KR102210371B1 - Resin compositions for sealing semiconductor and semiconductor device with the cured product thereof - Google Patents

Abstract

An object of the present invention is to provide a resin composition that provides a cured product having less thermal decomposition (weight reduction), excellent mechanical strength at high temperature, and excellent insulating properties even when placed under a high temperature of 200°C or higher for a long period of time.
The present invention,
(A) a cyanate ester compound having two or more cyanato groups in one molecule;
(B) inorganic filler;
(C) a silane coupling agent having a group represented by a primary amine, a secondary amine, a tertiary amine, or -N=CR ₂ (R is a monovalent hydrocarbon group) at the terminal; And
(D) Provides a composition comprising at least one compound selected from an amine compound other than the component (C), a phenol compound, a phosphine compound, and an adduct of a phosphine compound and a quinone compound.

Description

A semiconductor device equipped with a resin composition for sealing a semiconductor and a cured product thereof {RESIN COMPOSITIONS FOR SEALING SEMICONDUCTOR AND SEMICONDUCTOR DEVICE WITH THE CURED PRODUCT THEREOF}

The present invention relates to a resin composition for sealing a semiconductor. Specifically, it relates to a composition having a small coefficient of thermal expansion, excellent mechanical strength at high temperature, and excellent insulation property, and excellent thermal stability at high temperature for a long period of time, and a semiconductor device including a cured product of the composition.

Recently, semiconductor devices are facing remarkable technological innovation. Portable information such as smartphones and tablets, and communication terminals use TSV (through silicon via) technology to process large amounts of information at high speed. In the above technology, semiconductor devices are first connected in multiple layers and flip-chip connected to an 8-inch to 12-inch silicon interposer. After that, each interposer in which a plurality of multilayer connected semiconductor elements are mounted is sealed with a thermosetting resin. It is possible to obtain a thin, compact, multifunctional, high-speed semiconductor device capable of high-speed processing by grinding unnecessary cured resin on a semiconductor element and then into pieces. However, when the thermosetting resin is applied and sealed on the entire surface of the 8-inch to 12-thin silicone interposer, large warpage occurs from the difference in the coefficient of thermal expansion between the silicone and the thermosetting resin. If the warpage is large, it cannot be applied to the subsequent polishing process or reorganization process, which is a big technical task.

In addition, as a countermeasure against global warming, environmental measures at the global level such as conversion of energy from fossil fuels are in progress. For this reason, the number of hybrid vehicles and electric vehicles produced has been increasing. In addition, household electric appliances in emerging countries such as China and India are also on the rise in models equipped with inverter motors as measures to save energy.

In hybrid vehicles, electric vehicles, and inverter motors, power semiconductors that convert AC into DC, DC into AC, or transform voltage become important. However, silicon (Si), which has been used as a semiconductor for a long time, has a performance limit approaching, and it has become difficult to expect a dramatic performance improvement. Therefore, attention is focused on next-generation power semiconductors using materials such as silicon carbide (SiC), gallium nitride (GaN), and diamond. For example, in order to reduce the loss during power conversion, it is required to reduce the resistance of the power MOSFET. However, it is difficult to significantly reduce resistance in the current mainstream Si-MOSFET. Therefore, development of low-loss power MOSFETs using SiC, a semiconductor with a wide band gap (wide gap), is in progress.

SiC or GaN has excellent characteristics of about 3 times the band gap of Si and 10 times or more of the breaking field strength. In addition, there are features such as high temperature operation (there is a report of operation at 650°C in SiC), high thermal conductivity (SiC is equivalent to Cu), and a large saturation electron drift rate. As a result, when SiC or GaN is used, it is possible to reduce the on-resistance of the power semiconductor and significantly reduce the power loss of the power conversion circuit.

Power semiconductors are generally protected by transfer molding with an epoxy resin and potting and sealing with a silicone gel. In recent years, from the viewpoint of miniaturization and weight reduction (especially for automobile applications), transfer molding using an epoxy resin has become mainstream. However, the epoxy resin is a well-balanced thermosetting resin with excellent moldability, adhesion to the substrate, and mechanical strength, but thermal decomposition of the crosslinking point proceeds at a temperature exceeding 200°C, and the operating environment at high temperatures expected for SiC and GaN There is anxiety that it may not be possible to perform the role of a sealing material in (Non-Patent Document 1)

Therefore, as a material having excellent heat resistance, a thermosetting resin composition containing a cyanate resin is being studied. 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 properties. Patent Document 2 discloses a resin composition for sealing electronic parts containing a cyanate ester compound, at least one selected from a phenol resin, a melamine compound, and an epoxy resin, and an inorganic filler. In Patent Document 2, it is described that the composition has a high glass transition temperature and can suppress the warpage of the electronic component device. In addition, Patent Document 3 describes a thermosetting resin composition containing a cyanic acid ester compound, a phenol compound, and an inorganic filler having a specific structure. Patent Document 3 describes that the resin composition has excellent heat resistance and high mechanical strength.

Japanese Laid-Open Patent Publication No. Hei 8-283409 Japanese Laid-Open Patent Publication No. 2011-184650 Japanese Unexamined Patent Publication No. 2013-53218

Industrial Materials November, 2011 (vol59 No.11)

However, the conventional cyanate ester-containing resin composition has insufficient heat resistance and thermal decomposition occurs when it is left under a high temperature of 200°C or higher for a long time, or cracks occur due to a decrease in adhesion of a cured product to Cu lead frame (LF) or Ag plating. Has a problem. Therefore, in view of the above circumstances, the present invention aims to provide a resin composition that provides a cured product with less thermal decomposition (weight reduction), excellent mechanical strength at high temperature, and excellent insulation even when placed under a high temperature of 200°C or higher for a long period of time. do.

As a result of careful examination of the above problems, the present inventors completed the present invention by finding that a silane coupling agent having an amine structure at the terminal accelerates the cyclization reaction of the cyanate ester compound and further reduces the thermal expansion coefficient of the resulting cured product. It came to the following.

That is, the present invention

(A) Cyanate ester compound having two or more cyanato groups in one molecule

(B) inorganic filler

(C) a silane coupling agent having a group represented by a primary amine, a secondary amine, a tertiary amine, or -N=CR ₂ (R is a monovalent hydrocarbon group) at the terminal, and

(D) A composition comprising at least one compound selected from an amine compound other than the component (C), a phenol compound, a phosphine compound, and an adduct of a phosphine compound and a quinone compound.

The composition of the present invention provides a cured product having little thermal decomposition (weight reduction) even under a high temperature of 200°C or higher for a long period of time, and excellent in mechanical strength and insulation at high temperature.

Hereinafter, the present invention will be further described in detail.

(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 per molecule, and generally known ones can be used. The cyanate ester compound may be, for example, represented by the following formula (1).

In Formula 1, R ¹ and R ² are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ³ is any of the following.

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

As the cyanate ester compound of the present invention, for example, bis(4-cyanatophenyl)methane, bis(3-methyl-4-cyanatophenyl)methane, bis(3-ethyl-4-cyanatophenyl)methane, 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, 1,3- and 1,4-dicyanatobenzene, 2-tert-butyl-1,4-dicyana Tobenzene, 2,4-dimethyl-1,3-dicyanatobenzene, 2,5-di-tert-butyl-1,4-dicyanatobenzene, tetramethyl-1,4-dicyanatobenzene, 1 ,3,5-tricyanatobenzene, 2,2'- or 4,4'-dicyanatobiphenyl, 3,3', 5,5'-tetramethyl-4,4'-dicyanatobiphenyl, 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-tris(4-cyanatophenyl)ethane, bis(4-cyanatophenyl)ether; 4,4'-(1,3-phenylenediisopropylidene)diphenylcyanate, bis(4-cyanatophenyl)thioether, bis(4-cyanatophenyl)sulfone, tris(4-cyanato-phenyl) )Phosphine, tris(4-cyanatophenyl)phosphate, phenol novolak type cyanate, cresol novolac type cyanate, dicyclopentadiene novolac type cyanate, phenylaralkyl type cyanate ester, biphenylaralkyl type cyanate ester, And naphthalene aralkyl type cyanate ester, etc. are mentioned. These cyanate ester compounds can be used alone or in combination of two or more.

The cyanate ester compound is obtained by reacting phenols with cyanochloride under basic conditions. The cyanate ester compounds range from solids with a softening point of 106°C to liquids at room temperature, but may be appropriately selected according to the application. For example, when preparing a liquid resin composition, a liquid compound is used at room temperature, and when dissolving in a solvent to obtain a varnish, it is preferable to select it according to solubility or solution viscosity. In addition, when using transfer molding for sealing a power semiconductor, it is preferable to select a solid compound at room temperature.

In addition, those having a small equivalent weight of cyanate groups, that is, those having a low molecular weight during the functional period, have small cure shrinkage, and low thermal expansion and high Tg cured products can be obtained. When the cyanate group equivalent is large, the Tg is slightly lowered, but the triazine crosslinking interval becomes flexible, and low elasticity, high toughness, and low water absorption can be expected. It is preferable that the amount of chlorine bonded or remaining in the cyanate ester compound is 50 ppm or less, more preferably 20 ppm or less. If the amount of chlorine exceeds 50ppm, chlorine or chlorine ions freed by thermal decomposition when left under high temperature for a long time corrode the oxidized Cu frame, Cu wire, and Ag plating, and there is a possibility that the cured product may be peeled off or electrical defects. have. In addition, there is a fear that the insulating properties of the resin will also decrease.

(B) inorganic filler

In the present invention, the type of the inorganic filler is not particularly limited, and a known filler may be used as the inorganic filler for the resin composition for sealing a semiconductor. For example, fused silica, crystalline silica, silicas such as cristobalite, alumina, silicon nitride, aluminum nitride, boronite, titanium oxide, glass fiber, magnesium oxide, and zinc oxide. The average particle diameter and shape of these inorganic fillers may be selected according to the application. Among them, in order to obtain a coefficient of thermal expansion close to that of silicon, a fused silica is preferable, and a spherical shape is preferable. The average particle diameter of the inorganic filler is preferably 0.1 to 40 µm, and more preferably 0.5 to 15 µm. The average particle diameter can be obtained as a weight average value (or median diameter) by laser light diffraction or the like.

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

In the present invention, the blending amount of the inorganic filler may be 70 to 95% by mass, preferably 80 to 95% by mass, and more preferably 86 to 94.5% by mass of the total composition.

(C) Amine Silane coupling agent

(C) component is a silane coupling agent having a group represented by a primary amine, secondary amine, tertiary amine, or -N=CR ₂ (R is a monovalent hydrocarbon group) at the terminal (hereinafter referred to as amine-based silane coupling agent). Is). The composition of the present invention is characterized by containing an amine-based silane coupling agent. Since the amine-based silane coupling agent has excellent affinity with the cyanate ester, it can reinforce the binding with the inorganic filler, and can significantly improve the fluidity of the composition. Therefore, even if the inorganic filler is blended in the composition at a high concentration of 70 to 95% by mass, the moldability of the composition and the mechanical strength of the resulting cured product are not impaired. Further, by using an amine-based silane coupling agent, the cyclization reaction of the cyanate ester compound can be accelerated, and the thermal expansion coefficient of the resulting cured cyanate ester can be reduced. Further, as shown in the comparative examples described later, the effects of the present invention cannot be obtained with a mercapto-based silane coupling agent or an epoxy-based silane coupling agent.

The silane coupling agent is preferably a compound represented by the following formula (3).

In Formula 3, R ¹ is a methyl group or an ethyl group, R ² is an alkyl group having 1 to 3 carbon atoms, and R ³ is a group selected from groups represented by the following Formula 4,

a is an integer selected from 0-2.

Examples of the silane coupling agent represented by the above formula (3) include N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, and N-2 ( Aminoethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propyl Amine, N-phenyl-3-aminopropyltrimethoxysilane, and N,N-bis[3-(trimethoxysilyl)propyl]ethylenediamine, and the like. The silane coupling agent may be a commercial item, for example, KBM-602, KBM-603, KBE-603, KBM-903, KBE-903, KBE-9103, KBM-573 (all manufactured by Shin-Etsu Chemical Co., Ltd. ,) and XS1003 (manufactured by Chisso Corporation), etc. can be used.

The (C) silane coupling agent may be previously treated on the surface of the (B) inorganic filler. The method for surface treatment of the inorganic filler using the silane coupling agent may be according to a conventionally known method and is not particularly limited.

The blending amount of the component (C) is preferably 0.15 to 0.5% by mass, preferably 0.2 to 0.4% by mass in the composition. If the amount of the component (C) is too small, a sufficient bond cannot be formed between the cyanate ester and the inorganic filler, or the composition cannot obtain sufficient fluidity. In addition, if the amount of the component (C) is too large, the expansion coefficient of the cured product may increase, which is not preferable.

(D) component

The component (D) of the present invention is at least one compound selected from an amine compound other than the component (C), a phenol compound, a phosphine compound, and an adduct of a phosphine compound and a quinone compound. Examples of the amine compounds other than the component (C) include (a) tertiary amines or salts thereof, and (b) amine compounds having active hydrogen or salts thereof. The blending amount of the component (D) is preferably 0.1 to 3 mass%, preferably 0.2 to 1.5 mass% in the composition.

While the component (D) functions as a catalyst for the cyclization reaction of the cyanate ester compound, it can react with a cyanate group. In particular, the phenol compound is incorporated in the cyclization reaction of the cyanate group to form a phenol-modified triazine ring structure, and is preferable because it can impart high heat resistance to the cured product.

(a) As a tertiary amine or its salt, 1,8-diazabicyclo (5.4.0) undecene-7 (DBU), 1,5-diazabicyclo (4.3.0) nonene-5 ( DBN), and salts thereof. Specific examples of the DBU salt include DBU phenol salt, octylate, p-toluenesulfonate, formate, orthophthalate, trimellitic anhydride, phenol novolak resin salt, and tetraphenylborate salt. On the other hand, specific examples of the DBN salt include DBN phenol salt, octylate, p-toluenesulfonate, formate, orthophthalate, trimellitic anhydride, phenol novolak resin salt, and tetraphenylborate salt. .

(b) As an amine compound having active hydrogen or a salt thereof, for example, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4 ,4'-diaminodiphenylmethane, 3,3',5,5'-tetraethyl-4,4'-diaminodiphenylmethane, 2,4-diaminotoluene, 1,4-phenylenediamine, 1,3-phenylenediamine, diethyltoluenediamine, 3,4-diaminodiphenylether, 3,3-diaminodiphenylmethane, 3,4-diaminodiphenylmethane, 4,4-diaminodi Phenylmethane, 3,3'-diaminobenzidine, orthotolidine, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodi Aromatic amine compounds such as phenylmethane, 2,4-diaminotoluene, 2,6-diaminotoluene, 1,4-phenylenediamine, 1,3-phenylenediamine, and 1,8-diaminonaphthalene, N ,N'-bis(3-aminopropyl)ethylenediamine, 3,3-diaminodipropylamine, 1,8-diaminooctane, 1,10-diaminodecane, diethylenetriamine, triethylenetetramine, And chain aliphatic polyamines such as tetraethylenepentamine, 1,4-bis(3-aminopropyl)piperazine, N-(2-aminoethyl)piperazine, N-(2-aminoethyl)morpholine, N- And cyclic aliphatic polyamines such as aminoethylpiperazine and isophoronediamine. Polyamideamine is produced by condensation of dimer acid and polyamine. For example, adipic acid dihydrazide and 7,11-octadecadiene-1,18-dicarbohydrazide are mentioned. Further, examples of the imidazole-based mixture include 2-methylimidazole, 2-ethyl-4-methylimidazole, and 1,3-bis(hydrazinocarboethyl)-5-isopropylhydantoin. Examples of the guanidine-based compound include aliphatic amines such as 1,3-diphenylguanidine and 1,3-o-triguanidine.

(c) As a phenol compound, for example, phenol, alkylphenol, such as nonylphenol, dinonylphenol, octylphenol, 3(2-hydroxyphenyl)propionic acid, 3(2-hydroxyphenyl)propanol, 2- Known phenols such as methoxy-4-allylphenol, 2-allylphenol, and bisphenol F type resin, bisphenol A type resin, phenol novolak resin, phenol aralkyl type resin, biphenyl aralkyl type resin, and naphthalene aralkyl type resin And compounds.

(d) As a phosphine compound, ethylphosphine, phenylphosphine, dimethylphosphine, diphenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, triphenylphosphine, etc. are mentioned.

(e) As an adduct of a phosphine compound and a quinone compound, the compound represented by the following formula is mentioned, for example.

In Formula 5, P represents a phosphorus atom, R is independently of each other, an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms, and R'is independently a hydrogen atom or a monovalent of 1 to 12 carbon atoms It is a hydrocarbon group, and R'may be bonded to each other to form a ring.

As a phosphine compound used in the adduct of a phosphine compound and a quinone compound, tricyclohexylphosphine, tributylphosphine, dibutylphenylphosphine, butyldiphenylphosphine, ethyldiphenylphosphine, triphenylphosphine Pin, tris (4-methylphenyl) phosphine, tris (4-ethylphenyl) phosphine, tris (4-propylphenyl) phosphine, tris (4-butylphenyl) phosphine, tris (isopropylphenyl) phosphine, Tris(t-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris( 2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, etc. are mentioned. Among them, triphenylphosphine is preferred from the viewpoint of availability. Examples of the quinone compound include o-benzoquinone, p-benzoquinone, anthraquinone, diphenoquinone, and 1,4-naphthoquinone. Among them, p-benzoquinone is preferable. The method for preparing the adduct of the phosphine compound and the quinone compound may be performed according to a conventionally known method. For example, an adduct can be obtained by contacting and mixing organic tertiary phosphine and benzoquinones in a solvent. As the solvent, acetone, methyl ethyl ketone, or the like is preferably used.

As the adduct of the phosphine compound and the quinone compound, a compound represented by the following formula (6) is particularly preferable.

Conventionally, metal salts, metal complexes, etc. have been used as curing catalysts for cyanate ester compounds (Japanese Laid-Open Patent Publication No. 64-43527, Japanese Laid-Open Patent Publication No. Hei 11-106480, and Japanese Laid-Open Patent Publication No. 2005-506422). . However, transition metals are used as metal salts and metal complexes, and transition metals may accelerate oxidation deterioration of organic resins under high temperatures. In the composition of the present invention, the (C) component and (D) component function as a catalyst for the cyclization reaction of the cyanate ester compound. Therefore, it is not necessary to use metal salts and metal complexes. This can further improve long-term storage stability under high temperature.

In the sealing resin composition of the present invention, if necessary, various additives such as a release agent, a flame retardant, an ion trap agent, an antioxidant, an adhesion-imparting agent, a low stress agent, and a colorant may be added.

The mold release agent is not particularly limited, and a known one can be used. For example, carnauba wax, rice wax, candelilla wax, polyethylene, polyethylene oxide, polypropylene, montanic acid, montanic acid, saturated alcohol, 2-(2-hydroxyethylamino)-ethanol, ethylene glycol, glycerin Montanic acid wax, stearic acid, stearic acid ester, stearic acid amide, ethylenebisstearic acid amide, and a copolymer of ethylene and vinyl acetate, which are ester compounds such as the like. These can be used alone or in combination of two or more.

The flame retardant is not particularly limited, and any known flame retardant can be used. For example, a phosphazene compound, a silicon compound, a zinc molybdate-supported talc, a zinc molybdate-supported zinc oxide, aluminum hydroxide, magnesium hydroxide, molybdenum oxide, and antimony trioxide are mentioned.

The ion trapping agent is not particularly limited, and a known one can be used. For example, hydrotalcite), a bismuth hydroxide compound, a rare earth oxide, etc. are mentioned.

The method for preparing the composition of the present invention is not particularly limited. For example, stirring, dissolving, mixing, and dispersing the above (A) to (D) components simultaneously or separately, applying heat treatment as needed, and optionally adding other additives to these mixtures to mix, It can be obtained by stirring and dispersing. The device used for mixing is not particularly limited, but a grinding machine equipped with a stirring and heating device, two rolls, three rolls, a ball mill, a continuous extruder, a planetary mixer, a masscolloider, etc. I can. These devices may be appropriately combined and used.

The composition of the present invention can be molded using a conventionally employed molding method, for example, transfer molding, compression molding, injection molding, and molding method. It is preferable that the molding temperature of the composition of the present invention is 120 to 190°C for 45 to 600 seconds, and the postcure at 160 to 250°C for 2 to 16 hours.

Since the composition of the present invention has a small coefficient of thermal expansion, it is possible to reduce warpage when it is formed on an 8-inch wafer. In addition, it is possible to provide a cured product having less thermal decomposition (reduction in weight) when left under a high temperature of 200°C or higher for a long period of time, and excellent in mechanical strength and insulation at high temperature. Accordingly, it is possible to provide a semiconductor device having high temperature and long-term reliability. In addition, it can be used in the same apparatus as the epoxy resin composition generally used as a conventional transfer molding material, and the same molding conditions can be used. In addition, it is also excellent in productivity.

(Example)

Hereinafter, examples and comparative examples are shown and the present invention is described in more detail, but the present invention is not limited to the following examples. In addition, all of the parts in each example are mass parts.

[Examples 1 to 5, Comparative Examples 1 to 7]

Each component described below was uniformly melt-mixed using two hot rolls in the formulation shown in Table 1, cooled, and pulverized to obtain a resin composition.

(A) Cyanate ester compound

(A) Phenol novolak-type cyanate ester represented by the following formula (7) (Primer Set PT-60, manufactured by Longer Japan Corporation)

(B) 1,1-bis(4-cyanatophenyl)ethane represented by the following formula (8) (manufactured by Hanzman Japan Co., Ltd.)

(B) Inorganic filler: fused spherical silica having an average particle diameter of 14 μm (manufactured by Tatsumori)

(C) Amine-based silane coupling agent

(C) Silane coupling agent represented by the following formula (9): KBM-573 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.)

(D) Silane coupling agent represented by the following formula (10): KBM-903 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.)

(E) Silane coupling agent for comparative examples

Mercapto-based silane coupling agent: KBM-803 (manufactured by Shin-Etsu Chemical Co., Ltd.)

Epoxy clock silane coupling agent: KMB-403 (manufactured by Shin-Etsu Chemical High School)

(D) component

(F) Salt of DBU and phenol novolac: U CAT-SA831 (san aprose)

(G) Aromatic amine compound represented by the following formula (11)

(H) Biphenylaralkyl resin represented by the following formula (12)

(I) Phenol novolak resin represented by the following formula (13) (made by Meiwa Kasei Co., Ltd.)

(Tea) Compound represented by the following formula (14)

(E) Resin used in Comparative Example

(K) Epoxy resin: Biphenyl type epoxy resin YX-4000K (manufactured by Mitsubishi Chemical)

(T) Epoxy resin: Bis A type epoxy resin epicoater 828 (manufactured by Mitsubishi Chemical)

(F) other additives

(Far) Carbon Black Mitsubishi Carbon 3230MJ (Mitsubishi Chemical)

The composition was molded under the conditions of 175°C, 6.9 N/mm 2 and a molding time of 180 seconds. After that, it was further post-cured at 220° C. for 4 hours to obtain a test piece having each dimension described below. The following evaluation test was performed using the said test piece. Table 1 shows the results.

[200℃ bending strength]

According to JIS-K6911, a 10×100×4 mm test piece was prepared by the above-described method, and the test piece was left in an oven at 200°C for 3 minutes, and then bent at 3 points with an autograph tester (manufactured by Shimadzu Corporation), bending strength. Was measured.

[200℃ volume resistivity]

According to JIS-K6911, a test piece having a diameter of 90 mm and a thickness of 2 mm was prepared by the method described above, and the test piece was left in an oven at 200° C. for 5 minutes, and then the volume resistance value was measured.

[Glass transition temperature, linear expansion coefficient]

A test piece of 5×5×15 mm was prepared by the method described above, and the test piece was set in a thermal expansion meter (Rigaku TMA8140C), and the dimensional change to 300°C was measured at 5°C/min of temperature increase and 19.6 mN of load. Draw a graph of dimensional change and temperature, and two points at which the tangent line of the dimensional change-temperature curve is obtained below the temperature of the inflection point (A1, A2), and two points at which the tangent line is obtained above the temperature of the inflection point (B1, B2) was selected, and the intersection of the straight line connecting A1 and A2 and the straight line connecting B1 and B2 was taken as the glass transition degree. The slopes of A1 to A2 were taken as coefficients of linear expansion of Tg or less, and the slopes of B1 to B2 were taken as coefficients of linear expansion of Tg or more.

[Weight reduction after storage at 200℃×1000 hours]

A test piece having a diameter of 50 mm and a thickness of 3 mm was prepared by the method described above, and the test piece was stored in an oven at 200° C. for 1000 hours, and then the weight reduction rate was measured.

A cured product obtained from a composition using an epoxy-based silane coupling agent or a mercapto-based silane coupling agent has poor mechanical strength under high temperature, and has a large weight loss when stored at 200°C for 1000 hours (Comparative Examples 2, 6 and 7). . When the silane coupling agent is not contained at all, the dispersibility of the inorganic filler in the composition is poor, and a uniform composition cannot be obtained (Comparative Example 3). In addition, even if it contains (C) component, if it does not contain (D) component, the composition becomes a hardening defect (comparative example 5). In contrast, the composition of the present invention has a small coefficient of thermal expansion, has excellent mechanical strength even under high temperature, and has a small weight loss even when stored at 200°C for 1000 hours.

The cured product obtained by the resin composition of the present invention is excellent in mechanical strength at high temperature, insulation, and long-term storage stability, and has low thermal expansion. Therefore, it is preferable as a sealing material for a wafer mold or a sealing material for a power semiconductor.

Claims (4)

(A) Cyanate ester compound having two or more cyanato groups in one molecule
(B) Inorganic filler in an amount of 86 to 94.5% by mass of the total composition
(C) a silane coupling agent represented by the following formula (3):
(Chemical Formula 3)

[In Formula 3, R ¹ is a methyl group or an ethyl group, R ² is an alkyl group having 1 to 3 carbon atoms, and R ³ is a group selected from a group represented by the following Formula 4,
(Formula 4)

a is an integer selected from 0-2], and
(D) A composition comprising at least one compound selected from an amine compound other than the component (C), a phenol compound, a phosphine compound, and an adduct of a phosphine compound and a quinone compound. delete The method of claim 1,
The composition in which the component (D) is at least one selected from a tertiary amine or a salt thereof, an amine compound or a salt thereof having active hydrogen, a phenol compound, and a compound represented by the following formula (6).
(Formula 6)

A semiconductor device provided with a cured product of the composition according to any one of claims 1 and 3.