に示すものを用いた。
エポキシ樹脂A:化学式(1)で示されるエポキシ樹脂 NC−3000P(日本化薬株式会社製、当量273)
エポキシ樹脂B:化学式(2)で示される数平均分子量が1500以上のエポキシ樹脂 E−1800−6.5(日本石油化学株式会社製、当量240)
エポキシ樹脂C:オルソクレゾールノボラックエポキシ樹脂 ESCN195XL(住友化学株式会社製、当量197)
In addition, as each component shown in Table 1, what was shown below was used, respectively.
Epoxy resin A: Epoxy resin represented by chemical formula (1) NC-3000P (Nippon Kayaku Co., Ltd., equivalent 273)
Epoxy resin B: Epoxy resin having a number average molecular weight of 1500 or more represented by chemical formula (2) E-1800-6.5 (manufactured by Nippon Petrochemical Co., Ltd., equivalent 240)
Epoxy resin C: Orthocresol novolac epoxy resin ESCN195XL (Sumitomo Chemical Co., Ltd., equivalent 197)

フェノール樹脂A:化学式(3)で示されるフェノール樹脂硬化剤 MEH−7851S(明和化成株式会社製、当量198)
フェノール樹脂B:フェノールノボラック樹脂 BRG−556(昭和高分子株式会社製、当量104)
Phenol resin A: phenol resin curing agent represented by chemical formula (3) MEH-7851S (Maywa Kasei Co., Ltd., equivalent 198)
Phenol resin B: Phenol novolac resin BRG-556 (Showa Polymer Co., Ltd., equivalent 104)

硬化促進剤:DBU(DBU30重量%含有フェノールノボラック塩)
離型剤:カルナバワックス
顔料:カーボンブラック
無機充填材:球状溶融シリカ粉(平均粒径20μm)
カップリング剤:γ−グリシドキシプロピルトリメトキシシラン A−187(日本ユニカー株式会社製)
シリコーン化合物:化学式(4)で示されるシリコーン化合物において、両末端をアミンで変性したアミン当量5700のシリコーン化合物
密着付与剤:化学式(5)で示される密着付与剤
Curing accelerator: DBU (phenol novolak salt containing 30% by weight of DBU)
Mold release agent: carnauba wax pigment: carbon black inorganic filler: spherical fused silica powder (average particle size 20 μm)
Coupling agent: γ-glycidoxypropyltrimethoxysilane A-187 (Nihon Unicar Co., Ltd.)
Silicone compound: Silicone compound represented by the chemical formula (4), a silicone compound adhesion imparting agent having an amine equivalent of 5700 in which both ends are modified with amines: An adhesion imparting agent represented by the chemical formula (5)

次いで、これらの封止用樹脂組成物についてそれそれ下記のような評価試験を行った。   Subsequently, the following evaluation tests were performed on these sealing resin compositions.

[1]耐湿信頼性を調べるために以下の試験を行った。すなわち各封止用樹脂組成物を用いて試験用デバイスを封止した後、180℃で4時間アフターキュアを行った。次いでこのパッケージを30℃、相対湿度85重量%の雰囲気中に192時間放置して吸湿処理を行った後、これをMAX.温度260℃のIRリフロー炉に3回通した。この時点でパッケージにおけるクラック発生率を調べた。さらにこのパッケージを127℃の飽和水蒸気雰囲気中に放置し、不良(リーク不良、オープン不良)発生率を調べた。結果をまとめて表2に表す。 [1] The following tests were conducted to examine moisture resistance reliability. That is, after sealing the test device using each sealing resin composition, after-curing was performed at 180 ° C. for 4 hours. The package was then left in an atmosphere of 30 ° C. and a relative humidity of 85% by weight for 192 hours for moisture absorption treatment. It was passed through an IR reflow furnace at a temperature of 260 ° C. three times. At this time, the crack occurrence rate in the package was examined. Furthermore, this package was left in a saturated steam atmosphere at 127 ° C., and the occurrence rate of defects (leak defects, open defects) was examined. The results are summarized in Table 2.

[2]成形収縮率を調べるため、試験片を成形し、成形直後と180℃で4時間アフターキュアを行なった後での寸法変化率を測定した。また、BGAパッケージを成形して、成形したパッケージの反り量を測定した(パッケージ寸法:30mm×30mm、厚さ1.4mm、BT基盤:厚さ0.4mm)。結果をまとめて表3に示す。 [2] In order to examine the molding shrinkage rate, a test piece was molded, and the dimensional change rate was measured immediately after molding and after after-curing at 180 ° C. for 4 hours. Moreover, the BGA package was shape | molded and the curvature amount of the shape | molded package was measured (package dimension: 30 mm x 30 mm, thickness 1.4mm, BT base | substrate: thickness 0.4mm). The results are summarized in Table 3.

[3]成形作業性を調べるために以下の試験を行った。すなわち各封止用樹脂組成物を用いてダミーフレームを用いた連続成形を実施し、作業性および成形品外観を観察した。結果をまとめて表4に示す。 [3] The following tests were conducted to examine the molding workability. That is, continuous molding using a dummy frame was performed using each sealing resin composition, and workability and appearance of the molded product were observed. The results are summarized in Table 4.

[4]難燃性を調べるために、封止用樹脂組成物を成形、硬化し、120mm×12mm×0.8mmの試験片を作製した。この試験片について、UL94に基づく燃焼試験を実施し評価した。結果を表5に示す。 [4] In order to examine flame retardancy, the sealing resin composition was molded and cured to prepare a test piece of 120 mm × 12 mm × 0.8 mm. About this test piece, the combustion test based on UL94 was implemented and evaluated. The results are shown in Table 5.

Figure 2005162826
Figure 2005162826

Figure 2005162826
Figure 2005162826

Figure 2005162826
Figure 2005162826

Figure 2005162826
Figure 2005162826

表2〜表5に示されるように、実施例1〜5の封止用樹脂組成物を用いたものは成形収縮率、反り量が少ないと共に、高温下での耐クラック性およびその後の耐湿信頼性も良好であった。これに対して比較例1〜3の封止用樹脂組成物を用いたものは、一方の特性は良好となるものの、他方の特性が低下することが認められた。また、実施例1〜5の封止用樹脂組成物は成形作業性も問題なく、さらに十分な難燃性も保持していることが認められた。   As shown in Tables 2 to 5, those using the sealing resin compositions of Examples 1 to 5 have a low mold shrinkage and a small amount of warpage, and are resistant to cracking at high temperatures and subsequent moisture resistance. The property was also good. On the other hand, although the characteristic using one of the sealing resin compositions of Comparative Examples 1 to 3 was good, it was recognized that the other characteristic was deteriorated. In addition, it was confirmed that the sealing resin compositions of Examples 1 to 5 had no problem in molding workability and also retained sufficient flame retardancy.

Claims (4)

(a)エポキシ樹脂、(b)フェノール樹脂硬化剤、(c)硬化促進剤、(d)無機充填材および(e)カップリング剤を必須成分とする封止用樹脂組成物であって、
前記(a)エポキシ樹脂は下記化学式(1)で示されるエポキシ樹脂および下記化学式(2)で示される数平均分子量が1500以上のエポキシ樹脂を必須成分として含み、
Figure 2005162826
(但し、nは1以上の整数を表す)
Figure 2005162826
(但し、m、nは1以上の整数を、Rはアルキル基を表す)
前記(b)フェノール樹脂硬化剤は下記化学式(3)で示されるフェノール樹脂硬化剤を必須成分として含み、
Figure 2005162826
(但し、nは1以上の整数を表す)
実質的にハロゲン系難燃剤およびアンチモン化合物を含まないことを特徴とする封止用樹脂組成物。
(A) an epoxy resin, (b) a phenolic resin curing agent, (c) a curing accelerator, (d) an inorganic filler, and (e) a sealing resin composition comprising the coupling agent as essential components,
The (a) epoxy resin contains an epoxy resin represented by the following chemical formula (1) and an epoxy resin having a number average molecular weight represented by the following chemical formula (2) of 1500 or more as essential components.
Figure 2005162826
(However, n represents an integer of 1 or more)
Figure 2005162826
(However, m and n are integers of 1 or more, and R represents an alkyl group.)
The (b) phenol resin curing agent contains a phenol resin curing agent represented by the following chemical formula (3) as an essential component,
Figure 2005162826
(However, n represents an integer of 1 or more)
A sealing resin composition substantially free of a halogen-based flame retardant and an antimony compound.
前記化学式(1)で示されるエポキシ樹脂および前記化学式(2)で示される数平均分子量1500以上のエポキシ樹脂の含有量が、
0.05≦(化学式(2)で示される数平均分子量1500以上のエポキシ樹脂の含有量)/(化学式(1)で示されるエポキシ樹脂の含有量)≦0.5、
を満たすことを特徴とする請求項1記載の封止用樹脂組成物。
The content of the epoxy resin represented by the chemical formula (1) and the epoxy resin having a number average molecular weight of 1500 or more represented by the chemical formula (2)
0.05 ≦ (content of epoxy resin having a number average molecular weight of 1500 or more represented by chemical formula (2)) / (content of epoxy resin represented by chemical formula (1)) ≦ 0.5,
The resin composition for sealing according to claim 1, wherein:
(f)シリコーン化合物および(g)密着付与剤を必須成分として含み、
前記(f)シリコーン化合物が下記化学式(4)で示されるシリコーン化合物であり、
Figure 2005162826
(但し、l、m、nは0または1以上の整数を、Rはアルキル基を、Aはアミノ基、カルボキシル基、エポキシ基およびメチル基から選択される1価の官能基を表す)
前記(g)密着付与剤が下記化学式(5)で示される密着付与剤である
Figure 2005162826
ことを特徴とする請求項1または2記載の封止用樹脂組成物。
(F) containing a silicone compound and (g) an adhesion-imparting agent as essential components;
(F) the silicone compound is a silicone compound represented by the following chemical formula (4),
Figure 2005162826
(However, l, m, and n are 0 or an integer of 1 or more, R is an alkyl group, and A is a monovalent functional group selected from an amino group, a carboxyl group, an epoxy group, and a methyl group)
The (g) adhesion-imparting agent is an adhesion-imparting agent represented by the following chemical formula (5).
Figure 2005162826
The sealing resin composition according to claim 1, wherein the sealing resin composition is a sealing resin composition.
基板の片面に半導体素子が搭載され、前記半導体素子が搭載された前記基板の片面のみを樹脂組成物で封止してなる樹脂封止型半導体装置であって、前記樹脂組成物として請求項1乃至3のいずれか1項記載の封止用樹脂組成物を用いたことを特徴とする樹脂封止型半導体装置。   2. A resin-encapsulated semiconductor device in which a semiconductor element is mounted on one side of a substrate and only one side of the substrate on which the semiconductor element is mounted is sealed with a resin composition, wherein the resin composition is the resin composition. A resin-encapsulated semiconductor device using the encapsulating resin composition according to any one of claims 1 to 3.
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JP2008045086A (en) * 2006-08-21 2008-02-28 Hitachi Chem Co Ltd Epoxy resin composition for sealant and electronic component device
CN102690495A (en) * 2012-05-30 2012-09-26 日邦树脂(无锡)有限公司 Hot-melting type halogen-free fire-retardant heat conducting and dielectric insulating layer resin and application thereof
US8334596B2 (en) 2007-02-20 2012-12-18 Renesas Electronics Corporation Semiconductor device including coupling ball with layers of aluminum and copper alloys
US8697803B2 (en) * 2004-10-19 2014-04-15 Sumitomo Bakelite Company, Ltd. Epoxy resin composition and semiconductor device
JP2014156543A (en) * 2013-02-15 2014-08-28 Arakawa Chem Ind Co Ltd Curable composition for sealing electronic parts and cured product thereof
US20140350126A1 (en) * 2012-01-25 2014-11-27 Societe D'exploitation De Produits Pour Les Industries Chimiques Seppic New thickening polymer reducing the stickiness of glycerine-based cosmetic formulas

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US8697803B2 (en) * 2004-10-19 2014-04-15 Sumitomo Bakelite Company, Ltd. Epoxy resin composition and semiconductor device
US8921461B2 (en) * 2004-11-30 2014-12-30 Sumitomo Bakelite Co., Ltd Epoxy resin composition and semiconductor device
JP2008045086A (en) * 2006-08-21 2008-02-28 Hitachi Chem Co Ltd Epoxy resin composition for sealant and electronic component device
US8334596B2 (en) 2007-02-20 2012-12-18 Renesas Electronics Corporation Semiconductor device including coupling ball with layers of aluminum and copper alloys
US8395261B2 (en) 2007-02-20 2013-03-12 Renesas Electronics Corporation Semiconductor device
US20140350126A1 (en) * 2012-01-25 2014-11-27 Societe D'exploitation De Produits Pour Les Industries Chimiques Seppic New thickening polymer reducing the stickiness of glycerine-based cosmetic formulas
US9333162B2 (en) * 2012-01-25 2016-05-10 Societe D'exploitation De Produits Pour Les Industries Chimiques Seppic Thickening polymer reducing the stickiness of glycerine-based cosmetic formulas
CN102690495A (en) * 2012-05-30 2012-09-26 日邦树脂(无锡)有限公司 Hot-melting type halogen-free fire-retardant heat conducting and dielectric insulating layer resin and application thereof
JP2014156543A (en) * 2013-02-15 2014-08-28 Arakawa Chem Ind Co Ltd Curable composition for sealing electronic parts and cured product thereof

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