KR20150026830A - Resin compositions for sealing semiconductor and semiconductor device with the cured product thereof - Google Patents

Abstract

The purpose of the present invention is to provide a resin composition for granting a cured product with excellent reliability that has little pyrolysis (reduction in weight) even if the cured product is left for a long time at high temperatures of 200°C or higher, e.g. at high temperatures of 200 to 250°C, has excellent adhesion to Cu LF or Ag plating, and has excellent mechanical strength at high temperatures. The present invention provides a composition comprising (A) a cyanate ester compound having two or more cyanato groups in a molecule; (B) a phenol compound represented by chemical formula (1); and (C) an inorganic filler, wherein the molar ratio of phenolic hydroxyl groups in the (B) phenol compound is 0.1 to 0.4 with respect to the cyanato groups in the (A) cyanate ester compound. Also, the present invention provides a composition comprising: in addition to (A) to (C) components, (D) a mercaptopropyl group-containing alkoxysilane compound represented by chemical formula 3; (E) a material made by supporting a metal salt of molybdic acid on an inorganic carrier; and (F) a hydrotalcite-like compound and/or a calcined material of a hydrotalcite-like compound. In addition, the present invention provides a composition comprising, in addition to (A) to (C) components, (G) a releasing agent having an acid value of 30 or lower and a saponifiable value of 150 or lower with the proviso that the saponifiable value is equal to or greater than 80 and equal to or smaller than 150 when the acid value is smaller than 5, and the acid value is equal to or greater than 20 and equal to or smaller than 30 when the saponifiable value is smaller than 5.

Description

TECHNICAL FIELD [0001] The present invention relates to a resin composition for semiconductor encapsulation and a semiconductor device including the cured resin composition.

The present invention relates to a resin composition for semiconductor encapsulation. More specifically, the present invention relates to a resin composition which has excellent thermal stability for a long period of time at a high temperature and which gives a cured product having excellent adhesion with a Cu lead frame (LF) or Ag plating at a high temperature and a good mechanical strength, To a semiconductor device.

The present invention also provides a resin composition which has excellent thermal stability for a long period of time at a high temperature and which is less susceptible to corrosion or migration of Cu lead frame (LF), Ag plating, or Cu wire, To a semiconductor device having a cargo.

It is another object of the present invention to provide a composition which can provide a cured product excellent in reliability with excellent thermal stability for a long period at a high temperature and excellent adhesion with a Cu lead frame (LF) or Ag plating, And a semiconductor device comprising the cured product of the composition.

Recently, semiconductor devices are experiencing remarkable technological innovation. TSV (through silicon via) technology is used for portable information and communication terminals such as smart phones and tablets in order to process a large amount of information at a high speed. In this technique, semiconductor devices are firstly multilayered and flip-chip bonded to a silicon interposer of 8 inch to 12 inch. Thereafter, the thermosetting resin is sealed with an interposer thermosetting resin on which a plurality of semiconductor elements connected in a multilayer structure are mounted. An unnecessary hardened resin on a semiconductor element is polished and fragmented to obtain a thin and compact semiconductor device capable of high-speed multi-function processing. However, when a thermosetting resin is applied and sealed to the entire surface of a thin silicon interposer thinner from 8 inches to 12 inches, large deflection occurs due to a difference in thermal expansion coefficient between silicon and a thermosetting resin. If the warpage is large, it can not be applied to the subsequent polishing step or the discretization step, which is a great technical problem.

Recently, environmental measures such as the conversion of energy from fossil fuels as global warming countermeasures are proceeding at the district level. As a result, the production volume of hybrid cars and electric vehicles is increasing. In addition, household electric appliances in emerging countries such as China and India are increasingly equipped with inverter motors as energy saving measures.

In a hybrid car, an electric car, and an inverter motor, a power semiconductor that plays a role of converting alternating current into direct current, direct current into alternating current, or transforming voltage becomes important. However, since silicon (Si), which has been used for a long time as a semiconductor, has a performance limit, it has been difficult to expect a remarkable improvement in performance. Therefore, attention is focused on next generation power semiconductors using materials such as silicon carbide (SiC), gallium nitride (GaN), and diamond. For example, in order to reduce the loss in power conversion, it is required to lower the resistance of the power MOSFET. However, at present, it is difficult to significantly lower the resistance in the mainstream Si-MOSFET. Therefore, development of a low-loss power MOSFET using SiC having a wide bandgap (wide gap) semiconductor is underway.

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

Power semiconductors are generally protected by transfer molding with epoxy resin or by potting and sealing with silicone gel. In recent years, transfer molding by epoxy resin has become mainstream in view of small size and light weight (especially in automotive applications). However, although the epoxy resin is a thermosetting resin balanced in moldability, adhesion to a substrate and mechanical strength, thermal decomposition of the crosslinking point proceeds at a temperature exceeding 200 캜, and an operating environment at a high temperature expected for SiC and GaN (See Non-Patent Document 1).

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

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

Industrial materials November 2011 issue (vol59 No.11)

However, the conventional cyanate ester-containing resin composition is insufficient in heat resistance, and when it is left at a high temperature of 200 DEG C or more, for example, at a high temperature of 200 DEG C to 250 DEG C for a long time, pyrolysis occurs, There is a problem that the adhesion of the cured product is lowered and cracks are generated. Accordingly, in view of the above circumstances, the present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a copper foil having a low thermal decomposition (weight reduction) even at a high temperature of 200 ° C or higher, for example, It is an object of the present invention to provide a resin composition which has good mechanical strength at a high temperature and which gives a cured product excellent in reliability.

In view of the above circumstances, the present invention also provides a cured product having a small thermal decomposition (weight loss) and excellent adhesion to Cu LF or Ag plating even when it is left at a high temperature of 200 ° C or higher, for example, 200 ° C to 250 ° C for a long period of time And can provide a resin composition excellent in transfer moldability.

The present inventors have intensively studied in order to solve the above problems and found that a phenolic compound having a specific structure is blended with a composition containing a cyanate ester compound and an inorganic filler and that the blending amount of the phenol compound with respect to the cyanate ester compound is It has been found that the resulting cured product can have excellent thermal stability and has good mechanical strength even when exposed for a long time under a high temperature operating environment and can maintain excellent adhesion with Cu LF or Ag plating, .

That is, the present invention firstly relates to

(A) a cyanate ester compound having at least two cyanato groups in one molecule;

(B) a phenol compound represented by the following formula (1); And

(Wherein R ⁵ and R ⁶ are independently of each other a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁷ is independently selected from the group consisting of compounds represented by the following general formula (2)

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

(C) an inorganic filler,

Wherein the molar ratio of the phenolic hydroxyl group in the phenol compound (B) to the cyano group in the cyanate ester compound (A) is 0.1 to 0.4.

Further, the inventors of the present invention have found that the adhesion between a metal substrate and a cured product can be greatly improved by adding a mercaptopropyl group-containing alkoxysilane compound to the first composition. However, when the composition is allowed to stand at a high temperature for a long period of time, mercaptopropyl group-containing alkoxysilane compounds are oxidized to generate sulfate ions, so that the metal substrate is corroded and discolored.

The inventors of the present invention have further intensively studied to solve the above problems. As a result, the present inventors have found that a composition comprising a mercaptopropyl group-containing alkoxysilane compound in the first composition, a substance in which a metal molybdate is supported on an inorganic carrier, The present inventors have found that it is possible to suppress the corrosion of the metal substrate which is generated when the composition is left to stand for a long time under a high temperature and to maintain the excellent adhesion of the cured product to the metal substrate.

That is, the present invention secondly,

(A) a cyanate ester compound having at least two cyanato groups in one molecule;

(B) a phenol compound represented by the following formula (1);

(Formula 1)

(Wherein R ⁵ and R ⁶ are independently of each other a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁷ is independently selected from the group consisting of compounds represented by the following general formula (2)

(2)

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

(C) an inorganic filler;

(D) a compound represented by the following formula (3);

(Wherein R ⁸ and R ⁹ are independently of each other an alkyl group having 1 to 3 carbon atoms and d is an integer of 0 to 2)

(E) a material formed by supporting a molybdic acid metal salt on an inorganic carrier; And

(F) a hydrotalcite-like compound and / or a hydrotalcite-like compound,

Wherein the molar ratio of the phenolic hydroxyl group in the phenol compound (B) to the cyanato group in the cyanate ester compound (A) is 0.1 to 0.4.

The present inventors have also studied to improve the continuity formation of the first composition. As a result, it has been found that the first composition also contains a release agent having an acid value of 30 or less and a saponification value of 150 or less (provided that when the acid value is less than 5, Or more and 150 or less, and the acid value is 20 or more and 30 or less when the saponification value is less than 5), the inventors have found that the continuous formation of the resin composition can be improved, and the present invention has been accomplished.

That is, the present invention, thirdly,

(A) a cyanate ester compound having at least two cyanato groups in one molecule;

(B) a phenol compound represented by the following formula (1);

(Formula 1)

(Wherein R ⁵ and R ⁶ are independently of each other a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁷ is independently selected from the group consisting of compounds represented by the following general formula (2)

(2)

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

(C) an inorganic filler; And

(G) a release agent having an acid value of 30 or less and a saponification value of 150 or less (provided that the saponification value is 80 or more and 150 or less when the acid value is less than 5 and the acid value is 20 or more and 30 or less when the saponification value is less than 5)

Wherein the molar ratio of the phenolic hydroxyl group in the phenol compound (B) to the cyanato group in the cyanate ester compound (A) is 0.1 to 0.4.

The first composition of the present invention has a low thermal decomposition (weight loss) even when it is left at a high temperature of 200 ° C or higher, for example, at a high temperature of 200 ° C to 250 ° C for a long period of time and is excellent in adhesion to Cu LF or Ag plating, A cured product having mechanical strength can be provided. Therefore, the semiconductor device sealed with the cured product of the composition of the present invention has long-term reliability under high temperature.

The second composition of the present invention can suppress the discoloration of the metal substrate when it is allowed to stand for a long period of time at a high temperature of 200 ° C or higher, particularly 200 ° C to 250 ° C. Even if left for a long time at a high temperature, it is excellent in Cu LF, Ag plating, The adhesion can be maintained. In addition, the obtained cured product has excellent mechanical strength at high temperature. Therefore, the semiconductor device sealed with the cured product of the composition of the present invention has long-term reliability under high temperature.

The third composition of the present invention can provide a cured product having less thermal decomposition (weight loss) and excellent adhesion to Cu LF or Ag plating even when it is allowed to stand for a long time at a high temperature. Therefore, a semiconductor device sealed with a cured product of the composition of the present invention has long-term reliability under high temperature. Further, since the third composition of the present invention is excellent in continuous formability, it can be preferably used as a material for transfer molding.

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

(A) a cyanate ester compound

In the first, second and third compositions of the present invention, the component (A) is a cyanate ester compound having two or more cyanato groups in one molecule. The cyanate ester compound in the present invention is not particularly limited as long as it has two or more cyanato groups in one molecule, and generally known ones can be used. The cyanate ester compound may be represented by, for example, the following formula (4)

(Wherein R ¹ and R ² are independently of each other a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ³ is independently selected from the group consisting of compounds represented by the following general formula (5)

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

Examples of the cyanate ester compound of the present invention include bis (4-cyanatophenyl) methane, bis (3-methyl-4-cyanatophenyl) Bis (4-cyanatophenyl) ethane, 2,2-bis (4-cyanatophenyl) propane, 2,2-bis (4-cyanatophenyl) -1,1,1,3,3,3-hexafluoropropane, di (4-cyanatophenyl) thioether, 1,3- and 1,4-dicyanatobenzene, Di-tert-butyl-1,4-dicyanatobenzene, 2,4-dimethyl-1,3-dicyanatobenzene, 2,5- Methyl-1,4-dicyanatobenzene, 1,3,5-tricyanatobenzene, 2,2'- or 4,4'-dicyanatobiphenyl, 3,3 ', 5,5'- 4,4'-dicyanatobiphenyl, 1,3-, 1,4-, 1,5-, 1,6-, 1,8-, 2,6- or 2,7-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene, bis (4-cyanatophenyl) methane; 2,2-bis (4-cyanatophenyl) propane, 1,1,1-tris (4-cyanatophenyl) ethane, bis (4-cyanatophenyl) ether; Bis (4-cyanatophenyl) sulfone, bis (4-cyanatophenyl) sulfone, tris (4-cyanato-phenyl ) Phosphine, tris (4-cyanatophenyl) phosphate, phenol novolak cyanate, cresol novolac cyanate, dicyclopentadiene novolac cyanate, phenyl aralkyl cyanate ester, biphenyl aralkyl cyanate ester, Naphthalene aralkyl type cyanate esters, and the like. These cyanate ester compounds may be used singly or in combination of two or more.

The cyanate ester compound is obtained by reacting phenols with cyanogen chloride under basic conditions. The cyanate ester compound may be appropriately selected from among those having a wide range of properties from a solid state at a softening point of 106 캜 to a liquid state at room temperature, rather than the structure thereof. For example, when preparing a liquid epoxy resin composition, it is preferable to use a liquid compound at room temperature and, when it is dissolved in a solvent to prepare a varnish, it is preferably selected depending on solubility and solution viscosity. When used in transfer molding for power semiconductor sealing, it is preferable to select a compound which is solid at room temperature.

Further, when the equivalent of the cyanate group is small, that is, the molecular weight of the functional group is small, a cured product having a low curing shrinkage and low thermal expansion and high Tg can be obtained. When the equivalent of the cyanate group is large, the Tg is slightly lowered, but the triazine cross-linking interval becomes flexible, so that low carbonization, high strength and low absorption can be expected. It is preferable that the amount of chlorine bonded or remaining in the cyanate ester compound is 50 ppm or less, more preferably 20 ppm or less. If the amount of chlorine exceeds 50 ppm, chlorine or chlorine ions liberated by pyrolysis when allowed to stand for a long period at a high temperature may corrode an oxidized Cu frame, Cu wire or Ag plating, possibly causing peeling of the cured product or electrical failure have. In addition, there is a fear that the insulating property of the resin is lowered.

(B) a phenol compound

In the first, second and third compositions of the present invention, the phenol compound (B) has two or more phenolic hydroxyl groups in one molecule and is represented by the following formula (1).

(Formula 1)

Wherein R ⁵ and R ⁶ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and m is an integer of 0 to 10.

In the above formula (1), R ⁷ is independently selected from the following compounds of the following formula (2).

(2)

(Wherein, in the above formula (2), R ⁴ independently represents a hydrogen atom or a methyl group)

In the first composition of the present invention, the phenolic compound does not include those in which R ⁷ is CH ₂ (for example, phenol novolak resin) in the above formula (1). Phenol compounds in which R ⁷ is CH ₂ are liable to cause thermal decomposition when they are kept at a high temperature for a long period of time and may cause peeling or cracking at the interface between the copper lead frame and the cured product.

Examples of the phenol compound represented by the formula (1) include a bisphenol F type resin, a bisphenol A type resin, a phenol aralkyl type resin, a biphenyl aralkyl type resin and a naphthalene aralkyl type resin. These may be used alone or in combination of two or more.

In the second and third compositions of the present invention, a compound (for example, phenol novolak resin) wherein R ⁷ is CH ₂ in the above formula (1) may be included. However, the composition tends to have low heat resistance. However, since the reactivity between the cyanate compound and the compound is too high, there is a fear that the moldability is deteriorated. Accordingly, in the second and third compositions of the present invention, R ⁷ is particularly preferably other than CH ₂ .

Conventionally, as curing catalysts for cyanate ester compounds, metal salts, metal complexes and the like have been used (JP-A-64-43527, JP-A-11-106480, JP-A-2005-506422) . However, what is used as a metal salt or a metal complex is a transition metal, and transition metals may promote oxidation deterioration of the organic resin under high temperature. In the composition of the present invention, the phenol compound functions as a catalyst for the cyclization reaction of the cyanate ester compound. Therefore, it is not necessary to use a metal salt and a metal complex. As a result, the long-term storage stability at a high temperature can be further improved.

Further, a phenol compound having at least two hydroxyl groups in a molecule can be expected as a crosslinking agent connecting a triazine ring. Unlike an epoxy compound or an amine compound, a phenol compound can form a structure represented by -C-O-Ar- by bonding with a cyanate ester compound. Since the above structure is similar to the triazine ring structure formed when the cyanate ester compound is cured alone, it is expected that the heat resistance of the obtained cured product is further improved.

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

The blending amount of the phenol compound is such that the hydroxyl group is 0.1 to 0.4 mole with respect to 1 mole of the cyanato group. If the amount of the phenol compound is less than the above lower limit value, the reaction of the cyanato group becomes insufficient, and unreacted cyanato groups remain. The remaining cyano group undergoes hydrolysis in a high-humidity atmosphere. Therefore, if left under high temperature and high humidity, the mechanical strength is lowered, and the adhesion with the substrate is lowered. When the amount of the phenol compound is larger than the upper limit value, the curing reaction proceeds from a low temperature. As a result, the fluidity of the composition is lost and the moldability is deteriorated. Further, it is preferable that the halogen element, the alkali metal, and the like in the phenol compound are 10 ppm, particularly 5 ppm or less in extraction at 120 ° C under 2 atm.

(C) Inorganic filler

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

It is preferable that the inorganic filler is an impurity extracted at an extraction condition of 5 g of the sample and 50 g of water at 120 캜 and 2.1 atmospheric pressure, the chlorine ion being 10 ppm or less and the sodium ion being 10 ppm or less. If it exceeds 10 ppm, the humidity resistance characteristic of the semiconductor device sealed with the composition may be lowered.

In the present invention, the amount of the inorganic filler to be blended may be 60 to 94 mass%, preferably 70 to 92 mass%, and more preferably 75 to 90 mass% of the entire composition.

The inorganic filler is preferably compounded with a coupling agent such as a silane coupling agent or a titanate coupling agent, which has been surface-treated in advance, in order to strengthen the bonding strength between the resin and the inorganic filler. Examples of such coupling agents include epoxy silanes such as? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropylmethyldiethoxysilane and? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N - (aminoethyl) -? - aminopropyltrimethoxysilane, a reaction product of imidazole and? -glycidoxypropyltrimethoxysilane,? -aminopropyltriethoxysilane, N-phenyl-? -aminopropyltri It is preferable to use a silane coupling agent such as aminosilane such as methoxysilane, mercaptosilane such as gamma -mercaptosilane or gamma -episulfepoxypropyltrimethoxysilane. In the second composition of the present invention, an inorganic filler surface-treated with mercaptosilane such as? -Mercaptosilane or? -Episulfepoxypropyltrimethoxysilane can be used, but this is not so preferable. The amount of the coupling agent used in the surface treatment and the surface treatment method are not particularly limited.

The first composition

A first embodiment of the present invention is a resin composition comprising the above components (A) to (C). In addition to the above components (A) to (C), the first sealing resin composition of the present invention may further contain various additives such as a releasing agent, a flame retardant, an ion trapping agent, an antioxidant, Can be blended. The above-mentioned coupling agent may be used as the adhesion-imparting agent. In order to improve the adhesion with the metal frame, a mercapto-based silane coupling agent is particularly preferred.

The release agent is not particularly limited, and known ones can be used. (2-hydroxyethylamino) -ethanol, ethylene glycol, propylene glycol, propylene glycol, propylene glycol, propylene glycol, propylene glycol, butylene glycol, Stearic acid ester, stearic acid amide, ethylene bisstearic acid amide, and copolymers of ethylene and vinyl acetate, which are ester compounds with glycerin and the like. These may be used alone or in combination of two or more.

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

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

The second composition

The second embodiment of the present invention is a resin composition comprising the following components (D) to (F) in addition to the above components (A) to (C).

(D) Mercaptopropyl group  contain Alkoxysilane  compound

(D) is a compound represented by the following formula (6).

In Formula 6, R ⁸ and R ⁹ are each independently an alkyl group having 1 to 3 carbon atoms, and d is an integer of 0 to 2. Examples of the mercaptopropyl group-containing alkoxysilane compound include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3- Methyldiethoxysilane and the like.

The second composition of the present invention contains the mercaptopropyl group-containing alkoxysilane compound represented by the general formula (6), thereby greatly increasing the adhesion between the metal substrate such as the Cu alloy lead frame, Ag plating, Au plating and NiPdAu plating, . The blending amount of the component (D) is 0.3 to 1.0 part by weight, preferably 0.4 to 0.8 part by weight based on 100 parts by weight of the total of the components (A) and (B). If the amount of the component (D) is less than the lower limit value described below, the adhesion between the metal substrate and the cured product may be insufficient. Further, even if the amount of the component (D) exceeds the upper limit value, the adhesion is not further improved, which is not preferable from the economical point of view.

(E) Molybdic acid metal salt-carrying substance

The component (E) is a material formed by supporting a metal molybdate on an inorganic carrier. The component (E) has the effect of changing the pH of the composition from acidity to near neutral, and the effect of suppressing or capturing the lead frame or plating-derived glass of Cu ion or Ag ion. The second composition of the present invention is characterized by blending component (E) with component (F) described below. This makes it possible to suppress corrosion with the metal frame which occurs when the device sealed with the cured product of the encapsulating resin composition is allowed to stand for a long time at a high temperature and maintain excellent adhesion between the cured product and the metal frame under high temperature.

As the inorganic carrier for supporting the molybdic acid metal salt, those shown as the inorganic filler (C) can be used. Examples thereof include silicas such as fused silica and crystalline silica, talc, zinc oxide, alumina, silicon nitride, aluminum nitride, boron nitride, titanium oxide, glass fiber and the like. The inorganic carrier may be the same as or different from the component (C). Particularly preferred are silica, talc and zinc oxide.

As the molybdic acid metal salt, zinc molybdate, calcium molybdate, strontium molybdate, barium molybdate, or a mixture thereof can be used. Further, oxides of metals such as zinc, calcium, strontium and barium may be combined with the molybdic acid metal salt. And preferably zinc molybdate. Examples of the material formed by supporting zinc oxide molybdate on an inorganic carrier include KEMGARD series manufactured by SHERWIN-WILLIAMS.

The amount of the molybdic acid metal salt to be supported on the inorganic carrier is preferably 5 to 40 mass%, particularly 10 to 30 mass% with respect to the total amount of the inorganic carrier. If the content of the molybdic acid metal salt is too small, a sufficient effect may not be obtained, and if it is too large, the flowability and curability during molding may be deteriorated.

The amount of the component (E) to be added is preferably 3 to 30 parts by weight, more preferably 5 to 20 parts by weight based on 100 parts by weight of the total of the components (A) and (B). If the amount of the component (E) is less than the above lower limit value, the effect is not sufficiently obtained. Further, when the amount is added in excess of the upper limit value, the fluidity may be lowered.

(F) Hydrotalcite-like compounds

Component (F) is a fired product of a hydrotalcite-like compound and / or a hydrotalcite-like compound. The hydrotalcite-like compound is, for example, a layered multinary oxide represented by the following composition formula and functions as an anion exchanger.

In the above formula, M ^{2 +} is ^{Mg 2 +, Ca 2 +,} Zn 2 +, Co 2 +, Ni 2 +, Cu 2 +, a divalent metal ion such as Mn ^{2 +,} M ^{3 +} is Al ^{3 +} , Fe ^{3 +} , and Cr ^{3 +} , and A ^{n -} is an anion of n such as OH ^- , Cl ^- , CO ₃ ^{2 -} , SO ₄ ^{2 -,} and the like. x is a number larger than 0, particularly 0.10 to 0.50, more preferably 0.20 to 0.33, m is 0 or a number larger than 0, particularly 0 to 10, further 0 to 4. The fired product of the hydrotalcite-like compounds, for example, the formula _{^{M 2 + 1- x M 3 +}} x O 1 + x / 2 is a double oxide that can be represented by (x is an integer). Further, as the (F) component of the present _{invention, Mg 3 ZnAl 2 (OH)} 12 CO 3 · wH 2 O, Mg 3 ZnAl 2 (OH) may be used in the zinc-modified hydrotalcite-based compounds such as ₁₂ CO ₃ ( w is a real number.

 The calcined product of the hydrotalcite-like compound and the hydrotalcite-like compound has anion exchange capacity. Therefore, sulfate ions generated by the oxidation of the component (D) can be trapped, thereby preventing sulfidation and corrosion of the Cu lead frame and Ag plating. Also, by using the component (F) together with the component (E) as described above, problems such as corrosion and migration of Cu and Ag can be effectively prevented.

The component (F) of the present invention is preferably a hydrotalcite compound represented by the following formula (7) and / or a calcined product of the hydrotalcite compound.

In formula (7), a, b and c are numbers greater than 0, satisfying 2a + 3b-c = 2, and n is a number satisfying 0?

Examples of the hydrotalcite compound represented by the formula (7) include Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ .3.5H ₂ O, Mg _{4 .5} Al ₂ (OH) ₁₃ CO ₃ , Mg ₄ Al _{2 ) 12 CO 3 · 3.5H 2 O} , Mg 6 Al 2 (OH) 16 CO 3 · 4H 2 O, Mg 5 Al 2 (OH) 14 CO 3 · 4H 2 O, Mg 3 Al 2 (OH) 10 CO 3 1.7H ₂ O, and the like. Commercially available products include trade names "DHT-4A", "DHT-6", and "DHT-4A-2" (all manufactured by Kyodo Kagaku Kogyo Co., Ltd.).

The blending amount of the component (F) is preferably 1 to 10 parts by weight, and more preferably 2 to 8 parts by weight based on 100 parts by weight of the total of the components (A) and (B). If the amount of the component (F) is less than the above lower limit value, the effect is not sufficiently obtained. When the amount of the component (F) exceeds the upper limit value, addition of the component (F) may cause deterioration of hardenability and adhesion.

In the second sealing resin composition of the present invention, various additives such as a releasing agent, a flame retardant, an antioxidant, an adhesion-imparting agent, a low-stress agent, and a coupling agent other than the component (D) may be further blended if necessary.

The release agent is not particularly limited, and known ones can be used. For example, carnauba wax, rice wax, candelilla wax, polyethylene, polyethylene oxide, polypropylene, montanic acid, montanic acid, saturated alcohols, 2- (2-hydroxyethylamino) -ethanol, ethylene glycol, glycerin Stearic acid ester, stearic acid amide, ethylenebisstearic acid amide, and copolymers of ethylene and vinyl acetate, and the like. These may be used alone or in combination of two or more.

Examples of coupling agents other than the component (D) include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like (Aminoethyl) -? - aminopropyltrimethoxysilane, a reaction product of imidazole and? -Glycidoxypropyltrimethoxysilane,? -Aminopropyltriethoxysilane, N-phenyl-γ And aminosilane such as aminopropyltrimethoxysilane may be used alone or in combination of two or more.

The flame retardant is not particularly limited and known flame retardants can be used. For example, phosphazene compounds, silicon compounds, aluminum hydroxide, magnesium hydroxide, molybdenum oxide and antimony trioxide.

Third composition

 The third embodiment of the present invention is a resin composition comprising the following component (G) in addition to the above components (A) to (C).

(G) Releasing agent

The component (G) used in the third composition of the present invention is a release agent having an acid value of 30 or less and a saponification value of 150 or less. Preferably, the acid value is 10 to 25. The saponification value is preferably 70 to 140, more preferably 70 to 100. Either the acid value or the saponification value may be zero. When the acid value is less than 5, the saponification value is not less than 80 and not more than 150, preferably not less than 100 and not more than 150. When the saponification value is less than 5, the acid value is not less than 20 and not more than 30, preferably not less than 25 and not more than 30. If both the acid value and the saponification value are too small, the releasing agent is too miscible with the resin, so that it is not preferable because sufficient release effect (that is, continuous moldability) can not be exhibited. If the acid value and the saponification value are too large, the exudation of the surface of the cured product becomes severe, resulting in appearance defects. In particular, when the saponification value exceeds the upper limit value, the releasing agent is not solid at room temperature and may become a liquid (lubricating oil). When such a release agent is added to a composition and molded, it may be bleed out with time, which may deteriorate the appearance of the cured product, which is not preferable.

Examples of the release agent (G) include esters such as carnauba wax, rice wax, polyethylene oxide, montanic acid, montanic acid and saturated alcohol, 2- (2-hydroxyethylamino) -ethanol, ethylene glycol or glycerin Waxes such as compounds; Stearic acid, stearic acid esters, and copolymers of ethylene and vinyl acetate. These may be used singly or in combination of two or more kinds. Among them, polyethylene oxide or a fatty acid ester is preferable. The blending amount of the releasing agent is 0.3 to 1.5% by mass, preferably 0.35 to 0.8% by mass, and more preferably 0.35 to 0.5% by mass of the entire composition.

In the third sealing resin composition of the present invention, various additives such as a flame retardant, an ion trap agent, an antioxidant, an adhesion imparting agent, and a low stress agent may be further blended, if necessary. As the adhesion-imparting agent, the above-mentioned coupling agent can be used. In order to improve the adhesion with the metal frame, a mercapto-based silane coupling agent is particularly preferred.

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

The ion trap agent is not particularly limited and a known one can be used. Hydrotalcites, bismuth hydroxide compounds, rare earth oxides, and the like.

The method for producing the composition of the present invention is not particularly limited. For example, the components (A) to (C), the components (A) to (F) or the components (A) to (C) Stirring, dissolving, mixing, and dispersing the mixture while adding the other components to the mixture, adding the other additives to the mixture, stirring, and dispersing the mixture. Mixing and the like are not particularly limited. However, it is possible to use a grinding machine equipped with a stirrer and a heating device, a two-necked roll, a three-necked roll, a ball mill, a continuous extruder, a planatary mixer, a masscolloider ) Can be used. These devices may be suitably used in combination.

The composition of the present invention is useful for semiconductor packages such as transistor type, modular type, DIP type, SO type, flat pack type, ball grid array type and the like. The composition of the present invention may be molded according to a conventionally employed molding method. For example, transfer molding, compression molding, injection molding, casting and the like can be used. Especially preferred is transfer molding. The molding temperature of the composition of the present invention is preferably 45 to 180 seconds at 160 to 190 DEG C and 2 to 16 hours at 170 to 250 DEG C for postcure.

The first composition of the present invention has a low thermal decomposition (weight loss) when it is allowed to stand for a long period of time at a high temperature of 200 ° C or higher, particularly 200 ° C to 250 ° C and is excellent in adhesion with Cu LF or Ag plating, A cured product having mechanical strength can be provided. Therefore, the semiconductor device sealed with the cured product of the first composition of the present invention can have long-term reliability under high temperature. And can be used in the same apparatus as the epoxy resin composition generally used as a conventional transfer molding material, and the same molding conditions can be used. Also, productivity is excellent.

The second composition of the present invention has little pyrolysis (weight loss) when stored at a high temperature of 200 ° C or lower, particularly 200 ° C to 250 ° C for a long period of time. Further, even when left for a long time under a high temperature, excellent adhesion with Cu LF or Ag plating can be maintained, and corrosion of the metal frame can be effectively suppressed. Therefore, a semiconductor device sealed with a cured product of the second composition of the present invention can have high temperature long term reliability. And can be used in the same apparatus as the epoxy resin composition generally used as a conventional transfer molding material, and the same molding conditions can be used. Also, productivity is excellent.

The third composition of the present invention can provide a cured product having less thermal decomposition (weight reduction) when it is allowed to stand at a high temperature of 200 ° C or more, particularly 200 ° C to 250 ° C for a long period of time and excellent adhesion with Cu LF or Ag plating . Therefore, the semiconductor device sealed with the cured product of the third composition of the present invention can have long-term reliability under high temperature. Further, since the third composition of the present invention is excellent in continuous formability, it can be preferably used particularly as a transfer molding material.

(Example)

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the examples, "parts" are all parts by mass.

[Examples and Comparative Examples]

Each of the components described below was blended in the compositions shown in Tables 1 to 4, uniformly mixed with a high-speed kneader, uniformly kneaded with a heated two rolls, cooled and pulverized to obtain a resin composition.

[Components (A) to (C) used in the first, second and third compositions]

(A) a cyanate ester compound

 (A) cyanate ester compound (Prima Set PT-60, manufactured by Loner Japan Co., cyanate group equivalent 119) represented by the following formula (8)

 (B) The cyanate ester compound obtained in Synthesis Example 1

[Synthesis Example 1]

100 g of a phenol compound MEH-7851SS (manufactured by Meiwa Chemical Industry Co., Ltd.) was dissolved in 600 g of butyl acetate. The solution was cooled to about -15 DEG C and 32 g of gaseous chlorinated cyanide were introduced. Subsequently, 50 g of triethylamine was added dropwise over about 30 minutes while stirring, and the temperature was kept at -10 占 폚 or lower during this period. After holding at this temperature for an additional 30 minutes, cooling was stopped and the reaction mixture was filtered. The filtrate was continuously passed through an ion exchanger packing column. Subsequently, the solvent was removed under reduced pressure at a bath temperature of 70 ° C, and thereafter, volatile impurities (residual solvent, free triethylamine, and diethylcyanamide) were passed through a falling film evaporator Lt; RTI ID = 0.0 > 130 C. < / RTI > The obtained product was a cyanate ester compound (cyanate group equivalent: 208) represented by the following general formula (9).

(B) a phenol compound

 (C) A phenol compound (MEH-7800SS, manufactured by Meiwa Chemical Industry Co., Ltd., phenolic hydroxyl equivalent of 175) represented by the following formula (10)

 (D) a phenol compound represented by the following formula (11) (MEH-7851SS, Meiwa Kasei, phenolic hydroxyl equivalent 203)

 (E) Comparative phenol compounds

A phenol compound (TD-2131, phenolic hydroxyl equivalent equivalent 110, DIC) represented by the following formula (12)

(C) Inorganic filler

  (F) Fused spherical silica having an average particle diameter of 15 탆 (made by Datsu Mori)

[Other components used in the first composition]

Triphenylalkane type epoxy resin (EPPN-501H, Nippon Kayaku Co., epoxy equivalent 165)

Cresol novolak type epoxy resin (EPICRON N670, manufactured by DIC, epoxy equivalence 200)

Dimethylol melamine resin (S-176, made by Nippon Carbide)

· Carnauba wax (TOWAX-131, Doagasee now)

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

· Imidazole (manufactured by Shikoku Chemicals)

[Components (D) to (F) and other components used in the second composition]

(D) a mercaptopropyl group-containing alkoxysilane compound

(G) 3-mercaptopropyltrimethoxysilane: (CH ₃ O) ₃ -Si-C ₃ H ₆ -SH

(E) Component

  (A) Zinc oxide supported on molybdenum oxide (KEMGARD-911B, Shawin Willyamzze)

  (KEMGARD-911C, made by Sherwin Williams) containing zinc molybdate,

(F) Hydrotalcite-like compounds

(DHA-4A-2, manufactured by Kyowa Chemical Co., Ltd.) Mg ₆ Al ₂ (CO ₃ ) (OH) ₁₆ · 4H ₂ O

Other ingredients

Triphenylalkane type epoxy resin (EPPN-501H, Nippon Kayaku Co., epoxy equivalent 165)

· Carnauba wax (TOWAX-131, Doagasee now)

· Imidazole (manufactured by Shikoku Chemicals)

[Component (G) and other components used in the third composition]

(G) Releasing agent

  (K) Release agent 1: Polyethylene oxide (Ricoh wax PED-522, product of Clariant) having an acid value of 25 and a saponification value of 0,

  (Other) Releasing agent 2: Fatty acid ester having an acid value of 10 and a saponification value of 85 (TOWAX-131, manufactured by Toagosei Co., Ltd.)

  (Other) Release agent 3: Fatty acid ester (ITO-WAX TPNC-133, manufactured by Itosai Kogyo Co., Ltd.) having an acid value of 25 and a saponification value of 140

· Releasing agent for comparative purposes

  (Lower) Release agent 4: Polyethylene (Ricoh wax PE-522, Clariant Schaetz) having an acid value of 0 and a saponification value of 0,

  (Lower) Release agent 5: Polypropylene having an acid value of 86 and a saponification value of 0 and a maleic anhydride copolymer (Erekutor D121-41, manufactured by Nissan Chemical Industries, Ltd.)

Other ingredients

An epoxy resin compound (NC-3000, Nippon Kayaku, epoxy equivalent weight 272) represented by the following formula (13)

Silane coupling agent: 3-mercaptopropyltrimethoxysilane (KBM-803, Shin-Etsu Chemical Industries, Ltd.)

· Imidazole (manufactured by Shikoku Chemicals)

Evaluation of first composition

Each of the compositions of Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-7 was subjected to the following evaluation tests. The results are shown in Tables 1 and 2 below.

[Spiral flow]

Using a mold conforming to the EMMI standard, at 175 DEG C, 6.9 N / mm < 2 > and a molding time of 180 seconds.

[Weight change during storage at high temperature]

175 DEG C for 120 seconds, and a molding pressure of 6.9 MPa, and then subjected to post cure at 180 DEG C for 4 hours to obtain test specimens of 10 x 100 x 4 mm. The test piece was stored in an oven at 250 캜 for 500 hours, and the weight loss rate was measured.

[Confirmation of adhesion with Ag plated Cu LF]

Transfer molding was performed using a 100pin QFP lead frame made of a Cu alloy (Agin C7025) plated with a die pad portion (8 mm x 8 mm) and a wire bonding portion under conditions of 175 deg. C for 120 seconds and a molding pressure of 6.9 MPa. Followed by post cure at 180 占 폚 for 4 hours. A tie-bar was cut with a lead frame cutter to obtain a QFP package of 20 mm x 14 mm x 2.7 mm.

The above-mentioned 12 packages were stored in an oven at 250 ° C for 500 hours, and the presence or absence of cracks in the package after storage was visually confirmed. In addition, the presence of internal cracks and peeling with the lead frame was observed using an ultrasonic flaw detector. The number of packages in which cracking or peeling has occurred is shown in the table.

[Glass transition temperature]

175 占 폚 for 120 seconds, and a molding pressure of 6.9 MPa, and then post-curing at 250 占 폚 for 4 hours to obtain test specimens of 5 占 5 占 15 mm. The specimen was measured for dimensional change (Rigaku TMA8310) at a heating rate of 5 ° C / min and the glass transition point was determined from the intersection of the tangent line at 50 to 100 ° C and the tangent line at 270 to 290 ° C.

[Bending Strength, Bending Modulus]

Transfer molding was carried out in accordance with JIS-K6911 under conditions of 175 DEG C for 120 seconds and a molding pressure of 6.9 MPa, followed by post curing at 180 DEG C for 4 hours to obtain test specimens of 10 x 100 x 4 mm. The test piece was allowed to stand in an oven at 250 캜 for 3 minutes, and then bent at three points with an autograph tester (Shimadzu Corporation) to measure the bending strength and the bending elastic modulus.

[Moldability]

80pin QFP (14 x 20 x 2.7 mm) was subjected to 20 short shots at 175 DEG C for 120 seconds and 6.9 MPa, and the number of shots until adhesion to the mold and curl and runner breakage were observed.

The composition in which the molar ratio of the phenolic hydroxyl group to the cyanato group of the cyanate ester compound does not satisfy the range of the present invention and the cured product obtained from the composition using the phenol novolak resin have a weight The reduction rate is great. Further, when the cured product was allowed to stand at a high temperature for a long time, peeling and cracks were generated at the interface with the copper lead frame. On the other hand, the first composition of the present invention did not lose its weight even after being left at 250 DEG C for 500 hours, and did not cause peeling or cracking even when left for a long time at a high temperature. Further, the first composition of the present invention was excellent in continuous moldability and mechanical strength at high temperature.

Evaluation of the second composition

The following evaluation tests were carried out for each of the compositions of Examples 2-1 to 2-7 and Comparative Examples 2-1 to 2-4. The results are shown in Table 3 below.

[Confirmation of Cu LF corrosion]

A 100pin QFP lead frame (die pad portion) made of a Cu alloy (Olin C7025) was subjected to transfer molding at 175 占 폚 for 120 seconds under a molding pressure of 6.9 MPa, followed by post curing at 180 占 폚 for 4 hours. The tie bars were cut with a lead frame cutter to obtain a QFP package of 20 mm x 14 mm x 2.7 mm.

The package was stored in a 225 DEG C oven for 1000 hours. After the storage, the sealing resin was mechanically broken, and the presence or absence of discoloration of the die pad portion inside was observed.

[Check corrosion of Ag plating]

Transfer molding was performed using a 100pin QFP lead frame made of a Cu alloy (Agin C7025) with a die pad portion (8 mm x 8 mm) and a wire bonding portion of Ag plating at 175 DEG C for 120 seconds and a molding pressure of 6.9 MPa 180 ℃, post cure for 4 hours. The tie bars were cut with a lead frame cutter to obtain a QFP package of 20 mm x 14 mm x 2.7 mm.

The package was stored in a 225 DEG C oven for 1000 hours. After the storage, the sealing resin was mechanically broken, and the presence or absence of discoloration of the inside of the Ag plating die pad portion was observed.

[Confirmation of adhesion with Ag plated Cu LF]

Transfer molding was carried out under conditions of 175 占 폚 for 120 seconds and a molding pressure of 6.9 MPa using a die pin portion (8 mm 占 8 mm) and a 100-pin QFP lead frame made of a Cu alloy (Olin C7025) 180 ℃, post cure for 4 hours. The tie bars were cut with a lead frame cutter to obtain a QFP package of 20 mm x 14 mm x 2.7 mm.

The 12 packages were stored in an oven at 225 ° C for 1000 hours. After storage, using an ultrasonic probe, the presence of internal cracks and peeling with the lead frame was observed. The number of packages in which cracking or peeling has occurred is shown in the table.

[Bending Strength, Bending Modulus]

Transfer molding was carried out in accordance with JIS-K6911 under conditions of 175 DEG C for 120 seconds and a molding pressure of 6.9 MPa, followed by post curing at 180 DEG C for 4 hours to obtain test specimens of 10 x 100 x 4 mm.

The test piece was allowed to stand in an oven at 250 ° C for 3 hours and bent at three points with an autograph tester (Shimadzu Seisakusho Co., Ltd.) to measure the bending strength and the bending elastic modulus.

In a composition containing neither a molybdic acid metal salt-carrying substance nor a hydrogelthite-like compound, discoloration of the metal frame can not be suppressed when the film is allowed to stand for a long time at a high temperature, and peeling occurs at the interface between the metal frame and the cured product. On the other hand, in the specimen sealed with the second composition of the present invention, the metal frame did not discolor even at 1000 deg. C under 225 DEG C, and peeling or cracking did not occur. Further, the obtained cured product was also excellent in mechanical strength at high temperature.

Evaluation of the third composition

Each of the compositions of Examples 3-1 to 3-5 and Comparative Examples 3-1 to 3-4 was subjected to the following evaluation tests. The results are shown in Table 4 below.

[Spiral flow]

Using a mold conforming to the EMMI standard, at 175 DEG C, 6.9 N / mm < 2 > and a molding time of 180 seconds.

[Weight change during storage at high temperature]

175 DEG C for 120 seconds, and a molding pressure of 6.9 MPa, and then subjected to post cure at 180 DEG C for 4 hours to obtain test specimens of 10 x 100 x 4 mm. The test piece was stored in an oven at 250 ° C for 500 hours, and the weight loss rate was measured.

[Confirmation of adhesion with Ag plated Cu LF-1]

A 100pin QFP lead frame made of a Cu alloy (Olin C7025) having a die pad portion (8 mm x 8 mm) and a wire bonding portion Ag plated was subjected to transfer molding at 175 DEG C for 120 seconds under a molding pressure of 6.9 MPa, Four hours post cure. The tie bar was cut with a lead frame cutter to obtain a QFP package of 20 mm x 14 mm x 2.7 mm.

Twelve of the packages were stored in an oven at 225 ° C for 500 hours, and the presence or absence of cracks in the package after storage was visually confirmed. In addition, the presence of internal cracks and peeling with the lead frame was observed using an ultrasonic flaw detector. The number of packages in which cracking or peeling occurred is shown in the table.

[Moldability]

80pin QFP (14 x 20 x 2.7 mm) was subjected to 100 shot molding at 175 占 폚 for 120 seconds and 6.9 MPa, and the number of shots until adhesion to the mold and curl and runner breakage were observed.

A composition containing a releasing agent whose acid value and saponification value do not satisfy the range of the present invention is poor in continuous formability. In contrast, the third composition of the present invention is excellent in continuous formability. Further, the third composition of the present invention has a small weight reduction rate even when it is allowed to stand for a long time at a high temperature, and the adhesion with the metal frame can be maintained for a long time.

The resin composition of the present invention is good in continuous formability, and the cured product has high mechanical strength at high temperature and less weight loss even after long-term storage at a high temperature, and does not cause cracking of the package or peeling of the package. Therefore, it is possible to provide a semiconductor device excellent in high-temperature long-term reliability. In addition, the cured product of the second composition of the present invention can effectively suppress the discoloration of the metal frame when it is left to stand for a long time at a high temperature, and can maintain good adhesion with the metal frame under high temperature. Therefore, the composition of the present invention can provide a semiconductor device having high temperature and long-term reliability. The cured product of the third composition of the present invention can provide a semiconductor device having long-term thermal stability at a high temperature, capable of maintaining excellent adhesion with a metal frame, and having excellent long-term reliability at a high temperature, Since the continuous formation is excellent, it can be preferably used as a material for transfer molding.

Claims (16)

(A) a cyanate ester compound having at least two cyanato groups in one molecule;
(B) a phenol compound represented by the following formula (1); And
(Formula 1)

(Wherein R ⁵ and R ⁶ are independently of each other a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁷ is independently selected from the group consisting of compounds represented by the following general formula (2)
(2)

R ⁴ is independently a hydrogen atom or a methyl group, and m is an integer of 0 to 10)
(C) an inorganic filler,
Wherein the molar ratio of the phenolic hydroxyl group in the phenol compound (B) to the cyanato group in the cyanate ester compound (A) is 0.1 to 0.4. The method according to claim 1,
(A) is a compound represented by the following formula (4):
(Formula 4)

(Wherein R ¹ and R ² are independently of each other a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ³ is independently selected from the group consisting of compounds represented by the following general formula (5)
(Formula 5)

R ⁴ is independently a hydrogen atom or a methyl group, and n is an integer of 0 to 10). The method according to claim 1,
(B) has a phenolic hydroxyl equivalent of at least 111. (A) a cyanate ester compound having at least two cyanato groups in one molecule;
(B) a phenol compound represented by the following formula (1);
(Formula 1)

(Wherein R ⁵ and R ⁶ are independently of each other a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R ⁷ is independently selected from the group consisting of compounds represented by the following general formula (2)
(2)

R ⁴ are independently of each other a hydrogen atom or a methyl group and m is an integer of 0 to 10)
(C) an inorganic filler;
(D) a compound represented by the following formula (3);
(Formula 3)

(Wherein R ⁸ and R ⁹ are independently of each other an alkyl group having 1 to 3 carbon atoms and d is an integer of 0 to 2)
(E) a material formed by supporting a molybdic acid metal salt on an inorganic carrier; And
(F) a hydrotalcite-like compound and / or a hydrotalcite-like compound,
Wherein the molar ratio of the phenolic hydroxyl group in the phenol compound (B) to the cyanato group in the cyanate ester compound (A) is 0.1 to 0.4. 5. The method of claim 4,
(E) is a substance in which a metal molybdate is supported on an inorganic carrier selected from silica, talc and zinc oxide. 5. The method of claim 4,
Wherein the molybdic acid metal salt is zinc molybdate. 5. The method of claim 4,
(F) is a compound represented by the following general formula (7) and / or a fired product of the following compounds:
(Formula 7)

(Wherein a, b and c are numbers greater than 0, satisfying 2a + 3b-c = 2, and n is a number satisfying 0? N? 4). 5. The method of claim 4,
(A) is a compound represented by the following formula (4):
(Formula 4)

(Wherein R ¹ and R ² are independently of each other a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ³ is independently selected from the group consisting of compounds represented by the following general formula (5)
(Formula 5)

R ⁴ is independently a hydrogen atom or a methyl group, and n is an integer of 0 to 10). A semiconductor device comprising a cured product of the composition according to any one of claims 1 to 8. 10. The method of claim 9,
A semiconductor device comprising a semiconductor element made of SiC or GaN. (A) a cyanate ester compound having at least two cyanato groups in one molecule;
(B) a phenol compound represented by the following formula (1);
(Formula 1)

(Wherein R ⁵ and R ⁶ are independently of each other a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁷ is independently selected from the group consisting of compounds represented by the following general formula (2)
(2)

R ⁴ is independently a hydrogen atom or a methyl group, and m is an integer of 0 to 10)
(C) an inorganic filler; And
(G) a release agent having an acid value of 30 or less and a saponification value of 150 or less (provided that the saponification value is 80 or more and 150 or less when the acid value is less than 5 and the acid value is 20 or more and 30 or less when the saponification value is less than 5)
Wherein the molar ratio of the phenolic hydroxyl group in the phenol compound (B) to the cyanato group in the cyanate ester compound (A) is 0.1 to 0.4. 12. The method of claim 11,
(G) is at least one selected from fatty acid esters and polyethylene oxide. 12. The method of claim 11,
(A) is a compound represented by the following formula (4):
(Formula 4)

(Wherein R ¹ and R ² are independently of each other a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ³ is independently selected from the group consisting of compounds represented by the following general formula (5)
(Formula 5)

R ⁴ is independently a hydrogen atom or a methyl group, and n is an integer of 0 to 10). A semiconductor device comprising a cured product of the composition according to any one of claims 11 to 13. 15. The method of claim 14,
A semiconductor device comprising a semiconductor element made of SiC or GaN. A method of manufacturing a semiconductor device according to claim 14 or claim 15, comprising a step of forming the composition according to any one of claims 11 to 13 by transfer molding.