JP6950299B2 - Resin composition for encapsulant and electronic device using it - Google Patents

Description

The present invention relates to a resin composition for a sealing material and an electronic device using the same.

Various techniques have been developed for the purpose of improving the fluidity of the encapsulant for mold underfill used in the manufacture of electronic devices. Examples of this type of technology include the technology described in Patent Document 1. According to Patent Document 1, when a filler surface-treated with N-phenyl-3-aminopropyltrimethoxysilane is mixed with a resin material, a small viscosity can be realized in a wide range of share rates. .. Further, according to Patent Document 1, when a resin composition is prepared using a filler surface-treated with N-phenyl-3-aminopropyltrimethoxysilane, it is effective in reducing the cohesiveness of the filler. It is stated that.

JP-A-2015-140389

The present inventor has investigated the moldability when sealing a semiconductor package using a sealing resin composition. As a result, it was considered that the encapsulant for mold underfill described in Patent Document 1 has room for further improvement from the viewpoint of moldability.

In recent years, in the field of sealing resin compositions used for sealing flip-chip type semiconductor packages, it is required to reduce the gap between the package and the substrate. As a result of examination by the present inventor, the mold underfill material described in Patent Document 1 has such characteristics as the filling property of the sealing resin composition into an electronic device and the uniformity of the molded product obtained by curing the sealing resin composition. There was room for further improvement in terms of moldability.

As a result of investigating the cause of the decrease in moldability, the inventor of the present application has found that self-aggregation of the filler occurs in the sealing resin composition and clogging occurs in the gap between the package and the substrate. Further, it was found that the viscosity of the sealing resin composition becomes non-uniform in the molding process, so that the fluidity of the sealing resin composition decreases when the sealing resin composition is filled in the mold. bottom. Based on the above, the present invention provides a sealing resin composition having excellent moldability such as filling property of the sealing resin composition into an electronic device and uniformity of a molded product obtained by curing the sealing resin composition. The task is to do.

The present inventor has studied the raw materials of the sealing resin composition in order to improve the moldability of the sealing resin composition. As a result, it has been found that when the sealing resin composition contains a silane compound having a specific structure, a good effect of improving moldability can be obtained.
First, the present inventor considered to make a secondary or tertiary amine by introducing a nitrogen atom into a silane compound. This is because the conformation of the silane compound is considered to be effective in arranging the organic groups that chemically bond with the filler, using the triangular pyramid type, which is the conformation of the nitrogen atom, as the skeleton. Furthermore, of the three organic groups bonded to the nitrogen atom, one was designated as an organic group having active hydrogen, and two were designated as organic groups having a methoxy group or an ethoxy group at the ends. From the above, the present inventor has found that a good effect on moldability can be obtained by adopting a silane compound having a specific structure, and the present invention has been completed.

According to the present invention
Epoxy resin and
Hardener and
Filler and
A silane compound represented by the following general formula (1) and
A sealing material for a resin composition comprising,
The content of the filler is 70% by mass or more and 90% by mass or less with respect to 100% by mass of the total solid content of the resin composition for a sealing material.
Provided is a resin composition for a sealing material, wherein the cumulative 50% particle size D _{50 based on} the volume of the filler is 1.0 μm or more and 10.0 μm or less.

（上記一般式（１）中、Ｘは、下記一般式（Ｘ１）または（Ｘ２）を表す。
Ｒ^２及びＲ^３はそれぞれ独立して炭素数１以上１０以下の有機基を表す。
Ａはそれぞれ独立して、炭素数１以上１０以下の有機基を表す。Ａは互いに同一でもよく、互いに異なっていてもよい。Ａのうち少なくとも一つはメトキシ基またはエトキシ基である。
Ｂはそれぞれ独立して、炭素数１以上１０以下の有機基を表す。Ｂは互いに同一でもよく、互いに異なっていてもよい。Ｂのうち少なくとも一つはメトキシ基またはエトキシ基である。）

(In the above general formula (1), X represents the following general formula (X1) or (X2).
R ² and R ³ independently represent an organic group having 1 or more and 10 or less carbon atoms.
Each of A independently represents an organic group having 1 or more and 10 or less carbon atoms. A may be the same as each other or different from each other. At least one of A is a methoxy group or an ethoxy group.
Each B independently represents an organic group having 1 or more and 10 or less carbon atoms. B may be the same as each other or different from each other. At least one of B is a methoxy group or an ethoxy group. )

（上記一般式（Ｘ１）中、
＊^２は上記一般式（１）のＲ^２と結合することを表し、
＊^３は上記一般式（１）のＲ^３と結合することを表し、
Ｒ^１は独立して水素原子又は活性水素を有する炭素数１以上１０以下の有機基を表す。）

(In the above general formula (X1),
* ² represents a bond with ^{R 2} in formula (1),
* ³ represents a bond with ^{R 3} in formula (1),
R ¹ represents an organic group having 1 to 10 carbon atoms independently having a hydrogen atom or active hydrogen. )

（上記一般式（Ｘ２）中、
＊^２は上記一般式（１）のＲ^２と結合することを表し、
＊^３は上記一般式（１）のＲ^３と結合することを表し、
Ｒ^１はそれぞれ独立して水素原子又は活性水素を有する炭素数１以上１０以下の有機基を表す。Ｒ^１は互いに同一でもよく、互いに異なっていてもよい。
Ｒ^Ｘは炭素数１以上１０以下の有機基を表す。）

(In the above general formula (X2),
* ² represents a bond with ^{R 2} in formula (1),
* ³ represents a bond with ^{R 3} in formula (1),
R ¹ represents an organic group having 1 or more and 10 or less carbon atoms, each independently having a hydrogen atom or active hydrogen. R ¹ may be mutually the same or may be different from each other.
R ^X represents at least one but no more than 10 organic group having a carbon number. )

Further, according to the present invention.
With electronic devices
And and a molded body that seals the electronic element,
An electronic device is provided in which a cured product of the above-mentioned resin composition for a sealing material is used as the molded product.

According to the present invention, the dispersibility of the filler is excellent, and the moldability such as the filling property into an electronic device, the filling property into a mold, and the uniformity of a molded product obtained by curing a resin composition for sealing is improved. A resin composition for sealing can be provided.

It is sectional drawing of an example of the electronic device which concerns on this embodiment.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all drawings, similar components are designated by the same reference numerals, and description thereof will be omitted as appropriate.

The sealing resin composition according to the present embodiment contains an epoxy resin, a curing agent, a filler, and a silane compound having a specific structure represented by the following general formula (1).

（上記一般式（１）中、Ｘは、下記一般式（Ｘ１）または（Ｘ２）を表す。
Ｒ^２及びＲ^３はそれぞれ独立して炭素数１以上１０以下の有機基を表す。
Ａはそれぞれ独立して、炭素数１以上１０以下の有機基を表す。Ａは互いに同一でもよく、互いに異なっていてもよい。Ａのうち少なくとも一つはメトキシ基またはエトキシ基である。
Ｂはそれぞれ独立して、炭素数１以上１０以下の有機基を表す。Ｂは互いに同一でもよく、互いに異なっていてもよい。Ｂのうち少なくとも一つはメトキシ基またはエトキシ基である。）

(In the above general formula (1), X represents the following general formula (X1) or (X2).
R ² and R ³ independently represent an organic group having 1 or more and 10 or less carbon atoms.
Each of A independently represents an organic group having 1 or more and 10 or less carbon atoms. A may be the same as each other or different from each other. At least one of A is a methoxy group or an ethoxy group.
Each B independently represents an organic group having 1 or more and 10 or less carbon atoms. B may be the same as each other or different from each other. At least one of B is a methoxy group or an ethoxy group. )

（上記一般式（Ｘ１）中、
＊^２は上記一般式（１）のＲ^２と結合することを表し、
＊^３は上記一般式（１）のＲ^３と結合することを表し、
Ｒ^１は独立して水素原子又は活性水素を有する炭素数１以上１０以下の有機基を表す。）

(In the above general formula (X1),
* ² represents a bond with ^{R 2} in formula (1),
* ³ represents a bond with ^{R 3} in formula (1),
R ¹ represents an organic group having 1 to 10 carbon atoms independently having a hydrogen atom or active hydrogen. )

（上記一般式（Ｘ２）中、
＊^２は上記一般式（１）のＲ^２と結合することを表し、
＊^３は上記一般式（１）のＲ^３と結合することを表し、
Ｒ^１はそれぞれ独立して水素原子又は活性水素を有する炭素数１以上１０以下の有機基を表す。Ｒ^１は互いに同一でもよく、互いに異なっていてもよい。
Ｒ^Ｘは炭素数１以上１０以下の有機基を表す。）

(In the above general formula (X2),
* ² represents a bond with ^{R 2} in formula (1),
* ³ represents a bond with ^{R 3} in formula (1),
R ¹ represents an organic group having 1 or more and 10 or less carbon atoms, each independently having a hydrogen atom or active hydrogen. R ¹ may be mutually the same or may be different from each other.
R ^X represents at least one but no more than 10 organic group having a carbon number. )

From various experimental results, the present inventor has found that the silane compound represented by the above general formula (1) improves the dispersibility of the filler. That is, it was considered to introduce a nitrogen atom into the silane compound to obtain a secondary or tertiary amine. As the structure of the silane compound, it is effective that two of the organic groups bonded to the nitrogen atom are organic groups having a methoxy group or an ethoxy group at the terminals and one is an organic group having active hydrogen. I found that.

In the sealing resin composition containing the silane compound represented by the general formula (1), the dispersibility of the filler is improved as compared with the case where the conventional silane compound is contained. This makes it possible to prevent clogging due to self-aggregation of the filler and non-uniform viscosity of the sealing resin composition in the molding process. Thereby, the moldability of the sealing resin composition can be improved.

The reason why the dispersibility of the filler is improved in the sealing resin composition according to the present embodiment is presumed as follows, although the detailed mechanism is not clear.
As a premise, the organic groups that are chemically bonded to the filler are also bonded to each other. As a result, the molecule of the silane compound having an organic group that chemically bonds with the plurality of fillers binds to the filler and the molecule of the free silane compound. In the conventional silane compound, the conformation is not controlled, and the organic groups chemically bonded to the plurality of fillers are oriented in random directions with each other. As a result, the organic group chemically bonded to the filler is randomly bonded to the molecule of the filler and the free silane compound. Therefore, the fillers agglomerate with each other via the silane compound to form an agglomerate, and the agglomerate causes a decrease in moldability.

On the other hand, the conformation of the molecule of the silane compound according to the present embodiment has a nitrogen atom as a skeleton, and three organic groups bonded to nitrogen are arranged in a triangular pyramid shape. Of the above three organic groups, two are organic groups having a methoxy group or an ethoxy group at the terminal, and one is an organic group having active hydrogen. Here, the organic group having a methoxy group or an ethoxy group is an organic group that chemically bonds with a filler. The organic group having active hydrogen is an organic group that chemically bonds with an epoxy resin.
An organic group having a methoxy group or an ethoxy group at two ends arranged in a triangular cone-shaped conformation is derived from the conformation when the methoxy group or ethoxy group at one end is bonded to a filler. Due to molecular orbital restrictions, another terminal methoxy or ethoxy group is more likely to bind to the filler. It is considered that the organic group bonded to the packing material having such restrictions on the molecular orbital has a lower probability of binding to the free silane compound than the organic group in the conventional silane compound which is oriented in a random direction with each other.
Therefore, in the sealing resin composition according to the present embodiment, by containing the silane compound represented by the above general formula (1), it is possible to prevent the fillers from aggregating with each other via the silane compound, and to prevent the fillers from aggregating with each other. It is presumed that the dispersibility can be improved.

The skeleton containing the nitrogen atom of the silane compound according to the present embodiment is a monoamine type skeleton represented by the general formula (X1) or a diamine type skeleton represented by the general formula (X2). Can be mentioned. By having the skeleton represented by the general formula (X1) or the general formula (X2), it is possible to prevent the fillers from agglutinating with each other via the silane compound and improve the dispersibility of the fillers.

Hereinafter, each component constituting the sealing resin composition according to the present embodiment will be described in detail.
The sealing resin composition according to the present embodiment contains an epoxy resin, a curing agent, a filler, and a specific silane compound represented by the above general formula (1).

(Epoxy resin)
The sealing resin composition according to this embodiment contains an epoxy resin. As the epoxy resin, a monomer, an oligomer, or a polymer having two or more epoxy groups in one molecule can be used in general, and the molecular weight and molecular structure thereof are not limited.
Specific examples of the epoxy resin include biphenyl type epoxy resin; bisphenol A type epoxy resin, bisphenol F type epoxy resin, tetramethyl bisphenol F type epoxy resin and other bisphenol type epoxy resin; stillben type epoxy resin; phenol novolac type epoxy resin. , Novolak type epoxy resin such as cresol novolac type epoxy resin; polyfunctional epoxy resin such as triphenol methane type epoxy resin, alkyl modified triphenol methane type epoxy resin and the like; phenol having a phenylene skeleton Phenol aralkyl type epoxy resin such as aralkyl type epoxy resin, naphthol aralkyl type epoxy resin having a phenylene skeleton, phenol aralkyl type epoxy resin having a biphenylene skeleton, naphthol aralkyl type epoxy resin having a biphenylene skeleton; dihydroxynaphthalene type epoxy resin, dihydroxynaphthalene Naftor-type epoxy resin such as epoxy resin obtained by glycidyl etherification of the dimer of Includes one or more selected from the group consisting of bridge cyclic hydrocarbon compound modified phenolic epoxy resins.
Among these, it is preferable to include one or more types selected from the group consisting of biphenyl type epoxy resin, bisphenol type epoxy resin, phenol aralkyl type epoxy resin and polyfunctional epoxy resin, and phenol aralkyl type epoxy resin and many. It is more preferable to include a functional epoxy resin. As the polyfunctional epoxy resin, for example, it is preferable to use a triphenol methane type epoxy resin. This facilitates the bonding between the silane compound and the epoxy resin. Then, it is presumed that the possibility that the silane couplings are bonded to each other is reduced as compared with the case where other epoxy resins are used. Therefore, the dispersibility of the filler in the sealing resin composition can be improved.

In the present embodiment, the lower limit of the content of the epoxy resin in the sealing resin composition is, for example, 1% by mass or more with respect to 100% by mass of the total solid content of the sealing resin composition. It is preferably 3% by mass or more, more preferably 5% by mass or more. Thereby, the fluidity at the time of molding can be improved. Therefore, it is possible to improve the filling property and the molding stability.
Further, the upper limit of the content of the epoxy resin in the sealing resin composition is preferably, for example, 15% by mass or less with respect to 100% by mass of the total solid content of the sealing resin composition. It is more preferably mass% or less, and further preferably 13 mass% or less. Thereby, the dispersibility of the filler in the sealing resin composition can be improved.
In the present embodiment, the total solid content of the sealing resin composition indicates the total amount of the raw material components excluding the solvent.

(Hardener)
The sealing resin composition according to the present embodiment contains a curing agent. Specific examples of the curing agent contained in the sealing resin composition include a polyaddition type curing agent, a catalyst type curing agent, and a condensation type curing agent.

Specific examples of the heavy addition type curing agent include aliphatic polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), and metaxylerylene diamine (MXDA); diaminodiphenylmethane (DDM), m-phenylene. Aromatic polyamines such as diamine (MPDA) and diaminodiphenylsulfone (DDS); polyamine compounds such as dicyandiamide (DICY) and organic acid dihydralide; alicyclic such as hexahydrophthalic anhydride (HHPA) and methyltetrahydrophthalic anhydride (MTHPA). Group Acid Anhydrides; Acid anhydrides such as aromatic acid anhydrides such as trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), benzophenone tetracarboxylic acid (BTDA); novolak type phenolic resin, polyvinylphenol, aralkyl Examples thereof include phenol resin-based curing agents such as type phenol resins; polyether compounds such as polysulfide, thioester and thioether; isocyanate compounds such as isocyanate prepolymer and blocked isocyanate; and organic acids such as carboxylic acid-containing polyester resin. As the heavy addition type curing agent, one or a combination of two or more of the above specific examples can be used.

Specific examples of the catalytic curing agent include tertiary amine compounds such as benzyldimethylamine (BDMA) and 2,4,6-trisdimethylaminomethylphenol (DMP-30); 2-methylimidazole, 2 Examples include imidazole compounds such as −ethyl-4-methylimidazole (EMI24); Lewis acids such as the BF3 complex. As the catalyst type curing agent, one or a combination of two or more of the above specific examples can be used.

Specific examples of the condensation type curing agent include a resol type phenol resin; a urea resin such as a methylol group-containing urea resin; and a melamine resin such as a methylol group-containing melamine resin. As the condensation type curing agent, one or a combination of two or more of the above specific examples can be used.

Among the above-mentioned curing agents, it is preferable to contain a phenol resin-based curing agent.
As the phenol resin-based curing agent, a monomer, an oligomer, or a polymer having two or more phenolic hydroxyl groups in one molecule can be used in general, and the molecular weight and molecular structure thereof are not limited.
The phenolic resin-based curing agent used as the curing agent is, for example, a novolak-type phenol resin such as a phenol novolac resin or a cresol novolak resin; a polyvinyl phenol; a polyfunctional phenol resin such as a phenol resin having a triphenylmethane skeleton; a terpene-modified phenol. Modified phenol resins such as resins and dicyclopentadiene-modified phenolic resins; phenol-aralkyl resins with phenylene and / or biphenylene skeletrons, phenol-aralkyl-type phenol resins such as phenylene and / or naphthol-aralkyl resins with biphenylene skeleins; bisphenol A, bisphenol Includes one or more selected from the group consisting of bisphenol compounds such as F.
Among these, from the viewpoint of improving the dispersibility of the filler in the sealing resin composition,
It is more preferable to contain one or more kinds selected from the group consisting of novolak type phenol resin, polyfunctional phenol resin and phenol aralkyl resin, and further preferably to contain polyfunctional phenol resin or phenol aralkyl resin. Thereby, the polarities of the silane compound and the curing agent can be brought close to each other, and the dispersibility of the silane compound in the sealing resin composition can be improved. Therefore, the dispersibility of the filler bonded to the silane compound can be improved.

In the present embodiment, the upper limit of the content of the curing agent in the sealing resin composition is, for example, 9% by mass or less with respect to 100% by mass of the total solid content of the sealing resin composition. It is more preferably 8% by mass or less, and even more preferably 7% by mass or less. Thereby, the fluidity at the time of molding can be improved. Therefore, it is possible to improve the filling property and the molding stability.
Further, the lower limit of the content of the curing agent in the sealing resin composition is preferably, for example, 0.5% by mass or more with respect to 100% by mass of the total solid content of the sealing resin composition. It is more preferably 1% by mass or more, and further preferably 1.5% by mass or more. As a result, good curability can be exhibited and good moldability can be exhibited.

(Filler)
The sealing resin composition according to the present embodiment contains a filler.
Specific examples of the filler include an inorganic filler and an organic filler. Among the above specific examples, the filler preferably contains an inorganic filler.

Specific examples of the inorganic filler include synthetic spherical silica, fused crushed silica, molten spherical silica, crystalline silica, secondary aggregated silica, and fine powder silica; alumina, silicon nitride, aluminum nitride, and boron nitride. Metal compounds such as titanium oxide, silicon carbide, aluminum hydroxide, magnesium hydroxide, titanium white; talc; clay; mica; glass fiber and the like can be mentioned. As the inorganic filler, one or a combination of two or more of the above specific examples can be used. Among the above specific examples, as the inorganic filler, silica such as synthetic spherical silica, molten crushed silica, molten spherical silica, crystalline silica, secondary aggregated silica, and fine powder silica is preferably used, and synthetic spherical silica or molten spherical silica is used. It is more preferable to use silica. Thereby, the dispersibility of the filler in the sealing resin composition can be improved.

Specific examples of the organic filler include organosilicone powder and polyethylene powder. As the organic filler, one or a combination of two or more of the above specific examples can be used.

The lower limit of the content of the filler in the sealing resin composition is preferably, for example, 70% by mass or more, preferably 73% by mass, based on 100% by mass of the total solid content of the sealing resin composition. It is more preferably 75% by mass or more, and further preferably 75% by mass or more. This makes it possible to more effectively improve the fluidity and filling property of the sealing resin composition during molding. Further, the physical characteristics of the sealing resin composition can be brought close to those of the filler, and the physical characteristics such as mechanical strength and thermal characteristics can be improved.
Further, the upper limit of the content of the filler in the sealing resin composition is preferably, for example, 90% by mass or less with respect to 100% by mass of the total solid content of the sealing resin composition, 88. It is more preferably mass% or less, and further preferably 85 mass% or less. As a result, the agglomeration of the filler can be prevented and the dispersibility of the filler can be improved.

In the present embodiment, the lower limit of the cumulative 50% particle size (D ₅₀ ) based on the volume of the filler is, for example, preferably 1.0 μm or more, and more preferably 2.0 μm or more. As a result, the productivity can be improved, the non-uniform viscosity at the time of molding of the sealing resin composition can be prevented, and the moldability can be improved.
The upper limit of the cumulative 50% particle size (D ₅₀ ) based on the volume of the filler is, for example, preferably 10.0 μm or less, and more preferably 8.0 μm or less. As a result, it is possible to reliably suppress the occurrence of gate clogging during molding.
For the cumulative 50% particle size (D ₅₀ ) based on the volume of the filler, for example, a commercially available laser diffraction type particle size distribution measuring device (for example, SALD-7000 manufactured by Shimadzu Corporation) is used to determine the particle size distribution of the particles. It can be measured and calculated on a volume basis.

(Silane compound)
The sealing resin composition of the present embodiment contains a silane compound.
The silane compound according to the present embodiment includes a compound represented by the following general formula (1).

（上記一般式（１）中、Ｘは、下記一般式（Ｘ１）または（Ｘ２）を表す。
Ｒ^２及びＲ^３はそれぞれ独立して炭素数１以上１０以下の有機基を表す。
Ａはそれぞれ独立して、炭素数１以上１０以下の有機基を表す。Ａは互いに同一でもよく、互いに異なっていてもよい。Ａのうち少なくとも一つはメトキシ基またはエトキシ基である。
Ｂはそれぞれ独立して、炭素数１以上１０以下の有機基を表す。Ｂは互いに同一でもよく、互いに異なっていてもよい。Ｂのうち少なくとも一つはメトキシ基またはエトキシ基である。）

(In the above general formula (1), X represents the following general formula (X1) or (X2).
R ² and R ³ independently represent an organic group having 1 or more and 10 or less carbon atoms.
Each of A independently represents an organic group having 1 or more and 10 or less carbon atoms. A may be the same as each other or different from each other. At least one of A is a methoxy group or an ethoxy group.
Each B independently represents an organic group having 1 or more and 10 or less carbon atoms. B may be the same as each other or different from each other. At least one of B is a methoxy group or an ethoxy group. )

The general formula of the silane compound according to the present embodiment is preferably the above general formula (1), more preferably the following general formula (2), and further preferably the following general formula (3). As a result, although the detailed mechanism is not clear, the length between the organic group having active hydrogen bonded to the nitrogen atom and the terminal methoxy group and ethoxy group is determined by the silane compound, the epoxy resin and the filler. It is speculated that they can be adjusted to the appropriate length for bonding. Therefore, the dispersibility of the filler in the sealing resin composition can be improved.

（上記一般式（２）中、Ｒ^２は、炭素数１以上１０以下の有機基を表す。
Ａはそれぞれ独立して、炭素数１以上１０以下の有機基を表す。Ａは互いに同一でもよく、互いに異なっていてもよい。Ａのうち少なくとも一つはメトキシ基またはエトキシ基である。
Ｂはそれぞれ独立して、炭素数１以上１０以下の有機基を表す。Ｂは互いに同一でもよく、互いに異なっていてもよい。Ｂのうち少なくとも一つはメトキシ基またはエトキシ基である。）

(In the above general formula (2), R ² represents an organic group having 1 or more and 10 or less carbon atoms.
Each of A independently represents an organic group having 1 or more and 10 or less carbon atoms. A may be the same as each other or different from each other. At least one of A is a methoxy group or an ethoxy group.
Each B independently represents an organic group having 1 or more and 10 or less carbon atoms. B may be the same as each other or different from each other. At least one of B is a methoxy group or an ethoxy group. )

（上記一般式（３）中、Ａはそれぞれ独立して、炭素数１以上１０以下の有機基を表す。Ａは互いに同一でもよく、互いに異なっていてもよい。Ａのうち少なくとも一つはメトキシ基またはエトキシ基である。
Ｂはそれぞれ独立して、炭素数１以上１０以下の有機基を表す。Ｂは互いに同一でもよく、互いに異なっていてもよい。Ｂのうち少なくとも一つはメトキシ基またはエトキシ基である。）

(In the above general formula (3), A independently represents an organic group having 1 or more and 10 or less carbon atoms. A may be the same as or different from each other. At least one of A is methoxy. Group or ethoxy group.
Each B independently represents an organic group having 1 or more and 10 or less carbon atoms. B may be the same as each other or different from each other. At least one of B is a methoxy group or an ethoxy group. )

X in the above general formula (1) is represented by the following general formula (X1) or the following general formula (X2). Among these, X is preferably represented by the following general formula (X1). Thereby, the dispersibility of the filler can be improved.

（上記一般式（Ｘ１）中、
＊^２は上記一般式（１）のＲ^２と結合することを表し、
＊^３は上記一般式（１）のＲ^３と結合することを表し、
Ｒ^１は独立して水素原子又は活性水素を有する炭素数１以上１０以下の有機基を表す。）

(In the above general formula (X1),
* ² represents a bond with ^{R 2} in formula (1),
* ³ represents a bond with ^{R 3} in formula (1),
R ¹ represents an organic group having 1 to 10 carbon atoms independently having a hydrogen atom or active hydrogen. )

（上記一般式（Ｘ２）中、
＊^２は上記一般式（１）のＲ^２と結合することを表し、
＊^３は上記一般式（１）のＲ^３と結合することを表し、
Ｒ^１はそれぞれ独立して水素原子又は活性水素を有する炭素数１以上１０以下の有機基を表す。Ｒ^１は互いに同一でもよく、互いに異なっていてもよい。
Ｒ^Ｘは炭素数１以上１０以下の有機基を表す。）

(In the above general formula (X2),
* ² represents a bond with ^{R 2} in formula (1),
* ³ represents a bond with ^{R 3} in formula (1),
R ¹ represents an organic group having 1 or more and 10 or less carbon atoms, each independently having a hydrogen atom or active hydrogen. R ¹ may be mutually the same or may be different from each other.
R ^X represents at least one but no more than 10 organic group having a carbon number. )

^{R 1} in the general formula (X1) and the general formula (X2) is an organic group having a hydrogen atom or active hydrogen and having 1 or more and 10 or less carbon atoms, and having hydrogen or active hydrogen and having 1 or more and 7 or less carbon atoms. It is preferably a group, more preferably an organic group having hydrogen or active hydrogen and having 1 or more and 5 or less carbon atoms, and further preferably an organic group having hydrogen or active hydrogen and having 1 or more and 3 or less carbon atoms. , Hydrogen is even more preferred. This makes it possible to improve the affinity between the filler and the epoxy resin via the silane compound. Therefore, the dispersibility of the filler in the sealing resin composition can be improved.

The general formula (X1), an organic group having 1 to 10 carbon atoms and having an active hydrogen of R ¹ in the general formula (X2) comprises a functional group having active hydrogen. The organic group containing active hydrogen is preferably one or more selected from the group consisting of a primary or secondary amino group, a carboxyl group, a vinyl group, a glycidyl group and a mercapto group. Among these, one or more selected from the group consisting of a primary or secondary amino group, a carboxyl group, and a vinyl group is preferable, and a primary or secondary amino group is more preferable. As a result, a crosslinked structure can be formed between the epoxy resin and the filler via the silane compound, and the dispersibility of the filler in the sealing resin composition can be improved.

The general formula (X1), specific examples of R ¹ in the general formula (X2), aminoethyl group, a primary or an organic group having a secondary amino group such as aminopropyl group, a carboxymethyl group, a carboxyethyl group, etc. Organic group having a carboxyl group of; Examples thereof include an organic group having a vinyl group such as a vinyl ethyl group and a vinyl propyl group. Among these, an aminoethyl group or an aminopropyl group is preferable. Thereby, the dispersibility of the filler in the sealing resin composition can be improved.

The general formula (X1), R ^X in the general formula (X2), an organic group having 1 to 10 carbon atoms, preferably an organic group having 1 to 7 carbon atoms, 1 to 5 carbon atoms It is more preferable that the organic group has 1 or more carbon atoms and 3 or less carbon atoms, and the organic group having 2 carbon atoms is particularly preferable. Thereby, the conformation of the silane compound can be suitably controlled, and the affinity between the filler via the silane compound and the epoxy resin can be improved. Therefore, the dispersibility of the filler in the sealing resin composition can be improved.

Specific examples of the RX having 1 or more and 10 or less carbon atoms in the general formula (X1) and the general formula (X2) include an alkylene group and the like. The alkylene group may be, for example, a linear alkylene group or a branched alkylene group.
As the linear alkylene group, methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decanylene group, trimethylene group, tetramethylene group, pentamethylene group, Hexamethylene groups and the like can be mentioned.
As the branched alkylene group, -C (CH ₃ ) _2- , -CH (CH ₃ )-, -CH (CH ₂ CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₃ )-, Alkylmethylene groups such as -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ )-, -C (CH ₂ CH ₃ ) _2- ; -CH (CH ₃ ) CH _2- , -CH (CH ₃ ) CH ( _{CH 3) -, - C (} CH 3) 2 CH 2 -, - CH (CH 2 CH 3) CH 2 -, - , and the like alkyl ethylene group, such as _{- C (CH 2 CH 3)} 2 -CH 2 ..
The R ^X, among the above examples, is preferably an alkylene group of linear shape. Thereby, the dispersibility of the filler in the sealing resin composition can be improved.

^{R 2} and R ³ in the above formula (1) are independently organic groups having 1 or more and 10 or less carbon atoms, preferably 1 or more and 7 or less carbon atoms, and have 1 or more and 5 carbon atoms. The following organic groups are more preferable, and organic groups having 1 or more and 3 or less carbon atoms are more preferable. It is presumed that this makes it possible to shorten the distance between the organic group that chemically bonds with the filler and the nitrogen atom. Then, it is presumed that by shortening the above distance, the probability that the organic group chemically bonded to the filler can be bonded to the molecule of the free silane compound can be reduced. Therefore, the dispersibility of the filler in the sealing resin composition can be improved.

Specific examples of the organic group having 1 or more and 10 or less carbon atoms ^{of R 2} and R ³ in the general formula (1) include an alkylene group and the like. The alkylene group may be, for example, a linear alkylene group or a branched alkylene group.
As the linear alkylene group, methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decanylene group, trimethylene group, tetramethylene group, pentamethylene group, Hexamethylene groups and the like can be mentioned.
As the branched alkylene group, -C (CH ₃ ) _2- , -CH (CH ₃ )-, -CH (CH ₂ CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₃ )-, Alkylmethylene groups such as -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ )-, -C (CH ₂ CH ₃ ) _2- ; -CH (CH ₃ ) CH _2- , -CH (CH ₃ ) CH ( _{CH 3) -, - C (} CH 3) 2 CH 2 -, - CH (CH 2 CH 3) CH 2 -, - , and the like alkyl ethylene group, such as _{- C (CH 2 CH 3)} 2 -CH 2 ..
Of the above specific examples, R ² and R ^{3 are preferably linear alkylene groups.} Thereby, the dispersibility of the filler in the sealing resin composition can be improved.

Each of A in the general formula (1) is independently an organic group having 1 or more and 10 or less carbon atoms, preferably an organic group having 1 or more and 7 or less carbon atoms, and an organic group having 1 or more and 5 or less carbon atoms. It is more preferably a group, and even more preferably an organic group having 1 or more and 3 or less carbon atoms. It is presumed that this will reduce the energy constraints around the organic group that binds to the filler. Therefore, the probability of bonding between the silane compound and the filler can be increased, and the dispersibility of the filler in the sealing resin composition can be improved.

Specific examples of the organic group having 1 or more and 10 or less carbon atoms of A in the general formula (1) include an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkoxy group, an alkaline group and a cycloalkyl group. The group is mentioned.
Alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group and octyl. Examples include a group, a nonyl group, and a decyl group. Examples of the alkenyl group include an allyl group, a pentenyl group, a vinyl group and the like. Examples of the alkynyl group include an ethynyl group. Examples of the alkylidene group include a methylidene group and an ethylidene group. Examples of the aryl group include a tolyl group, a xsilyl group, a phenyl group, a naphthyl group, an anthrasenyl group and the like. Examples of the aralkyl group include a benzyl group and a phenethyl group. Alkoxy groups include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, s-butoxy group, isobutoxy group, t-butoxy group, n-pentyloxy group, neopentyloxy group, n. -Hexyloxy groups and the like. Examples of the alkaline group include a tolyl group and a xylyl group. Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group and the like. Among these, an alkoxy group is preferable. Further, among the alkoxy groups, a methoxy group and an ethoxy group are preferable. Thereby, the dispersibility of the filler in the sealing resin composition can be improved.

At least one of A in the general formula (1) is preferably a methoxy group or an ethoxy group, two or three of A is preferably a methoxy group or an ethoxy group, and all of A are methoxy groups. Alternatively, it is preferably an ethoxy group. A methoxy group or an ethoxy group is an organic group that chemically bonds with a filler. Although the detailed mechanism is not clear, in the case of having a triangular pyramidal conformation such as the silane compound according to the present embodiment, the more organic groups chemically bonded to the filler, the more on the surface of the filler. It is presumed that the density of the silane compound can be improved. As a result, the affinity between the filler and the epoxy resin can be improved, and the dispersibility of the filler in the sealing resin composition can be improved.

Each of B in the general formula (1) is independently an organic group having 1 or more and 10 or less carbon atoms, preferably an organic group having 1 or more and 7 or less carbon atoms, and an organic group having 1 or more and 5 or less carbon atoms. It is more preferably a group, and even more preferably an organic group having 1 or more and 3 or less carbon atoms. It is presumed that this will reduce the obstacles to the molecular orbital around the organic group that binds to the filler. Therefore, the probability of bonding between the silane compound and the filler can be increased, and the dispersibility of the filler in the sealing resin composition can be improved.

Specific examples of the organic group having 1 or more and 10 or less carbon atoms of B in the general formula (1) include an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkoxy group, an alkaline group and a cycloalkyl group. The group is mentioned.
Alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group and octyl. Examples include a group, a nonyl group, and a decyl group. Examples of the alkenyl group include an allyl group, a pentenyl group, a vinyl group and the like. Examples of the alkynyl group include an ethynyl group. Examples of the alkylidene group include a methylidene group and an ethylidene group. Examples of the aryl group include a tolyl group, a xsilyl group, a phenyl group, a naphthyl group, an anthrasenyl group and the like. Examples of the aralkyl group include a benzyl group and a phenethyl group. Alkoxy groups include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, s-butoxy group, isobutoxy group, t-butoxy group, n-pentyloxy group, neopentyloxy group, n. -Hexyloxy groups and the like. Examples of the alkaline group include a tolyl group and a xylyl group. Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group and the like. Among these, an alkoxy group is preferable. Further, among the alkoxy groups, a methoxy group and an ethoxy group are preferable. Thereby, the dispersibility of the filler in the sealing resin composition can be improved.

At least one of B in the general formula (1) is preferably a methoxy group or an ethoxy group, two or three of B are preferably a methoxy group or an ethoxy group, and all of B are methoxy groups. Alternatively, it is preferably an ethoxy group. A methoxy group or an ethoxy group is an organic group that chemically bonds with a filler. Although the detailed mechanism is not clear, in the case of having a triangular pyramidal conformation such as the silane compound according to the present embodiment, the more organic groups chemically bonded to the filler, the more on the surface of the filler. It is presumed that the silane compound density can be improved. As a result, the affinity between the filler and the epoxy resin can be improved, and the dispersibility of the filler in the sealing resin composition can be improved.

The silane compound represented by the above general formula (1) according to the present embodiment is not limited, but specifically, bis (3-trimethoxysilylpropyl) amine and bis (3-triethoxysilyl). Examples thereof include propyl) amine and N, N'-bis [3- (trimethoxysilyl) propyl] ethylenediamine. As the silane compound represented by the general formula (1), bis (3-trimethoxysilylpropyl) amine and bis (3-triethoxysilylpropyl) amine are preferably used among the above specific examples.

The lower limit of the content of the silane compound in the sealing resin composition is, for example, 0.01% by mass or more, more preferably 0.01% by mass, based on 100% by mass of the total solid content of the sealing resin composition. It is 0.05% by mass or more, more preferably 0.1% by mass or more. When the lower limit of the content of the silane compound is within the above range, the filler does not form agglomerates, and good dispersion of the filler can be realized.
The upper limit of the content of the silane compound in the sealing resin composition is, for example, 1.0% by mass or less, more preferably 1.0% by mass or less, based on 100% by mass of the total solid content of the sealing resin composition. It is preferably 0.8% by mass or less, more preferably 0.6% by mass or less, and particularly preferably 0.4% by mass or less. When the upper limit of the content of the silane compound is within the above range, the cross-linking of the silane compound makes it difficult for the filler to form aggregates, and good dispersion of the filler can be realized.

As the lower limit of the content of the silane compound in the sealing resin composition, for example, 0.01% by mass or more is preferable, and 0.15% by mass or more is more preferable with respect to 100% by mass of the epoxy resin. As a result, the silane compound on the surface of the filler and the epoxy resin can easily form a crosslinked structure, and good dispersion of the filler can be realized.
The upper limit of the content of the silane compound in the sealing resin composition is, for example, preferably 0.10% by mass or less, more preferably 0.05% by mass or less, based on 100% by mass of the epoxy resin. As a result, it becomes difficult for the silane compounds on the surface of the filler to form a crosslinked structure, and good dispersion of the filler can be realized.

As the lower limit of the content of the silane compound in the sealing resin composition, for example, 0.05% by mass or more is preferable, more preferably 0.1% by mass or more, and further, with respect to 100% by mass of the filler. It is preferably 0.2% by mass or more. As a result, a silane compound interface can be formed on the surface of the filler, and good dispersion of the filler can be realized.
The upper limit of the content of the silane compound in the sealing resin composition is, for example, preferably 0.5% by mass or less, more preferably 0.4% by mass or less, based on 100% by mass of the filler. , 0.3% by mass or less is more preferable. As a result, the silane compound is less likely to be crosslinked, and the surface-treated filler is less likely to form aggregates, so that good dispersion of the filler can be realized.

(Other ingredients)
In the sealing resin composition, if necessary, one of various additives such as a curing accelerator, a silane coupling agent, a mold release agent, a flame retardant, an ion scavenger, a colorant and a low stress agent, or Two or more types can be blended.
Hereinafter, the representative components will be described in detail.

(Curing accelerator)
The curing accelerator is not limited as long as it accelerates the curing reaction of the epoxy resin and the curing agent, and can be selected depending on the type of the epoxy resin and the curing agent.
Specific examples of the curing accelerator include phosphorus atom-containing compounds such as organic phosphine, tetra-substituted phosphonium compound, phosphobetaine compound, adduct of phosphine compound and quinone compound, and adduct of phosphonium compound and silane compound; -Methyl imidazole, 2-ethyl-4-methyl imidazole (EMI24), 2-phenyl-4-methyl imidazole (2P4MZ), 2-phenyl imidazole (2PZ), 2-phenyl-4-methyl-5-hydroxy imidazole (2P4MHZ) ), 1-benzyl-2-phenylimidazole (1B2PZ) and other imidazole compounds; 1,8-diazabicyclo [5.4.0] undecene-7, benzyldimethylamine and the like are exemplified by amidines and tertiary amines; Alternatively, a nitrogen atom-containing compound such as a quaternary ammonium salt of the tertiary amine can be mentioned. As the curing accelerator, one or a combination of two or more of the above specific examples can be used.

(Silane coupling agent)
As the silane coupling agent, a silane coupling agent having a structure different from that of the above-mentioned silane compound may be used in combination with the above-mentioned silane compound.
Specific examples of the silane coupling agent having a structure different from that of the above-mentioned silane compound include vinyl silanes such as vinyl trimethoxysilane and vinyl triethoxysilane; 2- (3,4-epylcyclohexyl) ethyltrimethoxysilane, 3 -Epoxysilanes such as glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane; p-styryltrimethoxysilane Styrylsilanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, methacrylsilanes such as 3-methacryloxypropyltriethoxysilane; 3-acryloxy Acrylic silanes such as propyltrimethoxysilane; N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane , 3-Aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane and other aminosilanes; isocyanurate silane; alkylsilane Ureidosilane such as 3-ureidopropyltrialkoxysilane; mercaptosilane such as 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane; isocyanatesilane such as 3-isocyanuppropyltriethoxysilane; titanium compound; aluminum Chelates; examples include aluminum / zirconium compounds. As the silane coupling agent, one or more of the above specific examples can be blended.

(Release agent)
The release agent is not limited, and a known release agent used in the sealing resin composition can be used.
As the release agent, for example, one or two types selected from natural waxes such as carnauba wax, synthetic waxes such as montanic acid ester wax and polyethylene oxide wax, higher fatty acids such as zinc stearate and their metal salts, and paraffin. The above can be included.

(Flame retardants)
The flame retardant is not limited, and a known flame retardant used in the sealing resin composition can be used.
Specific examples of the flame retardant include aluminum hydroxide, magnesium hydroxide, zinc borate, zinc molybdate, and phosphazene. As the flame retardant, one or more of the above specific examples can be blended.

(Colorant)
The colorant is not limited, and a known colorant used in the sealing resin composition can be used.
Specific examples of the colorant include carbon black, red iron oxide, and titanium oxide. As the colorant, one or more of the above specific examples can be blended.

(Ion scavenger)
The sealing resin composition according to this embodiment contains an ion scavenger. As the ion scavenger, if it is an anion scavenger that adsorbs anionic impurities in the sealing resin composition, it is a known ion scavenger depending on other components in the sealing resin composition. Can be used. The ion scavenger may be used as a neutralizing agent.
Specific examples of the ion scavenger include one or more types selected from hydrotalcites, zeolites, hydrotalcites, or hydroxides of elements selected from magnesium, aluminum, bismuth, titanium, and zirconium. Can be included.

(Low stress agent)
The low stress agent is not limited, and a known low stress agent used in the sealing resin composition can be used.
Specific examples of the low stress agent include silicone compounds such as silicone oil and silicone rubber; polybutadiene compounds; and acrylonitrile-butadiene copolymer compounds. As the low stress agent, one or more of the above specific examples can be blended.

Next, a method for producing the sealing resin composition according to the present embodiment will be described.

The method for producing the sealing resin composition according to the present embodiment is not limited, but is a surface treatment step of surface-treating the surface of the filler with a silane compound, and then aging to improve the compatibility between the silane compound and the filler. It is preferably carried out by a step and then a mixing step of mixing the surface-treated filler with other components.

The surface treatment step is performed, for example, by stirring the filler while spraying the silane compound on the filler in the mixer using a sprayer. As the atomizer, for example, a device capable of atomizing fine droplets equipped with a two-fluid nozzle or the like can be used. It is preferable to use such a sprayer because the surface of the filler is more uniformly treated with the silane compound.

The aging step is performed by allowing the filler surface-treated with the silane compound to stand at a temperature of 25 ° C. or higher and 60 ° C. or lower for 2 hours or more and 10 hours or less. Although the detailed mechanism is not clear, it is presumed that the aging process improves the compatibility between the filler and the silane compound. Then, it is presumed that the improvement in familiarity makes it difficult for the silane coupling agents bonded to the filler to crosslink with each other. As a result, in the mixing step, the probability that agglomerates of the filler are formed via the silane compound in the sealing resin composition can be reduced, and the dispersibility of the filler can be improved. Therefore, in such a sealing resin composition, agglomerates of the filler are less likely to be formed.
The aging step is mentioned as an element for improving the dispersibility of the filler and setting the values of the indexes such as viscosity, gel time and spiral flow into a desired numerical range.

The mixing step is performed by mixing the filler surface-treated with the silane compound and other components by a known method.
After mixing, the granules are further melt-kneaded with a kneader such as a roll, kneader or extruder, cooled and then crushed, crushed and then tablet-shaped, and if necessary, crushed as described above. As the sealing resin composition, a sieved product, a granular product produced by a granulation method in which the dispersity, fluidity, etc. are appropriately adjusted by a centrifugal milling method, a hot-cut method, or the like can be used.

In the sealing resin composition according to the present embodiment, the upper limit of the viscosity η1 measured at 110 ° C. and 0.2 rad / s ^{is preferably 1 × 10 8} Pa · s or less, for example, 1 × 10 ^{It is more preferably 7} Pa · s or less. Thereby, when the sealing resin composition is molded, the filling can be advanced by the holding pressure.
Further, in the sealing resin composition according to the present embodiment, the lower limit of the viscosity η1 ^{is preferably 1 × 10 5} Pa · s or more, and more preferably 1 × 10 ⁶ Pa · s or more. preferable. This facilitates the setting of the initial injection pressure during molding of the sealing resin composition. Therefore, the uniformity and stability of the molded product can be improved.
The viscosity η1 can be measured by, for example, an Ares type rheometer (ARES-2KSTD-FCO-STD manufactured by Rehometric Scientific).

For the sealing resin composition according to the present embodiment, the upper limit of the viscosity η2 measured at 110 ° C. and a rotation frequency of 500 rad / s ^{is preferably 1 × 10 7} Pa · s or less, for example, 1 × 10. ^{It is more preferably 6} Pa · s or less. As a result, it is possible to suppress a decrease in the fluidity of the sealing resin composition during molding of the sealing resin composition.
Regarding the sealing resin composition according to the present embodiment, the lower limit of the viscosity η2 measured at 110 ° C. and a rotation frequency of 500 rad / s ^{is preferably 1 × 10 1} Pa · s or more, for example, 1 × 10 ^{It is more preferably 2} Pa · s or more. This makes it possible to improve the uniformity and stability of the molded product during molding of the sealing resin composition.
The viscosity η2 can be measured by, for example, an Ares type rheometer (for example, ARES-2KSTD-FCO-STD manufactured by Rehometric Scientific).

From the viscosity η1 and the viscosity η2, the upper limit of the thixotropy TI calculated by the following formula ^{is preferably, for example, 6.0 × 10 -3} or less, and 5.7 × 10 ^-3 or less. Is more preferable, and 5.5 × 10 ^-3 or less is further preferable. When the thixotropy is within the above numerical range, that is, the viscosity of the sealing resin composition to which shear stress is applied is appropriately lowered, it is possible to prevent the fluidity of the sealing resin composition from being lowered. Therefore, the uniformity and stability of the molded product, which is a cured product of the sealing resin composition, can be improved.
The lower limit of the thixotropy TI may be, for example, 1.0 × 10 ⁻⁴ or more, or 1.0 × 10 ⁻³ or more.
(Thixotropy TI) = (viscosity η2) / (viscosity η1)

The spiral flow flow length of the sealing resin composition is not limited, and can be set according to the shape of the electronic device.
The upper limit of the spiral flow flow length is, for example, preferably 250 cm or less, and more preferably 200 cm or less. As a result, it is possible to prevent the occurrence of molding defects such as burrs, sink marks and shavings during molding and the contamination of the mold due to the excessively high fluidity of the sealing resin composition.
The lower limit of the spiral flow flow length is preferably 120 cm or more, and more preferably 150 cm or more. Thereby, when molding the sealing resin composition, the filling property can be improved more effectively by improving the fluidity.
For the spiral flow measurement, for example, a low-pressure transfer molding machine (“KTS-15” manufactured by Kotaki Seiki Co., Ltd.) is used, and the mold temperature is 175 ° C. for a mold for spiral flow measurement according to ANSI / ASTM D 3123-72. It can be carried out by injecting the sealing resin composition under the conditions of an injection pressure of 6.9 MPa and a curing time of 120 seconds, and measuring the flow length.

The upper limit of the gel time of the sealing resin composition according to the present embodiment is, for example, preferably 90 seconds or less, more preferably 50 seconds or less, and further preferably 48 seconds or less. Thereby, the molding cycle can be improved. The lower limit of the gel time is not limited, but can be, for example, 30 seconds or more.
The gel time was measured by placing 0.5 g of the sealing resin composition on a hot plate controlled at 175 ° C. and using a spatula about once / sec. It can be carried out by kneading with the stroke of (1) and measuring the time from the dissolution of the sealing resin composition by heat to the curing.

Hereinafter, a method for manufacturing an electronic device using a cured product of the sealing resin composition according to the present embodiment will be described.

The electronic device according to the present embodiment includes an electronic element and a molded body for sealing the electronic element, and the cured product of the above-mentioned sealing resin composition is used as the molded body.

The above-mentioned sealing resin composition is used for sealing an electronic element in an electronic device.
Examples of the electronic device include a semiconductor device and the like. Further, examples of the electronic element include a semiconductor element (semiconductor chip) and the like.
The sealing resin composition according to this embodiment is suitably used for a flip chip mounting type electronic device such as a flip chip BGA package.

In a flip chip mounting type electronic device, a solder bump is mounted on a pad of an electronic element, the solder bump is connected to a land of a substrate and mounted, and a resin composition for sealing is applied by a transfer molding method, a compression molding method or an injection. It is obtained by molding by a molding method and curing the sealing resin composition into a molded product.

The flip-chip mounting type semiconductor device thus obtained has a substrate and an electronic element electrically connected to the substrate via solder bumps, and is composed of a sealing resin composition. The electronic element is sealed by the molded body. When the electronic device is sealed using the sealing resin composition, the sealing resin composition is also filled in the gap between the substrate and the semiconductor element. As a result, the strength of the electronic device is improved by the cured product, and a highly reliable electronic device can be obtained. Further, the epoxy resin for encapsulating a semiconductor can be filled between the semiconductor element and the substrate without using a liquid underfill material, and molding can be performed in one step by a transfer molding method or the like.

In the electronic device using the sealing resin composition according to the present embodiment, the gap height (vertical distance) between the electronic element and the substrate may be, for example, 100 μm or less, 80 μm or less, or 60 μm or less. It may be 40 μm or less, or 30 μm or less. Even when the gap height is small as described above, the filling rate can be improved well. It is considered that this is because the dispersibility of the filler is improved and the filler does not aggregate through the silane compound, so that clogging due to the aggregate can be suppressed.
Further, the sealing resin composition according to the present embodiment can be suitably filled when the lower limit of the gap height (vertical distance) between the electronic element and the substrate is, for example, 25 μm or more.
In this embodiment, the gap height is the gap between the electronic device and the substrate, and the thickness of the electronic device is not taken into consideration.

FIG. 1 shows an example of the electronic device 100 according to the present embodiment.
The electronic device 100 includes a substrate 10, an electronic element 20 mounted on the substrate 10, and a molded body 50 for sealing the electronic element 20, and the molded body includes the sealing resin composition. A cured product of the material is used.
In the electronic device 100 shown in FIG. 1, the electronic element 20 and the substrate 10 are electrically connected via a solder bump 30, but the electronic device 100 is not limited to this.

The present invention is not limited to the above-described embodiment, and modifications, improvements, and the like within the range in which the object of the present invention can be achieved are included in the present invention.
Hereinafter, examples of reference embodiments of the present invention will be added.
[1]
Epoxy resin and
Hardener and
Filler and
The silane compound represented by the above general formula (1) and
Resin composition for encapsulant containing.
(In the above general formula (1), X represents the following general formula (X1) or (X2).
R ² and R ³ independently represent an organic group having 1 or more and 10 or less carbon atoms.
Each of A independently represents an organic group having 1 or more and 10 or less carbon atoms. A may be the same as each other or different from each other. At least one of A is a methoxy group or an ethoxy group.
Each B independently represents an organic group having 1 or more and 10 or less carbon atoms. B may be the same as each other or different from each other. At least one of B is a methoxy group or an ethoxy group. )
(In the above general formula (X1),
* ² represents a bond with ^{R 2} in formula (1),
* ³ represents a bond with ^{R 3} in formula (1),
R ¹ represents an organic group having 1 to 10 carbon atoms independently having a hydrogen atom or active hydrogen. )
(In the above general formula (X2),
* ² represents a bond with ^{R 2} in formula (1),
* ³ represents a bond with ^{R 3} in formula (1),
R ¹ represents an organic group having 1 or more and 10 or less carbon atoms, each independently having a hydrogen atom or active hydrogen. R ¹ may be mutually the same or may be different from each other.
R ^X represents at least one but no more than 10 organic group having a carbon number. )
[2]
The resin composition for a sealing material according to [1].
A resin composition for a sealing material having a thixotropy TI of 6.0 × 10 ^{-3 or less measured under the following conditions.}
(conditions)
Let η2 / η1 be the thixotropy TI, where η1 is the viscosity measured at 110 ° C. and a rotation frequency of 0.2 rad / s using a rheometer, and η2 is the viscosity measured at 110 ° C. and 500 rad / s rotation speed. ..
[3]
The resin composition for a sealing material according to [1] or [2].
A resin composition for a sealing material in which the content of the silane compound is 0.01% by mass or more and 1.0% by mass or less with respect to 100% by mass of the total solid content of the resin composition for a sealing material.
[4]
The resin composition for a sealing material according to any one of [1] to [3].
A resin composition for a sealing material in which the content of the filler is 70% by mass or more and 90% by mass or less with respect to 100% by mass of the total solid content of the resin composition for the sealing material.
[5]
The resin composition for a sealing material according to any one of [1] to [4].
A resin composition for a sealing material in which the cumulative 50% particle size D _{50 based on} the volume of the filler is 1.0 μm or more and 10.0 μm or less.
[6]
The resin composition for a sealing material according to any one of [1] to [5].
A resin composition for a sealing material having a gel time of 30 seconds or more and 90 seconds or less.
[7]
The resin composition for a sealing material according to any one of [1] to [6].
A resin composition for a sealing material having a spiral flow of 120 cm or more and 250 cm or less.
[8]
With electronic devices
It is equipped with a molded body that seals the electronic element.
An electronic device in which a cured product of the sealing resin composition according to any one of [1] to [7] is used as the molded product.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to the description of these Examples.

(Example 1)
The components used in Example 1 are shown in Table 1 below.
(Preparation of resin composition for sealing)
First, a filler and a silane compound were prepared from each component in the blending amounts shown in Table 1. Next, the filler was put into a mixer, and the filler was stirred while spraying the silane compound on the filler using a sprayer. The mixer was operated at a rotation speed of 4800 rpm for 3 minutes and then discharged to obtain a filler surface-treated with a silane compound. Next, the filler surface-treated with the silane compound was subjected to an aging step of allowing it to stand at 25 ° C. for 3 hours. After the aging step, the filler surface-treated with the above silane compound and the components other than the filler and the silane compound among the respective components in the blending amounts shown in Table 1 are mixed using a mixer at room temperature, and then. Roll kneading was performed at 70 to 100 ° C. to obtain a kneaded product. Then, after cooling the kneaded product, it was pulverized to obtain a sealing resin composition. The unit of the blending amount in Table 1 is a mass part.

(Example 2)
As shown in Table 1, a sealing resin composition was prepared in the same manner as in Example 1 except that each component and the blending amount of each component were changed.

(Comparative Example 1)
As shown in Table 1, a sealing resin composition was prepared in the same manner as in Example 1 except that each component and the blending amount of each component were changed.

(Epoxy resin)
Epoxy resin 1: Phenolic aralkyl type epoxy resin having a biphenylene skeleton represented by the following formula (5) (manufactured by Nippon Kayaku Co., Ltd., NC3000, softening point 57 ° C.)
Epoxy resin 2: The polyfunctional phenol resin represented by the following formula (6) and the phenols represented by the following formula (7) are represented by the polyfunctional phenol resin represented by the following formula (6) / the following formula (7). Phenols are mixed so that the weight ratio is 4 and glycidyl etherified (manufactured by Mitsubishi Chemical Co., Ltd., Epicoat YL6677).
When the polyfunctional phenol resin represented by the following formula (6) is glycidyl etherified, it becomes a triphenol methane type epoxy resin. Further, when the phenols represented by the following formula (7) are glycidyl etherified, they become a biphenyl type epoxy resin. That is, the epoxy resin 2 is a mixture of a triphenol methane type epoxy resin and a biphenyl type epoxy resin.

(Hardener)
Hardener 1: Phenol aralkyl resin having a biphenylene skeleton represented by the following formula (8) (GPH65 manufactured by Nippon Kayaku Co., Ltd.)
Hardener 2: Phenol resin having a triphenylmethane skeleton represented by the following formula (9) (manufactured by Air Water Inc., trade name HE910-20, softening point 88 ° C.)

(Filler)
Filler 1: Synthetic spherical silica (manufactured by Admatex, SO-E6, D ₅₀ : 2.0 μm)

(Silane compound)
Silane compound 1: Bis (3-trimethoxysilylpropyl) amine represented by the following formula (10) (manufactured by Momentive Performance Materials, A-1170)
Silane compound 2: Bis (3-triethoxysilylpropyl) amine represented by the following formula (11) (manufactured by Momentive Performance Materials, Y-119999)
Silane compound 3: N-phenyl-3-aminopropyltrimethoxysilane represented by the following formula (12) (KBM-573, manufactured by Shin-Etsu Chemical Co., Ltd.)

(Curing accelerator)
Curing Accelerator 1: Addition of a phosphonium compound represented by the following formula (13) and a silane compound The curing accelerator 1 was synthesized. The synthesis method will be described in detail.
249.5 g of phenyltrimethoxysilane and 384.0 g of 2,3-dihydroxynaphthalene were added to a flask containing 1800 g of methanol to dissolve it, and then 231.5 g of a 28% sodium methoxide-methanol solution was added dropwise under stirring at room temperature. Next, a solution prepared by dissolving 503.0 g of tetraphenylphosphonium bromide in 600 g of methanol was added dropwise to the flask under stirring at room temperature to precipitate crystals. The precipitated crystals were filtered, washed with water, and vacuum dried to obtain the above-mentioned curing accelerator 1 which is a pinkish white crystal of an adduct of a phosphonium compound and a silane compound.

(Colorant)
Colorant 1: Carbon black (manufactured by Mitsubishi Chemical Corporation, MA-600)

(Low stress agent)
Low stress agent 1: Acrylonitrile-butadiene copolymer compound (manufactured by PTI Japan, CTBN1008SP)

(Release agent)
Release agent 1: Montanic acid ester wax (manufactured by Clariant Japan, Recolve WE 4)

(Spiral flow)
Spiral flow was measured for the sealing resin compositions of Examples and Comparative Examples. A low-pressure transfer molding machine (KTS-15 manufactured by Kotaki Seiki Co., Ltd.) was diverted to insert molding, respectively, and used for spiral flow measurement dies according to ANSI / ASTM D 3123-72 at 175 ° C. and injection pressure of 6.9 MPa. The sealing resin composition was injected under the condition of holding pressure time of 120 seconds, and the flow length was measured. The unit of spiral flow in Table 1 is cm.
Here, the spiral flow is a parameter of fluidity, and the larger the value, the better the fluidity.

(Gel time)
The gel time was measured for the sealing resin compositions of Examples and Comparative Examples. The sealing resin composition was placed on a hot plate controlled at 175 ° C., and the spatula was used about once / sec. Knead with the stroke of. The time from when the sealing resin composition was melted by heat to when it was cured was measured and used as the gel time. The unit of gel time in Table 1 is seconds.

(Viscosity, thixotropic coefficient)
The viscosities of the sealing resin compositions of Examples and Comparative Examples were measured, and the thixotropy was calculated.
An Ares type rheometer (ARES-2KSTD-FCO-STD manufactured by Rehometric Scientific) was used for the measurement. The viscosity measured at a temperature of 110 ° C. and a rotation frequency of 0.2 rad / s was defined as η1, and the viscosity measured at a temperature of 110 ° C. and a rotation frequency of 500 rad / s was defined as η2. Moreover, the thixotropy TI was calculated from the following formula.
(Thixotropy TI) = η2 / η1

<Manufacturing of electronic devices>
A 10 mm × 10 mm × 250 μm flip-chip type package is placed on a 15 mm × 15 mm printed wiring board, and then heat treatment is performed at a peak temperature of 240 ° C. and a peak temperature time of 10 seconds to melt the solder bumps and flip-chip. The mold package and the printed wiring board were joined.
Here, the gap height (vertical distance) between the flip-chip type package and the substrate was measured. Specifically, the distance of the step between the package and the substrate was measured by a laser displacement meter, and the value obtained by subtracting the thickness of the package from the distance of the step was defined as the gap height. The gap between the substrate and the package after mounting was 30 μm.
Next, the substrate on which the package obtained above is mounted is placed in a mold, and using a molding machine (manufactured by TOWA, Y1E manual press), the mold temperature is 175 ° C., the injection pressure is 7.0 MPa, and the injection pressure is 18 seconds. Under the conditions, the obtained epoxy resin composition for sealing was injected into a mold and molded. Next, a curing treatment was performed at 175 ° C. for 180 seconds to prepare an electronic device.

(Filling rate)
The filling rate of the cured product of the sealing resin composition with respect to the gap (gap height: 30 μm) between the package and the substrate in the above electronic device was calculated by the transmission method of the ultrasonic exploration device (SAT).
Specifically, the image obtained by SAT is binarized into a portion filled with the cured product and a portion not filled with the cured product, and the area S1 of the portion filled with the cured product and the area not filled with the cured product are used. S2 was calculated. Next, the filling rate was calculated from the following formula.
(Equation) Filling rate [%] = 100 × S1 / (S1 + S2)

As shown in Table 1, the sealing resin composition of each example had a lower spiral flow than the sealing resin composition of each comparative example within a range that did not affect the molding speed. As a result, it was confirmed that molding defects and stains on the mold could be prevented due to the fluidity of the sealing resin composition being too high. Furthermore, it was confirmed that the filling property into the mold can be improved more effectively by providing appropriate fluidity.
Further, it was confirmed that the sealing resin composition of each example had a lower gel time and could improve the molding cycle as compared with the sealing resin composition of each comparative example.
Further, when the electronic device is manufactured using the sealing resin composition of each example, the filling rate can be improved as compared with the case of using the sealing resin composition of each comparative example, that is, the electronic device. It was confirmed that the filling property into the plastic can be improved.
Further, as shown in Table 1, it was confirmed that the sealing resin compositions of each example had higher η1 and η2 than the sealing resin compositions of each comparative example. This viscosity value is considered to reflect the dispersibility of the filler. That is, it was confirmed that the sealing resin composition of each example had improved dispersibility of the filler as compared with the sealing resin composition of each comparative example.
Therefore, the sealing resin composition of each example has improved dispersibility of the filler as compared with the sealing resin composition of each comparative example. As a result, it was confirmed that clogging due to self-aggregation of the filler does not occur, the viscosity in the molding process is kept uniform, and the moldability such as the uniformity of the molded product can be improved by improving the molding cycle.

Although the present invention has been described in more detail based on the above examples, these are examples of the present invention, and various configurations other than the above can be adopted.

10 Substrate 20 Electronic element 30 Solder bump 50 Molded body 100 Electronic device

Claims (6)

Epoxy resin and
Hardener and
Filler and
A silane compound represented by the following general formula (1) and
A sealing material for a resin composition comprising,
The content of the filler is 70% by mass or more and 90% by mass or less with respect to 100% by mass of the total solid content of the resin composition for a sealing material.
A resin composition for a sealing material, wherein the cumulative 50% particle size D _{50 based on} the volume of the filler is 1.0 μm or more and 10.0 μm or less .

(In the above general formula (1), X represents the following general formula (X1) or (X2).
R ² and R ³ independently represent an organic group having 1 or more and 10 or less carbon atoms.
Each of A independently represents an organic group having 1 or more and 10 or less carbon atoms. A may be the same as each other or different from each other. At least one of A is a methoxy group or an ethoxy group.
Each B independently represents an organic group having 1 or more and 10 or less carbon atoms. B may be the same as each other or different from each other. At least one of B is a methoxy group or an ethoxy group. )

(In the above general formula (X1),
* ² represents a bond with ^{R 2} in formula (1),
* ³ represents a bond with ^{R 3} in formula (1),
R ¹ represents an organic group having 1 to 10 carbon atoms independently having a hydrogen atom or active hydrogen. )

(In the above general formula (X2),
* ² represents a bond with ^{R 2} in formula (1),
* ³ represents a bond with ^{R 3} in formula (1),
R ¹ represents an organic group having 1 or more and 10 or less carbon atoms, each independently having a hydrogen atom or active hydrogen. R ¹ may be mutually the same or may be different from each other.
R ^X represents at least one but no more than 10 organic group having a carbon number. ) The resin composition for a sealing material according to claim 1.
A resin composition for a sealing material having a thixotropy TI of 6.0 × 10 ^{-3 or less measured under the following conditions.}
(conditions)
With a rheometer, 110 ℃, η1,110 ℃ the viscosity measured at a rotational frequency 0.2 rad / s, the viscosity measured at a rotation frequency 500 rad / s when the .eta.2, the .eta.2 / .eta.1 and thixotropic index TI do. The resin composition for a sealing material according to claim 1 or 2.
A resin composition for a sealing material in which the content of the silane compound is 0.01% by mass or more and 1.0% by mass or less with respect to 100% by mass of the total solid content of the resin composition for a sealing material. The resin composition for a sealing material according to any one of claims 1 to 3.
A resin composition for a sealing material, wherein the gel time of the resin composition for a sealing material is 30 seconds or more and 90 seconds or less. The resin composition for a sealing material according to any one of claims 1 to 4.
A resin composition for a sealing material having a spiral flow of 120 cm or more and 250 cm or less. With electronic devices
It is provided with a molded body for sealing the electronic element.
An electronic device in which a cured product of the resin composition for a sealing material according to any one of claims 1 to 5 is used as the molded product.

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