JP2018193505A - Silicone-modified epoxy resin composition and semiconductor device - Google Patents

Abstract

To provide a resin composition for semiconductor sealing, which maintains excellent thermal stability and high temperature and high humidity resistance and is capable of suppressing cracking and peeling by lowering an elastic modulus.SOLUTION: A silicone-modified epoxy resin composition contains: (A) a cyanate ester compound having two or more cyanato groups in one molecule; (B) a silicone-modified epoxy resin obtained by a hydrosilylation reaction between an alkenyl group-containing epoxy compound and an organopolysiloxane of a specific formula; and (C) a phenolic compound having two or more phenolic hydroxyl groups in one molecule and/or a silicone-modified phenolic resin obtained by a hydrosilylation reaction between an alkenyl group-containing phenolic compound and the organopolysiloxane. A molar ratio of epoxy groups in the epoxy resin to cyanato groups in the cyanate ester compound and a molar ratio of phenolic hydroxyl groups in the phenolic compound to cyanato groups in the cyanate ester compound are in specific ranges, respectively.SELECTED DRAWING: None

Description

  The present invention relates to a silicone-modified epoxy resin composition and a semiconductor device capable of reducing an elastic modulus and suppressing cracks and peeling while maintaining excellent thermal stability and high temperature and high humidity resistance.

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

  In recent years, as a measure against global warming, environmental measures on a global level such as energy conversion from fossil fuels have been promoted. For this reason, in the field of automobiles, the number of hybrid cars and electric cars produced is increasing. In emerging countries such as China and India, more and more models are equipped with inverter motors as energy saving measures for household electrical equipment.

  In hybrid vehicles, electric vehicles, and inverter motors, power semiconductors that convert AC to DC, convert DC to AC, and transform voltage are important. However, silicon (Si), which has been used as a semiconductor for many years, is approaching the performance limit. For example, in order to reduce power loss during power conversion, a dramatic improvement in performance such as a reduction in resistance of the power MOSFET is expected. It has become difficult. Accordingly, attention has been focused on next-generation power semiconductors using wide band gap semiconductors such as silicon carbide (SiC), gallium nitride (GaN), and diamond. Among these, development of a low-loss power MOSFET using SiC is in progress.

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

  The power semiconductor is generally protected by transfer molding using an epoxy resin and potting sealing using a silicone gel. Recently, transfer molding with epoxy resin is becoming mainstream from the viewpoint of miniaturization and weight reduction (especially for automobiles). However, the epoxy resin is a well-balanced thermosetting resin excellent in moldability, adhesion to the base material, and mechanical strength, but at a temperature exceeding 200 ° C., thermal decomposition of the crosslinking point proceeds. For this reason, it is expected that it is difficult to use an epoxy resin as a sealing material in an operating environment at a high temperature expected for SiC and GaN.

  Therefore, a thermosetting resin composition containing a cyanate resin has been studied as a material having excellent heat resistance characteristics. Among heat resistance properties, especially cyanate resin has a very small expansion coefficient and can suppress shrinkage stress during sealing and curing, so when sealing large diameter substrates such as large and thin wafers and metals Even so, it is possible to suppress warping of the substrate and the wafer.

  For example, Patent Document 1 describes that stable heat resistance can be obtained by forming an oxazole ring in a cured product of a phenol novolac resin by a reaction between a polyvalent cyanate ester and an epoxy resin. Furthermore, in Patent Document 1, the hydroxyl equivalent of the phenol novolac resin is 0.4 to 1.0 and the cyanate group equivalent of the polyvalent cyanate ester is 0.1 to 0.6 with respect to the epoxy equivalent 1 of the epoxy resin. It is described that a cured product having excellent heat resistance and water resistance can be provided. However, this composition has a problem that it requires a high-temperature and long-time thermosetting process to form an oxazole ring by the reaction of an epoxy group and a cyanato group, and is inferior in mass productivity.

  Patent Document 2 describes that a thermosetting resin composition having a specific structure and containing a cyanate ester compound, a phenol compound, and an inorganic filler has excellent heat resistance and high mechanical strength. However, since the moisture resistance is insufficient, there is a problem that peeling or cracking occurs when placed under high temperature and high humidity for a long time.

  Furthermore, in Patent Document 3, a phenol compound and an epoxy resin having a specific structure are blended with a composition containing a cyanate ester compound, and the blending amount of the phenol compound with respect to the cyanate ester compound and the blending of the epoxy resin with respect to the cyanate ester compound. It is described that by setting the amount within a specific range, a cured product having excellent thermal stability and high temperature and high humidity resistance can be provided. However, this composition has a high elastic modulus, and the suppression of peeling at the interface between the element mounting surface of the substrate and the cured product of the resin composition is not sufficient.

  In addition, since cracks in the package and peeling at the interface between the element mounting surface of the substrate and the cured product of the resin composition are problematic, as a means to prevent these, the stress is reduced, that is, the elasticity of the cured product It is also desirable to reduce the rate.

Japanese Patent Publication No. 6-15603 JP2013-53218A Japanese Patent Laid-Open No. 2006-210907

  An object of the present invention is to provide a silicone-modified epoxy resin composition and a semiconductor device capable of reducing the elastic modulus and suppressing cracks and peeling while maintaining excellent thermal stability and high temperature and high humidity resistance.

  The present inventors have intensively studied to solve the above problems, and contain a specific cyanate ester compound, a specific silicone-modified epoxy resin, a specific phenol compound and / or a specific silicone-modified phenol resin as a resin composition. And, by keeping the blending amount of the phenol compound with respect to the cyanate ester compound and the blending amount of the epoxy resin with respect to the cyanate ester compound within a specific range, the elastic modulus is lowered while maintaining excellent thermal stability, cracking and peeling. Has been found to be able to be suppressed, and the present invention has been made.

（上記式（１）中、Ｒは、互いに独立に、炭素数１〜１０の１価炭化水素基であり、ａは０．０１≦ａ≦１の正数であり、ｂは１≦ｂ≦３の正数であり、１．０１≦ａ＋ｂ＜４である。）
（Ｃ）１分子中に２個以上のフェノール性水酸基を有するフェノール化合物、及び／又は、アルケニル基含有フェノール化合物と上記平均組成式（１）で表されるオルガノポリシロキサンとのヒドロシリル化反応により得られるシリコーン変性フェノール樹脂
を含み、上記（Ａ）成分のシアネートエステル化合物中のシアナト基に対する上記（Ｂ）成分のエポキシ樹脂中のエポキシ基のモル比が０．０４〜０．３０であり、且つ、上記（Ａ）成分のシアネートエステル化合物中のシアナト基に対する上記（Ｃ）成分のフェノール化合物中のフェノール性水酸基のモル比が０．０８〜０．３０であることを特徴とするシリコーン変性エポキシ樹脂組成物。
〔２〕
（Ａ）成分が、下記一般式（２）で表される化合物である〔１〕記載のシリコーン変性エポキシ樹脂組成物。

［上記式中、Ｒ¹及びＲ²は、それぞれ独立に、水素原子又は炭素数１〜４のアルキル基であり、Ｒ³は、互いに独立に、下記式で表される２価の基のいずれかである。

Ｒ⁴は、互いに独立に、水素原子またはメチル基であり、ｎは０〜１０の整数である。］
〔３〕
（Ｂ）成分及び（Ｃ）成分における上記オルガノポリシロキサンが、下記式（ａ）〜（ｃ）で表される化合物から選ばれる少なくとも１種である〔１〕又は〔２〕記載のシリコーン変性エポキシ樹脂組成物。

（上記式（ａ）において、Ｒは上記と同じであり、Ｒ¹は水素原子又はＲの選択肢から選ばれる基であり、ｎ¹は０〜２００の整数であり、ｎ²は０〜２の整数であり、ｎ³は０〜１０の整数であり、且つ、ｎ¹、ｎ²、ｎ³は同時に０とならない。Ｒ²は下記式（ａ’）に示す基であり、

上記式（ａ’）において、Ｒ及びＲ¹は上記と同じであり、ｎ⁴は１〜１０の整数であり、括弧内に示される各シロキサン単位はランダムに結合していてもブロック単位を形成していてもよい。但し、上記式（ａ）の化合物は１分子中に少なくとも１個のケイ素原子に結合した水素原子を有する。）

（上記式（ｂ）において、Ｒは上記と同じであり、ｎ⁵は０〜１０の整数であり、ｎ⁶は１〜４の整数であり、但し、３≦ｎ⁵＋ｎ⁶≦１２を満たす数であり、括弧内に示される各シロキサン単位の結合順序は制限されない。）

（上記式（ｃ）において、Ｒ及びＲ¹は上記と同じであり、ｒは０〜３の整数であり、Ｒ⁷は水素原子、又は炭素数１〜１０の有機基であり、上記式（ｃ）の化合物は１分子中に少なくとも１個の、ケイ素原子に結合した水素原子を有する。）
〔４〕
上記（Ｃ）成分のアルケニル基含有フェノール化合物は、下記式で表される〔１〕〜〔３〕のいずれかに記載のシリコーン変性エポキシ樹脂組成物。

〔５〕
〔１〕〜〔４〕のいずれかに記載のシリコーン変性エポキシ樹脂組成物の硬化物で封止された半導体装置。 Accordingly, the present invention provides the following silicone-modified epoxy resin composition and semiconductor device.
[1]
(A) a cyanate ester compound having two or more cyanato groups in one molecule;
(B) a silicone-modified epoxy resin obtained by a hydrosilylation reaction between an alkenyl group-containing epoxy compound and an organopolysiloxane represented by the following average composition formula (1):

(In the above formula (1), R is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms, a is a positive number of 0.01 ≦ a ≦ 1, and b is 1 ≦ b ≦. 3 is a positive number, and 1.01 ≦ a + b <4.)
(C) Obtained by a hydrosilylation reaction between a phenol compound having two or more phenolic hydroxyl groups in one molecule and / or an alkenyl group-containing phenol compound and the organopolysiloxane represented by the above average composition formula (1). The molar ratio of the epoxy group in the epoxy resin of the component (B) to the cyanate group in the cyanate ester compound of the component (A) is 0.04 to 0.30, and A silicone-modified epoxy resin composition, wherein the molar ratio of the phenolic hydroxyl group in the phenol compound of the component (C) to the cyanate group in the cyanate ester compound of the component (A) is 0.08 to 0.30. object.
[2]
The silicone-modified epoxy resin composition according to [1], wherein the component (A) is a compound represented by the following general formula (2).

[In the above formula, R ¹ and R ² are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ³ is any one of divalent groups represented by the following formula, independently of each other: It is.

R ⁴ are each independently a hydrogen atom or a methyl radical, n is an integer of 0. ]
[3]
The silicone-modified epoxy according to [1] or [2], wherein the organopolysiloxane in the component (B) and the component (C) is at least one selected from compounds represented by the following formulas (a) to (c): Resin composition.

(In the formula (a), R is the same as above, R ¹ is a hydrogen atom or a group selected from the options of R, n ¹ is an integer from 0 to 200, and n ² is from 0 to 2. N ³ is an integer of 0 to 10, and n ¹ , n ² , and n ³ are not simultaneously 0. R ² is a group represented by the following formula (a ′),

In the above formula (a ′), R and R ¹ are the same as above, n ⁴ is an integer of 1 to 10, and each siloxane unit shown in parentheses forms a block unit even if they are randomly bonded You may do it. However, the compound of the above formula (a) has a hydrogen atom bonded to at least one silicon atom in one molecule. )

(In the above formula (b), R is the same as above, n ⁵ is an integer of 0 to 10, n ⁶ is an integer of 1 to 4, provided that 3 ≦ n ⁵ + n ⁶ ≦ 12 is satisfied. Number, and the bonding order of each siloxane unit shown in parentheses is not limited.)

(In the above formula (c), R and R ¹ are the same as above, r is an integer of 0 to 3, R ⁷ is a hydrogen atom or an organic group having 1 to 10 carbon atoms, and the above formula ( The compound of c) has at least one hydrogen atom bonded to a silicon atom in one molecule.)
[4]
The alkenyl group-containing phenol compound as the component (C) is a silicone-modified epoxy resin composition according to any one of [1] to [3] represented by the following formula.

[5]
A semiconductor device sealed with a cured product of the silicone-modified epoxy resin composition according to any one of [1] to [4].

  According to the resin composition of the present invention, by using a specific silicone-modified epoxy resin as an epoxy resin and a specific phenol compound and / or a silicone-modified phenol resin as a curing agent, excellent thermal stability and high temperature and high humidity resistance can be obtained. While maintaining, the elastic modulus can be reduced, cracking and peeling can be suppressed, and it is very useful as a resin composition for semiconductor encapsulation.

It is the schematic for demonstrating the method of determining the glass transition temperature in each composition of Examples 1-4 and Comparative Examples 1 and 2. FIG.

The resin composition of the present invention comprises the following components (A) to (C):
(A) a cyanate ester compound having two or more cyanato groups in one molecule;
(B) a silicone-modified epoxy resin obtained by a hydrosilylation reaction between an alkenyl group-containing epoxy compound and an organopolysiloxane represented by a specific average composition formula,
(C) It is obtained by a hydrosilylation reaction between a phenol compound having two or more phenolic hydroxyl groups in one molecule and / or an alkenyl group-containing phenol compound and an organopolysiloxane represented by the above specific average composition formula. Contains silicone-modified phenolic resin as an essential component.

［式中、Ｒ¹及びＲ²は、それぞれ独立に、水素原子又は炭素数１〜４のアルキル基であり、Ｒ³は、互いに独立に、下記式で表される２価の基のいずれかである。

Ｒ⁴は、互いに独立に、水素原子又はメチル基であり、ｎは０〜１０の整数である。］ (A) Cyanate ester compound The component (A) is a cyanate ester compound having two or more cyanato groups in one molecule. The cyanate ester compound only needs to have two or more cyanato groups in one molecule, and generally known ones can be used. Examples of the cyanate ester compound include those represented by the following general formula (2).

[Wherein, R ¹ and R ² are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ³ is, independently of each other, any one of divalent groups represented by the following formulae: It is.

R ⁴ are each independently a hydrogen atom or a methyl radical, n is an integer of 0. ]

  Examples of the cyanate ester compound of component (A) include bis (4-cyanatophenyl) methane, bis (3-methyl-4-cyanatophenyl) methane, and bis (3-ethyl-4-cyanatophenyl) methane. Bis (3,5-dimethyl-4-cyanatophenyl) methane, 1,1-bis (4-cyanatophenyl) ethane, 2,2-bis (4-cyanatophenyl) propane, 2,2-bis (4-cyanatophenyl) -1,1,1,3,3,3-hexafluoropropane, di (4-cyanatophenyl) thioether, 1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 2-tert-butyl-1,4-dicyanatobenzene, 2,4-dimethyl-1,3-dicyanatobenzene, 2,5-di-tert-butyl-1,4-dicyanatobenzene, Tramethyl-1,4-dicyanatobenzene, 1,3,5-tricyanatobenzene, 2,2′-dicyanatobiphenyl, 4,4′-dicyanatobiphenyl, 3,3 ′, 5,5′-tetramethyl -4,4'-dicyanatobiphenyl, 1,3-dicyanatonaphthalene, 1,4-dicyanatonaphthalene, 1,5-dicyanatonaphthalene, 1,6-dicyanatonaphthalene, 1,8-dicyanatonaphthalene, 2,6-dicyanatonaphthalene, 2,7-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene; 1,1,1-tris (4-cyanatophenyl) ethane, bis (4-cyanatophenyl) Ether; 4,4 ′-(1,3-phenylenediisopropylidene) diphenyl cyanate, bis (4-cyanatophenyl) thioether, bis (4-si Natophenyl) sulfone, tris (4-cyanato-phenyl) phosphine, tris (4-cyanatophenyl) phosphate, phenol novolac cyanate, cresol novolac cyanate, dicyclopentadiene novolac cyanate, phenylaralkyl cyanate ester, biphenylaralkyl type Examples include cyanate esters and naphthalene aralkyl type cyanate esters. These cyanate ester compounds can be used alone or in combination.

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

  In addition, those having a small equivalent amount of cyanate groups, that is, those having a low molecular weight between functional groups, have a small curing shrinkage, and a cured product having a low glass expansion temperature and a low thermal expansion can be obtained. A glass having a large cyanate group equivalent has a slightly lower glass transition temperature, but the triazine cross-linking interval becomes flexible, and low elasticity, high toughness and low water absorption can be expected. The chlorine bonded or remaining in the cyanate ester compound is preferably 50 ppm or less, more preferably 20 ppm or less. If the amount of chlorine exceeds 50 ppm, it will corrode Cu frame, Cu wire and Ag plating oxidized by chlorine or chlorine ions liberated by thermal decomposition when placed at high temperature for a long period of time. It can cause defects. Moreover, there exists a possibility that the insulation of resin may also fall. The amount of the (A) component cyanate ester compound is preferably 40 to 80 parts by mass, more preferably 50 parts per 100 parts by mass of the resin components (A), (B) and (C). -76 parts by mass.

(B) Silicone-modified epoxy resin The component (B) is a copolymer compound obtained by a hydrosilylation reaction between an alkenyl group-containing epoxy compound and a hydrogen organopolysiloxane represented by the following average composition formula (1). By containing this copolymer compound, the resin composition of the present invention can impart low elasticity.

  The alkenyl group-containing epoxy compound is not particularly limited as long as it has an epoxy group and an alkenyl group and is usually used as a resin composition for sealing a semiconductor.

  Among these, for example, cresol novolac type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene modified phenol type epoxy resin, biphenyl aralkyl type epoxy resin, triphenylalkane type epoxy resin, naphthol type epoxy resin, triazine derivative epoxy Examples thereof include resins and epoxycyclohexyl type epoxy resins, and those having alkenyl groups such as vinyl groups and allyl groups are used for these epoxy resins.

Among the epoxy compounds as described above, the use of a compound having the following structural formula is excellent in workability, and thus is mentioned as a suitable compound.

The hydrogen organopolysiloxane represented by the following average composition formula (1) has at least one SiH group, preferably 2 to 10 SiH groups, in one molecule. In the following formula (1), R is a monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms. Specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl Group, tert-butyl group, pentyl group, neopentyl group, hexyl group, octyl group, nonyl group, decyl group and other alkyl groups, phenyl group, tolyl group, xylyl group, naphthyl group and other aryl groups, benzyl group, phenylethyl Group, an aralkyl group such as a phenylpropyl group, and the like, preferably a methyl group, an ethyl group, and a phenyl group. In addition, groups in which some of the hydrogen atoms of these hydrocarbon groups are substituted with halogen atoms such as fluorine, bromine and chlorine can also be used.

The organopolysiloxane represented by the average composition formula (1) may be linear, cyclic, or branched. Examples thereof include those represented by the following formulas (a) to (c).

In the formula (a), R is the same as above, and R ¹ is a hydrogen atom or a group selected from R options. R ² is a group represented by the following formula (a ′).

In the above formula (a ′), R and R ¹ are the same as above, and n ⁴ is an integer of 1 to 10, preferably 0 to 2.

In the above formula (a), n ¹ is an integer of 0 to 200, preferably 0 to 20, n ² is 0 to 2, preferably 0 or 1, and n ³ is 0 to 10, preferably It is an integer of 0 to 6, and n ¹ , n ² and n ³ are not 0 at the same time. Each siloxane unit shown in parentheses may be bonded at random or may form a block unit. However, the compound of the above formula (a) has at least one, preferably 2 to 10 hydrogen atoms (SiH groups) bonded to silicon atoms in one molecule. Therefore, in the above formula (a), when n ² is 0, at least one of R ¹ in formulas (a) and (a ′) is a hydrogen atom.

In the above formula (b), R is the same as above, n ⁵ is an integer of 0 to 10, preferably 0 to 6, n ⁶ is an integer of 1 to 4, preferably 2 to 4, and 3 ≦ n ⁵ + n ⁶ ≦ 12, and the bonding order of the siloxane units shown in parentheses is not limited.

In the above formula (c), R and R ¹ are the same as described above, r is an integer of 0 to 3, R ⁷ is a hydrogen atom or an organic group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, particularly It is a monovalent hydrocarbon group, and the compound of the above formula (c) has at least one hydrogen atom bonded to a silicon atom in one molecule. Therefore, when r in the above formula (c) is 0, at least one of R ⁷ is a hydrogen atom.

Specific examples of R ⁷ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, octyl group, nonyl group, decyl group and the like. Alkyl groups such as alkyl groups, methoxy groups, ethoxy groups, propyl groups, isopropyl groups, butoxy groups, isobutoxy groups, tert-butoxy groups, aryl groups such as phenyl groups, tolyl groups, xylyl groups, naphthyl groups, benzyl groups, phenyl groups Examples thereof include an aralkyl group such as an ethyl group and a phenylpropyl group, and a hydrogen atom. Among them, a hydrogen atom, a methyl group and a phenyl group are preferable.

（上記式中、ｎは１〜１００の整数である。）

As the hydrogen organopolysiloxane, both terminal hydrogen methyl polysiloxane, both terminal hydrogen methyl phenyl polysiloxane and the like are suitable. For example, the following compounds are preferable.

(In the above formula, n is an integer of 1 to 100.)

  The hydrosilylation reaction for obtaining the silicone-modified epoxy resin as the component (B) may be performed according to a conventionally known method. For example, it can be obtained by heating reaction in the presence of a platinum-based catalyst such as chloroplatinic acid. The hydrosilyl reaction is particularly preferably carried out by heating to 60 to 120 ° C. in an inert solvent such as benzene and toluene. The mixing ratio of the epoxy compound and the polysiloxane is such that the number of SiH groups possessed by the polysiloxane with respect to one alkenyl group possessed by the epoxy compound is 1.0 or more, preferably 1.5 to 5.0.

  The epoxy resin reacts with a cyanate ester compound to form an oxazole ring, but is less reactive than the triazine ring formation of a cyanate group. In addition, when there are many ratios of an epoxy group, hardening time becomes long and is disadvantageous for transfer molding. Although there is an example using a tertiary amine such as triethylamine, there is a possibility that the storage stability is deteriorated.

  The compounding quantity of the said epoxy resin is a compounding quantity from which an epoxy group equivalent will be 0.04-0.30 mol with respect to 1 mol of cyanate groups of a cyanate ester compound. When the blending amount of the epoxy resin is less than the above lower limit value, the moisture absorption amount of the cured product of the resin composition of the present invention increases, and peeling occurs between the lead frame and the cured product under high temperature and high humidity. Moreover, when there are more amounts of an epoxy resin than the said upper limit, hardening of the resin composition of this invention will become inadequate, and it may cause the fall of the glass transition temperature of hardened | cured material, and the fall of a high temperature, high humidity storage characteristic.

(C) Phenol compound / silicone-modified phenol resin When a phenol compound is used as the component (C), the phenol compound is a phenol compound having two or more phenolic hydroxyl groups in one molecule, and 2 in one molecule. As long as it has one or more phenolic hydroxyl groups, generally known ones can be used. This phenol compound can be represented by the following general formula (3), for example.

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

R < ⁴ > is a hydrogen atom or a methyl group mutually independently, and m is an integer of 0-10.

  Examples of the phenol compound represented by the above formula (3) include bisphenol F type resin, bisphenol A type resin, phenol novolac resin, phenol aralkyl type resin, biphenyl aralkyl type resin, naphthalene aralkyl type resin, and the like. These may be used alone or in combination of two or more.

  When a silicone-modified phenol resin is used as the component (C), the silicone-modified phenol resin is obtained by a hydrosilylation reaction between the alkenyl group-containing phenol compound and the hydrogen organopolysiloxane represented by the above average composition formula (1). It is a copolymer compound obtained. By containing this copolymer, the resin composition of the present invention can impart low elasticity. The alkenyl group-containing phenol compound is not particularly limited as long as it has a phenolic hydroxyl group and an alkenyl group and is usually used as a resin composition for sealing a semiconductor. Examples of the phenol resin-based curing agent include phenol novolak resin, cresol novolak resin, phenol aralkyl type resin, biphenyl aralkyl type resin, bis A type phenol resin, bis F type phenol resin, dicyclopentadiene type phenol resin, and silicone modified type. Examples thereof include phenol resins and triphenolalkane resins, and those having alkenyl groups such as vinyl groups and allyl groups are used.

Among the phenol compounds as described above, use of a compound having the following structural formula is excellent in workability and tracking resistance, so that it is mentioned as a suitable compound.

  Moreover, as the hydrogen organopolysiloxane to be reacted with the alkenyl group-containing phenol compound, those having the same structure as that exemplified for the polysiloxane used in the component (B) are preferably used.

  The hydrosilylation reaction for obtaining the silicone-modified phenol resin as the component (C) may be performed according to a conventionally known method. For example, it can be obtained by heating reaction in the presence of a platinum-based catalyst such as chloroplatinic acid. The hydrosilylation reaction is particularly preferably performed by heating to 60 to 120 ° C. in an inert solvent such as benzene and toluene. The mixing ratio of the phenol compound and the polysiloxane is such that the number of SiH groups contained in the polysiloxane with respect to one alkenyl group contained in the phenol compound is 1.0 or more, preferably 1.5 to 5.0.

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

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

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

  The compounding quantity of a phenol compound is an quantity from which a phenolic hydroxyl group will be 0.08-0.30 mol with respect to 1 mol of cyanato groups. If the blending amount of the phenol compound is less than the above lower limit, the reaction of the cyanate group becomes insufficient, and an unreacted cyanato group remains. The remaining cyanato group undergoes hydrolysis in a high humidity atmosphere. For this reason, when it is placed under high temperature and high humidity, it may cause a decrease in mechanical strength and a decrease in adhesion to the substrate. Moreover, when there are more compounding quantities of a phenol compound than the said upper limit, hardening reaction will advance from low temperature. For this reason, the fluidity | liquidity of a resin composition may be impaired and a moldability may worsen.

  In addition, the content of halogen elements, alkali metals, etc. in the phenol compound is preferably 10 ppm, particularly 5 ppm or less when extracted at 120 ° C. under 2 atm.

(D) Other components In addition to the above components (A) to (C), the resin composition of the present invention includes an inorganic filler, a curing accelerator, a black pigment, a release agent, a flame retardant, Various additives such as an ion trapping agent, an antioxidant, and an adhesion imparting agent can be blended.

  Examples of the inorganic filler include silicas such as fused silica, crystalline silica, and cristobalite, alumina, silicon nitride, aluminum nitride, boron nitride, titanium oxide, glass fiber, magnesium oxide, and zinc oxide. The average particle size and shape of these inorganic fillers are not particularly limited, but are usually 1 to 50 μm, preferably 4 to 20 μm. The above average particle diameter is a value obtained by laser diffraction particle size distribution measurement such as Cirrus laser.

  The inorganic filler preferably has 10 ppm or less of chloro ions and 10 ppm or less of sodium ions as impurities extracted under the extraction conditions of 10 g of sample / 50 g of water in 20 hours at 125 ° C., 2.1 atm. More preferably, chloro ions are 5 ppm or less and sodium ions are 5 ppm or less. If it exists in the said range, there is no possibility that the moisture resistance characteristic of the semiconductor device sealed with the composition may fall, and it is preferable.

  The amount of the inorganic filler is preferably 150 to 1,500 parts by mass, more preferably 250 to 1, with respect to 100 parts by mass in total of the components (A), (B) and (C). 200 parts by mass. The inorganic filler is preferably 60 to 94% by mass, more preferably 70 to 92% by mass, and still more preferably 75 to 90% by mass of the entire resin composition.

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

  The curing accelerator is not particularly limited as long as it accelerates the curing reaction. Examples of the curing accelerator include triphenylphosphine, tributylphosphine, tri (p-methylphenyl) phosphine, tri (p-nonylphenyl) phosphine, triphenylphosphine / triphenylborane, tetraphenylphosphine / tetraphenylborate, tetra Phosphorus compounds such as phenylphosphine tetra (p-methylphenyl) borate or an adduct of triphenylphosphine and p-benzoquinone; triethylamine, benzyldimethylamine, α-methylbenzyldimethylamine, 1,8-diazabicyclo [5.4 0.0] tertiary amine compounds such as undecene-7; and imidazole compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and the like. These curing accelerators can be used alone or in combination of two or more. Further, these curing accelerators may be impregnated into porous silica or coated with a thermoplastic resin such as polymethyl methacrylate.

  The blending amount of the curing accelerator is not particularly limited as long as it is an effective amount, but is 0.1 to 5 parts by mass with respect to 100 parts by mass of the total amount of the component (A), the component (B) and the component (C). It is preferable that it is 0.5-2 mass parts.

  Examples of the black pigment include, but are not limited to, carbon black, furnace black, acetylene black and the like used in conventional sealing resin compositions, but carbon black is preferable. By making the resin composition of the present invention black, the semiconductor device manufactured using this as a semiconductor sealing material has the same good appearance and laser marking as a semiconductor device sealed with a conventional epoxy resin or the like Sex can be obtained. The black pigment content is preferably 1 part by mass or more, particularly preferably 3 parts by mass or more, based on 100 parts by mass of the total mass of the resin components [components (A) and (B)] in the resin composition. . If the amount is 1 part by mass or more, the glossiness is not excessively high, it is possible to suppress the appearance defect in which the semiconductor element traces are transferred to the surface of the semiconductor device, and the black color becomes satisfactory and the laser marking property is improved.

  The release agent is not particularly limited, and known ones can be used. Examples of the release agent include natural wax release agents such as carnauba wax, rice wax, and candelilla wax, synthetic polymer release agents such as polyethylene, polyethylene oxide, and polypropylene, lauric acid, stearic acid, and palmitic acid. And fatty acid derivative release agents such as behenic acid, serotic acid, montanic acid, stearic acid ester, stearic acid amide, and ethylene bis-stearic acid amide, and a copolymer of ethylene and vinyl acetate. These release agents can be used alone or in combination of two or more. It is preferable that the compounding quantity of these mold release agents is 0.5-5 mass parts with respect to 100 mass parts of total amounts of said (A) component, (B) component, and (C) component, and 1-3 masses. More preferably, it is a part.

  The flame retardant is not particularly limited, and known ones can be used. Examples of the flame retardant include phosphazene compounds, silicone compounds, zinc molybdate-supported talc, zinc molybdate-supported zinc oxide, aluminum hydroxide, magnesium hydroxide, molybdenum oxide, and antimony trioxide. The blending amount of the flame retardant is preferably 2 to 20 parts by mass and preferably 3 to 10 parts by mass with respect to 100 parts by mass of the total amount of the components (A), (B) and (C). More preferred.

  The ion trap agent is not particularly limited, and a known one can be used. Examples of the ion trapping agent include hydrotalcites, bismuth hydroxide compounds, rare earth oxides, and the like. It is preferable that the compounding quantity of an ion trap agent is 1-10 mass parts with respect to 100 mass parts of total amounts of said (A) component, (B) component, and (C) component, and is 1.5-5 mass parts. More preferably.

  The adhesiveness imparting agent is not particularly limited, and a known one can be used. As the adhesiveness imparting agent, for example, the coupling agent used for the surface treatment of the inorganic filler can be used. These adhesiveness imparting agents can be used alone or in combination of two or more. The compounding amount of the adhesion-imparting agent is preferably 0.2 to 5 parts by mass, and 0.5 to 3 parts by mass with respect to 100 parts by mass of the total amount of the components (A), (B) and (C). It is more preferable that

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

  The resin composition of the present invention is particularly effective as a sealing resin for semiconductor devices such as transistor type, module type, DIP type, SO type, flat pack type, and ball grid array type. The method for sealing the semiconductor device with the composition of the present invention is not particularly limited, and a conventional molding method such as transfer molding, injection molding, casting method or the like may be used. The composition of the present invention is preferably molded at 160 to 190 ° C. for 45 to 300 seconds, and post-curing is performed at 170 to 250 ° C. for 2 to 16 hours.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.

[Examples 1 to 3]
The components (A) and (B) synthesized in the following Synthesis Examples 1 to 5 and the following components were blended according to the composition shown in Table 1, and then melt-mixed uniformly at 100 ° C. for 3 minutes to be a thermosetting resin composition. Was prepared.

（ｎ＝０〜１０の混合物） (A) Cyanate ester compound Cyanate ester compound represented by the following formula (4) (Primaset PT-60, Lonza Japan Co., Ltd., cyanate group equivalent 119)

(Mixture of n = 0 to 10)

(B) Silicone-modified epoxy resin (E-01, E-02, E-03)
[Synthesis Example 1]
A 1 L separable flask was charged with 0.16 g of 0.5 mass% chloroplatinic acid toluene solution, 80 g of toluene, 323 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Kasei Kogyo Co., Ltd., MA-DGIC). The temperature was raised to 80 ° C. Thereafter, 81 g of 1,1,3,3-tetramethyldisiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise over 30 minutes and reacted at 90 ° C. for 4 hours. The obtained toluene solution was distilled under reduced pressure to obtain a silicone-modified epoxy resin E-01 having a structure represented by the following formula (5). The epoxy equivalent of E-01 was 169 g / eq.

[Synthesis Example 2]
A 1 L separable flask was charged with 0.16 g of 0.5 mass% chloroplatinic acid toluene solution, 80 g of toluene, and 296 g of o-allylphenylglycidyl ether (OAP-EP, manufactured by Yokkaichi Gosei Co., Ltd.). Raised to ° C. Thereafter, 110 g of 1,1,3,3-tetramethyldisiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise over 30 minutes and reacted at 90 ° C. for 4 hours. The obtained toluene solution was distilled under reduced pressure to obtain a silicone-modified epoxy resin E-02 having the structure of the following formula (6). The epoxy equivalent of E-02 was 257 g / eq.

[Synthesis Example 3]
A 1 L separable flask was charged with 0.16 g of a 0.5 mass% chloroplatinic acid toluene solution, 80 g of toluene, and 272 g of 1,2-epoxy-4-vinylcyclohexane (manufactured by Daicel). Was raised. Thereafter, 141 g of 1,1,3,3-tetramethyldisiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise over 30 minutes and reacted at 60 ° C. for 1 hour. The obtained toluene solution was distilled under reduced pressure to obtain a silicone-modified epoxy resin E-03 having the structure of the following formula (7). The epoxy equivalent of E-03 was 257 g / eq.

(C) Silicone-modified phenolic resin (P-01, P-02)
[Synthesis Example 4]
A 1 L separable flask was charged with 0.16 g of 0.5 mass% chloroplatinic acid toluene solution, 80 g of toluene, and 263 g of 2-allylphenol (manufactured by Yokkaichi Synthesis), and after stirring, the internal temperature was raised to 80 ° C. Thereafter, 124 g of 2,4,6,8-tetramethylcyclotetrasiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., KF-9902) was added dropwise over 30 minutes and reacted at 90 ° C. for 3 hours. The obtained toluene solution was distilled under reduced pressure to obtain a silicone-modified phenolic resin P-01 having the structure of the following formula (8). The hydroxyl equivalent of P-01 was 194 g / eq.

[Synthesis Example 5]
A 1 L separable flask was charged with 0.16 g of 0.5 mass% chloroplatinic acid toluene solution, 80 g of toluene, and 266 g of 2-allylphenol (manufactured by Yokkaichi Synthesis), and after stirring, the internal temperature was raised to 80 ° C. Thereafter, 140 g of 1,1,3,3-tetramethyldisiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., HM-H) was dropped over 30 minutes and reacted at 90 ° C. for 3 hours. The obtained toluene solution was distilled under reduced pressure to obtain a silicone-modified phenolic resin P-02 having the structure of the following formula (9). The hydroxyl equivalent of P-02 was 201 g / eq.

（ｎ＝０〜１０の混合物） (C) Phenolic resin Phenol compound represented by the following formula (10) (MEH-7851SS, manufactured by Meiwa Kasei, phenolic hydroxyl group equivalent 203)

(Mixture of n = 0 to 10)

[Comparative Examples 1 and 2]
In addition to the components used in Examples 1 to 3, each component was blended according to the composition described in Table 1, and then melted and mixed uniformly at 100 ° C. for 3 minutes to prepare a thermosetting resin composition.

（ｎ＝０〜１０の混合物） (B) Epoxy resin: epoxy resin compound represented by the following formula (10) (NC-3000, manufactured by Nippon Kayaku, epoxy equivalent 272)

(Mixture of n = 0 to 10)

Each composition obtained was evaluated according to the method shown below.
"Evaluation method"
-Preparation of hardened | cured material sample The test piece of Examples 1-4 and Comparative Examples 1 and 2 was produced as follows. The thermosetting epoxy resin composition was heat-cured at 150 ° C. for 1 hour and then at 180 ° C. for 4 hours to prepare a test piece for use in the following test.

-Measurement of glass transition temperature (Tg) After processing the hardened | cured material produced in Examples 1-4 and Comparative Examples 1 and 2 to a test piece of 5x5x15mm, respectively, those test pieces were made into a thermal dilatometer. It set to TMA8310 (made by Rigaku Corporation). And the dimensional change of the test piece was measured between 25 degreeC and 300 degreeC by the temperature increase program with the temperature increase rate of 5 degrees C / min. The relationship between this dimensional change and temperature was plotted on a graph. From the graph of the dimensional change and temperature thus obtained, the glass transition temperatures in Examples 1 to 4 and Comparative Examples 1 and 2 were determined by the glass transition temperature determination method described below.

[Method for determining glass transition temperature (Tg)]
In FIG. 1, two arbitrary temperatures at which the tangent of the dimensional change-temperature curve is obtained below the temperature of the inflection point are T1 and T2, and two arbitrary temperatures at which a similar tangent is obtained above the temperature of the inflection point. Were designated T1 ′ and T2 ′. The dimensional changes at T1 and T2 are D1 and D2, respectively, the straight line connecting the points (T1, D1) and (T2, D2), and the dimensional changes at T1 ′ and T2 ′ are D1 ′ and D2 ′, respectively. The intersection of the line connecting (T1 ′, D1 ′) and the point (T2 ′, D2 ′) was defined as the glass transition temperature (Tg).

-Bending strength and flexural modulus After obtaining a test piece of 100 x 10 x 4 mm according to JIS K 6911: 2006, the test piece was tested at room temperature (25 ° C) at an autograph tester (manufactured by Shimadzu Corporation). Were bent at 3 points, and the bending strength and the flexural modulus were measured.

  From the results shown in Table 1, it can be seen that Examples 1 to 4 are resin compositions that can reduce cracking and peeling while maintaining excellent thermal stability.

Claims (5)

(A) a cyanate ester compound having two or more cyanato groups in one molecule;
(B) a silicone-modified epoxy resin obtained by a hydrosilylation reaction between an alkenyl group-containing epoxy compound and an organopolysiloxane represented by the following average composition formula (1):

(In the above formula (1), R is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms, a is a positive number of 0.01 ≦ a ≦ 1, and b is 1 ≦ b ≦. 3 is a positive number, and 1.01 ≦ a + b <4.)
(C) Obtained by a hydrosilylation reaction between a phenol compound having two or more phenolic hydroxyl groups in one molecule and / or an alkenyl group-containing phenol compound and the organopolysiloxane represented by the above average composition formula (1). The molar ratio of the epoxy group in the epoxy resin of the component (B) to the cyanate group in the cyanate ester compound of the component (A) is 0.04 to 0.30, and A silicone-modified epoxy resin composition, wherein the molar ratio of the phenolic hydroxyl group in the phenol compound of the component (C) to the cyanate group in the cyanate ester compound of the component (A) is 0.08 to 0.30. object. The silicone-modified epoxy resin composition according to claim 1, wherein the component (A) is a compound represented by the following general formula (2).

[In the above formula, R ¹ and R ² are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ³ is any one of divalent groups represented by the following formula, independently of each other: It is.

R ⁴ are each independently a hydrogen atom or a methyl radical, n is an integer of 0. ] The silicone-modified epoxy resin composition according to claim 1 or 2, wherein the organopolysiloxane in the component (B) and the component (C) is at least one selected from compounds represented by the following formulas (a) to (c). object.

(In the formula (a), R is the same as above, R ¹ is a hydrogen atom or a group selected from the options of R, n ¹ is an integer from 0 to 200, and n ² is from 0 to 2. N ³ is an integer of 0 to 10, and n ¹ , n ² , and n ³ are not simultaneously 0. R ² is a group represented by the following formula (a ′),

In the above formula (a ′), R and R ¹ are the same as above, n ⁴ is an integer of 1 to 10, and each siloxane unit shown in parentheses forms a block unit even if they are randomly bonded You may do it. However, the compound of the above formula (a) has a hydrogen atom bonded to at least one silicon atom in one molecule. )

(In the above formula (b), R is the same as above, n ⁵ is an integer of 0 to 10, n ⁶ is an integer of 1 to 4, provided that 3 ≦ n ⁵ + n ⁶ ≦ 12 is satisfied. Number, and the bonding order of each siloxane unit shown in parentheses is not limited.)

(In the above formula (c), R and R ¹ are the same as above, r is an integer of 0 to 3, R ⁷ is a hydrogen atom or an organic group having 1 to 10 carbon atoms, and the above formula ( The compound of c) has at least one hydrogen atom bonded to a silicon atom in one molecule.) The alkenyl group-containing phenol compound as the component (C) is the silicone-modified epoxy resin composition according to any one of claims 1 to 3, which is represented by the following formula.

  The semiconductor device sealed with the hardened | cured material of the silicone modified epoxy resin composition of any one of Claims 1-4.

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