JP2010024266A - Epoxy resin composition and electronic component device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin composition excellent in fluidity, adhesiveness, dimensional stability and low stress, and an electronic component device. <P>SOLUTION: The resin composition has a composition containing (A) an epoxy resin, (B) a curing agent, and (C) a silicone compound, wherein the component (C) contains (c1) a silicone compound having S-OH at both molecular ends and (c2) a compound expressed by general formula (I-2) and a compound expressed by general formula (I-3), wherein R<SP>2</SP>is selected from 1-8C divalent hydrocarbon groups which may have a substituent and R<SP>3</SP>is selected from 1-8C monovalent hydrocarbon groups which may have a substituent, and all of R<SP>3</SP>s may be the same or different from each other. and the electronic component device is also provided. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an epoxy resin composition and an electronic component device using the same.

Conventionally, in the field of element sealing of electronic component devices such as transistors, C, and LS, 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, the package form of electronic components has been reduced in size and thickness, and the number of BGA packages capable of increasing the number of pins and reducing the pitch is increasing. In the future, it is expected that the pitch will be further narrowed, and a large capacity is generated between the wirings, which lowers the signal propagation speed, which may cause a delay in the operation speed of the LS.

  In order to solve this problem, with respect to the interlayer insulating film, development of an insulating material having a low relative dielectric constant (Low-k) is progressing, and it is expected that the insulating material will become porous in the future. .

  Therefore, since these electronic component packages are expected to have a problem of cracking in the package during the thermal cycle, a low-stress seal excellent in dimensional stability that prevents peeling of a weak interlayer insulating film. There is a need for the development of fastening materials.

  As a method for improving the thermal shock resistance of the epoxy resin composition, a method using silicone rubber particles (for example, see Patent Document 1), a method using liquid silicone (for example, see Patent Document 2), a silicone-modified epoxy resin or A method using a silicone-modified phenol resin (for example, see Patent Document 3) has been reported.

  However, the method using silicone rubber particles decreases fluidity, the method using liquid silicone reduces adhesion due to oozing, and the method using silicone-modified epoxy resin or silicone-modified phenolic resin has sufficient elastic modulus. There is a tendency that a reduction effect cannot be obtained. That is, in the present situation, no method has yet been presented for obtaining a cured epoxy resin excellent in fluidity, adhesiveness and low stress in the current epoxy resin composition.

JP 2005-320446 A JP 2006-249400 A JP 2006-249200 A

  The present invention has been made in view of such circumstances, and an object of the present invention is to provide an epoxy resin composition excellent in fluidity, adhesiveness, dimensional stability, and low stress and an electronic component device using the same. is there.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the intended purpose can be achieved by using a specific silicone compound, and the present invention has been completed. It was.

  The present invention comprises an epoxy resin composition containing (A) an epoxy resin, (B) a curing agent, and (C) a silicone compound, wherein (C) the silicone compound is (c1) represented by the following general formula (I-1) And (c2) both containing a silicone block copolymer compound containing units represented by the following general formulas (I-2) and (I-3) The present invention relates to an epoxy resin composition.

（式（Ｉ−１）中、Ｉは１以上の整数、Ｒ^１は炭素数１〜１８の置換基を有していてもよい１価の炭化水素基から選ばれ、全てが同一でも異なっていてもよい。）

(In Formula (I-1), I is an integer of 1 or more, R ¹ is selected from monovalent hydrocarbon groups optionally having a substituent having 1 to 18 carbon atoms, and all are the same or different. May be.)

（式（Ｉ−２）中、Ｒ^２は炭素数１〜１８の置換基を有していてもよい２価の炭化水素基から選ばれる。）

(In formula (I-2), R ² is selected from divalent hydrocarbon groups which may have a substituent having 1 to 18 carbon atoms.)

（式（Ｉ−３）中、Ｒ^３は炭素数１〜１８の置換基を有していてもよい１価の炭化水素基から選ばれ、全てが同一でも異なっていてもよい。）

(In Formula (I-3), R ³ is selected from monovalent hydrocarbon groups which may have a substituent having 1 to 18 carbon atoms, and all may be the same or different.)

Moreover, this invention relates to said epoxy resin composition whose ratio of said (c1) with respect to the total weight of a silicone compound is 30 weight% or more in (C) silicone compound.
Moreover, this invention relates to said epoxy resin composition whose ratio of said (c2) with respect to the total weight of a silicone compound is 15 weight% or more in (C) silicone compound.

Moreover, this invention relates to said epoxy resin composition formed by containing 1-50 weight part of (C) silicone compounds with respect to 100 weight part of (A) epoxy resin.
Moreover, this invention relates to said epoxy resin composition whose number average molecular weight Mn of said (c1) is 500-30000 in (C) silicone compound.

Moreover, this invention relates to said epoxy resin composition whose number average molecular weight Mn of said (c2) is 2000-20000 in (C) silicone compound.
In the silicone compound (C), the weight ratio of the above general formulas (I-2) and (I-3) in (c2) is (I-2) / (I-3) = 3. It is related with said epoxy resin composition which is / 7-7 / 3.

The present invention also relates to (C) a silicone compound, wherein the above (c2) is a triblock copolymer having a (I-2)-(I-3)-(I-2) type structure. Relates to the composition.
Moreover, this invention relates to said epoxy resin composition whose (c2) is a silicone block copolymer compound shown by the following general formula (I-4) in (C) silicone compound.

（式（Ｉ−４）中、ｍ_１＋ｍ_２は１以上の整数、ｎは１以上の整数、Ｒ^４は炭素数１〜１８の置換基を有していてもよい１価の炭化水素基から選ばれ、全てが同一でも異なっていてもよく、Ｒ^５は炭素数１〜１８の置換基を有していてもよい２価の炭化水素基から選ばれ、全てが同一でも異なっていてもよく、Ｒ^６は炭素数１〜１８の置換基を有していてもよい２価の炭化水素基から選ばれ、全てが同一でも異なっていてもよい。）

(In formula (I-4), m ₁ + m ₂ is an integer of 1 or more, n is an integer of 1 or more, and R ⁴ is a monovalent hydrocarbon group optionally having a substituent having 1 to 18 carbon atoms. All may be the same or different, and R ⁵ is selected from divalent hydrocarbon groups optionally having a substituent having 1 to 18 carbon atoms, and all may be the same or different. R ⁶ is selected from divalent hydrocarbon groups which may have a substituent having 1 to 18 carbon atoms, and all may be the same or different.

Moreover, this invention relates to the epoxy resin composition formed by further containing (D) inorganic filler in said epoxy resin composition.
Moreover, this invention relates to said epoxy resin composition formed by further containing (E) hardening accelerator in said epoxy resin composition.

  In the present invention, (A) the epoxy resin is a biphenyl type epoxy resin, a stilbene type epoxy resin, a diphenylmethane type epoxy resin, a sulfur atom-containing type epoxy resin, a novolac type epoxy resin, a dicyclopentadiene type epoxy resin, or a salicylaldehyde type. The present invention relates to the above epoxy resin composition comprising at least one selected from epoxy resins, epoxides of copolymerized epoxy resins of naphthols and phenols and aralkyl type phenol resins.

  In the present invention, (B) the curing agent is a biphenylene skeleton-containing phenol aralkyl resin, a phenol aralkyl resin, a naphthol aralkyl resin, a dicyclopentadiene type phenol resin, a triphenylmethane type phenol resin, a novolac type phenol resin, and a copolymer type. The present invention relates to the above epoxy resin composition comprising at least one selected from phenol aralkyl resins.

  Furthermore, this invention relates to the electronic component apparatus provided with the element sealed with said epoxy resin composition.

The epoxy resin composition according to the present invention can provide an epoxy resin composition excellent in fluidity, adhesiveness, dimensional stability, and low stress properties.
In addition, an electronic component device including an element sealed using the epoxy resin composition according to the present invention has high reliability, and can be suitably used particularly for a C package having a next-generation Low-K interlayer insulating film. Its industrial value is high.

Hereinafter, the best mode for carrying out the invention will be described in detail.
The epoxy resin composition of the present invention comprises an epoxy resin composition containing (A) an epoxy resin, (B) a curing agent, and (C) a silicone compound, of which (C) the silicone compound is (c1) the following general formula Both of the silicone compound having S-OH at both ends represented by (I-1) and (c2) the silicone block copolymer compound containing units represented by the following general formulas (I-2) and (I-3) It is characterized by containing.

（式（Ｉ−１）中、Ｉは１以上の整数、Ｒ^１は炭素数１〜１８の置換基を有していてもよい１価の炭化水素基から選ばれ、全てが同一でも異なっていてもよい。）

(In Formula (I-1), I is an integer of 1 or more, R ¹ is selected from monovalent hydrocarbon groups optionally having a substituent having 1 to 18 carbon atoms, and all are the same or different. May be.)

（式（Ｉ−２）中、Ｒ^２は炭素数１〜１８の置換基を有していてもよい２価の炭化水素基から選ばれる。）

(In formula (I-2), R ² is selected from divalent hydrocarbon groups which may have a substituent having 1 to 18 carbon atoms.)

（式（Ｉ−３）中、Ｒ^３は炭素数１〜１８の置換基を有していてもよい１価の炭化水素基から選ばれ、全てが同一でも異なっていてもよい。）

(In Formula (I-3), R ³ is selected from monovalent hydrocarbon groups which may have a substituent having 1 to 18 carbon atoms, and all may be the same or different.)

(C) Silicone Compound In the present invention, (C) silicone compound comprises (c1) a silicone compound having S—OH at both ends represented by the above general formula (I-1) and (c2) the above general formula (I— 2) and a silicone block copolymer compound containing a unit represented by (I-3).

The “monovalent hydrocarbon group optionally having a substituent having 1 to 18 carbon atoms” described as R ^{1 in} (I-1) above is a carbon that may be substituted or unsubstituted. It is meant to include a monovalent aliphatic hydrocarbon group, alicyclic hydrocarbon group, and aromatic hydrocarbon group having the numbers 1-18.

  More specifically, examples of the monovalent aliphatic hydrocarbon group having 1 to 18 carbon atoms that may be substituted or unsubstituted include a methyl group, an ethyl group, a propyl group, an isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, allyl group, vinyl group and other aliphatic hydrocarbon groups and their aliphatic hydrocarbon groups. Alkyl group, alkoxy group, aryl group, hydroxyl group, amino group, halogen atom, glycidyloxy group, epoxycyclohexyl group, epoxy group-containing group, methacryloxy group, mercapto group, imino group, ureido group, isocyanate The thing substituted by substituents, such as group, is mentioned.

  Examples of the monovalent alicyclic hydrocarbon group having 1 to 18 carbon atoms that may be substituted or unsubstituted include, for example, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group, and a cyclohexenyl group. Alicyclic hydrocarbon groups such as alkyl groups, alkoxy groups, aryl groups, aryloxy groups, hydroxyl groups, amino groups, halogen atoms, glycidyloxy groups, epoxycyclohexyl groups, epoxy groups, etc. Examples thereof include those substituted with a substituent such as an epoxy group-containing group, a methacryloxy group, a mercapto group, an imino group, a ureido group, and an isocyanate group.

  Examples of the monovalent aromatic hydrocarbon group having 1 to 18 carbon atoms which may be substituted or unsubstituted include aryl groups such as phenyl group and tolyl group, methylphenyl group, dimethylphenyl group, Aromatic carbonization such as alkyl group-substituted aryl groups such as ethylphenyl group, butylphenyl group and tert-butylphenyl group, alkoxy group-substituted aryl groups such as methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group and tert-butoxyphenyl group Examples thereof include a hydrogen group, and further include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a halogen atom, a glycidyloxy group, an epoxycyclohexyl group, an epoxy group-containing group, methacryloxy Group, mercapto group, imino group, ureido group, isocyanate Or it may be substituted with substituent such.

As the R ¹ in the above (I-1), is not particularly limited, it is preferably a monovalent hydrocarbon group selected from an alkyl group and an aryl group which may have a substituent. Among them, from the viewpoint of easy availability of raw materials, aryl such as phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, etc. Group: methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, octyl group, cyclohexyl group, epoxycyclohexylethyl group, glycidoxypropyl group, chloropropyl group, methacryloxy A substituent selected from linear or cyclic alkyl groups such as propyl group, mercaptopropyl group, aminopropyl group, N-phenylaminopropyl group, N-aminopropylaminopropyl group, ureidopropyl group, and isocyanatepropyl group is more preferable. .

“1” in the above (I-1) is not particularly limited as long as it is an integer of 1 or more.
The (c1) silicone compound having S-OH at both ends in the present invention is not particularly limited as long as the intended purpose can be achieved by containing (c1), but the number average molecular weight Mn is 300 to 50,000. It is preferable that it is 400-40000, it is more preferable that it is 500-30000. When the number average molecular weight Mn is 300 or less, the desired effect due to the inclusion of the above (C) is hardly exhibited, and when it is 50000 or more, the fluidity tends to deteriorate.

Examples of specific compounds of the above (I-1) are not limited to the following. For example, compounds available commercially, viscosity ^{20~35mm 2 / s, DMS-S12} ( AZmax Co., sold reagent name), X-21-5841 (Shin-Etsu Chemical Co., Ltd. having a viscosity of 30 mm ² / s , Trade name), KF-9701 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) having a viscosity of 60 mm ² / s, viscosity 45 to 85 mm ² / s, DMS-S15 (Azumax Co., Ltd., sales reagent name), viscosity 90 mm ² / s PRX-413 (trade name, manufactured by Toray Dow Corning Co., Ltd.), DMS-S21 with a viscosity of 90 to 120 mm ² / s (Azumax Co., Ltd., sales reagent name), DMS-S27 with a viscosity of 700 to 800 mm ² / s (Azumax Corporation, sales reagent name), DMS-S31 with a viscosity of 1000 mm ² / s (Azumax Corporation, sales reagent name), etc. Both end hydroxyl group polydimethylsilicone wherein R ¹ is a methyl group; Solid end PDS-9931 (Azumax Co., Ltd., sales reagent name) and the like R ¹ is a both end hydroxyl group polydiphenyl silicone; Viscosity 50-60 mm ² / s, PDS-1615 having a phenyl group content of 14 to 18% (Amax Co., Ltd., name of sales reagent), Viscosity 2000 to 3000 mm ² / s, PSD-0332 having a phenyl group content of 2.5 to 3.5% (Amax) (Both Co., Ltd., sales reagent name) and the like, and R ¹ is a methyl group and a phenyl group. The compound represented by (I-1) may be a commercially available compound as an industrial product or a reagent, or may be a compound synthesized by a known method.

The “divalent hydrocarbon group optionally having a substituent having 1 to 18 carbon atoms” described as R ^{2 in the} above (I-2) is a divalent aliphatic group having 1 to 18 carbon atoms. It is meant to include hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups.

  More specifically, the divalent aliphatic hydrocarbon group optionally having a substituent having 1 to 18 carbon atoms includes a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, Divalent aliphatic hydrocarbon groups such as octylene group, decylene group, dodecylene group, vinylene group, ethylidene group, vinylidene group, propenylene group, butadienylene group and the like, and alkyl group, alkoxy group, aryl group, hydroxyl group, amino group, Examples thereof include those substituted with a substituent such as a halogen atom, a group containing an epoxy group such as a glycidyloxy group, an epoxycyclohexyl group or an epoxy group, a methacryloxy group, a mercapto group, an imino group, a ureido group or an isocyanate group.

  Examples of the divalent alicyclic hydrocarbon group which may have a substituent having 1 to 18 carbon atoms include a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclopentenylene group, a cyclohexenylene group, Divalent alicyclic hydrocarbon groups such as cyclohexylidene groups and the like, and alkyl groups, alkoxy groups, aryl groups, aryloxy groups, hydroxyl groups, amino groups, halogen atoms, glycidyloxy groups, epoxycyclohexyl groups, epoxy groups, etc. And an epoxy group-containing group, a methacryloxy group, a mercapto group, an imino group, a ureido group, an isocyanate group and the like.

  Examples of the divalent aromatic hydrocarbon group which may have a substituent having 1 to 18 carbon atoms include divalent aromatic hydrocarbon groups such as a phenylene group, a biphenylene group and a terphenylene group, and an alkyl group thereof. , Alkoxy group, aryl group, aryloxy group, hydroxyl group, amino group, halogen atom, glycidyloxy group, epoxycyclohexyl group, epoxy group-containing group, methacryloxy group, mercapto group, imino group, ureido group And those substituted with a substituent such as an isocyanate group.

As the R ² of the (I-2), is not particularly limited, it is preferably a divalent hydrocarbon group selected from an alkyl group and an aryl group which may have a substituent. Among them, from the viewpoint of easy availability of raw materials, aryl such as phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, etc. Group: methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, octyl group, cyclohexyl group, epoxycyclohexylethyl group, glycidoxypropyl group, chloropropyl group, methacryloxy A substituent selected from linear or cyclic alkyl groups such as propyl group, mercaptopropyl group, aminopropyl group, N-phenylaminopropyl group, N-aminopropylaminopropyl group, ureidopropyl group, and isocyanatepropyl group is more preferable. .

The substituent for R ^{2 in} (I-2) is not particularly limited, but is preferably a monovalent hydrocarbon group selected from an alkyl group and an aryl group. Among these, from the viewpoint of easy availability of raw materials, chain or cyclic alkyl such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, octyl group, cyclohexyl group, etc. Group: A substituent selected from aryl groups such as a phenyl group, a p-tolyl group, an m-tolyl group, and an o-tolyl group is more preferable.

The “monovalent hydrocarbon group optionally having a substituent having 1 to 18 carbon atoms” described as R ^{3 in the} above (I-3) is a carbon that may be substituted or unsubstituted. It is meant to include a monovalent aliphatic hydrocarbon group, alicyclic hydrocarbon group, and aromatic hydrocarbon group having the numbers 1-18.
More specifically, in the silicone compound represented by the general formula (I-1), the substituent described as R ¹ can be given.

  In the present invention, (c2) the silicone block copolymer compound containing the units represented by the above general formulas (I-2) and (I-3) contains (c2) to the extent that the intended purpose can be achieved. The number average molecular weight Mn is preferably 500 to 30000, more preferably 1000 to 25000, and still more preferably 2000 to 20000, although there is no particular limitation. When the number average molecular weight Mn is less than 500, the desired effect due to the inclusion of the above (C) is hardly exhibited, and when it exceeds 30000, the fluidity tends to deteriorate.

  The above (c2) silicone block copolymer compound desirably has a distribution in the above range rather than a single molecular weight, particularly from the viewpoint of dispersibility. As the dispersibility is improved and the silicone domains are finely dispersed, the elastic modulus reducing effect and the stress reducing effect of the epoxy resin composition tend to increase.

  The weight ratio of the above general formulas (I-2) and (I-3) in the above (c2) in the present invention is not particularly limited as long as the intended purpose can be achieved by containing (c2). , (I-2) / (I-3) is preferably 3/7 to 7/3, more preferably 4/6 to 6/4, and even more preferably 5/5. If there are many units represented by (I-2) outside this range, the fluidity tends to be greatly reduced, and if many units represented by (I-3) are present, the adhesive force tends to be lowered. There is.

The weight ratio of the units represented by the general formulas (I-2) and (I-3) can be calculated from the integral value of protons derived from each unit by ¹ H-NMR measurement.
(C2) The silicone block copolymer compound containing the units represented by the general formulas (I-2) and (I-3) in the present invention has (I-2) units at both ends (I-2). A triblock copolymer having a-(I-3)-(I-2) type structure is preferable, and a linking group is included between the units. In particular, a structure represented by the following general formula (I-4) is preferable.

（式（Ｉ−４）中、ｍ_１＋ｍ_２は１以上の整数、ｎは１以上の整数、Ｒ^４は炭素数１〜１８の置換基を有していてもよい１価の炭化水素基から選ばれ、全てが同一でも異なっていてもよく、Ｒ^５は炭素数１〜１８の置換基を有していてもよい２価の炭化水素基から選ばれ、全てが同一でも異なっていてもよく、Ｒ^６は炭素数１〜１８の置換基を有していてもよい２価の炭化水素基から選ばれ、全てが同一でも異なっていてもよい。）

(In formula (I-4), m ₁ + m ₂ is an integer of 1 or more, n is an integer of 1 or more, and R ⁴ is a monovalent hydrocarbon group optionally having a substituent having 1 to 18 carbon atoms. All may be the same or different, and R ⁵ is selected from divalent hydrocarbon groups optionally having a substituent having 1 to 18 carbon atoms, and all may be the same or different. R ⁶ is selected from divalent hydrocarbon groups which may have a substituent having 1 to 18 carbon atoms, and all may be the same or different.

The “monovalent hydrocarbon group optionally having a substituent having 1 to 18 carbon atoms” described as R ^{4 in the} above (I-4) is a carbon that may be substituted or unsubstituted. It is meant to include a monovalent aliphatic hydrocarbon group, alicyclic hydrocarbon group, and aromatic hydrocarbon group having the numbers 1-18.
More specifically, in the silicone compound represented by the general formula (I-3), the substituent described as R ³ can be given.

The “divalent hydrocarbon group optionally having a substituent having 1 to 18 carbon atoms” described as R ^{5 in the} above (I-4) is a carbon that may be substituted or unsubstituted. It is meant to include a divalent aliphatic hydrocarbon group having a number of 1 to 18, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.
More specifically, in the silicone compound represented by the general formula (I-2), the substituent described as R ² can be given.

The “divalent hydrocarbon group optionally having a substituent having 1 to 18 carbon atoms” described as R ^{6 in} (I-4) above is a carbon that may be substituted or unsubstituted. It is meant to include a divalent aliphatic hydrocarbon group having a number of 1 to 18, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.

More specifically, in the silicone compound represented by the general formula (I-2), the substituent described as R ² can be given.
“M ₁ ”, “m ₂ ”, and “n” in the above (I-4) are not particularly problematic as long as m ₁ + m ₂ is an integer of 1 or more and n is an integer of 1 or more.

  Examples of the specific compound (I-4) are not limited to the following. For example, the SLM446200 series manufactured by Wacker is available. The compound represented by (I-4) may be a commercially available compound as an industrial product or a reagent, or may be a compound synthesized by a known method.

  The proportion of the above (c1) in the total weight of the (C) silicone compound in the present invention is not particularly limited as long as the intended purpose can be achieved by containing the above (C), but it is 20% by weight or more. Preferably, it is 25% by weight or more, more preferably 30% by weight or more. When the ratio of (c1) is 20% or less, the desired effect due to the inclusion of (C) tends to be difficult to be exhibited.

  The proportion of the above (c2) in the total weight of the (C) silicone compound in the present invention is not particularly limited as long as the intended purpose can be achieved by containing the above (C), but it is 10% by weight or more. Preferably, it is 12.5% by weight or more, more preferably 15% by weight or more. When the ratio of (c2) is less than 10 weight, the fluidity tends to decrease.

  The silicone compound (C) in the present invention comprises (c1) a silicone compound having S—OH at both ends represented by the above general formula (I-1) and (c2) the above general formulas (I-2) and (I It is important to include both of the silicone block copolymer compounds containing the unit represented by -3), and when only one of them is contained, the intended purpose by containing the above (C) cannot be achieved. .

  When (C) contains (c1) and does not contain (c2), the fluidity tends to decrease, and (C) contains (c2) and does not contain (c1). In the case, the adhesiveness, dimensional stability, and low stress properties tend to decrease.

  In the present invention, the content of the (C) silicone compound with respect to 100 parts by weight of the (A) epoxy resin is particularly limited as long as the intended purpose can be achieved by containing the (C). It is not something.

  For example, it is preferably in the range of 0.5 to 60 parts by weight, more preferably in the range of 1.0 to 50 parts by weight, and still more preferably in the range of 1.5 to 40 parts by weight. When the content is less than 0.5 parts by weight, the desired effect due to the inclusion of the (C) tends to be difficult to express. On the other hand, when content exceeds 60 weight part, there exists a tendency for a moldability and adhesiveness to fall.

  In the present invention, the mixing method of (c1) and (c2) is not particularly limited. For example, a method in which a part or the whole amount is added separately, a method of adding after mixing in advance, or a partial reaction after mixing. And a method of adding them.

  In the present invention, the method of using the above (C) is not particularly limited. For example, a method of adding as it is, a method of mixing with an inorganic filler in advance, a method of heating and mixing with an epoxy resin or a curing agent in advance, an epoxy in advance Examples thereof include a method of reacting with a resin or a curing agent.

(Epoxy resin composition)
The epoxy resin composition according to the present invention comprises (A) an epoxy resin, (B) a curing agent, and (C) a silicone compound. The epoxy resin composition according to the present invention may further contain (D) an inorganic filler and (E) a curing accelerator. Hereinafter, main components constituting the epoxy resin composition according to the present invention will be described.

(A) Epoxy Resin The (A) epoxy resin that can be used in the present invention is not particularly limited as long as it is an epoxy resin having two or more epoxy groups in one molecule. For example, phenols such as phenol novolac type epoxy resin, orthocresol novolak type epoxy resin, phenols such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F and / or α-naphthol, β-naphthol, dihydroxynaphthalene A novolak-type epoxy resin obtained by epoxidizing a novolak resin obtained by condensation or cocondensation of a naphthol compound such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde and the like with an aldehyde group under an acidic catalyst;
Bisphenol A, bisphenol F, bisphenol S, alkyl-substituted or unsubstituted biphenol, diglycidyl ethers such as stilbene phenols (bisphenol-type epoxy resin, biphenyl-type epoxy resin, stilbene-type epoxy resin),
Glycidyl ethers of alcohols such as butanediol, polyethylene glycol, polypropylene glycol;
Glycidyl ester type epoxy resins of carboxylic acids such as phthalic acid, isophthalic acid, tetrahydrophthalic acid;
Glycidyl-type or methylglycidyl-type epoxy resins such as those in which active hydrogen bonded to a nitrogen atom such as aniline or isocyanuric acid is substituted with a glycidyl group;
Vinylcyclohexene diepoxide obtained by epoxidizing the olefin bond in the molecule, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxy) cyclohexyl-5,5-spiro ( 3,4-epoxy) cycloaliphatic epoxy resins such as cyclohexane-m-dioxane;
Glycidyl ether of paraxylylene and / or metaxylylene modified phenolic resin;
Glycidyl ether of terpene-modified phenolic resin;
Glycidyl ether of dicyclopentadiene-modified phenolic resin;
Glycidyl ether of cyclopentadiene modified phenolic resin;
Glycidyl ether of polycyclic aromatic ring-modified phenolic resin;
Glycidyl ether of a naphthalene ring-containing phenolic resin;
Halogenated phenol novolac epoxy resin;
Hydroquinone type epoxy resin;
Trimethylolpropane type epoxy resin;
A linear aliphatic epoxy resin obtained by oxidizing an olefinic bond with a peracid such as peracetic acid;
Diphenylmethane type epoxy resin;
Epoxidized products of aralkyl-type phenol resins such as phenol aralkyl resins and naphthol aralkyl resins;
Sulfur atom-containing epoxy resin;
Naphthalene type epoxy resins may be mentioned, and these may be used alone or in combination of two or more.

  Among the above epoxy resins, biphenyl type epoxy resin, stilbene type epoxy resin, diphenylmethane type epoxy resin, sulfur atom-containing type epoxy resin, novolac type epoxy resin, dicyclopentadiene type epoxy resin in terms of reflow crack resistance and fluidity, Salicylaldehyde type epoxy resins, copolymerized epoxy resins of naphthols and phenols, phenol aralkyl resins, epoxidized aralkyl type phenol resins such as naphthol aralkyl resins, and naphthalene type phenol resins are preferred, and any one of them is used. It may be used alone or in combination of two or more.

However, in order to exhibit these performances, it is preferable to use them in total of 30% by weight or more, more preferably 50% by weight or more, based on the total amount of epoxy resin.
Specific examples of preferable epoxy resins are shown below.

The biphenyl type epoxy resin is not particularly limited as long as it is an epoxy resin having a biphenyl skeleton, but an epoxy resin represented by the following general formula (II) is preferable.
Among the epoxy resins represented by the following general formula (II), the positions where the oxygen atom is substituted in R ⁸ are 4 and 4 'positions, and the 3, 3', 5, 5 'positions are methyl groups. YX-4000H (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), all of which are hydrogen atoms, 4,4′-bis (2,3-epoxypropoxy) biphenyl, in which all R ⁸ are hydrogen atoms, and all R ⁸ Is a hydrogen atom, and when the positions where oxygen atoms are substituted in R ⁸ are the 4 and 4 'positions, the 3, 3', 5, 5 'positions are methyl groups, and the rest are hydrogen atoms YL-6121H (manufactured by Japan Epoxy Resin Co., Ltd., trade name) is available as a commercial product.

（式（ＩＩ）中、Ｒ^８は水素原子又は炭素数１〜１２のアルキル基又は炭素数４〜１８のアリール基を示し、それぞれ全てが同一でも異なってもよく、ｎは平均値であり、０〜１０の数を示す）

(In the formula (II), R ⁸ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an aryl group having 4 to 18 carbon atoms, all of which may be the same or different, and n is an average value, Shows a number from 0 to 10)

The stilbene type epoxy resin is not particularly limited as long as it is an epoxy resin having a stilbene skeleton, but an epoxy resin represented by the following general formula (III) is preferable.
Among the epoxy resins represented by the following general formula (III), the 3,3 ′, 5,5 ′ positions when R ⁹ is substituted with oxygen atoms at positions 4 and 4 ′ are methyl groups. The other is a hydrogen atom and all of R ¹⁰ are hydrogen atoms, and three of the 3, 3 ′, 5, 5 ′ positions are methyl groups, one is a tert-butyl group, and the others are hydrogen atoms and R 10 ESLV-210 (trade name, manufactured by Sumitomo Chemical Co., Ltd.), which is a mixed product in the case where all ¹⁰ are hydrogen atoms, is available as a commercial product.

（式（ＩＩＩ）中、Ｒ^９及びＲ^１０は水素原子又は炭素数１〜１８の１価の有機基を示し、それぞれ全てが同一でも異なってもよく、ｎは平均値であり、０〜１０の数を示す）

(In the formula (III), ^{R 9} and ^{R 10} represents a monovalent organic group having 1 to 18 carbon hydrogen atom or a carbon, may all respectively be the same or different, n is an average value, 0 Indicates the number of

  The diphenylmethane type epoxy resin is not particularly limited as long as it is an epoxy resin having a diphenylmethane skeleton, but an epoxy resin represented by the following general formula (IV) is preferable.

Among the epoxy resins represented by the following general formula (IV), all of R ¹¹ are hydrogen atoms, and 3, ¹² ′ when R 4 is substituted with oxygen atoms at positions 4 and 4 ′. YSLV-80XY (trade name, manufactured by Nippon Steel Chemical Co., Ltd.), in which the 5,5′-position is a methyl group and the other is a hydrogen atom, is commercially available.

（式（ＩＶ）中、Ｒ^１１及びＲ^１２は水素原子又は炭素数１〜１８の１価の有機基を示し、それぞれ全てが同一でも異なってもよく、ｎは平均値であり、０〜１０の数を示す）

(In the formula (IV), R ¹¹ and R ¹² represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, n is an average value, and 0 to 10 Indicates the number of

The sulfur atom-containing epoxy resin is not particularly limited as long as it is a sulfur atom-containing epoxy resin, and examples thereof include an epoxy resin represented by the following general formula (V). Among the epoxy resins represented by the following general formula (V), the tert-butyl group is 6, 6 when the positions where the oxygen atom is substituted in R ¹³ are the 4 and 4 'positions, and the tert-butyl group is 6, 6 YSLV-120TE (trade name, manufactured by Nippon Steel Chemical Co., Ltd.) in which the 'position is a methyl group and the other is a hydrogen atom is commercially available.

（式（Ｖ）中、Ｒ^１３は水素原子又は炭素数１〜１８の１価の有機基を示し、それぞれ全てが同一でも異なってもよく、ｎは平均値であり、０〜１０の数を示す）

(In the formula (V), R ¹³ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, n is an average value, and the number of 0 to 10 is Show)

  The novolak type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a novolak type phenol resin, but a method such as glycidyl etherification of a novolak type phenol resin such as phenol novolak, cresol novolak, or naphthol novolak is used. Epoxy resins that have been epoxidized by use are preferred, and for example, epoxy resins represented by the following general formula (VI) are more preferred.

Among the epoxy resins represented by the following general formula (VI), ESCN-190 and ESCN-195 (trade names, manufactured by Sumitomo Chemical Co., Ltd.) in which all of R ¹⁴ are hydrogen atoms and R ¹⁵ is a methyl group = 1. Etc. are available as commercial products.

（式（ＶＩ）中、Ｒ^１４及びＲ^１５は水素原子又は炭素数１〜１８の１価の有機基を示し、それぞれ全てが同一でも異なってもよく、は０〜３の整数、ｎは平均値であり、０〜１０の数を示す）

(In the formula (VI), R ¹⁴ and R ¹⁵ represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, each represents an integer of 0 to 3, and n is an average. Value, indicating a number from 0 to 10)

  The dicyclopentadiene type epoxy resin is not particularly limited as long as it is an epoxy resin epoxidized using a compound having a dicyclopentadiene skeleton as a raw material, but an epoxy resin represented by the following general formula (VII) is preferable.

  Among the epoxy resins represented by the following general formula (VII), HP-7200 (trade name, manufactured by Dainippon Ink & Chemicals, Inc.) in which = 0 is available as a commercial product.

（式（ＶＩＩ）中、Ｒ^１６は水素原子又は炭素数１〜１８の１価の有機基を示し、それぞれ全てが同一でも異なってもよく、は０〜３の整数、ｎは平均値であり、０〜１０の数を示す）

(In the formula (VII), R ¹⁶ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, is an integer of 0 to 3, and n is an average value. , Indicating a number from 0 to 10)

  The salicylaldehyde type epoxy resin is not particularly limited as long as it is an epoxy resin made from a compound having a salicylaldehyde skeleton, but a novolak type phenol resin of a compound having a salicylaldehyde skeleton and a compound having a phenolic hydroxyl group, etc. A salicylaldehyde type epoxy resin such as an epoxy resin obtained by glycidyl etherification of a salicylaldehyde type phenol resin is preferable, and an epoxy resin represented by the following general formula (VIII) is more preferable.

  Among epoxy resins represented by the following general formula (VIII), 1032H60 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), EPPN-502H (trade name, manufactured by Nippon Kayaku Co., Ltd.), etc. Is commercially available.

（式（ＶＩＩＩ）中、Ｒ^１７及びＲ^１８は水素原子又は炭素数１〜１８の１価の有機基を示し、それぞれ全てが同一でも異なってもよく、は０〜３の整数、ｋは０〜４の整数、ｎは平均値であり、０〜１０の数を示す）

(In the formula (VIII), R ¹⁷ and R ^{18 each} represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, an integer of 0 to 3, and k is 0. (Integer of ~ 4, n is an average value and represents a number of 0 ~ 10)

  The copolymer type epoxy resin of naphthols and phenols is not particularly limited as long as it is an epoxy resin made from a compound having a naphthol skeleton and a compound having a phenol skeleton, and a compound having a naphthol skeleton and a phenol skeleton. Those obtained by glycidyl etherification of a novolac type phenol resin using a compound having the following formula are preferred, and an epoxy resin represented by the following general formula (IX) is more preferred.

Among the epoxy resins represented by the following general formula (IX), NC-7300 (trade name, manufactured by Nippon Kayaku Co., Ltd.), in which R ²¹ is a methyl group = 1, j = 0, and k = 0, etc. It is available as a commercial product.

（式（ＩＸ）中、Ｒ^１９〜Ｒ^２１は水素原子又は炭素数１〜１８の１価の有機基を示し、それぞれ全てが同一でも異なってもよく、は０〜３の整数、ｊは０〜２の整数、ｋは０〜４の整数を示し、ｐは平均値で０〜１の数を示し、ｌ、ｍはそれぞれ平均値で０〜１１の数であり（ｌ＋ｍ）は１〜１１の数を示す）

(In the formula (IX), R ^{19 to} R ²¹ represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, an integer of 0 to 3, and j is 0. An integer of ˜2, k represents an integer of 0 to 4, p represents an average value of 0 to 1, and l and m each represent an average value of 0 to 11 (l + m) represents 1 to 11 Indicates the number of

  As the epoxy resin represented by the general formula (IX), a random copolymer including one structural unit and m structural units randomly, an alternating copolymer including alternately, a copolymer including regularly, The block copolymer contained in a block shape is mentioned, Any one of these may be used independently or may be used in combination of 2 or more type.

  Epoxidized products of aralkyl-type phenol resins such as phenol aralkyl resins and naphthol aralkyl resins include phenols such as phenol and cresol and / or naphthols such as naphthol and dimethylnaphthol, dimethoxyparaxylene, bis (methoxymethyl) biphenyl, and the like. There is no particular limitation as long as it is an epoxy resin made from a phenol resin synthesized from the above derivatives.

  For example, a phenol resin synthesized from phenols such as phenol and cresol and / or naphthols such as naphthol and dimethylnaphthol and dimethoxyparaxylene, bis (methoxymethyl) biphenyl, and derivatives thereof is preferably glycidyl ether, Epoxy resins represented by the following general formulas (X) and (XI) are more preferable.

Among the epoxy resins represented by the following general formula (X), = ^{0, R 40} is a hydrogen atom NC-3000S (trade name manufactured by Nippon Kayaku Co., Ltd.), = ^0, epoxy resins ^{R 40} is a hydrogen atom And CER-3000 (made by Nippon Kayaku Co., Ltd., trade name) in which an epoxy resin in which all R ^{8 in} the general formula (II) are hydrogen atoms is mixed at a weight ratio of 80:20 is commercially available. . Among epoxy resins represented by the following general formula (XI), ESN-175 (trade name, manufactured by Nippon Steel Chemical Co., Ltd.) where j = 0 and k = 0 is available as a commercial product.

（式（Ｘ）及び（ＸＩ）において、Ｒ^３７〜Ｒ^４１は水素原子又は炭素数１〜１８の１価の有機基を示し、それぞれ全てが同一でも異なってもよく、は０〜３の整数、ｊは０〜２の整数、ｋは０〜４の整数を示す）

(In the formulas (X) and (XI), R ^{37 to} R ^{41 each} represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, and an integer of 0 to 3) , J is an integer of 0-2, k is an integer of 0-4)

  The naphthalene type epoxy resin is not particularly limited as long as it is an epoxy compound containing a naphthalene ring. For example, a naphthol compound synthesized from a naphthol derivative such as naphthol, dihydroxynaphthalene, or dimethylnaphthol is preferably glycidyl etherified, and an epoxy resin represented by the following general formula (XI-a) is more preferable.

Among the epoxy resins represented by the following general formula (XI-a), EXA-4700, EXA-4701 wherein n = 1, all of R ⁴¹ and R ⁴² are hydrogen atoms, and all of R ⁴³ are glycidyloxy groups. (Dainippon ink chemical Co., Ltd., trade name), n = ^0, all ^{R 41} and ^{R 42} is a hydrogen ^atom, HP-4032 ^{R 43} is glycidyl group (Dainippon ink chemical Co., Ltd., EXA-4750 (trade name), n = 1, all of R ⁴¹ and R ⁴² are hydrogen atoms, one of R ⁴³ is a hydrogen atom, and the other is a glycidyloxy group (manufactured by Dainippon Ink and Chemicals, (Trade name) etc. are available as commercial products.

（式（ＸＩ−ａ）中、Ｒ^４１及びＲ^４２は水素原子又は炭素数１〜１８の１価の有機基を示し、Ｒ^４３は水素原子又はグリシジルオキシ基を示し、それぞれ全てが同一でも異なってもよく、ｎは平均値であり、０〜１０の数を示す。）

(In the formula (XI-a), R ⁴¹ and R ⁴² represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, R ⁴³ represents a hydrogen atom or a glycidyloxy group, and they are all the same or different. And n is an average value and represents a number from 0 to 10.)

About R < ⁸ > -R < ²¹ > and R < ³⁷ > -R < ⁴³ > in said general formula (II)-(XI) and (XI-a), "all may be the same or different, respectively" means, for example, formula ( ) Means that all ^{8 to} 88 R ⁸ may be the same or different. It means that all of R ^{9 to} R ²¹ and R ^{37 to} R ⁴³ may be the same or different with respect to the respective numbers included in the formula. R ^{8 to} R ²¹ and R ^{37 to} R ⁴³ may be the same as or different from each other. For example, all of R ⁹ and R ¹⁰ may be the same or different.

  “N” in the above general formulas (II) to (XI) and (XI-a) is preferably in the range of 0 to 10, and when it exceeds 10, the melt viscosity of the (B) curing agent is high. Therefore, the viscosity at the time of melt molding of the epoxy resin composition is also increased, and it is easy to cause unfilling failure and deformation of the bonding wire (gold wire connecting the element and the lead). The average n per molecule is more preferably set in the range of 0-4.

(B) Curing Agent The (B) curing agent that can be used in the present invention may be any phenol compound having two or more phenolic hydroxyl groups in one molecule generally used as a curing agent, and is particularly limited. is not. For example, a compound having two phenolic hydroxyl groups in one molecule such as resorcin, catechol, bisphenol A, bisphenol F, substituted or unsubstituted biphenol;
Phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol and other phenols and / or naphthols such as α-naphthol, β-naphthol, dihydroxynaphthalene and formaldehyde, acetaldehyde, propionaldehyde, A novolak-type phenolic resin obtained by condensation or cocondensation with aldehydes such as benzaldehyde and salicylaldehyde under an acidic catalyst;
Aralkyl-type phenol resins such as phenol aralkyl resins and naphthol aralkyl resins synthesized from phenols and / or naphthols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl;
Paraxylylene and / or metaxylylene-modified phenolic resin;
Melamine-modified phenolic resin;
Terpene-modified phenolic resin;
Dicyclopentadiene type phenol resin, dicyclopentadiene type naphthol resin synthesized by copolymerization from phenols and / or naphthols and dicyclopentadiene;
Cyclopentadiene modified phenolic resin;
Polycyclic aromatic ring-modified phenolic resin;
Biphenyl type phenolic resin;
Triphenylmethane phenol resin;
The phenol resin obtained by copolymerizing 2 or more types of these resin is mentioned, These may be used independently or may be used in combination of 2 or more type.

  Among the above-mentioned phenol compounds, from the viewpoint of reflow crack resistance, aralkyl type phenol resins, dicyclopentadiene type phenol resins, salicylaldehyde type phenol resins, benzaldehyde type and aralkyl type copolymer type phenol resins, and novolak type phenol resins are used. preferable.

  These aralkyl-type phenol resins, dicyclopentadiene-type phenol resins, salicylaldehyde-type phenol resins, benzaldehyde-type and aralkyl-type copolymer phenol resins, and novolak-type phenol resins can be used alone or in combination of two types. A combination of the above may also be used.

  The aralkyl type phenolic resin is not particularly limited as long as it is a phenolic resin synthesized from phenols and / or naphthols and dimethoxyparaxylene, bis (methoxymethyl) biphenyl or a derivative thereof, but the following general formula (XII) The phenol resin represented by (XIV) is preferable.

（式（ＸＩＩ）〜（ＸＩＶ）において、Ｒ^２２〜Ｒ^２８は水素原子又は炭素数１〜１８の１価の有機基を示し、それぞれ全てが同一でも異なってもよく、は０〜３の整数、ｋは０〜４の整数、ｊは０〜２の整数、ｎは平均値であり、０〜１０の数を示す）

(In the formulas (XII) to (XIV), R ^{22 to} R ²⁸ represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, and an integer of 0 to 3 K is an integer of 0 to 4, j is an integer of 0 to 2, n is an average value, and represents a number of 0 to 10)

Among the phenol resins represented by the above general formula (XII), MEH-7851 (trade name, manufactured by Meiwa Kasei Co., Ltd.), in which = 0 and R ²³ are all hydrogen atoms, is commercially available.

  Among the phenol resins represented by the above general formula (XIII), XL-225, XLC (trade name, manufactured by Mitsui Chemicals Co., Ltd.), MEH-7800 (trade name, Meiwa Kasei Co., Ltd.), where k = 0. Etc. are available as commercial products.

Among the phenol resins represented by the above general formula (XIV), SN-170 (trade name, manufactured by Nippon Steel Chemical Co., Ltd.) where j = 0, R ²⁷ k = 0, and R ²⁸ k = 0, etc. It is available as a commercial product.

  The dicyclopentadiene type phenol resin is not particularly limited as long as it is a phenol resin using a compound having a dicyclopentadiene skeleton as a raw material, but a phenol resin represented by the following general formula (XV) is preferable. Among the phenol resins represented by the following general formula (XV), DPP (trade name) manufactured by Nippon Petrochemical Co., Ltd., which is = 0 is available as a commercial product.

（式（ＸＶ）中、Ｒ^２９は水素原子又は炭素数１〜１８の１価の有機基を示し、それぞれ全てが同一でも異なってもよく、は０〜３の整数、ｎは平均値であり、０〜１０の数を示す）

(In the formula (XV), R ²⁹ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, is an integer of 0 to 3, and n is an average value. , Indicating a number from 0 to 10)

The salicylaldehyde type phenol resin is not particularly limited as long as it is a phenol resin using a compound having a salicylaldehyde skeleton as a raw material, but a phenol resin represented by the following general formula (XVI) is preferable.
Among the phenol resins represented by the following general formula (XVI), MEH-7500 (trade name, manufactured by Meiwa Kasei Co., Ltd.) in which = 0 and k = 0 are available as commercial products.

（式（ＸＶＩ）中、Ｒ^３０及びＲ^３１は水素原子又は炭素数１〜１８の１価の有機基を示し、それぞれ全てが同一でも異なってもよく、は０〜３の整数、ｋは０〜４の整数、ｎは平均値であり、０〜１０の数を示す）

(In the formula (XVI), R ³⁰ and R ³¹ represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, each represents an integer of 0 to 3, and k is 0. (Integer of ~ 4, n is an average value and represents a number of 0 ~ 10)

  The copolymer type phenol resin of benzaldehyde type and aralkyl type is not particularly limited as long as it is a copolymer type phenol resin of a phenol resin and an aralkyl type phenol resin using a compound having a benzaldehyde skeleton as a raw material. A phenol resin represented by the formula (XVII) is preferred.

  Among the phenol resins represented by the following general formula (XVII), HE-510 (trade name, manufactured by Air Water Chemical Co., Ltd.) having = 0, k = 0, and q = 0 is available as a commercial product. .

（式（ＸＶＩＩ）中、Ｒ^３２〜Ｒ^３４は水素原子又は炭素数１〜１８の１価の有機基を示し、それぞれ全てが同一でも異なってもよく、は０〜３の整数、ｋは０〜４の整数、ｑは０〜５の整数、ｌ、ｍはそれぞれ平均値で０〜１１の数であり（ｌ＋ｍ）は１〜１１の数を示す）

(In the formula (XVII), R ^{32 to} R ³⁴ represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, each represents an integer of 0 to 3, and k is 0. An integer of ~ 4, q is an integer of 0 to 5, l and m are average numbers of 0 to 11 respectively (l + m) represents a number of 1 to 11)

  The novolac type phenol resin is not particularly limited as long as it is a phenol resin obtained by condensation or cocondensation of phenols and / or naphthols and aldehydes in the presence of an acidic catalyst, but is represented by the following general formula (XVIII). Phenol resin is preferred.

Among phenol resins represented by the following general formula (XVIII) = 0, Tamanols 758 and 759 (trade name, manufactured by Arakawa Chemical Co., Ltd.), and R- ³⁵ are all hydrogen atoms, HP-850N (manufactured by Hitachi Chemical Co., Ltd.) , Trade names) etc. are available as commercial products.

（式（ＸＶＩＩＩ）中、Ｒ^３５及びＲ^３６は水素原子又は炭素数１〜１８の１価の有機基を示し、それぞれ全てが同一でも異なってもよく、は０〜３の整数、ｋは０〜４の整数、ｎは平均値であり、０〜１０の数を示す）

(In the formula (XVIII), R ³⁵ and R ^{36 each} represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different, is an integer of 0 to 3, and k is 0. (Integer of ~ 4, n is an average value and represents a number of 0 ~ 10)

“All may be the same or different” described for R ^{22 to} R ³⁶ in the above general formulas (XII) to (XVIII) means that, for example, all R ²² in the formula (XIV) are the same. It means that they may be different from each other.

For the other R ^{23 to} R ³⁶ , it means that all the numbers contained in the formula may be the same or different from each other. R ^{22 to} R ³⁶ may be the same as or different from each other. For example, all of R ²² and R ²³ may be the same or different, and all of R ³⁰ and R ³¹ may be the same or different.

  In the above general formulas (XII) to (XVIII), “n” is preferably in the range of 0 to 10, and when it exceeds 10, the melt viscosity of the (B) curing agent is increased, so that the epoxy resin composition Viscosity at the time of melt molding is increased, and unfilled defects and bonding wires (gold wires connecting elements and leads) are likely to be deformed. The average n per molecule is more preferably set in the range of 0-4.

  In the epoxy resin composition of the present invention, the equivalent ratio of (A) epoxy resin and (B) curing agent, that is, the ratio of the number of hydroxyl groups in the curing agent to the number of epoxy groups in the epoxy resin (number of hydroxyl groups in curing agent / The number of epoxy groups in the epoxy resin) is not particularly limited, but is preferably set in the range of 0.5 to 2 and more preferably 0.6 to 1.3 in order to suppress the respective unreacted components. . In order to obtain a sealing epoxy resin composition excellent in moldability and reflow resistance, it is more preferably set in the range of 0.8 to 1.2.

(D) Inorganic filler You may mix | blend an inorganic filler with the epoxy resin composition which becomes this invention as needed. Inorganic fillers that can be used may be those generally used for molding materials for sealing, and are not particularly limited.

  For example, fused silica, crystalline silica, silica gel, porous silica, glass, zeolite, calcium carbonate, calcium oxide, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, Examples thereof include fine particles such as steatite, spinel, mullite, titania, talc, clay and mica, or beads obtained by spheroidizing these. Among these, fused silica is preferable from the viewpoint of reducing the linear expansion coefficient. One of these inorganic fillers may be used alone, or two or more thereof may be used in combination.

From the viewpoint of reducing fluidity and linear expansion coefficient, it is preferable to use crystalline silica and fused silica, more preferably fused silica, and even more preferably spherical fused silica.
Furthermore, you may use together metal hydroxide type fillers, such as aluminum hydroxide, magnesium hydroxide, and a composite metal hydroxide, which have a flame-retardant effect.

  (D) Although there will be no restriction | limiting in particular if the compounding quantity of an inorganic filler will acquire the effect of this invention, It is preferable that it is the range of 55-90 volume% with respect to the total weight of an epoxy resin composition. These inorganic fillers are blended for the purpose of improving the thermal expansion coefficient, thermal conductivity, elastic modulus, etc. of the cured product. (D) When the blending amount of the inorganic filler is less than 55% by volume, these characteristics are improved. Tends to be insufficient, and when it exceeds 90% by volume, the viscosity of the epoxy resin composition is increased, the fluidity is lowered, and the molding tends to be difficult.

  Moreover, 1-50 micrometers is preferable and, as for the average particle diameter of (D) inorganic filler, 10-30 micrometers is more preferable. If it is less than 1 μm, the viscosity of the epoxy resin composition tends to increase, and if it exceeds 50 μm, the resin component and the inorganic filler are likely to be separated, resulting in unevenness of the cured product, variations in the cured product characteristics, There is a tendency for filling property to fall.

  From the viewpoint of fluidity, the particle shape of (D) inorganic filler is preferably spherical rather than square, and the particle size distribution of the inorganic filler is preferably distributed over a wide range. For example, when blending 75% by volume or more of the inorganic filler, it is preferable that 70% by weight or more of the filler be spherical particles and distributed over a wide range of 0.1 to 80 μm. Such an inorganic filler can easily form a close-packed structure, so that even if the blending amount is increased, an increase in the viscosity of the material is small, and an epoxy resin composition excellent in fluidity can be obtained.

(E) Hardening accelerator A hardening accelerator may be mix | blended with the epoxy resin composition which becomes this invention as needed. Examples of usable curing accelerators include diazabicycloalkenes such as 1,5-diazabicyclo [4.3.0] nonene-5 and 1,8-diazabicyclo [5.4.0] undecene-7. Cycloamidine compounds, derivatives thereof, phenol novolac salts thereof and these compounds to maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6- Quinone compounds such as dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, and π bonds such as diazophenylmethane A compound having an intramolecular polarization formed by adding a compound having a triethylenediamine, benzyldimethylamine, Tertiary amines such as liethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol and their derivatives, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole Imidazoles such as tetraphenylphosphonium and tetraphenylborate, tetrasubstituted phosphonium and tetrasubstituted borates, tetraethylboron salts such as 2-ethyl-4-methylimidazole and tetraphenylborate, N-methylmorpholine and tetraphenylborate, Triphenylphosphine, diphenyl (p-tolyl) phosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, tris (alkylalkoxyphenyl) phos Sphin, tris (dialkylphenyl) phosphine, tris (trialkylphenyl) phosphine, tris (tetraalkylphenyl) phosphine, tris (dialkoxyphenyl) phosphine, tris (trialkoxyphenyl) phosphine, tris (tetraalkoxyphenyl) phosphine, tris Organic phosphines such as alkylphosphine, dialkylarylphosphine, alkyldiarylphosphine, etc., complexes of these organic phosphines and organic borons, organic phosphines and maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1 , 4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4- Quinone compounds such as nzoquinone and phenyl-1,4-benzoquinone, compounds having intramolecular polarization formed by adding a compound having a π bond such as diazophenylmethane, these organic phosphines and 4-bromophenol, 3-bromophenol 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, 4-iodophenol, 3-iodophenol, 2-iodophenol, 4-bromo-2-methylphenol, 4- Bromo-3-methylphenol, 4-bromo-2,6-dimethylphenol, 4-bromo-3,5-dimethylphenol, 4-bromo-2,6-di-tert-butylphenol, 4-chloro-1-naphthol 1-bromo-2-naphthol, 6-bromo-2-naphthol, 4-bromo-4 ′ Halogenated phenol compounds such as hydroxybiphenyl after reacting a compound having intramolecular polarization obtained by dehydrohalogenation (JP 2004-156036 JP) and the like.

  When these curing accelerators are used in combination, from the viewpoint of fluidity, a compound having an intramolecular polarization formed by adding a compound having an organic phosphines and a π bond, an organic phosphine and a halogenated phenol compound are reacted. Later, a compound having intramolecular polarization obtained by dehydrohalogenation, and from the viewpoint of curability, intramolecular polarization obtained by reacting an organic phosphine with a halogenated phenol compound, followed by a dehydrohalogenation step. A compound having is preferred.

(E) If the hardening acceleration effect is achieved, there will be no restriction | limiting in particular the compounding quantity of a hardening accelerator.
However, from the viewpoint of improving the curability and fluidity at the time of moisture absorption of the epoxy resin composition, the total amount of the (E) curing accelerator is preferably 0.1 to 100 parts by weight of the total (A) epoxy resin. It is desirable to blend 10 parts by weight, more preferably 1 to 7.0 parts by weight. If the blending amount of the curing accelerator is less than 0.1 parts by weight, it is difficult to cure in a short time, and if it exceeds 10 parts by weight, the curing rate may be too high to obtain a good molded product.

(Various additives)
In the epoxy resin composition according to the present invention, the above-described components (A) epoxy resin, (B) curing agent, (C) silicone compound, (D) inorganic filler, and (E) curing accelerator are optionally included. In addition, various additives such as a coupling agent, an ion exchanger, a flame retardant, a release agent, a flexible agent, and a colorant exemplified below may be added.
However, the epoxy resin composition according to the present invention is not limited to the following additives, and various additives known in the art may be added as necessary.

(Coupling agent)
The epoxy resin composition of the present invention includes various silanes such as epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane, and vinyl silane as necessary in order to enhance the adhesion between the resin component and the inorganic filler. Known coupling agents such as compounds, titanium compounds, aluminum chelates, and aluminum / zirconium compounds can be added.

  The blending amount of the coupling agent is preferably 0.05 to 5% by weight, more preferably 0.1 to 2.5% by weight with respect to (D) the inorganic filler. If it is less than 0.05% by weight, the adhesion to the frame tends to be lowered, and if it exceeds 5% by weight, the moldability of the package tends to be lowered.

  Examples of the coupling agent include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, 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-amino Til) aminopropyldimethoxymethylsilane, N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxymethylsilylisopropyl) ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, N-β- (N-vinyl) Silane coupling agents such as (benzylaminoethyl) -γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, isopropyltriisostearoyl titanate , Isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, tetraoctyl bis (ditri Decyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, isopropyl triocta Titanates such as noyl 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 Coupling agents, etc., and these can be used alone It may be used in combination on. Among these, a coupling agent having a secondary amino group is preferable from the viewpoint of fluidity and wire flow.

(Ion exchanger)
An anion exchanger can be mix | blended with the epoxy resin composition of this invention as needed. In particular, when an epoxy resin composition is used as a molding material for sealing, it is preferable to blend an anion exchanger from the viewpoint of improving the moisture resistance and high-temperature standing characteristics of an electronic component device including an element to be sealed. .

  The anion exchanger used in the present invention is not particularly limited, and conventionally known anion exchangers can be used. For example, hydrotalcite, water content of an element selected from magnesium, aluminum, titanium, zirconium and bismuth can be used. An oxide etc. are mentioned, These can be used individually or in combination of 2 or more types. Especially, the hydrotalcite shown by the following general formula (XIX) is preferable.

（０＜Ｘ≦０．５、ｍは正の数）

(0 <X ≦ 0.5, m is a positive number)

  The amount of these anion exchangers is not particularly limited as long as it is a sufficient amount capable of capturing anions such as halogen ions, but is preferably in the range of 0.1 to 30% by weight with respect to (A) the epoxy resin. 1 to 5% by weight is more preferable.

(Flame retardants)
In the epoxy resin composition of the present invention, a flame retardant can be blended as necessary to impart flame retardancy. There is no restriction | limiting in particular as a flame retardant used in this invention, For example, the well-known organic or inorganic compound and metal hydroxide containing a halogen atom, an antimony atom, a nitrogen atom, or a phosphorus atom are mentioned, These 1 type is mentioned. It may be used alone or in combination of two or more. Although there will be no restriction | limiting in particular if the flame-retardant effect is achieved, the compounding quantity of a flame retardant is 1-30 weight% with respect to (A) epoxy resin, and 2-15 weight% is more preferable.

(Release agent)
In the epoxy resin composition of the present invention, a mold release agent may be blended in order to give good mold releasability from the mold during molding.
There is no restriction | limiting in particular as a mold release agent used in this invention, A conventionally well-known thing can be used.

  Examples include higher fatty acids such as carnauba wax, montanic acid and stearic acid, higher fatty acid metal salts, ester waxes such as montanic acid esters, polyolefin waxes such as polyethylene oxide and non-oxidized polyethylene, and the like. It may be used alone or in combination of two or more. Among these, higher fatty acids, oxidized or non-oxidized polyolefin-based waxes are preferable, and the blending amount thereof is preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight with respect to (A) the epoxy resin. preferable.

  If the blending amount of the polyolefin wax is less than 0.01% by weight, the releasability tends to be insufficient, and if it exceeds 10% by weight, the adhesiveness may be inhibited. As a higher fatty acid, for example, carnauba wax manufactured by Celerica NODA Co., Ltd. may be mentioned as a commercially available product.

  Examples of the polyolefin-based wax include low molecular weight polyethylene having a number average molecular weight of about 500 to 10,000 such as H4, PE, and PED series manufactured by Hoechst. Moreover, when using another mold release agent together with polyolefin-type wax, 0.1 to 10 weight% is preferable with respect to (A) epoxy resin, and 0.5 to 3 weight% is more preferable.

(Flexible agent)
In the epoxy resin composition of the present invention, a flexible agent such as silicone oil and silicone rubber powder can be used in combination with the silicone compound (C) as necessary.
The flexible agent that can be used in combination is not particularly limited as long as it is a known flexible agent that is generally used.

  For example, silicone-based, styrene-based, olefin-based, urethane-based, polyester-based, polyether-based, polyamide-based, polybutadiene-based thermoplastic elastomers, NR (natural rubber), NBR (acrylonitrile-butadiene rubber), acrylic rubber, urethane It has a core-shell structure such as rubber, rubber particles such as silicone powder, methyl methacrylate-styrene-butadiene copolymer (MBS), methyl methacrylate-silicone copolymer, methyl methacrylate-butyl acrylate copolymer, etc. Examples thereof include rubber particles. One of these flexible agents may be used alone, or two or more thereof may be combined.

(Coloring agent)
You may mix | blend well-known colorants, such as carbon black, an organic dye, an organic pigment, a titanium oxide, a red lead, a bengara, with the epoxy resin composition of this invention.

(Preparation of epoxy resin composition)
The epoxy resin composition of the present invention can be prepared by any method as long as various components can be uniformly dispersed and mixed. As a general technique, there can be mentioned a method in which components of a predetermined blending amount are sufficiently mixed with a mixer or the like, then melt-kneaded with a mixing roll, an extruder or the like, and then cooled and pulverized.

More specifically, for example, a method of uniformly stirring and mixing predetermined amounts of the above-described components, kneading with a kneader, roll, extruder, or the like that has been heated to 70 to 140 ° C., cooling, pulverizing, etc. Can be obtained at
The epoxy resin composition is easy to handle when it is tableted with a size and weight suitable for the molding conditions of the package.

(Electronic component equipment)
The electronic component device according to the present invention includes an element sealed with the epoxy resin composition of the present invention. Electronic component devices include, for example, lead frames, wired tape carriers, wiring boards, glass, silicon wafers, and other supporting members, active elements such as semiconductor chips, transistors, diodes, thyristors, capacitors, resistors, coils, etc. And those in which the element portion is sealed with the epoxy resin composition of the present invention.

  More specifically, for example, after fixing a semiconductor element on a lead frame and connecting the terminal part of the element such as a bonding pad and the lead part by wire bonding or bump, the transfer is performed using the epoxy resin composition of the present invention. DP (Dual nlne Package), PLCC (Plastc Leaded Chopper), QFP (Quad Flat Package), SOP (Small Outlet Package), SOJ (Small Outlet Jl-Lead Package) General resin-encapsulated type C such as Outline Package), TQFP (Thn Quad Flat Package), semiconductor chip connected to tape carrier by bump , TCP (Tape Carrage Package) sealed with the epoxy resin composition of the present invention, semiconductor chip, transistor, diode, thyristor connected to wiring formed on a wiring board or glass by wire bonding, flip chip bonding, solder, etc. COB (Chip On Board) module, hybrid C, multi-chip module, and wiring board connected to the back side, in which active elements such as capacitors and / or passive elements such as capacitors, resistors, and coils are sealed with the epoxy resin composition of the present invention After mounting the element on the surface of the organic substrate on which the terminal for forming is formed, connecting the element and the wiring formed on the organic substrate by bump or wire bonding, the element is sealed with the epoxy resin composition of the present invention BGA ( Ball Grd Array), CSP (Chp Sze) Package).

Moreover, the epoxy resin composition of this invention can be used effectively also in a printed circuit board.
As a method for sealing an electronic component device using the epoxy resin composition 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 Hereinafter, although an Example demonstrates this invention more concretely, this invention is not restrict | limited to these Examples.
[Preparation of epoxy resin composition and evaluation of properties]
(Examples 1-6 and Comparative Examples 1-7)

(A) Epoxy resin Epoxy resin 1: Mixture of biphenyl aralkyl type epoxy resin and biphenyl type epoxy resin having an epoxy equivalent of 241 and a softening point of 89 ° C. (trade name “CER-3000L” manufactured by Japan Epoxy Resin Co., Ltd.).
Epoxy resin 2: Biphenyl type epoxy resin having an epoxy equivalent of 196 and a melting point of 106 ° C. (trade name “YX-4000H” manufactured by Japan Epoxy Resin Co., Ltd.).

(B) Curing agent Curing agent 1: Biphenylene skeleton-containing phenol aralkyl resin (Maywa Kasei Co., Ltd., trade name “MEH-7851”) having a hydroxyl group equivalent of 199 and a softening point of 89 ° C.
Curing agent 2: Triphenylmethane type phenol resin having a hydroxyl group equivalent of 104 and a softening point of 83 ° C. (Madewa Kasei Co., Ltd., trade name “MEH-7500”).
Curing agent 3: Novolak type phenol resin having a hydroxyl group equivalent of 106 and a softening point of 82 ° C. (trade name “HP-850N”, manufactured by Hitachi Chemical Co., Ltd.).

(C) Silicone Compound Silicone Compound 1: Polydimethylsilicone having both end hydroxyl groups having a viscosity of 90 mm ² / s and a number average molecular weight Mn3095 (trade name “PRX-413” manufactured by Toray Dow Corning Co., Ltd.).
Silicone compound 2: silicone having a number average molecular weight Mn of 6179 and a weight ratio of the above (I-2) and (I-3) units of (I-2) / (I-3) = 5/5 (developed by Wacker, developed Product number SLJ1661-02).
Silicone compound 3: Silicone having a number average molecular weight Mn of 6000 and a weight ratio of the above (I-2) and (I-3) units of (I-2) / (I-3) = 7/3 (developed by Wacker, developed) Product number SLJ1734).

  The number average molecular weight Mn used above is obtained by a gel per emission chromatography (GPC) method. 1 mg of the compound is dissolved in 1 ml of toluene (silicone compound 1) or tetrahydrofuran (silicone compounds 2 and 3) to form a solution, and GPC as a pump (manufactured by Hitachi, Ltd., L-6200 type), column (manufactured by Tosoh Corporation) TSKgel-G2000HXL and TSKgel-G1000HXL), detector (manufactured by Hitachi, Ltd., L-3300R type), toluene (silicone compound 1) or tetrahydrofuran (silicone compounds 2 and 3) as an eluent at a temperature of 30 ° C. The measurement was performed under the condition of a flow rate of 1.0 ml / mn, and calculation was performed using a standard polystyrene calibration curve.

(D) Inorganic filler Fused silica: Spherical fused silica having an average particle size of 17.5 μm and a specific surface area of 3.8 m ² / g.
(E) Curing accelerator An addition reaction product of tributylphosphine and 1,4-benzoquinone.

(Other various additives)
Coupling agent: Epoxy silane (γ-glycidoxypropyltrimethoxysilane).
Colorant: Carbon black (trade name “MA-100” manufactured by Mitsubishi Chemical Corporation).
Mold release agent: Carnauba wax (manufactured by Celerica NODA).

  The epoxy resin compositions of Examples 1 to 6 and Comparative Examples 1 to 7, respectively, were prepared by blending the above components in parts by weight shown in Table 1 and performing roll kneading under conditions of a kneading temperature of 80 ° C. and a kneading time of 15 minutes. I got a thing.

  Next, each epoxy resin composition obtained by Examples 1-6 and Comparative Examples 1-7 was evaluated by each test shown below. The evaluation results are shown in Tables 1 and 2. The epoxy resin composition was molded using 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 175 ° C. for 6 hours.

(1) The spiral flow epoxy resin composition was molded using a spiral flow measurement mold according to EMM-1-66 under the above conditions, and the flow distance (cm) was determined.

(2) Flexural modulus Using Tensilon manufactured by A & D, a three-point support bending test based on JS-K-6911 was performed at room temperature (25 ° C.) to determine the elastic modulus. For the measurement, a test piece having dimensions of 70 mm × 10 mm × 3 mm was used.

(3) Adhesive strength An epoxy resin composition was molded on the surface of a solder resist (manufactured by Taiyo Ink Manufacturing Co., Ltd., trade name “PSR-4000AUS5”) to a diameter of 3.6 mm and a height of 3 mm, and a bond tester manufactured by Dage Precision Industries. Was used to measure the strength at which the molded product peeled off by applying a shear stress under the conditions of a head speed of 150 μm / sec and 260 ° C.

(4) Molding shrinkage rate It measured according to the test method based on JS-K-6911.

  As shown in Table 1, it is clear that Examples 1 to 6 containing the silicone compound (C) according to the present invention are all excellent in fluidity, elastic modulus reduction effect, adhesiveness and molding shrinkage. It is.

  On the other hand, as shown in Table 2, Comparative Example 1 and Comparative Example 4 containing no silicone are inferior in the elastic modulus reducing effect and molding shrinkage, and S-is present at both ends shown in the above (c1). In Comparative Examples 2 and 5 using only the silicone compound having OH, the fluidity is greatly reduced, and Comparative Examples 3, 6 and 7 using only the silicone compound represented by (c2) are molded. It is clear that the shrinkage is inferior.

  Therefore, the epoxy resin composition containing the (C) silicone compound according to the present invention can provide an epoxy resin composition excellent in fluidity, low stress, adhesion and dimensional stability, and is extremely suitable industrially. It is.

Claims (14)

(A) An epoxy resin, (B) a curing agent, and (C) an epoxy resin composition containing a silicone compound, of which (C) the silicone compound is (c1) both represented by the following general formula (I-1) An epoxy resin composition comprising both a silicone compound having S-OH at the terminal and (c2) a silicone block copolymer compound containing units represented by the following general formulas (I-2) and (I-3) .

(In Formula (I-1), I is an integer of 1 or more, R ¹ is selected from monovalent hydrocarbon groups optionally having a substituent having 1 to 18 carbon atoms, and all are the same or different. May be.)

(In formula (I-2), R ² is selected from divalent hydrocarbon groups which may have a substituent having 1 to 18 carbon atoms.)

(In Formula (I-3), R ³ is selected from monovalent hydrocarbon groups which may have a substituent having 1 to 18 carbon atoms, and all may be the same or different.)   (C) The epoxy resin composition according to claim 1, wherein in the silicone compound, the ratio of (c1) to the total weight of the silicone compound is 30% by weight or more.   (C) The epoxy resin composition according to claim 1 or 2, wherein in the silicone compound, the proportion of the above (c2) in the total weight of the silicone compound is 15% by weight or more.   The epoxy resin composition according to claim 1, wherein (C) the silicone compound is contained in an amount of 1 to 50 parts by weight with respect to 100 parts by weight of the (A) epoxy resin.   (C) In the silicone compound, the number average molecular weight Mn of the above (c1) is 500 to 30000. The epoxy resin composition according to any one of claims 1 to 4.   (C) In the silicone compound, the number average molecular weight Mn of the above (c2) is 2000 to 20000. The epoxy resin composition according to any one of claims 1 to 5.   (C) In the silicone compound, the weight ratio of the above general formulas (I-2) and (I-3) in the above (c2) is (I-2) / (I-3) = 3/7 to 7/3. The epoxy resin composition according to any one of claims 1 to 6.   (C) In the silicone compound, (c2) is a triblock copolymer having a (I-2)-(I-3)-(I-2) type structure. Epoxy resin composition. (C) In the silicone compound, (c2) is a silicone block copolymer compound represented by the following general formula (I-4): The epoxy resin composition according to any one of claims 1 to 8.

(In formula (I-4), m ₁ + m ₂ is an integer of 1 or more, n is an integer of 1 or more, and R ⁴ is a monovalent hydrocarbon group optionally having a substituent having 1 to 18 carbon atoms. All may be the same or different, and R ⁵ is selected from divalent hydrocarbon groups optionally having a substituent having 1 to 18 carbon atoms, and all may be the same or different. R ⁶ is selected from divalent hydrocarbon groups which may have a substituent having 1 to 18 carbon atoms, and all may be the same or different.   The epoxy resin composition formed by further containing (D) an inorganic filler in the epoxy resin composition according to claim 1.   The epoxy resin composition according to any one of claims 1 to 10, further comprising (E) a curing accelerator in the epoxy resin composition according to any one of claims 1 to 10.   (A) epoxy resin is biphenyl type epoxy resin, stilbene type epoxy resin, diphenylmethane type epoxy resin, sulfur atom containing type epoxy resin, novolac type epoxy resin, dicyclopentadiene type epoxy resin, salicylaldehyde type epoxy resin, naphthols The epoxy resin composition according to any one of claims 1 to 11, comprising at least one selected from a copolymerization type epoxy resin with phenols and an epoxidized product of an aralkyl type phenol resin.   (B) The curing agent is selected from a biphenylene skeleton-containing phenol aralkyl resin, a phenol aralkyl resin, a naphthol aralkyl resin, a dicyclopentadiene type phenol resin, a triphenylmethane type phenol resin, a novolac type phenol resin, and a copolymer type phenol aralkyl resin. The epoxy resin composition according to any one of claims 1 to 12, comprising at least one kind.   The electronic component apparatus provided with the element sealed with the epoxy resin composition in any one of Claims 1-13.