JP2019006972A - Production method of resin composition for encapsulation and method for manufacturing electronic device - Google Patents

Abstract

To provide a production method of a resin composition for encapsulation which gives an excellent appearance and improves adhesiveness to metal.SOLUTION: A production method of a resin composition for encapsulation for encapsulating an electronic element is provided, which includes: a pulverizing step of pulverizing particles of a diaminotriazine compound having a specific structure to obtain a pulverized product; and a mixing step of mixing the pulverized product with an epoxy resin, a curing agent and a filler. In a volume-basis grain size distribution of the pulverized product, when a grain size where a cumulative frequency of the distribution reaches 50% is referred as D, Dis 0.1 μm or more and 2.0 μm or less.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a sealing resin composition and a method for producing an electronic device.

  Various techniques have been developed as sealing resin compositions for sealing electronic components. For example, Patent Document 1 discloses a sealing resin composition that prevents metal ion migration and galvanic corrosion due to ionic halogen, has excellent moisture resistance, and maintains the merits of conventional compositions. Have been described. According to Patent Document 1, by adding a predetermined amount of 2-vinyl-4,6-diamino-s-triazine, electrolytic corrosion can be prevented and a sealing resin composition excellent in moisture resistance can be obtained. Have been described.

JP 62-25118 A

The present inventors examined the appearance and adhesiveness of the sealing resin composition described in Patent Document 1. As a result, it was found that the sealing resin composition has room for further improvement in terms of appearance and adhesion.
Then, this invention makes it a subject to provide the manufacturing method of the resin composition for sealing which is excellent in an external appearance and improves adhesiveness with a metal.

When the present inventors examined the external appearance of the resin composition for sealing described in Patent Document 1 and the electronic device using the same, it was found that white foreign matter was generated on the surface of the resin composition for sealing. When the sealing resin composition in which such white foreign matters are generated is applied to an electronic device as it is, the appearance is deteriorated.
Then, when the present inventors examined the substance used as the origin of a white foreign material, it discovered that a white foreign material originates in a diaminotriazine compound.

By the way, an electronic device using the sealing resin composition may become high temperature during use. Moreover, in the manufacturing process of an electronic device, when there exists a reflow process, it may be exposed to high temperature. When the electronic device reaches a high temperature, the sealing resin composition and the metal part may be peeled off due to the difference in thermal expansion coefficient between the sealing resin composition and the metal part inside the electronic device. is there. If this peeling occurs, the life of the electronic device can be prolonged and long-term electrical reliability cannot be realized.
In order to realize long-term reliability of an electronic device, the present inventors examined the adhesive strength between the sealing resin composition described in Patent Document 1 and a metal such as Cu, Au, and Ni. As a result, it was found that the sealing resin composition described in Patent Document 1 has insufficient adhesive strength with metal and is inferior in adhesion.

For sealing resin compositions using a diaminotriazine compound, the present inventors have provided adhesive strength between the sealing resin composition and metal, and electrical reliability of an electronic device using the sealing resin composition. In order to improve the above, a method for introducing a diaminotriazine compound into a sealing resin composition was examined. As a result, the particles of the diaminotriazine compound are pulverized to a specific particle size, and then the diaminotriazine compound particles, the epoxy resin, the curing agent, and the filler are mixed, from the viewpoint of the adhesive strength described above. It has been found that a good effect can be obtained.
Furthermore, the present inventors produce a pulverized product by pulverizing the particles of the diaminotriazine compound, and set the particle size D _{50 at} which the cumulative frequency of the volume-based particle size distribution of the pulverized product is 50% within a specific numerical range. It was. Using this pulverized product, a sealing resin composition and an electronic device using the same were produced. Then, it turned out that the number of the white foreign materials which arise on the resin composition for sealing and the electronic device surface can be reduced.
In addition, the present inventors have found that when set to within a specific numerical range of the D ₅₀ of the pulverized diamino triazine compound, improve the sealing resin composition, Cu, the bonding strength between metals such as Au and Ni Furthermore, it has been found that long-term electrical reliability of an electronic device using the encapsulating resin composition can be improved.
From the above, the present inventors have produced a sealing resin composition by a specific manufacturing method, so that the sealing resin composition and the appearance of the electronic device, the adhesion of the sealing resin composition and the metal, Furthermore, the present invention has been completed by finding that a good effect can be obtained in terms of electrical reliability of the electronic device.

According to the present invention,
A method for producing a sealing resin composition for sealing an electronic element,
A pulverization step of pulverizing particles of a diaminotriazine compound represented by the following general formula (1) to obtain a pulverized product;
A mixing step of mixing the pulverized product, an epoxy resin, a curing agent, and a filler,
When the particle size of which cumulative frequency of volume-based particle size distribution of the pulverized material is 50% and the D _50, D ₅₀ is 0.1μm or more 2.0μm or less, it provides the manufacturing method of the sealing resin composition Is done.

（上記一般式（１）中、Ｒは水素原子、炭素原子、酸素原子、窒素原子、硫黄原子、リン原子及びケイ素原子からなる群より選択される１種または２種以上の原子によって形成される基を表し、前記Ｒは活性水素を有する官能基を含む。）

(In the general formula (1), R is formed of one or more atoms selected from the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom and a silicon atom. R represents a functional group having active hydrogen.)

Moreover, according to the present invention,
The sealing resin composition obtained by the manufacturing method of the said sealing resin composition is provided.

Furthermore, according to the present invention,
A manufacturing process for obtaining a sealing resin composition by the method for manufacturing a sealing resin composition,
Mounting electronic elements on a substrate;
And a step of sealing the electronic element using the sealing resin composition.

  According to the present invention, the sealing resin composition and the appearance of the electronic device, the adhesion of the sealing resin composition and the metal, and the production of the sealing resin composition that improves the electrical reliability of the electronic device. A method is provided.

It is sectional drawing which shows an example of the manufacturing method 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 the drawings, the same reference numerals are given to the same components, and the description will be omitted as appropriate.

According to this embodiment,
A method for producing a sealing resin composition for sealing an electronic element,
A pulverization step of pulverizing particles of a diaminotriazine compound represented by the following general formula (1) to obtain a pulverized product;
A mixing step of mixing the pulverized product, an epoxy resin, a curing agent, and a filler,
When the particle size of which cumulative frequency of volume-based particle size distribution of the pulverized material is 50% and the D _50, D ₅₀ is 0.1μm or more 2.0μm or less, it provides the manufacturing method of the sealing resin composition Is done.

（上記一般式（１）中、Ｒは水素原子、炭素原子、酸素原子、窒素原子、硫黄原子、リン原子及びケイ素原子からなる群より選択される１種または２種以上の原子によって形成される基を表し、前記Ｒは活性水素を有する官能基を含む。）

(In the general formula (1), R is formed of one or more atoms selected from the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom and a silicon atom. R represents a functional group having active hydrogen.)

  Based on various experimental results, the present inventors pulverized the diaminotriazine compound particles represented by the general formula (1) to a specific particle size, and then the diaminotriazine compound particles, the epoxy resin, When the curing agent and the filler are mixed, the sealing resin composition and the external appearance of the electronic device, the adhesiveness between the sealing resin composition and the metal, and the electrical effects of the electronic device are good. It was found that it can be obtained.

First, the reason why the diaminotriazine compound represented by the general formula (1) is used will be described.
In recent years, in an electronic device employing a lead frame, inexpensive Cu is used instead of Au as a material for a bonding wire used for connecting an electronic element and a lead frame.
The Cu wire is more reactive and inferior in corrosion resistance than the Au wire. Thus, sulfur-containing compounds such as thiol and sulfide; halogen ions such as Cl ion and Br ion; halides such as chloride and bromide; organic acids such as formic acid, acetic acid, phosphoric acid, nitric acid and sulfuric acid; phosphate ions and nitric acid When the sealing resin composition contains organic acid ions such as ions and sulfate ions, the Cu wire is corroded. As a result, there is a disadvantage that the reliability and life of the electronic device are reduced.
In recent years, there is a demand for reducing the size of electronic devices in the market. In accordance with this requirement, it is required to use a thin Cu wire having a diameter of 1 mil or less as a bonding wire of an electronic device. Therefore, the resin composition for sealing has been required to suppress corrosion on the Cu wire.
Conventionally, as a compound for improving adhesion between a sealing resin composition and a metal, that is, as an adhesion assistant, 4,4′-dithiomorpholine, di-2-benzothiazolyl disulfide, 1,3,5 -Sulfur-containing compounds such as triazine-2,4,6-trithiol have been used.
As a result of studying a sealing resin composition that does not corrode metal parts such as Cu wire, the present inventors have adopted a diaminotriazine compound as an adhesion assistant instead of the sulfur-containing compound.

  The diaminotriazine compound according to this embodiment has a structure represented by the general formula (1). The shape of the particles of the diaminotriazine compound as a raw material is an irregular shape, and includes coarse particles having a particle size of the order of mm. In the present embodiment, the particle size of the irregularly shaped particles means the largest of the lengths between any two points in the particles. In the diaminotriazine compound particles, the diaminotriazine compound forms crystals. Due to this crystal structure, the particles of the diaminotriazine compound are excellent in mechanical properties. The particles of such a diaminotriazine compound may be reduced in particle size even when stirred with other components of the sealing resin composition such as an epoxy resin, a curing agent and a filler using a stirrer such as a mixer. was difficult. Therefore, coarse particles of a diaminotriazine compound have been mixed as a raw material in a conventional sealing resin composition.

By the way, when the present inventors examined the external appearance of the sealing resin composition containing a diaminotriazine compound, it turned out that a white foreign material arises in the sealing resin composition and an electronic device using the same. First, the present inventors considered to investigate the cause of white foreign matter. Specifically, the sealing resin composition was dissolved in acetone, and white foreign matters were extracted. Here, as the sealing resin composition, an epoxy resin, a curing agent, a filler, and a diaminotriazine compound were used. This white foreign material was dissolved in tetrahydrofuran (THF) and subjected to Fourier transform infrared spectroscopy. In the infrared spectroscopic spectrum obtained by this measurement, a peak believed to be derived from shrinkage of the N—H bond was confirmed in the vicinity of 3800 cm ⁻¹ to 2700 cm ⁻¹ . Here, the sealing resin composition did not contain a substance having an N—H bond in addition to the diaminotriazine compound. Thereby, it was estimated that a white foreign material originates in a diaminotriazine compound.
The present inventors considered that if the cause of white foreign matter is a diaminotriazine compound, the generation of white foreign matter can be suppressed by eliminating coarse particles of the diaminotriazine compound. Therefore, before mixing the diaminotriazine compound with the other components of the encapsulating resin composition, the diaminotriazine compound was screened using a 100 μm order sieve to remove coarse particles to some extent. Here, the reason is that the particle shape is an irregular shape, so that even if the particle size is larger than the size of the sieve, it may pass through the sieve. Using the sieved diaminotriazine compound particles, a sealing resin composition and an electronic device using the same were prepared. Then, it turned out that the number of the white foreign materials which arise on the resin composition for sealing, and the electronic device surface using the same decreases. Thus, it was confirmed that the white foreign matter was a substance derived from the diaminotriazine compound.
As described above, the present inventors have found that the white foreign matter is derived from a diaminotriazine compound.

However, the generation of white foreign matters could not be completely suppressed only by removing coarse particles by sieving. The following two reasons were considered as this reason. The first reason was presumed that, as described above, particles having an irregular shape pass through the sieve even if the particle diameter is larger than the sieve eyes. The second reason was presumed that even if coarse particles were removed by sieving, the diaminotriazine compound aggregated again to form coarse aggregates.
From the above, in order to suppress the occurrence of white foreign matter, the present inventors reduced the particles of the diaminotriazine compound to a specific numerical range by a method other than sieving, and further reduced the shape of the particles to prevent aggregation. Was considered to be effective to have a shape with a small specific surface area.

As described above, the particles of the diaminotriazine compound are excellent in mechanical properties, and even when stirred together with other components of the encapsulating resin composition, the particle size cannot be reduced. Therefore, the present inventors considered to pulverize the diaminotriazine compound particles using a pulverizer such as a jet mill pulverizer to produce a pulverized product. This is because it was considered that the particles of the diaminotriazine compound were crushed by hitting each other to produce a pulverized product having a small particle size. Furthermore, it is because the particles of the diaminotriazine compound having an irregular shape can be made close to a spherical shape having a small specific surface area by colliding the particles of the diaminotriazine compound with each other to produce a pulverized product.
And, as a result of examining the pulverization process in which the particles of the diaminotriazine compound are collided with each other using a pulverizer such as a jet mill pulverizer, the present inventors can control the particle size of the pulverized product of the diaminotriazine compound to be smaller than that before pulverization. In addition, it was confirmed that the pulverized product of the diaminotriazine compound can be formed into a substantially spherical shape or a substantially elliptical shape.

When the present inventors examined the size of the pulverized product that can suppress the occurrence of white foreign matter in the sealing resin composition, there is no large pulverized product that itself causes white foreign matter. It was possible to identify a numerical value range of D ₅₀ of the pulverized product in which no causative aggregates were formed. The D ₅₀ of the pulverized product is a value at which the cumulative frequency of the volume-based particle size distribution of the pulverized product is 50%.
Then, the pulverized product of diamino triazine compound D ₅₀ of the numerical range, an epoxy resin, a curing agent, by kneading the filler, to produce an electronic device using the sealing resin composition and this However, it has been found that generation of white foreign matters can be suppressed.

Furthermore, a resin composition for encapsulating a D ₅₀ of the pulverized diamino triazine compound by the above numerical range, Cu, can be improved adhesive strength between the metal such as Au and Ni was revealed. Although the detailed mechanism is not clear about this reason, it estimates as follows.
First, in the diaminotriazine compound represented by the general formula (1), R, which is a group having active hydrogen, and amino groups at the 2nd and 4th positions are considered to form a bond with the glycidyl group of the epoxy resin. Further, it is considered that the lone electron pair of the nitrogen atom of the amino group at the 2nd and 4th positions and the lone electron pair of the nitrogen atom at the 1st, 3rd and 5th positions interact with the metal, respectively. Thereby, it is estimated that the epoxy resin and the metal interact with each other via the diaminotriazine compound, thereby improving the adhesion between the sealing resin composition and the metal.
Further, by the above-described pulverization step, D ₅₀ of the pulverized product of the diaminotriazine compound can be made smaller than before pulverization, and the shape of the pulverized product of the diaminotriazine compound can be substantially spherical or elliptical. Thereby, it is considered that the specific surface area of the diaminotriazine compound is larger than that before the pulverization step. Therefore, it is estimated that the bond which a diamino triazine compound, an epoxy resin, and a metal can form can be increased.
From the above, it is presumed that the adhesive strength between the sealing resin composition and the metal can be improved. And it is thought that the electrical reliability of an electronic device can be improved by improving adhesiveness.

  As described above, the sealing resin composition according to the present embodiment has the appearance of the sealing resin composition and the electronic device, the adhesion between the sealing resin composition and the metal, and the electrical reliability of the electronic device. It is estimated that it can be improved.

(Method for producing resin composition for sealing)
First, the manufacturing method of the resin composition for sealing concerning this embodiment is demonstrated.
The encapsulating resin composition according to the present embodiment is prepared by pulverizing particles of a diaminotriazine compound to prepare a pulverized product, and after the pulverizing step, the pulverized product, an epoxy resin, a curing agent, and a filling And a mixing step of mixing the material.

(Crushing process)
The pulverization step is a step of pulverizing the particles of the diaminotriazine compound to produce a pulverized product. Here, the pulverization step is performed so that the D ₅₀ of the pulverized product obtained in the pulverization step is smaller than the D ₅₀ of the particles of the diaminotriazine compound.
In addition, when using together 2 or more types of diaminotriazine compounds, it is preferable to perform a grinding | pulverization process about each diaminotriazine compound.

A method of pulverizing particles of a diaminotriazine compound to produce a pulverized product is performed by stirring the particles and hitting the particles.
As described above, since the particles of the diaminotriazine compound are excellent in mechanical properties, even if they are stirred together with the other components of the sealing resin composition, the particles cannot be pulverized and the particle size cannot be reduced. Therefore, stirring is preferably performed using only the diaminotriazine compound.
Examples of the agitating device include an air-flow pulverizer such as a jet mill; a ball mill such as a vibrating ball mill, a continuous rotary ball mill, and a batch ball mill; a pot mill such as a wet pot mill and a planetary pot mill; a pulverizer such as a roller mill. Is mentioned. Among the specific examples, the stirring device is preferably a jet mill grinder (manufactured by Seishin Enterprise Co., Ltd., single track jet mill).

The upper limit of D ₅₀ of the pulverized diaminotriazine compound is preferably 2.0 μm or less, more preferably 1.8 μm or less, still more preferably 1.6 μm or less, and 1.4 μm or less. It is particularly preferable that Thereby, the diaminotriazine compound with a large particle size which causes a white foreign material as above-mentioned can be removed. Moreover, the adhesive strength of the resin composition for sealing and a metal can be improved because the specific surface area of a diaminotriazine compound increases.
Further, the lower limit value of D ₅₀ of the pulverized diaminotriazine compound is preferably 0.1 μm or more, more preferably 0.3 μm or more, still more preferably 0.5 μm or more, and More preferably, it is 7 μm or more, and particularly preferably 1.0 μm or more. Thereby, it can suppress that the particle | grains of a diamino triazine compound aggregate by interaction, and can suppress generation | occurrence | production of a white foreign material. This is because particles having a small particle size have a larger specific surface area than particles having a large particle size, and thus tend to aggregate. Therefore, the pulverized product of the diaminotriazine compound is preferably at least the above lower limit value.
The D ₅₀ of the pulverized product of the diaminotriazine compound is measured, for example, by measuring the particle size distribution on a volume basis using a commercially available laser diffraction particle size distribution analyzer (for example, SALD-7000, manufactured by Shimadzu Corporation). The cumulative 50% particle size can be obtained.

The upper limit value of the maximum particle size of the pulverized diaminotriazine compound is, for example, preferably 20 μm or less, more preferably 15 μm or less, still more preferably 12 μm or less, and even more preferably 10 μm or less. preferable. This can remove large particles that themselves cause white foreign matter.
In addition, the lower limit value of the maximum particle size of the pulverized product of diaminotriazine compound can be set to 0.1 μm or more, for example.
In the present embodiment, the particle size of the pulverized product can be evaluated using, for example, a commercially available laser diffraction particle size distribution measuring device (for example, SALD-7000 manufactured by Shimadzu Corporation).

The shape of the pulverized product of the diaminotriazine compound preferably includes a substantially spherical shape or a substantially elliptical shape, and more preferably a substantially spherical shape or a substantially elliptical shape. Thereby, when the volume of a ground material is the same, a specific surface area can be made small compared with another shape. Accordingly, while preventing aggregation of pulverized _together, it is possible to reduce the _{D 50,} it is possible to suppress the generation of white foreign matter.

(Mixing process)
After the pulverization step, a mixing step is performed. The mixing step is a step of mixing the pulverized product obtained in the pulverizing step, the epoxy resin, the curing agent, and the filler.

The mixing method is not limited and can be performed by a conventionally known method. A specific method is illustrated below.
First, the pulverized product of the diaminotriazine compound obtained in the above pulverization step and other materials are uniformly mixed at room temperature using a mixer or the like. Subsequently, it melt-kneads using kneading machines, such as a heating roll, a kneader, and an extruder. Next, the obtained kneaded product can be cooled and pulverized to obtain a sealing resin composition.

The encapsulating resin composition of the present embodiment can be used as the powder shape obtained in the mixing step. Moreover, it does not restrict | limit including the shaping | molding process which shape | molds the resin composition for sealing of a powder shape after the said mixing process in a tablet shape or a sheet | seat shape.
Although it does not limit as a shaping | molding process, you may shape | mold into a tablet shape by tableting shaping | molding, and you may shape | mold into a sheet | seat shape with an extruder.

  The sealing resin composition according to this embodiment is obtained by the above-described method for manufacturing a sealing resin composition.

Next, each component contained in the encapsulating resin composition will be described.
The sealing resin composition includes an epoxy resin, a curing agent, a filler, and a diaminotriazine compound.

(Epoxy resin)
The epoxy resin indicates a compound (monomer, oligomer and polymer) having two or more epoxy groups in one molecule and does not limit the molecular weight and molecular structure.
Specific examples of epoxy resins include crystalline epoxy resins such as biphenyl type epoxy resins, bisphenol type epoxy resins, and stilbene type epoxy resins; novolak type epoxy resins such as phenol novolac type epoxy resins and cresol novolac type epoxy resins; Polyfunctional epoxy resins such as phenol methane type epoxy resins and alkyl-modified triphenol methane type epoxy resins; Phenol aralkyl type epoxy resins such as phenylene skeleton-containing phenol aralkyl type epoxy resins and biphenylene skeleton-containing phenol aralkyl type epoxy resins; Dihydroxynaphthalene type epoxy Naphthol type epoxy resins such as epoxy resins obtained by glycidyl etherification of dimers of resin and dihydroxynaphthalene; triglycidyl isocyanurate Triazine nucleus-containing epoxy resins such as monoallyl diglycidyl isocyanurate; dicyclopentadiene-modified phenol type bridged cyclic hydrocarbon compound-modified phenol type epoxy resins and epoxy resins. As an epoxy resin, it can use 1 type or in combination of 2 or more types among the said specific examples.
Among the above specific examples, the epoxy resin preferably includes a phenol aralkyl type epoxy resin or a biphenyl type epoxy resin. Thereby, the functional group and amino group having active hydrogen in R of the diaminotriazine compound and the glycidyl group of the epoxy resin can be suitably bonded by alleviating the steric hindrance between the diaminotriazine compound and the epoxy resin. Presumed to be possible. Therefore, the adhesive strength between the sealing resin composition and the metal can be improved.

The lower limit of the content of the epoxy resin in the sealing resin composition is, for example, preferably 0.1 parts by mass or more with respect to 100 parts by mass of the solid content of the sealing resin composition. It is more preferably 3 parts by mass or more, and further preferably 0.5 parts by mass or more. Thereby, an epoxy resin and a diamino triazine compound can fully form a bond. Therefore, the adhesive strength between the sealing resin composition and the metal can be improved.
Moreover, it is preferable that the upper limit of content of the epoxy resin in the resin composition for sealing is 20 mass parts or less with respect to 100 mass parts of solid content of the resin composition for sealing, for example, 15 masses More preferably, it is more preferably 10 parts by mass or less. Thereby, the linear expansion coefficient of the resin composition for sealing can be set within an appropriate range. Therefore, the high temperature storage characteristics can be improved.
In addition, in this embodiment, solid content of the resin composition for sealing shows the sum total of the components except a solvent among the components contained in the resin composition for sealing.

(Curing agent)
As the curing agent, a known curing agent can be selected according to the type of the epoxy resin. Specific examples of the curing agent include a polyaddition type curing agent, a catalyst type curing agent, and a condensation type curing agent.

  Specific examples of the polyaddition type curing agent include aliphatic polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), and metaxylylenediamine (MXDA); diaminodiphenylmethane (DDM), m-phenylene. Aromatic polyamines such as diamine (MPDA) and diaminodiphenylsulfone (DDS); polyamine compounds such as dicyandiamide (DICY) and organic acid dihydrazide; alicyclic rings such as hexahydrophthalic anhydride (HHPA) and methyltetrahydrophthalic anhydride (MTHPA) Acid anhydrides; acid anhydrides such as aromatic acid anhydrides such as trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), and benzophenone tetracarboxylic acid (BTDA); novolac-type phenolic resins, polyvinylphenol Phenolic resin-based curing agents such as aralkyl-type phenolic resins; polymercaptan compounds such as polysulfide, thioester and thioether; isocyanate compounds such as isocyanate prepolymers and blocked isocyanates; organic acids such as carboxylic acid-containing polyester resins . As a polyaddition type hardening | curing agent, it can use 1 type or in combination of 2 or more types among the said specific examples.

  Specific examples of the catalyst-type curing agent include tertiary amine compounds such as benzyldimethylamine (BDMA) and 2,4,6-trisdimethylaminomethylphenol (DMP-30); 2-methylimidazole, 2 -Imidazole compounds such as ethyl-4-methylimidazole (EMI24); Lewis acids such as BF3 complexes. As a catalyst type hardening | curing agent, it can use 1 type or in combination of 2 or more types among the said specific examples.

  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 more of the above specific examples can be used in combination.

As a hardening | curing agent, it is preferable that a phenol resin type hardening | curing agent is included among the said specific examples.
As the phenol resin-based curing agent, monomers, oligomers and polymers in general having two or more phenolic hydroxyl groups in one molecule can be used, and the molecular weight and molecular structure are not limited.
Specific examples of the phenolic resin-based curing agent include novolak-type phenol resins such as phenol novolak resin, cresol novolak resin, bisphenol novolak resin, and phenol-biphenyl novolak resin; polyvinylphenol; polyfunctional type such as triphenolmethane type phenol resin. Phenol resins; modified phenol resins such as terpene-modified phenol resins and dicyclopentadiene-modified phenol resins; phenol aralkyl type phenol resins such as phenylene skeleton and / or biphenylene skeleton-containing phenol aralkyl resins, phenylene and / or biphenylene skeleton-containing naphthol aralkyl resins; Examples thereof include bisphenol compounds such as bisphenol A and bisphenol F. As a phenol resin type hardening | curing agent, it can use 1 type or in combination of 2 or more types among the said specific examples.
As a phenol resin type hardening | curing agent, it is preferable to contain a phenylene skeleton and / or a biphenylene skeleton containing phenol aralkyl resin among the said specific examples. Thereby, an epoxy resin can be hardened | cured favorably in the resin composition for sealing. Therefore, it can prevent that the adhesive strength of an epoxy resin and a metal falls by inadequate hardening.

The lower limit of the content of the curing agent in the sealing resin composition is preferably, for example, 0.5 parts by mass or more with respect to 100 parts by mass of the solid content of the sealing resin composition. More preferably, it is more preferably 1.5 parts by mass or more, and even more preferably 2 parts by mass or more. Thereby, an epoxy resin can be hardened | cured favorably in the resin composition for sealing. Therefore, it can prevent that the adhesive strength of an epoxy resin and a metal falls because hardening of the resin composition for sealing is inadequate.
Moreover, it is preferable that the upper limit of content of the hardening | curing agent in the resin composition for sealing is 10 mass parts or less with respect to 100 mass parts of solid content of the resin composition for sealing, and is 8 mass parts or less. More preferably, it is more preferably 6 parts by mass or less, and still more preferably 5 parts by mass or less. Thereby, it can prevent that the addition amount of a hardening | curing agent becomes excess with respect to an epoxy resin. Therefore, hardening of the resin composition for sealing becomes insufficient, and it can prevent that the adhesive strength of an epoxy resin and a metal falls.

(Filler)
As the filler, an appropriate filler can be selected according to the use of the electronic device, and specific examples include inorganic fillers and organic fillers. Among the above specific examples, the filler preferably includes an inorganic filler. Thereby, the thermal expansion coefficient of the resin composition for sealing can be reduced. Therefore, the adhesiveness at the time of high-temperature storage of the sealing resin composition and the metal can be improved.

  Specific examples of the inorganic filler include silica such as fused crushed silica, fused spherical silica, crystalline silica, secondary agglomerated silica, and finely divided silica; alumina, silicon nitride, aluminum nitride, boron nitride, titanium oxide, carbonized Metal compounds such as silicon, aluminum hydroxide, magnesium hydroxide and titanium white; talc; clay; mica; glass fiber and the like. As an inorganic filler, it can use 1 type or in combination of 2 or more types among the said specific examples. Among the above specific examples, the inorganic filler is preferably silica such as fused crushed silica, fused spherical silica, crystalline silica, secondary agglomerated silica, and finely divided silica, and more preferably fused spherical silica.

  Specific examples of the organic filler include organosilicone powder and polyethylene powder. As an organic filler, it can use 1 type or in combination of 2 or more types among the said specific examples.

The lower limit of the content of the filler in the sealing resin composition is, for example, preferably 70 parts by mass or more, and 75 parts by mass or more with respect to 100 parts by mass of the solid content of the sealing resin composition. It is more preferable that it is 80 parts by mass or more. Thereby, the friction between the filler and the other components in the sealing resin composition can be increased, and the viscosity of the sealing resin composition can be improved. Therefore, when molding the sealing resin composition into a tablet shape or sheet shape, or when producing an electronic device using the sealing resin composition, molding such as burrs and sink marks due to low viscosity It can suppress that a defect generate | occur | produces and an external appearance falls.
Moreover, it is preferable that the upper limit of content of the filler in the resin composition for sealing is less than 95 mass parts with respect to solid content of the resin composition for sealing, and is 93 mass parts or less, for example. More preferably, it is preferably 90 parts by mass or less. Thereby, the viscosity of the resin composition for sealing can be adjusted to the suitable range which performs a mixing process.

The upper limit of the volume-based cumulative 50% particle size D ₅₀ of the filler is, for example, preferably 50 μm or less, more preferably 45 μm or less, and even more preferably 40 μm or less. Thereby, it can suppress that a big filler and its aggregate are exposed from the resin composition for sealing, and an external appearance falls.
Further, the lower limit value of the volume-based cumulative 50% particle size D ₅₀ of the filler is preferably 0.1 μm or more, and more preferably 0.2 μm or more.
The volume-based cumulative 50% particle size D ₅₀ of the filler is, for example, based on the particle size distribution of the particles using a commercially available laser diffraction particle size distribution measuring device (for example, SALD-7000, manufactured by Shimadzu Corporation). And can be determined by the cumulative 50% particle size.

(Diaminotriazine compound)
The diaminotriazine compound is a compound represented by the following general formula (1). Thereby, it can suppress that the particle | grains of a diaminotriazine compound aggregate by the interaction of diaminotriazine compounds. Therefore, generation | occurrence | production of a white foreign material can be suppressed.
In the present embodiment, only one diaminotriazine compound may be used, or two or more diaminotriazine compounds may be used in combination.

（上記一般式（１）中、Ｒは水素原子、炭素原子、酸素原子、窒素原子、硫黄原子、リン原子及びケイ素原子からなる群より選択される１種または２種以上の原子によって形成される基を表し、前記Ｒは活性水素を有する官能基を含む。）

(In the general formula (1), R is formed of one or more atoms selected from the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom and a silicon atom. R represents a functional group having active hydrogen.)

R is a group formed by one or more atoms selected from the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a silicon atom. For example, a group formed by one or more atoms selected from the group consisting of a carbon atom, a hydrogen atom and an oxygen atom is preferable.
R is a monovalent group. Here, monovalent means valence. That is, R has one bond that bonds to another atom.

  When R is a group containing a carbon atom, R is, for example, preferably an organic group having 1 to 10 carbon atoms, and more preferably hydrogen or an organic group having 1 to 8 carbon atoms. Thereby, the reactivity of an epoxy resin and a diaminotriazine compound can be improved, and the joining strength of the resin composition for sealing and a metal can be improved.

R includes a functional group having an active hydrogen.
Examples of the functional group having active hydrogen include one or more functional groups selected from the group consisting of primary amino group, secondary amino group, hydroxyl group, carboxyl group, vinyl group, glycidyl group and mercapto group. It preferably includes a group, more preferably includes a hydroxyl group or a carboxyl group, and still more preferably includes a hydroxyl group. Thereby, the diaminotriazine compound can improve the reactivity with respect to the glycidyl group of an epoxy resin. And an epoxy resin and a diaminotriazine compound can couple | bond together suitably. Therefore, the bonding strength between the sealing resin composition and the metal can be improved.

  R preferably contains, for example, two or more functional groups having active hydrogen. The diaminotriazine compound can improve the reactivity with respect to the glycidyl group of an epoxy resin. And an epoxy resin and a diaminotriazine compound can couple | bond together suitably. Therefore, the bonding strength between the sealing resin composition and the metal can be improved.

R in the general formula (1) is not limited as long as it includes a functional group having active hydrogen.
Specific examples of R include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, Alkyl groups such as heptyl, octyl, nonyl and decyl; alkenyl groups such as allyl, pentenyl and vinyl; alkynyl such as ethynyl; alkylidene such as methylidene and ethylidene; tolyl and xylyl Aryl groups such as benzyl group and phenethyl group; cycloalkyl groups such as adamantyl group, cyclopentyl group, cyclohexyl group and cyclooctyl group; tolyl group, xylyl group, etc. Having an active hydrogen as described above for a hydrogen atom such as an alkaryl group It includes those substituted with ability group.
As R, for example, a group in which a hydrogen atom of an alkyl group is substituted with the above-described functional group having active hydrogen is preferable. Specific examples of such R include —CH ₂ CH ₂ OH, —CH ₂ CH ₂ CH ₂ CH (OH) CH ₂ OH, and the like. R is preferably, for example, —CH ₂ CH ₂ OH or —CH ₂ CH ₂ CH ₂ CH (OH) CH ₂ OH. Thereby, a diamino triazine compound and an epoxy resin interact suitably, and can improve the joining strength of the resin composition for sealing, and a metal.

In this embodiment, the upper limit of the content of the diaminotriazine compound is preferably, for example, 2.0 parts by mass or less, and 1.8 parts by mass with respect to 100 parts by mass of the solid content of the encapsulating resin composition. More preferably, it is more preferably 1.5 parts by mass or less, still more preferably 1.2 parts by mass or less, and still more preferably 1.0 parts by mass or less. Thereby, generation | occurrence | production of a white foreign material can be suppressed, maintaining the adhesive strength of the resin composition for sealing and a metal sufficiently.
Moreover, it is preferable that it is 0.01 mass part or more with respect to 100 mass parts of solid content of the resin composition for sealing, and the lower limit of content of a diamino triazine compound is 0.03 mass part or more, for example. More preferably. Thereby, an epoxy resin and a metal and a diamino triazine compound can fully form a bond. Thereby, the adhesive strength of the resin composition for sealing and a metal can be improved.

(Other ingredients)
In the sealing resin composition, various additives such as a coupling agent, a fluidity-imparting agent, a release agent, an ion scavenger, a curing accelerator, a low stress agent, a colorant, and a flame retardant are included as necessary. 1 type, or 2 or more types can be mix | blended suitably.

(Coupling agent)
Specific examples of the coupling agent include vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane; 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3 -Epoxy silanes such as glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane; styrylsilanes such as p-styryltrimethoxysilane; 3-methacryloxypropyl Methacrylic silanes such as methyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane; 3-acryloxypropylto Acrylic silane such as methoxysilane; N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3 Aminosilanes such as aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, phenylaminopropyltrimethoxysilane; Nurate silane; alkyl silane; ureido silane such as 3-ureidopropyltrialkoxysilane; mercaptosilane such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; Isocyanate silane such as pills triethoxysilane; titanium-based compounds; aluminum chelates; aluminum / zirconium compounds. As a coupling agent, 1 type (s) or 2 or more types can be mix | blended among the said specific examples.

(Fluidity imparting agent)
The fluidity imparting agent can suppress the reaction of a curing accelerator having no latency such as a phosphorus atom-containing curing accelerator during melt kneading of the resin composition. Thereby, productivity of the resin composition for sealing can be improved.
As the fluidity-imparting agent, specifically, two or more constituting an aromatic ring such as catechol, pyrogallol, gallic acid, gallic acid ester, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene and derivatives thereof A compound in which a hydroxyl group is bonded to each adjacent carbon atom.

(Release agent)
Specific examples of mold release agents include natural waxes such as carnauba wax; synthetic waxes such as montanic acid ester wax and oxidized polyethylene wax; higher fatty acids such as zinc stearate and metal salts thereof; paraffin; erucic acid amide, etc. Examples thereof include carboxylic acid amides. As a mold release agent, 1 type (s) or 2 or more types can be mix | blended among the said specific examples.

(Ion scavenger)
Specific examples of the ion scavenger include hydrotalcites such as hydrotalcite and hydrotalcite-like substances; hydrous oxides of elements selected from magnesium, aluminum, bismuth, titanium, and zirconium. As an ion trapping agent, 1 type (s) or 2 or more types can be mix | blended among the said specific examples.

(Curing accelerator)
Specific examples of the curing accelerator include diazabicycloalkenes such as 1,8-diazabicyclo (5,4,0) undecene-7 and derivatives thereof; amine compounds such as tributylamine and benzyldimethylamine; Imidazole compounds such as methylimidazole; organic phosphines such as triphenylphosphine, methyldiphenylphosphine, 4-hydroxy-2- (triphenylphosphonium) phenolate; tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetrabenzoate borate, Teto such as tetraphenylphosphonium / tetranaphthoic acid borate, tetraphenylphosphonium / tetranaphthoyloxyborate, tetraphenylphosphonium / tetranaphthyloxyborate Substituted phosphonium tetra-substituted borate such as triphenylphosphine and adduct of benzoquinone and the like. As a hardening accelerator, 1 type (s) or 2 or more types can be mix | blended among the said specific examples.

(Low stress agent)
Specific examples of the low stress agent include silicone compounds such as silicone oil and silicone rubber; polybutadiene compounds; acrylonitrile-butadiene copolymer compounds such as acrylonitrile-carboxyl-terminated butadiene copolymer compounds. As a low stress agent, 1 type (s) or 2 or more types can be mix | blended among the said specific examples.

(Coloring agent)
Specific examples of the colorant include carbon black, bengara, and titanium oxide. As a coloring agent, 1 type (s) or 2 or more types can be mix | blended among the said specific examples.

(Flame retardants)
Specific examples of the flame retardant include aluminum hydroxide, magnesium hydroxide, zinc borate, zinc molybdate, phosphazene, and carbon black. As a flame retardant, 1 type (s) or 2 or more types can be mix | blended among the said specific examples.

  Next, an electronic device using the sealing resin composition according to this embodiment will be described.

  The encapsulating resin composition according to this embodiment is used for an encapsulating resin layer that encapsulates an electronic element. A method for forming the sealing resin layer is not limited, and examples thereof include a transfer molding method, a compression molding method, and an injection molding. By these methods, the sealing resin layer can be formed by molding and curing the sealing resin composition.

The electronic element is not limited, but a semiconductor element is preferable.
Examples of the semiconductor element include, but are not limited to, an integrated circuit, a large-scale integrated circuit, a transistor, a thyristor, a diode, and a solid-state imaging element.
Among these, as a semiconductor element in which the sealing resin composition of the present embodiment is useful, a semiconductor element in which a metal portion is exposed. Thereby, corrosion of the metal part can be suppressed. A transistor is an example of a semiconductor element in which such a metal portion is exposed. Among the transistors, the encapsulating resin composition of the present embodiment can be effectively used for encapsulating MIS transistors in which the gate electrode is exposed.

  Although it does not limit as a base material, For example, wiring boards, such as an interposer, a lead frame, etc. are mentioned.

  When electrical connection between the electronic element and the base material is necessary, it may be appropriately connected. The method of electrical connection is not limited, and examples thereof include wire bonding and flip chip connection. Among these, as a semiconductor element in which the sealing resin composition of the present embodiment is useful, a semiconductor element in which a metal portion is exposed. Thereby, corrosion of the metal part can be suppressed. As an electrical connection method in which such a metal portion is exposed, wire bonding can be mentioned.

An electronic device is obtained by forming a sealing resin layer that seals the electronic element with the sealing resin composition. The electronic device is not limited, but a semiconductor device obtained by molding a semiconductor element is preferable.
Specific types of semiconductor devices include MAP (Mold Array Package), QFP (Quad Flat Package), SOP (Small Outline Package), CSP (Chip Size Package), and QFN (Quad Flat Package). ), SON (Small Outline Non-leaded Package), BGA (Ball Grid Array), LF-BGA (Lead Frame BGA), FCBGA (Flip Chip BGA), MAPBGA (Molded Array BGA), MAPBGA (Molded Array BGA) ), Fan-In type eWLB, Fan-Out type eWLB, etc. I can get lost.

Below, an example of the electronic device using the sealing resin composition which concerns on this embodiment is demonstrated.
FIG. 1 is a cross-sectional view showing an electronic device 100 according to this embodiment.
The electronic device 100 of the present embodiment includes an electronic element 20, a bonding wire 40 connected to the electronic element 20, and a sealing resin layer 50. The sealing resin layer 50 includes the above-described sealing resin. It is comprised with the hardened | cured material of the resin composition for a stop.
More specifically, the electronic element 20 is fixed on the base material 30 via the die attach material 10, and the electronic device 100 receives the bonding wire 40 from an electrode pad (not shown) provided on the electronic element 20. The outer lead 34 is connected via the connector. The bonding wire 40 can be set while taking into consideration the electronic element 20 to be used. For example, a Cu wire can be used.

Below, the manufacturing method of the electronic device using the resin composition for sealing concerning this embodiment is demonstrated.
The manufacturing method of the electronic device according to the present embodiment includes, for example, a manufacturing process for obtaining a sealing resin composition by the above-described manufacturing method of a sealing resin composition, a process of mounting an electronic element on a substrate, Sealing the electronic device using the sealing resin composition.

The electronic device 100 is formed by the following method, for example.
First, an electronic element is mounted on a substrate. Specifically, the electronic element 20 is fixed on the die pad 32 (substrate 30) using the die attach material 10, and the die pad 32 (base material 30) that is a lead frame is connected by the bonding wire 40. Thereby, an object to be sealed is formed.
The electronic device 100 is manufactured by sealing the object to be sealed with the sealing resin composition and forming the sealing resin layer 50.
In the electronic device 100 in which the electronic element 20 is sealed, if necessary, the sealing resin composition is cured at a temperature of about 80 ° C. to 200 ° C. for about 10 minutes to 10 hours. Installed in equipment.

  The electronic device 100 uses the above-described sealing resin composition as the sealing resin 50, and the adhesion between the sealing resin layer 50 and the electronic element 20, the bonding wire 40, the electrode pad 22, and the like is sufficient. And high temperature storage characteristics. Even when a Cu wire is used as the bonding wire 40, sufficient high-temperature storage characteristics and the like can be exhibited.

  As mentioned above, although this invention was demonstrated based on embodiment, this invention is not limited to the said embodiment, The structure can also be changed in the range which does not change the summary of this invention.

EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, this invention is not limited to description of these Examples at all.
Details of the components used in each Example and each Comparative Example are shown below.

(Epoxy resin)
Epoxy resin 1: Biphenylene skeleton-containing phenol aralkyl type epoxy resin (Nippon Kayaku Co., Ltd., NC3000L)
Epoxy resin 2: biphenyl type epoxy resin (Mitsubishi Chemical Co., YX4000K)

(Curing agent)
Curing agent 1: Biphenylene skeleton-containing phenol aralkyl resin (Maywa Kasei Co., Ltd., MEH-7851SS)
Curing agent 2: Biphenylene skeleton-containing phenol aralkyl resin (Nippon Kayaku Co., Ltd., GPH-65)

(Filler)
Filler 1: fused spherical silica (D ₅₀ 31 μm, specific surface area 1.6 m ² / g, Denka FB-508S)
Filler 2: fused spherical silica (D ₅₀ 24.9 μm, specific surface area 1.5 m ² / g, manufactured by Tokai Minerals, ES-35)
Filler 3: fused spherical silica (D ₅₀ 10.8 μm, specific surface area 5.1 m ² / g, Denka FB-105)
Filler 4: fused spherical silica (D ₅₀ 0.5 μm, specific surface area 6.4 m ² / g, Admatex SC-2500-SQ)
Filler 5: fused spherical silica (D ₅₀ 1.5 μm, specific surface area 4.4 m ² / g, Admatex SC-5500-SQ)
The volume-based cumulative 50% particle size D ₅₀ of each filler is determined by measuring the particle size distribution of the particles on a volume basis using a commercially available laser diffraction particle size distribution analyzer (SALD-7000, manufactured by Shimadzu Corporation). The cumulative 50% particle size was obtained.

(Diaminotriazine compound)
Diaminotriazines 1-2 were prepared as raw materials for the diaminotriazine compounds.
Diaminotriazine compound 1: particles of 2,4-diamino-6- (4,5-dihydroxypentyl) -1,3,5-triazine represented by the following formula (C2) Diaminotriazine compound 2: the following formula (C3 The particles of 2,4-diamino-6- [2- (3,4-dihydroxyphenyl) ethyl] -1,3,5-triazine represented by the following formula: First, the synthesis method of diaminotriazine compounds 1-2 will be described in detail below. Will be explained.

<Synthesis of Diaminotriazine Compound 1>
In a separable flask equipped with a condenser and a stirrer, 13.7 g (0.1 mol) of 2,4-diamino-6-vinyl-s-triazine, 0.224 g (0.001 mol) of palladium acetate, 0.52 g of triphenylphosphine (0.002 mol) was charged, and the inside of the flask was replaced with argon. Further, 11 g (0.1 mol) of 3-chloro-1,2-propanediol, 20.2 g (0.2 mol) of triethylamine, and 200 ml of tetrahydrofuran were charged into the flask and heated at 60 ° C. for 24 hours. The reaction solution was concentrated, dissolved in 200 ml of ethyl acetate, and washed with water. The ethyl acetate solution of the reaction product was transferred to a flask, and 1 g of palladium carbon was added. The reaction system was replaced with hydrogen, and the mixture was stirred for 12 hours while supplying hydrogen from the balloon filled with hydrogen into the flask. The reaction solution was concentrated by filtration and recrystallized with a mixed solvent of hexane / ethyl acetate. The precipitated crystals were filtered and dried under reduced pressure to obtain particles of diaminotriazine compound 1 represented by the following formula (C2).

<Synthesis of Diaminotriazine Compound 2>
In a separable flask equipped with a condenser and a stirrer, 18.9 g (0.1 mol) of 4-bromocatechol, 13.7 g (0.1 mol) of 2,4-diamino-6-vinyl-s-triazine, 0. 224 g (0.001 mol) and 0.52 g (0.002 mol) of triphenylphosphine were charged, and the inside of the flask was purged with argon. Further, 20.2 g (0.2 mol) of triethylamine and 200 ml of tetrahydrofuran were charged into the flask and heated at 60 ° C. for 24 hours. The reaction solution was concentrated, dissolved in 200 ml of ethyl acetate, and washed with water. The ethyl acetate solution of the reaction product was transferred to a flask, and 1 g of palladium carbon was added. The reaction system was replaced with hydrogen, and the mixture was stirred for 12 hours while supplying hydrogen from the balloon filled with hydrogen into the flask. The reaction solution was concentrated by filtration, recrystallized with a mixed solvent of hexane / ethyl acetate, and the precipitated crystals were filtered and dried under reduced pressure to obtain particles of diaminotriazine compound 2 represented by the following formula (C3).

<Crushing step of diaminotriazine compounds 1-2>
The particles of the diaminotriazine compounds 1 and 2 obtained by the synthesis method were jet milled using a jet mill (manufactured by Seishin Enterprise Co., Ltd., single track jet mill). The pulverized product of diaminotriazine compound 1 thus obtained was designated as diaminotriazine compound 1-A. Further, the pulverized product of diaminotriazine compound 2 was designated as diaminotriazine compound 2-A.

<Diaminotriazine compounds 1-2 not subjected to a pulverization step>
Moreover, the particles of the diaminotriazine compounds 1 and 2 obtained by the above synthesis method were respectively screened. Of the diaminotriazine compound 1, the particles that passed through the sieve were designated as diaminotriazine compound 1-B. Of the diaminotriazine compound 2, the particles that passed through the sieve were designated as diaminotriazine compound 2-B.
The screening was performed using an electromagnetic sieve shaker (manufactured by Lecce, AS450 Basic). The sieve used the thing based on JISZ8801-1. Moreover, the opening of the sieve was 25 μm.
Further, the particles of the diaminotriazine compounds 1 and 2 obtained by the above synthesis method were taken as a diaminotriazine compound 1-C and a diaminotriazine compound 2-C, respectively.

It is shown below each diamino triazine compound, D _50, the maximum particle size and shape.
Diaminotriazine compound 1-A: jet mill pulverized product of 2,4-diamino-6- (4,5-dihydroxypentyl) -1,3,5-triazine represented by the above formula (C2) (D ₅₀ : 1) 0.1 μm, maximum particle size: 8.5 μm, substantially spherical shape and substantially Ryukyu shape)
Diaminotriazine compound 1-B: sieved product of 2,4-diamino-6- (4,5-dihydroxypentyl) -1,3,5-triazine represented by the above formula (C2) (D ₅₀ : 2. 1 μm, maximum particle size: 24.3 μm, irregular shape)
Diaminotriazine compound 1-C: 2,4-diamino-6- (4,5-dihydroxypentyl) -1,3,5-triazine particles represented by the above formula (C2) itself (D ₅₀ : not measurable, Maximum particle size: 2.3mm, irregular shape)
Diaminotriazine compound 2-A: jet mill pulverized product of 2,4-diamino-6- [2- (3,4-dihydroxyphenyl) ethyl] -1,3,5-triazine represented by the above formula (C3) (D ₅₀ : 1.3 μm, maximum particle size: 10.0 μm, substantially spherical shape and substantially Ryukyu shape)
Diaminotriazine compound 2-B: A sieved product of 2,4-diamino-6- [2- (3,4-dihydroxyphenyl) ethyl] -1,3,5-triazine represented by the above formula (C3) ( D ₅₀ : 2.4 μm, maximum particle size: 24.9 μm, irregular shape)
Diaminotriazine compound 2-C: 2,4-diamino-6- [2- (3,4-dihydroxyphenyl) ethyl] -1,3,5-triazine particles represented by the above formula (C3) (D ₅₀ : measurement not possible, maximum particle size: 2.6 mm, irregular shape)
_{Incidentally, D 50} is a laser diffraction particle size distribution analyzer (manufactured by Shimadzu Corporation, SALD-7000) was used to measure the particle size distribution of the particles on a volume basis, was determined by the cumulative 50% particle diameter. The laser diffraction particle size distribution measuring apparatus has a measurement limit of 200 μm. Since diaminotriazine compounds 1-C and 2-C contained particles larger than 200 μm, D ₅₀ could not be measured.
The maximum particle diameter was performed using the same laser diffraction particle size distribution measuring apparatus and measurement of D _50. In addition, since the diaminotriazine compounds 1-C and 2-C had particles of 200 μm or more which is the measurement limit of the laser diffraction particle size distribution analyzer, the maximum particle size was evaluated by direct observation using an optical microscope. .

(Coupling agent)
Coupling agent 1: phenylaminopropyltrimethoxysilane (manufactured by Dow Corning Toray, CF4083)

(Fluidity imparting agent)
-Fluidity-imparting agent 1: 2,3-dihydroxynaphthalene (manufactured by Air Water)

(Release agent)
Release agent 1: erucic acid amide (manufactured by NOF Corporation, Alflow P-10)
Release agent 2: Oxidized polyethylene wax (Clariant PED191)
Release agent 3: carnauba wax (TOWAX-132 manufactured by Toa Gosei Co., Ltd.)

(Ion scavenger)
・ Ion-trapping agent 1: Hydrotalcite (manufactured by Kyowa Chemical Industry Co., Ltd., DHT-4H)

(Curing accelerator)
Curing accelerator 1: 4-hydroxy-2- (triphenylphosphonium) phenolate (manufactured by KEI Kasei Co., Ltd.)

(Low stress agent)
Low stress agent 1: silicone oil having polyalkylene ether group, methyl group, etc. (FZ-3730, manufactured by Toray Dow Corning)
Low stress agent 2: Acrylonitrile-carboxyl-terminated butadiene copolymer (PTN Japan, CTBN1008SP)

(Coloring agent)
Colorant 1: Carbon black (Mitsubishi Chemical Co., MA600)

Example 1
Each component of the compounding quantity described in the following Table 1 was mixed using a mixer at room temperature, and then biaxially kneaded at a temperature of 70 ° C. or higher and 100 ° C. or lower. Subsequently, after cooling to normal temperature, it grind | pulverized and the resin composition for sealing of Example 1 was obtained.

(Example 2, Comparative Examples 1-4)
Except having made the compounding quantity of each component as shown in Table 1, it carried out similarly to Example 1, and obtained each resin composition for sealing of Example 2 and Comparative Examples 1-4.

(Manufacture of electronic devices using resin composition for sealing)
A 3.5 mm × 3.5 mm Test Element Group chip (TEG chip) was mounted on a 352-pin BGA. Next, wire bonding was performed on the electrode pad with a wire pitch of 80 μm using a copper wire having a copper purity of 99.99 mass% and a diameter of 25 μm.
Using the low-pressure transfer molding machine (“Y series” manufactured by TOWA), the obtained structure was subjected to each of the obtained conditions under conditions of a mold temperature of 175 ° C., an injection pressure of 6.9 MPa, and a curing time of 2 minutes. Sealing molding was performed using the sealing resin compositions of Examples and Comparative Examples to produce a 352-pin BGA package. Thereafter, the obtained BGA package was post-cured at 175 ° C. for 4 hours to obtain an electronic device.

(Evaluation)
The sealing resin composition of each Example and each Comparative Example and an electronic device using the same were evaluated by the following methods.

(Appearance, white foreign substance diameter)
The sealing resin composition of each example and each comparative example was adjusted with a powder molding press (S-20-A, manufactured by Tamagawa Machinery Co., Ltd.) so that the mass was 15 g, size φ18 mm × height about 30 mm. And tableting was performed at a tableting pressure of 600 Pa to obtain a tablet.
For each of the sealing resin compositions of each Example and each Comparative Example, the number of white foreign matters was measured by observing the surface of 30 obtained tablets under a microscope, and the average value of the number was determined as the appearance evaluation result. did.
Moreover, about each Example and each comparative example in which the white foreign material was observed, the white foreign material diameter was measured by microscopic observation.
Here, the white foreign substance diameter was calculated by the following method. First, the maximum value among the lengths connecting arbitrary two points in each white foreign matter was defined as the diameter of each white foreign matter. Next, an average value of individual white foreign substance diameters calculated from all white foreign substances generated in 30 tablets was calculated, and this was used as an evaluation result of the white foreign substance diameter. The evaluation results are shown in Table 1 below.

(Identification of white foreign matter)
The white foreign matter was identified using the sealing resin composition of Comparative Example 2 in which white foreign matter was observed. First, the sealing resin composition was dissolved in acetone. Next, a substance that was insoluble in acetone was dissolved in THF, applied to a KBr plate, and dried to obtain a thin film. About this thin film, the FT-IR measurement was performed using the Fourier-transform infrared spectrophotometer (the Perkin-Elmer make, PARAGON1000). The obtained FT-IR spectrum is shown in FIG. As a result, a peak presumed to originate from the stretching of the N—H bond was observed in the vicinity of 3800 cm ⁻¹ to 2700 cm ⁻¹ . Therefore, it was confirmed that the white foreign matter is derived from coarse particles of the diaminotriazine compound.

(Adhesion)
About the resin composition for sealing of each Example and each comparative example, the adhesiveness with respect to Cu was evaluated with the following method.
On the substrate made of Cu, the sealing resin compositions of the respective examples and comparative examples were integrally formed under conditions of a temperature of 175 ° C. and a pressure of 6.9 MPa for 2 minutes, and post-treated at a temperature of 175 ° C. for 4 hours. I did a cure. Thereafter, the shear adhesive strength with each substrate was measured under normal temperature (25 ° C.) and 260 ° C. conditions. The shear adhesive strength at normal temperature was normal temperature Cu adhesion, and the shear adhesive strength at 260 ° C. was 260 ° C. Cu adhesiveness. The evaluation results are shown in Table 1 below.

(High temperature storage characteristics)
In order to evaluate the long-term electrical reliability of the electronic device using the sealing resin composition of each example and each comparative example, a high temperature storage life (HTSL) was performed by the following method. It was.
The electronic device using the sealing resin composition of each example and each comparative example was stored under conditions of a temperature of 200 ° C. and 1000 hours. For the electronic device after storage, the electrical resistance value between the wire and the electrode pad was measured and evaluated according to the following criteria. The evaluation results are shown in Table 1 below.
(Circle): The average value of the electrical resistance value of an electronic device shows less than 110% with respect to the average value of an initial electrical resistance value.
(Triangle | delta): The average value of the electrical resistance value of an electronic apparatus shows 110% or more and less than 120% with respect to the average value of an initial electrical resistance value.
X: The average value of the electrical resistance value of the electronic device is 120% or more with respect to the average value of the initial electrical resistance value.

As shown in Table 1, no white foreign matter was observed in the sealing resin compositions of Examples 1 and 2, and it was confirmed that the sealing resin compositions of the comparative examples were superior in appearance. .
Moreover, it was confirmed that the sealing resin composition of Examples 1-2 can improve normal temperature Cu adhesiveness and 260 degreeC Cu adhesiveness compared with the sealing resin composition of each comparative example. Note that the room temperature Cu adhesion of Example 1 is 0.1 N / mm ² greater than that of Comparative Example 1. Further, the 260 ° C. Cu adhesion of Example 1 is 0.04 N / mm ² larger than that of Comparative Example 1. It seems that these adhesive strengths do not seem to be different on the numerical value. However, the electronic device needs to exhibit adhesion in a micro area. Therefore, the improvement in the adhesion strength that seems to be the same as the above-mentioned difference has a significant effect on the long-term reliability of the electronic device.
In addition, it was confirmed that the electronic device using the sealing resin composition of each example was excellent in long-term electrical reliability compared to the electronic device using the sealing resin composition of each comparative example. It was done.

DESCRIPTION OF SYMBOLS 100 Electronic device 10 Die attach material 20 Electronic element 30 Base material 32 Die pad 34 Outer lead 40 Bonding wire 50 Sealing resin layer

Claims (9)

A method for producing a sealing resin composition for sealing an electronic element,
A pulverization step of pulverizing particles of a diaminotriazine compound represented by the following general formula (1) to obtain a pulverized product;
A mixing step of mixing the pulverized product, an epoxy resin, a curing agent, and a filler,
Manufacturing method of the case where the cumulative frequency of volume-based particle size distribution of the pulverized material has a particle diameter at 50% and D _50, D ₅₀ is 0.1μm or more 2.0μm or less, the encapsulating resin composition.

(In the general formula (1), R is formed of one or more atoms selected from the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom and a silicon atom. R represents a functional group having active hydrogen.) It is a manufacturing method of the resin composition for closure according to claim 1,
The method for producing a sealing resin composition, wherein the pulverized product has a substantially spherical shape or a substantially elliptical shape. It is a manufacturing method of the resin composition for closure according to claim 1 or 2,
The manufacturing method of the resin composition for sealing whose maximum particle size of the said ground material is 20 micrometers or less. It is a manufacturing method of the resin composition for closure according to any one of claims 1 to 3,
In the diaminotriazine compound represented by the general formula (1), the functional group having active hydrogen is composed of a primary amino group, a secondary amino group, a hydroxyl group, a carboxyl group, a vinyl group, a glycidyl group, and a mercapto group. The manufacturing method of the resin composition for sealing which is 1 type (s) or 2 or more types selected from a group. It is a manufacturing method of the resin composition for closure according to any one of claims 1 to 4,
The content of the diaminotriazine compound in the sealing resin composition is 0.01 parts by mass or more and 2.0 parts by mass or less with respect to 100 parts by mass of the solid content of the sealing resin composition. A method for producing a resin composition for stopping. It is a manufacturing method of the resin composition for closure according to any one of claims 1 to 5,
The said epoxy resin is a manufacturing method of the resin composition for sealing containing a phenol aralkyl type epoxy resin or a biphenyl type epoxy resin. A method for producing a sealing resin composition according to any one of claims 1 to 6,
Resin for sealing whose content of the said epoxy resin in the said resin composition for sealing is 0.1 to 20 mass parts with respect to 100 mass parts of solid content of the resin composition for sealing A method for producing the composition. It is a manufacturing method of the resin composition for closure according to any one of claims 1 to 7,
The said hardening | curing agent is a manufacturing method of the resin composition for sealing which is a phenol resin type hardening | curing agent. A manufacturing process for obtaining a sealing resin composition by the method for manufacturing a sealing resin composition according to any one of claims 1 to 8,
Mounting electronic elements on a substrate;
And a step of sealing the electronic element using the sealing resin composition.

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