JP7686367B2 - Method for producing encapsulating resin composition - Google Patents

Description

The present invention relates to a method for producing a powder and an encapsulating resin composition.

Patent Document 1 (JP Patent Publication 62-25118 A) describes an encapsulating resin composition for encapsulating electronic components. The document describes an encapsulating resin composition that contains an epoxy resin, a novolac phenolic resin, a specified amount of 2-vinyl-4,6-diamino-s-triazine, and a specified amount of inorganic filler, as a technology aimed at providing an encapsulating resin composition that prevents electrolytic corrosion caused by metal ion migration and ionic halogens, has excellent moisture resistance, and retains the advantages of conventional compositions. The document also describes that by blending a specified amount of 2-vinyl-4,6-diamino-s-triazine, an encapsulating resin composition that prevents electrolytic corrosion and has excellent moisture resistance can be obtained.

Japanese Unexamined Patent Publication No. 62-25118

The present inventors have examined the technology described in Patent Document 1 and have found that the encapsulating resin composition described therein has room for improvement in terms of narrow path filling ability and adhesion to metal members.
The present invention provides an encapsulating resin composition that is excellent in narrow-path filling property and adhesion between a metal member and an encapsulating material.

According to the present invention,
Provided is a powder composed of one or more compounds selected from the group consisting of 3-amino-1,2,4-triazole and 4-amino-1,2,4-triazole, the powder having an average particle size _d50 of 0.2 μm or more and 20 μm or less, as measured by a laser diffraction method.

According to the present invention,
A step of obtaining the following component (A) by grinding a raw material composed of one or more compounds selected from the group consisting of 3-amino-1,2,4-triazole and 4-amino-1,2,4-triazole;
A step of heating and kneading a mixture containing the component (A) and the following component (B);
The present invention provides a method for producing an encapsulating resin composition, comprising the steps of:
(A) a powder composed of the above compound, the powder having an average particle size _d50 of 0.2 μm or more and 20 μm or less, as measured by a laser diffraction method; (B) an epoxy resin;

In addition, according to the present invention, it is also possible to provide, for example, an encapsulating resin composition obtained by the above-mentioned method for producing an encapsulating resin composition according to the present invention, and a semiconductor device in which a semiconductor element is encapsulated with the encapsulating resin composition.

The present invention provides a sealing resin composition that has excellent narrow passage filling properties and adhesion between metal members and sealing materials.

1 is a cross-sectional view showing a configuration of a semiconductor device according to an embodiment. 1 is a cross-sectional view showing a configuration of a semiconductor device according to an embodiment.

The following describes the embodiments with reference to the drawings. In all drawings, similar components are given the same reference numerals and the description will be omitted as appropriate. The drawings are schematic and do not necessarily correspond to the actual dimensional ratios. In this embodiment, the composition may contain each component alone or in combination of two or more kinds.

(Powder: Component (A))
In this embodiment, the powder is a powder composed of one or more compounds selected from the group consisting of 3-amino-1,2,4-triazole and 4-amino-1,2,4-triazole. The average particle size d ₅₀ of the powder measured by a laser diffraction method is 0.2 μm or more and 20 μm or less. By using such a powder as an additive to the encapsulating resin composition, the filling ability of the encapsulating resin composition into a narrow passage can be improved. In addition, the adhesion between the encapsulating material obtained by using the encapsulating resin composition and the metal member can be excellent. Therefore, a semiconductor device with excellent reliability can be obtained. In addition, by using such a powder as an additive to the encapsulating resin composition, for example, it is also possible to improve the curing characteristics of the encapsulating resin composition at low temperatures. In addition, such a powder can be suitably used in the encapsulating resin composition as an additive such as an adhesion assistant.
The composition of the powder will be described in more detail below.

The powder is composed of aminotriazole compounds, specifically, one or more compounds selected from the group consisting of 3-amino-1,2,4-triazole and 4-amino-1,2,4-triazole.
From the viewpoints of improving adhesion to metal members and being easily available, the powder component preferably contains 3-amino-1,2,4-triazole, and more preferably is 3-amino-1,2,4-triazole.
From the same viewpoint, the content of 3-amino-1,2,4-triazole in the powder is preferably 50% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, still more preferably 95% by mass or more, and even more preferably 100% by mass, based on the total mass of the powder.

The average particle size d ₅₀ of the powder is 0.2 μm or more, preferably 0.5 μm or more, and more preferably 1 μm or more, from the viewpoint of suppressing thickening of the resin.
From the viewpoints of improving dispersibility in the encapsulating resin composition to which the powder is blended and eliminating undissolved coarse particles of the powder during molding, the particle size is 20 μm or less, preferably 10 μm or less, and more preferably 5 μm or less.

Here, the average particle size d ₅₀ of the powder, and the maximum particle size d _max , particle size d ₁₀ and particle size d ₉₀ of the powder described below are all measured on a volume basis using a dry particle size distribution by a laser diffraction method.

The _maximum particle size d of the powder is preferably 100 μm or less, more preferably 70 μm or less, even more preferably 50 μm or less, still more preferably 20 μm or less, and even more preferably 10 μm or less, from the viewpoints of improving the dispersibility of the encapsulating resin composition in which the powder is blended and of eliminating residual coarse particles of the powder during molding.
From the viewpoint of suppressing thickening of the resin, the maximum particle size d _max of the powder may be, for example, 1 μm or more, and preferably 5 μm or more.

From the viewpoint of suppressing thickening of the resin, the particle diameter d ₁₀ of the powder is preferably 0.1 μm or more, more preferably 0.2 μm or more, even more preferably 0.3 μm or more, and still more preferably 0.5 μm or more.
In addition, from the viewpoint of improving the dispersibility of the encapsulating resin composition into which the powder is blended and eliminating the undissolved coarse particles of the powder during molding, the particle size _d10 of the powder is preferably 10 μm or less, more preferably 8 μm or less, even more preferably 6 μm or less, and even more preferably 4 μm or less.

From the viewpoint of suppressing thickening of the resin, the particle size d ₉₀ of the powder is preferably 1 μm or more, more preferably 2 μm or more, even more preferably 3 μm or more, and even more preferably 5 μm or more.
In addition, from the viewpoint of improving the dispersibility of the encapsulating resin composition into which the powder is blended and eliminating residual coarse _particles of the powder during molding, the particle size d of the powder is preferably 50 μm or less, more preferably 30 μm or less, even more preferably 20 μm or less, and even more preferably 10 μm or less.

In this embodiment, the powder is preferably a pulverized product of a raw material composed of the above-mentioned compounds, and more preferably a jet mill pulverized product of such a raw material.
The powder can be obtained, for example, by pulverizing a raw material preferably composed of the above-mentioned compounds.
By obtaining the powder of this embodiment by pulverizing the raw material using a pulverizing device such as a jet mill pulverizing device, the amount of coarse particles can be reduced, which improves the dispersibility of the encapsulating resin composition in which the powder is mixed, eliminates the residual coarse particles of the powder during molding, and improves the adhesion between the encapsulating material and the metal member, thereby improving the reliability of the semiconductor device.

(Method for producing encapsulating resin composition)
The powder in this embodiment is suitably blended into an encapsulating resin composition.
The method for producing the encapsulating resin composition includes, for example, the following steps 1 and 2.
(Step 1) A step of obtaining the following component (A) by pulverizing a raw material composed of one or more compounds selected from the group consisting of 3-amino-1,2,4-triazole and 4-amino-1,2,4-triazole; (Step 2) A step of heating and kneading a mixture containing the component (A) and the following component (B); (A) A powder composed of the above compound, the powder having an average particle size d ₅₀ of 0.2 μm or more and 20 μm or less as measured by a laser diffraction method; and (B) an epoxy resin.

(Step 1)
Step 1 is a step of obtaining the aforementioned powder, i.e., component (A), and more specifically, a step of obtaining a pulverized product by pulverizing the above-mentioned raw material.
The raw material is, for example, in particulate form, and in this case, step 1 is carried out by stirring the raw material particles and causing the particles to collide with each other.

Step 1 can be carried out, for example, using a grinding device. Specific examples of grinding devices include airflow grinders such as jet mills; ball mills such as vibration ball mills, continuous rotary ball mills, and batch ball mills; pot mills such as wet pot mills and planetary pot mills; and grinders such as roller mills. From the viewpoint of stably obtaining powders having desired particle size characteristics, the stirring device is preferably a jet mill grinder, and more preferably a vertical jet grinder. Specific examples of vertical jet grinders include, for example, Sk Jet-O-Mill, manufactured by Seishin Enterprise Co., Ltd.
Step 1 preferably also includes a step of pulverizing the raw material with a jet mill.

In addition, by adjusting the grinding conditions in step 1, component (A) having the preferred particle size characteristics described above can be obtained.

(Step 2)
Step 2 is a step of heating and kneading a mixture containing components (A) and (B).
Here, the mixture can be obtained, for example, by uniformly mixing components (A) and (B) and other appropriate components at room temperature using a mixer, etc. Component (B) and other components will be described later.
The heat kneading is a process of melt kneading using a kneading machine such as a heated roll, a kneader, or an extruder.
The heating temperature can be set depending on the types of components, such as the epoxy resin, contained in the mixture, and can be, for example, about 100°C to 120°C.

The kneaded product obtained in step 2 can be cooled and pulverized to obtain an encapsulating resin composition. After pulverization, the product may be molded to obtain a particulate or sheet-like encapsulating resin composition. For example, the product may be compressed into tablets to obtain a particulate encapsulating resin composition. For example, a sheet-like encapsulating resin composition may be obtained by a vacuum extruder. The degree of dispersion, flowability, etc. of the obtained encapsulating resin composition may be appropriately adjusted.

The encapsulating resin composition thus obtained is obtained by heating and kneading a mixture containing components (A) and (B), and therefore has excellent filling ability into narrow passages and excellent adhesion between the encapsulating material and metal members. More specifically, this embodiment also makes it possible to improve adhesion between the encapsulating material and a member made of Ag, Ni, Cu, or an alloy containing one or more of these. In addition, such an encapsulating resin composition has excellent moldability at low temperatures, for example, 150° C. or lower.
Moreover, by using such an encapsulating resin composition, a semiconductor device with excellent reliability can be obtained.

The components contained in the encapsulating resin composition will be described below.
First, component (A) is the above-mentioned powder.
The content of component (A) in the encapsulating resin composition is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and even more preferably 0.04% by mass or more, based on the entire encapsulating resin composition, from the viewpoint of stably improving the adhesion between the encapsulating material and the metal member. Also, from the viewpoint of making the flowability and storage stability of the encapsulating resin composition favorable, the content of component (A) is preferably 1% by mass or less, more preferably 0.5% by mass or less, and even more preferably 0.2% by mass or less, based on the entire encapsulating resin composition.

(Component (B))
The epoxy resin of component (B) is a compound having two or more epoxy groups in one molecule, and may be any of a monomer, oligomer, and polymer.
Specifically, the epoxy resin is one or more selected from the group consisting of crystalline epoxy resins such as biphenyl-type epoxy resins, bisphenol-type epoxy resins, and stilbene-type epoxy resins; novolac-type epoxy resins such as phenol novolac-type epoxy resins and cresol novolac-type epoxy resins; polyfunctional epoxy resins such as trisphenylmethane-type epoxy resins and alkyl-modified triphenolmethane-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; naphthol-type epoxy resins such as dihydroxynaphthalene-type epoxy resins and epoxy resins obtained by glycidyl etherifying a dimer of dihydroxynaphthalene; triazine nucleus-containing epoxy resins such as triglycidyl isocyanurate and monoallyl diglycidyl isocyanurate; and bridged cyclic hydrocarbon compound-modified phenol-type epoxy resins such as dicyclopentadiene-modified phenol-type epoxy resins.

From the viewpoint of improving adhesion to metal members, the epoxy resin is preferably one or more selected from the group consisting of trisphenylmethane type epoxy resins, biphenyl aralkyl type multifunctional epoxy resins, orthocresol type bifunctional epoxy resins, biphenyl type bifunctional epoxy resins, and bisphenol type bifunctional epoxy resins, and more preferably biphenyl aralkyl type multifunctional epoxy resins.

From the viewpoint of obtaining suitable fluidity during molding and improving filling property and moldability, the content of the epoxy resin in the encapsulating resin composition is preferably 2 mass % or more, more preferably 3 mass % or more, and even more preferably 4 mass % or more, based on the entire encapsulating resin composition.
Furthermore, from the viewpoint of improving the reliability of a device obtained using the encapsulating resin composition, the content of the epoxy resin in the encapsulating resin composition is preferably 40 mass % or less, more preferably 30 mass % or less, even more preferably 20 mass % or less, and even more preferably 10 mass % or less, based on the entire encapsulating resin composition.

Moreover, from the viewpoint of improving the adhesion between the encapsulating material and the metal member while improving the curing property of the encapsulating resin composition at low temperature, the encapsulating resin composition preferably does not contain a maleimide compound.
Here, the maleimide compound is specifically a compound having two or more maleimide groups. Preferably, the encapsulating resin composition does not intentionally contain a maleimide compound, and the content of the maleimide compound in the encapsulating resin composition is more preferably substantially 0 mass%, for example, below the detection limit.

The mixture used in the method for producing an encapsulating resin composition or the obtained encapsulating resin composition may contain components other than the components (A) and (B). For example, the encapsulating resin composition may contain one or both of the following components (C) and (D).
(C) Inorganic filler (D) Silane coupling agent

(Component (C))
Component (C) is an inorganic filler. As the inorganic filler, any inorganic filler that is generally used in semiconductor encapsulation resin compositions can be used.
Specific examples of component (C) include silica such as fused silica, crystalline silica, and amorphous silicon dioxide, alumina, talc, titanium oxide, silicon nitride, and aluminum nitride. These inorganic fillers may be used alone or in combination of two or more.

From the viewpoint of excellent versatility, component (C) preferably contains silica. Examples of the shape of silica include spherical silica and crushed silica.
From the viewpoint of improving the balance between narrow passage filling ability, adhesion and reliability, it is also preferable that component (C) contains fused spherical silica and amorphous silicon dioxide.

From the viewpoint of improving moldability, the average diameter (d ₅₀ ) of component (C) is preferably 5 μm or more, more preferably 10 μm or more.
From the viewpoint of improving the narrow-part filling ability, the average diameter of component (B) is preferably 80 μm or less, more preferably 50 μm or less, and even more preferably 40 μm or less.
Here, the particle size distribution of component (C) can be obtained by measuring the particle size distribution of the particles on a volume basis using a commercially available laser diffraction particle size distribution measuring device (for example, SALD-7000, manufactured by Shimadzu Corporation).

From the viewpoint of improving moldability, the maximum particle size of component (C) is preferably 10 μm or more, and more preferably 20 μm or more.
From the viewpoint of improving the narrow-part-filling ability, the maximum particle size of component (B) is preferably 100 μm or less, more preferably 80 μm or less, and even more preferably 50 μm or less.

The content of component (C) in the encapsulating resin composition is preferably 50 mass % or more, more preferably 60 mass % or more, and even more preferably 65 mass % or more, based on the entire encapsulating resin composition, from the viewpoint of improving the low moisture absorption and low thermal expansion properties of the encapsulating material formed using the encapsulating resin composition and more effectively improving the moisture resistance reliability and reflow resistance of the obtained semiconductor device.
In addition, from the viewpoint of more effectively improving the fluidity and filling property during molding of the encapsulating resin composition, the content of the component (C) in the encapsulating resin composition is preferably 95 mass % or less, and more preferably 90 mass % or less, based on the entire encapsulating resin composition.

(Component (D))
Component (D) is a silane coupling agent.
Examples of component (D) include aminosilanes such as epoxysilane, mercaptosilane, and phenylaminosilane. From the viewpoint of improving the adhesion between the sealing material and the metal member, component (D) is preferably an epoxysilane or an aminosilane, and more preferably a secondary aminosilane. From the same viewpoint, component (D) is preferably one or more selected from the group consisting of phenylaminopropyltrimethoxysilane and γ-glycidoxypropyltrimethoxysilane.

From the viewpoint of obtaining favorable fluidity during molding of the encapsulating resin composition, the content of the component (D) in the encapsulating resin composition is preferably 0.01 mass % or more, and more preferably 0.05 mass % or more, based on the entire encapsulating resin composition.
From the viewpoints of suppressing the moisture absorption of the cured product, significantly improving the package crack resistance, and reducing the volatile content as well as realizing good curability, the content of component (D) in the encapsulating resin composition is preferably 2.0 mass % or less, more preferably 1.0 mass % or less, and even more preferably 0.5 mass % or less, based on the entire encapsulating resin composition.

(Hardening agent)
The mixture used in the method for producing an encapsulating resin composition or the obtained encapsulating resin composition may further contain a curing agent as a component other than the above-mentioned components. The curing agents can be roughly divided into three types, for example, polyaddition type curing agents, catalyst type curing agents, and condensation type curing agents, and one or more of these can be used.

Examples of polyaddition type curing agents include aliphatic polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), and metaxylylenediamine (MXDA), aromatic polyamines such as diaminodiphenylmethane (DDM), m-phenylenediamine (MPDA), and diaminodiphenylsulfone (DDS), as well as polyamine compounds including dicyandiamide (DICY) and organic acid dihydralazide; hexahydrophthalic anhydride (HHPA), methyltetrahydrophthalic anhydride (MTHPA), and other polyamines. ), and aromatic acid anhydrides such as trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), and benzophenonetetracarboxylic acid (BTDA); phenolic resin hardeners such as novolac-type phenolic resins and polyvinylphenol; polymercaptan compounds such as polysulfides, thioesters, and thioethers; isocyanate compounds such as isocyanate prepolymers and blocked isocyanates; and organic acids such as carboxylic acid-containing polyester resins.

Examples of catalyst-type curing agents include tertiary amine compounds such as benzyldimethylamine (BDMA) and 2,4,6-trisdimethylaminomethylphenol (DMP-30); imidazole compounds such as 2-methylimidazole and 2-ethyl-4-methylimidazole (EMI24); and Lewis acids such as _BF3 complexes.

Examples of condensation type curing agents include phenolic resins; urea resins such as urea resins containing methylol groups; and melamine resins such as melamine resins containing methylol groups.

Among these, phenolic resin curing agents are preferred from the viewpoint of improving the balance of flame resistance, moisture resistance, electrical properties, curing properties, storage stability, etc. As the phenolic resin curing agent, any monomer, oligomer, or polymer having two or more phenolic hydroxyl groups in one molecule can be used, and there are no limitations on the molecular weight or molecular structure.

Examples of phenolic resin hardeners used as the hardener include novolac-type phenolic resins such as phenol novolac resin, cresol novolac resin, and bisphenol novolac; polyvinylphenol; multifunctional phenolic resins such as phenol-hydroxybenzaldehyde resin and triphenolmethane-type phenolic resin; modified phenolic resins such as terpene-modified phenolic resin and dicyclopentadiene-modified phenolic resin; aralkyl-type phenolic resins such as phenol aralkyl resins having one or more selected from a phenylene skeleton and a biphenylene skeleton, and naphthol aralkyl resins having one or more selected from a phenylene and a biphenylene skeleton; and bisphenol compounds such as bisphenol A and bisphenol F. These may be used alone or in combination of two or more. Among these, from the viewpoint of improving the insulating properties of a semiconductor device obtained by using the encapsulating resin composition, it is more preferable to use one or more selected from the group consisting of biphenylaralkyl type phenolic resins, novolac type phenolic resins, biphenylene skeleton-containing phenolaralkyl type resins, and biphenylene skeleton-containing phenolaralkyl type-formaldehyde polycondensates.

In the present embodiment, the content of the curing agent in the encapsulating resin composition is, from the viewpoint of realizing excellent fluidity during molding and improving filling property and moldability, preferably 1 mass % or more, more preferably 2 mass % or more, and further preferably 3 mass % or more, based on the entire encapsulating resin composition.
In addition, from the viewpoint of improving the moisture resistance reliability and reflow resistance of a semiconductor device obtained using the encapsulating resin composition, the content of the curing agent in the encapsulating resin composition is preferably 25 mass % or less, more preferably 15 mass % or less, and even more preferably 10 mass % or less, based on the entire encapsulating resin composition.

The mixture used in the method for producing an encapsulating resin composition or the resulting encapsulating resin composition may contain components other than those described above, and may contain, as appropriate, one or more of various additives such as a curing accelerator, a fluidity imparting agent, a release agent, an ion trapping agent, a low-stress component, a flame retardant, a colorant, and an antioxidant.

Among these, the curing accelerator may contain one or more types selected from phosphorus atom-containing compounds such as organic phosphines, tetra-substituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, and adducts of phosphonium compounds and silane compounds; nitrogen atom-containing compounds such as amidines and tertiary amines, exemplified by 1,8-diazabicyclo[5.4.0]undecene-7, benzyldimethylamine, and 2-methylimidazole, and quaternary salts of the above amidines and amines; and polyhydroxynaphthalene compounds such as 2,3-dihydroxynaphthalene. Among these, it is more preferable to contain a phosphorus atom-containing compound from the viewpoint of improving the curing property. In addition, from the viewpoint of improving the balance between moldability and curing property, it is more preferable to contain a compound having latency, such as a tetra-substituted phosphonium compound, a phosphobetaine compound, an adduct of a phosphine compound and a quinone compound, or an adduct of a phosphonium compound and a silane compound.

From the viewpoint of improving the curing properties of the encapsulating resin composition, the content of the curing accelerator in the encapsulating resin composition is preferably 0.01 mass % or more, more preferably 0.05 mass % or more, and even more preferably 0.1 mass % or more, based on the entire encapsulating resin composition.
In addition, from the viewpoint of obtaining favorable fluidity during molding of the encapsulating resin composition, the content of the curing accelerator in the encapsulating resin composition is preferably 2.0 mass % or less, more preferably 1.0 mass % or less, and even more preferably 0.5 mass % or less, based on the entire encapsulating resin composition.

The release agent can include one or more selected from the group consisting of natural waxes such as carnauba wax; synthetic waxes such as Montan acid ester wax and oxidized polyethylene wax; higher fatty acids and metal salts thereof such as zinc stearate; paraffin; and carboxylic acid amides such as erucic acid amide.
From the viewpoint of improving the releasability of a cured product of the encapsulating resin composition, the content of the release agent in the encapsulating resin composition is preferably 0.01 mass % or more, more preferably 0.05 mass % or more, even more preferably 0.1 mass % or more, and is preferably 2.0 mass % or less, more preferably 1.0 mass % or less, and even more preferably 0.5 mass % or less, based on the entire encapsulating resin composition.

A specific example of the ion scavenger is hydrotalcite.
From the viewpoint of improving the reliability of the encapsulating material, the content of the ion scavenger in the encapsulating resin composition is preferably 0.01 mass % or more, more preferably 0.05 mass % or more, and is preferably 1.0 mass % or less, more preferably 0.5 mass % or less, based on the entire encapsulating resin composition.

Specific examples of low stress components include silicones such as silicone oil and silicone rubber; and acrylonitrile butadiene rubber.
From the viewpoint of improving the reliability of the encapsulating material, the content of the low stress component in the encapsulating resin composition is preferably 0.01 mass % or more, more preferably 0.05 mass % or more, even more preferably 0.1 mass % or more, and is preferably 5 mass % or less, more preferably 3 mass % or less, and even more preferably 1 mass % or less, based on the entire encapsulating resin composition.

Specific examples of flame retardants include aluminum hydroxide, magnesium hydroxide, zinc borate, zinc molybdate, and phosphazene.
From the viewpoint of improving the flame retardancy of the encapsulating material, the content of the flame retardant in the encapsulating resin composition is preferably 1 mass % or more, more preferably 5 mass % or more, and is preferably 20 mass % or less, more preferably 10 mass % or less, based on the entire encapsulating resin composition.

Specific examples of colorants include carbon black and red iron oxide.
From the viewpoint of obtaining a preferable color tone of the encapsulating material, the content of the colorant in the encapsulating resin composition is preferably 0.1 mass % or more, more preferably 0.2 mass % or more, and is preferably 2 mass % or less, more preferably 1 mass % or less, based on the entire encapsulating resin composition.

Specific examples of antioxidants include hindered phenol compounds, hindered amine compounds, and thioether compounds.

Next, the shape of the encapsulating resin composition will be described.
In the present embodiment, the shape of the encapsulating resin composition can be selected depending on the molding method of the encapsulating resin composition, and examples thereof include particulate shapes such as tablets, powders, and granules; and sheets.

(Semiconductor device)
The semiconductor device in this embodiment is a semiconductor element encapsulated with the cured product of the encapsulating resin composition in this embodiment. Specific examples of the semiconductor element include integrated circuits, large-scale integrated circuits, transistors, thyristors, diodes, solid-state imaging elements, etc. The semiconductor element is preferably an element that does not involve light input or output, excluding optical semiconductor elements such as light receiving elements and light emitting elements (light emitting diodes, etc.).

The substrate of the semiconductor device is, for example, a wiring board such as an interposer, or a lead frame. The semiconductor element is electrically connected to the substrate by wire bonding or flip chip connection, etc.

Examples of semiconductor devices obtained by encapsulating a semiconductor element by encapsulation molding using an encapsulating resin composition include Mold Array Package (MAP), Quad Flat Package (QFP), Small Outline Package (SOP), Chip Size Package (CSP), Quad Flat Non-leaded Package (QFN), Small Outline Non-leaded Package (SON), Ball Grid Array (BGA), Lead Flame BGA (LF-BGA), Flip Chip BGA (FCBGA), Molded Array Process BGA (MAPBGA), Embedded Wafer-Level BGA (eWLB), Fan-In type eWLB, and Fan-Out type eWLB.
The present invention will be described in more detail below with reference to the drawings.

1 and 2 are cross-sectional views showing the configuration of a semiconductor device. Note that, in this embodiment, the configuration of the semiconductor device is not limited to that shown in FIGS.
First, the semiconductor device 100 shown in FIG. 1 includes a semiconductor element 20 mounted on a substrate 30 and a sealing material 50 that seals the semiconductor element 20 .
The encapsulant 50 is composed of a cured product obtained by curing the encapsulating resin composition of the present embodiment described above.

Also, FIG. 1 illustrates a case where the substrate 30 is a circuit board. In this case, as shown in FIG. 1, a plurality of solder balls 60, for example, are formed on the other side of the substrate 30 opposite to the side on which the semiconductor element 20 is mounted. The semiconductor element 20 is mounted on the substrate 30 and electrically connected to the substrate 30 via the wire 40. On the other hand, the semiconductor element 20 may be flip-chip mounted on the substrate 30. Here, the wire 40 is not limited to, but examples thereof include Ag wire, Ni wire, Cu wire, Au wire, and Al wire, and preferably, the wire 40 is made of Ag, Ni, or Cu, or an alloy containing one or more of these.

The sealing material 50 seals the semiconductor element 20 so as to cover, for example, one surface of the semiconductor element 20 opposite to the surface facing the substrate 30. In the example shown in FIG. 1, the sealing material 50 is formed so as to cover the other surface and the side surface of the semiconductor element 20.
In the present embodiment, the encapsulant 50 is formed of a cured product of the above-mentioned encapsulating resin composition. Therefore, in the semiconductor device 100, the encapsulant 50 and the wires 40 have excellent adhesion, and thus the semiconductor device 100 has excellent reliability.
The encapsulant 50 can be formed, for example, by encapsulating and molding an encapsulating resin composition using a known method such as transfer molding or compression molding.

Figure 2 is a cross-sectional view showing the configuration of a semiconductor device 100 in this embodiment, and shows an example different from that in Figure 1. The semiconductor device 100 shown in Figure 2 uses a lead frame as the substrate 30. In this case, the semiconductor element 20 is mounted, for example, on the die pad 32 of the substrate 30, and is electrically connected to the outer lead 34 via the wire 40. The encapsulant 50 is composed of a cured product of the encapsulating resin composition in this embodiment, similar to the example shown in Figure 1.

The above describes embodiments of the present invention, but these are merely examples of the present invention, and various configurations other than those described above can also be adopted.

The present embodiment will be described in detail below with reference to examples and comparative examples. Note that the present embodiment is not limited in any way to the descriptions of these examples.

Example 1
In this example, a powder consisting of a pulverized aminotriazole compound was prepared by the following method.
Using a single track jet mill STJ-200 device (manufactured by Seishin Enterprise Co., Ltd.), 3-amino-1,2,4-triazole was fed into the device at a constant rate from a hopper using a constant feeder. The feeding speed was 20 kg/h. The particle size distribution was controlled by the pressure (air) of the device, and aminotriazole powder was prepared using compressed air of 0.7 to 0.75 MPa.

The particle size characteristics of the obtained powder were measured by a laser diffraction method and a dry particle size distribution analyzer, and the results are shown below.
_d50 = 2.3 μm
_dmax = 9.9 μm
_d10 = 0.61 μm
_d90 =5.4 μm

(Examples 2 and 3 and Comparative Example 1)
The powder obtained in Example 1 or other powders were used to prepare encapsulating resin compositions. The composition of the raw materials for the encapsulating resin compositions of each example is shown in Table 1.

(Method for producing encapsulating resin composition)
The components shown in Table 1 were mixed in a mixer to obtain a mixture. The mixture was then heated to 90 to 120° C. and roll-kneaded, and then cooled and pulverized to obtain an encapsulating resin composition in the form of a powder.

The details of each component in Table 1 are as follows. The blending ratio of each component shown in Table 1 indicates the blending ratio (mass %) to the entire resin composition.

(raw materials)
(Inorganic filler)
(C) Inorganic filler 1: fused spherical silica, manufactured by Denka, average diameter 31 μm
(C) Inorganic filler 2: Amorphous silicon dioxide (ES-355, manufactured by Tokai Minerals Co., Ltd.) 99.35 wt% surface-treated with γ-aminopropyltriethoxysilane 0.65 wt% (C) Inorganic filler 3: Fused spherical silica, FB-105, manufactured by Denka Co., Ltd., average diameter 10.6 μm, upper cutoff 71 μm
(C) Inorganic filler 4: fused spherical silica, manufactured by Admatechs Co., Ltd., SC-2500-SQ, average diameter 0.6 μm, upper cutoff 45 μm
(C) Inorganic filler 5: fused spherical silica, manufactured by Admatechs Co., Ltd., SC-5500-SQ, average diameter 1.6 μm, upper cutoff 45 μm

(Silane coupling agent)
(D) Silane coupling agent 1: N-phenyl-3-aminopropyltrimethoxysilane, manufactured by Dow Corning Toray Co., Ltd., CF4083

(Epoxy resin)
(B) Epoxy resin 1: phenol aralkyl type epoxy resin containing a biphenylene skeleton, manufactured by Nippon Kayaku Co., Ltd., NC3000L

(Hardening agent)
Phenolic resin hardener 1: Phenol-4,4'-bischloromethylbiphenyl-formaldehyde polycondensate Phenolic resin hardener 2: Phenol aralkyl resin containing biphenylene skeleton, manufactured by Meiwa Kasei Co., Ltd., MEH-7851SS

(Cure Accelerator)
Curing accelerator 1: 4-hydroxy-2-(triphenylphosphonium)phenolate, manufactured by Kei-I Chemicals Co., Ltd. Curing accelerator 2: 2,3-dihydroxynaphthalene, manufactured by Air Water Co., Ltd.

(Release Agent)
Release agent 1: Erucic acid amide, NOF Corp. Release agent 2: Oxidized polyethylene wax, Clariant Japan, Licowax PED191
Release agent 3: Carnauba wax, manufactured by Toa Chemical Industries, Ltd., TOWAX-132

(Coloring Agent)
Colorant 1: Carbon black, manufactured by Tokai Carbon Co., Ltd., ERS-2001

(Ion Scavenger)
Ion scavenger 1: Magnesium aluminum hydroxide carbonate hydrate, manufactured by Kyowa Chemical Industry Co., Ltd., DHT-4H

(Adhesion aid)
Adhesion aid 1: 3-amino-1,2,4-triazole powder, d ₅₀ =120 μm, d _max =700 μm, d ₁₀ =39 μm, d ₉₀ =230 μm
(A) Adhesion assistant 2: Powder obtained in Example 1 (3-amino-1,2,4-triazole pulverized by a jet mill), d ₅₀ =2.3 μm, d _max =9.9 μm, d ₁₀ =0.61 μm, d ₉₀ =5.4 μm

(Low stress agent)
Low stress agent 1: Carboxyl-terminated butadiene-acrylonitrile copolymer, manufactured by Ube Industries, Ltd., CTBN1008SP
Stress reducing agent 2: Melt reactant A obtained in Production Example 1

(Production Example 1)
66.1 parts by mass of an epoxy resin represented by the following formula (8) (bisphenol A type epoxy resin, manufactured by Javan Epoxy Resins, jER (registered trademark) YL6810, softening point 45°C, epoxy equivalent 172) was heated and melted at 140°C, and 33.1 parts by mass of organopolysiloxane 1 (organopolysiloxane represented by the following formula (7)) and 0.8 parts by mass of triphenylphosphine were added and melt-mixed for 30 minutes to obtain a molten reaction product A.

(In the above formula (7), the average value of n7 is 7.5.)

(evaluation)
Using the resin composition obtained in each example, an evaluation sample was prepared by the following method, and the curing characteristics, adhesion and reliability of the obtained sample were evaluated by the following methods.

(Narrow passage filling property)
Simulated mold filling: An evaluation mold was used to simulate narrow-path filling, which had six square pillars of 9 mm x 9 mm x 0.42 mm (thickness) in a rectangular flow path of 145 mm in length, 15 mm in width, and 0.5 mm in thickness (the distance between the square pillars was 3 mm), and an evaluation mold was used to simulate narrow-path filling, which had six square pillars of 9 mm x 9 mm x 0.45 mm (thickness) in a rectangular flow path of 145 mm in length, 15 mm in width, and 0.5 mm in thickness (the distance between the square pillars was 3 mm). Transfer molding was performed at a mold temperature of 175°C, an injection pressure of 9.8 MPa, and a curing time of 2 minutes, and the filling of 80 μm and 50 μm gaps (unfilled, presence or absence of voids) was evaluated by the following method.
That is, the filling property on six square pillars with thicknesses of 0.42 mm and 0.45 mm was evaluated (thickness: 80 μm and 50 μm gaps, total of six consecutive filling properties). At this time, a light was irradiated onto the obtained molded product, and the filling of the resin was judged based on the degree of light transmission, and the evaluation criteria were as follows.
×: The filling rate of the 6-unit molded part is less than 35%. △: The filling rate of the 6-unit molded part is 35% or more and less than 65%. ○: The filling rate of the 6-unit molded part is 65% or more.

(Adhesion)
For the encapsulating resin composition obtained in each example, the die shear strength in post-mold cure (PMC) was measured as an index of adhesion by the following method.
For the encapsulating resin composition obtained in each example, ten adhesion strength test pieces of 3.6 mmφ×3 mm were molded onto a 9×29 mm rectangular test copper lead frame or nickel plate under conditions of a mold temperature of 175° C., an injection pressure of 10 MPa, and a curing time of 180 seconds using a low-pressure transfer molding machine (manufactured by Yamashiro Seiki Co., Ltd., “AV-600-50-TF”).
Thereafter, the die shear strength of the sample cured under the conditions of 175°C for 3 hours was measured at room temperature (RT, 25°C) or 260°C using an automatic die shear measurement device (Nordson Advanced Technology Corp., DAGE4000 model) to determine the die shear strength (MPa).

(Reliability: Temperature cycle test)
For the encapsulating resin composition obtained in each example, TO-220 (package size: 114 mm x 30 mm, thickness: 1.3 mm, no chip mounted, lead frame: Cu or Ni plated product) was molded using a low pressure transfer molding machine (Apic Yamada's "MSL-06M") at a mold temperature of 175°C, injection pressure of 10 MPa, and curing time of 180 seconds, and then cured at 175°C for 4 hours to produce a test semiconductor device. The encapsulated test semiconductor device was subjected to a temperature cycle test by repeating 100 cycles at -40°C to 150°C, and the presence or absence of package cracks and peeling between members was judged. The measurement results are shown in Table 1 as "Number of defects/number of samples". Samples with a "number of defects/number of samples" of 4/10 or less were considered to have passed the test.

As can be seen from Table 1, the encapsulating resin compositions obtained in each Example had excellent narrow-path filling properties, no aggregation during molding, suppressed residual dissolution of coarse powder particles, and excellent adhesion to metal members. In addition, by using the encapsulating resin compositions obtained in each Example, semiconductor devices with excellent reliability were obtained.

20 Semiconductor element 30 Substrate 32 Die pad 34 Outer lead 40 Wire 50 Sealing material 60 Solder ball 100 Semiconductor device

Claims (4)

A step of obtaining the following component (A) by grinding a raw material composed of one or more compounds selected from the group consisting of 3-amino-1,2,4-triazole and 4-amino-1,2,4-triazole;
A step of heating and kneading a mixture containing the component (A) and the following component (B);
A method for producing an encapsulating resin composition comprising:
The maximum particle size _dmax of the component (A) measured by a laser diffraction method is 100 μm or less,
The particle size _d10 of the component (A) measured by a laser diffraction method is 0.1 μm or more and 10 μm or less,
The particle size _d90 of the component (A) measured by a laser diffraction method is 1 μm or more and 50 μm or less,
The method for producing an encapsulating resin composition, wherein the encapsulating resin composition does not contain a maleimide compound .
(A) a powder composed of the above compound, the powder having an average particle size _d50 of 0.2 μm or more and 20 μm or less, as measured by a laser diffraction method; (B) an epoxy resin; The method for producing an encapsulating resin composition according to claim 1 , wherein the step of obtaining component (A) comprises a step of pulverizing the raw material with a jet mill. The method for producing an encapsulating resin composition according to claim 1 or 2 , wherein the mixture further comprises component (C): an inorganic filler. The method for producing an encapsulating resin composition according to claim 1 , wherein the mixture further comprises a component (D): a silane coupling agent.

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