JP2018193504A - Silicone-modified epoxy resin composition and semiconductor device - Google Patents

Abstract

A silicone-modified epoxy resin composition having excellent tracking resistance and a semiconductor device sealed with the resin composition are provided. A silicone-modified epoxy resin obtained by a hydrosilylation reaction of the following components (A) to (C), (A) an alkenyl group-containing epoxy compound and an organopolysiloxane represented by the following average composition formula (1): In said formula (1), R is a C1-C10 monovalent hydrocarbon group mutually independent, a is a positive number of 0.01 <= a <= 1, b is 1 <= b <= 3. It is a positive number and 1.01 ≦ a + b <4. (B) Silicone modified phenolic resin (C) black pigment (D) inorganic filler (provided by hydrosilylation reaction of alkenyl group-containing phenol compound and organopolysiloxane represented by the above average composition formula (1) A silicone-modified epoxy resin composition comprising (C) excluding black pigment) as an essential component. [Selection figure] None

Description

  The present invention relates to a silicone-modified epoxy resin composition excellent in tracking resistance and a semiconductor device.

  Conventionally, resin-encapsulated semiconductor devices such as diodes, transistors, ICs, and LSIs have been mainly used. Among them, epoxy resin is more moldable, adhesive, electrical, mechanical, and moisture resistant than other thermosetting resins. Due to its excellent properties and the like, an epoxy resin composition has been widely used as a sealing resin for semiconductor devices. However, in recent years, in the electronic equipment market, semiconductor devices have become smaller, lighter, higher performance, and higher integration of semiconductor elements. The resin composition is required to be more reliable than ever.

  As a result of downsizing and thinning, the circuit pitch width and the distance between lead terminals are also reduced, and it is difficult to secure a spatial distance and a creepage distance for electrically insulating them. Therefore, the performance improvement of the sealing material which is an insulator is requested | required, and especially the improvement of tracking resistance is requested | required.

  As a method for improving the tracking resistance in a sealing material such as an epoxy resin composition, the amount of the inorganic filler is increased (Patent Document 1) or a small amount of silicone rubber powder is added in addition to the inorganic filler. (Patent Document 2), blending an alicyclic epoxy resin system having a cyclohexane polyether skeleton and a dicyclopentadiene type phenol resin, etc., which does not contain a benzene skeleton that easily forms an electric conduction path (Patent Document 3), In addition, it is known to contain an aminotriazine-modified novolak resin or melamine resin as a curing agent (Patent Document 4). On the other hand, since the thinning of semiconductor elements and the thinning of wires are advancing, fluidity during molding is an important characteristic, but to increase the amount of inorganic filler to increase tracking resistance Can also be a factor that impairs the fluidity during molding. In addition, since aromatics greatly contribute to the heat resistance of the resin composition, non-aromatic epoxy resins cause a decrease in heat resistance and greatly affect reliability.

JP 2008-143950 A JP2013-203865A JP 2005-213299 A JP 2010-031126 A

  An object of the present invention is to provide a silicone-modified epoxy resin composition having excellent tracking resistance and a semiconductor device sealed with the resin composition.

  As a result of intensive studies to achieve the above object, the present inventors have found that a silicone-modified epoxy resin composition containing a specific silicone-modified epoxy resin, a specific silicone-modified phenol resin, a black pigment, and an inorganic filler is the above-mentioned problem. And the present invention has been completed.

〔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。〕
（Ｂ）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
（Ｃ）黒色顔料
（Ｄ）無機充填材（但し、（Ｃ）黒色顔料は除く）
を必須成分として含む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）成分及び（Ｂ）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〕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、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、

式（ａ’）において、Ｒ及びＲ¹は上記と同じであり、ｎ⁴は１〜１０の整数である。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、且つ、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、または炭素数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。〕
〔３〕
上記（Ｂ）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〕又は〔２〕記載のシリコーン変性エポキシ樹脂組成物。

〔４〕
上記（Ｄ）無機充填材の配合量は、上記（Ａ）成分及び（Ｂ）成分の合計１００質量部に対して１５０〜１，５００質量部であり、且つ、樹脂組成物全体の６０〜９４質量％である〔１〕〜〔３〕のいずれか１項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１項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]
The following components (A) to (D),
(A) 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. Positive number, and 1.01 ≦ a + b <4. ]
(B) Silicone-modified phenolic resin obtained by hydrosilylation reaction between an alkenyl group-containing phenol compound and the organopolysiloxane represented by the above average composition formula (1) (C) Black pigment (D) Inorganic filler (However, ( C) Excluding black pigment)
A silicone-modified epoxy resin composition comprising an essential component.
[2]
The silicone-modified epoxy resin composition according to [1], wherein the organopolysiloxane in the component (A) and the component (B) is at least one selected from the compounds represented by the following formulas (a) to (c).

[In the above 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 from 0 to 10, and n ¹ , n ² , and n ³ are not 0 at the same time. R ² is a group represented by the following formula (a ′),

In the formula (a ′), R and R ¹ are the same as above, and n ⁴ is an integer of 1 to 10. 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 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, and 3 ≦ n ⁵ + n ⁶ ≦ 12 is satisfied. It is a 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, The compound c) has a hydrogen atom bonded to at least one silicon atom in one molecule. ]
[3]
The alkenyl group-containing phenol compound as the component (B) is a silicone-modified epoxy resin composition according to [1] or [2] represented by the following formula.

[4]
The blending amount of the inorganic filler (D) is 150 to 1,500 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B), and 60 to 94 of the entire resin composition. The silicone-modified epoxy resin composition according to any one of [1] to [3], which is mass%.
[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 silicone-modified phenol resin as a curing agent, the formation of a carbonized conductive path that causes a short circuit is suppressed, and tracking resistance is reduced. Can increase the sex.

The resin composition of the present invention is
(A) Silicone-modified epoxy resin obtained by hydrosilylation reaction between an alkenyl group-containing epoxy compound and an organopolysiloxane represented by a specific average composition formula (B) An alkenyl group-containing phenol compound and the above specific average composition formula Silicone-modified phenolic resin obtained by hydrosilylation reaction with the represented organopolysiloxane (C) black pigment, and (D) inorganic filler (however, (C) black pigment is excluded)
As an essential component.

(A) Silicone-modified epoxy resin The component (A) 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 ensure high heat resistance, hygroscopicity, tracking resistance and fluidity.

  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, as the epoxy resin, 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 resin And epoxy cyclohexyl type epoxy resins, and those having an alkenyl group such as vinyl group or allyl group are used as 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 tracking resistance, and thus is exemplified 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 0 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 a hydrogen atom bonded to at least one 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 (A) 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 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.

(B) Silicone-modified phenolic resin The silicone-modified phenolic resin of component (B) reacts with an epoxy group as a curing agent. Component (B) is a copolymer compound obtained by a hydrosilylation reaction between an alkenyl group-containing phenol compound and the hydrogen organopolysiloxane represented by the above average composition formula (1). By containing this copolymer compound, the resin composition of the present invention can ensure high heat resistance, hygroscopicity, tracking resistance and fluidity.

  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.

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

  The hydrosilylation reaction for obtaining the silicone-modified phenol 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 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.

  As a blending ratio of the silicone-modified epoxy resin (A) as the main agent and the silicone-modified phenol resin (B) as the curing agent, the ratio of epoxy group / phenolic hydroxyl group is in the range of 0.6 to 1.6. Is preferable, and the range of 0.8 to 1.3 is more preferable.

(C) Black pigment The black pigment which is the component (C) is a pigment for making the resin composition of the present invention black. As a pigment to be used, for example, it is used in a conventional sealing resin composition. Carbon black, furnace black, acetylene black, and the like, which are not limited thereto, but carbon black is preferred. 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 blending amount of the pigment is preferably 1 part by mass or more, particularly preferably 3 parts by mass or more with respect to 100 parts by mass of the total mass of the resin components [(A) and (B) components] 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 upper limit of the pigment is preferably 10 parts by mass or less.

(D) Inorganic filler (D) As an inorganic filler which is a component, for example, silica such as fused silica, crystalline silica, cristobalite, alumina, silicon nitride, aluminum nitride, boron nitride, titanium oxide, glass fiber , Magnesium oxide, zinc oxide and the like. However, the black pigment cited as the component (C) is excluded.

  The average particle size and shape of the inorganic filler 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 blending amount of the inorganic filler is preferably 150 to 1,500 parts by mass, more preferably 250 to 1,200 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B). . 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.

(E) Other components In addition to the above components (A) to (D), the resin composition of the present invention includes a curing accelerator, a mold release agent, a flame retardant, an ion trap agent, and an antioxidant as necessary. Various additives such as an adhesion-imparting agent can be blended.

  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. Especially, what coated the strongly basic imidazole compound with the thermoplastic resin is preferable.

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

  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) and (B) component, More preferably, it is 1-3 mass parts. is there.

  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. It is preferable that the compounding quantity of a flame retardant is 2-20 mass parts with respect to 100 mass parts of total amounts of said (A) and (B) component, More preferably, it is 3-10 mass parts.

  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) and (B) component, More preferably, it is 1.5-5 mass parts.

  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, more preferably 0.5 to 100 parts by mass of the total amount of the components (A), (B) and (C). ~ 3 parts by mass.

  The method for producing the resin composition of the present invention is not particularly limited. For example, the above components (A) to (E) may be stirred or dissolved, mixed, or dispersed at the same time or separately, if necessary 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 material 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 resin 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. As conditions for molding the resin composition of the present invention, it is preferable to perform post-cure at 170 to 250 ° C. for 2 to 16 hours at 160 to 190 ° C. for 45 to 300 seconds.

  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 are blended according to the composition shown in Table 1, and are uniformly melt-mixed, cooled and pulverized with two heat rolls. I got a thing.

(A) 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, and 323 g of monoallyl diglycidyl isocyanuric acid (MA-DGIC, manufactured by Shikoku Kasei Kogyo Co., Ltd.). 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 (1). 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-allylphenyl glycidyl ether (Okachi Chemical Co., Ltd., OAP-EP). The temperature was raised to 80 ° 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 (2). The epoxy equivalent of E-02 was 257 g / eq.

[Synthesis Example 3]
A 2 L separable flask was charged with 1.68 g of 0.5 mass% chloroplatinic acid toluene solution, 200 g of toluene, and 1,2-epoxy-4-vinylcyclohexane (2.4 mol, 596.06 g), and after stirring, The temperature was raised to 80 ° C. Thereafter, 2,4,6,8-tetramethylcyclotetrasiloxane (1 mol, 240.51 g) was added dropwise over 1 hour and reacted at 100 ° C. for 2 hours. 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 (3). The epoxy equivalent of E-03 was 200 g / eq.

(B) 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 Chemical Co., Ltd.). . 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 (4). 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 Chemical Co., Ltd.). 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 (5). The hydroxyl equivalent of P-02 was 201 g / eq.

(C) Black pigment, carbon black (Mitsubishi Chemical Corporation 3230MJ)

(D) Inorganic filler / fused silica powder (average particle size 16 μm, manufactured by Tatsumori)

(E) Other component curing accelerator, triphenylphosphine (TPP (registered trademark), manufactured by Hokuko Chemical Co., Ltd.)
・ 2-Ethyl-4-methylimidazole (Curazole 2E4MZ, manufactured by Shikoku Chemicals Co., Ltd.)
Other additives, Carnauba wax (TOWAX-131, manufactured by Toa Kasei Co., Ltd.)
Silane coupling agent 3-mercaptopropyltrimethoxysilane (KBM-803, manufactured by Shin-Etsu Chemical Co., Ltd.) and 3-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) are mixed at a ratio of 1: 5. What was done was used.

[Comparative Examples 1-3]
In addition to the components used in Examples 1 to 3, the following epoxy resin and phenol resin were blended according to the composition described in Table 1, and melted and mixed uniformly with two heat rolls, cooled and pulverized to obtain a composition. Obtained.

・ Epoxy resin: Multifunctional epoxy resin (EPPN-501H, manufactured by Nippon Kayaku)
-Phenol resin: Phenol novolac resin (TD-2131, manufactured by DIC)

Each composition obtained was evaluated according to the method shown below.
"Evaluation method"
-Tracking resistance: According to Japanese Industrial Standards JIS C 2134: 2007, a 50 mmφ × 3 mmt test piece was molded, and then post-cured at 180 ° C. for 4 hours. Then, what was stored for 48 hours in an atmosphere of 25 ° C./50% Rh was used as a test piece.

<Test Method> Two platinum electrodes are brought into contact with the surface of the test piece, and a 0.1% ammonium chloride aqueous solution is dropped at intervals of one drop every 30 seconds while a voltage is applied between the electrodes. Measurement is performed at N = 5, and in each case, evaluation is performed with the value of the maximum voltage (CTI: comparative tracking index) that can endure without generating a tracking failure and a continuous flame in a measurement period of 50 drops. This time, the tracking resistance of each resin composition was evaluated by measuring the number of drops of 0.1% ammonium chloride aqueous solution when the applied voltage was fixed at 600V.

  From the results of Table 1, it can be seen that Examples 1 to 3 are resin compositions having excellent tracking resistance.

Claims (5)

The following components (A) to (D),
(A) 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. Positive number, and 1.01 ≦ a + b <4. ]
(B) Silicone-modified phenolic resin obtained by hydrosilylation reaction between an alkenyl group-containing phenol compound and the organopolysiloxane represented by the above average composition formula (1) (C) Black pigment (D) Inorganic filler (However, ( C) Excluding black pigment)
A silicone-modified epoxy resin composition comprising an essential component. The silicone-modified epoxy resin composition according to claim 1, wherein the organopolysiloxane in the component (A) and the component (B) is at least one selected from compounds represented by the following formulas (a) to (c).

[In the above 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 from 0 to 10, and n ¹ , n ² , and n ³ are not 0 at the same time. R ² is a group represented by the following formula (a ′),

In the formula (a ′), R and R ¹ are the same as above, and n ⁴ is an integer of 1 to 10. 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 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, and 3 ≦ n ⁵ + n ⁶ ≦ 12 is satisfied. It is a 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, The compound c) has a hydrogen atom bonded to at least one silicon atom in one molecule. ] The alkenyl group-containing phenol compound as the component (B) is a silicone-modified epoxy resin composition according to claim 1 or 2 represented by the following formula.

  The blending amount of the inorganic filler (D) is 150 to 1,500 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B), and 60 to 94 of the entire resin composition. It is a mass%, The silicone modified epoxy resin composition of any one of Claims 1-3.   The semiconductor device sealed with the hardened | cured material of the silicone modified epoxy resin composition of any one of Claims 1-4.