TWI714625B - Resin composition, cured product, sealing film and sealing structure - Google Patents

Abstract

The present invention provides a resin composition containing a thermosetting component and an inorganic filler, and the inorganic filler contains alumina, and the total mass of the resin composition after excluding the solvent is used as a reference. The content is 72% by mass or more.

Description

Resin composition, cured product, sealing film and sealing structure

The invention relates to a resin composition, a cured product, a sealing film, and a sealing structure.

As electronic equipment becomes lighter, thinner, shorter, and smaller, electronic component devices (semiconductor devices, etc.) are becoming smaller and thinner. The form of semiconductor devices that are almost the same size as semiconductor elements (semiconductor wafers such as silicon wafers), or the form of packaging semiconductor devices on semiconductor devices (package on package (PoP)) is popular, and the future is expected The miniaturization and thinning of parts and devices will further advance.

If the miniaturization of semiconductor elements gradually progresses and the number of terminals gradually increases, it is difficult to provide all external connection terminals (terminals for external connection) on the semiconductor element. For example, when the external connection terminals are reluctantly installed, the distance between the terminals will become narrow and the height of the terminals will decrease, making it difficult to ensure the connection reliability after the semiconductor device is assembled. Therefore, in order to realize the miniaturization and thinning of electronic component devices, many new packaging methods have been proposed.

For example, a packaging method has been proposed, which can use solid or liquid resin (sealing resin) after re-arranging semiconductor elements obtained by singulating semiconductor wafers at appropriate intervals. The semiconductor element is sealed, and external connection terminals are provided on the sealing portion for sealing the semiconductor element on the outside of the semiconductor element; and, a semiconductor device is proposed, which is fabricated using this mounting method (for example, refer to Patent Document 1 below) ~3). [Prior Art Document] (Patent Document)

Patent Document 1: Japanese Patent No. 3616615 　　 Patent Document 2: Japanese Patent Application Publication No. 2001-244372 　　 Patent Document 3: Japanese Patent Application Publication No. 2001-127095

However, when the thermal conductivity of the sealing portion (cured material of the sealing resin) for sealing the sealed body is low, the heat dissipation will be poor. Therefore, low thermal conductivity may cause the deterioration of the device and the device to catch fire. At this time, it is conceivable to make the thickness of the sealing portion (seal thickness) on the sealed body thinner to improve heat dissipation. However, a package form such as a package-on-package (PoP) has the advantage of stacking the central processing unit (CPU) and memory, which are usually packaged separately, to reduce the package area. On the other hand, due to the overall device The thickness of the slab is increased, so it is easy to have doubts that the heat dissipation will be reduced. Therefore, there is a limit in improving the heat dissipation performance by reducing the thickness of the sealing portion.

The present invention was developed in view of the above-mentioned problems, and its object is to provide a resin composition and a cured product thereof, which can obtain a cured product having excellent thermal conductivity. In addition, an object of the present invention is to provide a sealing film and a sealing structure, which are obtained by using the aforementioned resin composition.

The thermal conductivity of the cured product of the conventional sealing resin composition (film-like epoxy resin composition, etc.) is about 1.2 W/m•K. In response to this point, the inventor found that a cured product with excellent thermal conductivity can be obtained by using a resin composition, and completed the present invention. The resin composition contains a thermosetting component and a specific amount of inorganic filler. Contains alumina.

The resin composition of the present invention contains a thermosetting component and an inorganic filler, and the inorganic filler contains alumina, and based on the total mass of the resin composition after excluding the solvent, the content of the inorganic filler is 72 Mass% or more.

With the resin composition of the present invention, a cured product with excellent thermal conductivity can be obtained. For example, a cured product can be obtained with a thermal conductivity exceeding 2.5 W/m•K (preferably 2.7 W/m• Thermal conductivity above K). As long as the thermal conductivity of the cured product of the sealing resin composition can be improved, the heat dissipation of the electronic component device (semiconductor device, etc.) can be improved, and the progress of device deterioration, device ignition, etc. can be suppressed, and the electronic component device includes the resin The sealing part of the hardened part of the composition. In particular, with the resin composition of the present invention, it is possible to improve heat dissipation, which is a problem to be solved, in a package form (PoP etc.) with increased thickness. With the resin composition of the present invention, it is possible to obtain a cured product having excellent thermal conductivity while ensuring the filling property of the resin composition.

The aforementioned thermosetting component may include a thermosetting resin. The aforementioned thermosetting resin preferably contains an epoxy resin.

The aforementioned thermosetting component may further include a curing agent. The aforementioned hardener preferably contains a phenol resin.

The aforementioned thermosetting component may further include a curing accelerator. The aforementioned hardening accelerator preferably contains an imidazole compound.

The aforementioned epoxy resin includes an epoxy resin that is liquid at 25°C, and the content of the epoxy resin that is liquid at 25°C is based on the total mass of the resin composition after excluding the mass of the solvent. More preferably, it is 5% by mass or more, and more preferably is 7% by mass or more.

Based on the total mass of the resin composition excluding the mass of the solvent, the content of the aforementioned inorganic filler is preferably 93% by mass or less, and more preferably 85% by mass or less.

The average particle size of the aforementioned inorganic filler is preferably 0.01 to 25 μm, more preferably 0.01 to 10 μm.

The content of alumina in the aforementioned inorganic filler is preferably 50% by mass or more.

The resin composition of the present invention may further contain a solvent.

The cured product of the present invention is a cured product of the resin composition of the present invention.

However, generally, the sealing of electronic components such as semiconductor elements (the sealing step in the packaging method) is often performed at the end of the process of manufacturing electronic components such as semiconductor devices. At this time, the assembling method is to implement the steps of forming a circuit and an external connection terminal on a sealed structure (sealed molded article) obtained by sealing the electronic component, and the circuit is used to arrange the external connection terminal.

The conventional assembly method sometimes seals a plurality of electronic components (semiconductor elements, etc.) to obtain a sealed structure, and then cuts the sealed structure to obtain a plurality of electronic component devices (semiconductor devices, etc.). At this time, the more electronic components to be reconfigured, the more electronic component devices that can be manufactured in one step. Therefore, research is being conducted to make the sealing structure larger. At present, there is a tendency that, for example, in order to use semiconductor manufacturing equipment for wiring formation, the sealing structure is formed into a wafer shape and the diameter of the wafer shape is increased. In addition, in order to be able to increase the size and use a printed wiring board manufacturing apparatus that is cheaper than a semiconductor manufacturing apparatus, etc., research is being conducted on panelization of the sealed structure.

When electronic parts are sealed, a mold is sometimes used for molding, which uses a mold to mold a solid or liquid resin sealing material. In some cases, transfer injection molding is used, which melts a pellet-shaped resin sealing material and flows the resin into a mold to seal it. However, in transfer molding, molten resin is poured in to perform molding. Therefore, when a large area is to be sealed, an unfilled portion may be generated. Therefore, in recent years, compression molding has begun to be used in which a resin sealing material is supplied to a mold or a sealed body before molding. Since compression molding is to supply the resin sealing material directly to the mold or the sealed body, it has the advantage that even if a large area is sealed, unfilled parts are not easily generated.

Compression molding and transfer molding use solid or liquid resin sealing materials. However, when the size of the sealed body is increased, the liquid resin sealing material may cause liquid flow or the like, and it may be difficult to uniformly supply the sealed body. In addition, since the resin must be uniformly supplied to the body to be sealed, a solid resin sealing material may not be a conventional pellet-shaped resin, but a pellet or powder resin sealing material. However, particle or powder resin sealing material is difficult to uniformly supply the resin sealing material to the mold or to be sealed, and because it is particles or powder, the resin sealing material can become a source of dust, which may contaminate the device or Doubts about clean rooms.

In addition, since the mold molding is to mold the resin in the mold, when the sealing structure is enlarged, the mold must be enlarged. However, when the mold is enlarged, high mold accuracy is required, so the technical difficulty will increase, and the manufacturing cost of the mold will increase significantly.

In contrast, the resin composition of the present invention can be made into a film for sealing to seal a body to be sealed, and has a film shape. The sealing film of the present invention contains the resin composition of the present invention. At this time, the resin can be uniformly supplied to the sealed body and dust generation can be reduced. In addition, it is possible to obtain a landfill capability, which can not only be sealed by plastic molding, but also It can be sealed by a molding method (laminating, pressurizing, etc.) that does not require a mold (a mold for high pressure, etc.).

In the sealing film of the present invention, the content of the solvent is preferably 0.2 to 1.5% by mass. The higher the content of the solvent (organic solvent, etc.), the lower the minimum melt viscosity of the film-like resin composition that is important for filling the sealed body (for example, electronic parts such as semiconductor elements). We believe that the reason should be that the solvent improves the fluidity of the film-like resin composition. In addition, an appropriate amount of solvent imparts viscosity to the film-like resin composition, and it is easy to prevent peeling from the film-like support and the film-like resin composition itself from cracking. When the content of the solvent is 0.2~1.5% by mass, these effects are likely to be maximized without causing other undesirable situations.

The thickness of the sealing film of the present invention is preferably 20 to 250 μm.

The sealing structure of the present invention includes a body to be sealed and a sealing part that seals the body to be sealed, and the sealing part includes a cured product of the resin composition of the present invention. The aforementioned sealed body may be an electronic component.

According to the present invention, it is possible to provide a resin composition and a cured product thereof, which can obtain a cured product having excellent thermal conductivity. Furthermore, according to the present invention, it is possible to provide a sealing film and a sealing structure, which are obtained using the aforementioned resin composition.

In this specification, the numerical range represented by "～" means the range that includes the numerical values described before and after "～" as the minimum and maximum values, respectively. In the numerical ranges described in stages in this specification, the upper limit or lower limit of the numerical range of a certain stage can be replaced with the upper limit or lower limit of the numerical range of another stage. In the numerical range described in this specification, the upper limit or the lower limit of the numerical range may be replaced with the value disclosed in the examples. The so-called "A or B" may include any of A and B, and may include both A and B. Unless otherwise specified, the materials exemplified in this specification may be used alone or in combination of two or more. In the present specification, the content of each component in the composition means the total amount of the plurality of substances present in the composition when there are multiple substances corresponding to each component in the composition, unless otherwise specified.

"Liquid epoxy resin" is an epoxy resin that is liquid at 25°C. The so-called "liquid at 25°C" means that the viscosity at 25°C measured with an E-type viscometer is below 400 Pa•s.

One embodiment of the present invention will be described below.

<Resin composition and hardened product> "The resin composition of this embodiment contains a thermosetting component and an inorganic filler." Examples of thermosetting components include (A) thermosetting resins (excluding compounds equivalent to curing agents), (B) curing agents, and (C) curing accelerators. The thermosetting component may contain a thermosetting resin without containing a curing agent and/or a curing accelerator. In addition to the thermosetting component, the resin composition of this embodiment also contains (D) an inorganic filler, and the (D) inorganic filler contains alumina. The resin composition of this embodiment may be in the form of a varnish or in the form of a film (film for sealing). The cured product of this embodiment is a cured product of the resin composition of this embodiment.

(Thermosetting component) [Component (A): Thermosetting resin] 　　 As the thermosetting resin, for example, epoxy resin, phenoxy resin, cyanate ester resin, thermosetting polyimide, melamine resin , Urea resin, unsaturated polyester, alkyd resin, polyurethane, etc. From the standpoint of easily obtaining a cured product having excellent thermal conductivity, as the thermosetting resin, epoxy resin is preferred. As the epoxy resin, at least one selected from the group consisting of an epoxy resin that is liquid at 25°C and an epoxy resin that is not liquid at 25°C can be used.

The epoxy resin can be used without particular limitation as long as it is a resin having two or more glycidyl groups in one molecule. As the epoxy resin, for example, bisphenol A type epoxy resin, bisphenol AP type epoxy resin, bisphenol AF type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, double Phenol C type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol G type epoxy resin, bisphenol M type epoxy resin, bisphenol S type epoxy resin (hexylene glycol Bisphenol S diglycidyl ether, etc.), bisphenol P type epoxy resin, bisphenol PH type epoxy resin, bisphenol TMC type epoxy resin, bisphenol Z type epoxy resin, phenolic novolac type epoxy Resin (ortho-cresol novolak type epoxy resin, etc.), biphenyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, bixylenol type epoxy resin (dixylenol two Glycidyl ether, etc.), hydrogenated bisphenol A epoxy resin (hydrogenated bisphenol A glycidyl ether, etc.), the dibasic acid modified diglycidyl ether epoxy resin, aliphatic epoxy resin of these resins Resin etc. An epoxy resin may be used individually by 1 type, and may use 2 or more types together.

Examples of liquid epoxy resins include: bisphenol A type glycidyl ether, bisphenol AD type glycidyl ether, bisphenol S type glycidyl ether, and bisphenol F type glycidyl ether , Hydrogenated bisphenol A type glycidyl ether, ethylene oxide adduct bisphenol A type glycidyl ether, propylene oxide adduct bisphenol A type glycidyl ether, naphthalene resin glycidyl Base ether, trifunctional or tetrafunctional glycidylamine, etc.

Examples of commercially available epoxy resins include "EXA-4700 (trade name, the same below)" (tetrafunctional naphthalene type epoxy resin) manufactured by DIC Co., Ltd., "EPICLON HP-4032" and "EXA- 4750" (multifunctional solid epoxy resin containing naphthalene skeleton), "NC-7000" (multifunctional solid epoxy resin containing naphthalene skeleton) manufactured by Nippon Kayaku Co., Ltd.; Nippon Kayaku Co., Ltd. The epoxide of the condensate of phenols and aromatic aldehydes with phenolic hydroxyl groups such as "EPPN-502H" (see phenol epoxy resin) manufactured by the company (see phenol epoxy resin); manufactured by DIC Dicyclopentadiene aralkyl type epoxy resin such as "EPICLON HP-7200H" (multifunctional solid epoxy resin containing dicyclopentadiene skeleton); "NC-3000H" (containing biphenyl) manufactured by Nippon Kayaku Co., Ltd. Frame polyfunctional solid epoxy resin) and other biphenyl aralkyl type epoxy resins; "EPICLON N-660", "EPICLON N-690", "EPICLON N-740" (phenol novolac type) manufactured by DIC Corporation Epoxy resin) and "N500P-1" (ortho-cresol novolac type epoxy resin), "EOCN-104S" manufactured by Nippon Kayaku Co., Ltd. Novolac type epoxy resins; manufactured by Nissan Chemical Industry Co., Ltd. "TEPIC" isotonic (2,3-epoxypropyl) isocyanurate; "EPICLON 860", "EPICLON 900-IM", "EPICLON EXA-4816" and "EPICLON" manufactured by DIC Co., Ltd. EXA-4822", "ARALDITE AER280" manufactured by Asahi CIBA Co., Ltd., "Epotohto YD-134", "YD-8125" and "YDF8170" manufactured by Totoh Chemical Co., Ltd. (Nippon Steel & Sumikin Chemical Co., Ltd.) , "JER834", "jER872", "jER807", "jER815", "jER825", "jER827", "jER828", "jER1001", "jER1004" manufactured by Japan Epoxy Resins Co., Ltd. (Mitsubishi Chemical Corporation) ”, “jER1007” and “jER1009”, “ELA-134” manufactured by Sumitomo Chemical Co., Ltd., “DER-330”, “DER-301” and “DER-361” manufactured by DOW Chemical and other bisphenol A types Epoxy resin; Bisphenol F epoxy resin such as "jER806" manufactured by Japan Epoxy Resins Co., Ltd. (Mitsubishi Chemical Co., Ltd.); Aliphatic epoxy resin such as "Denacol DLC301" manufactured by Nagase ChemteX Co., Ltd., etc. These epoxy resins may be used individually by 1 type, and may use 2 or more types together.

From the viewpoint of easy to obtain excellent fluidity, the content of the thermosetting resin is preferably 1% by mass or more, more preferably 3% by mass or more based on the total mass of the resin composition after excluding the mass of the solvent , More preferably 4% by mass or more, particularly preferably 4% by mass or more, very preferably 5% by mass or more, very preferably 10% by mass or more, and still more preferably 15% by mass or more. From the viewpoint of easily suppressing the occurrence of cracks and cracks on the film surface, the content of the thermosetting resin is preferably 30% by mass or less, more preferably, based on the total mass of the resin composition after excluding the mass of the solvent 25% by mass or less, more preferably 20% by mass or less.

When the resin composition is an epoxy resin composition containing epoxy resin, from the viewpoint of easily obtaining a cured product with excellent thermal conductivity, the content of the epoxy resin is based on the total mass of the thermosetting resin. It is preferably 50% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more. Based on the total mass of the thermosetting resin, the content of the epoxy resin may be 100% by mass.

From the viewpoint of easily suppressing the occurrence of cracks and cracks on the film surface, the content of the liquid epoxy resin is preferably 0.5% by mass or more based on the total mass of the resin composition after excluding the mass of the solvent, and more preferably It is 1 mass% or more, more preferably 3 mass% or more, particularly preferably 5 mass% or more, extremely preferably 7 mass% or more, and very preferably 9 mass% or more. From the viewpoint of easily suppressing the excessively high viscosity of the film and the viewpoint of easily suppressing the fusion edge, the content of the liquid epoxy resin is preferably 20 based on the total mass of the resin composition after excluding the mass of the solvent. % By mass or less, more preferably 15% by mass or less, still more preferably 13% by mass or less.

From the viewpoint of easily suppressing cracks and cracks on the film surface, based on the total mass of the thermosetting resin, the content of the liquid epoxy resin is preferably 20% by mass or more, more preferably 30% by mass or more , More preferably 50% by mass or more. From the viewpoint of easily suppressing the excessive viscosity of the film and the viewpoint of easily suppressing the fusion edge, based on the total mass of the thermosetting resin, the content of the liquid epoxy resin is preferably 95% by mass or less, and more It is preferably 90% by mass or less, and more preferably 80% by mass or less. The content of the liquid epoxy resin may be 100% by mass based on the total mass of the thermosetting resin.

When the resin composition contains (A) component (epoxy resin, etc.), (B) component, (C) component, and (D) component, from the viewpoint of easily suppressing cracks and cracks on the film surface, (A) )-(D) The total mass of components is used as a reference. The content of the liquid epoxy resin is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 3% by mass or more, and particularly preferably 5 Mass% or more, very preferably 7% by mass or more, and very preferably 9% by mass or more. From the standpoint of easily suppressing the excessive viscosity of the film and the standpoint of easily suppressing fusion, the content of the liquid epoxy resin is preferably 20 mass based on the total mass of the components (A) to (D) % Or less, more preferably 15% by mass or less, still more preferably 13% by mass or less.

[Component (B): Curing agent] "" is not particularly limited as a curing agent, and examples include phenolic curing agents (phenol resins, etc.), acid anhydride curing agents, active ester curing agents, cyanate ester curing agents, and the like. When the (A) component contains an epoxy resin, the (B) curing agent can be used without particular limitation as long as it is a compound having two or more functional groups that react with glycidyl groups in one molecule. Examples of such hardeners include phenol resins and acid anhydrides. From the viewpoint of easily obtaining a cured product having excellent thermal conductivity, the curing agent is preferably a phenol resin. The curing agent may be used alone or in combination of two or more kinds.

The phenol resin is not particularly limited as long as it has two or more phenolic hydroxyl groups in one molecule, and a conventional phenol resin can be used. Examples of phenol resins include: resins obtained by condensation or co-condensation of phenols and/or naphthols and aldehydes with acidic catalysts, biphenyl skeleton type phenol resins, p-xylene modified phenol resins, and isobenzene Dimethyl-p-xylylene modified phenol resin, melamine modified phenol resin, terpene modified phenol resin, dicyclopentadiene modified phenol resin, cyclopentadiene modified phenol resin, polycyclic aromatic ring modified High quality phenol resin, xylylene modified naphthol resin, etc. Examples of phenols include phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, and bisphenol F. Examples of naphthols include α-naphthol, β-naphthol, and dihydroxynaphthalene. Examples of aldehydes include formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and salicaldehyde.

Examples of commercially available phenol resins include "PHENOLITE LF2882", "PHENOLITE LF2822", "PHENOLITE TD-2090", "PHENOLITE TD-2149", "PHENOLITE VH-4150", and "PHENOLITE manufactured by DIC Co., Ltd. VH4170", "XLC-LL" and "XLC-4L" manufactured by Mitsui Chemicals Co., Ltd., "SN-100", "SN-300", "SN-395" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. and "SN-400", "SK Resin HE910" made by Air Water Co., Ltd., "PAPS-PN2" (molecular weight distribution aggregation type novolak resin) made by Asahi Organic Materials Co., Ltd., Qunrong Chemical Industry Co., Ltd. "ELP40" etc.

From the viewpoint of excellent curability of the thermosetting resin, based on the total mass of the resin composition after excluding the mass of the solvent, the content of the hardener is preferably 1-20% by mass, more preferably 2~ 15% by mass, more preferably 3-10% by mass.

As the mixing ratio of epoxy resin and hardener (phenol resin, etc.), the equivalent of the glycidyl group of epoxy resin (epoxy equivalent) and the functional group (phenolic hydroxyl group, etc.) that can react with the glycidyl group in the hardener The ratio of the equivalent (phenolic hydroxyl equivalent, etc.) of) (the equivalent of the glycidyl group of the epoxy resin / the functional group that reacts with the glycidyl group in the hardener) is preferably 0.7 to 2.0, more preferably 0.8 ~1.8, more preferably 0.9 to 1.7. When the aforementioned ratio is 0.7 or more or 2.0 or less, unreacted epoxy resin and/or unreacted hardener are not likely to remain, and the desired properties of the cured product are easily obtained.

[Component (C): Hardening accelerator] 　　 can be used as a hardening accelerator without any particular limitation, preferably at least one selected from the group consisting of amine hardening accelerators and phosphorus hardening accelerators . In particular, from the viewpoints of easily obtaining a cured product with excellent thermal conductivity, the viewpoint of abundant derivatives, and the viewpoint of easily obtaining the desired active temperature, the curing accelerator is preferably an amine-based curing accelerator, and more preferably At least one selected from the group consisting of imidazole compounds, aliphatic amines and alicyclic amines, and more preferably imidazole compounds. As an imidazole compound, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, etc. are mentioned, for example. A hardening accelerator may be used individually by 1 type, and may use 2 or more types together. Examples of commercially available hardening accelerators include "2P4MZ" and "1B2MZ" manufactured by Shikoku Chemical Industry Co., Ltd.

Based on the total amount of the thermosetting resin (epoxy resin, etc.) and the curing agent (phenol resin, etc.), the content of the curing accelerator is preferably within the following range. From the viewpoint of easily obtaining a sufficient hardening acceleration effect, the content of the hardening accelerator is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and still more preferably 0.3% by mass or more. From the point of view that it is not easy to harden during the steps (such as coating and drying) when manufacturing the sealing film or during storage of the sealing film, and it is easy to prevent the sealing film from cracking and forming defects as the melt viscosity rises. The content of the hardening accelerator is preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably 1.5% by mass or less. From these viewpoints, the content of the hardening accelerator is preferably 0.01 to 5% by mass, more preferably 0.1 to 3% by mass, and still more preferably 0.3 to 1.5% by mass.

(Component (D): Inorganic filler) The "inorganic filler" contains alumina (alumina particles, etc.). Commercial products of inorganic fillers containing alumina include, for example, "AA-1.5" manufactured by Sumitomo Chemical Co., Ltd., "DAW20" manufactured by Denka Co., Ltd., and the like.

The inorganic filler may include constituent materials other than alumina (alumina particles, etc.). In other words, the resin composition of the present embodiment may contain a kind of particles including alumina and constituent materials other than alumina, or may include a kind of particles including alumina and components other than alumina.

From the viewpoint of the effect of improving the thermal conductivity more excellently, based on the total mass of the inorganic filler, the content of alumina in the inorganic filler is preferably 50% by mass or more, more preferably 70% by mass or more , More preferably 80% by mass or more, particularly preferably 90% by mass or more. Based on the total mass of the inorganic filler, the content of alumina may also be 100% by mass.

As constituent materials other than alumina, constituent materials contained in conventional inorganic fillers can be used, and are not limited to specific ones. Examples of constituent materials other than alumina include barium sulfate, barium titanate, silica, talc, clay, magnesium carbonate, calcium carbonate, alumina, silicon nitride, and aluminum nitride. As the inorganic filler containing silicon oxide, for example, amorphous silicon oxide, crystalline silicon oxide, fused silica, spherical silicon oxide, etc. can be mentioned. From the viewpoint that it is easy to obtain the effect of improving the dispersibility in the resin and the effect of suppressing the deposition in the varnish by surface modification, etc., and the viewpoint that the desired cured product characteristics are easily obtained due to the relatively small coefficient of thermal expansion As a constituent material other than alumina, silicon oxide is preferred. Examples of commercially available inorganic filler materials containing silicon oxide include "SC2500-SXJ", "SC5500-SXE" and "SC2050-KC" manufactured by Admatechs Co., Ltd. The constituent materials other than alumina may be used alone or in combination of two or more.

The inorganic filler material can undergo surface modification. The method of surface modification is not particularly limited. From the viewpoints of easy handling, abundant types of functional groups, and easy imparting of desired characteristics, it is preferable to use a silane coupling agent for surface modification.

As a silane coupling agent, for example, alkyl silane, alkoxy silane, vinyl silane, epoxy silane, amino silane, acryl silane, methacryl silane, mercapto silane, thioether silane, Isocyanatosilane, thiosilane, styrylsilane, alkylchlorosilane, etc.

Specific examples of the silane coupling agent include, for example, methyl trimethoxy silane, dimethyl dimethoxy silane, trimethyl methoxy silane, methyl triethoxy silane, and methyl triphenoxy. Silane, Ethyl Trimethoxy Silane, n-Propyl Trimethoxy Silane, Diisopropyl Dimethoxy Silane, Isobutyl Trimethoxy Silane, Diisobutyl Dimethoxy Silane, Isobutyl Triethyl Oxysilane, n-hexyl trimethoxy silane, n-hexyl triethoxy silane, cyclohexyl methyl dimethoxy silane, n-octyl triethoxy silane, n-dodecyl methoxy silane, phenyl Trimethoxysilane, diphenyldimethoxysilane, triphenylsilanol, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, n-octyldimethylchlorosilane, tetraethyl Oxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2 -Aminoethyl)aminopropylmethyldimethoxysilane, 3-phenylaminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxysilane Propylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, bis(3-(triethoxysilane) Yl)propyl)disulfide, bis(3-(triethoxysilyl)propyl)tetrasulfide, vinyl triethoxysilane, vinyl trimethoxysilane, vinyl triethoxy Silane, vinyl triisopropoxy silane, allyl trimethoxy silane, diallyl dimethyl silane, 3-methacryloxy propyl trimethoxy silane, 3-methacryloxy silane 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, N-(1, 3-Dimethylbutyryl)-3-aminopropyl triethoxysilane, aminosilane (phenylaminosilane, etc.), etc. The silane coupling agent may be used alone or in combination of two or more.

From the viewpoint of easily inhibiting the aggregation of the inorganic filler and easily dispersing the inorganic filler, the average particle size of the inorganic filler is preferably 0.01 μm or more, more preferably 0.1 μm or more, and even more preferably 0.3 μm or more. It is preferably 0.5 μm or more. From the viewpoint of easily suppressing the deposition of inorganic fillers in the varnish and making it easy to produce a homogeneous sealing film, the average particle size of the inorganic fillers is preferably 25 μm or less, more preferably 10 μm or less, and further preferably 5 Below μm. From these viewpoints, the average particle size of the inorganic filler is preferably 0.01 to 25 μm, more preferably 0.01 to 10 μm, further preferably 0.1 to 10 μm, particularly preferably 0.3 to 5 μm, and very preferably 0.5～5 μm. The average particle size of the inorganic filler may be 10-18 μm.

From the viewpoint of excellent fluidity of the resin composition, it is preferable to use a combination of plural kinds of inorganic fillers having mutually different average particle diameters. In the combination of inorganic fillers, the maximum average particle diameter is preferably 15-25 μm. Preferably, it is used in combination: an inorganic filler with an average particle diameter of 15-25 μm, an inorganic filler with an average particle diameter of 0.5-2.5 μm, and an inorganic filler with an average particle diameter of 0.1-1.0 μm.

The so-called "average particle size" refers to the particle size at the point equivalent to 50% of the volume when the total volume of the particles is set to 100% to obtain the cumulative power distribution curve obtained from the particle size. The particle size distribution measuring device of the radiation scattering method is used for measurement. The average particle diameter of each inorganic filler to be combined can be confirmed from the average particle diameter of each inorganic filler at the time of mixing, and can be confirmed by measuring the particle size distribution.

From the viewpoint of improving the thermal conductivity and easily suppressing the warpage of the sealed structure (such as electronic components such as semiconductor devices) due to the difference in the thermal expansion coefficient between the sealed body and the sealed body, the solvent is eliminated The total mass of the resin composition after mass is taken as a reference, and the content of the inorganic filler (the total amount of the inorganic filler containing alumina and the inorganic filler not containing alumina) is 72% by mass or more. From the viewpoint of increasing the thermal conductivity and the viewpoint that it is easier to suppress the warpage of the sealing structure, the content of the inorganic filler is preferably based on the total mass of the resin composition after excluding the mass of the solvent It is 72.5% by mass or more, more preferably 73% by mass or more. From the viewpoint that it is easy to prevent the sealing film from cracking during the drying step when the sealing film is made, and from the viewpoint that the melt viscosity of the sealing film increases and the fluidity is reduced, and it is easy to fully seal the sealed body (electronic parts, etc.) In terms of the total mass of the resin composition after excluding the mass of the solvent, the content of the inorganic filler is preferably 93% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass or less , Particularly preferably 84.5 mass% or less, extremely preferably 81 mass% or less, and very preferably 80 mass% or less. From these viewpoints, based on the total mass of the resin composition after excluding the mass of the solvent, the content of the inorganic filler is preferably 72 to 93 mass%, more preferably 72 to 90 mass%, and still more preferably It is 72 to 85% by mass, particularly preferably 72 to 84.5% by mass, extremely preferably 72 to 81% by mass, and very preferably 73 to 80% by mass.

Based on the total mass of the resin composition excluding the mass of the solvent, the content of the inorganic filler (alumina particles, etc.) containing alumina is preferably within the following range. From the viewpoint of further improving the thermal conductivity, the content of the inorganic filler containing alumina is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass or more. From the viewpoint of easily ensuring sufficient landfillability, the content of the inorganic filler containing alumina is preferably 85% by mass or less, more preferably 80% by mass or less, and still more preferably 75% by mass or less.

((E) component: solvent) 　　 The resin composition of this embodiment may contain (E) solvent, and may not contain (E) solvent. As the solvent, conventional organic solvents can be used. The organic solvent is preferably a solvent that can dissolve components other than the inorganic filler, for example: aliphatic hydrocarbons, aromatic hydrocarbons, terpenes, halogens, esters, ketones, alcohols , Aldehydes, etc. A solvent may be used individually by 1 type, and may use 2 or more types together.

From the viewpoint of low environmental load and easy dissolution of thermosetting resin (epoxy resin, etc.) and hardener (phenol resin, etc.), the solvent is preferably from esters, ketones and alcohols At least one selected from the group. Among them, ketones are preferred from the viewpoint that it is particularly easy to dissolve thermosetting resins (epoxy resins, etc.) and hardeners (phenol resins, etc.). From the viewpoint of less volatilization at room temperature (25°C) and easy removal during drying, the solvent is preferably selected from the group consisting of acetone, methyl ethyl ketone and methyl isobutyl ketone At least one of.

((F) Component: Elastomer) 　　 The resin composition of this embodiment may contain (F) an elastomer (flexible agent) as needed. From the viewpoint of excellent dispersibility and solubility, elastomers are preferably used from polybutadiene particles, styrene butadiene particles, acrylic elastomers, silicone powders, silicone oils, and silicone elastomers. At least one selected from the group consisting of. Elastomer may be used individually by 1 type, and may use 2 or more types together.

When the elastomer is in the form of particles, the average particle diameter of the elastomer is not particularly limited. In Embedded Wafer-Level Ball Grid Array (eWLB) applications, it is necessary to fill between semiconductor elements. Therefore, when the sealing film is used in eWLB applications, the average elastomer The particle size is preferably 50 μm or less. From the viewpoint of excellent dispersion of the elastomer, the average particle diameter of the elastomer is preferably 0.1 μm or more.

Examples of commercially available elastomers include "HTR280" manufactured by Nagase ChemteX Co., Ltd. and the like. In addition, some commercially available elastomer components are not elastomer monomers but elastomers dispersed in a liquid resin (for example, liquid epoxy resin) in advance. The elastomer can be used without problems. Examples of such commercially available products include "MX-136" and "MX-965" manufactured by Kaneka Co., Ltd.

(Other components) "The resin composition of this embodiment can further contain other additives." Specific examples of such additives include, for example, pigments, dyes, mold release agents, antioxidants, surface tension regulators, and the like.

<The film for sealing> 　　 The film for sealing of this embodiment contains the resin composition of this embodiment. The sealing film of the present embodiment may be a form in which the resin composition of the present embodiment is formed into a film, and it is composed of the resin composition of the present embodiment. The sealing film of the present embodiment can be used, for example, for sealing semiconductor elements, filling electronic parts that have been placed on printed wiring boards, and the like.

From the standpoint of easily suppressing the unevenness of the in-plane thickness during coating, the thickness (film thickness) of the sealing film is preferably 20 μm or more, more preferably 30 μm or more, and still more preferably 50 μm or more, Especially preferably, it is 100 μm or more. From the viewpoint of easily obtaining a certain dryness in the depth direction during coating, the thickness of the sealing film is preferably 250 μm or less, more preferably 200 μm or less, and still more preferably 150 μm or less. From these viewpoints, the thickness of the sealing film is preferably 20 to 250 μm, more preferably 30 to 250 μm, still more preferably 50 to 200 μm, and particularly preferably 100 to 150 μm. In addition, a plurality of sheets of the sealing film can be laminated to produce a sealing film with a thickness of more than 250 μm.

The content of the inorganic filler (the total amount of the inorganic filler containing alumina and the inorganic filler not containing alumina) in the sealing film relative to the total mass of the sealing film after removing the solvent is preferably Within the following range. From the viewpoint of further improving the thermal conductivity and easily suppressing the warpage of the sealing structure, the content of the inorganic filler is preferably 72% by mass or more, more preferably 72.5% by mass or more, and still more preferably 73 Mass% or more. From the standpoint of preventing the fluidity reduction due to the increase in the melt viscosity of the sealing film and the ease of sealing the body (electronic parts, etc.) to be sealed sufficiently, it is preferably 93% by mass or less, more preferably 90% by mass or less, and more It is preferably 85% by mass or less, particularly preferably 84.5% by mass or less, very preferably 81% by mass or less, and very preferably 80% by mass or less. From these viewpoints, the content of the inorganic filler is preferably 72 to 93% by mass, more preferably 72 to 90% by mass, still more preferably 72 to 85% by mass, particularly preferably 72 to 84.5% by mass. It is preferably 72.5 to 81% by mass, and very preferably 73 to 80% by mass.

The content of the solvent (organic solvent, etc.) contained in the sealing film relative to the total mass of the sealing film (including the mass of the solvent) is preferably within the following range. From the viewpoint that it is easy to prevent the sealing film from becoming brittle and cause problems such as cracking of the sealing film, and it is easy to suppress the increase in the minimum melt viscosity and reduce the landfillability, the content of the solvent is preferably 0.2% by mass or more, and more preferably 0.3% by mass or more, more preferably 0.5% by mass or more, particularly preferably 0.6% by mass or more, and extremely preferably 0.7% by mass or more. From the viewpoint of easily suppressing the disadvantages of excessively strong adhesiveness of the sealing film and reducing the handling properties and easily suppressing the disadvantages such as blistering due to the volatilization of the solvent (organic solvent, etc.) when the sealing film is heat-cured The content of the solvent is preferably 1.5% by mass or less, more preferably 1% by mass or less. From these viewpoints, the content of the solvent is preferably 0.2 to 1.5% by mass, more preferably 0.3 to 1% by mass, still more preferably 0.5 to 1% by mass, particularly preferably 0.6 to 1% by mass, and very preferably 0.7-1% by mass.

The sealing film of this embodiment can be produced specifically as follows.

First, the constituent components ((A) thermosetting resin, (B) curing agent, (C) curing accelerator, (D) inorganic filler, (E) solvent, etc.) of the resin composition of this embodiment are mixed, Then, a varnish (varnish-like resin composition) is produced. The mixing method is not particularly limited, and a grinder, mixer, and stirring blade can be used. The solvent (organic solvent, etc.) can be used for the purpose of dissolving and dispersing the constituent components of the resin composition, which is the material of the sealing film, to prepare a varnish or assisting in preparing the varnish. It is possible to remove most of the solvent in the drying step after coating.

After coating the varnish prepared in the above manner on a support (film-like support, etc.), it is heated and dried by blowing hot air or the like to produce a sealing film. The coating method is not particularly limited. For example, a comma coater, a bar coater, a kiss coater, a roll coater, a gravure coater, a die coater, etc. can be used Coating device.

As a film-like support, a polymer film, metal foil, etc. can be used. Examples of polymer films include polyolefin films such as polyethylene films and polypropylene films; vinyl films such as polyvinyl chloride films; polyester films such as polyethylene terephthalate; polycarbonate films; acetylene fibers Plain film; tetrafluoroethylene film, etc. Examples of the metal foil include copper foil and aluminum foil.

The thickness of the support is not particularly limited, but from the viewpoint of excellent handling and drying properties, it is preferably 2 to 200 μm. When the thickness of the support is 2 μm or more, it is easy to suppress the inconvenience of breaking of the support during coating and the inconvenience of bending due to the weight of the varnish. When the thickness of the support is 200 μm or less, in the drying step, when hot air is blown from both the coating surface and the back surface, it is easy to suppress the disadvantages that hinder the drying of the solvent in the varnish.

On the sealing film already formed on the support, a protective layer may be arranged for the purpose of protecting the sealing film. The formation of the protective layer can improve the handling, and can avoid the inconvenience that the sealing film sticks to the back surface of the support during winding.

As the protective layer, a polymer film, metal foil, etc. can be used. Examples of polymer films include polyolefin films such as polyethylene films and polypropylene films; vinyl films such as polyvinyl chloride films; polyester films such as polyethylene terephthalate; polycarbonate films; acetylene films Cellulose film; tetrafluoroethylene film, etc. Examples of the metal foil include copper foil and aluminum foil.

The sealing film produced in the above-mentioned manner can obtain a cured product of the sealing film by the following steps and thereby produce a sealing structure (for example, an electronic component device such as a semiconductor device): Landfill target) the step of facing the state of the sealing film; the step of heating and melting the sealing film and applying pressure to fill the sealed body; and, heating the sealing film with landfill ability by heating Hardening step.

<Sealing structure> 　　 The sealing structure of this embodiment includes a body to be sealed and a sealing part that seals the body to be sealed, and the sealing part contains a cured product of the resin composition of this embodiment (this embodiment The cured product of the resin composition contained in the sealing film). Examples of the sealing structure include electronic component devices. The electronic component device includes an electronic component and a sealing portion that seals the electronic component, and the sealing portion includes a cured product of the resin composition of this embodiment. Examples of electronic components include: semiconductor elements; semiconductor wafers; integrated circuits; semiconductor elements; filters such as surface acoustic wave (SAW) filters; passive components such as detectors. The electronic component device may be the following: a semiconductor device equipped with a semiconductor element or a semiconductor wafer as an electronic component; a printed circuit board, etc. The sealing structure of this embodiment may include a plurality of to-be-sealed bodies. The plurality of sealed bodies may be of the same type or different types.

Next, the manufacturing method of the electronic component device using the sealing film of this embodiment is demonstrated. Here, the case where the electronic component is a semiconductor element is explained. FIG. 1 is a schematic cross-sectional view for explaining a method of manufacturing an electronic component device, that is, a semiconductor device, as an embodiment of a method of manufacturing a sealed structure. The manufacturing method of this embodiment includes the following steps: a step of arranging a plurality of semiconductor elements 20 as sealed objects (filled objects) and arranging them on a substrate 30 having a temporary fixing material 40 (Figure 1(a)) ; The sealing film 10 with a support (equipped with the support 1 and the sealing film 2 provided on the support 1) is opposed to the semiconductor element 20, and then the sealing film 2 is pressed (laminated) under heating The step of embedding the semiconductor element 20 in the sealing film 2 on the semiconductor element 20 (Figure 1(b)); and curing the sealing film 2 in which the semiconductor element 20 is embedded to obtain a cured product 2a The steps (Figure 1(c)). In this embodiment, after the semiconductor element 20 is sealed with the sealing film 2 by the build-up method, the sealing film 2 is thermally cured to obtain a sealed structure (electronic component device), which has a landfill The semiconductor element 20 in the hardened product 2a, but it is also possible to obtain a sealed structure by compression molding.

The layering machine used in the layering method is not particularly limited, and examples thereof include roll-type and balloon-type layering machines. From the viewpoint of landfillability, the stacker may be a balloon type capable of vacuum pressurization.

Laminating is usually performed below the softening point of the support. The lamination temperature is preferably near the lowest melt viscosity of the sealing film. The pressure at the time of lamination varies depending on the size and density of the sealed object (for example, electronic parts such as semiconductor elements) to be filled. The pressure during lamination, for example, can be in the range of 0.2 to 1.5 MPa, or in the range of 0.3 to 1.0 MPa. The stacking time is not particularly limited, and it may be 20 to 600 seconds, 30 to 300 seconds, or 40 to 120 seconds.

The curing of the sealing film can be performed, for example, under atmospheric pressure or in an inert gas. The curing temperature (heating temperature) is not particularly limited, and may be 80 to 280°C, 100 to 240°C, or 120 to 200°C. If the curing temperature is 80°C or higher, the curing of the sealing film will proceed sufficiently and the occurrence of defects can be suppressed. When the curing temperature is below 280°C, there is a tendency to suppress thermal damage to other materials. The curing time (heating time) is not particularly limited, and may be 30 to 600 minutes, 45 to 300 minutes, or 60 to 240 minutes. When the curing time is within these ranges, the curing of the sealing film will proceed sufficiently and better production efficiency can be obtained. In addition, the curing conditions can be combined with a plurality of conditions.

The preferred embodiments of the present invention have been described above, but the present invention is not necessarily limited to the above-mentioned embodiments, and may be appropriately modified within the scope not departing from the gist of the present invention. [Example]

The following examples are given to illustrate the present invention in more detail, but the present invention is not limited in any way by these examples.

The following components are used as components for obtaining a varnish-like epoxy resin composition (varnish) for the sealing film (film-like epoxy resin composition).

(A) Component: Thermosetting resin (epoxy resin) 　A1: Bisphenol F epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name jER806, epoxy equivalent 160 g/eq, liquid at 25°C Epoxy resin) 　A2: A naphthalene skeleton-containing polyfunctional solid epoxy resin (manufactured by DIC Co., Ltd., trade name EXA-4700, epoxy equivalent of 182 g/eq, epoxy resin that does not show liquid at 25°C) 　A3: Bisphenol F type epoxy resin containing polybutadiene elastomer particles (manufactured by Kaneka Co., Ltd., trade name MX-136, the content of liquid epoxy resin is 75% by mass, the content of elastomer particles is 25% by mass, and the The oxygen equivalent is 226 g/eq, the average particle size of the elastomer particles is 0.1 μm, and it contains the epoxy resin that shows liquid at 25°C) 　A4: epoxy resin containing silicone elastomer particles (bisphenol F type liquid A mixture of epoxy resin and bisphenol A liquid epoxy resin, manufactured by Kaneka Co., Ltd., trade name MX-965, liquid epoxy resin content of 75% by mass, and elastomer particle content of 25% by mass, contained in Liquid epoxy resin components at 25°C) 　A5: o-cresol novolac epoxy resin (manufactured by DIC Co., Ltd., trade name N500P-1, epoxy equivalent 201 g/eq, no liquid at 25°C Epoxy resin) 　A6: A bisphenol A epoxy resin containing a flexible skeleton (manufactured by DIC Co., Ltd., trade name EPICLON EXA-4816, epoxy equivalent 403 g/eq, liquid ring at 25°C) Oxygen resin)

(B) Component: Hardener (phenol resin) 　B1: Phenolic novolac resin (manufactured by Asahi Organic Materials Co., Ltd., trade name PAPS-PN2, phenolic hydroxyl equivalent 104 g/eq, does not show liquid at 25°C Phenolic resin) 　B2: Alkylphenol novolac resin (manufactured by Qunrong Chemical Industry Co., Ltd., trade name ELP40, phenolic hydroxyl equivalent 140 g/eq)

(C) Ingredient: Hardening accelerator C1: 2-Phenyl-4-methylimidazole (manufactured by Shikoku Chemical Industry Co., Ltd., trade name 2P4MZ) 　C2: 1-Benzyl-2-methylimidazole (Shikoku Made by Chemical Industry Co., Ltd., 1B2MZ)

(D) Component: Inorganic filler D1: Alumina particles (manufactured by Sumitomo Chemical Co., Ltd., trade name AA-1.5, average particle size 1.5 μm) 　D2: Alumina particles (manufactured by Denka Co., Ltd., trade name DAW20, average Particle size 20 μm) 　D3: Silica particles (manufactured by Admatechs Co., Ltd., trade name SC2500-SXJ, anilinosilane treatment, average particle size 0.5 μm) 　D4: Silica particles (manufactured by Admatechs Co., Ltd., trade name SC5500- SXE, aniline silane treatment, average particle size 1.6 μm) 　D5: Silica slurry (manufactured by Admatechs Co., Ltd., trade name SC2050-KC, silicone oligomer treatment, average particle size 0.5 μm, methyl isobutyl ketone Solvent dilution (content of silica filler 70% by mass))

(E) Ingredient: Solvent 　E1: Methyl ethyl ketone

(F) Component: Elastomer 　F1: Polymer elastomer (manufactured by Nagase ChemteX Co., Ltd., trade name HTR280, epoxy modified linear elastomer)

<Production of film for sealing> (Example 1) 　　 In a 10 L polyethylene container, 172 g of organic solvent E1 was added. After adding 542 g of the inorganic filler D1 to the aforementioned container, a stirring blade was used to disperse the inorganic filler D1 to obtain a dispersion liquid. 48 g of thermosetting resin A1, 12 g of thermosetting resin A2, and 38 g of hardener B1 were added to this dispersion and stirred. After confirming that the hardening agent B1 is dissolved, 0.8 g of the hardening accelerator C1 is added, and the mixture is further stirred for 1 hour to obtain a mixed liquid. This mixed liquid was filtered with a nylon #200 mesh (opening 75 μm), and the filtrate was collected to prepare a varnish-like epoxy resin composition. Use a coater to coat this varnish-like epoxy resin composition on the following film-like support under the following conditions, and prepare a sealing film (film-like epoxy resin) with a film thickness of 100 μm on the support. Resin composition). • Coating head style: chipped wheel coater • Coating and drying speed: 1 m/min • Drying conditions (temperature/furnace length): 110℃/3.3 m, 130℃/3.3 m, 140℃/3.3 m •Film-like support: Polyethylene terephthalate film after 38 μm

The surface of the sealing film is protected by the protective layer (12 μm thick polyethylene terephthalate film) arranged on the side opposite to the support in the sealing film. In addition, in each of the following evaluations, the evaluation is performed after peeling the support and the protective layer. The following examples and comparative examples are also the same.

(Example 2) 　　 141 g of organic solvent E1 was added to a 10 L polyethylene container. After adding 493 g of the inorganic filler D1 to the aforementioned container, a stirring blade was used to disperse the inorganic filler D1 to obtain a dispersion. To this dispersion, 88 g of thermosetting resin A1, 22 g of thermosetting resin A2, and 38 g of hardener B1 were added and stirred. After confirming the dissolution of the hardening agent B1, 1.4 g of the hardening accelerator C1 was added, and the mixture was further stirred for 1 hour to obtain a mixed solution. This mixed liquid was filtered with a nylon #200 mesh (opening 75 μm), and the filtrate was collected to prepare a varnish-like epoxy resin composition. Using a coater, this varnish-like epoxy resin composition was coated on a film-like support in the same manner as in Example 1 to produce a sealing film (film-like epoxy resin composition) with a film thickness of 100 μm .

(Example 3) "In a 10 L polyethylene container, 114 g of organic solvent E1 was added. After adding 401 g of the inorganic filler D1 to the aforementioned container, a stirring blade was used to disperse the inorganic filler D1 to obtain a dispersion. 48 g of thermosetting resin A1, 12 g of thermosetting resin A2, and 38 g of hardener B1 were added to this dispersion and stirred. After confirming that the hardening agent B1 is dissolved, 0.8 g of the hardening accelerator C1 is added, and the mixture is further stirred for 1 hour to obtain a mixed liquid. This mixed liquid was filtered with a nylon #200 mesh (opening 75 μm), and the filtrate was collected to prepare a varnish-like epoxy resin composition. Using a coater, this varnish-like epoxy resin composition was coated on a film-like support in the same manner as in Example 1 to produce a sealing film (film-like epoxy resin composition) with a film thickness of 100 μm .

(Example 4) 　　 149 g of organic solvent E1 was added to a 10 L polyethylene container. After adding 423 g of the inorganic filler D1 to the aforementioned container, 104 g of the inorganic filler D3 was added, and a stirring blade was used to disperse the inorganic filler D1 and D3 to obtain a dispersion. 48 g of thermosetting resin A1, 12 g of thermosetting resin A2, and 38 g of hardener B1 were added to this dispersion and stirred. After confirming that the hardening agent B1 is dissolved, 0.8 g of the hardening accelerator C1 is added, and the mixture is further stirred for 1 hour to obtain a mixed liquid. This mixed liquid was filtered with a nylon #200 mesh (opening 75 μm), and the filtrate was collected to prepare a varnish-like epoxy resin composition. Using a coater, this varnish-like epoxy resin composition was coated on a film-like support in the same manner as in Example 1 to produce a sealing film (film-like epoxy resin composition) with a film thickness of 100 μm .

(Comparative Example 1) 　　 96 g of organic solvent E1 was added to a 10 L polyethylene container. After adding 328 g of the inorganic filler D1 to the aforementioned container, a stirring blade was used to disperse the inorganic filler D1 to obtain a dispersion liquid. 144 g of thermosetting resin A1, 36 g of thermosetting resin A2, and 114 g of hardener B1 were added to this dispersion and stirred. After confirming the dissolution of the hardening agent B1, 2.3 g of the hardening accelerator C1 was added, and the mixture was further stirred for 1 hour to obtain a mixed solution. This mixed liquid was filtered with a nylon #200 mesh (opening 75 μm), and the filtrate was collected to prepare a varnish-like epoxy resin composition. Using a coater, this varnish-like epoxy resin composition was coated on a film-like support in the same manner as in Example 1 to produce a sealing film (film-like epoxy resin composition) with a film thickness of 100 μm .

(Comparative Example 2) 　　 4629 g of organic solvent E1 was added to a 10 L polyethylene container. After adding 6622 g of the inorganic filler D3 to the aforementioned container, a stirring blade was used to disperse the inorganic filler D3 to obtain a dispersion. To this dispersion, 680 g of thermosetting resin A1, 240 g of thermosetting resin A2, 202 g of thermosetting resin A3, 78 g of thermosetting resin A4, and 711 g of hardener B1 were added and stirred. After confirming that the hardening agent B1 is dissolved, 15 g of hardening accelerator C1 is added, and the mixture is further stirred for 1 hour to obtain a mixed solution. This mixed liquid was filtered with a nylon #200 mesh (opening 75 μm), and the filtrate was collected to prepare a varnish-like epoxy resin composition. Using a coater, this varnish-like epoxy resin composition was coated on a film-like support in the same manner as in Example 1 to produce a sealing film (film-like epoxy resin composition) with a film thickness of 100 μm .

(Comparative Example 3) 　　 Except that the coating and drying speed of Comparative Example 1 was changed from 1 m/min to 0.5 m/min, the rest was carried out in the same manner as Comparative Example 1 to produce a sealing film with a film thickness of 100 μm ( Film-like epoxy resin composition).

(Example 5) "In a 10 L polyethylene container, 83 g of organic solvent E1 was added. After adding 151 g of the inorganic filler D5 to the aforementioned container, and adding 660 g of the inorganic filler D2 and 53 g of the inorganic filler D4, a stirring blade was used to disperse the inorganic filler D2, D4, and D5 to obtain a dispersion. The average particle size of the inorganic fillers D2, D4, and D5 is 16 μm. 34 g of thermosetting resin A5, 11 g of thermosetting resin A6, and 28 g of hardener B2 were added to this dispersion and stirred. After confirming the dissolution of the hardener B2, 7 g of the elastomer F1 and 0.5 g of the hardening accelerator C2 were added, and the mixture was further stirred for 1 hour to obtain a mixed solution. This mixed liquid was filtered with a nylon #150 mesh (opening 106 μm), and the filtrate was collected to prepare a varnish-like epoxy resin composition. Using a coater, this varnish-like epoxy resin composition was applied to a film-like support in the same manner as in Example 1 to produce a sealing film (film-like epoxy resin composition) with a film thickness of 125 μm .

(Example 6) "In a 10 L polyethylene container, 83 g of organic solvent E1 was added. After adding 98 g of the inorganic filler D5 to the aforementioned container, 430 g of the inorganic filler D2 and 34 g of the inorganic filler D4 were added, and a stirring blade was used to disperse the inorganic filler D2, D4, and D5 to obtain a dispersion. The average particle size of the inorganic fillers D2, D4, and D5 is 18 μm. 21 g of thermosetting resin A5, 7 g of thermosetting resin A6, and 17 g of hardener B2 were added to this dispersion and stirred. After confirming the dissolution of the hardener B2, 8 g of the elastomer F1 and 0.14 g of the hardening accelerator C1 were added, and the mixture was further stirred for 1 hour to obtain a mixed solution. This mixed liquid was filtered with a nylon #150 mesh (opening 106 μm), and the filtrate was collected to prepare a varnish-like epoxy resin composition. Using a coater, this varnish-like epoxy resin composition was applied to a film-like support in the same manner as in Example 1 to produce a sealing film (film-like epoxy resin composition) with a film thickness of 125 μm .

(Example 7) "In a 10 L polyethylene container, 83 g of organic solvent E1 was added. After adding 68.6 g of the inorganic filler D3 to the aforementioned container, 463 g of the inorganic filler D2 and 34.3 g of the inorganic filler D4 were added, and a stirring blade was used to disperse the inorganic filler D2, D3, and D4 to obtain a dispersion. The average particle size of the inorganic fillers D2, D3, and D4 is 18 μm. In this dispersion, 18.3 g of thermosetting resin A5, 4.6 g of thermosetting resin A6, and 14.4 g of hardener B2 were added and stirred. After confirming that the hardener B2 was dissolved, 5.6 g of the elastomer F1 and 0.11 g of the hardening accelerator C1 were added, and the mixture was further stirred for 1 hour to obtain a mixed solution. This mixed liquid was filtered with a nylon #150 mesh (opening 106 μm), and the filtrate was collected to prepare a varnish-like epoxy resin composition. Using a coater, this varnish-like epoxy resin composition was applied to a film-like support in the same manner as in Example 1 to produce a sealing film (film-like epoxy resin composition) with a film thickness of 125 μm .

(Example 8) "In a 10 L polyethylene container, 83 g of organic solvent E1 was added. After adding 68.6 g of the inorganic filler D3 to the aforementioned container, 463 g of the inorganic filler D2 and 34.3 g of the inorganic filler D4 were added, and a stirring blade was used to disperse the inorganic filler D2, D3, and D4 to obtain a dispersion. The average particle size of the inorganic fillers D2, D3, and D4 is 18 μm. To this dispersion, 17.9 g of thermosetting resin A5, 4.5 g of thermosetting resin A6, and 14 g of hardener B2 were added and stirred. After confirming that the hardener B2 was dissolved, 6.4 g of the elastomer F1 and 0.11 g of the hardening accelerator C1 were added, and the mixture was further stirred for 1 hour to obtain a mixed solution. This mixed liquid was filtered with a nylon #150 mesh (opening 106 μm), and the filtrate was collected to prepare a varnish-like epoxy resin composition. Using a coater, this varnish-like epoxy resin composition was applied to a film-like support in the same manner as in Example 1 to produce a sealing film (film-like epoxy resin composition) with a film thickness of 125 μm .

<Evaluation> (1) Thermal conductivity A of the cured product of the sealing film 　　 Under the following conditions, the sealing film (thickness 100 μm or 125 μm) of Examples 1 to 8 and Comparative Examples 1 to 3 was compared with copper foil. Laminate on both sides to obtain a sealing film with copper foil on both sides. •Laminating device: Vacuum pressurized laminator manufactured by Mingji Mfg. Co., Ltd., trade name "MVLP-500" •Laminating temperature: 90℃ •Laminating pressure: 0.5 MPa •Vacuum suction time: 30 seconds •Laminating time: 40 second

Under the following conditions, the obtained double-sided copper foil-attached sealing film was cured to produce a copper foil-attached epoxy resin cured product. • Oven: manufactured by ESPEC Co., Ltd., trade name "SAFETY OVEN SPH-201" • Oven temperature: 140°C • Heating time: 120 minutes

The produced copper foil with a cured epoxy resin of copper foil is removed by etching to obtain a cured epoxy resin (cured product of the sealing film). The obtained cured epoxy resin was cut into 1 cm square, and the thermal diffusivity was measured using the following device. • Thermal diffusivity measuring device: "LFA447" (Xenon Flash Analyzer) manufactured by NETZSCH

In addition, the specific gravity of the obtained cured epoxy resin was measured using the following hydrometer. • Hydrometer: "SD200L" product name manufactured by ALFA MIRAGE

In addition, the specific heat of the cured epoxy resin obtained was determined by differential scanning calorimetry under the following conditions. •Differential scanning calorimetry device: trade name "Q-200" manufactured by TA Instruments Japan •Test conditions: 25°C, 10 minutes (constant) → 25～60°C (10°C/min) → 60°C, 10 minutes ( for sure)

Using the obtained thermal diffusivity, specific gravity, and specific heat, the thermal conductivity is determined by the following formula (1).　 Thermal conductivity = thermal diffusivity × specific gravity × specific heat•••(1)

Then, the thermal conductivity is evaluated based on the following evaluation criteria. The results of Examples 1 to 4 are shown in Table 1. In addition, the thermal conductivity of Examples 5 to 8 is equivalent to that of Examples 1 to 4 (evaluation: A). For example, the thermal conductivity of Example 5 is 2.73 W/m·K.　"A": Thermal conductivity＞2.5 W/m•K 　「B": Thermal conductivity≦2.5 W/m•K

(2) Thermal conductivity B of the cured product of the sealing film 　　 The sealing films (thickness 125 μm) of Examples 5 to 8 were superimposed on 4 sheets, and a hand-pressing device was used to produce a laminated film with a thickness of 500 μm under the following conditions . •Hand pressure device: "BIG HEART" manufactured by Imoto Seisakusho Co., Ltd. •Hand pressure molding temperature: 140℃ •Hand pressure molding time: 30 minutes •Forming load: 20 kN

The obtained laminated film with a thickness of 500 μm was cured under the following conditions to produce an epoxy resin cured product (cured product of the sealing film). • Oven temperature: 140℃ • Heating time: 90 minutes

The obtained cured epoxy resin was cut into 1 cm square, and the thermal conductivity of the cured epoxy resin was measured by the temperature gradient method using a thermal resistivity measuring device. Then, the thermal conductivity is evaluated based on the following evaluation criteria. The results are shown in Table 2.　"A": Thermal conductivity＞2.5 W/m•K 　「B": Thermal conductivity≦2.5 W/m•K

(3) Solvent content of the sealing film 　　 The obtained sealing film is cut into a 5 cm square sample, and the sample is added to an aluminum cup whose mass has been measured in advance, and then the mass of the aluminum cup containing the sample is measured. Then, directly use the oven at 180°C to heat the sample for 10 minutes while it is placed in an aluminum cup, and then place it at room temperature (25°C) for 10 minutes. Then, the mass of the aluminum cup containing the sample was measured again. Then, subtract the separately measured mass of the aluminum cup from the measured value of the mass of the aluminum cup containing the sample (before heating and after heating) to obtain the mass of the sealing film before and after heating, respectively. Then, the value obtained by subtracting the mass of the sealing film after heating from the mass of the sealing film before heating is divided by the mass of the sealing film before heating to obtain the ratio as the solvent content. The results are shown in Tables 1 and 2.

(4) Landfillability 　　 4 sheets of sealing film with a thickness of 100 μm or 125 μm are respectively stacked to obtain a laminated film with a thickness of 400 μm or 500 μm. In the following procedure, an 8-inch-size eWLB package was produced using the laminated film. Figure 2 is a diagram showing the layout of the silicon wafer in this measurement. First, as shown in FIG. 2, a 350 μm-thick silicon wafer (a 7.3 mm square silicon wafer 60 and a 3 mm square silicon wafer 70) is placed on the stainless steel plate 50. Then, the laminated film was cut into a circle with a diameter of 20 cm and placed on the aforementioned silicon wafer. Then, a compression molding apparatus (manufactured by APIC YAMADA Co., Ltd., trade name: WCM-300) was used to obtain a sealed body (sealed structure) under the following conditions. • Compression molding temperature: 140℃ • Compression molding pressure: 25 MPa • Compression molding time: 10 minutes

Then, the produced sealing body was heated and hardened under the following conditions to produce a hardened product. In this way, an eWLB package is obtained. • Oven: manufactured by ESPEC Co., Ltd., trade name "SAFETY OVEN SPH-201" • Oven temperature: 140°C • Heating time: 120 minutes

The landfillability of the hardened material produced is evaluated based on the following evaluation criteria. The results are shown in Table 1 and Table 2.　「A」: It can be filled without holes, and the surface is smooth.　「B」: Some holes can be observed, and the surface is smooth.　「C」: Holes can be observed, but the surface is not smooth.

[Table 1]

[Table 2]

<Evaluation result> 　　As shown in Table 1 and Table 2, a resin composition containing a thermosetting component and an inorganic filler, wherein the inorganic filler contains alumina and the resin composition is based on a mass that excludes the solvent As a reference, the content of the inorganic filler is 72% by mass or more. At this time, the thermal conductivity of the cured product can achieve excellent effects. It can be seen from Example 4 shown in Table 1 that even if the inorganic filler contains silicon oxide, the thermal conductivity of the cured product can still achieve excellent effects.

From the above results, it can be seen that a resin composition contains a thermosetting component and an inorganic filler, wherein the inorganic filler contains alumina, and the total mass of the resin composition after excluding the solvent is used as a reference. The inorganic filler The content of the material is 72% by mass or more. In this case, the thermal conductivity of the cured product can achieve excellent effects, and the filling property is excellent.

1‧‧‧Support 2‧‧‧Film for sealing 2a‧‧‧Hardened object 10‧‧‧Film for sealing with support 20‧‧‧Semiconductor element 30‧‧‧Substrate 40‧‧‧Temporary fixing material 50 ‧‧‧Stainless steel plate 60‧‧‧7.3 mm square silicon wafer 70‧‧‧3 mm square silicon wafer

Fig. 1 is a schematic cross-sectional view for explaining one embodiment of a method of manufacturing a sealing structure.　　 Fig. 2 is a diagram showing an example of the arrangement of silicon wafers used in the evaluation of the buried properties in the embodiment.

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1‧‧‧Support

2‧‧‧Film for sealing

2a‧‧‧hardened object

10‧‧‧Film for sealing with support

20‧‧‧Semiconductor components

30‧‧‧Substrate

40‧‧‧Temporary fixing materials

Claims (15)

A resin composition containing a thermosetting component and an inorganic filler, and the thermosetting component further includes: epoxy resin, hardener, and 2-phenyl-4-methylimidazole and/or 1-benzene Methyl-2-methylimidazole, the aforementioned inorganic filler contains alumina and further contains silica, and the content of the aforementioned inorganic filler is 72 based on the total mass of the aforementioned resin composition excluding the mass of the solvent % By mass or more, and the content of alumina in the inorganic filler is 70% by mass or more. The resin composition according to claim 1, wherein the curing agent contains a phenol resin. The resin composition according to claim 1 or 2, wherein the epoxy resin includes an epoxy resin that is liquid at 25°C, and the total mass of the resin composition after excluding the solvent is calculated as a reference The content of the epoxy resin that is liquid at 25°C is 5 mass% or more. The resin composition according to claim 1 or 2, wherein the epoxy resin includes an epoxy resin that is liquid at 25° C. The total mass of the aforementioned resin composition after removing the mass of the solvent is used as a reference, and the content of the epoxy resin that is liquid at 25° C. is 7 mass% or more. The resin composition according to claim 1, wherein the content of the inorganic filler is 93% by mass or less based on the total mass of the resin composition excluding the mass of the solvent. The resin composition according to claim 1, wherein the content of the inorganic filler is 85% by mass or less based on the total mass of the resin composition excluding the mass of the solvent. The resin composition according to claim 1, wherein the average particle size of the inorganic filler is 0.01 to 25 μm. The resin composition according to claim 1, wherein the average particle diameter of the inorganic filler is 0.01 to 10 μm. The resin composition according to claim 1, which further contains a solvent. A cured product which is a cured product of the resin composition according to any one of claims 1 to 9. A film for sealing comprising the resin composition according to any one of claims 1 to 9. The sealing film according to claim 11, wherein the content of the solvent is 0.2 to 1.5% by mass. The sealing film as described in claim 11 or 12, Its thickness is 20~250μm. A sealing structure comprising a body to be sealed and a sealing part that seals the body to be sealed, and the sealing part includes a cured product of the resin composition according to any one of claims 1 to 9. The sealed structure according to claim 14, wherein the sealed body is an electronic component.

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