Method for producing resin composition for sealing

Abstract

To provide a sealing resin composition having excellent narrow passage filling properties and excellent adhesion between a metal member and a sealing material.SOLUTION: A powder has at least one compound selected from the group consisting of 3-amino-1,2,4-triazole and 4-amino-1,2,4-triazole. When measured by laser diffraction, the powder has an average particle size d50 of 0.2 μm or more and 20 μm or less.SELECTED DRAWING: None

Description

[Technology Field]

[0001] The present invention relates to a method for producing powders and encapsulating resin compositions. [Background technology]

[0002] Patent Document 1 (Japanese Patent Publication No. 62-25118) describes a encapsulating resin composition for sealing electronic components. This document describes a encapsulating resin composition that prevents ion migration of metals and galvanic corrosion caused by ionic halogens, has excellent moisture resistance, and retains the advantages of conventional compositions. The composition comprises an epoxy resin, a novolac-type phenolic resin, a predetermined amount of 2-vinyl-4,6-diamino-s-triazine, and a predetermined amount of inorganic filler. The document states that by incorporating a predetermined amount of 2-vinyl-4,6-diamino-s-triazine, a encapsulating resin composition that prevents galvanic corrosion and has excellent moisture resistance can be obtained. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Unexamined Patent Publication No. 62-25118 [Overview of the project] [Problems that the invention aims to solve]

[0004] When the present inventors examined the technology described in Patent Document 1, it became clear that there is room for improvement in the sealing resin composition described in the said document in terms of narrow passage filling ability and adhesion to metal members. The present invention provides a sealing resin composition that exhibits excellent narrow passage filling ability and adhesion between metal members and sealing materials. [Means for solving the problem]

[0005] According to the present invention, A powder comprising one or more compounds selected from the group consisting of 3-amino-1,2,4-triazole and 4-amino-1,2,4-triazole, wherein the average particle size d of the powder is measured by laser diffraction. 50A powder is provided in which the particle size is between 0.2 μm and 20 μm.

[0006] According to the present invention, The process involves 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 to obtain the following component (A), A step of heating and kneading a mixture containing the above component (A) and the following component (B), A method for producing a sealing resin composition is provided, which includes the following. (A) A powder composed of the compound, wherein the average particle size d of the powder is measured by laser diffraction. 50 Powder with a particle size of 0.2 μm or more and 20 μm or less. (B) Epoxy resin

[0007] Furthermore, according to the present invention, it is also possible to provide, for example, a encapsulating resin composition obtained by the method for manufacturing the encapsulating resin composition according to the present invention as described above, and a semiconductor device in which a semiconductor element is encapsulated with such encapsulating resin composition. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a sealing resin composition that exhibits excellent narrow passage filling ability and adhesion between metal members and sealing materials. [Brief explanation of the drawing]

[0009] [Figure 1] This is a cross-sectional view showing the configuration of a semiconductor device in an embodiment. [Figure 2] This is a cross-sectional view showing the configuration of a semiconductor device in an embodiment. [Modes for carrying out the invention]

[0010] The embodiments will be described below with reference to the drawings. In all drawings, similar components are denoted by the same reference numerals, and their descriptions are omitted as appropriate. Also, the figures are schematic diagrams and do not necessarily correspond to the actual dimensional ratios. Furthermore, in this embodiment, the composition may contain each component individually or in combination of two or more.

[0011] (Powder: Component (A)) In this embodiment, the powder is 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 of the powder is measured by laser diffraction. 50 The particle size is between 0.2 μm and 20 μm. By using such powder as an additive to the encapsulating resin composition, the packing ability of the encapsulating resin composition into narrow passages can be improved. Furthermore, the adhesion between the encapsulating material obtained using the encapsulating resin composition and the metal component can be improved. As a result, a semiconductor device with superior reliability can be obtained. In addition, by using such powder as an additive to the encapsulating resin composition, it is possible to improve, for example, the curing characteristics of the encapsulating resin composition at low temperatures. Moreover, such powder can be suitably used in the encapsulating resin composition as an additive such as an adhesion aid. The composition of the powder will be explained in more detail below.

[0012] The powder consists of one or more 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 viewpoint of improving adhesion to metal components and ease of availability, the components of the powder preferably contain 3-amino-1,2,4-triazole, and more preferably 3-amino-1,2,4-triazole. From the same perspective, 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, still more preferably 90% by mass or more, even more preferably 95% by mass or more, and even more preferably 100% by mass, based on the total powder.

[0013] The average particle diameter d of the powder 50 is 0.2 μm or more, preferably 0.5 μm or more, and more preferably 1 μm or more, from the perspective of suppressing the thickening of the resin. Also, from the perspective of improving the dispersibility in the sealing resin composition in which the powder is blended and eliminating the remaining undissolved coarse particles of the powder during molding, it is 20 μm or less, preferably 10 μm or less, and more preferably 5 μm or less.

[0014] Here, the average particle diameter d of the powder 50 , and the maximum particle diameter d of the powder described later max , the particle diameter d 10 and the particle diameter d 90 are all measured by the laser diffraction method based on the volume standard of the dry particle size distribution.

[0015] The maximum particle diameter d of the powder max is preferably 100 μm or less, more preferably 70 μm or less, still more preferably 50 μm or less, even more preferably 20 μm or less, and even more preferably 10 μm or less, from the perspective of improving the dispersibility in the sealing resin composition in which the powder is blended and eliminating the remaining undissolved coarse particles of the powder during molding. ' Also, from the perspective of suppressing the thickening of the resin, the maximum particle diameter d of the powder max may be, for example, 1 μm or more, and preferably 5 μm or more.

[0016] The particle diameter d of the powder 10 is preferably 0.1 μm or more, more preferably 0., from the perspective of suppressing the thickening of the resin. Also, from the perspective of improving the dispersibility in the sealing resin composition in which the powder is blended and eliminating the remaining undissolved coarse particles of the powder during molding, the particle diameter d of the powder10 The particle size 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.

[0017] Powder particle size d 90 From the viewpoint of suppressing the thickening of the resin, the thickness 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. Furthermore, from the viewpoint of improving the dispersibility of the sealing resin composition into which the powder is incorporated and eliminating undissolved coarse powder particles during molding, the particle size d of the powder 90 The particle size 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.

[0018] In this embodiment, the raw material is preferably a pulverized product of the above-mentioned compounds, and more preferably a jet-milled product of such raw material. Furthermore, the powder can be obtained, for example, by grinding a raw material preferably composed of the compounds described above. By using a pulverizing device such as a jet mill to pulverize the raw materials and obtain the powder in this embodiment, the amount of coarse particles can be reduced. This improves the dispersibility of the encapsulating resin composition into which the powder is blended, eliminates undissolved coarse particles of the powder during molding, and improves the adhesion between the encapsulating material and the metal component. Furthermore, this improves the reliability of the semiconductor device.

[0019] (Method for manufacturing encapsulating resin composition) The powder in this embodiment is suitably incorporated into the encapsulating resin composition. A method for producing a encapsulating resin composition includes, for example, the following steps 1 and 2. (Step 1) A step to obtain the following component (A) by grinding a raw material consisting 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 process of heating and kneading a mixture containing component (A) and the following component (B). (A) A powder composed of the above compound, wherein the average particle size d of the powder is measured by laser diffraction. 50 Powder with a particle size of 0.2 μm or more and 20 μm or less. (B) Epoxy resin

[0020] (Process 1) Step 1 is the process of obtaining the aforementioned powder, i.e., component (A), and specifically, it is the process of obtaining a pulverized product by pulverizing the above 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 them to collide with each other.

[0021] Step 1 can be carried out, for example, using a grinding device. Specific examples of grinding devices include air-jet grinders such as jet mills; ball mills such as vibrating 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 powder with desired particle size characteristics, the stirring device is preferably a jet mill grinder, and more preferably a vertical jet grinder. A specific example of a vertical jet grinder is, for example, the Sk Jet-O-Mill manufactured by Seishin Corporation. Furthermore, step 1 preferably includes the step of grinding the raw material with a jet mill.

[0022] Furthermore, by adjusting the grinding conditions in step 1, component (A) having the aforementioned desirable particle size characteristics can be obtained.

[0023] (Process 2) Step 2 involves heating and kneading a mixture containing components (A) and (B). Here, the mixture can be obtained by uniformly mixing components (A) and (B), along with other components as appropriate, at room temperature using a mixer or the like. Component (B) and the other components will be described later. Heating and kneading is a process of melting and kneading using a kneading machine such as a heated roll, kneader, or extruder. The heating temperature can be set according to the type of epoxy resin and other components contained in the mixture, and can be set to, for example, around 100°C to 120°C.

[0024] The kneaded material obtained in step 2 can be cooled and pulverized to obtain a sealing resin composition. Alternatively, after pulverization, it may be molded to obtain a granular or sheet-like sealing resin composition. For example, a granular sealing resin composition may be obtained by tablet molding. Alternatively, a sheet-like sealing resin composition may be obtained, for example, by a vacuum extruder. Furthermore, the degree of dispersion and fluidity of the obtained sealing resin composition may be adjusted as appropriate.

[0025] The sealing resin composition obtained in this way is obtained by heating and kneading a mixture containing components (A) and (B), and therefore exhibits excellent filling properties in narrow passages and excellent adhesion between the sealing material and the metal member. More specifically, this embodiment also makes it possible to improve the adhesion between the sealing material and a member composed of Ag, Ni, Cu, or an alloy containing one or more of these. Furthermore, such a sealing resin composition exhibits excellent moldability at low temperatures, for example, 150°C or below. Furthermore, by using such a encapsulating resin composition, a semiconductor device with excellent reliability can be obtained.

[0026] The following describes the components contained in the encapsulating resin composition. First, component (A) is the aforementioned powder. From the viewpoint of stably improving the adhesion between the sealing material and the metal member, the content of component (A) in the sealing 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, relative to the entire sealing resin composition. Furthermore, from the viewpoint of providing favorable fluidity and storage properties for the sealing resin composition, 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, relative to the entire sealing resin composition.

[0027] (Component (B)) The epoxy resin of component (B) is a compound having two or more epoxy groups in one molecule, and may be a monomer, oligomer, or polymer. Specifically, epoxy resins are 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 etherification of 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.

[0028] From the viewpoint of improving adhesion with metal members, the epoxy resin is preferably one or more selected from the group consisting of trisphenylmethane type epoxy resin, biphenyl aralkyl type polyfunctional epoxy resin, orthocresol type difunctional epoxy resin, biphenyl type difunctional epoxy resin, and bisphenol type difunctional epoxy resin, and more preferably biphenyl aralkyl type polyfunctional epoxy resin.

[0029] The epoxy resin content in the sealing resin composition is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 4% by mass or more, relative to the total sealing resin composition, from the viewpoint of obtaining suitable fluidity during molding and improving filling properties and moldability. Furthermore, from the viewpoint of improving the reliability of the device obtained using the sealing resin composition, the epoxy resin content in the sealing resin composition is preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less, and even more preferably 10% by mass or less, based on the total amount of the sealing resin composition.

[0030] Furthermore, the sealing resin composition preferably does not contain maleimide compounds, from the viewpoint of improving the adhesion between the sealing material and the metal component while also improving the curability of the sealing resin composition at low temperatures. Here, the maleimide compound is specifically a compound having two or more maleimide groups. Furthermore, the sealing resin composition preferably does not intentionally contain the maleimide compound, and the content of the maleimide compound in the sealing resin composition is more preferably substantially 0% by mass, for example, below the detection limit.

[0031] The mixture used in the method for producing the sealing resin composition, or the resulting sealing resin composition, may contain components other than components (A) and (B). For example, the sealing resin composition may contain one or both of the following components (C) and (D). (C) Inorganic filler (D) Silane coupling agent

[0032] (Component (C)) Component (C) is an inorganic filler. As the inorganic filler, those commonly 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 individually or in combination of two or more.

[0033] Component (C) preferably contains silica from the viewpoint of excellent versatility. Examples of silica forms include spherical silica and crushed silica. Furthermore, from the viewpoint of improving the balance between narrow passage filling ability, adhesion, and reliability, it is also preferable that component (C) contains molten spherical silica and amorphous silicon dioxide.

[0034] Average diameter (d) of component (C) 50 The thickness of the material is preferably 5 μm or more, and more preferably 10 μm or more, from the viewpoint of improving moldability. Furthermore, from the viewpoint of improving narrow-area filling performance, 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 on a volume basis using a commercially available laser diffraction particle size distribution analyzer (for example, Shimadzu Corporation's SALD-7000).

[0035] Furthermore, 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 moldability. Furthermore, from the viewpoint of improving narrow-space filling performance, 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.

[0036] The content of component (C) in the encapsulating resin composition is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 65% ​​by mass or more, relative to the entire encapsulating resin composition, from the viewpoint of improving the low hygroscopicity and low thermal expansion of the encapsulating material formed using the encapsulating resin composition, and more effectively improving the moisture resistance reliability and reflow resistance of the resulting semiconductor device. Furthermore, from the viewpoint of more effectively improving the fluidity and fillability of the sealing resin composition during molding, the content of component (C) in the sealing resin composition is preferably 95% by mass or less, and more preferably 90% by mass or less, relative to the entire sealing resin composition.

[0037] (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 epoxysilane or aminosilane, and more preferably secondary aminosilane. From a similar viewpoint, component (D) is preferably one or more selected from the group consisting of phenylaminopropyltrimethoxysilane and γ-glycidoxypropyltrimethoxysilane.

[0038] The content of component (D) in the sealing resin composition is preferably 0.01% by mass or more, and more preferably 0.05% by mass or more, relative to the entire sealing resin composition, from the viewpoint of obtaining favorable fluidity when molding the sealing resin composition. Furthermore, from the viewpoint of suppressing the hygroscopicity of the cured product, significantly improving package crack resistance, reducing volatile components, and achieving good curability, the content of component (D) in the sealing resin composition is preferably 2.0% by mass or less, more preferably 1.0% by mass or less, and even more preferably 0.5% by mass or less, relative to the entire sealing resin composition.

[0039] (Hardening agent) The mixture used in the method for producing the encapsulating resin composition, or the resulting encapsulating resin composition, may further contain a curing agent as a component other than those described above. Curing agents can be broadly classified into three types, for example, polyaddition curing agents, catalytic curing agents, and condensation curing agents, and one or more of these types can be used.

[0040] 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 dihydrazides; alicyclic acid anhydrides such as hexahydrophthalic anhydride (HHPA) and methyltetrahydrophthalic anhydride (MTHPA), and acid anhydrides including aromatic acid anhydrides such as trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), and benzophenonetetracarboxylic acid (BTDA); phenolic resin curing agents 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.

[0041] Examples of catalytic 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.

[0042] Examples of condensation-type curing agents include phenolic resins, urea resins such as methylol group-containing urea resins, and melamine resins such as methylol group-containing melamine resins.

[0043] Among these, phenolic resin curing agents are preferred from the viewpoint of improving the balance of flame resistance, moisture resistance, electrical properties, curability, and storage stability. As phenolic resin curing agents, monomers, oligomers, and polymers in general that have two or more phenolic hydroxyl groups in one molecule can be used, and their molecular weight and molecular structure are not limited.

[0044] Examples of phenolic resin curing agents used as curing agents include novolac-type phenolic resins such as phenol novolac resin, cresol novolac resin, and bisphenol novolac; polyvinylphenol; polyfunctional 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 resin having one or more selected from phenylene skeletons and biphenylene skeletons, and naphthol aralkyl resin having one or more selected from phenylene and biphenylene skeletons; and bisphenol compounds such as bisphenol A and bisphenol F. These may be used individually or in combination of two or more types. Among these, from the viewpoint of improving the insulating properties of semiconductor devices obtained using the sealing resin composition, it is more preferable to use one or more selected from the group consisting of biphenylaralkyl type phenol resin, novolac type phenol resin, biphenylene skeleton-containing phenolaralkyl type resin, and biphenylene skeleton-containing phenolaralkyl type-formaldehyde polycondensate.

[0045] In this embodiment, the content of the curing agent in the sealing resin composition is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 3% by mass or more, relative to the total sealing resin composition, from the viewpoint of achieving excellent fluidity during molding and improving filling and moldability. Furthermore, with respect to semiconductor devices obtained using the sealing resin composition, from the viewpoint of improving moisture resistance reliability and reflow resistance, the content of the curing agent in the sealing resin composition is preferably 25% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, relative to the total sealing resin composition.

[0046] Furthermore, the mixture used in the method for producing the encapsulating resin composition, or the resulting encapsulating resin composition, may contain components other than those described above. For example, one or more additives such as curing accelerators, fluidity imparters, mold release agents, ion scavengers, low-stress components, flame retardants, colorants, and antioxidants may be appropriately blended.

[0047] Of these, the curing accelerator may include one or more selected from the following: phosphorus-containing compounds such as organophosphines, tetrasubstituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, and adducts of phosphonium compounds and silane compounds; nitrogen-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 include phosphorus-containing compounds from the viewpoint of improving curability. Furthermore, from the viewpoint of improving the balance between moldability and curability, it is more preferable to include latent compounds such as tetrasubstituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, and adducts of phosphonium compounds and silane compounds.

[0048] From the viewpoint of improving the curing characteristics of the encapsulating resin composition, the content of the curing accelerator in the encapsulating resin composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, relative to the total encapsulating resin composition. Furthermore, from the viewpoint of obtaining favorable fluidity during molding of the sealing resin composition, the content of the curing accelerator in the sealing resin composition is preferably 2.0% by mass or less, more preferably 1.0% by mass or less, and even more preferably 0.5% by mass or less, relative to the total sealing resin composition.

[0049] The release agent may include one or more types selected from the group consisting of, for example, natural waxes such as carnauba wax; synthetic waxes such as montanic acid ester wax and polyethylene oxide wax; higher fatty acids such as zinc stearate and their metal salts; paraffin; and carboxylic acid amides such as erucic acid amide. The content of the release agent in the sealing resin composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, and also preferably 2.0% by mass or less, more preferably 1.0% by mass or less, and even more preferably 0.5% by mass or less, relative to the entire sealing resin composition, from the viewpoint of improving the release properties of the cured product of the sealing resin composition.

[0050] Hydrotalcite is a specific example of an ion scavenger. From the viewpoint of improving the reliability of the sealing material, the content of the ion scavenger in the sealing resin composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and preferably 1.0% by mass or less, and more preferably 0.5% by mass or less, relative to the total sealing resin composition.

[0051] 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 sealing material, the content of low-stress components in the sealing resin composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, and also preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less, relative to the total sealing resin composition.

[0052] 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 sealing material, the content of the flame retardant in the sealing resin composition is preferably 1% by mass or more, more preferably 5% by mass or more, preferably 20% by mass or less, and more preferably 10% by mass or less, relative to the total sealing resin composition.

[0053] Specific examples of colorants include carbon black and red iron oxide. From the viewpoint of obtaining a desirable color tone for the sealing material, the content of the coloring agent in the sealing resin composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, preferably 2% by mass or less, and more preferably 1% by mass or less, relative to the total sealing resin composition.

[0054] Specific examples of antioxidants include hindered phenol compounds, hindered amine compounds, and thioether compounds.

[0055] Next, the shape of the encapsulating resin composition will be described. In this embodiment, the shape of the sealing resin composition can be selected according to the molding method of the sealing resin composition, and examples include particulate forms such as tablets, powders, and granules; and sheet forms.

[0056] (Semiconductor device) The semiconductor device in this embodiment is characterized by the encapsulation of semiconductor elements by a cured product of the encapsulation resin composition described above. Specific examples of semiconductor elements include integrated circuits, large-scale integrated circuits, transistors, thyristors, diodes, and solid-state image sensors. The semiconductor elements are preferably so-called elements that do not involve the input or output of light, excluding photosensitive elements and light-emitting elements (such as light-emitting diodes).

[0057] The substrate for semiconductor devices is, for example, a wiring board such as an interposer, or a lead frame. Semiconductor elements are electrically connected to the substrate by methods such as wire bonding or flip-chip connections.

[0058] Examples of semiconductor devices obtained by encapsulating semiconductor elements using encapsulation molding with a encapsulation resin composition include MAP (Mold Array Package), QFP (Quad Flat Package), SOP (Small Outline Package), CSP (Chip Size Package), QFN (Quad Flat Non-leaded Package), SON (Small Outline Non-leaded Package), BGA (Ball Grid Array), LF-BGA (Lead Flame BGA), FCBGA (Flip Chip BGA), MAPBGA (Molded Array Process BGA), eWLB (Embedded Wafer-Level BGA), Fan-In type eWLB, and Fan-Out type eWLB. Further details will be explained below with reference to the diagrams.

[0059] Figures 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 those shown in Figures 1 and 2. First, the semiconductor device 100 shown in Figure 1 comprises a semiconductor element 20 mounted on a substrate 30 and a sealing material 50 that encloses the semiconductor element 20. The sealing material 50 is composed of a cured product obtained by curing the sealing resin composition in this embodiment described above.

[0060] Furthermore, Figure 1 illustrates a case where the substrate 30 is a circuit board. In this case, as shown in Figure 1, for example, a plurality of solder balls 60 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 wires 40. On the other hand, the semiconductor element 20 may also be flip-chip mounted on the substrate 30. Here, the wires 40 are not limited to, but examples include Ag wires, Ni wires, Cu wires, Au wires, and Al wires, and preferably the wires 40 are composed of Ag, Ni, or Cu or an alloy containing one or more of these.

[0061] The sealing material 50 seals the semiconductor element 20, for example, by covering the other side of the semiconductor element 20 that is opposite to the side facing the substrate 30. In the example shown in Figure 1, the sealing material 50 is formed to cover the other side and the side of the semiconductor element 20. In this embodiment, the sealing material 50 is made of a cured product of the sealing resin composition described above. Therefore, in the semiconductor device 100, the sealing material 50 and the wire 40 have excellent adhesion, and as a result, the semiconductor device 100 has excellent reliability. The sealing material 50 can be formed, for example, by sealing a sealing resin composition using a known method such as transfer molding or compression molding.

[0062] Figure 2 is a cross-sectional view showing the configuration of the semiconductor device 100 in this embodiment, and shows an example different from 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 a die pad 32 on the substrate 30 and is electrically connected to the outer lead 34 via a wire 40. The encapsulating material 50 is made of a cured product of the encapsulating resin composition in this embodiment, similar to the example shown in Figure 1.

[0063] The embodiments of the present invention have been described above, but these are merely examples, and various other configurations can also be adopted. [Examples]

[0064] This embodiment will be described in detail below with reference to examples and comparative examples. However, this embodiment is not limited in any way to the descriptions of these examples.

[0065] (Example 1) In this example, a powder consisting of pulverized aminotriazole compounds was prepared using the following method. A single-track jet mill STJ-200 (manufactured by Seishin Kigyo Co., Ltd.) was used to feed 3-amino-1,2,4-triazole from a hopper using a quantitative feeder. Processing was carried out at a feeding speed of 20 kg / h. The particle size distribution is controlled by the pressure (air) of the device, and aminotriazole powder was prepared using compressed air at a pressure of 0.7 to 0.75 MPa.

[0066] The particle size characteristics of the obtained powder were measured using laser diffraction and a dry particle size analyzer, and the results are shown below. d 50 = 2.3 μm d max = 9.9 μm d 10 = 0.61 μm d 90 = 5.4 μm

[0067] (Examples 2, 3 and Comparative Example 1) A sealing resin composition was prepared using the powder obtained in Example 1 or other powders. The raw material formulations for each example of the sealing resin composition are shown in Table 1.

[0068] (Method for manufacturing encapsulating resin composition) The components shown in Table 1 were mixed using a mixer to obtain a mixture. Next, the obtained mixture was heated to 90-120°C, roll-kneaded, cooled, and pulverized to obtain a granular sealing resin composition.

[0069] Details of each component in Table 1 are as follows. The blending ratios of each component shown in Table 1 represent their proportion (mass%) relative to the total resin composition.

[0070] (raw materials) (Inorganic filler) (C) Inorganic filler 1: Molten spherical silica, manufactured by Denka Co., Ltd., average diameter 31 μm (C) Inorganic filler 2: Amorphous silicon dioxide (Tokai Mineral Co., Ltd., ES-355) 99.35 wt% surface-treated with γ-aminopropyltriethoxysilane 0.65 wt% (C) Inorganic filler 3: Molten spherical silica, manufactured by Denka Co., Ltd., FB-105, average diameter 10.6 μm, upper limit cut 71 μm (C) Inorganic filler 4: Molten spherical silica, manufactured by Admatex, SC-2500-SQ, average diameter 0.6 μm, upper limit cut 45 μm (C) Inorganic filler 5: Molten spherical silica, manufactured by Admatex, SC-5500-SQ, average diameter 1.6 μm, upper limit cut 45 μm

[0071] (Silane coupling agent) (D) Silane coupling agent 1: N-phenyl-3-aminopropyltrimethoxysilane, manufactured by Toray Dow Corning, CF4083

[0072] (Epoxy resin) (B) Epoxy resin 1: Biphenylene skeleton-containing phenol aralkyl type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., NC3000L

[0073] (Hardening agent) Phenolic resin curing agent 1: Phenol-4,4'-bischloromethylbiphenyl-formaldehyde polycondensate Phenolic resin curing agent 2: Biphenylene skeleton-containing phenol aralkyl type resin, manufactured by Meiwa Kasei Co., Ltd., MEH-7851SS

[0074] (Curing accelerator) Curing accelerator 1: 4-hydroxy-2-(triphenylphosphonium)phenolate, manufactured by K.I. Chemicals Co., Ltd. Curing accelerator 2: 2,3-dihydroxynaphthalene, manufactured by Air Water Corporation.

[0075] (Release agent) Release agent 1: Erucic acid amide, manufactured by NOF Corporation. Release agent 2: Polyethylene oxide wax, manufactured by Clariant Japan, Ricowax PED191 Release agent 3: Carnauba wax, manufactured by Toa Chemical Co., Ltd., TOWAX-132

[0076] (Coloring agent) Coloring agent 1: Carbon black, manufactured by Tokai Carbon Co., Ltd., ERS-2001

[0077] (Ion scavenger) Ion scavenger 1: Magnesium aluminum hydroxide carbonate hydrate, manufactured by Kyowa Chemical Industry Co., Ltd., DHT-4H

[0078] (Adhesion enhancer) Adhesion aid 1: 3-amino-1,2,4-triazole powder, d 50 =120μm, d max =700μm, d 10 =39μm, d 90 =230μm (A) Adhesion aid 2: Powder obtained in Example 1 (3-amino-1,2,4-triazole pulverized with a jet mill), d 50 =2.3μm, d max =9.9μm, d 10 =0.61μm, d 90 = 5.4 μm

[0079] (Stress-reducing agent) Low-stress agent 1: Carboxylate-terminated butadiene / acrylonitrile copolymer, manufactured by Ube Industries, Ltd., CTBN1008SP Low-stress agent 2: Molten reactant A obtained in manufacturing example 1

[0080] (Manufacturing Example 1) 66.1 parts by mass of epoxy resin represented by the following formula (8) (bisphenol A type epoxy resin, manufactured by Javan Epoxy Resin, 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 molten reaction product A.

[0081] [Formula 1]

[0082] [chemical 2]

[0083] (In equation (7) above, the mean value of n7 is 7.5.)

[0084] (evaluation) Using the resin compositions obtained in each example, evaluation samples were prepared by the following method, and the curing properties, adhesion, and reliability of the obtained samples were evaluated by the following method.

[0085] (Narrow passage filling property) Simulated mold filling performance: Using two evaluation molds, one simulating narrow-path filling with a rectangular channel measuring 145 mm in length, 15 mm in width, and 0.5 mm in thickness containing six rectangular prisms measuring 9 mm × 9 mm × 0.42 mm (thickness) (with a spacing of 3 mm between the prisms), and the other simulating narrow-path filling with a rectangular channel measuring 145 mm in length, 15 mm in width, and 0.5 mm in thickness containing six rectangular prisms measuring 9 mm × 9 mm × 0.45 mm (thickness) (with a spacing of 3 mm between the prisms), 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. The filling performance (unfilled, presence or absence of voids) of 80 μm and 50 μm gaps was determined by the following method. Specifically, the filling capacity of six rectangular prisms with thicknesses of 0.42 mm and 0.45 mm (filling capacity of a total of six rows within a gap of 80 μm and 50 μm, respectively) was evaluated. At this time, the resulting molded product was illuminated with light, and the degree of resin filling was judged by the amount of light transmitted, with the following evaluation criteria. ×: Filling rate of the 6-unit mold section is less than 35% △: Filling rate of the 6-unit mold section is 35% or more but less than 65%. ○: Filling rate of the 6-unit mold section is 65% or higher.

[0086] (Adhesion) For the sealing resin compositions obtained in each example, the die shear strength in post-mold curing (PMC) was measured as an indicator of adhesion using the following method. For each example, ten 3.6mmφ×3mm adhesion strength test pieces were molded onto a 9×29mm strip-shaped copper lead frame or nickel plate using a low-pressure transfer molding machine (Yamashiro Seiki Co., Ltd., "AV-600-50-TF") under the conditions of a mold temperature of 175°C, injection pressure of 10MPa, and curing time of 180 seconds, using the encapsulating resin composition obtained in each example. Subsequently, the die shear strength (MPa) of the samples cured at 175°C for 3 hours was determined by measuring the die shear strength at room temperature (RT, 25°C) or 260°C using an automated die shear measuring device (Nordson Advanced Technologies, DAGE4000).

[0087] (Reliability: Temperature cycling test) For each example, a TO-220 package (package size 114mm x 30mm, thickness 1.3mm, no chip mounted, lead frame made of Cu or Ni plated) was molded using a low-pressure transfer molding machine (Apic Yamada "MSL-06M") at a mold temperature of 175°C, injection pressure of 10MPa, and curing time of 180 seconds. A test semiconductor device was then fabricated by curing at 175°C for 4 hours. The sealed test semiconductor device was subjected to a temperature cycling test, repeating 100 cycles between -40°C and 150°C, to determine the presence or absence of package cracks and delamination between components. The measurement results are shown in Table 1 as "Number of defects / Number of samples". A "Number of defects / Number of samples" of 4 / 10 or less was considered acceptable.

[0088] [Table 1]

[0089] Table 1 shows that the encapsulating resin compositions obtained in each example exhibited excellent narrow-path filling properties, no aggregation during molding, suppressed undissolved coarse powder particles, and excellent adhesion to metal components. Furthermore, highly reliable semiconductor devices were obtained by using the encapsulating resin compositions obtained in each example. [Explanation of symbols]

[0090] 20 Semiconductor elements 30 circuit boards 32 die pads 34 Outer lead 40 wires 50 Sealing material 60 Solder Balls 100 Semiconductor Devices

Claims

1. 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, wherein the powder has an average particle size d measured by a laser diffraction method. 50 The powder has a particle size of 0.2 μm or more and 20 μm or less.

2. The maximum particle size d of the powder measured by laser diffraction method max 2. The powder according to claim 1, wherein the particle size is 100 μm or less.

3. The particle size d of the powder measured by laser diffraction method 10 3. The powder according to claim 1, wherein the particle size is 0.1 μm or more and 10 μm or less.

4. The particle size d of the powder measured by laser diffraction method 90 4. The powder according to claim 1, wherein the particle size is 1 μm or more and 50 μm or less.

5. 5. The powder according to claim 1, which is a jet mill pulverized product of a raw material composed of the compound.

6. 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: (A) A powder composed of the compound, the powder having an average particle size d measured by a laser diffraction method. 50 is 0.2 μm or more and 20 μm or less, (B) Epoxy resin

7. 7. The method for producing an encapsulating resin composition according to claim 6, wherein the step of obtaining component (A) comprises a step of pulverizing the raw materials with a jet mill.

8. The maximum particle size d of the component (A) measured by laser diffraction method max 8. The method for producing an encapsulating resin composition according to claim 6, wherein the average particle size is 100 μm or less.

9. The particle size d of the component (A) measured by laser diffraction method 10 9. The method for producing an encapsulating resin composition according to claim 6, wherein the average particle size is 0.1 μm or more and 10 μm or less.

10. The particle size d of the component (A) measured by laser diffraction method 90 10. The method for producing an encapsulating resin composition according to claim 6, wherein the average particle size is 1 μm or more and 50 μm or less.

11. 11. The method for producing an encapsulating resin composition according to claim 6, wherein the mixture further comprises a component (C): an inorganic filler.

12. 12. The method for producing an encapsulating resin composition according to claim 6, wherein the mixture further comprises a component (D): a silane coupling agent.

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