Compression molding sealant and electronic parts device

Abstract

The present invention provides a compression molding sealant in which wire deviation caused by compression molding is suppressed, and an electronic component device including an element sealed by the compression molding sealant. A compression molding sealant is a compression molding sealant containing an epoxy resin, a hardener, and an inorganic filler, wherein in an image obtained by observing a compression molded body formed by compression molding the compression molding sealant on a substrate through a silicon chip using an ultrasonic flaw detection device, the area of ​​the area corresponding to the compression molded body on the chip, excluding black spots, is 86% or more relative to the entire area of ​​the area corresponding to the compression molded body on the chip.

Description

Technical Field

[0001] The present disclosure relates to a sealing material for compression molding and an electronic component device. Background Art

[0002] In the field of component sealing of electronic parts such as transistors and integrated circuits (IC), resin sealing has long been the mainstream in terms of productivity and cost. In addition, in recent years, high-density mounting of electronic parts on printed wiring boards has been promoted. Along with this, surface-mounted packages are becoming the mainstream in semiconductor devices compared to existing pin-insertion packages. In order to increase the mounting density and reduce the mounting height, surface-mounted ICs, large-scale integrated circuits (LSIs), etc. have become thin and small packages, and the volume occupied by the components relative to the package has become larger, and the wall thickness of the package has become very thin.

[0003] In addition, due to the multifunctionality and high capacity of components, the chip area is increased and the number of pins is increased. As a result, the number of pads (electrodes) increases, which is also promoting the reduction of pad spacing and pad size, the so-called narrow pad spacing. In addition, in order to cope with further miniaturization and lightness, the form of packaging has gradually changed from Quad Flat Package (QFP), Small Outline Package (SOP), etc. to Chip Size Package (CSP), Ball Grid Array (BGA), etc., which are easier to cope with multi-pin and can achieve higher density installation.

[0004] As a method for resin sealing of electronic component devices, in addition to the commonly used transfer molding method, compression molding method and the like can also be cited (for example, refer to Patent Document 1). The compression molding method is a method in which a powdery resin composition, i.e., a sealing material, is supplied in a manner facing an object to be sealed (a substrate on which electronic components such as semiconductor chips are provided, etc.) held in a mold, and the object to be sealed and the sealing material are compressed to thereby perform resin sealing.

[0005] [Prior art literature]

[0006] [Patent Document]

[0007] Patent Document 1: Japanese Patent Application Publication No. 2008-279599 Summary of the invention

[0008] [Problems to be solved by the invention]

[0009] As packages become more multifunctional, built-in wires become thinner, so it has become a challenge to suppress the occurrence of wire deviation not only in transfer molding but also in compression molding.

[0010] In view of the above circumstances, an object of a first embodiment of the present disclosure is to provide a compression molding sealant that suppresses wire deviation caused by compression molding, and an electronic component device including an element sealed by the compression molding sealant.

[0011] [Technical means to solve the problem]

[0012] The embodiments of the present disclosure include the following.

[0013] <1> A compression molding sealant comprising an epoxy resin, a hardener, and an inorganic filler.

[0014] In an image obtained by observing a compressed body formed by compression molding the compression molding sealing material on a substrate via a silicon chip using an ultrasonic flaw detection device, the area of ​​the area corresponding to the compression molded body on the chip, excluding black spots, is more than 86% of the total area of ​​the area corresponding to the compression molded body on the chip.

[0015] <2> The compression molding sealant according to <1>, wherein the inorganic filler is a material treated with a coupling agent.

[0016] <3> The compression molding seal material according to <2>, wherein the coupling agent is a silane coupling agent.

[0017] <4> The compression molding sealant according to <2> or <3>, wherein the coupling agent has at least one functional group selected from the group consisting of a (meth)acryloyl group, an epoxy group, and a phenyl group.

[0018] <5> The compression molding seal material according to any one of <2> to <4>, wherein the coupling agent has a secondary amino group.

[0019] <6> The compression molding sealant according to any one of <1> to <5>, wherein the inorganic filler has a local maximum value at 0.1 μm to 2 μm in a volume-based particle size distribution.

[0020] <7> An electronic component device including: a component; and a cured product of the compression molding sealant according to any one of <1> to <6> for sealing the component.

[0021] [Effects of the Invention]

[0022] According to the first embodiment of the present disclosure, there can be provided a sealing material for compression molding in which deviation of lead wires caused by compression molding is suppressed, and an electronic component device including an element sealed by the sealing material for compression molding. DETAILED DESCRIPTION

[0023] Below, the form for implementing the present invention is described in detail. But the present invention is not limited to the following embodiments. In the following embodiments, except for the particularly explicit situation, its constituent elements (also comprising element steps etc.) are not necessary. The same is true about numerical value and its range, and the present invention is not limited.

[0024] In the present disclosure, the term "step" includes not only steps that are independent of other steps, but also steps that cannot be clearly distinguished from other steps as long as the purpose of the step is achieved.

[0025] In the present disclosure, in a numerical range represented by “to”, numerical values ​​described before and after including “to” are respectively regarded as the minimum value and the maximum value.

[0026] In the numerical range recorded in stages in the present disclosure, the upper limit or lower limit recorded in one numerical range may also be replaced by the upper limit or lower limit of the numerical range recorded in other stages. In addition, in the numerical range recorded in the present disclosure, the upper limit or lower limit of the numerical range may also be replaced by the value shown in the embodiment.

[0027] In the present disclosure, each component may include multiple equivalent substances. When multiple substances equivalent to each component exist in the composition, unless otherwise specified, the content or content of each component refers to the total content or content of the multiple substances present in the composition.

[0028] In the present disclosure, particles corresponding to each component may include multiple types of particles. When multiple types of particles corresponding to each component are present in the composition, the particle size of each component refers to the value for the mixture of the multiple types of particles present in the composition unless otherwise specified.

[0029] In the present disclosure, the term “(meth)acryloyl group” refers to at least one of an acryloyl group and a methacryloyl group, and the term “(meth)acryloyloxy group” refers to at least one of an acryloyloxy group and a methacryloyloxy group.

[0030] <Seal materials for compression molding>

[0031] The sealing material disclosed herein is a sealing material for compression molding, and is a sealing material for compression molding containing an epoxy resin, a hardener and an inorganic filler. In an image obtained by observing a compression molded body formed by compression molding the sealing material for compression molding on a substrate via a silicon chip using an ultrasonic flaw detection device, the area of ​​the area corresponding to the compression molded body on the chip, excluding black spots, is more than 86% of the total area of ​​the area corresponding to the compression molded body on the chip.

[0032] Hereinafter, the sealing material for compression molding is also referred to as "sealing material". In addition, in an image obtained by observing a compression-molded body formed by compression molding a sealing material for compression molding on a substrate via a silicon chip using an ultrasonic flaw detector, the area of ​​the image corresponding to the compression-molded body on the silicon chip is also referred to as "SAT image". In addition, the ratio of the area excluding black dots to the area of ​​the entire SAT image is also referred to as "non-black dot ratio".

[0033] The sealing material disclosed herein has a non-black spot ratio within the above range when it is made into a compression-molded body, and thus can suppress wire deviation caused by compression molding. The reason for this is not yet determined, but is presumed as follows.

[0034] In the SAT image, for example, a region where the resin is locally biased (hereinafter also referred to as a "resin-rich region") appears as a black spot. It is believed that the formation of the resin-rich region is due to, for example, bubble breaking occurs due to the gas dissolved in the sealing material under reduced pressure during compression molding, and the amount of inorganic filler in the bubble breaking site is locally reduced. For example, in a sealing material with low fluidity, even if a region where the amount of inorganic filler is locally reduced is produced, it is difficult for the inorganic filler to flow relative to the region due to flow. Therefore, it is believed that the region where the amount of inorganic filler is locally reduced is directly hardened, thereby forming a resin-rich region. It is also believed that the fluidity of the sealing material that produces a large amount of resin-rich regions in this way is low, so when the pressure during compression molding is applied to the wire, the position of the wire is easily offset (i.e., wire deviation).

[0035] In contrast, the sealant disclosed in the present invention, which can obtain a compression molded body with a large non-black spot ratio, is believed to be easy to flow into due to the flow, even if there is a part where the inorganic filler is locally small due to bubble breaking during decompression, and the generation of a resin-rich area can be suppressed. Moreover, the sealant that can suppress the generation of a resin-rich area has high fluidity, so it is speculated that the deviation of the wire caused by compression molding can be suppressed.

[0036] Furthermore, since the sealant having a large number of resin-rich regions has low fluidity, bubbles generated during compression molding are likely to remain, and a compression molded body having voids may be obtained. The voids may appear as black spots in the SAT image.

[0037] However, the sealant disclosed in the present invention, which can obtain a compression molded body with a large non-black spot ratio, is considered to be difficult to generate resin-rich regions and pores due to its high fluidity. Thus, it is speculated that the sealant with high fluidity in which the generation of resin-rich regions and pores is suppressed is not likely to cause wire deviation during compression molding.

[0038] Here, the SAT image of the compression-molded body of the sealing material is obtained as follows.

[0039] Specifically, first, a compression molding substrate is prepared in which a chip is arranged on one side of the substrate. As a substrate, for example, a substrate with a size of 240 mm in width × 74 mm in length × 0.45 mm in thickness can be cited. As a silicon chip, for example, each chip with a size of 10 mm in width × 8 mm in length × 0.4 mm in thickness and made of silicon can be cited. Moreover, the compression molding substrate can be obtained by, for example, arranging a total of 12 chips (3 in width × 4 in length) in a state where they are spaced apart from each other at a spacing distance of 8 mm in the central portion of one side of the substrate.

[0040] A compression molding substrate having a silicon chip disposed on one side of the substrate is used, and the compression molding on the silicon chip is observed using an ultrasonic flaw detector. As described above, not only pores but also resin-rich areas can be confirmed as black spots. Furthermore, by using a metal chip having a mirror surface instead of a silicon chip, the resin-rich areas also appear as black spots. On the other hand, when a compression molding directly compression-molded on a substrate (general resin substrate, metal substrate, etc.) without a chip is observed using an ultrasonic flaw detector, although pores can be confirmed as black spots, it is difficult for the resin-rich areas to appear as black spots.

[0041] Next, a sealing material to be measured is compression molded on the surface of the compression molding substrate on which the chip is arranged using a compression mold device.

[0042] The molding conditions during compression molding were as follows: mold temperature: 175° C., molding pressure: about 10 MPa, curing time: 120 seconds, and vacuum holding time: 3 seconds.

[0043] In addition, the thickness of the compressed body obtained by the compression molding (i.e., the compressed body for measuring the non-black spot ratio) can be, for example, 0.8 mm in an area where no chip is configured (i.e., an area where the compressed body is directly provided on the substrate) and 0.4 mm on the chip.

[0044] Next, the obtained compression molded body is observed by using an ultrasonic tomography (Scanning Acoustic Tomograph, SAT) (i.e., an ultrasonic flaw detection device, such as Hitachi Power Solutions Co., Ltd., model: FS200III A) to obtain an image. The SAT observation condition is a probe frequency of 50 MHz.

[0045] In the obtained image, a region corresponding to the image of the compression-molded body molded on the chip of the compression-molding substrate is referred to as a "SAT image".

[0046] In the SAT image, when the contrast range of the image is set to (0 to 255), the area from 0 to 99 is defined as "black dots", and the area from 100 to 255 is defined as "other than black dots".

[0047] The non-black dot ratio in the SAT image was determined by analyzing a total of 12 chips of 10 mm×8 mm according to the above definition and summing the results.

[0048] Hereinafter, each component contained in the sealing material of the present disclosure will be described in detail.

[0049] (Epoxy resin)

[0050] The type of the epoxy resin is not particularly limited as long as it has an epoxy group in the molecule.

[0051] Epoxy resins include, specifically, novolac epoxy resins (phenol novolac epoxy resins, o-cresol novolac epoxy resins, etc.), which are obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenolic compounds such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, and naphthol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthalene with an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, and propionaldehyde under an acidic catalyst to obtain a novolac resin, and then epoxidizing the novolac resin; triphenylmethane epoxy resins, which are obtained by condensing or co-condensing the phenolic compound with an aromatic aldehyde compound such as benzaldehyde and salicylaldehyde under an acidic catalyst to obtain triphenylmethane. a phenol resin and epoxidizing the triphenylmethane phenol resin; a copolymerized epoxy resin, which is obtained by co-condensing the phenol compound and the naphthol compound with an aldehyde compound under an acidic catalyst to obtain a novolac resin and epoxidizing the novolac resin; a diphenylmethane epoxy resin as a diglycidyl ether of bisphenol A, bisphenol F, etc.; a biphenyl epoxy resin as a diglycidyl ether of an alkyl-substituted or unsubstituted biphenol; a styrene epoxy resin as a diglycidyl ether of a styrene-based phenol compound; an epoxy resin containing sulfur atoms as a diglycidyl ether of bisphenol S, etc.; an epoxy resin as a glycidyl ether of alcohols such as butanediol, polyethylene glycol, and polypropylene glycol; an epoxy resin as a phthalic acid, isophthalic acid, Glycidyl ester epoxy resins of glycidyl esters of polycarboxylic acid compounds such as dicarboxylic acid and tetrahydrophthalic acid; glycidylamine epoxy resins obtained by replacing the active hydrogen bonded to the nitrogen atom of aniline, diaminodiphenylmethane, isocyanuric acid, etc. with a glycidyl group; dicyclopentadiene epoxy resins obtained by epoxidizing a co-condensation resin of dicyclopentadiene and a phenol compound; alicyclic epoxy resins such as diepoxy vinylcyclohexene, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane, etc. obtained by epoxidizing an olefin bond in a molecule; glycidylamine epoxy resins as p-xylene-modified phenol resins; p-xylene modified epoxy resin as a glycidyl ether of a meta-xylene modified phenol resin; a meta-xylene modified epoxy resin as a glycidyl ether of a meta-xylene modified phenol resin; a terpene modified epoxy resin as a glycidyl ether of a terpene modified phenol resin; a dicyclopentadiene modified epoxy resin as a glycidyl ether of a dicyclopentadiene modified phenol resin; a cyclopentadiene modified epoxy resin as a glycidyl ether of a cyclopentadiene modified phenol resin; a polycyclic aromatic ring modified epoxy resin as a glycidyl ether of a polycyclic aromatic ring modified phenol resin; a naphthalene type epoxy resin as a glycidyl ether of a phenol resin containing a naphthalene ring; a halogenated phenol novolac type epoxy resin; a hydroquinone type epoxy resin; a trimethylolpropane type epoxy resin; a linear aliphatic epoxy resin obtained by oxidizing an olefin bond using a peracid such as peracetic acid;Aralkyl epoxy resins are obtained by epoxidizing aralkyl phenol resins such as phenol aralkyl resins and naphthol aralkyl resins; etc. Furthermore, epoxides of silicone resins and epoxides of acrylic resins can also be cited as epoxy resins. These epoxy resins can be used alone or in combination of two or more. ;

[0052] Among the epoxy resins, from the viewpoint of the balance between reflow resistance and fluidity, an epoxy resin selected from the group consisting of biphenyl type epoxy resins, distyrene type epoxy resins, diphenylmethane type epoxy resins, sulfur atom-containing epoxy resins, novolac type epoxy resins, dicyclopentadiene type epoxy resins, triphenylmethane type epoxy resins, copolymer type epoxy resins and aralkyl type epoxy resins is preferred.

[0053] The epoxy equivalent (molecular weight / number of epoxy groups) of the epoxy resin is not particularly limited, but is preferably 100 to 1000 g / eq, more preferably 150 to 500 g / eq, from the viewpoint of balancing various properties such as moldability, reflow resistance, and electrical reliability.

[0054] The epoxy equivalent of the epoxy resin is a value measured by a method in accordance with Japanese Industrial Standards (JIS) K 7236:2009.

[0055] When the epoxy resin is solid, the softening point or melting point is not particularly limited, but is preferably 40°C to 180°C from the viewpoint of moldability and reflow resistance, and more preferably 50°C to 130°C from the viewpoint of workability during preparation of the sealing material.

[0056] The melting point of the epoxy resin is a value measured by differential scanning calorimetry (DSC), and the softening point of the epoxy resin is a value measured by a method (ring and ball method) in accordance with JIS K 7234:1986.

[0057] From the viewpoints of strength, fluidity, heat resistance, moldability, etc., the content of the epoxy resin in the sealing material is preferably 0.5 to 50 mass %, more preferably 2 to 30 mass %, and even more preferably 2 to 20 mass %.

[0058] (Hardener)

[0059] The type of hardener is not particularly limited, and can be selected according to the type of resin, the required properties of the sealing material, and the like.

[0060] Examples of the curing agent include phenol curing agents, amine curing agents, acid anhydride curing agents, polythiol curing agents, polyaminoamide curing agents, isocyanate curing agents, blocked isocyanate curing agents, etc. From the viewpoint of improving heat resistance, the curing agent is preferably a curing agent having a phenolic hydroxyl group in the molecule (phenol curing agent).

[0061] Specific examples of the phenol curing agent include: polyphenol compounds such as resorcinol, catechol, bisphenol A, bisphenol F, and substituted or unsubstituted biphenols; novolac-type phenol resins obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenolic compounds such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol, and naphthol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthalene with an aldehyde compound such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and salicylic acid aldehyde in the presence of an acid catalyst; and polyphenol compounds such as polyphenols such as polyphenols and dimethoxy-p-xylene and bis(methoxy-methyl)benzene. Aralkyl-type phenol resins such as phenol aralkyl resins synthesized from phenolic compounds such as cyclopentadiene and dicyclopentadiene, aralkyl-type phenol resins such as phenol aralkyl resins and naphthol aralkyl resins synthesized from cyclopentadiene and dicyclopentadiene; cyclopentadiene-modified phenol resins; polycyclic aromatic ring-modified phenol resins; biphenyl-type phenol resins; triphenylmethane-type phenol resins obtained by condensing or co-condensing the phenolic compounds with aromatic aldehyde compounds such as benzaldehyde and salicylic aldehyde under an acidic catalyst; phenol resins obtained by copolymerizing two or more of these, etc. These phenol curing agents may be used alone or in combination of two or more.

[0062] The functional group equivalent of the hardener (hydroxyl equivalent in the case of a phenol hardener) is not particularly limited, but is preferably 70 g / eq to 1000 g / eq, more preferably 80 g / eq to 500 g / eq, from the viewpoint of balancing various properties such as formability, reflow resistance, and electrical reliability.

[0063] The functional group equivalent of the curing agent (hydroxyl group equivalent in the case of a phenol curing agent) is set to a value measured by a method in accordance with JIS K0070:1992.

[0064] When the curing agent is solid, the softening point or melting point is not particularly limited, but is preferably 40°C to 180°C from the viewpoint of formability and reflow resistance, and more preferably 50°C to 130°C from the viewpoint of workability during production of the sealing material.

[0065] The melting point or softening point of the curing agent is set to a value measured in the same manner as the melting point or softening point of the epoxy resin.

[0066] The equivalent ratio of epoxy resin to hardener, i.e., the ratio of the number of functional groups in the hardener to the number of epoxy groups in the epoxy resin (number of functional groups in the hardener / number of epoxy groups in the epoxy resin) is not particularly limited. From the perspective of suppressing the number of unreacted components, it is preferably set within the range of 0.5 to 2.0, and more preferably within the range of 0.6 to 1.3. From the perspective of formability and reflow resistance, it is further preferably set within the range of 0.8 to 1.2.

[0067] (Inorganic filler)

[0068] The material of the inorganic filler is not particularly limited.

[0069] As the material of the inorganic filler, specifically, there can be listed: spherical silica, crystalline silica, glass, aluminum oxide, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, magnesium oxide, silicon carbide, beryllium oxide, zirconium oxide, zircon, forsterite, steatite, spinel, mullite, titanium dioxide, talc, clay, mica and other inorganic materials. Inorganic fillers with flame retardant effects can also be used. As inorganic fillers with flame retardant effects, there can be listed aluminum hydroxide, magnesium hydroxide, composite metal hydroxides such as composite hydroxides of magnesium and zinc, zinc borate, etc.

[0070] The shape of the inorganic filler is not particularly limited, but is preferably spherical in terms of filling properties and mold abrasion resistance.

[0071] The inorganic filler can be used alone or in combination of two or more. Furthermore, the so-called "using two or more inorganic fillers in combination" includes, for example, the case of using two or more inorganic fillers with the same composition and different average particle sizes; the case of using two or more inorganic fillers with the same average particle size and different compositions; and the case of using two or more inorganic fillers with different average particle sizes and compositions.

[0072] As the inorganic filler, among the above-mentioned specific examples, preferably, spherical silica, crystalline silica, and alumina are mentioned, and more preferably, spherical silica is mentioned.

[0073] The content of inorganic filler relative to the whole seal material is not particularly limited. With respect to the viewpoints of the thermal expansion coefficient, thermal conductivity, elastic coefficient and other characteristics of the compression molded body of the seal material further improving, the content of inorganic filler is preferably more than 30 volume % of the whole seal material, more preferably more than 35 volume %, and then preferably more than 40 volume %, particularly preferably more than 45 volume %, and most preferably more than 50 volume %. With respect to the viewpoints such as the improvement of fluidity, the reduction of viscosity, the content of inorganic filler is preferably less than 99 volume % of the whole seal material, more preferably less than 98 volume %, and then preferably less than 97 volume %.

[0074] In addition, the content of the inorganic filler relative to the entire sealing material of the present disclosure for compression molding purposes can be set to 60% to 99% by volume, 70% to 99% by volume, 73% to 99% by volume, or 75% to 99% by volume.

[0075] The content of the inorganic filler in the sealant is determined as follows. First, the total mass of the cured product (compression molded product) of the sealant is measured, the cured product is calcined at 400°C for 2 hours, and then calcined at 700°C for 3 hours to evaporate the resin component, and the mass of the remaining inorganic filler is measured. The volume is calculated based on the obtained masses and their respective specific gravities, and the ratio of the volume of the inorganic filler to the total volume of the sealant is obtained, and is set as the content of the inorganic filler.

[0076] In the case where the inorganic filler is particulate, its average particle size is not particularly limited. For example, the volume average particle size of the entire inorganic filler is preferably less than 80 μm, or less than 50 μm, or less than 40 μm, or less than 30 μm, or less than 25 μm, or less than 20 μm, or less than 15 μm. In addition, the volume average particle size of the entire inorganic filler is preferably more than 0.1 μm, more preferably more than 0.2 μm, and further preferably more than 0.3 μm. If the volume average particle size of the inorganic filler is more than 0.1 μm, there is a tendency that the viscosity of the sealant is further suppressed. If the volume average particle size is less than 80 μm, there is a tendency that the filling property in a narrow gap is further improved.

[0077] The average particle size of the inorganic filler can be measured by the following method.

[0078] The inorganic filler as the measurement object is added to the solvent (pure water), and after ultrasonic treatment for 300 seconds, the particle size distribution is measured. The volume-based particle size distribution is measured using a laser diffraction particle size distribution measuring device (Horiba Manufacturing Co., Ltd., trade name: LA-920). In addition, the volume average particle size is obtained as the particle size (D50%) when the accumulation from the small diameter side in the volume-based particle size distribution becomes 50%.

[0079] The specific surface area of ​​the inorganic filler is preferably 0.7 m 2 / g~4.0m 2 / g, more preferably 0.9m 2 / g~3.0m 2 / g, and more preferably 1.0 m 2 / g~2.5m 2 / g.

[0080] There is a tendency that the smaller the specific surface area of ​​the inorganic filler is, the higher the fluidity of the sealing material is.

[0081] The specific surface area (Brunauer-Emmett-Teller, BET) specific surface area) of the inorganic filler can be measured according to JIS Z 8830:2013 and based on the nitrogen adsorption capacity. As an evaluation device, QUANTACHROME: AUTOSORB-1 (trade name) can be used. When measuring the BET specific surface area, it is believed that the moisture adsorbed on the surface and structure of the sample will affect the gas adsorption capacity, so it is preferred to first perform a pretreatment to remove moisture by heating.

[0082] In the pretreatment, the pressure of the measuring cell into which 0.05 g of the measuring sample was put was reduced to 10 Pa or less by a vacuum pump, and then the pressure was heated at 110° C. and maintained for more than 3 hours, and then naturally cooled to room temperature (25° C.) while maintaining the reduced pressure. After the pretreatment, the evaluation temperature was set to 77 K, and the evaluation pressure range was set to be less than 1 under the relative pressure (equilibrium pressure relative to the saturated vapor pressure) for measurement.

[0083] From the viewpoint of improving the filling property in the narrow gap, the maximum particle size (cut point) of the inorganic filler can be controlled. The maximum particle size of the inorganic filler can also be appropriately adjusted, and from the viewpoint of filling property, it is preferably less than 105 μm, more preferably less than 75 μm, also less than 60 μm, and also less than 40 μm. The maximum particle size can be measured by a laser diffraction particle size distribution meter (Horiba Manufacturing Co., Ltd., trade name: LA-920).

[0084] From the viewpoint of improving both thermal conductivity and fluidity, the inorganic filler preferably has a local maximum at 0.1 μm to 2 μm in the volume-based particle size distribution. The inorganic filler may also have local maximums in the regions of 0.1 μm to 2 μm and greater than 2 μm in the volume-based particle size distribution.

[0085] Examples of the inorganic filler having a local maximum value at 0.1 μm to 2 μm in the volume-based particle size distribution include a mixture of a first inorganic filler having a volume average particle size of 0.1 μm to 2 μm and a second inorganic filler having a volume average particle size greater than 2 μm.

[0086] When the inorganic filler is a mixture of a first inorganic filler and a second inorganic filler, the proportion of the first inorganic filler relative to the entire composition can be, for example, in the range of 2 mass % to 30 mass %, and from the viewpoint of fluidity or filling property in a narrow passage portion, preferably in the range of 2.5 mass % to 25 mass %, and more preferably in the range of 2.6 mass % to 20 mass %.

[0087] The volume average particle size of the first inorganic filler is, for example, 0.1 μm to 2.0 μm, preferably 0.2 μm to 1.5 μm, and more preferably 0.3 μm to 1.0 μm. The volume average particle size of the second inorganic filler is, for example, in the range of more than 2.0 μm and less than 75 μm, preferably 5.0 μm to 55 μm, and more preferably 8.0 μm to 20 μm.

[0088] The BET specific surface area of ​​the first inorganic filler is, for example, 1.0 m 2 / g~20m 2 / g, preferably 2m 2 / g~17m 2 / g, more preferably 3m 2 / g~15m 2 / g, and more preferably 3.5m 2 / g~10m 2 / g. The BET specific surface area of ​​the second inorganic filler can be, for example, 0.5 m 2 / g~10m 2 / g, preferably 0.7m 2 / g~7m 2 / g, more preferably 0.9m 2 / g~5m 2 / g, and more preferably 1.0 m 2 / g~4.5m 2 / g.

[0089] As the first inorganic filler, for example, powders of spherical silica, alumina, calcium silicate, calcium carbonate, magnesium oxide, potassium titanate, silicon nitride, aluminum nitride, boron nitride, beryllium oxide, zirconium oxide, zirconium and titanium dioxide, as well as beads formed by spheroidizing these, glass fibers, etc., among which spherical silica is preferred from the perspective of improving fluidity. As the second inorganic filler, for example, powders of spherical silica, alumina, calcium silicate, calcium carbonate, magnesium oxide, potassium titanate, silicon nitride, aluminum nitride, boron nitride, beryllium oxide, zirconium oxide, zirconium and titanium dioxide, as well as beads formed by spheroidizing these, glass fibers, etc., among which spherical silica and alumina are preferred, and spherical silica is more preferred from the perspective of reducing filling properties and linear expansion coefficient. The combination of the first inorganic filler and the second inorganic filler is preferably a combination of spherical silica and alumina, a combination of spherical silica and spherical silica, and a combination of alumina and alumina. Wherein, especially with respect to the viewpoint of both the improvement of fluidity and the improvement of thermal conductivity, as the combination of the first inorganic filler and the second inorganic filler, it is preferably a combination of spherical silica and alumina. In addition, especially with respect to the viewpoint of improving fluidity, as the combination of the first inorganic filler and the second inorganic filler, it is preferably a combination of spherical silica and spherical silica.

[0090] The inorganic filler may be a material treated with a coupling agent. In particular, when the inorganic filler is a mixture of the first inorganic filler and the second inorganic filler, it is preferred that at least the first inorganic filler is a material treated with a coupling agent. By using a mixture of the first inorganic filler and the second inorganic filler treated with a coupling agent as the inorganic filler, it is easy to control the non-black spot ratio when the compression molded body is made within the range. Furthermore, the second inorganic filler may be a material treated with a coupling agent or an untreated material.

[0091] In the case where the first inorganic filler is a material treated with a coupling agent, the mass reduction rate of the first inorganic filler treated with a coupling agent at 800°C can be, for example, in the range of 0.27% to 1.0%. From the perspective of controlling the non-black spot ratio within the above range, it is preferably in the range of 0.3% to 0.9%, and more preferably in the range of 0.35% to 0.8%.

[0092] Regarding the mass reduction rate at 800°C, first, the mass W0 of the inorganic filler to be measured is measured without preheating, etc. Then, heating is performed at a rate of 10°C / min, and the mass W1 of the inorganic filler when it reaches 800°C is measured, and the mass reduction rate (%) is calculated by the following formula.

[0093] Formula: Mass reduction rate (%) = ((W0-W1) / W0) × 100

[0094] The type of coupling agent used to treat the inorganic filler is not particularly limited, and known coupling agents can be used. Examples of the coupling agent include silane coupling agents, titanium coupling agents, zirconium coupling agents, and aluminum coupling agents, among which silane coupling agents or titanium coupling agents are preferred, and silane coupling agents are more preferred. The coupling agent used to treat the inorganic filler can be used alone or in combination of two or more.

[0095] The coupling agent for treating the inorganic filler preferably has at least one functional group selected from the group consisting of a (meth)acryloyl group, an epoxy group, and a phenyl group (hereinafter also referred to as a specific functional group), and more preferably has a phenyl group.

[0096] The coupling agent may be a coupling agent having a functional group including a specific functional group. Examples of the functional group including a specific functional group include (meth)acryloyloxy, glycidyloxy, phenylamino, etc. The coupling agent is preferably a silane coupling agent having a functional group including a specific functional group, and more preferably a silane coupling agent in which the functional group including the specific functional group is bonded to a silicon atom directly or via a chain hydrocarbon group having 1 to 5 carbon atoms.

[0097] In addition, the coupling agent may be a coupling agent having at least one selected from the group consisting of a primary amino group, a secondary amino group, and a tertiary amino group, and may be a coupling agent having a secondary amino group.

[0098] Examples of the silane coupling agent include compounds in which at least one of an alkoxy group and a halogen atom is directly bonded to a Si atom.

[0099] Specific examples of the silane coupling agent include vinyl trichlorosilane, vinyl triethoxysilane, vinyl tri(β-methoxyethoxy)silane, γ-methacryloxypropyl trimethoxysilane, 8-methacryloxyoctyl trimethoxysilane, β-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, γ-glycidoxypropyl trimethoxysilane, vinyl triacetoxysilane, γ-mercaptopropyl trimethoxysilane, γ-aminopropyl triethoxysilane, γ-[bis(β-hydroxyethyl)]aminopropyl triethoxysilane, N- β-(Aminoethyl)-γ-aminopropyltrimethoxysilane, γ-(β-aminoethyl)aminopropyldimethoxymethylsilane, N-(trimethoxysilylpropyl)ethylenediamine, N-(dimethoxymethylsilylisopropyl)ethylenediamine, methyltrimethoxysilane, methyltriethoxysilane, N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, γ-phenylaminopropyltrimethoxysilane, vinyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, etc.

[0100] Examples of the titanium coupling agent include isopropyl triisostearoyl titanate, isopropyl tri(dioctyl pyrophosphate) titanate, isopropyl tri(N-aminoethyl-aminoethyl) titanate, tetraoctyl bis(di-tridecyl phosphite) titanate, tetra(2,2-diallyloxymethyl-1-butyl)bis(di-tridecyl phosphite) titanate, bis(dioctyl pyrophosphate)oxyacetate titanate, bis(dioctyl pyrophosphate)ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacrylate isostearyl titanate, isopropyl tri-dodecylbenzenesulfonyl titanate, isopropyl isostearyl diacryloyl titanate, isopropyl tri(dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, and tetraisopropyl bis(dioctyl phosphite) titanate.

[0101] The amount of the coupling agent used in the treatment of the inorganic filler is not particularly limited, and can be set in consideration of the specific surface area of ​​the inorganic filler, the minimum coating area of ​​the coupling agent, and the like.

[0102] The amount of the coupling agent used in the treatment of the inorganic filler is in the range of 0.1 to 2.0 parts by mass, preferably 0.2 to 1.5 parts by mass, and more preferably 0.3 to 1.0 parts by mass, based on 100 parts by mass of the inorganic filler to be treated.

[0103] The method for obtaining the inorganic filler treated with the coupling agent is not particularly limited, and examples thereof include a method of adding the inorganic filler to be treated to a liquid containing a coupling agent and a solvent, and removing the solvent by drying.

[0104] (additive)

[0105] The sealing material disclosed herein may contain other components as additives as needed. Examples of additives include coupling agents, hardening accelerators, ion exchangers, mold release agents, flame retardants, colorants, stress relaxants, etc. In addition to these additives, the sealing material may also contain various additives well known in the technical field as needed.

[0106] -Coupling agent-

[0107] The sealing material disclosed herein may contain a coupling agent as an additive. The coupling agent used as an additive may be the same coupling agent as the coupling agent used to treat the inorganic filler. The coupling agent used as an additive may be used alone or in combination of two or more.

[0108] As a sealing material using a coupling agent as an additive, for example, there can be mentioned a sealing material containing a first coupling agent attached to the surface of an inorganic filler and a second coupling agent used as an additive. In the case where the sealing material contains both the first coupling agent and the second coupling agent, the second coupling agent may be the same as the first coupling agent or different from the first coupling agent.

[0109] When the sealing material contains the first coupling agent and the second coupling agent, the mass ratio of the first coupling agent to the second coupling agent (first coupling agent / second coupling agent) is in the range of more than 0 and 0.2, preferably more than 0 and 0.15, and more preferably more than 0 and 0.1.

[0110] When the sealing material contains a coupling agent, the content of the coupling agent relative to the entire sealing material is preferably 3 mass % or less, more preferably 2 mass % or less, further preferably 1 mass % or less, particularly preferably 0.5 mass % or less. From the viewpoint of exerting its effect, it is preferably 0.1 mass % or more, more preferably 0.15 mass % or more, further preferably 0.18 mass % or more.

[0111] In addition, the content of the silane coupling agent may be 0.01 parts by mass or more, or 0.02 parts by mass or more, relative to 100 parts by mass of the inorganic filler. The content of the silane coupling agent is preferably 5 parts by mass or less, and more preferably 2.5 parts by mass or less, relative to 100 parts by mass of the inorganic filler. From the perspective of both fluidity and package formability, the content of the coupling agent is preferably 0.05 parts by mass to 2.0 parts by mass, more preferably 0.1 parts by mass to 1.5 parts by mass, and further preferably 0.2 parts by mass to 1.0 parts by mass, and particularly preferably 0.2 parts by mass to 0.5 parts by mass, relative to 100 parts by mass of the inorganic filler.

[0112] Furthermore, the content and content of the coupling agent respectively represent the content and content of all coupling agents contained in the sealant. That is, when the sealant contains the first coupling agent and the second coupling agent, the content and content of the coupling agent respectively represent the total content and total content of the first coupling agent and the second coupling agent.

[0113] -Hardening accelerator-

[0114] The sealant of the present disclosure may contain a hardening accelerator as an additive. The type of the hardening accelerator is not particularly limited and can be selected according to the type of epoxy resin, the required properties of the sealant, and the like.

[0115] Examples of the curing accelerator include diazabicycloolefins such as 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), and cyclic amidine compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 2-heptadecylimidazole; derivatives of the cyclic amidine compounds; phenol novolac salts of the cyclic amidine compounds or their derivatives; and Compounds with intramolecular polarization formed by adding maleic anhydride, 1,4-benzoquinone, 2,5-toluoquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone and other quinone compounds, compounds having π bonds such as diazonium methane; cyclic amidinium compounds such as tetraphenylborate of DBU, tetraphenylborate of DBN, tetraphenylborate of 2-ethyl-4-methylimidazole, tetraphenylborate of N-methylmorpholine; pyridine, triethylamine, triethylenediamine, benzyldimethylamine, triethylamine tertiary amine compounds such as alcoholamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; derivatives of the tertiary amine compounds; ammonium salt compounds such as tetra-n-butylammonium acetate, tetra-n-butylammonium phosphate, tetraethylammonium acetate, tetra-n-hexylammonium benzoate, and tetrapropylammonium hydroxide; primary phosphines such as ethylphosphine and phenylphosphine, secondary phosphines such as dimethylphosphine and diphenylphosphine, triphenylphosphine, diphenyl (p-toluene) phosphine, tri (alkylphenyl) phosphine, tri (alkoxyphenyl) phosphine, tri (alkyl alkoxyphenyl) phosphine, tri (dialkylphenyl) phosphine, tri (trialkylphenyl) phosphine, tri (tetraalkylphenyl) phosphine, tri (dialkoxyphenyl) phosphine, tri (trialkoxyphenyl) phosphine, Organic phosphines such as tri(tetraalkoxyphenyl)phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine, trinaphthylphosphine, tri(benzyl)phosphine and other tertiary phosphine; phosphine compounds such as complexes of the organic phosphine and organic boron; compounds with intramolecular polarization formed by adding the organic phosphine or the phosphine compound to maleic anhydride, 1,4-benzoquinone, 2,5-toluoquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, anthraquinone and other quinone compounds, and compounds having π bonds such as diazonophenylmethane;The organic phosphine or the phosphine compound is reacted with 4-bromophenol, 3-bromophenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, 4-iodophenol, 3-iodophenol, 2-iodophenol, 4-bromo-2-methylphenol, 4-bromo-3-methylphenol, 4-bromo-2,6-dimethylphenol, 4-bromo-3,5-dimethylphenol, 4-bromo-2,6-di-tert-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, Compounds with intramolecular polarization obtained by reacting halogenated phenol compounds such as phenol, 6-bromo-2-naphthol, 4-bromo-4'-hydroxybiphenyl, etc. and then undergoing a dehydrohalogenation step; tetrasubstituted phosphonium compounds such as tetraphenylphosphonium, tetraphenylborates of tetrasubstituted phosphonium such as tetraphenylphosphonium tetra-p-toluene borate, and salts of tetrasubstituted phosphonium and phenol compounds; phosphorbetaine; adducts of phosphonium compounds and silane compounds, etc. The hardening accelerator can be used alone or in combination of two or more. ;

[0116] Among these, particularly preferred hardening accelerators include triphenylphosphine, an adduct of triphenylphosphine and a quinone compound, an adduct of tributylphosphine and a quinone compound, and an adduct of tri-p-tolylphosphine and a quinone compound.

[0117] When the sealant contains a hardening accelerator, the amount of the hardening accelerator is preferably 0.1 to 30 parts by mass, more preferably 1 to 15 parts by mass, relative to 100 parts by mass of the resin component (i.e., the total of the epoxy resin and the hardener). If the amount of the hardening accelerator is 0.1 parts by mass or more relative to 100 parts by mass of the resin component, there is a tendency to harden well in a short time. If the amount of the hardening accelerator is 30 parts by mass or less relative to 100 parts by mass of the resin component, there is a tendency to obtain a good molded product whose hardening speed is not too fast.

[0118] -Ion Exchanger-

[0119] The sealing material disclosed in the present invention may contain an ion exchanger as an additive. From the viewpoint of improving the moisture resistance and high temperature storage characteristics of the electronic component device including the sealed element, the sealing material preferably contains an ion exchanger. There is no particular limitation on the ion exchanger, and existing known ion exchangers can be used. Specifically, hydrotalcite compounds and hydrated oxides containing at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium and bismuth can be listed. The ion exchanger can be used alone or in combination of two or more. Among them, the hydrotalcite represented by the following general formula (A) is preferred.

[0120] Mg (1-X) Al X (OH)2(CO3) X / 2 ·mH2O……(A)

[0121] (0<X≦0.5, m is a positive number)

[0122] When the sealing material contains an ion exchanger, the content thereof is not particularly limited as long as it is an amount sufficient to capture ions such as halogen ions, and is preferably 0.1 to 30 parts by mass, more preferably 1 to 10 parts by mass, based on 100 parts by mass of the resin component.

[0123] -Release agent-

[0124] From the viewpoint of obtaining good demoulding properties of the mold during molding, the sealant disclosed herein may contain a release agent as an additive. The release agent is not particularly limited, and an existing known release agent can be used. Specifically, examples include: ester waxes such as carnauba wax, octadecanoic acid, stearic acid, higher fatty acids, higher fatty acid metal salts, octadecanoic acid esters, oxidized polyethylene, non-oxidized polyethylene, and other polyolefin waxes. The release agent can be used alone or in combination of two or more.

[0125] When the seal material contains a release agent, the amount of the release agent is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the resin component. If the amount of the release agent is 0.01 parts by mass or more relative to 100 parts by mass of the resin component, there is a tendency to fully obtain releasability. If it is 10 parts by mass or less, there is a tendency to obtain better adhesion and curability.

[0126] In addition, content of a mold release agent may be less than 0.1 mass part, and may be less than 0.01 mass part with respect to 100 mass parts of resin components.

[0127] -Flame retardant-

[0128] The sealing material disclosed herein may contain a flame retardant as an additive. The flame retardant is not particularly limited, and any flame retardant known in the art may be used. Specifically, organic or inorganic compounds containing halogen atoms, antimony atoms, nitrogen atoms, or phosphorus atoms, metal hydroxides, and the like may be cited. The flame retardant may be used alone or in combination of two or more.

[0129] When the sealant contains a flame retardant, the amount thereof is not particularly limited as long as it is an amount sufficient to obtain the desired flame retardant effect, for example, preferably 1 to 30 parts by mass, more preferably 2 to 20 parts by mass, based on 100 parts by mass of the resin component.

[0130] -Colorants-

[0131] The sealing material disclosed herein may further contain a colorant as an additive. As the colorant, known colorants such as carbon black, organic dyes, organic pigments, titanium oxide, red lead, and red lead may be cited. The content of the colorant may be appropriately selected according to the purpose, etc. The colorant may be used alone or in combination of two or more.

[0132] - Stress Relief Agents -

[0133] The sealing material disclosed herein may contain stress relaxants such as silicone oil and silicone rubber particles as additives. By containing stress relaxants, the warping deformation of the package and the generation of package cracks can be further reduced. As stress relaxants, commonly used known stress relaxants (flexible agents) can be listed. Specifically, thermoplastic elastomers such as silicone, styrene, olefin, urethane, polyester, polyether, polyamide, and polybutadiene can be listed, rubber particles such as natural rubber (natural rubber, NR), acrylonitrile butadiene rubber (acrylonitrile butadiene rubber, NBR), acrylic rubber, urethane rubber, silicone powder, methyl methacrylate-styrene-butadiene copolymer (Methacrylate methyl styrene butadiene, MBS), methyl methacrylate-silicone copolymer, methyl methacrylate-butyl acrylate copolymer, etc. have core-shell structures. One stress relaxant can be used alone, or two or more can be used in combination.

[0134] (Method for preparing sealing material)

[0135] The preparation method of the sealing material is not particularly limited. As a general method, a method in which the components are fully mixed using a mixer, etc., melt-kneaded by a mixing roll, an extruder, etc., and then cooled and crushed can be cited. More specifically, for example, a method in which the components are stirred and mixed, kneaded by a kneader, a roll, an extruder, etc. preheated to 70°C to 140°C, and then cooled and crushed can be cited.

[0136] (Characteristics of sealing materials)

[0137] When the sealing material of the present disclosure is made into a compression-molded body, the non-black spot ratio is 86% or more, preferably 89% or more, and more preferably 91% or more from the viewpoint of suppressing wire deviation caused by compression molding.

[0138] As a method for obtaining a sealing material having a non-black spot ratio of 86% or more when formed into a compression molded body, as described above, for example, a method of using a mixture of a first inorganic filler and a second inorganic filler treated with a coupling agent as the inorganic filler can be cited. When the mixture is used as the inorganic filler, for example, the non-black spot ratio when formed into a compression molded body can be controlled by adjusting the type and amount of the coupling agent used to treat the first inorganic filler.

[0139] The sealing material disclosed in the present invention may be solid or liquid at room temperature and pressure (e.g., 25° C., atmospheric pressure), preferably solid. The shape of the sealing material when solid is not particularly limited, and examples thereof include powder, granular, sheet, etc. From the perspective of operability, the size and mass of the sealing material when it is sheet are preferably the size and mass that are consistent with the molding conditions of the package.

[0140] <Electronic components and devices>

[0141] An electronic component device according to one aspect of the present disclosure includes a component sealed by the sealing material. In other words, the electronic component device includes a component and a cured product of the sealing material that seals the component.

[0142] As electronic component devices, there can be listed electronic component devices in which the following element parts are sealed with a sealing material, wherein the element parts are obtained by mounting elements (active elements such as semiconductor chips, transistors, diodes, thyristors, etc.; passive elements such as capacitors, resistors, coils, etc.) on supporting members such as lead frames, tape carriers with completed wiring, wiring boards, glass, silicon wafers, and organic substrates.

[0143] More specifically, there are general resin-sealed ICs such as Dual Inline Package (DIP), Plastic Leaded Chip Carrier (PLCC), Quad Flat Package (QFP), Small Outline Package (SOP), Small Outline J-lead package (SOJ), Thin Small Outline Package (TSOP), and Thin Quad Flat Package (TQFP), which have a structure in which components are fixed on a lead frame and the terminal portion of the component such as a bonding pad is connected to the lead portion by wire bonding, bumps, etc., and then sealed using a sealing material and compression molding; Tape Carrier Package (TCP), which has a structure in which components connected to a tape carrier by bumps are sealed by a sealing material; Chip on Board (Chip On Board (COB) modules, hybrid ICs, multi-chip modules, etc., which have a structure in which a component connected to the wiring formed on a supporting member by wire bonding, flip chip bonding, solder, etc. is sealed by a sealing material; Ball Grid Array (BGA), Chip Size Package (CSP), Multi Chip Package (MCP), etc., which have a structure in which a component is mounted on the surface of a supporting member with a wiring board connection terminal formed on the back, and after connecting the component to the wiring formed on the supporting member by bumps or wire bonding, the component is sealed by a sealing material. In addition, a sealing material can also be preferably used in a printed wiring board.

[0144] The method of sealing the electronic component device using the sealing material is not particularly limited, and a general compression molding method and the like are exemplified.

[0145] [Example]

[0146] Hereinafter, the embodiment will be described in detail with reference to examples, but the scope of the embodiment is not limited to these examples.

[0147] <Production of sealing materials>

[0148] First, the following components are prepared.

[0149] (A) Epoxy resin

[0150] [Epoxy resin A1] jER YX-4000 (trade name) manufactured by Mitsubishi Chemical Corporation

[0151] [Epoxy resin A2] EPOTOHTO YSLV-80XY (trade name) manufactured by Nippon Steel Chemicals & Materials Co., Ltd.

[0152] 〔Epoxy Resin A3〕 EPPN-501HY (trade name) produced by Nippon Kayaku Co., Ltd.

[0153] (B) Hardener

[0154] [Hardener B1] MEH-7851 (trade name) manufactured by Meiwa Chemical Co., Ltd.

[0155] [Hardener B2] MEH-7500 (trade name) manufactured by Meiwa Chemical Co., Ltd.

[0156] (C) Inorganic fillers

[0157] [Inorganic filler C1] Silica particles (first inorganic filler, volume average particle size 0.5 μm, specific surface area 5.5 m 2 / g, spherical silica) (mass reduction rate at 800°C: 0.38%)

[0158] [Inorganic filler C2] A coupling agent (3-methacryloxypropyltrimethoxysilane, also known as γ-methacryloxypropyltrimethoxysilane, trade name "KBM-503", 0.7 parts by mass relative to 100 parts by mass of silica particles) was used to coat silica particles (first inorganic filler, volume average particle size 0.5 μm, specific surface area 5.5 m 2 / g, spherical silica) (mass reduction rate at 800°C: 0.41%)

[0159] [Inorganic filler C3] A coupling agent (3-glycidyloxypropyltrimethoxysilane, also known as γ-glycidyloxypropyltrimethoxysilane, trade name "KBM-403", 0.6 parts by mass relative to 100 parts by mass of silica particles) was used to coat silica particles (first inorganic filler, volume average particle size 0.5 μm, specific surface area 5.5 m 2 / g, spherical silica) (mass reduction rate at 800°C: 0.38%)

[0160] [Inorganic filler C4] Silica particles (first inorganic filler, volume average particle size 0.5 μm, specific surface area 5.5 m 2 / g, spherical silica not treated with coupling agent)

[0161] [Inorganic filler C5] Silica particles (second inorganic filler, volume average particle size 15 μm, specific surface area 4.0 m 2 / g, spherical silicon dioxide)

[0162] [Inorganic filler C6] Silica particles (second inorganic filler, volume average particle size 15 μm, specific surface area 4.0 m 2 / g, spherical silica not treated with coupling agent)

[0163] [Inorganic filler C7] A coupling agent (N-phenyl-3-aminopropyltrimethoxysilane, also known as γ-anilinopropyltrimethoxysilane, trade name "KBM-573", 0.9 parts by mass relative to 100 parts by mass of silica particles) was used to coat silica particles (first inorganic filler, volume average particle size 0.5 μm, specific surface area 5.5 m 2 / g, spherical silica) (mass reduction rate at 800°C: 0.73%)

[0164] [Inorganic filler C8] A coupling agent (N-phenyl-3-aminopropyltrimethoxysilane, also known as γ-anilinopropyltrimethoxysilane, trade name "KBM-573", 1.0 part by mass relative to 100 parts by mass of silica particles) was used to coat silica particles (first inorganic filler, volume average particle size 0.5 μm, specific surface area 5.5 m 2 / g, spherical silicon dioxide)

[0165] (D) Coupling agent as additive

[0166] [Coupling agent D1] N-phenyl-3-aminopropyltrimethoxysilane (silane coupling agent, trade name "KBM-573", manufactured by Shin-Etsu Chemical Co., Ltd.)

[0167] [Coupling agent D2] 3-methacryloxypropyltrimethoxysilane (silane coupling agent, trade name "KBM-503", manufactured by Shin-Etsu Chemical Co., Ltd.)

[0168] [Coupling agent D3] 3-glycidyloxypropyltrimethoxysilane (silane coupling agent, trade name "KBM-403", manufactured by Shin-Etsu Chemical Co., Ltd.)

[0169] (E) Hardening accelerator

[0170] [Accelerator E1] Addition product of tri-p-tolylphosphine and 1,4-benzoquinone

[0171] The components shown in Table 1 and Table 2 were mixed in the amounts shown in the tables (parts by mass) and fully mixed using a mixer, and then melt-mixed at 100° C. for 2 minutes using a twin-screw mixer. Then, after the melt was cooled, the solid material was crushed into a powder, thereby preparing the target powdered sealing material. In the table, blank columns indicate that the components were not mixed.

[0172] Tables 1 and 2 show the contents of the inorganic filler relative to the entire sealing material obtained.

[0173] In addition, Tables 1 and 2 show the ratio of non-black dots in the SAT image of the compression molded body obtained by the above-mentioned method for the obtained sealing material.

[0174] In addition, the volume-based particle size distribution of the inorganic filler contained in the obtained sealing material was determined by the above-mentioned method. As a result, it was found that the particle size distribution had local maximum values ​​at 0.5 μm and 15 μm in any of the Examples and Comparative Examples.

[0175] The obtained sealing materials were evaluated by various tests shown below. The evaluation results are shown in Tables 1 and 2.

[0176] <Evaluation of spiral flow length>

[0177] The spiral flow measurement mold according to the standard (EMMI-1-66) was used, and the oil pressure converted to the plunger bottom pressure was 70kgf / cm 2 (6.86MPa) was injected into the obtained sealing material, and the molding was performed under the conditions of 175°C and 120 seconds, and the length of the molded product at this time was set as the flow distance (spiral flow length). Then, the conversion value of the flow distance in each embodiment and the comparative example was calculated when the flow distance in Comparative Example 1 was set to 100. The results are shown in Tables 1 and 2. Furthermore, with respect to the conversion value of the flow distance, the larger the value, the longer the flow distance.

[0178] <Evaluation of wire deviation>

[0179] The obtained sealing material is used and a compression molding machine (PMC-1040 manufactured by TOWA Corporation) is used to seal the package under the molding conditions of a molding temperature of 175°C and a molding time of 120 seconds. The package is post-cured at 175°C for 5 hours to obtain a semiconductor device. The semiconductor device is a ball grid array (BGA) package (resin sealing part size: 228mm×67mm×thickness 1mm), and the chip size is 7.5mm×7.5mm. In addition, regarding the wire, the gold wire diameter is 18μm and the average gold wire length is 5mm. Then, for the manufactured package, a soft X-ray analysis device is used to observe the deformation state of the gold wire and investigate the presence or absence of deformation (deformation rate relative to the initial shape). Specifically, the maximum displacement of the wire is measured by X-ray, and the deformation rate is calculated by dividing the value of the obtained maximum displacement by the wire arc length and multiplying it by 100, and the deformation rate is set as the wire deviation rate.

[0180] Then, the converted values ​​of the wire deviation rates in each example and comparative example were obtained when the wire deviation rate in comparative example 1 was set to 100. The results are shown in Tables 1 and 2. In addition, regarding the converted values ​​of the wire deviation rates, the smaller the value, the lower the wire deviation rate.

[0181] [Table 1]

[0182]

[0183] [Table 2]

[0184]

[0185] The results in Tables 1 and 2 show that the sealing materials of Examples having a non-black dot ratio of 86% or more in the SAT image when formed into a compression molded body have a lower incidence of wire deviation than the comparative examples.

[0186] The disclosure of International Patent Application No. PCT / JP2019 / 035934 filed on September 12, 2019 is incorporated in its entirety into this specification by reference.

[0187] All documents, patent applications, and technical specifications described in this specification are cited and incorporated into this specification to the same extent as if each document, patent application, and technical specification was specifically and individually described as being incorporated by reference.

Claims

1. A compression molding sealant, comprising an epoxy resin, a hardener and an inorganic filler, The inorganic filler is a material treated with a coupling agent. The inorganic filler treated with the coupling agent has a mass reduction rate at 800° C. in the range of 0.35% to 0.8%. In an image obtained by observing a compressed body formed by compressing the compression molding sealing material on a substrate through a silicon chip using an ultrasonic flaw detection device, the area of ​​the area corresponding to the compression molding on the silicon chip, excluding black spots, is more than 86% of the total area of ​​the area corresponding to the compression molding on the silicon chip.

2. The compression molding seal material according to claim 1, wherein The coupling agent is a silane coupling agent.

3. The compression molding seal material according to claim 1 or 2, wherein: The coupling agent has at least one functional group selected from the group consisting of a (meth)acryloyl group, an epoxy group, and a phenyl group.

4. The compression molding seal material according to claim 1 or 2, wherein: The coupling agent has a secondary amino group.

5. The compression molding seal material according to claim 1 or 2, wherein: The inorganic filler has a maximum value at 0.1 μm to 2 μm in the volume-based particle size distribution.

6. An electronic component device comprising: An element; and a cured product of the compression molding sealant according to any one of claims 1 to 5 for sealing the element.

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