JP2015048423A - Semiconductor sealing resin composition and semiconductor device including cured product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition excellent in transfer-molding and capable of providing a cured product having less thermal decomposition (weight loss) even when placed in a high temperature of 200°C or more, for example, 200-250°C for a long period and excellent adhesion to a CuLF or an Ag plating film.SOLUTION: The resin composition comprises: (A) a cyanate ester compound having two or more cyanate groups in one molecule; (B) a phenolic compound having two or more phenolic hydroxyl groups in one molecule; (C) an inorganic filler; and (D) a release agent having an acid value of 30 or less and a saponification value of 150 or less (where, when the acid value is less than 5, the saponification value is 80 or more and 150 or less, and when the saponification value is less than 5, the acid value is 20 or more and 30 or less). A molar ratio of a phenolic hydroxyl group in (B) the phenolic compound to a cyanate group in (A) the cyanate ester compound is 0.1-0.4.

Description

  The present invention relates to a semiconductor sealing resin composition. Specifically, it is possible to provide a highly reliable cured product having excellent thermal stability for a long time at a high temperature and having excellent adhesion with a Cu lead frame (LF) or Ag plating. The present invention also relates to a composition excellent in transfer moldability, and a semiconductor device comprising a cured product of the composition.

  In recent years, semiconductor devices have undergone remarkable technological innovation. TSV (through silicon via) technology is used so that portable information such as smartphones and tablets and communication terminals can process large volumes of information at high speed. In this technique, first, semiconductor elements are connected in multiple layers and flip-chip connected to an 8 inch to 12 inch silicon interposer. Thereafter, the interposer on which a plurality of semiconductor elements connected in multiple layers are mounted is sealed with a thermosetting resin. After polishing unnecessary cured resin on the semiconductor element, it is separated into individual pieces, and a thin, small, multifunctional, and high-speed semiconductor device can be obtained. However, when a thermosetting resin is applied to the entire surface of a thin silicon interposer of 8 inches to 12 inches and sealed, a large warp occurs due to the difference in thermal expansion coefficient between silicon and the thermosetting resin. If the warpage is large, it cannot be applied to the subsequent polishing process or singulation process, which is a major technical problem.

  In recent years, as a measure against global warming, environmental measures on a global level such as energy conversion from fossil fuels have been promoted. Therefore, the number of hybrid cars and electric cars produced is increasing. In addition, household electrical appliances in emerging countries such as China and India are also increasingly equipped with inverter motors as energy saving measures.

  For hybrid vehicles, electric vehicles, and inverter motors, power semiconductors that play a role of converting AC to DC, converting DC to AC, and transforming voltage are important. However, silicon (Si), which has been used as a semiconductor for many years, is approaching its performance limit, and it has become difficult to expect dramatic performance improvements. Accordingly, attention has been focused on next-generation power semiconductors using materials such as silicon carbide (SiC), gallium nitride (GaN), and diamond. For example, a reduction in resistance of a power MOSFET is required to reduce loss during power conversion. However, it is difficult to significantly reduce the resistance in the current mainstream Si-MOSFET. Therefore, development of a low-loss power MOSFET using SiC, which is a semiconductor with a wide band gap (wide gap), is in progress.

  SiC and GaN have excellent characteristics that the band gap is about 3 times that of Si and the breakdown electric field strength is 10 times or more. In addition, there are also features such as high-temperature operation (SiC reports 650 ° C operation), high thermal conductivity (SiC is equivalent to Cu), and large saturated electron drift velocity. As a result, if SiC or GaN is used, the on-resistance of the power semiconductor can be lowered and the power loss of the power conversion circuit can be greatly reduced.

  The power semiconductor is generally protected by transfer molding using an epoxy resin and potting sealing using a silicone gel. Recently, transfer molding using an epoxy resin is becoming mainstream from the viewpoint of miniaturization and weight reduction (particularly for automobiles). However, epoxy resin is a well-balanced thermosetting resin with excellent moldability, adhesion to the substrate, and mechanical strength, but at temperatures exceeding 200 ° C, the thermal decomposition of the cross-linking point proceeds, and SiC and GaN are transformed. There is anxiety that it may not serve as a sealing material in the expected high-temperature operating environment (Non-Patent Document 1).

  Therefore, a thermosetting resin composition containing a cyanate resin has been studied as a material having excellent heat resistance. For example, Patent Document 1 describes a curable resin composition containing a cyanate ester compound, an epoxy resin, and a curing catalyst, and describes that the cured product is excellent in curing shrinkage, heat resistance, and electrical characteristics. Patent Document 2 describes an electronic component sealing resin composition containing a cyanate ester compound, at least one selected from a phenol compound, a melamine compound, and an epoxy resin, and an inorganic filler. Patent Document 2 describes that the composition has a high glass transition temperature and can suppress warping of an electronic component device. Patent Document 3 describes a thermosetting resin composition containing a cyanate ester compound having a specific structure, a phenol compound, and an inorganic filler. Patent Document 3 describes that the resin composition has excellent heat resistance and high mechanical strength.

JP-A-8-283409 JP 2011-184650 A JP2013-53218A

Industrial Materials November 2011 Issue (vol59 No.11)

  However, conventional cyanate ester-containing resin compositions are insufficient in heat resistance, causing problems such as thermal decomposition when placed at a high temperature of 200 ° C. or higher for a long period of time, and reduced adhesion of a cured product to CuLF or Ag plating. As a result, cracks and the like are generated. Therefore, in view of the above circumstances, the present invention has a low thermal decomposition (weight reduction) even when placed at a high temperature of 200 ° C. or higher, for example, 200 ° C. to 250 ° C. for a long time, and has excellent adhesion to CuLF and Ag plating. An object of the present invention is to provide a resin composition that can give a product and is excellent in transfer moldability.

  As a result of intensive studies to solve the above problems, the inventors of the present invention formulated a phenol compound in a composition containing a cyanate ester compound and an inorganic filler, and specified a blending amount of the phenol compound with respect to the cyanate ester compound. It was found that the cured product obtained had an excellent thermal stability by being in the range. However, the composition is not sufficiently continuous.

  Accordingly, the present inventors have further studied diligently, and in the above composition, a release agent having an acid value of 30 or less and a saponification value of 150 or less (however, when the acid value is less than 5, the saponification value) Is 80 or more and 150 or less, and when the saponification value is less than 5, the acid value is 20 or more and 30 or less), and it is found that the continuous moldability of the resin composition can be improved. It came.

That is, the present invention
(A) Cyanate ester compound having two or more cyanato groups in one molecule (B) Phenol compound having two or more phenolic hydroxyl groups in one molecule (C) Inorganic filler, and (D) Acid value A release agent having a saponification value of 30 or less and a saponification value of 150 or less (however, when the acid value is less than 5, the saponification value is 80 or more and 150 or less, and when the saponification value is less than 5, the acid value is 20). Is 30 or less)
The molar ratio of the phenolic hydroxyl group in the (B) phenol compound to the cyanate group in the (A) cyanate ester compound is 0.1 to 0.4.

  The composition of the present invention can provide a cured product that has little thermal decomposition (weight reduction) even when placed at a high temperature for a long period of time and is excellent in adhesion to CuLF and Ag plating. Therefore, a semiconductor device sealed with a cured product of the composition of the present invention has long-term reliability at high temperatures. Moreover, since the composition of this invention is excellent in continuous moldability, it can be used conveniently as a material for transfer molding.

  The present invention will be described in more detail below.

（式中、Ｒ^１及びＲ^２は、互いに独立に、水素原子または炭素数１〜４のアルキル基であり、Ｒ^３は、互いに独立に、下記のいずれかである。

Ｒ^４は水素原子またはメチル基であり、ｎは０〜１０の整数である） (A) Cyanate ester compound The component (A) is a cyanate ester compound having two or more cyanato groups in one molecule. The cyanate ester compound in the present invention may be one having two or more cyanato groups in one molecule, and generally known ones can be used. The cyanate ester compound can be represented, for example, by the following general formula (1).

(In the formula, R ¹ and R ² are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ³ is each independently one of the following:

R ⁴ is a hydrogen atom or a methyl group, and n is an integer of 0 to 10)

  Examples of the cyanate ester compound of the present invention include bis (4-cyanatophenyl) methane, bis (3-methyl-4-cyanatophenyl) methane, bis (3-ethyl-4-cyanatophenyl) methane, and bis. (3,5-dimethyl-4-cyanatophenyl) methane, 1,1-bis (4-cyanatophenyl) ethane, 2,2-bis (4-cyanatophenyl) propane, 2,2-bis (4 -Cyanatophenyl) -1,1,1,3,3,3-hexafluoropropane, di (4-cyanatophenyl) thioether, 1,3- and 1,4-dicyanatobenzene, 2-tert-zotyl -1,4-dicyanatobenzene, 2,4-dimethyl-1,3-dicyanatobenzene, 2,5-di-tert-butyl-1,4-dicyanatobenzene, tetramethyl-1, -Dicyanatobenzene, 1,3,5-tricyanatobenzene, 2,2'- or 4,4'-dicyanatobiphenyl, 3,3 ', 5,5'-tetramethyl-4,4'-dicyanato Biphenyl, 1,3-, 1,4-, 1,5-, 1,6-, 1,8-, 2,6-, or 2,7-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene Bis (4-cyanatophenyl) methane; 2,2-bis (4-cyanatophenyl) propane, 1,1,1-1 tris (4-cyanatophenyl) ethane, bis (4-cyanatophenyl) Ether; 4,4 ′-(1,3-phenylenediisopropylpyridene) diphenyl cyanate, bis (4-cyanatophenyl) thioether, bis (4-cyanatophenyl) sulfone, tris (4-cyanato-phenyl) phosphine , Tris (4-cyanatophenyl) phosphate, phenol novolac cyanate, cresol novolac cyanate, dicyclopentadiene novolac cyanate, phenylaralkyl cyanate ester, biphenylaralkyl cyanate ester, naphthalene aralkyl cyanate ester, etc. . These cyanate ester compounds can be used alone or in combination.

  The cyanate ester compound can be obtained by reacting phenols and cyanogen chloride under basic conditions. The cyanate ester compound can be appropriately selected from those having a wide range of properties from a solid having a softening point of 106 ° C. to a liquid at room temperature, depending on the application. For example, when a liquid epoxy resin composition is produced, a liquid compound is used at room temperature, and when it is dissolved in a solvent to form a varnish, it is preferably selected according to solubility and solution viscosity. Moreover, when using it by transfer molding for power semiconductor sealing, it is preferable to select a solid compound at room temperature.

  Moreover, the thing with small equivalent of a cyanate group, ie, the thing with a small molecular weight between functional groups, has a small cure shrinkage, and can obtain the hardened | cured material of low thermal expansion and high Tg. Those having a large cyanate group equivalent have a slight decrease in Tg, but the triazine cross-linking interval becomes flexible, and low elasticity, high toughness, and low water absorption can be expected. The chlorine bonded or remaining in the cyanate ester compound is preferably 50 ppm or less, more preferably 20 ppm or less. When the amount of chlorine exceeds 50 ppm, chlorine or chlorine ions liberated by thermal decomposition when placed under high temperature for a long period of time corrode the oxidized Cu frame, Cu wire, and Ag plating, and peeling of the cured product or electrical It can cause defects. In addition, the insulating properties of the resin may be reduced.

上記式中、Ｒ^５及びＲ^６は、互いに独立に、水素原子または炭素数１〜４のアルキル基であり、ｍは０〜１０の整数である。
上記式中、Ｒ^７は、互いに独立に、下記のいずれかである。

（上記式中、Ｒ^４は、互いに独立に、水素原子またはメチル基である） (B) The phenol compound (B) component is a phenol compound having two or more phenolic hydroxyl groups in one molecule, and generally known compounds are those having two or more phenolic hydroxyl groups in one molecule. Can be used. The phenol compound can be represented by the following general formula (2), for example.

In said formula, R < ⁵ > and R < ⁶ > are a hydrogen atom or a C1-C4 alkyl group mutually independently, and m is an integer of 0-10.
In the above formulae, R ⁷ is independently of each other below.

(In the above formula, R ^{4 s} independently of one another are a hydrogen atom or a methyl group)

Examples of the phenol compound represented by the above formula (2) include bisphenol F type resin, bisphenol A type resin, phenol novolac resin, phenol aralkyl type resin, biphenyl aralkyl type resin, and naphthalene aralkyl type resin. These may be used alone or in combination of two or more. In addition, the composition containing a compound (for example, phenol novolac resin) in which R ⁷ is CH ₂ in the above formula (2) may be inferior in heat resistance, or may be inferior in moldability due to too early reactivity with a cyanate compound. There is. Accordingly, it is particularly preferred that R ⁷ is other than CH ₂ .

  Conventionally, metal salts, metal complexes, and the like have been used as curing catalysts for cyanate ester compounds (Japanese Patent Laid-Open Nos. 64-43527, 11-106480, and 2005-506422). However, transition metals are used as metal salts and metal complexes, and transition metals are likely to promote oxidative degradation of organic resins at high temperatures. In the composition of the present invention, the phenol compound functions as a catalyst for the cyclization reaction of the cyanate ester compound. Therefore, it is not necessary to use metal salts and metal complexes. Thereby, long-term storage stability under high temperature can be further improved.

  In addition, a phenol compound having at least two hydroxyl groups in one molecule can be expected as a crosslinking agent that connects triazine rings. Unlike an epoxy compound or an amine compound, a phenol compound can form a structure represented by —C—O—Ar— by bonding with a cyanate ester compound. Since this structure is similar to the triazine ring structure formed when the cyanate ester compound is cured alone, it can be expected to further improve the heat resistance of the resulting cured product.

  A phenol compound having a small hydroxyl equivalent, for example, a phenol compound having a hydroxyl equivalent of 110 or less has high reactivity with a cyanate group. Therefore, the curing reaction proceeds when the composition is melt-kneaded at 120 ° C. or lower, and the fluidity may be significantly impaired, which is not preferable for transfer molding. Therefore, it is particularly preferable that the phenol compound has a hydroxyl equivalent of 111 or more.

  The compounding amount of the phenol compound is such that the hydroxyl group is 0.1 to 0.4 mol per 1 mol of cyanato group. When the amount of the phenol compound is less than the above lower limit, the reaction of the cyanate group becomes insufficient, and an unreacted cyanato group remains. The remaining cyanato group undergoes hydrolysis in a high humidity atmosphere. For this reason, when placed under high temperature and high humidity, it causes a decrease in mechanical strength and a decrease in adhesion to the substrate. Moreover, when there is more quantity of a phenol compound than the said upper limit, hardening reaction will advance from low temperature. Therefore, the fluidity of the composition is impaired, and the moldability is deteriorated. Further, the halogen element and alkali metal in the phenol compound are preferably 10 ppm, particularly 5 ppm or less when extracted at 120 ° C. under 2 atm.

(C) Inorganic filler In this invention, the kind in particular of an inorganic filler is not restrict | limited, A well-known thing can be used as an inorganic filler of the resin composition for semiconductor sealing. Examples thereof include silicas such as fused silica, crystalline silica, cristobalite, alumina, silicon nitride, aluminum nitride, boron nitride, titanium oxide, glass fiber, magnesium oxide, and zinc oxide. The average particle size and shape of these inorganic fillers may be selected according to the application. Among them, in order to obtain a thermal expansion coefficient close to that of silicon, fused silica is preferable, and a spherical shape is preferable. The average particle size of the inorganic filler is preferably 0.1 to 40 μm, more preferably 0.5 to 15 μm. The average particle diameter can be obtained, for example, as a weight average value (or median diameter) by a laser light diffraction method or the like.

  The inorganic filler is preferably 10 ppm or less of chlorine ions and 10 ppm or less of sodium ions as impurities extracted under the extraction conditions of 5 g of sample and 50 g of water at 120 ° C. and 2.1 atm. If it exceeds 10 ppm, the moisture resistance of the semiconductor device encapsulated with the composition may deteriorate.

  In the present invention, the blending amount of the inorganic filler can be 60 to 94% by weight, preferably 70 to 92% by weight, more preferably 75 to 90% by weight of the entire composition.

  In order to increase the bond strength between the resin and the inorganic filler, the inorganic filler is preferably blended in advance with a surface treatment with a coupling agent such as a silane coupling agent or a titanate coupling agent. As such a coupling agent, epoxy silane such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N -Β (aminoethyl) -γ-aminopropyltrimethoxysilane, reaction product of imidazole and γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, etc. It is preferable to use a silane coupling agent such as mercaptosilane such as aminosilane, γ-mercaptosilane, and γ-episulfideoxypropyltrimethoxysilane. Here, the blending amount of the coupling agent used for the surface treatment and the surface treatment method are not particularly limited.

(D) Release agent The component (D) used in the present invention is a release agent having an acid value of 30 or less and a saponification value of 150 or less. Preferably, the acid value is 10-25. Also preferably, the saponification value is 70 to 140, more preferably 70 to 100. Either one of the acid value and the saponification value may be zero. However, when the acid value is less than 5, the saponification value is 80 or more and 150 or less, preferably 100 or more and 150 or less, and when the saponification value is less than 5, the acid value is 20 or more and 30 or less, preferably 25 or more and 30 or less. It is necessary to be. A release agent having both an acid value and a saponification value that are too small is not preferable because the compatibility with the resin is too good and a sufficient release effect (that is, continuous moldability) cannot be exhibited. Further, if the acid value and saponification value are too large, the surface of the cured product may be exuded and the appearance may be poor. In particular, when the saponification value exceeds the upper limit, the release agent may become a liquid (lubricating oil) instead of a solid at room temperature. If such a release agent is added to the composition and molded, it is not preferred because it may bleed out over time and impair the appearance of the cured product.

  Examples of the release agent of the present invention include carnauba wax, rice wax, polyethylene oxide, montanic acid, montanic acid and saturated alcohol, ester compounds such as 2- (2-hydroxyethylamino) -ethanol, ethylene glycol, or glycerin. And the like; stearic acid, stearic acid ester, copolymer of ethylene and vinyl acetate, and the like. These may be used alone or in combination of two or more. Among these, polyethylene oxide or fatty acid ester is preferable. The compounding quantity of a mold release agent is 0.3-1.5 mass% of the whole composition, Preferably it is 0.35-0.8 mass%, More preferably, it is 0.35-0.5 mass%.

  If necessary, the sealing resin composition of the present invention may further contain various additives such as a flame retardant, an ion trap agent, an antioxidant, an adhesion promoter, and a low stress agent. Moreover, the coupling agent mentioned above can be used as an adhesiveness imparting agent. In order to improve the adhesion to the metal frame, a mercapto silane coupling agent is particularly suitable.

  The flame retardant is not particularly limited, and a known flame retardant can be used. Examples include phosphazene compounds, silicone compounds, zinc molybdate-supported talc, zinc molybdate-supported zinc oxide, aluminum hydroxide, magnesium hydroxide, molybdenum oxide, and antimony trioxide.

  The ion trapping agent is not particularly limited, and known ones can be used. Examples thereof include hydrotalcites, bismuth hydroxide compounds, rare earth oxides, and the like.

  The method for producing the composition of the present invention is not particularly limited. For example, the above components (A) to (D) may be stirred or dissolved, mixed or dispersed simultaneously or separately, if necessary with heat treatment, and optionally mixed with other additives. It can be obtained by stirring and dispersing. Although the apparatus used for mixing etc. is not specifically limited, A raikai machine provided with stirring and a heating apparatus, 2 rolls, 3 rolls, a ball mill, a continuous extruder, a planetary mixer, a mass collider, etc. can be used. You may use combining these apparatuses suitably.

  The composition of the present invention is useful for semiconductor packages such as transistor type, module type, DIP type, SO type, flat pack type, and ball grid array type. Molding of the composition of the present invention may be performed in accordance with a molding method conventionally employed. For example, transfer molding, compression molding, injection molding, casting method and the like can be used. Particularly preferred is transfer molding. The molding temperature of the composition of the present invention is preferably 160 to 190 ° C. for 45 to 180 seconds, and the post cure is 170 to 250 ° C. for 2 to 16 hours.

  The composition of the present invention is a cured product that has less thermal decomposition (weight reduction) when placed at a high temperature of 200 ° C. or higher, particularly 200 ° C. to 250 ° C. for a long period of time, and is excellent in adhesion to CuLF and Ag plating. Can be provided. Therefore, a semiconductor device sealed with a cured product of the composition of the present invention can have long-term reliability at high temperatures. Furthermore, since the composition of this invention is excellent in continuous moldability, it can be used especially suitably as a transfer molding material.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated in detail, this invention is not restrict | limited to the following Example. In addition, all the parts in each example are mass parts.

[Examples 1 to 5, Comparative Examples 1 to 4]
Each component shown below was blended with the composition shown in Table 1, mixed uniformly with a high-speed mixer, then uniformly kneaded with a heated two roll, cooled and pulverized to obtain a resin composition.

（ｎ＝０〜１０の混合物） (A) Cyanate ester compound (I) Cyanate ester compound represented by the following formula (3) (Primaset PT-60, Lonza Japan Co., Ltd., cyanate group equivalent 119)

(Mixture of n = 0 to 10)

（ｎ＝０〜１０の混合物） (B) Cyanate ester compound obtained in Synthesis Example 1 below
[Synthesis Example 1]
100 g of the phenol compound MEH-7785SS (manufactured by Meiwa Kasei) was dissolved in 600 g of butyl acetate. The solution was cooled to about −15 ° C. and 32 g of gaseous cyanogen chloride was introduced. Then, over a period of about 30 minutes, 50 g of triethylamine was added dropwise with stirring while maintaining the temperature below -10 ° C. After maintaining this temperature for an additional 30 minutes, cooling was stopped and the reaction mixture was filtered. The filtrate was continuously passed through an ion exchanger packed column. Subsequently, the solvent is removed under reduced pressure at a bath temperature of 70 ° C., after which volatile impurities (including solvent residues, free triethylamine, diethyl cyanamide) are removed using a falling film evaporator at 1 mbar, 130 ° C. Removed. The obtained product was a cyanate ester compound (cyanate group equivalent 208) represented by the following formula (4).

(Mixture of n = 0 to 10)

（ｎ＝０〜１０の混合物）
（ニ）下記式（６）で示すフェノール化合物（ＭＥＨ−７８５１ＳＳ、明和化成製、フェノール性水酸基当量２０３）

（ｎ＝０〜１０の混合物）
（ホ）下記式（７）で示すフェノール化合物（ＴＤ−２１３１、ＤＩＣ製、フェノール性水酸基当量１１０）

（ｎ＝０〜１０の混合物）
(B) Phenol compound (C) Phenol compound represented by the following formula (5) (MEH-7800SS, manufactured by Meiwa Kasei Co., Ltd., phenolic hydroxyl group equivalent 175)

(Mixture of n = 0 to 10)
(D) Phenol compound represented by the following formula (6) (MEH-7851SS, manufactured by Meiwa Kasei Co., Ltd., phenolic hydroxyl group equivalent 203)

(Mixture of n = 0 to 10)
(E) Phenol compound represented by the following formula (7) (TD-2131, manufactured by DIC, phenolic hydroxyl group equivalent 110)

(Mixture of n = 0 to 10)

(C) Inorganic filler (f) Fused spherical silica with an average particle size of 15 μm (manufactured by Tatsumori)

(D) Release agent (g) Release agent 1: Polyethylene oxide having an acid value of 25 and a saponification value of 0 (Licowax PED-522, manufactured by Clariant)
(H) Release agent 2: Fatty acid ester having an acid value of 10 and a saponification value of 85 (TOWAX-131, manufactured by Toagosei Co., Ltd.)
(I) Release agent 3: Fatty acid ester having an acid value of 25 and a saponification value of 140 (ITO-WAX TP NC-133, manufactured by Ito Oil Co., Ltd.)

-Release agent for comparative example (nu) Release agent 4: Polyethylene having a acid value of 0 and a saponification value of 0 (Licowax PE-522, manufactured by Clariant)
(L) Mold release agent 5: Polypropylene and maleic anhydride copolymer of acid value 86 and saponification value 0 (Electol D121-41, manufactured by Nissan Chemical Industries, Ltd.)

（ｎ＝０〜１０の混合物）

・シランカップリング剤：３−メルカプトプロピルトリメトキシシラン（ＫＢＭ−８０３、信越化学工業株製）
・イミダゾール（四国化成社製） (E) Other components-Epoxy resin compound represented by the following formula (8) (NC-3000, manufactured by Nippon Kayaku, epoxy equivalent 272)

(Mixture of n = 0 to 10)

Silane coupling agent: 3-mercaptopropyltrimethoxysilane (KBM-803, manufactured by Shin-Etsu Chemical Co., Ltd.)
・ Imidazole (manufactured by Shikoku Chemicals)

  The following evaluation tests were performed for each composition. The results are shown in Table 1 below.

[Spiral flow]
Using a mold conforming to the EMMI standard, measurement was performed under the conditions of 175 ° C., 6.9 N / mm ² , and a molding time of 180 seconds.

[Change in weight during storage at high temperatures]
Transfer molding was performed at 175 ° C. for 120 seconds under a molding pressure of 6.9 MPa, and then post-curing was performed at 180 ° C. for 4 hours to obtain a 10 × 100 × 4 mm test piece. The test piece was stored in an oven at 250 ° C. for 500 hours, and the weight loss rate was measured.

[Adhesion confirmation with Ag-plated CuLF-1]
A 100-pin QFP lead frame made of Cu alloy (Olin C7025) with Ag-plated die pad part (8mm x 8mm) and wire bonding part was transfer molded at 175 ° C x 120 seconds under a molding pressure of 6.9MPa, then 180 ° C for 4 hours post Cure. The tie bar was cut with a lead frame cutter to obtain a QFP package of 20 mm × 14 mm × 2.7 mm.
Twelve of these packages were stored in an oven at 225 ° C. for 500 hours, and the presence or absence of cracks in the package was visually confirmed after storage. Moreover, the presence or absence of peeling from the internal crack and the lead frame was observed using an ultrasonic flaw detector. The number of packages with cracks or delamination is listed in the table.

[Formability]
80 pin QFP (14 × 20 × 2.7 mm) was molded at 175 ° C. × 120 seconds at 6.9 MPa for 100 shots, and the number of shots until die sticking, cull and runner breakage were observed.

  A composition containing a release agent whose acid value and saponification value do not satisfy the scope of the present invention has poor continuous moldability. On the other hand, the composition of this invention is excellent in continuous moldability. Furthermore, the composition of the present invention has a low weight loss rate even at a high temperature for a long period of time, and can maintain the adhesion to the metal frame for a long time.

  Since the cured product of the composition of the present invention has long-term thermal stability at high temperatures and can maintain excellent adhesion with a metal frame, a semiconductor device having excellent long-term reliability at high temperatures can be obtained. Can be provided. Furthermore, since the composition of the present invention is excellent in continuous moldability, it can be suitably used as a transfer molding material.

Claims (7)

(A) Cyanate ester compound having two or more cyanato groups in one molecule (B) Phenol compound having two or more phenolic hydroxyl groups in one molecule (C) Inorganic filler, and (D) Acid value A release agent having a saponification value of 30 or less and a saponification value of 150 or less (however, when the acid value is less than 5, the saponification value is 80 or more and 150 or less, and when the saponification value is less than 5, the acid value is 20). Is 30 or less)
(A) The molar ratio of the phenolic hydroxyl group in the phenol compound (B) to the cyanate group in the cyanate ester compound is 0.1 to 0.4. The composition according to claim 1, wherein the component (D) is at least one selected from fatty acid esters and polyethylene oxide. The composition according to claim 1 or 2, wherein the component (A) is a compound represented by the following general formula (1).

(In Formula (1), R < ¹ > and R < ² > are a hydrogen atom or a C1-C4 alkyl group mutually independently, and R < ³ > is either of the following independently of each other.

R ⁴ are each independently a hydrogen atom or a methyl radical, n is an integer of 0). (B) The composition of any one of Claims 1-3 whose component is a compound represented by following General formula (2).

(In the formula (2), R ⁵ and R ⁶ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁷ is each independently one of the following:

R < ⁴ > is a hydrogen atom or a methyl group mutually independently, and m is an integer of 0-10.   The semiconductor device provided with the hardened | cured material of the composition of any one of Claims 1-4.   6. The semiconductor device according to claim 5, wherein a semiconductor element made of SiC or GaN is mounted.   The method for producing a semiconductor device according to claim 5, comprising a step of molding the composition according to claim 1 by transfer molding.