JP5205907B2 - Epoxy resin composition for sealing and electronic component device - Google Patents

Description

  The present invention relates to an epoxy resin composition for sealing, and an electronic component device including an element sealed with the epoxy resin composition for sealing.

  Conventionally, in the field of element sealing of electronic component devices such as transistors and ICs, resin sealing has been the mainstream in terms of productivity and cost, and epoxy resin molding materials have been widely used. This is because epoxy resins are balanced in various properties such as electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesiveness with inserts.

  In recent years, along with the high density mounting of electronic component devices on printed wiring boards, surface mount type packages have become the mainstream in place of conventional pin insertion type packages. Surface-mount ICs, LSIs, etc. are thin and small packages in order to increase the mounting density and reduce the mounting height, and the volume occupied by the device package increases, resulting in a very thick package. It has become thinner.

  In addition, in order to cope with further reduction in size and weight, CSP (Quad Flat Package), SOP (Small Outline Package), and other forms of packages are easy to cope with higher pin count and CSP capable of higher density mounting. It is shifting to an area mounting package such as BGA (Ball Grid Array) including (Chip Size Package). In recent years, these packages have been developed with new structures such as a face-down type, a stacked (stacked) type, a flip chip type, and a wafer level type in order to realize high speed and multiple functions. Many of them have a single-side sealed package form in which only one surface on the element mounting surface side is sealed with a sealing material such as an epoxy resin molding material, and then solder balls are formed on the back surface and bonded to the circuit board. Have. In addition, as substrates used for single-sided sealed packages, glass substrate epoxy resin substrates, hard circuit substrates such as glass substrate bismaleimide / triazine resin substrates, and flexible circuit substrates such as polyimide resin film substrates are mainly used. Is done. Furthermore, instead of the conventional one-chip / one-cavity sealing method, the resin-sealing process for producing a single-side-sealed package has been developed as a batch mold type sealing method that seals multiple chips in one cavity. As a result, production efficiency is improved and costs are reduced.

  The single-side sealed package has a single-side sealed shape as the electronic component device. Therefore, when it is cooled from the molding temperature to room temperature or due to the difference in physical properties between the substrate and the molding material, the heat in the reflow process Due to the history, there is a problem that warp deformation tends to occur starting from the central part of the electronic component device. Along with this warp deformation, a difference in height occurs in the plurality of solder balls arranged on the same surface of the element mounting substrate, and when a test such as a package D / C operation inspection process is performed in such a state, Problems such as failure to perform sufficient inspection due to hindered connector connection may occur. In addition, when the electronic component device is surface-mounted on a mounting substrate, some of the solder balls may not be completely connected to the corresponding wiring layer, which may reduce the reliability of the connection portion.

  Therefore, as a technique for reducing the warpage deformation amount, a method of increasing the Tg of the cured epoxy resin molding material by increasing the crosslink density by using a polyfunctional resin for the epoxy resin and the phenol resin is disclosed. (For example, refer to Patent Document 1).

  On the other hand, using a crystalline epoxy resin and a polyfunctional phenol resin to reduce the viscosity of the epoxy resin molding material for sealing, and filling the filler with a high filling material achieves both low expansion coefficient and high Tg of the cured product. And a method for improving the reflow crack resistance is disclosed (for example, see Patent Documents 2 to 4).

JP-A-11-163224 Japanese Patent Laid-Open No. 11-35803 Japanese Patent Laid-Open No. 11-100100 JP-A-11-163224

  However, since the melt viscosity of the resin is high only by the method described in Patent Document 2, it is difficult to ensure sufficient fluidity for the molding material. Further, if the fluidity is ensured by reducing the amount of the filler, it may cause a decrease in reflow crack resistance accompanying an increase in water absorption of the cured product.

  In addition, in the methods described in Patent Documents 3 and 4, the improvement in fluidity is not satisfactory, and when such an epoxy resin molding material for sealing is used in a batch mold type electronic component device, it is not filled. May cause.

  The present invention has been made in view of such a situation, and even when used in a single-sided sealed package of a collective mold type, the amount of warpage deformation can be reduced, and the amount of change in warpage after the reflow process can be reduced. Sealing epoxy resin molding material (sealing epoxy resin composition) that can reduce the amount of change, and further sealing epoxy with excellent fluidity during molding, heat hardness, and reflow crack resistance The present invention intends to provide a resin molding material. The present invention is also intended to provide an electronic component device including an element sealed with the sealing epoxy resin molding material.

  As a result of intensive studies to solve the above problems, the inventors of the present invention contain an epoxy resin and a curing agent having a phenolic hydroxyl group at a specific ratio, and further a silicone compound having a specific epoxy equivalent. It has been found that the above-described object can be achieved by an epoxy resin composition for sealing containing the present invention, and the present invention has been completed.

（Ｒ^１は置換または非置換の炭素数１〜１２の１価の炭化水素基を示し、シリコーン化合物中のＲ^１は互いに同一でも異なっていてもよい。Ｘはエポキシ基を含む１価の有機基を示し、シリコーン化合物中のＸは互いに同一でも異なっていてもよい。）
（Ｃ）エポキシ基を有するシリコーン化合物は、さらに結合（ｃ）を有していてもよい。

（Ｒ^１は置換または非置換の炭素数１〜１２の１価の炭化水素基を示し、シリコーン化合物中のＲ^１は互いに同一でも異なっていてもよい。）
また、本発明においては、（Ａ）エポキシ樹脂として、例えば、下記一般式（Ｉ）で示されるエポキシ樹脂を含むエポキシ樹脂を用いることが好ましい。

（Ｒ^１は、置換又は非置換の炭素数１〜１２の炭化水素基、及び置換又は非置換の炭素数１〜１２のアルコキシ基から選ばれ、互いに同一でも異なっていてもよい。ｎは０〜４の整数を示す。Ｒ^２は、置換又は非置換の炭素数１〜１２の炭化水素基、及び置換又は非置換の炭素数１〜１２のアルコキシ基から選ばれ、互いに同一でも異なっていてもよい。ｍは０〜６の整数を示す。）
さらに、本発明においては、（Ｂ）フェノール性水酸基を有する硬化剤として、例えば、下記一般式（ＩＩ）で示されるフェノール樹脂を含む硬化剤を用いることが好ましい。

（Ｒは、水素原子、置換又は非置換の炭素数１〜１２の１価の炭化水素基、及び水酸基から選ばれ、互いに同一でも異なっていてもよい。ｎは０又は１〜１０の整数を示す。）
（Ｂ）フェノール性水酸基を有する硬化剤は、さらに下記一般式（ＩＩＩ）で示されるフェノール・アラルキル樹脂を含んでいてもよい。

（Ｒ^１〜Ｒ^９は、水素原子、及び置換又は非置換の炭素数１〜１２の１価の炭化水素基から選ばれ、互いに同一でも異なっていてもよい。ｉは０又は１〜３の整数を示し、ｎは０又は１〜１０の整数を示す。）
この場合、一般式（ＩＩ）で示されるフェノール樹脂（α）の水酸基と一般式（ＩＩＩ）で示されるフェノール・アラルキル樹脂（β）の水酸基のモル比が、（α）／（β）＝０．１〜９であることが好ましい。
さらに、本発明においては、（Ｄ）無機充填材の含有量が、封止用エポキシ樹脂組成物の全重量に対し、８５重量％〜９５重量％であることが好ましい。
本発明の封止用エポキシ樹脂組成物は、エリア実装型の電子部品装置に好ましく用いられる。
また、本発明は、上記の封止用エポキシ樹脂組成物により封止された素子を備えた電子部品装置に関する。 The present invention comprises (A) an epoxy resin, (B) a curing agent having a phenolic hydroxyl group, and (C) a silicone compound having an epoxy group, and (A) the epoxy group of the epoxy resin and (B) the curing agent. It is related with the epoxy resin composition for sealing whose equivalent ratio (hydroxyl group / epoxy group) with a phenolic hydroxyl group is 1.05-1.2, and (C) the epoxy equivalent of a silicone compound is 600-1400.
In the present invention, (C) the silicone compound having an epoxy group has, for example, the following bonds (a) and (b), and has a functional group selected from R ¹ , a hydroxyl group, and an alkoxy group at the terminal. It is preferable to use a compound.

(R ¹ represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and R ¹ in the silicone compound may be the same or different from each other. X is a monovalent organic group containing an epoxy group. And X in the silicone compound may be the same as or different from each other.)
(C) The silicone compound having an epoxy group may further have a bond (c).

(R ¹ represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and R ¹ in the silicone compound may be the same as or different from each other.)
Moreover, in this invention, it is preferable to use the epoxy resin containing the epoxy resin shown, for example by the following general formula (I) as (A) epoxy resin.

(R ¹ is selected from a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms and a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, and may be the same or different from each other. N is 0. And R ² is selected from a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms and a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, and may be the same or different from each other. M is an integer of 0-6.)
Furthermore, in this invention, it is preferable to use the hardening | curing agent containing the phenol resin shown, for example by the following general formula (II) as (B) hardening | curing agent which has a phenolic hydroxyl group.

(R is selected from a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and a hydroxyl group, and may be the same or different. N is an integer of 0 or 1 to 10. Show.)
(B) The curing agent having a phenolic hydroxyl group may further contain a phenol-aralkyl resin represented by the following general formula (III).

(R ^{1 to} R ⁹ are selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and may be the same or different from each other. Represents an integer, and n represents 0 or an integer of 1 to 10.)
In this case, the molar ratio of the hydroxyl group of the phenol resin (α) represented by the general formula (II) to the hydroxyl group of the phenol aralkyl resin (β) represented by the general formula (III) is (α) / (β) = 0. 1 to 9 is preferable.
Furthermore, in this invention, it is preferable that content of (D) inorganic filler is 85 weight%-95 weight% with respect to the total weight of the epoxy resin composition for sealing.
The epoxy resin composition for sealing of the present invention is preferably used for an area mounting type electronic component device.
Moreover, this invention relates to the electronic component apparatus provided with the element sealed with said epoxy resin composition for sealing.

  ADVANTAGE OF THE INVENTION According to this invention, the epoxy resin composition for sealing which can aim at reduction of the curvature change amount after a reflow process and during a reflow process can be provided, and electronic parts, such as a single-sided sealing type package of a batch mold type, can be provided using this. If sealed, a product with good connection reliability at the time of mounting can be obtained, and its industrial value is great. Moreover, the epoxy resin composition for sealing of the present invention is excellent in fluidity as a material for sealing an electronic component device, and is further excellent in heat hardness and reflow crack resistance.

  The epoxy resin composition for sealing according to the present invention comprises (A) an epoxy resin, (B) a curing agent having a phenolic hydroxyl group, and (C) a silicone compound having an epoxy group, and (A) an epoxy resin. The equivalent ratio (hydroxyl group / epoxy group) of the group and the phenolic hydroxyl group of the (B) curing agent is 1.05 to 1.2, and the epoxy equivalent of the (C) silicone compound is 600 to 1400. To do.

In the present invention, the equivalent ratio of (A) the epoxy resin and (B) the curing agent having a phenolic hydroxyl group, that is, the ratio of the number of hydroxyl groups in the curing agent to the number of epoxy groups in the epoxy resin (the number of hydroxyl groups in the curing agent). In order to obtain an epoxy resin composition for sealing in which the amount of warpage change after initial and heating and the amount of warpage change during initial and heating are reduced. Set to the range. More preferably 1.05 to 1.1.

  The (A) epoxy resin used in the present invention preferably contains a compound represented by the following general formula (I).

（一般式（Ｉ）中のＲ^１は、置換又は非置換の炭素数１〜１２の炭化水素基、及び置換又は非置換の炭素数１〜１２のアルコキシ基から選ばれ、互いに同一でも異なっていてもよい。ｎは０〜４の整数を示す。またＲ^２は、置換又は非置換の炭素数１〜１２の炭化水素基、及び置換又は非置換の炭素数１〜１２のアルコキシ基から選ばれ、互いに同一でも異なっていてもよい。ｍは０〜６の整数を示す。）

(R ¹ in the general formula (I) is selected from a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms and a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, and is the same or different from each other. N represents an integer of 0 to 4. R ² is selected from a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms and a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms. And may be the same or different from each other, and m represents an integer of 0 to 6.)

The hydrocarbon group having 1 to 12 carbon atoms is preferably an alkyl group, specifically, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a t-butyl group, a pentyl group, or a hexyl group. , Heptyl group, octyl group, 2-ethylhexyl group and the like.
Specific examples of the alkoxy group having 1 to 12 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
Furthermore, examples of the substituent that the hydrocarbon group or the alkoxy group may have include a halogen atom.

  Examples of the epoxy resin represented by the general formula (I) include epoxy resins represented by the following general formulas (IV) to (XXII).

  Especially, the epoxy resin shown by the said general formula (IV) is preferable from a viewpoint of a flame retardance and a moldability. As such a compound, YX-8800 (trade name of Japan Epoxy Resin Co., Ltd.) and the like are available. The amount of the epoxy resin represented by the general formula (I) is preferably 10% by weight or more, more preferably 40% by weight or more based on the total amount of the epoxy resin (A) in order to exhibit its performance. More preferably, it is 60% by weight or more.

  In the epoxy resin composition for sealing of the present invention, a conventionally known epoxy resin can be used in combination as required. Examples of the epoxy resins that can be used in combination include phenol novolac type epoxy resins, orthocresol novolac type epoxy resins, and epoxy resins having a triphenylmethane skeleton, such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F. And / or naphthols such as α-naphthol, β-naphthol and dihydroxynaphthalene and compounds having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde in an acidic catalyst. Epoxy resin, bisphenol A, bisphenol F, bisphenol S, alkyl-substituted or unsubstituted biphenol Diglycidyl ethers such as diols, stilbene type epoxy resins, hydroquinone type epoxy resins, polybasic acids such as phthalic acid and dimer acid, and glycidyl ester type epoxy resins obtained by the reaction of epichlorohydrin, and polyamines such as diaminodiphenylmethane and isocyanuric acid Glycidylamine type epoxy resin obtained by reaction of epichlorohydrin, epoxidized product of co-condensation resin of dicyclopentadiene and phenol, epoxy resin having naphthalene ring, xylylene skeleton, phenol / aralkyl resin containing biphenylene skeleton, naphthol / aralkyl resin It is obtained by oxidizing aralkyl type phenolic resin such as trimethylolpropane type epoxy resin, terpene modified epoxy resin, olefin bond with peracid such as peracetic acid. Linear aliphatic epoxy resins, alicyclic epoxy resins, such as a sulfur atom-containing epoxy resins. These may be used in combination or in combination of two or more with these alone.

  Among them, biphenyl type epoxy resin, bisphenol F type epoxy resin, stilbene type epoxy resin and sulfur atom-containing epoxy resin are preferable from the viewpoint of fluidity and reflow resistance, and novolac type epoxy resin is preferable from the viewpoint of curability, From the viewpoint of low hygroscopicity, dicyclopentadiene type epoxy resin is preferable, and from the viewpoint of heat resistance and low warpage, naphthalene type epoxy resin and triphenylmethane type epoxy resin are preferable, and contains at least one of these epoxy resins Therefore, it is preferable to use them together.

  Examples of the biphenyl type epoxy resin include an epoxy resin represented by the following general formula (XXIII). Examples of the bisphenol F type epoxy resin include an epoxy resin represented by the following general formula (XXIV). Examples of the resin include an epoxy resin represented by the following general formula (XXV), and examples of the sulfur atom-containing epoxy resin include an epoxy resin represented by the following general formula (XXVI).

（ここで、Ｒ^１〜Ｒ^８は水素原子、及び置換又は非置換の炭素数１〜１０の一価の炭化水素基から選ばれ、互いに同一でも異なっていてもよい。ｎは０〜３の整数を示す。）

(Here, R ^{1 to} R ⁸ are selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different from each other. N is 0 to 3). Indicates an integer.)

The biphenyl type epoxy resin represented by the general formula (XXIII) can be obtained by reacting a biphenol compound with epichlorohydrin by a known method. As R < ¹ > -R < ⁸ > in general formula (XXIII), it is C1-C10, such as a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a tert- butyl group, for example. C1-C10 alkenyl groups, such as an alkyl group, a vinyl group, an allyl group, a butenyl group, etc. are mentioned.

  Examples of the biphenyl type epoxy resin represented by the general formula (XXIII) include 4,4′-bis (2,3-epoxypropoxy) biphenyl or 4,4′-bis (2,3-epoxypropoxy) -3. , 3 ′, 5,5′-tetramethylbiphenyl as the main component, epichlorohydrin and 4,4′-biphenol or 4,4 ′-(3,3 ′, 5,5′-tetramethyl) biphenol An epoxy resin obtained by reacting is used. Among these, an epoxy resin mainly composed of 4,4'-bis (2,3-epoxypropoxy) -3,3 ', 5,5'-tetramethylbiphenyl is preferable. As such a compound, YX-4000 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.) and the like are commercially available.

（ここで、Ｒ^１〜Ｒ^８は水素原子、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシル基、炭素数６〜１０のアリール基、及び炭素数６〜１０のアラルキル基から選ばれ、互いに同一でも異なっていてもよい。ｎは０〜３の整数を示す。）

(Here, R ^{1 to} R ⁸ are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 6 to 10 carbon atoms. And may be the same or different from each other, and n represents an integer of 0 to 3.)

The bisphenol F-type epoxy resin represented by the general formula (XXIV) can be obtained by reacting a bisphenol F compound with epichlorohydrin by a known method. As R < ¹ > -R < ⁸ > in general formula (XXIV), it is C1-C10, such as a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a tert- butyl group, for example. Examples thereof include an alkoxyl group having 1 to 10 carbon atoms such as an alkyl group, a methoxy group, an ethoxy group, a propoxy group and a butoxy group, an aryl group such as a phenyl group and a naphthyl group, and an aralkyl group such as a benzyl group and a phenethyl group.

As the bisphenol F type epoxy resin represented by the general formula (XXIV), for example, R ¹ , R ³ , R ⁶ and R ⁸ are methyl groups, and R ² , R ⁴ , R ⁵ and R ⁷ are hydrogen atoms. YSLV-80XY (trade name, manufactured by Tohto Kasei Co., Ltd.) whose main component is an epoxy resin where n = 0 is available as a commercial product.

（ここで、Ｒ^１〜Ｒ^８は水素原子、及び置換又は非置換の炭素数１〜５の一価の炭化水素基から選ばれ、互いに同一でも異なっていてもよい。ｎは０〜１０の整数を示す。）

(Here, R ^{1 to} R ⁸ are selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 5 carbon atoms, and may be the same or different from each other. N is 0 to 10). Indicates an integer.)

As R < ¹ > -R < ⁸ > in general formula (XXV), it is C1-C5, such as a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a tert-butyl group, for example. C1-C5 alkenyl groups, such as an alkyl group, a vinyl group, an allyl group, a butenyl group, etc. are mentioned.

  The stilbene type epoxy resin represented by the above general formula (XXV) can be obtained by reacting a stilbene phenol as a raw material with epichlorohydrin in the presence of a basic substance. Examples of the raw material stilbene phenols include 3-tert-butyl-4,4′-dihydroxy-3 ′, 5,5′-trimethylstilbene, 3-tert-butyl-4,4′-dihydroxy-3. ', 5', 6-trimethylstilbene, 4,4'-dihydroxy-3,3 ', 5,5'-tetramethylstilbene, 4,4'-dihydroxy-3,3'-di-tert-butyl-5 , 5′-dimethylstilbene, 4,4′-dihydroxy-3,3′-di-tert-butyl-6,6′-dimethylstilbene and the like, among them 3-tert-butyl-4,4′- Dihydroxy-3 ′, 5,5′-trimethylstilbene and 4,4′-dihydroxy-3,3 ′, 5,5′-tetramethylstilbene are preferred. These stilbene type phenols may be used alone or in combination of two or more.

（ここで、Ｒ^１〜Ｒ^８は水素原子、置換又は非置換の炭素数１〜１０のアルキル基、及び置換又は非置換の炭素数１〜１０のアルコキシ基から選ばれ、互いに同一でも異なっていてもよい。ｎは０〜３の整数を示す。）

(Here, R ^{1 to} R ⁸ are selected from a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, which may be the same or different from each other. (N represents an integer of 0 to 3.)

The epoxy resin represented by the general formula (XXVI) can be obtained by reacting a thiodiphenol compound with epichlorohydrin by a known method. As R < ¹ > -R < ⁸ > in general formula (XXVI), it is C1-C10, such as a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a tert-butyl group, for example. Examples thereof include an alkyl group, a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

Among the sulfur atom-containing epoxy resins represented by the general formula (XXVI), R ² , R ³ , R ⁶ and R ⁷ are hydrogen atoms, and R ¹ , R ⁴ , R ⁵ and R ⁸ are alkyl groups. An epoxy resin is preferred, and an epoxy resin in which R ² , R ³ , R ⁶ and R ⁷ are hydrogen atoms, R ¹ and R ⁸ are tert-butyl groups, and R ⁴ and R ⁵ are methyl groups is more preferred. As such a compound, YSLV-120TE (trade name, manufactured by Toto Kasei Co., Ltd.) and the like are available as commercial products.

  Examples of the novolac type epoxy resin include an epoxy resin represented by the following general formula (XXVII).

（ここで、Ｒは水素原子、及び置換又は非置換の炭素数１〜１０の一価の炭化水素基からそれぞれ独立して選ばれ、ｎは０〜１０の整数を示す。）

(Here, R is independently selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 0 to 10.)

  The novolak-type epoxy resin represented by the general formula (XXVII) can be easily obtained by reacting novolak-type phenol resin with epichlorohydrin. Especially, as R in general formula (XXVII), it is a C1-C10 alkyl group, such as a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a methoxy group, an ethoxy group C1-C10 alkoxyl groups, such as a propoxy group and a butoxy group, are preferable, and a hydrogen atom or a methyl group is more preferable. n is preferably an integer of 0 to 3. Among the novolak type epoxy resins represented by the general formula (XXVII), orthocresol novolak type epoxy resins are preferable. As such a compound, ESCN-190 (trade name, manufactured by Sumitomo Chemical Co., Ltd.) is available as a commercial product.

  Examples of the dicyclopentadiene type epoxy resin include an epoxy resin represented by the following general formula (XXVIII).

（ここで、Ｒ^１及びＲ^２は水素原子、及び置換又は非置換の炭素数１〜１０の一価の炭化水素基からそれぞれ独立して選ばれ、ｎは０〜１０の整数を示し、ｍは０〜６の整数を示す。）

(Wherein R ¹ and R ² are each independently selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, n represents an integer of 0 to 10; Represents an integer of 0 to 6.)

R ¹ in the above formula (XXVIII) is, for example, a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, or a tert-butyl group, a vinyl group, an allyl group, or a butenyl group. And substituted or unsubstituted monovalent hydrocarbon groups having 1 to 10 carbon atoms such as alkenyl groups, halogenated alkyl groups, amino group-substituted alkyl groups, mercapto group-substituted alkyl groups, and the like. Among them, methyl groups and ethyl groups Alkyl groups and hydrogen atoms such as methyl groups and hydrogen atoms are more preferable. Examples of R ² include a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, and a tert-butyl group, an alkenyl group such as a vinyl group, an allyl group, and a butenyl group, and an alkyl halide. Examples thereof include substituted or unsubstituted monovalent hydrocarbon groups having 1 to 10 carbon atoms such as a group, an amino group-substituted alkyl group, and a mercapto group-substituted alkyl group, and among them, a hydrogen atom is preferable. As such a compound, HP-7200 (trade name, manufactured by Dainippon Ink and Chemicals, Inc.) is available as a commercial product.

  Examples of the naphthalene type epoxy resin include an epoxy resin represented by the following general formula (XXIXa) and the following general formula (XXIXb). Examples of the triphenylmethane type epoxy resin include an epoxy resin represented by the following general formula (XXX). Etc.

（ここで、Ｒ^１〜Ｒ^３は水素原子、及び置換又は非置換の炭素数１〜１２の一価の炭化水素基から選ばれ、それぞれ同一でも異なっていてもよい。ｐは１又は０で、ｌ及びｍはそれぞれ０〜１１の整数であって、（ｌ＋ｍ）が１〜１１の整数でかつ（ｌ＋ｐ）が１〜１２の整数となるよう選ばれる。ｉは０〜３の整数、ｊは０〜２の整数、ｋは０〜４の整数を示す。）

(Here, R ^{1 to} R ³ are selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and each may be the same or different. P is 1 or 0. , L and m are each an integer of 0 to 11, wherein (l + m) is an integer of 1 to 11 and (l + p) is an integer of 1 to 12. i is an integer of 0 to 3, j Represents an integer of 0 to 2, and k represents an integer of 0 to 4.)

As the naphthalene type epoxy resin represented by the general formula (XXIXa), there are random copolymers containing 1 constituent unit and m constituent units at random, alternating copolymers containing alternating constituents, copolymer containing regularly Examples thereof include block copolymers which are included in a combined or block form, and any one of these may be used alone, or two or more may be used in combination. R ^{1 to} R ³ in the general formula (XXIXa) are a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group or the like, an alkyl group having 1 to 12 carbon atoms, a methoxy group, an ethoxy group C1-C12 alkoxyl groups, such as a group, a propoxy group, and a butoxy group, are preferable, and a hydrogen atom or a methyl group is more preferable. As the above compound in which R ¹ and R ² are hydrogen atoms and R ³ is a methyl group, NC-7000 (trade name, manufactured by Nippon Kayaku Co., Ltd.) is commercially available.

（ここで、Ｒ^１〜Ｒ^３は水素原子、及び置換又は非置換の炭素数１〜１２の一価の炭化水素基から選ばれ、それぞれ同一でも異なっていてもよい。ｎは１〜１０の整数である。ｉは０〜４の整数、ｊは０〜２の整数、ｋは０〜４の整数を示す。）

(Here, R ^{1 to} R ³ are selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and each may be the same or different. N is 1 to 10). I is an integer from 0 to 4, j is an integer from 0 to 2, and k is an integer from 0 to 4.)

R ^{1 to} R ³ in the general formula (XXIXb) include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group and the like, an alkyl group having 1 to 12 carbon atoms, a methoxy group, and an ethoxy group. C1-C12 alkoxyl groups, such as a group, a propoxy group, and a butoxy group, are preferable, and a hydrogen atom or a methyl group is more preferable. As the above compound in which R ^{1 to} R ³ are hydrogen atoms, ESN-175 (product of Toto Kasei Co., Ltd.) and the like are available as commercial products.

（ここで、Ｒは水素原子、及び置換又は非置換の炭素数１〜１０の一価の炭化水素基から選ばれ、ｎは１〜１０の整数を示す。）

(Here, R is selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 1 to 10.)

  R in the general formula (XXX) is a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group or other alkyl group having 1 to 10 carbon atoms, a methoxy group, an ethoxy group, or a propoxy group. C1-C10 alkoxyl groups, such as a butoxy group, are preferable, and a hydrogen atom or a methyl group is more preferable. As said compound whose R is a hydrogen atom, E-1032 (Japan Epoxy Resin Co., Ltd. brand name) etc. can be obtained as a commercial item.

  These epoxy resins may be used alone or in combination of two or more.

  The curing agent having a phenolic hydroxyl group (B) used in the present invention preferably contains a phenol resin having a structure represented by the following general formula (XXXI), and in addition, an epoxy resin composition for sealing. Those commonly used can also be used in combination. Examples of the phenol resin having a structure represented by the following general formula (XXXXI) include a phenol resin consisting only of the structure of (XXXI) as a repeating unit, a phenol resin consisting of the structure of (XXXI) and another repeating unit, and the like. The structure of (XXXI) and other repeating units in the phenol resin may be combined randomly, in blocks, or alternately.

（ここで、Ｒは水素原子、置換又は非置換の炭素数１〜１２の一価の炭化水素基、及び水酸基から選ばれ、互いに同一でも異なっていてもよい。ｉは０または１〜３の整数を示す。）

(Here, R is selected from a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and a hydroxyl group, and may be the same or different from each other. Indicates an integer.)

  Examples of R in the general formula (XXXI) include a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a pentyl group, a hexyl group, Chain alkyl groups such as octyl group, decyl group and dodecyl group, cyclic alkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopentenyl group and cyclohexenyl group, and aryl group-substituted alkyl groups such as benzyl group and phenethyl group , Alkoxy groups substituted alkyl groups such as methoxy group substituted alkyl groups, ethoxy group substituted alkyl groups, butoxy group substituted alkyl groups, amino group substituted alkyl groups such as dimethylamino group, diethylamino group, hydroxyl group substituted alkyl groups, phenyl groups, naphthyl groups , Unsubstituted aryl group such as biphenyl group, tolyl group, dimethylphenol Alkyl group-substituted aryl groups such as ethyl group, ethylphenyl group, butylphenyl group, t-butylphenyl group, dimethylnaphthyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, t-butoxyphenyl group, methoxynaphthyl group, etc. And an alkoxy group-substituted aryl group, an amino group-substituted aryl group such as a dimethylamino group and a diethylamino group, and a hydroxyl group-substituted aryl group.

  The structure represented by the general formula (XXXI) can be obtained by subjecting a corresponding phenol compound and a compound having a corresponding aldehyde group to a condensation reaction under an acidic catalyst. Examples of the phenol resin having a structure represented by the general formula (XXXI) include phenol resins represented by the following general formulas (XXXII) to (XXXIV).

（ここで、一般式（ＸＸＸＩＩ）〜（ＸＸＸＩＶ）に示されるＲは水素原子、置換又は非置換の炭素数１〜１２の一価の炭化水素基、及び水酸基から選ばれ、互いに同一でも異なっていてもよい。またＸは芳香環を含む基を示す。ｉは０又は１〜３の整数を示し、ｎ及びｍは０又は１〜１０の整数を示す。）

(Here, R shown in the general formulas (XXXII) to (XXXIV) is selected from a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and a hydroxyl group, and the same or different from each other. X represents a group containing an aromatic ring, i represents an integer of 0 or 1 to 3, and n and m represent 0 or an integer of 1 to 10.)

  Examples of R in the general formulas (XXXII) to (XXXIV) include a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a pentyl group, Chain alkyl groups such as hexyl group, octyl group, decyl group, dodecyl group, cyclic alkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopentenyl group, cyclohexenyl group, and aryl groups such as benzyl group and phenethyl group Substituted alkyl group, methoxy group substituted alkyl group, ethoxy group substituted alkyl group, alkoxy group substituted alkyl group such as butoxy group substituted alkyl group, amino group substituted alkyl group such as dimethylamino group, diethylamino group, hydroxyl group substituted alkyl group, phenyl group , Unsubstituted aryl group such as naphthyl group and biphenyl group, tolyl group Alkyl group-substituted aryl groups such as dimethylphenyl group, ethylphenyl group, butylphenyl group, t-butylphenyl group, dimethylnaphthyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, t-butoxyphenyl group, methoxynaphthyl group Examples include alkoxy group-substituted aryl groups, amino group-substituted aryl groups such as dimethylamino group and diethylamino group, hydroxyl group-substituted aryl groups, alkenyl groups such as vinyl group, allyl group and butenyl group. Among them, hydrogen atom, methyl A group or a hydroxyl group is preferred. Moreover, n and m show 0 or the integer of 1-10, and 6 or less are more preferable on average.

  X in the general formula (XXXIV) is, for example, an arylene group such as a phenylene group, a biphenylene group or a naphthylene group, an alkyl group-substituted arylene group such as a tolylene group or a xylylene group, an alkoxyl group-substituted arylene group, a benzyl group or a phenethyl group. An aralkyl group, an aralkyl group-substituted arylene group, and the like. Among them, a substituted or unsubstituted phenylene group and a biphenylene group are preferable.

  Of the phenol resins represented by the general formulas (XXXII) to (XXXIV), examples of preferred phenol resins from the viewpoint of low warpage include the phenol resins represented by the following general formulas (II) and (XXXV). It is done.

（ここで、Ｒは水素原子、置換又は非置換の炭素数１〜１２の一価の炭化水素基から選ばれ、互いに同一でも異なっていてもよい。ｎは０又は１〜１０の整数を示す。）

(Here, R is selected from a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and may be the same or different from each other. N represents 0 or an integer of 1 to 10). .)

（ここで、Ｒは水素原子、置換又は非置換の炭素数１〜１２の一価の炭化水素基から選ばれ、互いに同一でも異なっていてもよい。ｎ及びｍは１〜１０の整数を示す。）

(Here, R is selected from a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and may be the same or different. N and m represent an integer of 1 to 10. .)

  Examples of R in the general formulas (II) and (XXXV) include a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a pentyl group, Chain alkyl groups such as hexyl group, octyl group, decyl group, dodecyl group, cyclic alkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopentenyl group, cyclohexenyl group, and aryl groups such as benzyl group and phenethyl group Substituted alkyl group, methoxy group substituted alkyl group, ethoxy group substituted alkyl group, alkoxy group substituted alkyl group such as butoxy group substituted alkyl group, amino group substituted alkyl group such as dimethylamino group, diethylamino group, hydroxyl group substituted alkyl group, phenyl group , Naphthyl group, biphenyl group and other unsubstituted aryl group, tolyl group, dimethyl group Alkyl group-substituted aryl groups such as ruphenyl group, ethylphenyl group, butylphenyl group, t-butylphenyl group, dimethylnaphthyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, t-butoxyphenyl group, methoxynaphthyl group, etc. An alkoxy group-substituted aryl group, an amino group-substituted aryl group such as a dimethylamino group and a diethylamino group, and a hydroxyl group-substituted aryl group. Among them, a hydrogen atom or a methyl group is preferable. For example, the following general formulas (XXXVI) and (XXXII) ) And the like. Moreover, n and m show 0 or the integer of 1-10, and 6 or less are more preferable on average.

（ここで、ｎは０又は１〜１０の整数を示す。）

(Here, n represents 0 or an integer of 1 to 10.)

（ここで、ｎ及びｍは０又は１〜１０の整数を示す。）

(Here, n and m represent 0 or an integer of 1 to 10.)

  As the phenol resin represented by the above general formula (XXXVI), MEH-7500 manufactured by Meiwa Kasei Co., Ltd. can be mentioned as a commercially available product. As the phenol resin represented by the above general formula (XXXVII), Sumikin Air -Product name HE510 by Water Chemical Co., Ltd. is mentioned.

  From the viewpoint of flame retardancy, a phenol / aralkyl resin or a naphthol / aralkyl resin represented by the following general formula (III) or (XXXIX) is preferable.

（ここで、Ｒ^１〜Ｒ^９は水素原子、置換又は非置換の炭素数１〜１２の一価の炭化水素基から選ばれ、互いに同一でも異なっていてもよい。ｉは０又は１〜３の整数を示し、ｎは０又は１〜１０の整数を示す。）

(Here, R ^{1 to} R ⁹ are selected from a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and may be the same or different from each other. I is 0 or 1-3. And n represents an integer of 0 or 1 to 10.)

（ここで、Ｒは水素原子、置換又は非置換の炭素数１〜１２の一価の炭化水素基から選ばれ、互いに同一でも異なっていてもよい。ｉは０又は１〜３の整数を示し、ｎは０又は１〜１０の整数を示す。）

(Here, R is selected from a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and may be the same or different. I represents an integer of 0 or 1-3. , N represents 0 or an integer of 1-10.)

R ^{1 to} R ⁹ in the general formula (III) and R in the general formula (XXXIX) include, for example, a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and a sec-butyl group. Chain alkyl groups such as t-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, cyclic alkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopentenyl group, cyclohexenyl group, Aryl group-substituted alkyl groups such as benzyl group and phenethyl group, methoxy group-substituted alkyl groups, ethoxy group-substituted alkyl groups, alkoxy group-substituted alkyl groups such as butoxy group-substituted alkyl groups, and amino group-substituted alkyl groups such as dimethylamino group and diethylamino group Groups, hydroxyl-substituted alkyl groups, phenyl groups, naphthyl groups, biphenyl groups, etc. Reel group, tolyl group, dimethylphenyl group, ethylphenyl group, butylphenyl group, t-butylphenyl group, dimethylnaphthyl group and other alkyl group-substituted aryl groups, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, t-butoxy Examples include an alkoxy group-substituted aryl group such as a phenyl group and a methoxynaphthyl group, an amino group-substituted aryl group such as a dimethylamino group and a diethylamino group, and a hydroxyl group-substituted aryl group. Among them, a hydrogen atom or a methyl group is preferable. Examples thereof include a phenol / aralkyl resin represented by the formula (XL) and a naphthol / aralkyl resin represented by the following general formula (XLI) or (XLII). n shows 0 or the integer of 1-10, and 6 or less is more preferable on average.

（ここで、ｎは０又は１〜１０の整数を示す。）

(Here, n represents 0 or an integer of 1 to 10.)

（ここで、ｎは０又は１〜１０の整数を示す。）

(Here, n represents 0 or an integer of 1 to 10.)

（ここで、ｎは０又は１〜１０の整数を示す。）

(Here, n represents 0 or an integer of 1 to 10.)

  As a phenol aralkyl resin shown by the said general formula (XL), the product name MEH-7851 by Meiwa Kasei Co., Ltd. is mentioned as a commercial item. Moreover, as a naphthol aralkyl resin shown by the said general formula (XLI), Nippon Steel Chemical Co., Ltd. brand name SN-475 is mentioned as a commercial item, As a naphthol aralkyl resin shown by the said general formula (XLII) Is a product name SN-170 manufactured by Nippon Steel Chemical Co., Ltd. as a commercial product.

  The phenol / aralkyl resins and naphthol / aralkyl resins represented by the general formulas (XL) to (XLII) may be partially or preliminarily mixed with acenaphthylene from the viewpoint of flame retardancy. Although acenaphthylene can be obtained by dehydrogenating acenaphthene, a commercially available product may be used. Further, it can be used as a polymer of acenaphthylene or a polymer of acenaphthylene and other aromatic olefins. (B) As a method of pre-mixing part or all of the curing agent with acenaphthylene, (B) a method of finely grinding the curing agent and acenaphthylene, respectively, and mixing them with a mixer or the like in a solid state, dissolving both components A method of removing the solvent after being uniformly dissolved in the solvent, (B) a method of melt-mixing both at a temperature equal to or higher than the softening point of the curing agent and / or acenaphthylene, etc. Therefore, a melt mixing method with less contamination of impurities is preferable. In that case, acenaphthylene may superpose | polymerize or react with (B) hardening | curing agent during mixing.

  It is preferable to use the phenol resin (α) of the general formula (II) and the phenol aralkyl resin (β) of the general formula (III) together, and the combined ratio (molar ratio of hydroxyl group) is the hydroxyl group / phenol of the phenol resin (α). -It is more preferable from the viewpoint of curvature and flame retardance that the hydroxyl group of the aralkyl resin (β) is in the range of 0.1 to 9. More preferably, the range of 0.5 to 5, particularly preferably 0.3 to 3 is desirable.

  In the present invention, in addition to the above, it is possible to use a curing agent generally used in an epoxy resin composition for sealing. For example, phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F , Phenols such as phenylphenol and aminophenol and / or naphthols such as α-naphthol, β-naphthol and dihydroxynaphthalene and compounds having an aldehyde group such as formaldehyde, acetaldehyde and propionaldehyde in an acidic catalyst Novolak-type phenolic resin, phenols and / or naphthols, phenol / aralkyl resins, naphthol / aralkyl resins, etc. synthesized from dimethoxyparaxylene or bis (methoxymethyl) biphenyl Aralkyl type phenol resin, paraxylylene and / or metaxylylene modified phenol resin, melamine modified phenol resin, terpene modified phenol resin, dicyclopentadiene modified phenol resin, cyclopentadiene modified phenol resin, polycyclic aromatic ring modified phenol resin, etc. One of these may be used alone, or two or more may be used in combination.

The silicone compound (silicon-containing polymer) having (C) an epoxy group used in the present invention preferably has the following bonds (a) and (b), and the terminal is R ¹ , a hydroxyl group or an alkoxy group. In order to reduce the warpage amount after heating and the initial warpage change amount, there is no particular limitation as long as the epoxy equivalent is 600 to 1400. Examples thereof include branched polysiloxane. More preferably, 900-1400 is desirable.

（ここで、Ｒ^１は置換または非置換の炭素数１〜１２の１価の炭化水素基から選ばれ、シリコーン化合物中のＲ^１は互いに同一でも異なっていてもよい。Ｘはエポキシ基を含む１価の有機基を示し、シリコーン化合物中のＸは互いに同一でも異なっていてもよい。）

(Wherein, R ¹ is selected from monovalent hydrocarbon groups of the substituted or unsubstituted 1 to 12 carbon atoms, R ¹ in the silicone compound may be the same or different from each other .X comprises epoxy groups A monovalent organic group, and X in the silicone compound may be the same or different from each other.

R ¹ in the general formulas (a) and (b) is a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, or an octyl group. , Alkyl groups such as 2-ethylhexyl group, alkenyl groups such as vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, phenyl group, tolyl group, xylyl group, naphthyl group, biphenyl group, benzyl group And an aralkyl group such as a phenethyl group. Among them, a methyl group or a phenyl group is preferable. X in the general formula (b) is 2,3-epoxypropyl group, 3,4-epoxybutyl group, 4,5-epoxypentyl group, 2-glycidoxyethyl group, 3-glycidoxy Propyl group, 4-glycidoxybutyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3- (3,4-epoxycyclohexyl) propyl group and the like, among which 3-glycidoxypropyl group is mentioned. preferable. Moreover, the terminal of (C) silicone compound needs to be either the above-mentioned R < ¹ >, a hydroxyl group, or an alkoxy group from the point of the storage stability of a polymer. Examples of the alkoxy group in this case include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Furthermore, the epoxy equivalent of (C) silicone compound is 600-1400. If it is smaller than 600, the fluidity of the epoxy resin composition for sealing tends to decrease. If it is larger than 1400, it is difficult to reduce the amount of warpage and the amount of initial warpage after heating, and the cured product surface oozes out. It tends to cause molding defects.

  (C) The silicone compound is preferable from the viewpoint of coexistence of fluidity and low warpage of the sealing epoxy resin composition obtained by further having the following bond (c).

（ここで、Ｒ^１は置換又は非置換の炭素数１〜１２の１価の炭化水素基から選ばれ、シリコーン化合物中のＲ^１は互いに同一でも異なっていてもよい。）

(Wherein, R ¹ is selected from monovalent hydrocarbon group having 1 to 12 carbon atoms substituted or unsubstituted, R ¹ in the silicone compound may be the same or different from each other.)

R ¹ in the general formula (c) is methyl group, ethyl group, propyl group, butyl group, isopropyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl. Alkyl groups such as vinyl groups, vinyl groups, allyl groups, butenyl groups, pentenyl groups, hexenyl groups and other alkenyl groups, phenyl groups, tolyl groups, xylyl groups, naphthyl groups, biphenyl groups and other aryl groups, benzyl groups, phenethyl groups, etc. And a methyl group or a phenyl group is preferable.

  Such a softening point of the silicone compound (C) is preferably set to 40 ° C to 120 ° C, and more preferably set to 50 ° C to 100 ° C. If it is lower than 40 ° C, the mechanical strength of the cured product of the resulting epoxy resin composition for sealing tends to decrease. If it is higher than 120 ° C, the dispersibility of the (C) silicone compound in the epoxy resin composition for sealing Tend to decrease. (C) As a method for adjusting the softening point of the silicone compound, (C) the molecular weight of the silicone compound, the structural bond unit (for example, (a) to (c) content ratio, etc.), the organic group bonded to the silicon atom It is possible by setting the type, but in particular from the viewpoint of the dispersibility of the (C) silicone compound in the epoxy resin composition for sealing and the fluidity of the resulting epoxy resin composition for sealing (C) silicone compound It is preferable to adjust the softening point by setting the content of the aryl group therein. Examples of the aryl group in this case include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and a biphenyl group, and a phenyl group is more preferable. (C) The content of the phenyl group in the monovalent organic group bonded to the silicon atom in the silicone compound is 60 mol% to 99 mol%, preferably 70 mol% to 85 mol, based on the number of moles of all organic groups. By setting the mol%, a (C) silicone compound having a desired softening point can be obtained.

  (C) The weight average molecular weight (Mw) of the silicone compound is a value measured by gel permeation chromatography (GPC) and converted using a standard polystyrene calibration curve, preferably 1000 to 30000, more preferably 2000 to 20000. More preferably, it is 3000-10000. Moreover, it is preferable that (C) silicone compound is a random copolymer.

  (C) The manufacturing method of a silicone compound can be manufactured by a well-known method without a restriction | limiting in particular. For example, organochlorosilane, organoalkoxysilane, siloxane, or an organic solvent that can dissolve the raw materials and reaction products thereof, which can form the above units (a) to (c) by hydrolysis condensation reaction, and It can be obtained by mixing all the hydrolyzable groups of the raw material in a mixed solution with a hydrolyzable amount of water and subjecting it to a hydrolytic condensation reaction. At this time, in order to reduce the amount of chlorine contained as an impurity in the sealing epoxy resin composition, it is preferable to use organoalkoxysilane and / or siloxane as a raw material. In this case, it is preferable to add an acid, a base, or an organometallic compound as a catalyst for promoting the reaction.

  (C) The organoalkoxysilane and / or siloxane used as a raw material for the silicone compound include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and phenyl. Trimethoxysilane, phenyltoethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, methylvinyldimethoxysilane, phenylvinyldimethoxysilane, diphenyldimethoxysilane, methylphenyldiethoxysilane, methylvinyldiethoxysilane, phenylvinyldiethoxysilane, Diphenyldiethoxysilane, dimethyldiethoxysilane, tetramethoxysilane, tetraethoxysilane, dimethoxydiethoxysilane, -Glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyl (methyl) dimethoxysilane, 3-glycidoxypropyl (methyl) diethoxysilane, 3-glycidoxypropyl (Phenyl) dimethoxysilane, 3-glycidoxypropyl (phenyl) diethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (methyl) dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (methyl) Examples include diethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (phenyl) dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (phenyl) diethoxysilane, and hydrolytic condensates thereof. .

  (C) The content of the silicone compound is preferably 0.01 wt% to 5 wt%, more preferably 0.1 to 4 wt%, and more preferably 0.5 wt% to 3 wt% of the entire epoxy resin composition for sealing. Is more preferable.

  In the present invention, a curing accelerator can be further used. As the curing accelerator to be used, an addition reaction product of (E) a tertiary phosphine compound and a quinone compound is preferable. (E) The addition reaction product of the tertiary phosphine compound and the quinone compound is not particularly limited as long as it acts as a curing accelerator for the epoxy resin composition for sealing. To an addition reaction product of a phosphine compound represented by the following general formula (XLIII) and a quinone compound represented by the following general formula (XLIV).

（ここで、式（ＸＬＩＩＩ）中のＲ^１〜Ｒ^３は、置換又は非置換の炭素数１〜１２のアルキル基もしくは置換又は非置換の炭素数６〜１２のアリール基を示し、互いに同一でも異なっていてもよい。また、式（ＸＬＩＶ）中のＲ^４〜Ｒ^６は、水素原子または炭素数１〜１２の炭化水素基を示し、互いに同一でも異なっていてもよく、Ｒ^４とＲ^５が結合して環状構造となっていてもよい。）

(Wherein R ^{1 to} R ³ in formula (XLIII) represent a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, R ^{4 to} R ⁶ in formula (XLIV) represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and may be the same as or different from each other, and R ⁴ and R ⁵ May be combined to form a ring structure.)

R ^{1 to} R ³ in the general formula (XLIII) represent a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, but are substituted or unsubstituted. There is no restriction | limiting in particular as a C1-C12 alkyl group of, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, n-butyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group Chain alkyl groups such as octyl group, decyl group and dodecyl group, cyclic alkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopentenyl group and cyclohexenyl group, aryl group-substituted alkyl such as benzyl group and phenethyl group Group, methoxy group-substituted alkyl group, ethoxy group-substituted alkyl group, butoxy group-substituted alkyl group, etc. Chiruamino group, an amino group-substituted alkyl group such as a diethylamino group, a hydroxyl group-substituted alkyl group.

  Examples of the substituted or unsubstituted aryl group having 6 to 12 carbon atoms include unsubstituted aryl groups such as phenyl group and naphthyl group, tolyl group, dimethylphenyl group, ethylphenyl group, butylphenyl group, and t-butylphenyl group. Alkyl group-substituted aryl groups such as dimethylnaphthyl group, alkoxy group-substituted aryl groups such as methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, t-butoxyphenyl group and methoxynaphthyl group, amino such as dimethylamino group and diethylamino group Examples include a group-substituted aryl group and a hydroxyl group-substituted aryl group.

  Examples of the phosphine compound represented by the general formula (XLIII) include triphenylphosphine, diphenyl-p-tolylphosphine, tri-p-tolylphosphine, diphenyl-p-methoxyphenylphosphine, tri-p-methoxyphenylphosphine, and tricyclohexyl. Phosphine, dicyclohexylphenylphosphine, dicyclohexyl-p-tolylphosphine, cyclohexyldiphenylphosphine, cyclohexyldi-p-tolylphosphine, tributylphosphine, dibutylphenylphosphine, dibutyl-p-tolylphosphine, butyldiphenylphosphine, butyldi-p-tolylphosphine, Trioctylphosphine, dioctylphenylphosphine, dioctyl-p-tolylphosphine, octyldiphenylphosphine Emissions, include octyl di -p- tolyl phosphine, triphenylphosphine or tributylphosphine is preferred from the viewpoint of inter alia curing fluidity properties.

R ^{4 to} R ⁶ in the general formula (XLIV) represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, but the hydrocarbon group having 1 to 12 carbon atoms is not particularly limited. Or an unsubstituted aliphatic hydrocarbon group having 1 to 12 carbon atoms, a substituted or unsubstituted alicyclic hydrocarbon group having 1 to 12 carbon atoms, and a substituted or unsubstituted aromatic hydrocarbon group having 1 to 12 carbon atoms. Etc.

  Examples of the substituted or unsubstituted aliphatic hydrocarbon group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a t-butyl group, and a pentyl group. , Alkyl groups such as hexyl group, octyl group, decyl group, dodecyl group, allyl group, methoxy group, ethoxy group, propoxyl group, n-butoxy group, alkoxy group such as t-butoxy group, dimethylamino group, diethylamino group Alkylamino groups such as methylthio group, ethylthio group, butylthio group, dodecylthio group and other alkylthio groups, amino group substituted alkyl groups, alkoxy substituted alkyl groups, hydroxyl group substituted alkyl groups, substituted alkyl groups such as aryl group substituted alkyl groups, amino Substituents such as group-substituted alkoxy groups, hydroxyl group-substituted alkoxy groups, aryl group-substituted alkoxy groups, etc. Such as alkoxy groups.

  Examples of the substituted or unsubstituted alicyclic hydrocarbon group having 1 to 12 carbon atoms include, for example, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group, a cyclohexenyl group, and the like, and an alkyl group, an alkoxy group, and an aryl group. Examples thereof include those substituted with a group, a hydroxyl group, an amino group, halogen and the like.

  Examples of the substituted or unsubstituted aromatic hydrocarbon group having 1 to 12 carbon atoms include an aryl group such as a phenyl group and a tolyl group, a dimethylphenyl group, an ethylphenyl group, a butylphenyl group, and a t-butylphenyl group. Alkyl group substituted aryl groups, alkoxy groups substituted aryl groups such as methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, t-butoxyphenyl group, aryloxy groups such as phenoxy group, crezoxy group, phenylthio group, tolylthio group, diphenylamino group And those substituted with an amino group, halogen or the like.

Further, the quinone compound represented by the general formula (XLIV) may have a cyclic structure in which R ⁴ and R ⁵ are bonded. The polycyclic quinone compound having a cyclic structure by bonding R ⁴ and R ⁵ used in the present invention is not particularly limited, and examples thereof include the following general groups in which a substituted tetramethylene group, tetramethine group and the like are bonded. And polycyclic quinone compounds represented by the formulas (XLV) to (XLVII).

  Examples of the quinone compound represented by the general formula (XLIV) include 1,4-benzoquinone, 2,3-dimethoxy-1,4benzoquinone, 2,5-dimethoxy-1,4-benzoquinone, methoxy-1,4-benzoquinone. 2,3-dimethyl-1,4-benzoquinone, 2,5-dimethyl-1,4-benzoquinone, methyl-1,4-benzoquinone, 2,5-di-t-butyl-1,4-benzoquinone, t -Butyl-1,4-benzoquinone, phenyl-1,4-benzoquinone and the like can be mentioned, among which 1,4-benzoquinone is preferable from the viewpoint of fluidity and curability.

  Examples of the structure of the addition reaction product of the phosphine compound represented by the general formula (XLIII) and the quinone compound represented by the general formula (XLIV) include compounds represented by the following general formula (XLVIII).

（ここで、Ｒ^１〜Ｒ^３は、置換又は非置換の炭素数１〜１２のアルキル基もしくは置換又は非置換の炭素数６〜１２のアリール基を示し、互いに同一でも異なっていてもよい。Ｒ^４〜Ｒ^６は水素原子又は炭素数１〜１２の炭化水素基を示し、互いに同一でも、異なっていてもよく、Ｒ^４とＲ^５が結合して環状構造となっていてもよい。）

(Here, R ^{1 to} R ³ represent a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and may be the same as or different from each other. R ^{4 to} R ⁶ represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and may be the same as or different from each other, and R ⁴ and R ⁵ may be bonded to form a cyclic structure.

(E) An example of an addition reaction product of a tertiary phosphine compound and a quinone compound is an addition reaction product of triphenylphosphine and methyl-1,4-benzoquinone, an addition reaction product of tricyclohexylphosphine and 1,4-benzoquinone, Addition reaction product of tricyclohexylphosphine and methyl-1,4-benzoquinone, Addition reaction product of tricyclohexylphosphine and 2,3-dimethyl-1,4-benzoquinone, Tricyclohexylphosphine and 2,5-dimethyl-1, Addition reaction product of 4-benzoquinone, addition reaction product of tricyclohexylphosphine and methoxy-1,4-benzoquinone, addition reaction product of tricyclohexylphosphine and 2,3-dimethoxy-1,4-benzoquinone, tricyclohexylphosphine And 2,5-dimethoxy-1,4-ben Addition reaction product of quinone, addition reaction product of cyclohexyldiphenylphosphine and 1,4-benzoquinone, addition reaction product of cyclohexyldiphenylphosphine and methyl-1,4-benzoquinone, cyclohexyldiphenylphosphine and 2,3-dimethyl-1 , 4-benzoquinone addition reaction product, cyclohexyldiphenylphosphine and 2,5-dimethyl-1,4-benzoquinone addition reaction product, cyclohexyldiphenylphosphine and methoxy-1,4-benzoquinone addition reaction product, cyclohexyldiphenyl Addition reaction product of phosphine and 2,3-dimethoxy-1,4-benzoquinone, addition reaction product of cyclohexyl diphenylphosphine and 2,5-dimethoxy-1,4-benzoquinone, cyclohexyl di-p-tolylphosphine and 1, -Addition reaction product of benzoquinone, addition reaction product of cyclohexyldi-p-tolylphosphine and methyl-1,4-benzoquinone, cyclohexyldi-p-tolylphosphine and 2,3-dimethyl-1,4-benzoquinone Addition reaction product, addition reaction product of cyclohexyldi-p-tolylphosphine and 2,5-dimethyl-1,4-benzoquinone, addition reaction product of cyclohexyldi-p-tolylphosphine and methoxy-1,4-benzoquinone, Addition reaction product of cyclohexyldi-p-tolylphosphine and 2,3-dimethoxy-1,4-benzoquinone, addition reaction product of cyclohexyldi-p-tolylphosphine and 2,5-dimethoxy-1,4-benzoquinone, Dicyclohexyl phenylphosphine and 1,4-benzoquinone addition reaction product, dicyclohexyl Addition reaction product of ruphenylphosphine and methyl-1,4-benzoquinone, Addition reaction product of dicyclohexylphenylphosphine and 2,3-dimethyl-1,4-benzoquinone, Dicyclohexylphenylphosphine and 2,5-dimethyl-1, Addition reaction product of 4-benzoquinone, addition reaction product of dicyclohexylphenylphosphine and methoxy-1,4-benzoquinone, addition reaction product of dicyclohexylphenylphosphine and 2,3-dimethoxy-1,4-benzoquinone, dicyclohexylphenylphosphine Reaction product of 2,5-dimethoxy-1,4-benzoquinone, addition reaction product of dicyclohexylphenylphosphine and 1,4-benzoquinone, addition reaction product of dicyclohexyl-p-tolylphosphine and 1,4-benzoquinone , Addition reaction product of hexyl-p-tolylphosphine and methyl-1,4-benzoquinone, addition reaction product of dicyclohexyl-p-tolylphosphine and 2,3-dimethyl-1,4-benzoquinone, dicyclohexyl-p-tolylphosphine And 2,5-dimethyl-1,4-benzoquinone addition reaction product, dicyclohexyl-p-tolylphosphine and methoxy-1,4-benzoquinone addition reaction product, dicyclohexyl-p-tolylphosphine and 2,3-dimethoxy -1,4-benzoquinone addition reaction product, dicyclohexyl-p-tolylphosphine and 2,5-dimethoxy-1,4-benzoquinone addition reaction product, dicyclohexyl-p-tolylphosphine and 1,4-benzoquinone Addition product, tributylphosphine and 1,4-benzoquinone Addition reaction product, addition reaction product of tributylphosphine and methyl-1,4-benzoquinone, addition reaction product of tributylphosphine and 2,3-dimethyl-1,4-benzoquinone, tributylphosphine and 2,5-dimethyl-1 , 4-benzoquinone addition reaction product, tributylphosphine and methoxy-1,4-benzoquinone addition reaction product, tributylphosphine and 2,3-dimethoxy-1,4-benzoquinone addition reaction product, tributylphosphine and 2 , 5-Dimethoxy-1,4-benzoquinone addition reaction product, dibutylphenylphosphine and methyl-1,4-benzoquinone addition reaction product, dibutylphenylphosphine and 2,3-dimethyl-1,4-benzoquinone Addition products, dibutylphenylphosphine and 2,5-dimethyl-1,4-benzo Addition reaction product of quinone, addition reaction product of dibutylphenylphosphine and methoxy-1,4-benzoquinone, addition reaction product of dibutylphenylphosphine and 2,3-dimethoxy-1,4-benzoquinone, dibutylphenylphosphine and 2 , 5-Dimethoxy-1,4-benzoquinone addition reaction, dibutyl-p-tolylphosphine and methyl-1,4-benzoquinone addition reaction, dibutyl-p-tolylphosphine and 2,3-dimethyl-1 , 4-benzoquinone addition reaction product, dibutyl-p-tolylphosphine and 2,5-dimethyl-1,4-benzoquinone addition reaction product, dibutyl-p-tolylphosphine and methoxy-1,4-benzoquinone Addition reactant, dibutyl-p-tolylphosphine and 2,3-dimethoxy-1,4-benzoquinone Addition reaction product, addition reaction product of dibutyl-p-tolylphosphine and 2,5-dimethoxy-1,4-benzoquinone, addition reaction product of butyldiphenylphosphine and 1,4-benzoquinone, butyldiphenylphosphine and methyl-1 , 4-benzoquinone addition reaction, butyldiphenylphosphine and 2,3-dimethyl-1,4-benzoquinone addition reaction, butyldiphenylphosphine and 2,5-dimethyl-1,4-benzoquinone addition reaction Product, addition reaction product of butyldiphenylphosphine and methoxy-1,4-benzoquinone, addition reaction product of butyldiphenylphosphine and 2,3-dimethoxy-1,4-benzoquinone, butyldiphenylphosphine and 2,5-dimethoxy- Addition reaction product with 1,4-benzoquinone, butyl di-p-tolylphos Addition reaction product of benzene and 1,4-benzoquinone, addition reaction product of butyldi-p-tolylphosphine and methyl-1,4-benzoquinone, butyldi-p-tolylphosphine and 2,3-dimethyl-1,4 -Addition reaction product of benzoquinone, addition reaction product of butyldi-p-tolylphosphine and 2,5-dimethyl-1,4-benzoquinone, addition reaction of butyldi-p-tolylphosphine and methoxy-1,4-benzoquinone Product, addition reaction product of butyldi-p-tolylphosphine and 2,3-dimethoxy-1,4-benzoquinone, addition reaction product of butyldi-p-tolylphosphine and 2,5-dimethoxy-1,4-benzoquinone, Addition reaction product of trioctylphosphine and 1,4-benzoquinone, addition reaction of trioctylphosphine and methyl-1,4-benzoquinone Reaction product, addition reaction product of trioctylphosphine and 2,3-dimethyl-1,4-benzoquinone, addition reaction product of trioctylphosphine and 2,5-dimethyl-1,4-benzoquinone, trioctylphosphine and methoxy- Addition reaction product of 1,4-benzoquinone, addition reaction product of trioctylphosphine and 2,3-dimethoxy-1,4-benzoquinone, addition of trioctylphosphine and 2,5-dimethoxy-1,4-benzoquinone Reaction product, addition reaction product of dioctylphenylphosphine and 1,4-benzoquinone, addition reaction product of dioctylphenylphosphine and methyl-1,4-benzoquinone, dioctylphenylphosphine and 2,3-dimethyl-1,4-benzoquinone Addition reaction product with dioctylphenylphosphine and 2,5-dimethyl-1 Addition reaction product of 4-benzoquinone, addition reaction product of dioctylphenylphosphine and methoxy-1,4-benzoquinone, addition reaction product of dioctylphenylphosphine and 2,3-dimethoxy-1,4-benzoquinone, dioctylphenylphosphine And 2,5-dimethoxy-1,4-benzoquinone addition reaction product, dioctyl-p-tolylphosphine and 1,4-benzoquinone addition reaction product, dioctyl-p-tolylphosphine and methyl-1,4-benzoquinone Reaction product of dioctyl-p-tolylphosphine with 2,3-dimethyl-1,4-benzoquinone, dioctyl-p-tolylphosphine with 2,5-dimethyl-1,4-benzoquinone Addition reactants, dioctyl-p-tolylphosphine and methoxy-1,4-benzox Reaction product of dioctyl-p-tolylphosphine and 2,3-dimethoxy-1,4-benzoquinone, dioctyl-p-tolylphosphine and 2,5-dimethoxy-1,4-benzoquinone Addition reaction product of octyldiphenylphosphine and 1,4-benzoquinone, addition reaction product of octyldiphenylphosphine and methyl-1,4-benzoquinone, octyldiphenylphosphine and 2,3-dimethyl-1,4 -Addition reaction product of benzoquinone, addition reaction product of octyldiphenylphosphine and 2,5-dimethyl-1,4-benzoquinone, addition reaction product of octyldiphenylphosphine and methoxy-1,4-benzoquinone, octyldiphenylphosphine and Addition reaction product with 2,3-dimethoxy-1,4-benzoquinone Addition reaction product of octyldiphenylphosphine and 2,5-dimethoxy-1,4-benzoquinone, addition reaction product of octyldi-p-tolylphosphine and 1,4-benzoquinone, octyldi-p-tolylphosphine and methyl-1 , 4-benzoquinone addition reaction, octyldi-p-tolylphosphine and 2,3-dimethyl-1,4-benzoquinone addition reaction, octyldi-p-tolylphosphine and 2,5-dimethyl-1,4 -Addition reaction product of benzoquinone, addition reaction product of octyldi-p-tolylphosphine and methoxy-1,4-benzoquinone, addition reaction of octyldi-p-tolylphosphine and 2,3-dimethoxy-1,4-benzoquinone Product, addition reaction between octyldi-p-tolylphosphine and 2,5-dimethoxy-1,4-benzoquinone Product, addition reaction product of triphenylphosphine and 1,4-benzoquinone, addition reaction product of triphenylphosphine and methyl-1,4-benzoquinone, triphenylphosphine and 2,3-dimethyl-1,4-benzoquinone Addition reaction product of triphenylphosphine and 2,5-dimethyl-1,4-benzoquinone, addition reaction product of triphenylphosphine and methoxy-1,4-benzoquinone, triphenylphosphine and 2,3 -Addition reaction product of dimethoxy-1,4-benzoquinone, addition reaction product of triphenylphosphine and 2,5-dimethoxy-1,4-benzoquinone, addition of diphenyl-p-tolylphosphine and 1,4-benzoquinone Reaction product, addition reaction product of diphenyl-p-tolylphosphine and methyl-1,4-benzoquinone Addition reaction product of diphenyl-p-tolylphosphine and 2,3-dimethyl-1,4-benzoquinone, addition reaction product of diphenyl-p-tolylphosphine and 2,5-dimethyl-1,4-benzoquinone, diphenyl- Addition reaction product of p-tolylphosphine and methoxy-1,4-benzoquinone, addition reaction product of diphenyl-p-tolylphosphine and 2,3-dimethoxy-1,4-benzoquinone, diphenyl-p-tolylphosphine and 2 , 5-dimethoxy-1,4-benzoquinone addition reaction product, tri-p-tolylphosphine and 1,4-benzoquinone addition reaction product, tri-p-tolylphosphine and methyl-1,4-benzoquinone Addition reaction product, addition reaction product of tri-p-tolylphosphine and 2,3-dimethyl-1,4-benzoquinone, tri-p-to Addition reaction product of rylphosphine and 2,5-dimethyl-1,4-benzoquinone, addition reaction product of tri-p-tolylphosphine and methoxy-1,4-benzoquinone, tri-p-tolylphosphine and 2,3 -Addition reaction product of dimethoxy-1,4-benzoquinone, addition reaction product of tri-p-tolylphosphine and 2,5-dimethoxy-1,4-benzoquinone, tri-p-methoxyphenylphosphine and 1,4- Addition reaction product of benzoquinone, addition reaction product of tri-p-methoxyphenylphosphine and methyl-1,4-benzoquinone, addition of tri-p-methoxyphenylphosphine and 2,3-dimethyl-1,4-benzoquinone Reaction product, addition reaction product of tri-p-methoxyphenylphosphine and 2,5-dimethyl-1,4-benzoquinone, tri-p-meth Addition reaction product of siphenylphosphine and methoxy-1,4-benzoquinone, addition reaction product of tri-p-methoxyphenylphosphine and 2,3-dimethoxy-1,4-benzoquinone, tri-p-methoxyphenylphosphine Addition reaction product of 2,5-dimethoxy-1,4-benzoquinone, addition reaction product of diphenyl-p-methoxyphenylphosphine and 1,4-benzoquinone, diphenyl-p-methoxyphenylphosphine and methyl-1,4- Addition reaction product of benzoquinone, addition reaction product of diphenyl-p-methoxyphenylphosphine and 2,3-dimethyl-1,4-benzoquinone, diphenyl-p-methoxyphenylphosphine and 2,5-dimethyl-1,4- Addition reaction product with benzoquinone, diphenyl-p-methoxyphenylphosphine and Addition reaction product with toxi-1,4-benzoquinone, addition reaction product of diphenyl-p-methoxyphenylphosphine and 2,3-dimethoxy-1,4-benzoquinone, diphenyl-p-methoxyphenylphosphine and 2,5- Addition reaction product of dimethoxy-1,4-benzoquinone, addition reaction product of triphenylphosphine and t-butyl-1,4-benzoquinone, addition reaction product of tricyclohexylphosphine and t-butyl-1,4-benzoquinone Addition reaction product of tributylphosphine and t-butyl-1,4-benzoquinone, addition reaction product of trioctylphosphine and t-butyl-1,4-benzoquinone, dicyclohexylphenylphosphine and t-butyl-1,4- Addition reaction product with benzoquinone, dibutylphenylphosphine and t-butyl-1,4 -Addition reaction product of benzoquinone, addition reaction product of dioctylphenylphosphine and t-butyl-1,4-benzoquinone, addition reaction product of cyclohexyldiphenylphosphine and t-butyl-1,4-benzoquinone, butyldiphenylphosphine and Addition reaction product of t-butyl-1,4-benzoquinone, addition reaction product of octyldiphenylphosphine and t-butyl-1,4-benzoquinone, dicyclohexyl-p-tolylphosphine and t-butyl-1,4-benzoquinone An addition reaction product of dibutyl-p-tolylphosphine and t-butyl-1,4-benzoquinone, an addition reaction product of dioctyl-p-tolylphosphine and t-butyl-1,4-benzoquinone, Cyclohexyl di-p-tolylphosphine and t-butyl-1,4-benzoquino An addition reaction product of butyldi-p-tolylphosphine and t-butyl-1,4-benzoquinone, an addition reaction product of octyldi-p-tolylphosphine and t-butyl-1,4-benzoquinone, Addition reaction product of triphenylphosphine and t-butyl-1,4-benzoquinone, addition reaction product of diphenyl-p-tolylphosphine and t-butyl-1,4-benzoquinone, diphenyl-p-methoxyphenylphosphine and t -Addition reaction product of butyl-1,4-benzoquinone, addition reaction product of tri-p-tolylphosphine and t-butyl-1,4-benzoquinone, tri-p-methoxyphenylphosphine and t-butyl-1, Addition reaction product of 4-benzoquinone, addition reaction of triphenylphosphine and 2,5-di-t-butyl-1,4-benzoquinone Product, addition reaction product of tricyclohexylphosphine and 2,5-di-t-butyl-1,4-benzoquinone, addition reaction product of tributylphosphine and 2,5-di-t-butyl-1,4-benzoquinone , Addition reaction product of trioctylphosphine and 2,5-di-t-butyl-1,4-benzoquinone, addition reaction product of dicyclohexylphenylphosphine and 2,5-di-t-butyl-1,4-benzoquinone , Addition reaction product of dibutylphenylphosphine and 2,5-di-t-butyl-1,4-benzoquinone, addition reaction product of dioctylphenylphosphine and 2,5-di-t-butyl-1,4-benzoquinone Addition reaction product of cyclohexyldiphenylphosphine and 2,5-di-t-butyl-1,4-benzoquinone, butyldiphenylphosphine and 2,5- Addition reaction product of di-t-butyl-1,4-benzoquinone, addition reaction product of octyldiphenylphosphine and 2,5-di-t-butyl-1,4-benzoquinone, dicyclohexyl-p-tolylphosphine and 2 , 5-di-t-butyl-1,4-benzoquinone addition reaction product, dibutyl-p-tolylphosphine and 2,5-di-t-butyl-1,4-benzoquinone addition reaction product, dioctyl- Addition reaction product of p-tolylphosphine and 2,5-di-t-butyl-1,4-benzoquinone, cyclohexyl di-p-tolylphosphine and 2,5-di-t-butyl-1,4-benzoquinone Addition reaction product of butyldi-p-tolylphosphine and 2,5-di-t-butyl-1,4-benzoquinone, octyldi-p-tolylphosphine and 2,5-di- -Addition reaction product of butyl-1,4-benzoquinone, addition reaction product of triphenylphosphine and 2,5-di-t-butyl-1,4-benzoquinone, diphenyl-p-tolylphosphine and 2,5- Addition reaction product of di-t-butyl-1,4-benzoquinone, addition reaction product of diphenyl-p-methoxyphenylphosphine and 2,5-di-t-butyl-1,4-benzoquinone, tri-p- Addition reaction product of tolylphosphine and 2,5-di-t-butyl-1,4-benzoquinone, addition of tri-p-methoxyphenylphosphine and 2,5-di-t-butyl-1,4-benzoquinone Reaction product, addition reaction product of triphenylphosphine and phenyl-1,4-benzoquinone, addition reaction product of tricyclohexylphosphine and phenyl-1,4-benzoquinone, Addition reaction product of tilphosphine and phenyl-1,4-benzoquinone, addition reaction product of trioctylphosphine and phenyl-1,4-benzoquinone, addition reaction product of dicyclohexylphenylphosphine and phenyl-1,4-benzoquinone, Addition reaction product of dibutylphenylphosphine and phenyl-1,4-benzoquinone, addition reaction product of dioctylphenylphosphine and phenyl-1,4-benzoquinone, addition reaction product of cyclohexyldiphenylphosphine and phenyl-1,4-benzoquinone Addition reaction product of butyldiphenylphosphine and phenyl-1,4-benzoquinone, addition reaction product of octyldiphenylphosphine and phenyl-1,4-benzoquinone, dicyclohexyl-p-tolylphosphine and phenyl-1,4-benzoquinone Reaction product of dibutyl-p-tolylphosphine with phenyl-1,4-benzoquinone, addition reaction product of dioctyl-p-tolylphosphine with phenyl-1,4-benzoquinone, cyclohexyldi-p -Addition reaction product of tolylphosphine and phenyl-1,4-benzoquinone, addition reaction product of butyldi-p-tolylphosphine and phenyl-1,4-benzoquinone, octyldi-p-tolylphosphine and phenyl-1,4- Addition reaction product of benzoquinone, addition reaction product of triphenylphosphine and phenyl-1,4-benzoquinone, addition reaction product of diphenyl-p-tolylphosphine and phenyl-1,4-benzoquinone, diphenyl-p-methoxyphenyl Addition reaction product of phosphine and phenyl-1,4-benzoquinone, tri-p Addition reaction product of an tolylphosphine and phenyl-1,4-benzoquinone, an addition reaction products of the avian -p- methoxyphenyl phosphine and phenyl-1,4-benzoquinone and the like.

  Among these, from the viewpoint of the reactivity between the phosphine compound and the quinone compound, addition reaction product of triphenylphosphine and 1,4-benzoquinone, addition reaction of diphenyl-p-tolylphosphine and 1,4-benzoquinone. , Addition reaction product of diphenyl-p-methoxyphenylphosphine and 1,4-benzoquinone, addition reaction product of cyclohexyldiphenylphosphine and 1,4-benzoquinone, addition reaction product of dicyclohexylphenylphosphine and 1,4-benzoquinone Addition reaction product of tricyclohexylphosphine and 1,4-benzoquinone, addition reaction product of trioctylphosphine and 1,4-benzoquinone, addition reaction product of tributylphosphine and 1,4-benzoquinone, trioctylphosphine and 1 , 4-Benzoquinone addition reaction product Addition reaction product of triphenylphosphine and methyl-1,4-benzoquinone, addition reaction product of diphenyl-p-tolylphosphine and methyl-1,4-benzoquinone, diphenyl-p-methoxyphenylphosphine and methyl-1,4 -Addition reaction product of benzoquinone, addition reaction product of cyclohexyldiphenylphosphine and methyl-1,4-benzoquinone, addition reaction product of dicyclohexylphenylphosphine and methyl-1,4-benzoquinone, tricyclohexylphosphine and methyl-1, Addition reaction product of 4-benzoquinone, addition reaction product of trioctylphosphine and methyl-1,4-benzoquinone, addition reaction product of tributylphosphine and methyl-1,4-benzoquinone, and trioctylphosphine and methyl-1, Addition with 4-benzoquinone Applied Physics is preferable. Further, from the viewpoint of fluidity and curability, an addition reaction product of triphenylphosphine and 1,4-benzoquinone and an addition reaction product of tributylphosphine and 1,4-benzoquinone are more preferable.

  (E) Although there is no restriction | limiting in particular as a manufacturing method of the addition reaction product of a tertiary phosphine compound and a quinone compound, For example, an phosphine compound used as a raw material and a quinone compound are subjected to addition reaction in an organic solvent in which both are dissolved. And a method of isolation. Specifically, a solution obtained by dissolving 41.6 g (1 mol) of triphenylphosphine in 120 g of acetone and a solution of 17.6 g (1 mol) of 1,4-benzoquinone in 80 g of acetone are used at room temperature to 80 ° C. And the yellow-brown crystals deposited after standing for 2 to 5 hours are collected by filtration. As a solvent at this time, a mixed solvent of acetone and toluene may be used instead of acetone. Further, (B) can be produced by a method of addition reaction in a phenol resin used as a curing agent having a phenolic hydroxyl group, and in this case, in the state dissolved in the phenol resin as it is without isolating the addition reaction product, It can be used as a compounding component of an epoxy resin composition.

  (E) Although there is no restriction | limiting in particular in the compounding quantity of the addition reaction material of a tertiary phosphine compound and a quinone compound, in order to exhibit the performance, 30 weight% or more is preferable with respect to all the hardening accelerators, 50 weight% The above is more preferable, and 60% by weight or more is more preferable.

  (E) When only the addition reaction product of a tertiary phosphine compound and a quinone compound is used as a curing accelerator, the blending amount is 0.2 to 10 with respect to the total amount of (A) epoxy resin and (B) curing agent. % By weight is preferred. If it is less than 0.2% by weight, the curability tends to be insufficient, and if it exceeds 10% by weight, the fluidity tends to decrease.

  The epoxy resin composition for sealing of the present invention preferably contains (E) an addition reaction product of a tertiary phosphine compound and a quinone compound, but is generally used for epoxy resin compositions for sealing other than that. The hardening accelerator currently made can be used together. Examples of the curing accelerator used in combination include 1,8-diazabicyclo [5.4.0] undecene-7, 1,5-diazabicyclo [4.3.0] nonene-5, 5,6-dibutylamino-1. , 8-diazabicyclo [5.4.0] undecene-7 and the like, derivatives thereof, and maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2, Quinones such as 3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone Benzyldimethylamine, a compound with intramolecular polarization formed by adding a compound having a π bond, such as a compound, diazophenylmethane, or a phenol resin Tertiary amines such as triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol and their derivatives, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole Imidazoles such as tributylphosphine, dialkylarylphosphine such as dimethylphenylphosphine, alkyldiarylphosphine such as methyldipheniphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, etc. Tris (alkylphenyl) phosphine, Tris (alkoxyphenyl) phosphine, Tris (alkylalkoxyphenyl) phosphine, Tris (dialkylphenyl) Phosphine, tris (trialkylphenyl) phosphine, tris (tetraalkylphenyl) phosphine, tris (dialkoxyphenyl) phosphine, tris (trialkoxyphenyl) phosphine, tris (tetraalkoxyphenyl) phosphine, diphenylphosphine, diphenyl (p-tolyl) ) Organic phosphines such as phosphine, derivatives thereof, phosphorus compounds having intramolecular polarization formed by adding a compound having a π bond such as maleic anhydride, diazophenylmethane, phenol resin, etc., tetraphenylphosphonium tetraphenylborate , Triphenylphosphine tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate, N-methylmorpholine tetraphenylborate, etc. Ron salts and derivatives thereof, and the like complexes of organic phosphines and organic boron compound. These curing accelerators may be used alone or in combination of two or more.

  It is preferable to further mix (D) an inorganic filler in the sealing epoxy resin composition of the present invention. (D) The inorganic filler is blended into the composition for hygroscopicity, linear expansion coefficient reduction, thermal conductivity improvement and strength improvement. For example, fused silica, crystalline silica, alumina, zircon, calcium silicate , Calcium carbonate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite, titania, etc., or beads spheroidized from these, A glass fiber etc. are mentioned, These may be used independently or may be used in combination of 2 or more type. Among these, fused silica is preferable from the viewpoint of reducing the linear expansion coefficient, and alumina is preferable from the viewpoint of high thermal conductivity, and the filler shape is preferably spherical from the viewpoint of fluidity and mold wear during molding.

  (D) The blending amount of the inorganic filler is preferably 70 to 96% by weight with respect to the epoxy resin composition for sealing, from the viewpoints of flame retardancy, moldability, hygroscopicity, linear expansion coefficient reduction and strength improvement, From the viewpoint of hygroscopicity and reduction in linear expansion coefficient, 85 to 95% by weight is more preferable, and 90 to 94% by weight is more preferable. If the amount is less than 70% by weight, the flame retardancy and the reflow resistance tend to decrease, and if it exceeds 96% by weight, the fluidity tends to be insufficient.

  In the sealing epoxy resin composition of the present invention, an ion trapping agent can be further blended as necessary from the viewpoint of improving the moisture resistance and high temperature storage characteristics of a semiconductor element such as an IC. The ion trapping agent is not particularly limited, and conventionally known ones can be used. Examples thereof include hydrotalcites and hydrated oxides of elements selected from magnesium, aluminum, titanium, zirconium, and bismuth. These may be used alone or in combination of two or more. Of these, hydrotalcite represented by the following composition formula (XLIX) is preferable.

Mg _1-X Al _X (OH) ₂ (CO ₃ ) _{X / 2} · mH ₂ O (XLIX)
(0 <X ≦ 0.5, m is a positive number)

  The compounding amount of the ion trapping agent is not particularly limited as long as it is a sufficient amount capable of capturing anions such as halogen ions, but from the viewpoint of fluidity and bending strength, (A) 0.1 to 30 wt. % Is preferable, 0.5 to 10% by weight is more preferable, and 1 to 5% by weight is further preferable.

  In addition, the sealing epoxy resin composition of the present invention includes an epoxy silane, a mercapto silane, an amino silane, an alkyl silane, a ureido silane, and a vinyl silane as necessary in order to enhance the adhesion between the resin component and the inorganic filler. Various known coupling agents such as various silane compounds, titanium compounds, aluminum chelates, and aluminum / zirconium compounds can be added. Examples of these include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ- Aminopropyltriethoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropylmethyldimethoxysilane, γ- [bis (β-hydroxyethyl)] aminopropyltriethoxysilane, N-β- (Aminoethyl) -γ-aminopropyltrimethoxysilane, γ- (β-aminoethyl) aminopropyldimethoxymethylsilane, N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxymethylsilylisopropyl) ethylenediamine, methyltrimethoxy Silane, dimethyldimethoxysilane, methyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxysilane, γ Silane coupling agents such as mercaptopropylmethyldimethoxysilane, isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri N-aminoethyl-aminoethyl) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctyl pyrophosphate) oxy Acetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacrylisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl Phenyl titanate, tetraisopropyl bis (dioctyl phosphite) titanate And titanate-based coupling agents, and the like. These may be used alone or in combination of two or more.

  The blending amount of the coupling agent is preferably 0.05 to 5% by weight, more preferably 0.1 to 2.5% by weight, based on the inorganic filler (D). If it is less than 0.05% by weight, the adhesion to various package components tends to be reduced, and if it exceeds 5% by weight, molding defects such as voids tend to occur.

  A flame retardant can be blended in the sealing epoxy resin composition of the present invention as necessary. Conventionally known brominated epoxy resins and antimony trioxide can be used as the flame retardant, and conventionally known non-halogen and non-antimony flame retardants can be used. For example, red phosphorus coated with a thermosetting resin such as red phosphorus, phenol resin, phosphorous ester, phosphorus compound such as triphenylphosphine oxide, melamine, melamine derivative, melamine modified phenolic resin, compound having triazine ring, Nitrogen-containing compounds such as cyanuric acid derivatives and isocyanuric acid derivatives, phosphorus and nitrogen-containing compounds such as cyclophosphazene, metal complex compounds such as dicyclopentadienyl iron, zinc oxide, zinc stannate, zinc borate, and zinc molybdate Examples thereof include metal oxides such as zinc compounds, iron oxide and molybdenum oxide, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, and composite metal hydroxides represented by the following composition formula (L).

^{_{p (M 1 a O b)}} · q (M 2 c O d) · r (M 3 c O d) · mH 2 O (L)
(Here, M ¹ , M ² and M ³ represent different metal elements, a, b, c, d, p, q and m are positive numbers, and r is 0 or a positive number.)

M ¹ , M ² and M ^{3 in the} composition formula (L) are not particularly limited as long as they are different metal elements, but from the viewpoint of flame retardancy, M ¹ is a metal element of the third period, group IIA Preferably selected from metal elements belonging to the alkaline earth metal elements, group IVB, group IIB, group VIII, group IB, group IIIA and group IVA, and M ² is selected from transition metal elements of groups IIIB to IIB, More preferably, M ¹ is selected from magnesium, calcium, aluminum, tin, titanium, iron, cobalt, nickel, copper and zinc, and M ² is selected from iron, cobalt, nickel, copper and zinc. From the viewpoint of fluidity, it is preferable that M ¹ is magnesium, M ² is zinc or nickel, and r = 0. The molar ratio of p, q and r is not particularly limited, but preferably r = 0 and p / q is 1/99 to 1/1. In addition, the classification of metal elements is a long-period type periodic rate table in which the typical element is the A group and the transition element is the B group (source: Kyoritsu Shuppan Co., Ltd. “Chemical Dictionary 4”, reduced on February 15, 1987) Plate 30th printing). The above flame retardants may be used alone or in combination of two or more.

  Furthermore, in the sealing epoxy resin composition of the present invention, as other additives, higher fatty acids, higher fatty acid metal salts, ester waxes, polyolefin waxes, polyethylene, release agents such as polyethylene oxide, carbon black, etc. If necessary, a color relieving agent, a silicone oil, a stress relaxation agent such as rubber powder, and the like can be blended.

  The epoxy resin composition for sealing of the present invention can be prepared by any method as long as various raw materials can be uniformly dispersed and mixed. As a general method, a raw material having a predetermined blending amount is mixed with a mixer or the like. A method of cooling and pulverizing after mixing sufficiently, melt-kneading with a mixing roll, an extruder or the like can be mentioned. It is easy to use if it is tableted with dimensions and weight that match the molding conditions.

  As an electronic component device provided with an element sealed with an epoxy resin composition for sealing obtained in the present invention, a lead frame, a wired tape carrier, a wiring board, glass, a silicon wafer, etc. on a support member such as a semiconductor chip An electronic component device in which active elements such as transistors, diodes and thyristors, and passive elements such as capacitors, resistors, and coils are mounted, and necessary portions are sealed with the epoxy resin composition for sealing of the present invention Etc. As such an electronic component device, for example, a semiconductor element is fixed on a lead frame, a terminal portion of a device such as a bonding pad and a lead portion are connected by wire bonding or a bump, and then the sealing epoxy resin of the present invention is used. DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Out Package), which are sealed by transfer molding using the composition. General resin-sealed ICs such as lead package, TSOP (Thin Small Outline Package), and TQFP (Thin Quad Flat Package) A semiconductor chip connected to a tape carrier by a bump is sealed with a tape carrier package (TCP) sealed with an epoxy resin composition for sealing of the present invention, wiring formed on a wiring board or glass, wire bonding, flip chip bonding, COB (Chip On) in which active elements such as semiconductor chips, transistors, diodes, thyristors and / or passive elements such as capacitors, resistors, coils, etc. connected by solder or the like are sealed with the sealing epoxy resin composition of the present invention. (Board) After mounting a semiconductor chip on an interposer substrate on which a module, a hybrid IC, a multichip module, and a terminal for connecting a motherboard are formed, and connecting the wiring formed on the semiconductor chip and the interposer substrate by bump or wire bonding, the present invention One side sealing packages such as BGA (Ball Grid Array), CSP (Chip Size Package), MCP (Multi Chip Package), etc., in which the semiconductor chip mounting side is sealed with an epoxy resin composition for sealing. Especially, the single-sided sealing type package provided with the element sealed with the epoxy resin composition for sealing obtained in the present invention has a characteristic that the amount of warpage is small. Furthermore, the epoxy resin composition for sealing of the present invention can also be used effectively for printed circuit boards.

  As a method for sealing an element using the epoxy resin composition for sealing of the present invention, a low-pressure transfer molding method is the most common, but an injection molding method, a compression molding method, or the like may be used.

  EXAMPLES Next, although an Example demonstrates this invention, the scope of the present invention is not limited to these Examples.

Examples 1-4, Comparative Examples 1-8
The following components are blended in parts by weight shown in Table 1 and Table 2, respectively, and roll kneading is performed under conditions of a kneading temperature of 80 ° C. and a kneading time of 10 minutes. An epoxy resin composition was prepared.

  As an epoxy resin, a dihydroanthracene type epoxy resin having an epoxy equivalent of 180 and a melting point of 105 ° C. (epoxy resin 1, trade name Epicoat YX-8800 manufactured by Japan Epoxy Resin Co., Ltd.), a biphenyl type epoxy resin having an epoxy equivalent of 192 and a melting point of 109 ° C. (epoxy) Resin 2, Japan Epoxy Resin Co., Ltd. product name Epicoat YX-4000), epoxy equivalent 252 and melting point 80 ° C. naphthalene type resin (Epoxy Resin 3, Toto Kasei Co., Ltd. product name ESN-175) were used. A phenolic resin having a hydroxyl group equivalent of 103 and a softening point of 86 ° C. as a curing agent (curing agent 1, trade name MEH-7500 manufactured by Meiwa Kasei Co., Ltd.), a phenol aralkyl resin having a hydroxyl group equivalent of 200 and a softening point of 80 ° C. (hardening agent 2, Meiwa) Kasei Co., Ltd. trade name MEH-7851) was used.

  An addition reaction product (curing accelerator) of tributylphosphine and 1,4-benzoquinone was used as a curing accelerator.

  Polysiloxane (silicon-containing polymer 1, product name AY42-119 manufactured by Toray Dow Corning Co., Ltd.) having a softening point of 80 ° C. was used as the silicone compound. Products having an epoxy equivalent weight of 1780 and 1530 were used.

  Further, as silicone compounds having different epoxy equivalents, polysiloxane having an epoxy equivalent of 1270 and a softening point of 65 ° C. (silicon-containing polymer 2, sample name HU307C manufactured by Toray Dow Corning Co., Ltd.), a polysiloxane having an epoxy equivalent of 980 and a softening point of 45 ° C. Siloxane (silicon-containing polymer 3, sample name HU307B manufactured by Toray Dow Corning Co., Ltd.) was used.

Spherical fused silica having an average particle diameter of 17.5 μm and a specific surface area of 3.8 m ² / g was used as the inorganic filler.

  As a coupling agent, γ-glycidoxypropyltrimethoxysilane (trade name A-187 manufactured by Nihon Unicar Co., Ltd.) was used.

  As other additives, carnauba wax (manufactured by Clariant) and carbon black (trade name MA-600, manufactured by Mitsubishi Chemical Corporation) were used.

  The produced epoxy resin compositions for sealing of Examples and Comparative Examples were evaluated by the following tests. The results are shown in Tables 3 and 4.

The epoxy resin composition for sealing was molded by a transfer molding machine under conditions of a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds. Further, post-curing was performed at 180 ° C. for 5 hours.
(1) Spiral flow (fluidity index)
The sealing epoxy resin composition was molded under the above conditions using a spiral flow measurement mold according to EMMI-1-66, and the flow distance (cm) was determined.
(2) Hardness upon heating The sealing epoxy resin composition was molded into a disk having a diameter of 50 mm and a thickness of 3 mm under the above-mentioned conditions, and measured immediately using a Shore D hardness meter.
(3) Reflow crack resistance BGA (substrate thickness: 0.5 mm) having an external dimension of 40 mm × 40 mm × 1.8 mm mounted with a 10 mm × 10 mm × 0.3 mm silicon chip is used with an epoxy resin composition for sealing. Molding was performed under conditions of a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds, and post-curing was performed at 180 ° C. for 5 hours to obtain an evaluation semiconductor package. The obtained semiconductor package was humidified under the conditions of 85 ° C. and 85% RH, and after 48 hours, subjected to reflow treatment under the conditions of 240 ° C. and 10 seconds. The presence or absence of cracks was observed, and the number of semiconductor packages for evaluation (8 pieces) ) For the number of cracking packages.
(4) Warpage amount 40 mm by using an epoxy resin composition for sealing on a glass substrate epoxy resin substrate (trade name MCL-E-679 manufactured by Hitachi Chemical Co., Ltd.) having a substrate size of 60 mm × 90 mm × 0.4 mm. Single-side sealing was performed in a range of × 70 mm × 0.6 mm, and the amount of change in warpage was evaluated. The amount of warpage is measured by measuring the displacement in the height direction using a variable temperature three-dimensional shape measuring machine (Tetec Co., Ltd.) in the long side direction of the sealing range, and calculating the difference between the maximum and minimum values. As evaluated. The initial warpage amount at room temperature, the warpage amount at room temperature after 260 ° C. heat treatment, and the warpage amount at 260 ° C. heating were measured.

The epoxy equivalent was measured as follows.
Calibration curve: Samples (several types) with known weight ratio of epoxy groups to the total weight of epoxy resin (epoxy (%)) were measured with a Fourier transform type near-infrared spectroscopic analyzer, and the absorption of epoxy groups was 6300. Absorbances in the ˜6000 ⁻¹ region were respectively determined, and a calibration curve was prepared by a partial least square method.
Measurement: A blank test was performed with a Fourier transform type near-infrared spectroscopic analyzer without filling the sample. Next, the sample was filled and the absorbance in the 6300 to 6000 ⁻¹ region was determined. The epoxy (%) of the sample was quantified from the obtained absorbance. The epoxy equivalent of the sample was determined by the following formula (epoxy group molecular weight: 43).
Epoxy equivalent = 4300 / epoxy (%)

Examples 1 to 4 using polysiloxane having an epoxy equivalent of 600 to 1400 and an equivalent ratio of epoxy resin to phenol curing agent of 1.05 to 1.20 have fluidity shown by spiral flow. Furthermore, the amount of change in warpage after initial and after heating, the amount of change during initial and during heating was small, the hardness during heating was high, and the reflow crack resistance was excellent.
In Comparative Examples 1 and 2 in which the equivalent ratio of the epoxy resin and the curing agent is 0.9 and 1.0, respectively, the initial warpage amount is small, but the warpage is caused by heating. The amount of change was large. In Comparative Example 3 in which the equivalent ratio of the epoxy resin and the curing agent was 1.3, both the amount of warpage change after heating and the amount of warpage change during heating were small, but the hardness during heating was low. Comparative Examples 4 to 6 containing no polysiloxane had problems such as low fluidity, a large amount of change after heating, and a large amount of change during heating. In Comparative Examples 7 and 8, in which the molecular weights of the polysiloxanes were 1780 and 1530, respectively, the fluidity was low and the amount of warpage change after heating was large.

Claims (10)

  (A) an epoxy resin, (B) a curing agent having a phenolic hydroxyl group, and (C) a silicone compound having an epoxy group, (A) an epoxy group of the epoxy resin, and (B) a phenolic hydroxyl group of the curing agent The epoxy resin composition for sealing wherein the equivalent ratio (hydroxyl group / epoxy group) is 1.05 to 1.2, and (C) the epoxy equivalent of the silicone compound is 600 to 1400. The sealing according to claim ¹ , wherein (C) the silicone compound having an epoxy group has the following bonds (a) and (b), and has a functional group selected from R ¹ , a hydroxyl group and an alkoxy group at the terminal. Epoxy resin composition.

(R ¹ represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and R ¹ in the silicone compound may be the same or different from each other. X is a monovalent organic group containing an epoxy group. And X in the silicone compound may be the same as or different from each other.) (C) The epoxy resin composition for sealing according to claim 2, wherein the silicone compound having an epoxy group further has a bond (c).

(R ¹ represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and R ¹ in the silicone compound may be the same as or different from each other.) (A) The epoxy resin composition for sealing in any one of Claims 1-3 in which an epoxy resin contains the epoxy resin shown by the following general formula (I).

(R ¹ is selected from a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms and a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, and may be the same or different from each other. N is 0. And R ² is selected from a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms and a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, and may be the same or different from each other. M is an integer of 0-6.) (B) The epoxy resin composition for sealing in any one of Claims 1-4 in which the hardening | curing agent which has a phenolic hydroxyl group contains the phenol resin shown by the following general formula (II).

(R is selected from a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and a hydroxyl group, and may be the same or different. N is an integer of 0 or 1 to 10. Show.) (B) The epoxy resin composition for sealing according to claim 5, wherein the curing agent having a phenolic hydroxyl group further contains a phenol-aralkyl resin represented by the following general formula (III).

(R ^{1 to} R ⁹ are selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and may be the same or different from each other. Represents an integer, and n represents 0 or an integer of 1 to 10.)   The molar ratio of the hydroxyl group of the phenol resin (α) represented by the general formula (II) and the hydroxyl group of the phenol aralkyl resin (β) represented by the general formula (III) is (α) / (β) = 0.1 The sealing epoxy resin composition according to claim 6, which is 9.   Furthermore, (D) the epoxy resin composition for sealing in any one of Claims 1-7 which contains an inorganic filler 85weight%-95weight% with respect to the total weight of the epoxy resin composition for sealing. .   The epoxy resin composition for sealing according to any one of claims 1 to 8, which is used for an area mounting type electronic component device.   The electronic component apparatus provided with the element sealed with the epoxy resin composition for sealing in any one of Claims 1-9.