TWI696655B - Molding material composition for sealing SiC and GaN elements, electronic parts device - Google Patents

Abstract

The molding material composition for SiC and GaN device sealing of the present invention contains (A) maleimide resin, (B) hardener, (D) hardening accelerator and (E) filler, and the above (E) filler Contains (e-1) hollow structure filler.

Description

Molding material composition for sealing SiC and GaN elements, electronic parts device

The invention relates to a molding material composition for sealing SiC and GaN elements and an electronic component device.

Previously, epoxy resin molding materials have been widely used in the fields of transistors, ICs (integrated circuits) and other electronic parts sealing. The reason for this is that epoxy resins have excellent balance between electrical characteristics, moisture resistance, mechanical characteristics, and adhesion to interposers.

In recent years, opportunities for energy saving worldwide have increased against the background of uneasiness about the future depletion of resources and energy or the so-called problem of global warming. Power devices (power semiconductors) called "key components of energy-saving technology" that control or convert power are receiving attention. For power semiconductors, power conversion efficiency is one of the items that determines its performance. Nowadays, the research and development of compound semiconductors such as silicon carbide (SiC) and gallium nitride (GaN), which have higher conversion efficiency than previous Si devices, and the circulation in the market are booming.

In particular, SiC devices have higher withstand voltage characteristics than Si devices. Therefore, if the SiC device is applied, a power semiconductor module with higher withstand voltage can be realized. Along with this, peripheral components other than power semiconductor elements are required to have higher withstand voltage characteristics, such as tracking resistance and higher dielectric breakdown voltage.

The SiC device can be exemplified by the fact that it can perform high-temperature operation compared to the previous Si device. The above-mentioned higher withstand voltage characteristics mean that the heat generation of the device itself also becomes higher. Therefore, the ability to perform high-temperature operations also requires higher heat resistance for peripheral members. Regarding SiC devices, there are also reports of operations at temperatures above 300°C, and higher glass transition temperatures and higher thermal decomposition resistance are required for molding materials for sealing.

As a technique for providing a high glass transition temperature to the molding material for sealing and ensuring reliability at high temperatures, there are proposed epoxy resins, phenol resins, compounds having a maleimide group, and phenol compounds having an alkenyl group An epoxy resin composition for sealing as an essential component (for example, Patent Document 1). In addition, there has been proposed a resin composition for sealing obtained by mixing a maleimide compound and a benzoxanthene compound at a specific ratio and adding a triazole-based compound (for example, Patent Document 2). Furthermore, an organic-inorganic nano-hybrid resin using a copolymer of maleimide resin and cyanate resin as a resin component and inorganic nano particles as an inorganic component has been proposed (for example, Patent Document 3). Furthermore, there have been reports of a resin composition for sealing (for example, Patent Document 4) in which a maleimide compound, a diamidide compound, an amine compound, and a catalyst are blended at a specific ratio. [Prior Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 2006-299246 Patent Document 2: Japanese Patent Laid-Open No. 2015-101667 Patent Document 3: Japanese Patent Laid-Open No. 2013-010843 Patent Document 4: Japanese Patent Laid-Open No. 2015-147850 Bulletin

[Problems to be solved by the invention]

In order to ensure reliability at high temperatures, a higher glass transition temperature (Tg) and higher adhesion to semiconductor insert parts are required. However, it is usually difficult to balance these in most cases. If a resin with a higher glass transition temperature (Tg) is used, there are many cases where peeling from semiconductor insertion parts occurs. Furthermore, it is difficult to ensure sufficient adhesion to semiconductor insertion parts, and also to take into account the moldability of molding materials related to the productivity of semiconductor parts. In addition, in Patent Document 4, a diazoimide compound is added to ensure adhesion. However, the use of an amine compound as a hardener may cause insufficient electrical characteristics when sealing a SiC element or the like to which a high voltage is applied.

The present invention has been completed in view of this actual situation, and the molding material composition for sealing has a relatively high glass transition temperature (Tg). Furthermore, the molding material composition for sealing can obtain a cured product having high thermal decomposition resistance, excellent curability and moldability, high voltage resistance, good adhesion to semiconductor insertion parts, and high reliability. Furthermore, the present invention can also be applied to electronic component devices using the molding material composition for sealing. [Technical means to solve the problem]

The inventors of the present invention found that the combination of a specific resin and a filler used as resins for SiC and GaN devices satisfies the reliability in the operating environment of a power device, and completed the present invention.

That is, the present invention is related to the following. [1] A molding material composition for SiC and GaN element sealing, which contains (A) maleimide resin, (B) hardener, (D) hardening accelerator, and (E) filler, and (E) ) The filler contains (e-1) hollow structure filler. [2] The molding material composition for SiC and GaN device sealing as described in [1] above, wherein the (A) maleimide resin is a maleimide resin represented by the following general formula (I).

(式中，R¹ 分別獨立地為碳數1～10之烴基，並且烴基可經鹵素原子取代；於存在複數個R¹ 之情形時，該複數個R¹ 可相互相同亦可不同；p分別獨立地為0～4之整數，q為0～3之整數，z為0～10之整數) [3]如上述[1]或[2]之SiC及GaN元件密封用成形材料組合物，其中上述(B)硬化劑係酚系硬化劑及苯并㗁𠯤樹脂之至少1種，上述酚系硬化劑係下述通式(II)所表示之酚系硬化劑、及下述通式(III)所表示之酚系硬化劑之1種或2種，上述苯并㗁𠯤樹脂係由下述通式(IV)所表示。[Chem 1]

(In the formula, R ^{1 is} independently a hydrocarbon group having 1 to 10 carbon atoms, and the hydrocarbon group may be substituted with a halogen atom; in the presence of a plurality of R ¹ , the plurality of R ¹ may be the same as or different from each other; p respectively Independently an integer of 0 to 4, q is an integer of 0 to 3, and z is an integer of 0 to 10) [3] The molding material composition for SiC and GaN device sealing as described in [1] or [2] above, wherein At least one of the above (B) hardener-based phenol-based hardeners and benzo resins, the above-mentioned phenol-based hardeners are phenol-based hardeners represented by the following general formula (II), and the following general One or two of the phenolic hardeners represented by the formula (III), and the above benzo resins are represented by the following general formula (IV).

(式中，x為0～10)[Chem 2]

(In the formula, x is 0～10)

(式中，y1為0～10)[Chemical 3]

(In the formula, y1 is 0～10)

(式中，X1為碳數1～10之伸烷基、氧原子、或直接鍵；R² 及R³ 分別獨立地為碳數1～10之烴基；於存在複數個R² 及R³ 之情形時，複數個R² 及複數個R³ 分別可相同亦可不同；m1及m2分別獨立地為0～4之整數) [4]如上述[1]至[3]中任一項之SiC及GaN元件密封用成形材料組合物，其進而包含(C)熱硬化性樹脂，且該(C)熱硬化性樹脂係選自下述通式(V)～(VII)所表示之環氧樹脂、一分子中具有至少2個氰酸酯基之氰酸酯單體、及下述通式(VIII)所表示之含烯丙基之耐地醯亞胺(nadiimido)樹脂中之至少1種。[Chem 4]

(In the formula, X1 is a C 1-10 alkylene group, an oxygen atom, or a direct bond; R ² and R ³ are each independently a C 1-10 hydrocarbon group; in the presence of a plurality of R ² and R ³ In this case, plural R ² and plural R ³ may be the same or different; m1 and m2 are independently integers of 0 to 4) [4] SiC as described in any one of [1] to [3] above And a molding material composition for GaN element sealing, which further comprises (C) thermosetting resin, and the (C) thermosetting resin is selected from epoxy resins represented by the following general formulas (V) to (VII) . At least one of a cyanate monomer having at least 2 cyanate groups in one molecule, and an allyl group-containing nadiimido resin represented by the following general formula (VIII).

(式中，n1為0～10)[Chemical 5]

(In the formula, n1 is 0～10)

(式中，n2為0～10)[化6]

(In the formula, n2 is 0～10)

[化7]

(式中，R⁴ 係碳數1～10之伸烷基、碳數4～8之伸環烷基、碳數6～18之二價芳香族基、通式「-A¹ -C₆ H₄ -(A¹ )_m -(其中，m表示0或1之整數，各A¹ 分別獨立地為碳數1～10之伸烷基、碳數4～8之伸環烷基)」所表示之基、或通式「-C₆ H₄ -A² -C₆ H₄ -(此處，A² 係「-CH₂ -」、「-C(CH₃ )₂ -」、 「-CO-」、「-O-」、「-S-」或「-SO₂ -」所表示之基)」所表示之基) [5]如上述[1]至[4]中任一項之SiC及GaN元件密封用成形材料組合物，其中上述(D)硬化促進劑係(d-1)有機磷系硬化促進劑與(d-2)咪唑系硬化促進劑。 [6]如上述[1]至[5]中任一項之SiC及GaN元件密封用成形材料組合物，其中上述(e-1)中空結構填充材之平均粒徑為3～100 μm。 [7]如上述[1]至[6]中任一項之SiC及GaN元件密封用成形材料組合物，其中上述(e-1)中空結構填充材係選自二氧化矽、氧化鋁、二氧化矽-氧化鋁化合物中之至少1種，且該(e-1)中空結構填充材之含量相對於上述(E)填充材總量為1～50質量%。 [8]如上述[1]至[6]中任一項之SiC及GaN元件密封用成形材料組合物，其中上述(e-1)中空結構填充材包含有機化合物，且該(e-1)中空結構填充材之含量相對於(E)填充材總量為0.5～10質量%。 [9]如上述[1]至[6]中任一項之SiC及GaN元件密封用成形材料組合物，其中上述(e-1)中空結構填充材包含倍半矽氧烷化合物，且該(e-1)中空結構填充材之含量相對於(E)填充材總量為0.5～10質量%。 [10]如上述[1]至[9]中任一項之SiC及GaN元件密封用成形材料組合物，其中上述(D)硬化促進劑係(d-1)有機磷系硬化促進劑與(d-2)咪唑系硬化促進劑，且上述(d-2)咪唑系硬化促進劑係與雙酚A型環氧樹脂(液狀)以其質量比設為1/20進行反應時之反應起始溫度在85℃以上且未達175℃之咪唑系硬化促進劑。 [11]如上述[4]至[10]中任一項之SiC及GaN元件密封用成形材料組合物，其中上述(C)熱硬化性樹脂係一分子中具有至少2個氰酸酯基之氰酸酯單體，且相對於上述(A)成分之100質量份為10～50質量份。 [12]如上述[4]至[11]中任一項之SiC及GaN元件密封用成形材料組合物，其中上述(C)熱硬化性樹脂係下述通式(VIII)所表示之含烯丙基之耐地醯亞胺樹脂，進而上述(D)硬化促進劑含有(d-3)酸系硬化促進劑。[Chem 8]

(In the formula, R ⁴ is a C 1-10 alkylene group, a C 4-8 cycloalkyl group, a C 6-18 divalent aromatic group, the general formula "-A ¹ -C ₆ H ₄ -(A ¹ ) _m -(where m represents an integer of 0 or 1, and each A ^{1 is} independently an alkylene group having 1 to 10 carbon atoms and a cycloalkylene group having 4 to 8 carbon atoms)" Base, or the general formula "-C ₆ H ₄ -A ² -C ₆ H ₄ -(Here, A ² is "-CH ₂ -", "-C(CH ₃ ) ₂ -", "-CO- ", "-O-", "-S-" or "-SO ₂ -" represents the base)") (5) SiC and any of the above [1] to [4] A molding material composition for GaN element sealing, wherein the above (D) hardening accelerator system (d-1) organophosphorus curing accelerator and (d-2) imidazole curing accelerator. [6] The molding material composition for sealing SiC and GaN devices according to any one of the above [1] to [5], wherein the average particle diameter of the (e-1) hollow structure filler is 3 to 100 μm. [7] The molding material composition for SiC and GaN device sealing according to any one of the above [1] to [6], wherein the (e-1) hollow structure filler is selected from silica, alumina, and At least one of the silica-alumina compounds, and the content of the (e-1) hollow structure filler is 1 to 50% by mass relative to the total amount of the (E) filler. [8] The molding material composition for sealing SiC and GaN elements according to any one of the above [1] to [6], wherein the above (e-1) hollow structure filler contains an organic compound, and the (e-1) The content of the hollow structure filler is 0.5 to 10% by mass relative to the total amount of (E) filler. [9] The molding material composition for sealing SiC and GaN devices according to any one of the above [1] to [6], wherein the above (e-1) hollow structure filler includes a sesquisilane compound, and the ( e-1) The content of the hollow structure filler is 0.5 to 10% by mass relative to the total amount of (E) filler. [10] The molding material composition for sealing SiC and GaN devices according to any one of the above [1] to [9], wherein the above (D) hardening accelerator system (d-1) organophosphorus curing accelerator and ( d-2) Imidazole-based hardening accelerator, and the above (d-2) imidazole-based hardening accelerator is reacted with bisphenol A epoxy resin (liquid) at a mass ratio of 1/20 Imidazole-based hardening accelerators with an initial temperature above 85°C and less than 175°C. [11] The molding material composition for SiC and GaN device sealing according to any one of the above [4] to [10], wherein the above (C) thermosetting resin is one having at least 2 cyanate groups in one molecule The cyanate ester monomer is 10 to 50 parts by mass with respect to 100 parts by mass of the component (A). [12] The molding material composition for sealing SiC and GaN devices according to any one of the above [4] to [11], wherein the (C) thermosetting resin is an alkene-containing compound represented by the following general formula (VIII) The propylidene diimide resin and the (D) hardening accelerator further contain (d-3) acid-based hardening accelerator.

(式中，R⁴ 係碳數1～10之伸烷基、碳數4～8之伸環烷基、碳數6～18之二價芳香族基、通式「-A¹ -C₆ H₄ -(A¹ )_m -(其中，m表示0或1之整數，各A¹ 分別獨立地為碳數1～10之伸烷基、碳數4～8之伸環烷基)」所表示之基、或通式「-C₆ H₄ -A² -C₆ H₄ -(此處，A² 係「-CH₂ -」、「-C(CH₃ )₂ -」、 「-CO-」、「-O-」、「-S-」或「-SO₂ -」所表示之基)」所表示之基) [13]如上述[12]之SiC及GaN元件密封用成形材料組合物，其中上述(d-3)酸系硬化促進劑係選自對甲苯磺酸、其胺鹽及三氟化硼胺錯合物中之至少1種。 [14]一種電子零件裝置，其具備由如上述[1]至[13]中任一項之SiC及GaN元件密封用成形材料組合物之硬化物密封之SiC及GaN元件。 [發明之效果][化9]

(In the formula, R ⁴ is a C 1-10 alkylene group, a C 4-8 cycloalkyl group, a C 6-18 divalent aromatic group, the general formula "-A ¹ -C ₆ H ₄ -(A ¹ ) _m -(where m represents an integer of 0 or 1, and each A ^{1 is} independently an alkylene group having 1 to 10 carbon atoms and a cycloalkylene group having 4 to 8 carbon atoms)" Base, or the general formula "-C ₆ H ₄ -A ² -C ₆ H ₄ -(Here, A ² is "-CH ₂ -", "-C(CH ₃ ) ₂ -", "-CO- ", "-O-", "-S-", or "-SO ₂ -" (base represented by ")") [13] The molding material composition for SiC and GaN device sealing as described in [12] above Wherein the (d-3) acid-based hardening accelerator is at least one selected from p-toluenesulfonic acid, its amine salt, and boron trifluoride amine complex. [14] An electronic component device comprising SiC and GaN elements sealed by a cured product of the molding material composition for sealing SiC and GaN elements according to any one of the above [1] to [13]. [Effect of invention]

According to the present invention, the molding material composition for sealing has a relatively high glass transition temperature (Tg). Furthermore, the molding material composition for sealing can obtain a cured product having high thermal decomposition resistance, excellent curability and moldability, high voltage resistance, good adhesion to semiconductor insertion parts, and high reliability. Furthermore, the present invention can also be applied to electronic component devices using the molding material composition for sealing.

Hereinafter, the present invention will be described in detail. (Molding material composition for SiC and GaN element sealing) The molding material composition for SiC and GaN element sealing of the present invention contains (A) maleimide resin, (B) hardener, (D) hardening accelerator and ( E) Filling material. The (E) filler mentioned above contains (e-1) a hollow structure filler.

First, the present invention describes each component of a molding material composition for sealing SiC and GaN devices (hereinafter, also simply referred to as a molding material composition for sealing). [(A) Maleimide resin] The maleimide resin of (A) component used in the present invention may be represented by the following general formula (I) and contains two or more males in one molecule Compounds with amide imino groups. (A) The component maleimide resin is a resin that hardens by forming a three-dimensional network structure by reacting maleimide groups with heat. In addition, the above-mentioned maleimide resin imparts a higher glass transition temperature (Tg) to the cured product through a cross-linking reaction to improve heat resistance and thermal decomposition resistance.

[化10]

In the above general formula (I), R ^{1 is} independently a hydrocarbon group having 1 to 10 carbon atoms, and the hydrocarbon group may be substituted with a halogen atom. p is independently an integer from 0 to 4, and q is an integer from 0 to 3. Examples of the hydrocarbon group having 1 to 10 carbon atoms include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and heptyl groups; substituted alkyl groups such as chloromethyl and 3-chloropropyl groups; ; Alkenyl groups such as vinyl, allyl, butenyl, pentenyl and hexenyl; aryl groups such as phenyl, tolyl and xylyl; monovalent hydrocarbon groups such as benzyl and phenethyl . In addition, when there are plural R ^1s , the plural R ^1s may be the same as or different from each other. z is an integer from 0 to 10, and may also be an integer from 0 to 4.

The maleimide resin represented by the above general formula (I) is relatively easily added at a temperature of 170° C. or higher in the presence of the following (B) component hardener and (D) component hardening accelerator Reaction, and imparts higher heat resistance to the cured product of the molding material composition for sealing.

Specific examples of the maleimide resin represented by the general formula (I) include, for example, N,N'-(4,4'-diphenylmethane)bismaleimide and bis(3- Ethyl-5-methyl-4-maleimidophenyl)methane, polyphenylmethanemaleimide, etc. In addition, the above-mentioned maleimide resin can be obtained as a commercially available product, for example, BMI and BMI having N=0,4′-(4,4′-diphenylmethane)bismaleimide with z=0 as the main component. -70 (manufactured by KI Chemical Industry Co., Ltd.), BMI-1000 (manufactured by Daiwa Chemical Industry Co., Ltd.), BMI-2300 with polyphenylmethane maleimide with z=0 to 2 as the main component (Manufactured by Yamato Chemical Industry Co., Ltd.) etc.

The maleimide resin of the above component (A) may be used by premixing a part or the total amount thereof with a part or the total amount of the hardener of the following component (B) in advance. The method of premixing is not particularly limited, and a well-known mixing method can be used. For example, the pre-mixing method may include the following method: after melting the component (B) at 50 to 180°C using a stirring device, the maleimide resin of the component (A) is slowly added while stirring Mix. After all of it is melted, it is further stirred for about 10 to 60 minutes to prepare a pre-mixed resin. Furthermore, two or more kinds of hardeners of component (B) may be used for premixing.

The maleimide resin of the above-mentioned component (A) may be a horse other than the maleimide resin represented by the above general formula (I) and other than the maleimide resin represented by the above general formula (I) Laimide resin. Examples of maleimide resins that can be used in combination include m-phenylene bismaleimide, 2,2-bis[4-(4-maleimidophenoxy)phenyl] Propane, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, etc. A previously known maleimide resin other than these may also be used in combination. Furthermore, when blending maleimide resins other than the maleimide resin represented by the general formula (I) above, the blending amount is relative to 100 masses of the maleimide resin (A) component The part may be 30 parts by mass or less, 20 parts by mass or less, or 10 parts by mass or less.

The content of the component (A) may be 30 to 70% by mass or 35 to 65% by mass with respect to the total content of the components (A) to (C) as 100% by mass. If the content of (A) component is 30% by mass or more, the heat resistance of the molding material composition for sealing can be improved. If the content of the component (A) is 70% by mass or less, the adhesion between the hardened product of the molding material composition for sealing and the semiconductor insertion part can be improved.

[(B) Hardener] The hardener of the component (B) used in the present invention may also contain at least one of the following phenol-based hardeners and benzo resins, and the above-mentioned phenol-based hardeners are One or two of the phenolic hardeners represented by the general formula (II) and the phenolic hardeners represented by the general formula (III) above, the benzo resin is composed of the general formula (IV ). The above component (B) can relatively easily undergo an addition reaction with the component (A) in the presence of the following organophosphorus curing accelerator of the component (d-1). The component (B) has a tendency to indirectly reduce the self-polymerization reaction of the maleimide resin as the component (A) and relax the peeling stress. In addition, the heat resistance, adhesion, and moldability of the molding material composition for sealing are improved.

The phenolic hardener is represented by the following general formulas (II) and (III), and has at least two hydroxyl groups in one molecule.

(式中，x為0～10)[Chem 11]

(In the formula, x is 0～10)

(式中，y1為0～10)[化12]

(In the formula, y1 is 0～10)

In the above general formula (II), x is 0 to 10, and may be 1 to 4. In addition, in the above general formula (III), y1 is 0 to 10, and may be 0 to 3.

The phenol resin represented by the above general formula (II) can be obtained as a commercially available product MEH-7500 (manufactured by Meiwa Chemical Industry Co., Ltd.), and the phenol resin represented by the above general formula (III) can be obtained as a commercially available product SN- 485 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.).

The aforementioned benzo㗁𠯤 resin has two benzo㗁𠯤 rings in one molecule, and is represented by the following general formula (IV).

[Chem 13]

In the above general formula (IV), X1 is a C 1-10 alkylene group, an oxygen atom, or a direct bond. R ² and R ³ are each independently a hydrocarbon group having 1 to 10 carbon atoms.

The carbon number of the alkylene group of X1 is 1-10, and it can also be 1-3. Specific examples of the alkylene group include methylene group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group and the like. The alkylene can be methylene, ethyl, propyl, or methylene.

Examples of the hydrocarbon groups having 1 to 10 carbon atoms for R ² and R ³ include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and heptyl groups; vinyl, allyl, and butyl Alkenyl groups such as alkenyl, pentenyl and hexenyl; aryl groups such as phenyl, tolyl and xylyl; monovalent hydrocarbon groups such as aralkyl such as benzyl and phenethyl. In addition, when there are plural R ² and R ³ , plural R ² and plural R ³ may be the same or different, respectively.

m1 is independently an integer of 0 to 4, and may be an integer of 0 to 2, or 0. m2 is independently an integer of 0 to 4, and may be an integer of 0 to 2, or 0.

As specific examples of the benzoxanthene resin represented by the general formula (IV), for example, resins represented by the following formulas (IV-1) to (IV-4) can be cited. One type of these resins may be used, or two or more types may be used in combination.

[化14]

[化15]

[Chem 16]

[化17]

As the benzoxanthene resin, the benzoxanthene resin represented by the above formula (IV-1) may also be used. In addition, in the benzo㗁𠯤 resin represented by the general formula (VI), the content of the benzo㗁𠯤 resin represented by the above formula (IV-1) may be 50-100% by mass, and It may be 60 to 100% by mass or 70 to 100% by mass.

The benzo㗁𠯤 resin represented by the above formula (IV-1) can be obtained in the form of commercially available products such as benzo㗁𠯤P-d (manufactured by Shikoku Chemical Industry Co., Ltd.).

As the component (B), the compounds represented by the general formulae (II) to (IV) may be used alone, or two or more of these may be used in combination. From the viewpoint of heat resistance, the benzoxanthene resin represented by the general formula (IV) can be used alone or as a main component of the (B) component. From the viewpoint of productivity and formability, the phenol resins represented by the general formula (II) and the general formula (III) may be used alone or in combination. When the phenol resins represented by the general formula (IV) and/or the general formula (III) are used in combination, the balance of heat resistance and moldability can be obtained It is an excellent molding material composition for sealing and is one of the embodiments of the present invention.

In the present invention, from the viewpoint of the balance of heat resistance, adhesion, and formability, the content of (B) component may be 20 to 250 parts by mass relative to 100 parts by mass of (A) component, or It may be 30 to 200 parts by mass, or may be 40 to 150 parts by mass. Regarding the content of the component (B), when two or more components (B) are used in combination, the total amount thereof may be within the above range.

In the present invention, previously known phenolic hardeners and/or benzoxanthenes other than the compounds represented by the general formulae (II) to (IV) may be used in combination. In addition, the present invention can also use an acid anhydride or an amine hardener.

[(C) Thermosetting resin] The molding material composition for sealing of the present invention may further include a thermosetting resin of (C) component. (C) The thermosetting resin of the component can be carried out in the presence of the phosphorus curing accelerator as the component (d-1) or the imidazole curing accelerator as the component (d-2) and the curing agent of the component (B) Addition reaction. In addition, the thermosetting resin of the component (C) may be selected from epoxy resins represented by the following general formulas (V) to (VII), and cyanate monomers having at least 2 cyanate groups in one molecule. At least one of the allyl-containing diamidide-resistant resin represented by the following general formula (VIII).

(Epoxy resins represented by general formulas (V) to (VII)) The epoxy resins represented by the following general formulas (V) to (VII) have two or more epoxy groups in one molecule and contain three Phenyl methane skeleton and/or naphthalene skeleton. The above-mentioned epoxy resin has the effect of improving the moldability by starting the reaction from a relatively low temperature, and generating hydroxyl groups during the addition reaction to impart adhesion. In addition, the epoxy resin has a function of performing crosslinking reaction with the curing agent of the component (B) to improve moldability and adhesion. The above epoxy resin has this effect, and also has the following (d-2) component imidazole hardening accelerator to promote the self-polymerization reaction of the (A) component maleimide resin to improve molding for sealing The hardenability of the material composition gives good formability. One type of the epoxy resin may be used, or two or more types may be used in combination.

(式中，n1為0～10)[Chemical 18]

(In the formula, n1 is 0～10)

(式中，n2為0～10)[Chem 19]

(In the formula, n2 is 0～10)

[化20]

In the above general formula (V), n1 is 0 to 10, and may be 0 to 3. In addition, in the above general formula (VI), n2 is 0 to 10, and may be 0 to 3.

The epoxy resin represented by the above general formula (V) can be obtained in the form of a commercially available product EPPN-502H (manufactured by Nippon Kayaku Co., Ltd.), and the epoxy resin represented by the above general formula (VI) can be in the form of a commercially available product Obtain ESN-375 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), and the epoxy resin represented by the above general formula (VII) can be obtained as HP-4710 (manufactured by DIC) in the form of a commercially available product.

From the viewpoint of improving the productivity and the fluidity of the molding material composition for sealing, the softening point of the epoxy resins represented by the general formulas (V) to (VII) may be 55 to 100°C or 60 to 90 ℃, can also be 65 ~ 85 ℃.

In the molding material composition for sealing of the present invention, the content of the epoxy resin as the component (C) can be adjusted as follows from the viewpoint of balancing the glass transition point, adhesion, moldability, and the like. Regarding the content of the epoxy resin as the component (C), (c)/[(b-1)+(b-2)] (equivalent ratio) may be 0.2 to 1.5 or 0.3 to 1.2. (b-1) The hydroxyl group of the phenolic hardener of the component (B). In addition, (b-2) is a hydroxy group generated when benzo㗁𠯤 opens a ring. (c) is an epoxy group possessed by the epoxy resin of the component (C). If the equivalent ratio is 0.2 or more, the moldability becomes good, and if it is 1.5 or less, the heat resistance, the thermal decomposition resistance, the flame retardancy, etc. become good respectively. Furthermore, when two or more types of epoxy resins are used, the total amount thereof may be within the above range.

In addition, the content of the epoxy resin as the component (C) may be 25 to 200 parts by mass, or 30 to 200 parts by mass relative to 100 parts by mass of the maleimide resin of the component (A). 40 to 150 parts by mass, or 50 to 100 parts by mass. By setting it as 25 mass parts or more, adhesiveness becomes good, and when setting it as 200 mass parts or less, heat resistance becomes good.

As the above epoxy resin, in addition to the epoxy resins represented by the general formulas (V) to (VII), known epoxy resins that can be used as semiconductor element sealing materials can also be used in combination. Examples of epoxy resins that can be used in combination include phenol novolac epoxy resins, o-cresol novolac epoxy resins, biphenyl epoxy resins, and dicyclopentadiene epoxy resins. Epoxy resins other than these can also be used in combination. In addition, when epoxy resins other than the epoxy resins represented by the general formulas (V) to (VII) are used together, the blending amount may be 30 parts by mass or less relative to 100 parts by mass of the epoxy resin. It may be 20 parts by mass or less or 10 parts by mass or less.

(Cyanate monomer having at least 2 cyanate groups in one molecule) The cyanate monomer having at least 2 cyanate groups in one molecule (hereinafter, also simply referred to as cyanate monomer) is A compound having at least 2 cyanate groups in one molecule mainly has the effect of improving the adhesion to semiconductor insertion parts. The cyanate ester monomer easily undergoes a trimerization reaction in the presence of the hardener of the component (B) by the following organophosphorus hardening accelerator of the component (d-1) to form three well rings. Therefore, the molding material composition for sealing is given high heat resistance and high adhesion. The above cyanate monomer has a relatively small molecular weight and a low curing stress during a cross-linking reaction that functions as a peeling stress, so it is particularly advantageous for adhesion. Furthermore, since the curing shrinkage rate of the cured product is relatively large, it is also advantageous in terms of formability. Furthermore, in the present invention, the term "cyanate monomer" refers to a cyanate compound that does not include a structure in which a part of the molecular structure repeats in the molecule.

From the viewpoint of the balance between heat resistance, adhesion, and formability, the content of the cyanate monomer as the component (C) relative to 100 parts by mass of the component (A) can be set to 10 to 50 parts by mass. It can be set to 20 to 40 parts by mass. By setting the content of the cyanate monomer as the component (C) to 10 parts by mass or more, the adhesion between the cured product of the molding material composition for sealing and the semiconductor insertion part can be improved. By setting the content of the cyanate monomer as the component (C) to 50 parts by mass or less, the heat resistance and moldability of the molding material composition for sealing can be improved. Furthermore, the content of (B) component and (C) component may be prepared so that the content of (A) component may become 30-70 mass% with respect to the total content of 100% by mass of (A) to (C) components.

The cyanate monomer is not particularly limited as long as it has at least two cyanate groups in one molecule. For example, bis(4-cyanate phenyl) methane, 1,1-bis(4-cyanate phenyl) ethane, 2,2-bis(4-cyanate phenyl) Propane, bis(3-methyl-4-cyanate phenyl) methane, bis(3,5-dimethyl-4-cyanate phenyl) methane, etc., with 2 cyanic acid in one molecule Ester group compound, bis(3,5-dimethyl-4-cyanate phenyl)-4-cyanate group phenyl-1,1,1-ethane, etc., there are 3 in one molecule Cyanate group compounds, etc. It is also possible to use previously known compounds other than these.

As a specific example of the cyanate ester monomer, for example, Primaset LECy (Japan Lonza Co., Ltd.), which has 1,1-bis(4-cyanoylphenyl)ethane as a main component, can be obtained as a commercially available product. Manufacturing), CYTESTER (registered trademark) TA (manufactured by Mitsubishi Gas Chemical Co., Ltd.), which has 2,2-bis(4-cyanoylphenyl) propane as the main component, etc.

In the case of using a cyanate monomer as the (C) component, the present invention may also use a cyanate resin containing a repetitive structure in the molecule, such as a novolac type cyanate ester.

(Allyl group-containing diamidite resin represented by general formula (VIII)) Allyl group-containing diamidite resin represented by the following general formula (VIII) (Imide resin) is a compound having two allyl groups in one molecule, and reacts allyl groups with each other or allyl groups and maleimide groups by heating, thereby forming a three-dimensional network structure and hardening Of resin. The above-mentioned diamidimide resin is expected to be improved from the adhesiveness of its resin skeleton. In addition, the above-mentioned diamidimide resin imparts a higher glass transition temperature (Tg) to the cured product through a cross-linking reaction, thereby improving heat resistance and thermal decomposition resistance.

[化21]

In the above general formula (VIII), R ⁴ is a C 1-10 alkylene group, a C 4-8 cycloalkyl group, a C 6-18 divalent aromatic group, and the general formula "-A ¹ -C ₆ H ₄ -(A ¹ ) _m -(where m represents an integer of 0 or 1, and each A ^{1 is} independently an alkylene group having 1 to 10 carbon atoms and a cycloalkyl group having 4 to 8 carbon atoms) )" or the general formula "-C ₆ H ₄ -A ² -C ₆ H _4- (here, A ² is "-CH ₂ -", "-C(CH ₃ ) ₂ -", The base indicated by "-CO-", "-O-", "-S-" or "-SO ₂ -").

Specific examples of the allyl group-containing diamidide resin represented by the general formula (VIII) include resins represented by the following formulas (VIII-1) and (VIII-2). Among them, the resin represented by formula (VIII-1) may be used from the viewpoint of tracking resistance and adhesion. The reason for this is that in the resin represented by formula (VIII-1), since the distance between allyl groups in the resin is sufficient, the steric hindrance is small, the reaction proceeds sufficiently, and the three-dimensional network structure is closely formed, thereby The cohesion of the diamidimide resin skeleton is increased. One type of these resins may be used, or two or more types may be used in combination.

[化22]

[化23]

From the viewpoint of the balance between the curing shrinkage rate and the adhesiveness, the content of the diazoimide resin as the component (C) relative to 100 parts by mass of the component (A) may be 30 to 250 parts by mass, or may be 50 to 200 parts by mass.

The allyl group-containing diamidimide resin represented by the above general formula (VIII) can be obtained as BANI-M (manufactured by Maruzen Petrochemical Co., Ltd.) and BANI-X (Maruzen Petrochemical Co., Ltd.) in the form of commercially available products. Manufacturing) etc.

From the viewpoint of uniform dispersibility and productivity, the component (C) may be pre-mixed with a part or the total amount of the maleimide resin of the component (A) in advance and used. The method of premixing is not particularly limited, and a well-known mixing method can be used. For example, the method of pre-mixing is to melt the component (C) at 50 to 180°C using a stirring device, and slowly add and mix the maleimide resin of component (A) while stirring. Examples include a method of preparing a pre-mixed resin by further stirring for about 10 to 30 minutes after all of them are melted.

[(D) Hardening accelerator] The hardening accelerator of the (D) component used in the present invention may also be (d-1) organophosphorus curing accelerator, (d-2) imidazole curing accelerator, in close contact From the viewpoint of the balance between the properties and the moldability, these can be used together. ((d-1) Organophosphorus hardening accelerator) (d-1) The organophosphorus hardening accelerator of component is mainly used to promote the crosslinking reaction of (A) component and (B) component, (B) component and the above Crosslinking reaction of epoxy resin, trimerization reaction of cyanate ester monomer, etc. (d-1) The component has the effect of indirectly reducing the self-polymerization reaction between the (A) components by promoting these reactions, thereby suppressing the generation of peeling stress with the semiconductor insertion part.

Examples of the organophosphorus hardening accelerator as component (d-1) include triphenylphosphine, tri(4-methylphenyl)phosphine, tri(4-ethylphenyl)phosphine, tri(4- Propylphenyl)phosphine, tri(4-butylphenyl)phosphine, tri(2,4-dimethylphenyl)phosphine, tri(2,4,6-trimethylphenyl)phosphine, tributyl Tertiary phosphines such as phosphine and methyldiphenylphosphine; tetraphenylphosphonium tetraphenylphosphonium tetraphenylborate, tetrabutylphosphonium tetrabutylphosphonate and other tetrasubstituted phosphonium tetrasubstituted borate. These can be used alone or in combination of two or more types. The previously known organic phosphorus-based hardening accelerators other than these can also be used alone or in combination of two or more kinds.

From the viewpoint of the balance between curability and adhesion to semiconductor insertion parts, the content of the organic phosphorus-based curing accelerator of (d-1) component can be 0.1 to 10 parts by mass with respect to 100 parts by mass of (A) component The part may be 0.1 to 6 parts by mass, 0.3 to 5 parts by mass, or 0.5 to 3 parts by mass. When two or more kinds of organic phosphorus-based hardening accelerators are used in combination, the total amount thereof may be within the above range.

((d-2) Imidazole hardening accelerator) (d-2) The component imidazole hardening accelerator is mainly used to ensure the moldability of the molding material composition for sealing by promoting the self-polymerization reaction of the component (A). (d-2) The function of the component is promoted by the presence of the above-mentioned epoxy resin, and can impart good curability and moldability to the molding material composition for sealing of the present invention. In addition, the present invention has the advantage of improving the moldability and adhesion by accelerating the addition reaction of the hardener of the component (B) with the epoxy resin and the self-polymerization reaction of the epoxy resin. In addition, in the present invention, the term "imidazole-based hardening accelerator" is synonymous with an imidazole compound containing a nitrogen atom at the 1, 3 position on the 5-membered ring.

Examples of the (d-2) component imidazole hardening accelerator include 2-methylimidazole, 2-ethylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2,4-diamino-6-[2'-methylimidazolyl -(1')]-Ethyl Mizujijing, 2-phenyl-4-methyl-5-dihydroxymethylimidazole, etc. These can be used alone or in combination of two or more. In addition, the present invention can also apply a previously known imidazole-based hardening accelerator other than the above.

In the present invention, the above-mentioned (d-2) component can be appropriately selected and used as necessary. From the viewpoints of the moldability of the molding material composition for sealing and the balance between the adhesiveness of the cured product of the composition and the semiconductor insertion part, 2,4-diamino-6-[2'-methyl Imidazolyl-(1')]-ethyl mesitane, 2-phenyl-4-methyl-5-dihydroxymethylimidazole and other compounds with relatively high active temperatures are used alone or in combination of two or more. Specifically, when the imidazole compound and the bisphenol A type epoxy resin (liquid) are reacted at a mass ratio of 1/20, the reaction initiation temperature may be 85°C or more and less than 175°C, or may be 100°C or higher but not up to 160°C, or 100°C or higher and 150°C or lower. These imidazole compounds can be used alone or in combination of two or more. In addition, here, the reaction initiation temperature refers to the use of DSC (Differential scanning calorimetry, differential scanning calorimetry), at a heating rate of 10 ℃ / min for the composition containing the imidazole compound and bisphenol A epoxy resin During heating, the temperature at the intersection of the tangent to the steepest part of the rising peak of the heating or endothermic peak and the temperature axis. If the reaction initiation temperature of the component (d-2) is 85°C or higher, the peeling from the semiconductor insertion part can be reduced, and if it does not reach 175°C, the moldability of the molding material composition for sealing can be improved.

In the present invention, in order to control the self-polymerization reaction of (A) component, the crosslinking reaction of (A) component and (B) component, and the crosslinking reaction of (B) component and the above epoxy resin, and the above cyanate Monomer trimerization reaction, etc., to obtain the balance between the curability of the molding material composition for sealing and the stress generated during curing, thereby reducing the peeling from the semiconductor insertion part, and also (d-1) component and (d- 2) The content ratio of the ingredients is correct. Specifically, the content ratio of (d-1) component to (d-2) component [(d-1)/(d-2)] can be set to 3/1 to 1/3 in terms of mass ratio, and It can be set from 2/1 to 1/3 or from 2/1 to 1/2. If there are many (d-1) components, the moldability may become insufficient, and if there are many (d-2) components, the adhesion between the cured product of the molding material composition for sealing and the semiconductor insertion part may change Not enough.

From the viewpoint of the balance between the hardenability and the adhesion to the semiconductor insertion part, the content of the imidazole-based hardening accelerator of (d-2) component can be 0.1 to 4 parts by mass relative to 100 parts by mass of (A) component , It may be 0.3 to 3 parts by mass, or 0.5 to 2 parts by mass. When two or more imidazole hardening accelerators are used in combination, the total amount thereof may be within the above range.

((d-3) Acid-based hardening accelerator) When the (C) component uses the allyl group-containing diamidide-resistant resin represented by the above general formula (VIII), the hardening of the (D) component is accelerated The agent may further contain the acidic hardening accelerator of (d-3) component. (d-3) The acid-based hardening accelerator of the component is mainly used to promote the hardenability of the maleimide resin of the component (A) and the above-mentioned diimide-resistant resin, so that the reaction proceeds from a relatively low temperature . In addition, the acid-based hardening accelerator of the component (d-3) also promotes the reaction of the hardener of the component (B) with the epoxy resin, thereby improving the moldability and adhesion. Generally, maleimide resin has high heat resistance, but the curing reaction requires a higher temperature. In the present invention, the reaction can be started at a relatively low temperature by reacting the maleimide resin of component (A), the above-mentioned diimide-resistant resin and the acidic hardening accelerator of (d-3) component To improve formability.

As the acid-based hardening accelerator of (d-3) component, for example, p-toluenesulfonic acid, trifluoromethanesulfonic acid, or their amine salts, pyridine sulfate, phosphoric acid, boron trifluoride ether complex , Boron trifluoride amine complex, etc. Among these, in the present invention, at least one selected from p-toluenesulfonic acid, its amine salt, and boron trifluoride amine complex can be used from the viewpoint of reactivity and resin physical properties. In addition, from the viewpoint of adhesion, it may be p-toluenesulfonic acid, and from the viewpoint of curability, it may also be a boron trifluoride amine complex. These can be used alone or in combination of two or more.

When using the allyl group-containing diamidide resin represented by the general formula (VIII) as the component (C), from the viewpoint of the balance of curability and thermal decomposition, (d- 3) The content of the acid-based hardening accelerator of the component may be 0.1 to 10 parts by mass, 0.3 to 5 parts by mass, or 0.5 to 3 parts by mass with respect to 100 parts by mass of the above-mentioned diaimide-resistant resin. When two or more acid-based hardening accelerators are used in combination, the total amount may be within the above range.

[(E) Filling material] The filling material of the (E) component used in the present invention includes (e-1) a hollow structure filling material, and may further contain (e-2) inorganic materials commonly used in sealing molding materials Filler. In order to reduce the peeling of the cured product of the molding material composition for sealing and semiconductor insertion parts, from the viewpoint of mechanical strength and linear expansion coefficient, the content of the filler of the component (E) relative to the total amount of the molding material composition for sealing The amount may be 60 to 95% by mass, 65 to 90% by mass, or 70 to 85% by mass. If the content of the filler is 60% by mass or more, the linear expansion coefficient is small and sufficient mechanical strength can be ensured, and if it is 95% by mass or less, good fluidity can be obtained.

(e-1) Hollow structure filler The (e-1) component hollow structure filler used in the present invention mainly relieves the stress at the time of hardening accompanying the self-polymerization reaction of the component (A) itself. In addition, by reducing the elastic modulus of the hardened product of the molding material composition for sealing, the stress accompanying thermal shrinkage is also relieved, thereby preventing the peeling of the hardened product from the semiconductor insertion part. The elastic modulus of the hardened product of the molding material composition for sealing may be 10 to 15 GPa. If the elastic modulus is 15 GPa or less, the peeling of the cured product and the inserted part can be reduced, and if the elastic modulus is 10 GPa or more, the moldability is good. Here, the "hollow structure filler" in the present invention refers to a filler having one or more hollow structures inside the filler. The filler for the hollow structure is not particularly limited. It can also be so-called hollow glass and hollow silica filled with soda lime glass, borosilicate glass, aluminum silicate, mullite, quartz, etc. as the main components. It can also be a polysiloxane based on a polysiloxane compound such as a sesquisiloxane compound having a three-dimensional network structure represented by (CH ₃ SiO _3/2 )n which crosslinks the silica bond to form a three-dimensional network. Hollow structural filler. It may also be an organic-based hollow-structure filler that uses an organic compound synthesized using a thermoplastic or thermosetting resin as a starting material, and the like as a main component. In addition, the "silsesquioxane compound" in this specification refers to a structure having a three-dimensional network represented by (CH ₃ SiO _3/2 )n crosslinking a siloxane bond and having a side chain Among the compounds with organic functional groups such as radicals and phenyl groups, the compounds whose side chains are methyl groups are at least 80%. Among the above "hollow structure fillers", especially inorganic hollow structure fillers and polysiloxane hollow structure fillers have high heat resistance due to the hollow structure filler itself, so it can be used for molding with higher heat resistance for sealing Material composition.

From the viewpoint of preventing separation from the inserted part, the ratio of (e-1) hollow structure filler to the total amount of the molding material composition for sealing is set to (α), and the elastic modulus of the hollow structure filler is ( Unit: GPa) is set to (β). The type and addition amount of the hollow structure filler may be selected so that (α)/(β) becomes 0.002 to 0.250, or the type and addition amount of the hollow structure filler may be selected from 0.003 to 0.150. If (α)/(β) is 0.002 or more, the stress accompanying the curing of the molding material composition for sealing and/or heat shrinkage is sufficiently relaxed, and if it is 0.250 or less, the insulation withstand voltage can be sufficiently obtained , Traceability and other reliability.

In addition, the elastic modulus of the hollow structure filler of component (e-1) may be 0.1 to 15 GPa, or may be 0.2 to 12 GPa. Among them, the inorganic hollow structure fillers such as hollow glass and hollow silica having a relatively high elastic modulus have a relatively high tendency to suppress shrinkage of the sealing resin during curing, and the stress generated during curing decreases. In addition, polysilicone hollow structure fillers such as sesquisiloxane compounds with relatively low elastic modulus can be added in small amounts to reduce the elastic modulus of the sealing material, and the tendency to relieve stress during heat shrinkage is higher, so it is preferred . Inorganic hollow structure fillers such as hollow glass and hollow silica and polysilicone hollow structure fillers such as silsesquioxane compounds can be used together with a relatively small amount of addition to reduce peeling from inserted parts. It can also be applied to sealing resins that require high heat resistance, and is one of the embodiments of the present invention. The elastic modulus of the hollow structure filler of the present invention can be, for example, a dynamic ultra-fine hardness tester (manufactured by Shimadzu Corporation), device name: DUH-211SR, load-unload test, load: 5.0 mN, speed 1.5 mN /s) for measurement.

From the standpoint of taking into account the tracking resistance and other insulating properties, (e-1) when the hollow structure filler is an inorganic component, it may contain a compound selected from silica, alumina, and silica-alumina compound. At least one of the inorganic hollow structure fillers, and/or the polysiloxane-based hollow structure fillers containing silsesquioxane compounds. Among them, it may also be an inorganic hollow structure filler containing at least one selected from silica-alumina compound and alumina, and/or a polysilicon system hollow structure filler containing a silsesquioxane compound . In addition, in the case of an organic component, an organic hollow structure filler made of acrylic resin, polyester resin, or the like can be selected.

(e-1) The component hollow structure filler has an air layer inside, so it tends to have a lower thermal conductivity than a normal filler. Since the tracking resistance is greatly affected by the thermal conductivity, in most cases, the reduction in thermal conductivity is accompanied by the reduction in tracking resistance. When the hollow structure filler is an inorganic component, the component (e-1) contains a silica-alumina compound with good thermal conductivity and/or alumina to reduce the tracking resistance. Also, regarding the silsesquioxane compound, it is presumed that the addition of a relatively small amount can reduce peeling, so that the influence on the tracking resistance is reduced.

From the viewpoint of reducing the corrosion of semiconductor inserts caused by ionic impurities, it is preferable that the hollow structure filler used in the present invention does not contain alkali metals and/or alkaline earth metals. When it is impossible to prevent mixing, it is preferably reduced as much as possible.

The (e-1) component hollow structure filler contains at least one kind selected from silica, alumina, silica-alumina compound, and the content of alkali metal, alkaline earth metal, etc. is relatively small, for example, in Kainospheres (manufactured by Kansaimatec Co., Ltd.) with aluminum silicate and mullite (a compound of silica and alumina) as the main components are obtained from the market, and similarly E-SPHERES (manufactured by Pacific Cement Co., Ltd., commodities) Name) etc. In addition, as a polysiloxane-based hollow structure filler material containing a sesquisiloxane compound (a sesquisiloxane compound-based filler), for example, polymethyl silsesquioxane as a main component is available on the market NH-SBN04 (manufactured by NIKKO RICA Co., Ltd., trade name), etc.

From the viewpoints of reducing peeling from semiconductor insertion parts and taking into consideration the productivity and formability of the molding material composition for sealing, the average particle diameter of the hollow structure filler of (e-1) component may be 3 to 100 μm, It can also be 3 to 60 μm. If the average particle size is 3 μm or more, peeling is reduced, and if the average particle size is 100 μm or less, the productivity and moldability of the molding material composition for sealing become good. In addition, here, the average particle diameter refers to the central value (D50) measured by the laser diffraction scattering method (for example, manufactured by Shimadzu Corporation, device name: SALD-3100).

As a hollow structure filler with an average particle diameter of 3 to 100 μm, Kainospheres75 (average particle diameter of 35 μm), etc., which are the above-mentioned Kainospheres (manufactured by Kansaimatec Co., Ltd.) series, etc., are available on the market as E-SPHERES E-SPHERES SL75 (average particle size 55 μm), E-SPHERES SL125 (average particle size 80 μm), etc. of Pacific Cement (manufactured under the trade name) series. In addition, Glass Bubbles K37 (average particle size 45 μm), Glass Bubbles iM30K (average particle size 16 μm) (both are manufactured by 3M Japan), ADVANCELL HB-2051 (average particle size) are also available on the market 20 μm, Sekisui Chemical Industry Co., Ltd.), NH-SBN04 (average particle size 4 μm, NIKKO RICA Co., Ltd.), etc.

In the inorganic hollow structure filler containing at least one selected from the above-mentioned silica, alumina, and silica-alumina compounds, and the polysiloxane-based hollow structure filler containing the silsesquioxane compound, etc. In the case of an inorganic component, the content of (e-1) component hollow structure filler relative to the total amount of (E) component filler may be 1 to 50% by mass, or 2 to 45% by mass, or It is 5-20% by mass. If the content of (e-1) component hollow structure filler is 1% by mass or more, peeling is reduced, and if the content of (e-1) component hollow structure filler is 50% by mass or less, insulation such as insulation withstand voltage Performance and formability become good. Especially in the case where the hollow structure filler of (e-1) component contains silsesquioxane compound, its content may be 0.5 to 10% by mass relative to the total amount of filler of (E) component, or 1.0 to 6% by mass, or 1.2 to 5% by mass. Here, when the component (e-1) contains silica, alumina, and silica-alumina compound, its content may be 60% by mass or more, or 80% by mass or more, or 90% by mass or more. In addition, when the component (e-1) contains a silsesquioxane compound, its content may be 30% by mass or more, 50% by mass or more, or 80% by mass or more. In addition, when the component (e-1) is an organic component, its content may be 0.5 to 10% by mass or 1.5 to 7% by mass relative to the total amount of the filler of the component (E). If the content of the organic component of (e-1) component is 0.5% by mass or more, peeling is reduced, and if the content of the organic component of (e-1) component is 10% by mass or less, the insulation performance and formability such as insulation withstand voltage Become good.

(e-2) Inorganic fillers In the present invention, previously known inorganic fillers can be used. Examples of the inorganic filler include crystalline silica, fused silica, synthetic silica, alumina, aluminum nitride, boron nitride, zircon, calcium silicate, calcium carbonate, and titanic acid. Barium etc. From the viewpoint of fluidity and reliability, it may be crystalline silicon dioxide, molten silicon dioxide, synthetic silicon dioxide, or molten spherical silicon dioxide or synthetic silicon dioxide as the main component. In addition, if the inorganic filler of the component (e-2) is polysilicone powder having polymethylsilsesquioxane or the like as a main component, peeling is reduced.

(e-2) The average particle diameter of the component is usually about 1 to 30 μm, or about 3 to 25 μm, or about 5 to 20 μm. If the average particle size is 1 μm or more, the moldability such as flow characteristics and curability can be improved, and if the average particle size is 30 μm or less, the mechanical strength and adhesion can be improved. In addition, particles having a particle diameter of 0.1 μm or more and 1.0 μm or less may be included as the (e-2) component. The content of the particles may be 10 to 40% by mass, 10 to 30% by mass, or 10 to 20% by mass relative to the total amount of (e-2) component. By setting the content of the particles to 10% by mass or more, the adhesion can be improved, and by setting the content of the particles to 40% by mass or less, the moldability such as flow characteristics and curability can be improved. In addition, the particle diameter of the (e-2) component can be measured by a laser diffraction scattering method measuring device, etc. In the present invention, the device name: SALD-3100, which is manufactured by Shimadzu Corporation, is used. The particle size.

Furthermore, from the viewpoint of adhesion, the component (e-2) may contain fine particles. The fine particles mentioned here may have a particle size of 0.3 μm or less or particles having a particle size of 0.1 μm or less. The lower limit of the particle size of the fine particles is not particularly limited, and is 0.01 μm or more. When fine particles are contained, the content may be 0.5 to 10% by mass or 0.5 to 5% by mass relative to the total amount of (e-2) component. By setting the content of the fine particles to 0.5% by mass or more, adhesion can be improved, and by setting the content of the fine particles to 10% by mass or less, moldability such as flow characteristics and curability can be improved. In addition, the particle size of the fine particles is based on the measurement sequence described in JIS Z8901: 2006 8.3.2b), for any 100 particles, by TEM (Transmission Electron Microscopy, transmission electron microscope) or SEM (Scanning Electron Microscope , Scanning electron microscope) respectively measure the particle size in a fixed direction (the diameter obtained by approximating the respective particle image obtained by using a circle as the particle size), plot the data on a logarithmic probability paper and calculate the number basis Median path. In addition, as the compounding ratio, a value calculated by volume conversion based on the particle diameter is used. In addition, the specific gravity of molten spherical silica and synthetic silica is set to 2.2.

If the above-mentioned fine particles are pre-mixed with a part or the total amount of the maleimide resin, especially component (A), and then used, the curability of the molding material composition for sealing is improved, and the adhesion and moldability are improved. The method of premixing is not particularly limited, and a well-known mixing method can be used. It is presumed that the reason for the improved adhesion is that the fine particles and the (A) component are sufficiently mixed, and the stress (peeling stress) generated during hardening accompanying the self-polymerization reaction of the (A) component is reduced. In addition, the "melted spherical silica" in the present invention refers to a silica having a true sphericity of 0.8 or more, obtained by crushing and spheroidizing natural silica by gasification melting, etc. . The "average particle diameter" refers to the "medium diameter" measured by SALD-3100, the device name manufactured by Shimadzu Corporation.

As an example of a method for obtaining the above-mentioned (e-2) component, for example, 95% by mass of molten spherical silica (for example, FB-105, manufactured by the Electric Chemical Industry Co., Ltd.) with respect to an average particle diameter of 15 μm can be exemplified. 3% by mass of synthetic spherical silica with an average particle size of 0.6 μm (for example, SO-25R, manufactured by Admatechs), and then mixed with 2% by mass of a primary particle size of 12 nm and an aggregate diameter of 200 nm (0.2 μm) Synthetic silicon dioxide (for example, Reolosil QS-102, manufactured by Tokuyama Co., Ltd.), etc. Preparations other than these can also be carried out. In addition, in the present invention, commercially available products such as molten spherical silica mixed with a specific ratio or a mixture of molten spherical silica and synthetic silica can also be used directly.

The above-mentioned (e-2) component can be made into a molding material by usually mixing with the above-mentioned (A) component and/or (C) component using a mixer or the like, followed by kneading with a biaxial or uniaxial extruder, etc. . It is also possible to produce a molding material by mixing a part or the total amount of component (A) and/or component (C) in advance with a masterbatch and then using a twin-screw or single-screw extruder.

As an example of the masterbatch of the component (e-2), for example, after pre-mixing the total amount of the component (A) and the component (C), the above-mentioned SO- 25R, 5 mass% of the total amount of the premix, the above-mentioned Reolosil QS-102, after stirring with a mixer or the like, and then mixing with a general twin-screw extruder. Other methods can also be used. In addition, the present invention may also add a conventionally known silane coupling agent and/or mold release agent when the mixer is stirring.

The content of the inorganic filler of the component (e-2) relative to the total filler of the component (E) may be 50 to 99.5% by mass or 55 to 98% by mass.

In the present invention, crystalline silicon dioxide, aluminum oxide, zircon, calcium silicate, calcium carbonate, barium titanate, aluminum nitride, boron nitride, etc., which are commonly used in sealing and molding materials, can also be used as (e-2) Inorganic fillers other than ingredients (except for those with hollow structures). When these are used together as an inorganic filler, the content can be set to 30% by mass or less of the total amount of the inorganic filler containing the (e-2) component, or 20% by mass or less, or 10 Mass% or less.

In addition, from the viewpoint of flow characteristics, linear expansion coefficient, thermal conductivity, etc., the content of the (E) component relative to the total amount of the molding material composition for sealing may be 60 to 95% by mass, or 65 to 90% by mass. , Can also be 70 to 85% by mass.

[Other components] (Silane coupling agent) The silane coupling agent may be added to the molding material composition for sealing of the present invention from the viewpoints of moisture resistance, mechanical strength, and adhesion to semiconductor insertion parts. In the present invention, epoxyglycol such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, etc.; 3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, etc. Aminosilane; mercaptosilanes such as 3-mercaptopropyltrimethoxysilane; isocyanatesilanes such as 3-isocyanatopropyltriethoxydisilazane and other previously known silane coupling agents. From the viewpoint of adhesion, epoxy silanes such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, secondary aminosilanes, and isocyanates can be used Alkyl silanes are used alone or in combination. In addition, the silane coupling agent may be used simply after being mixed with the above-mentioned component (E), or it may be used after surface-treating a part or the entire amount of it in advance. In addition, the present invention may also add an aluminate-based coupling agent or a titanate-based coupling agent.

The addition amount of the silane coupling agent may be 0.01 to 1% by mass, 0.03 to 0.7% by mass, or 0.05 to 0.5% by mass relative to the total amount of the molding material composition for sealing. By setting the addition amount of the silane coupling agent to 0.01% by mass or more, the adhesion to the semiconductor insertion part can be improved, and by setting it to 1% by mass or less, the decrease in the hardenability during molding can be reduced.

(Stress relief agent) In the present invention, in order to reduce the stress at the interface between the molding material composition for sealing and the semiconductor insert during molding or temperature cycle test, etc., thereby reducing the peeling of these interfaces, it may be added separately A previously known stress reliever (also known as a low-stress agent) such as liquid polysiloxane may be used in combination of two or more kinds.

In the present invention, in the case of adding a previously known stress reliever such as liquid polysiloxane, from the viewpoint of balance with flow characteristics, etc., its content can be adjusted relative to the total amount of (A) component 100 The mass part is set to 5 to 30 mass parts. In the case of adding two or more kinds of stress relaxants in the present invention, the total amount can be set within the above range.

(Release agent) In the present invention, in order to achieve good productivity of the molding material composition for sealing, a release agent may be added. Examples of mold release agents that can be added include natural waxes such as carnauba wax, fatty acid ester-based waxes, fatty amide-based waxes, non-oxidized polyethylene-based mold release agents, and oxidized polyethylene-based mold release agents. Polysiloxane-based release agent, etc. Release agents other than these can also be added. In addition, the release agent may be used alone or in combination of two or more kinds. From the viewpoint of taking into consideration both adhesion and mold releasability, waxes with relatively low molecular weights such as carnauba wax and fatty acid ester-based waxes can also be used in combination with waxes with relatively large molecular weights such as oxidized polyethylene. In addition, the oxidized polyethylene mold release agent having a softening point of 110°C to 125°C easily bleeds out from the resin system used in the present invention and exhibits high mold release properties.

In the molding material composition for sealing of the present invention, in addition to the above components, colorants such as flame retardants, carbon black, organic dyes, titanium oxide, and iron dans, which are usually formulated in such compositions, may be formulated as needed.

Examples of the flame retardant include phosphorus compounds such as aluminum hydroxide, magnesium hydroxide, zinc borate, zinc oxide, and phosphate esters, melamine, and cyclophosphazene. It is also possible to use previously known flame retardants other than these. One of these may be used alone, or two or more may be used in combination.

In addition, from the viewpoint of improving the moisture resistance and high-temperature storage characteristics of the semiconductor element, an anion exchanger plasma trapping agent may be blended into the molding material composition for sealing of the present invention. Examples of the anion exchanger include aluminum magnesium carbonates, hydrated oxides of elements selected from magnesium, aluminum, titanium, zirconium, bismuth, and the like. It is also possible to use previously known anion exchangers other than these. These can be used alone or in combination of two or more.

In the molding material composition for sealing of the present invention, the content of (A) component, (B) component, (C) component, (D) component, and (E) component may be 80% by mass or more, or 90% by mass % Or more, and further preferably 95% by mass or more.

The molding material composition for sealing of the present invention can be prepared by uniformly dispersing and mixing the above-mentioned components in a specific amount. The preparation method is not particularly limited, and as a general method, for example, a blender or the like can be used to sufficiently mix the above components in a specific amount, followed by melt mixing by a mixing roller, extruder, etc. Afterwards, it is cooled and crushed.

The molding material composition for sealing obtained in the above manner has a high glass transition temperature (Tg), and can obtain high thermal decomposition resistance, excellent curability and moldability, and high voltage resistance, and is compatible with semiconductor insertion parts Hardened product with good adhesion and high reliability. The glass transition temperature of the hardened product of the molding material composition for sealing may be 230°C or higher, 240°C or higher, 250°C or higher, 255°C or higher, or 260°C or higher, or It is above 270℃. In addition, the thermal decomposition temperature of the cured product of the molding material composition for sealing may be 380°C or higher, or 385°C or higher. Furthermore, the glass transition temperature and thermal decomposition temperature of the hardened product can be measured by the method described in the examples.

(Electronic component device) The electronic component device of the present invention has an element sealed by the hardened product of the sealing molding material composition. The above-mentioned electronic component device refers to a complete set of supporting members such as lead frames, single-crystal silicon semiconductor elements or compound semiconductor elements such as SiC and GaN, wires for electrically connecting the same, bumps and other members, and other constituent members An electronic component device in which necessary parts are sealed by the hardened product of the above-mentioned molding material composition for sealing. In addition, the molding material composition for sealing can provide an electronic component device which is excellent in heat resistance and excellent in adhesion with semiconductor insertion parts, and is unlikely to cause peeling and cracking even after high-temperature storage or after a temperature cycle test. In particular, when a compound semiconductor element such as SiC or GaN is used as a supporting member, the electronic component device sealed with the hardened material of the sealing molding material composition can obtain good characteristics.

As a method of sealing using the molding material composition for sealing of the present invention, the most common method is transfer molding, and injection molding, compression molding, and the like can also be used. The forming temperature may be 150-250°C, 160-220°C, or 170-200°C. The forming time may be 30 to 600 seconds, or 45 to 300 seconds, or 60 to 200 seconds. In addition, in the case of post-curing, the heating temperature is not particularly limited, and may be, for example, 150 to 250°C or 180 to 220°C. In addition, the heating time is not particularly limited, and may be, for example, 0.5 to 10 hours, or 1 to 8 hours.

The molding material composition for sealing of the first aspect contains (a-1) the maleimide resin represented by the above general formula (I); (B) is selected from (b-1) and (b-2) ), at least one of the above, (b-1) is one or two of the phenolic hardeners represented by the above general formula (II), and the phenolic hardeners represented by the above general formula (III), the above ( b-2) is a benzoxanthene resin represented by the general formula (IV); (c-1) is at least 1 selected from the epoxy resins represented by the general formulas (V) to (VII) (D-1) organophosphorus hardening accelerator; (d-2) imidazole hardening accelerator; and (E) molding material composition for sealing containing a filler of (e-1) hollow structure filler.

One aspect of each component is as described above. From the viewpoint of the balance of heat resistance, adhesion, and formability, the content of (B) component may be 20 to 250 parts by mass relative to 100 parts by mass of (a-1) component, or 30 to 200 parts by mass, or 40 to 150 parts by mass. From the viewpoint of the balance between the hardenability and the adhesion to the semiconductor insertion part, the content of the (d-1) component may be 0.1 to 10 parts by mass relative to 100 parts by mass of the (a-1) component , May be 0.3 to 5 parts by mass, or 0.5 to 3 parts by mass.

The second aspect of the molding material composition for sealing contains (a-1) the maleimide resin represented by the above general formula (I); (c-2) has at least 2 cyanate groups in one molecule Cyanate monomer; (B) at least one selected from (b-1) and (b-2), the above (b-1) is a phenolic hardener represented by the above general formula (II), And one or two of the phenolic hardeners represented by the above general formula (III), the above (b-2) is represented by the above general formula (IV); benzo㗁𠯤resin; (d -1) Organophosphorus-based hardening accelerator; and (d-2) imidazole-based hardening accelerator, and the content of the above (a-1) component relative to the above (a-1) component, (B) component, and (c -2) A molding material composition for sealing having a total content of 100% by mass of 30 to 70% by mass.

One aspect of each component is as described above. From the viewpoint of heat resistance and adhesion to semiconductor insertion parts, the content of (a-1) component is relative to that of (a-1) component, (B) component, and (c-2) component The total content is 100% by mass and 30 to 70% by mass, or 35 to 65% by mass. From the viewpoint of the balance between heat resistance and adhesion, moldability, etc., the content of the (c-2) component can be 10 to 50 parts by mass relative to 100 parts by mass of the (a-1) component. It is 20-40 parts by mass. From the viewpoint of the balance between the hardenability and the adhesion to the semiconductor insertion part, the content of the (d-1) component may be 0.1 to 10 parts by mass relative to 100 parts by mass of the (a-1) component , May be 0.3 to 5 parts by mass, or 0.5 to 3 parts by mass.

The third aspect of the molding material composition for sealing contains (a-1) a maleimide resin represented by the above general formula (I), and (c-3) an ene-containing compound represented by the above general formula (VIII) Propyl diamidimide resin, (b-1) phenolic hardener, (c-1) epoxy resin, (D) hardening accelerator, and (E) including (e-1) hollow structure filler The filler, the component (b-1) and the component (c-1) each include a triphenylmethane skeleton and/or naphthalene skeleton, and the component (D) includes (d-1) a phosphorus-based hardening accelerator, (d -2) A molding material composition for sealing of an imidazole hardening accelerator and (d-3) an acid hardening accelerator.

One aspect of each component is as described above. From the viewpoint of the balance of heat resistance, adhesion, and formability, the content of (b-1) component may be 20 to 250 parts by mass relative to 100 parts by mass of (a-1) component. It may be 30 to 200 parts by mass or 40 to 150 parts by mass. From the viewpoint of adhesion and heat resistance, the content of the component (c-1) may be 30 to 200 parts by mass relative to 100 parts by mass of the maleimide resin of the component (a-1). It may be 40 to 150 parts by mass, or 50 to 100 parts by mass. From the viewpoint of the balance of hardening shrinkage and adhesiveness, the content of (c-3) component may be 30 to 250 parts by mass relative to 100 parts by mass of (a-1) component, or 50 to 200 parts by mass. From the viewpoint of the balance between the hardenability and the adhesion to the semiconductor insertion part, the content of (d-1) component may be 0.1 to 6 parts by mass relative to 100 parts by mass of (a-1) component , May be 0.3 to 5 parts by mass, or 0.5 to 3 parts by mass. From the viewpoint of the balance between the hardenability and the adhesion to the semiconductor insertion part, the content of (d-2) component may be 0.1 to 4 parts by mass relative to 100 parts by mass of (a-1) component , It may be 0.3 to 3 parts by mass, or 0.5 to 2 parts by mass. From the viewpoint of the balance between curability and thermal decomposition properties, the content of (d-3) component may be 0.1 to 10 parts by mass relative to 100 parts by mass of (c-3) component, or 0.3 to 5 parts by mass, or 0.5 to 3 parts by mass. [Example]

Next, the present invention will be specifically described by examples, but the present invention is not limited by these examples.

(Examples 1A to 23A, Examples 1B to 3B, Examples 1C to 11C, Comparative Examples 1A to 4A, Comparative Examples 1B to 6B, and Comparative Examples 1C to 3C) Using hybrid biaxial roller pairs Table 1-1, Table 1-2, and the components of the types and blending amounts described in Tables 2 to 5 are kneaded to prepare a molding material composition for sealing. The kneading temperature in each example and comparative example was set to about 120°C. Furthermore, the blank columns in each table indicate that they are not deployed.

The details of each component described in Table 1-1, Table 1-2, and Tables 2 to 5 for preparing the molding material composition for sealing are as follows.

<Maleimide resin> [(A) component] ·BMI-1000: N,N'-(4,4'-diphenylmethane) bismaleimide (the z in general formula (I) = 0 as the main component), manufactured by Yamato Chemical Industry Co., Ltd., trade name·BMI-2300: polyphenylmethane maleimide (with z=0 to 2 in the general formula (I) as the main component), Daiwa Chemical Industry Co., Ltd., trade name, and in Examples 1B to 3B and Comparative Examples 1B to 6B, the total amount of the above-mentioned maleimide resin system is added to cyanic acid as the (C) component It is used after premixing in the total amount of ester monomers. In the pre-mixing, the total amount of cyanate monomers is melted at 110 to 130°C, and while maintaining the temperature, maleimide resin is slowly added for mixing, and after the total amount is melted, the mixture is further stirred for about 10 minutes.

<Hardener> [(B) component] (phenolic hardener with specific skeleton) MEH-7500: triphenylmethane type phenol resin (phenol resin with x=1 to 4 in the general formula (II) as the main component ), manufactured by Meiwa Chemical Industry Co., Ltd., trade name, hydroxyl equivalent of 97, softening point of 110 ℃ · SN-485: naphthol aralkyl resin (in general formula (III) y1 = 0 ~ 3 phenol resin as the main component ), Nippon Steel & Sumitomo Chemical Co., Ltd., trade name, hydroxyl equivalent 215, softening point 87℃

(Benzo&#134116; resin with a specific structure) · Benzo&#134116; Pd: Benzo&#134116; resin [Benzo&#134116; resin represented by formula (IV-1) ], Shikoku Chemical Industry (share) manufacturing, trade name

<Thermosetting resin> [(C)component] (Epoxy resin with specific skeleton) · EPPN-502H: Triphenylmethane type epoxy resin (n1=0 to 3 epoxy resin in general formula (V) Main component), manufactured by Nippon Kayaku Co., Ltd., trade name, epoxy equivalent 168, softening point 67°C. ESN-375: naphthol aralkyl type epoxy resin (n2 in general formula (VI) = 0 ～3 epoxy resin as main component), manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., trade name, epoxy equivalent 172, softening point 75℃ ·HP-4710: dihydroxy naphthol novolac epoxy resin (general formula (Epoxy resin represented by (VII)), DIC (share) manufacturing, trade name, epoxy equivalent 161, softening point 82°C

(Cyanate monomer) Primaset LECy: a cyanate compound containing 1,1-bis(4-cyanophenylphenyl)ethane as the main component (99% or more), manufactured by Lonza Japan Co., Ltd., Trade name · CYTESTER (registered trademark) TA: cyanate compound containing 2,2-bis(4-cyanoylphenyl) propane as the main component (99% or more), manufactured by Mitsubishi Gas Chemical Co., Ltd. name

(Allyl-containing diamidimide-resistant resin) · BANI-M: N,N'-(methylenedi-p-benzene)-bis(allylbicyclo[2.2.1]-5-heptene- 2,3-dicarboxylimide), Maruzen Petrochemical Co., Ltd., trade name·BANI-X: N,N'-m-xylylene-bis(allylbicyclo[2.2.1]-5- (Heptene-2,3-dicarboxylimide), Maruzen Petrochemical Co., Ltd., trade name

<hardening accelerator> [(D) component] (d-1) component: organophosphorus curing accelerator·PP-200: triphenylphosphine, manufactured by Beixing Chemical Industry Co., Ltd., trade name·TPTP: tri(4 -Methylphenyl)phosphine, manufactured by Beixing Chemical Industry Co., Ltd., trade name

(d-2) Ingredient: imidazole-based hardening accelerator 2E4MZ: 2-ethyl-4-methylimidazole, manufactured by Shikoku Chemical Industry Co., Ltd., trade name (reaction start with bisphenol A type epoxy resin) Temperature: 90°C) 2MZ-A: 2,4-Diamino-6-[2'-methylimidazolyl-(1')]-ethyl junsanjing, manufactured by Shikoku Chemical Industry Co., Ltd., Trade name (Initial temperature of reaction with bisphenol A epoxy resin: 120°C) · 2P4MHZ-PW: 2-phenyl-4-methyl-5-dihydroxymethylimidazole, Shikoku Chemical Industry Co., Ltd. Manufacturing, trade name (reaction starting temperature with bisphenol A epoxy resin: 129°C) · 2PHZ-PW: 2-phenyl-4,5-dihydroxymethylimidazole, manufactured by Shikoku Chemical Industry Co., Ltd. 2. Trade name (reaction starting temperature with bisphenol A epoxy resin: 155°C) 2MZ-H: 2-methylimidazole, manufactured by Shikoku Chemical Industry Co., Ltd., trade name (with bisphenol A ring Oxygen resin reaction start temperature: 75℃)

(d-3) Ingredient: acid-based hardening accelerator • AC-4B50: boron trifluoride imidazole complex, manufactured by Stella Chemifa (stock), trade name • p-toluenesulfonic acid: manufactured by Tokyo Chemical Industry Co., Ltd.

<Amine Hardener> 4,4'-Diaminodiphenylmethane: manufactured by Tokyo Chemical Industry Co., Ltd.

<Filling material> [(E) component] (e-1) component: hollow structure filler • Kainospheres 75: amorphous aluminum (30 to 70%) and mullite (30 to 70%) as main components Inorganic hollow structure filler, average particle size 35 μm, manufactured by Kansaimatec (share), trade name, modulus of elasticity 8 GPa · E-SPHERES SL75: Amorphous aluminum (65-85%) and mullite (20 ～30%) Inorganic hollow structure filler as the main component, average particle size 55 μm, manufactured by Pacific Cement Co., Ltd., trade name, elastic modulus 10 GPa · E-SPHERES SL125: amorphous aluminum (65～ 85%) Inorganic hollow structure filler with mullite (20-30%) as the main component, average particle size 80 μm, Pacific Cement (Co., Ltd.), trade name, elastic modulus 10 GPa · Glass Bubbles K37: Soda-lime glass, borosilicate glass, synthetic silica mixture type inorganic hollow structure filler, average particle size 45 μm, manufactured by 3M Japan Co., Ltd., trade name, elastic modulus 7 GPa · Glass Bubbles iM30K: sodium Lime glass, borosilicate glass, synthetic silica mixture type inorganic hollow structure filler, average particle size 16 μm, manufactured by 3M Japan Co., Ltd., trade name, modulus of elasticity 7 GPa ADVANCELL HB-2051: acrylic System porous hollow structure filler, average particle diameter 20 μm, Sekisui Chemical Industry Co., Ltd., trade name, elastic modulus 0.3 GPa ·NH-SBN04: polymethyl silsesquioxane series single hole hollow structure filler, Average particle diameter 4 μm, manufactured by NIKKO RICA (share), trade name, elastic modulus 1.0 GPa The value of the elastic modulus here is made by a dynamic ultra-small hardness tester (Shimadzu Corporation), device name: DUH -211SR, load-unload test, load: 5.0 mN, speed 1.5 mN/s, pressure: triangular cone pressure)) The average of the values obtained 5 times.

(e-2) Ingredient: Inorganic filler·EP-5518: Polysilicone elastomer containing polymethyl silsesquioxane as the main component, manufactured by Toray Dow Corning Co., Ltd., trade name, average particle diameter 3 μm · FB-105: Fused spherical silica, manufactured by the Electrochemical Industry Co., Ltd., trade name, average particle diameter 18 μm, specific surface area 4.5 m ² /g · SO-25R: inorganic filler (synthetic spherical dioxide) Silicon), Admatechs (share), trade name, average particle size 0.6 μm · Reolosil QS-102: inorganic filler (synthetic silicon dioxide), Tokuyama (share) manufacture, trade name, primary particle size 12 nm (0.012 μm ), Condensation diameter 200 nm (0.2 μm)

<Other components> · KBM-403: Silane coupling agent, 3-glycidoxypropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd., trade name·KBM-603: Silane coupling agent, N-2-( Aminoethyl)-3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., trade name·KBE-9007: silane coupling agent, 3-isocyanatopropyltriethoxysilane, Shin-Etsu Chemical Industry (stock) manufacturing, trade name·PED191: mold release agent (dropping point: 115°C oxidized polyethylene mold release agent), Clariant (stock) manufacturing, trade name·HW-4252E: mold release agent (average number Oxidized polyethylene mold release agent with a molecular weight of 1,000), manufactured by Mitsui Chemicals Co., Ltd., trade name·MA-600: colorant (carbon black), manufactured by Mitsubishi Chemical Co., Ltd., trade name

The characteristics of the molding material composition for sealing prepared in Examples 1A to 23A and Comparative Examples 1A to 4A were measured and evaluated according to the measurement conditions shown below. The evaluation results are shown in Table 1-1, Table 1-2, and Table 2. In addition, as long as it is not clearly described, the molding of the molding material is performed by a transfer molding machine under conditions of a mold temperature of 185°C, a molding pressure of 10 MPa, and a curing time of 180 seconds. In addition, post-hardening was performed at 200°C for 8 hours.

<Evaluation items> (1) Glass transition temperature (Tg) As one of the standards for the heat resistance of the cured product of the molding material composition for sealing, the glass transition temperature (Tg) was measured. First, the mold material composition for sealing was molded under the above conditions using a mold with a length of 4 mm × 4 mm × height of 20 mm, and then post-hardened under the above conditions to produce a molded product (4 mm × 4 mm × thickness 20 mm). This molded product was cut into a desired size and used as a test piece. The test piece was measured using a TMA (Thermo Mechanical Analysis) method using a thermal analysis device (manufactured by Seiko Instruments Co., Ltd., trade name: SSC/5200). The glass transition temperature (Tg). In addition, 250 degreeC or more was set as the pass.

(2) Bending modulus of elasticity Using a test piece of 100 mm in length × 10 mm in width × 4 mm in thickness, the elastic modulus of the molding material composition for sealing at room temperature (20°C) was measured by a three-point bending method. For the measurement, Autograph AG-X manufactured by Shimadzu Corporation was used. The span length is set to 64 mm, and the head speed is set to 2 mm/min. The average value of N=4 was set as the bending elastic modulus, and the bending elastic modulus was 15 GPa or less as a pass.

(3) Initially peel off the TO-247 package island (8.5×11.5 mm) in the center of the electroless nickel-plated lead frame to fix the SiC wafer (6×6×0.15 mmt, without surface protection film), form the seal under the above conditions Using the molding material composition, further, post-curing was performed under the above-mentioned conditions, and 10 molded products were produced. The molded product was observed using an ultrasonic imaging device (manufactured by Hitachi, Ltd., FS300II) to confirm whether the island around the SiC wafer and the molding material composition for sealing were peeled off. The case where 3 or less of the 10 packages where the peeling of the island part was observed was regarded as a pass. In addition, the wafer is fixed to the lead frame using lead-free solder in a 5% formic acid and 95% nitrogen atmosphere at 340°C/13 minutes. In addition, before the lead frame is to be formed into a molding material composition for sealing, a plasma cleaner AC-300 manufactured by Nordson Co., Ltd. is used after 60 seconds of argon plasma treatment.

(4) Peeling after leaving at high temperature After peeling and observing the TO-247 package in (3) above and leaving it at 250°C for 250 hours, use an ultrasonic imaging device (manufactured by Hitachi, Ltd., FS300II) to confirm the peeling. There is nothing. The case where the number of packages where the peeled area of the island part is 20% or more is 10 or less is 3 or less is considered as a pass.

100 mm×2 mmt之試片並進行後硬化之後，依據ASTM-D3638測定耐追蹤性(CTI)。試驗器使用Yamayoshikenki有限公司製造之YST-112-1S。再者，將400 V以上設為合格。(5) Production of tracking resistance (CTI)

After a 100 mm×2 mmt test piece was post-hardened, the tracking resistance (CTI) was measured according to ASTM-D3638. The tester used YST-112-1S manufactured by Yamayoshikenki Co., Ltd. In addition, 400 V or more is regarded as a pass.

100 mm×2 mmt之試片並進行後硬化之後，依據ASTM-D149測定室溫(25℃)下之絕緣破壞電壓。測定係以「短時間法」進行。試驗器使用Yamayoshikenki有限公司製造之YST-243BD-100RO。將以n＝3進行測定時之平均值為10 kV/mm以上設為合格。(6) Production of insulation withstand voltage (insulation breakdown voltage)

After a 100 mm×2 mmt test piece was post-hardened, the insulation breakdown voltage at room temperature (25°C) was measured according to ASTM-D149. The measurement is carried out by the "short time method". The tester used YST-243BD-100RO manufactured by Yamayoshikenki Co., Ltd. The average value when measuring with n=3 was 10 kV/mm or more, and it was set as the pass.

(7) Continuous formability using a mold release load measurement forming machine (manufactured by KYOCERA Co., Ltd., trade name: GM-500), PBGA (Plastic Ball Grid Array, plastic ball grid array; 30 mm × 30 mm × 1 mm, t/2 holes) 300 shots of continuous forming. The mold temperature was set at 185°C, and the molding time was set at 180 seconds. In addition, the evaluation is based on the following criteria. A: It can be formed continuously until it reaches 300 shots, and there is no mold contamination. B: Although the mold is dirty, it can be continuously formed until it reaches 300 shots. C: It cannot be achieved because it is attached to the mold, etc. Continuous forming up to 300 shots

*1：與雙酚A型環氧樹脂之反應起始溫度[Table 1-1]

*1: Starting temperature of reaction with bisphenol A epoxy resin

*1：與雙酚A型環氧樹脂之反應起始溫度[Table 1-2]

*1: Starting temperature of reaction with bisphenol A epoxy resin

[Table 2]

In Examples 1A to 23A using the molding material composition for sealing containing the components (A) to (E), the glass transition temperature of the cured product is 250° C. or higher, the initial peeling or peeling after high-temperature storage, continuous moldability, etc. Both showed good results. In addition, the tracking resistance (CTI) is also 400 V or more, and the insulation breakdown voltage at room temperature is also 10 kV/m or more. In Comparative Examples 1A to 4A lacking any of the components (A) to (E), all of the items, such as glass transition temperature, peel resistance, and continuous formability, or a plurality of items became insufficient results.

The characteristics of the molding material composition for sealing prepared in Examples 1B to 3B and Comparative Examples 1B to 6B were measured and evaluated under the measurement conditions shown below. The evaluation results are shown in Table 3 and Table 4. In addition, as long as it is not clearly described, the molding material is formed by a transfer molding machine under conditions of a mold temperature of 190°C, a molding pressure of 10 MPa, and a curing time of 240 seconds. In addition, the post-hardening system was carried out at 220°C for 4 hours.

<Evaluation items> (8) Glass transition temperature (Tg) As one of the standards for the heat resistance of the cured product of the molding material composition for sealing, the glass transition temperature (Tg) was measured. First, using a mold of 4 mm in length × 4 mm in width × 20 mm in height, the molding material composition for sealing was molded under the above conditions, and then post-hardened under the above conditions to produce a molded product (4 mm in length × horizontal 4 mm × thickness 20 mm). The molded product was cut into a desired size and used as a test piece, and the glass transition temperature (Tg) of the test piece was measured by the TMA method using a thermal analyzer (manufactured by Seiko Instruments Co., Ltd., trade name: SSC/5200). In addition, 250 degreeC or more was set as the pass.

(9) Peel and observe to prepare 10 fixed SiC wafers (6×6×0.15 mmt, no surface protection film) in the center of TO-247 packaged islands (8.5×11.5 mm) of electroless nickel-plated lead frames. A molded product obtained by molding the molding material composition for sealing under the above conditions. The molded product was observed using an ultrasonic imaging device (manufactured by Hitachi, Ltd., FS300II) to confirm whether the island around the SiC wafer and the molding material composition for sealing were peeled off. Observation was performed before and after post-hardening, and the case where 3 or less of the 10 packages where peeling of the island part was observed was regarded as a pass. In addition, the wafer is fixed to the lead frame using lead-free solder in an environment of 5% formic acid and 95% of nitrogen at 340°C/13 minutes. In addition, before the lead frame is to be molded with the sealing material composition, a plasma cleaner AC-300 manufactured by Nordson Co., Ltd. is used after 60 seconds of argon plasma treatment.

(10) Peeling after leaving at high temperature After peeling and observing the TO-247 package in (9) above and leaving it at 250°C for 250 hours, use an ultrasonic imaging device (manufactured by Hitachi, Ltd., FS300II) to confirm the peeling. There is nothing. The case where the number of packages where the peeled area of the island part is 20% or more is 10 or less is 3 or less is considered as a pass.

(11) Curability Curability was measured using a JSR vulcanizer (manufactured by A&D Co., Ltd., trade name: Curelastometer Model 7). The vulcanization torque (curelast torque) after the mold temperature of 190°C and the molding time of 240 seconds was measured, and 5 N·m or more was regarded as a pass.

100 mm×2 mmt之試片並進行後硬化之後，依據ASTM-D3638測定耐追蹤性(CTI)。試驗器使用Yamayoshikenki有限公司製造之YST-112-1S。再者，將400 V以上設為合格。(12) Production of tracking resistance (CTI)

After a 100 mm×2 mmt test piece was post-hardened, the tracking resistance (CTI) was measured according to ASTM-D3638. The tester used YST-112-1S manufactured by Yamayoshikenki Co., Ltd. In addition, 400 V or more is regarded as a pass.

100 mm×2 mmt之試片並進行後硬化之後，依據ASTM-D149測定室溫(25℃)下之絕緣破壞電壓。測定係以「短時間法」進行。試驗器使用Yamayoshikenki有限公司製造之YST-243BD-100RO。將以n＝3進行測定時之平均值為10 kV/mm以上設為合格。(13) Production of insulation withstand voltage (insulation breakdown voltage)

After a 100 mm×2 mmt test piece was post-hardened, the insulation breakdown voltage at room temperature (25°C) was measured according to ASTM-D149. The measurement is carried out by the "short time method". The tester used YST-243BD-100RO manufactured by Yamayoshikenki Co., Ltd. The average value when measuring with n=3 was 10 kV/mm or more, and it was set as the pass.

(14) Flexural modulus of elasticity Using a test piece of 100 mm in length×10 mm in width×4 mm in thickness, the elastic modulus of the molding material composition for sealing at normal temperature (20° C.) was measured by a three-point bending method. For the measurement, Autograph AG-X manufactured by Shimadzu Corporation was used. The span length is set to 64 mm, and the head speed is set to 2 mm/min. The average value of N=4 was set as the bending elastic modulus, and the bending elastic modulus was 15 GPa or less as a pass.

(15) Continuous moldability using a mold release load measuring machine (manufactured by KYOCERA Co., Ltd., trade name: GM-500), for PBGA (Plastic Ball Grid Array, 30 mm×30 mm×1 mm, t/2 holes) 300 shots of continuous forming were performed. The mold temperature was set to 190°C, and the molding time was set to 240 seconds. In addition, the evaluation is based on the following criteria. A: It can be formed continuously until it reaches 300 shots, and there is no mold contamination. B: Although the mold is dirty, it can be continuously formed until it reaches 300 shots. C: It cannot be achieved because it is attached to the mold, etc. Continuous forming up to 300 shots

[table 3]

[Table 4]

Comparative Examples 1B to 6B lacking any of (A) component to (E) component of the present invention are any items or pluralities of glass transition temperature (Tg), peeling from semiconductor insertion parts, curability, and formability The specific characteristics cannot be satisfied in each project. On the other hand, it was found that Examples 1B to 3B containing all the components (A) to (E) satisfy all the above items.

The characteristics of the molding material composition for sealing prepared in Examples 1C to 11C and Comparative Examples 1C to 3C were measured and evaluated under the measurement conditions shown below. Table 5 shows the evaluation results. In addition, as long as it is not clearly described, the molding of the molding material is performed by a transfer molding machine under conditions of a mold temperature of 185°C, a molding pressure of 10 MPa, and a curing time of 180 seconds. In addition, in the case where there is no particular description, post-hardening was carried out at 200°C for 8 hours.

<Evaluation item> (16) Glass transition temperature (Tg) As one of the standards for the heat resistance of the cured product of the molding material composition for sealing, the glass transition temperature (Tg) was measured. First, the mold material composition for sealing was molded under the above conditions using a mold with a length of 4 mm × 4 mm × a height of 20 mm, and then, post-hardening was performed under the conditions of 185°C and 8 hours or 200°C and 8 hours. To produce a molded product (4 mm in length × 4 mm in width × 20 mm in thickness). The molded products were cut into desired sizes as test pieces, and the glass transition temperature (Tg) of the test pieces was measured using a TMA method using a thermal analyzer (manufactured by Seiko Instruments Co., Ltd., trade name: SSC/5200). For the evaluation of the low-temperature reactivity, the difference between the Tg hardened after 185°C and the Tg hardened after 200°C was less than 15°C, and the difference between 15g and above was C.

(17) Thermal decomposition temperature (1% weight reduction temperature) As another standard for the heat resistance of the cured product of the molding material for sealing, the thermal decomposition temperature of TG-DTA is measured. The seal molding material composition was molded under the above-mentioned conditions, and further post-cured at 200° C. for 8 hours to produce a molded product (4 mm in length×4 mm in width×20 mm in thickness). A powder obtained by cutting the molded product at the same size as in (16) above was used as a test piece, and the test piece was sufficiently ground in a mortar, and the temperature was raised from room temperature at a rate of 10°C/min. (25 ℃) heated to 600 ℃. According to the obtained weight change table, the temperature at which a weight loss of 1% is confirmed is taken as the thermal decomposition temperature. The measuring device uses "EXSTAR6000" manufactured by Seiko Instruments Inc. In addition, 385 degreeC or more was set as the pass.

3.5 mm之布丁狀成形物自成形品之下部，並自0.5 mm之高度以速度0.1 mm/秒沿剪切方向剝離，於常溫(25℃)或250℃之條件下測定成形物與鍍鎳層之密接力。將該測定進行4次，求出平均值。再者，將常溫下4 MPa以上設為合格，將250℃下3 MPa以上設為合格。(18) For the adhesion of the nickel-plated surface, 4 pieces of electroless nickel (manufactured by Mitsui Hi-Tech Co., Ltd., trade name "VQFP208p") were formed under the above conditions, and then the seal molding material composition was formed under the above conditions The molded product after hardening. Use a bonding tester (manufactured by Xijin Shoji Co., Ltd., SS-30WD) to form on the nickel-plated surface

The pudding-shaped molded product of 3.5 mm is peeled from the lower part of the molded product and from the height of 0.5 mm at a speed of 0.1 mm/sec in the shearing direction. The molded product and the nickel-plated layer are measured under the conditions of normal temperature (25℃) or 250℃ Relay. This measurement was performed 4 times, and the average value was obtained. In addition, 4 MPa or more at normal temperature was set as the pass, and 3 MPa or more at 250°C was set as the pass.

(19) Observe the package after being placed at 250℃×250 hours. Observe the TO-247 package island (8.5×11.5 mm) in the center of the electroless nickel-plated lead frame. Fix the SiC wafer (6×6×0.15 mmt, no surface protection film) ), the molding material composition for sealing was molded under the above conditions, and further, post-curing was performed under the above conditions to produce 10 molded products, respectively. The molded product was observed using an ultrasonic imaging device (manufactured by Hitachi, Ltd., FS300II) to confirm whether the island around the SiC wafer and the molding material composition for sealing were peeled off. The case where 3 or less of the 10 packages where the peeling of the island part was observed was regarded as a pass. In addition, the wafer is fixed to the lead frame using lead-free solder in a 5% formic acid and 95% nitrogen atmosphere at 340°C/13 minutes. In addition, before the lead frame is to be formed into a molding material composition for sealing, a plasma cleaner AC-300 manufactured by Nordson Co., Ltd. is used after 60 seconds of argon plasma treatment. After the TO-247 package after peeling observation above was left at 250°C for 250 hours, use an ultrasonic imaging device (manufactured by Hitachi, Ltd., FS300II) to confirm the peeling. The case where the number of packages where the peeled area of the island part is 20% or more is 10 or less is 3 or less is considered as a pass.

100 mm×2 mmt之試片並進行後硬化之後，依據ASTM-D3638測定耐追蹤性(CTI)。試驗器使用Yamayoshikenki有限公司製造之YST-112-1S。再者，將400 V以上設為合格。(20) Production of electrical characteristics and tracking resistance (CTI)

After a 100 mm×2 mmt test piece was post-hardened, the tracking resistance (CTI) was measured according to ASTM-D3638. The tester used YST-112-1S manufactured by Yamayoshikenki Co., Ltd. In addition, 400 V or more is regarded as a pass.

100 mm×2 mmt之試片並進行後硬化之後，依據ASTM-D149測定室溫(25℃)下之絕緣破壞電壓。測定係以「短時間法」進行。試驗器使用Yamayoshikenki有限公司製造之YST-243BD-100RO。將以n＝3進行測定時之平均值為10 kV/mm以上設為合格。(21) Production of insulation withstand voltage (insulation breakdown voltage)

After a 100 mm×2 mmt test piece was post-hardened, the insulation breakdown voltage at room temperature (25°C) was measured according to ASTM-D149. The measurement is carried out by the "short time method". The tester used YST-243BD-100RO manufactured by Yamayoshikenki Co., Ltd. The average value when measuring with n=3 was 10 kV/mm or more, and it was set as the pass.

(22) Continuous moldability using a mold release load measuring machine (manufactured by KYOCERA Co., Ltd., trade name: GM-500), for PBGA (Plastic Ball Grid Array, 30 mm × 30 mm × 1 mm, t/2 holes) 300 shots of continuous forming were performed. The mold temperature was set at 185°C, and the molding time was set at 180 seconds. In addition, the evaluation is based on the following criteria. A: Continuous molding is possible until 300 shots are reached, and there is almost no mold contamination, etc. C: Continuous molding up to 300 shots cannot be achieved due to attachment to the mold, etc.

(23) Storage life The gelation time immediately after manufacturing (initial) of the molding material composition for sealing and after leaving it at 25°C for 7 days was measured by the hot plate method at 185°C. Based on these gelation times, the evaluation was performed on the following criteria. A: The change in gel time from the initial stage is less than 15% C: The change in gel time from the initial stage is more than 15%

[table 5]

The molding material compositions for sealing of Examples 1C to 11C are all excellent in formability, and the cured products of the molding material composition for sealing show a high glass transition temperature (Tg), high thermal decomposition resistance, and high voltage resistance , Good adhesion with semiconductor insert parts and high reliability. [Industry availability]

The molding material composition for SiC and GaN device sealing of the present invention can be used for electronic parts and the like.

Claims (14)

A molding material composition for SiC and GaN element sealing, which contains (A) maleimide resin, (B) hardener, (D) hardening accelerator, and (E) filler, and the above (E) filler Contains (e-1) hollow structure filler. The molding material composition for sealing SiC and GaN devices according to claim 1, wherein the above (A) maleimide resin is a maleimide resin represented by the following general formula (I),

(In the formula, R ^{1 is} independently a hydrocarbon group having 1 to 10 carbon atoms, and the hydrocarbon group may be substituted with a halogen atom; in the presence of a plurality of R ¹ , the plurality of R ¹ may be the same as or different from each other; p respectively (Independently an integer of 0~4, q is an integer of 0~3, z is an integer of 0~10). The molding material composition for sealing SiC and GaN devices according to claim 1, wherein the above (B) hardener is selected from phenolic hardeners and benzo

At least one resin, one or two of the phenolic hardeners represented by the following general formula (II), and one or two of the phenolic hardeners represented by the following general formula (III), Benzo

The resin system is represented by the following general formula (IV), [Chem 2]

(In the formula, x is 0~10)

(In the formula, y1 is 0~10)

(In the formula, X1 is a C 1-10 alkylene group, an oxygen atom, or a direct bond; R ² and R ³ are independently C 1-10 hydrocarbon groups; in the presence of a plurality of R ² and R ³ In this case, plural R ² and plural R ³ may be the same or different; m1 and m2 are independently integers of 0 to 4). The molding material composition for sealing SiC and GaN elements according to claim 1, further comprising (C) a thermosetting resin selected from the rings represented by the following general formulas (V) to (VII) At least one of an oxygen resin and an allyl group-containing nadiimido resin represented by the following general formula (VIII), [Chem. 5]

(In the formula, n1 is 0~10)

(In the formula, n2 is 0~10)

(In the formula, R ⁴ is a C 1-10 alkylene group, a C 4-8 cycloalkyl group, a C 6-18 divalent aromatic group, the general formula "-A ¹ -C ₆ H _4- (A ¹ ) _m- (where m represents an integer of 0 or 1, and each A ^{1 is} independently an alkylene group having a carbon number of 1-10, a cycloalkyl group having a carbon number of 4-8)" Base, or the general formula "-C ₆ H ₄ -A ² -C ₆ H ₄ -(Here, A ² is "-CH ₂ -", "-C(CH ₃ ) ₂ -", "-CO- ”, “-O-”, “-S-” or “-SO ₂ -” represents the basis)” represents the basis). The molding material composition for sealing SiC and GaN devices according to claim 1, which further contains a cyanate monomer having at least 2 cyanate groups in one molecule. The molding material composition for sealing SiC and GaN devices according to claim 1, wherein the above (D) curing accelerator (d-1) organophosphorus curing accelerator and (d-2) imidazole curing accelerator. The molding material composition for SiC and GaN device sealing according to claim 1, wherein the average particle diameter of the above-mentioned (e-1) hollow structure filler is 3 to 100 μm. The molding material composition for SiC and GaN device sealing according to claim 7, wherein the (e-1) hollow structure filler is at least one selected from silica, alumina, and silica-alumina compound, and The content of the (e-1) hollow structure filler is 1 to 50% by mass relative to the total amount of the (E) filler. The molding material composition for sealing SiC and GaN elements according to claim 7, wherein the above (e-1) hollow structure filler contains an organic compound, and the content of the (e-1) hollow structure filler is relative to (E) filling The total amount of wood is 0.5~10% by mass. The molding material composition for sealing SiC and GaN devices according to claim 7, wherein the above (e-1) hollow structure filler contains a silsesquioxane compound, and the content of the (e-1) hollow structure filler is relative to (E) The total amount of filler is 0.5 to 10% by mass. The molding material composition for sealing SiC and GaN devices according to claim 6, wherein the above (D) hardening accelerator (d-1) organophosphorus hardening accelerator and (d-2) imidazole hardening accelerator, and (d-2) Imidazole-based hardening accelerator and imidazole with a bisphenol A type epoxy resin (liquid) at a mass ratio of 1/20 when the reaction initiation temperature is 85°C or more and less than 175°C Department of hardening accelerator. The molding material composition for SiC and GaN device sealing according to claim 5, wherein the content of the cyanate monomer having at least 2 cyanate groups in the above-mentioned molecule is 10 to 100 parts by mass of the (A) component 50 parts by mass. The molding material composition for sealing SiC and GaN devices according to claim 4, wherein the above (C) thermosetting resin is an allyl group-containing diamidide resin represented by the following general formula (VIII), and further (D) The hardening accelerator contains (d-3) acid-based hardening accelerator, and the above (d-3) acid-based hardening accelerator is selected from p-toluenesulfonic acid, its amine salt and boron trifluoride amine complex At least one,

(In the formula, R ⁴ is a C 1-10 alkylene group, a C 4-8 cycloalkyl group, a C 6-18 divalent aromatic group, the general formula "-A ¹ -C ₆ H _4- (A ¹ ) _m- (where m represents an integer of 0 or 1, and each A ^{1 is} independently an alkylene group having a carbon number of 1-10, a cycloalkyl group having a carbon number of 4-8)" Base, or the general formula "-C ₆ H ₄ -A ² -C ₆ H ₄ -(Here, A ² is "-CH ₂ -", "-C(CH ₃ ) ₂ -", "-CO- ”, “-O-”, “-S-” or “-SO ₂ -” represents the basis)” represents the basis). An electronic component device comprising SiC and GaN elements sealed by a hardened product of the molding material composition for sealing SiC and GaN elements according to any one of claims 1 to 13.