TW202126719A - Resin composition, cured product, sealing film, and sealing structure - Google Patents

Abstract

Provided is a resin composition containing a thermosetting component and an inorganic filler, wherein the inorganic filler includes aluminum oxide, and the content of the inorganic filler is at least 72 mass%, the total mass of the resin composition (excluding the mass of a solvent) serving as a reference.

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, the miniaturization and thinning of electronic parts and devices (semiconductor devices, etc.) is progressing. 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 the semiconductor device (package on package (PoP)) is popular, and electronics are expected in the future. 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 achieve 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 with 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 manufactured using this assembly method (for example, refer to Patent Document 1 below) ~3).

[Prior Technical Literature]

(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 performance will be poor. Therefore, low thermal conductivity may cause deterioration of the device and fire of the device. In this case, 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 increases, so it is easy to suspect that the heat dissipation will be reduced consider. 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 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 1.2W/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 Above mass%.

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 2.5W/m‧K (preferably 2.7W/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 degradation and device performance can be suppressed. For example, the electronic component device is provided with a sealing part containing a cured product of the resin 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. According to 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 hardening 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. Preferably it is 5 mass% or more, and more preferably it is 7 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, 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 parts such as semiconductor elements (the sealing step in the packaging method) is often performed at the end of the process of manufacturing electronic parts such as semiconductor devices. At this time, the assembling method is to implement a step of forming a circuit and an external connection terminal on a sealed structure (sealed molded article) made by sealing the electronic component, and the circuit is used to arrange the external connection terminal.

In the conventional assembly method, a plurality of electronic components (semiconductor elements, etc.) are sometimes sealed to obtain a sealed structure, and then the sealed structure is cut 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 underway to make the sealing structure larger. At present, there is a tendency that, for example, in order to use a semiconductor manufacturing device for wiring formation, a 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. For example, transfer molding is sometimes used, which melts a pellet-shaped resin sealing material and causes the resin to flow into a mold for sealing. However, in transfer molding, molten resin is poured into the molding process. Therefore, it is necessary to When sealing a large area, there is a possibility of unfilled parts. 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, an unfilled part is not easily generated.

Compression molding and transfer molding use solid or liquid resin sealing materials. However, when the body to be sealed increases in size, the liquid resin sealing material may cause liquid flow or the like, and it may be difficult to uniformly supply the body to be sealed. 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 may be used. However, particle or powder resin sealing material is difficult to uniformly supply the resin sealing material to the mold or the to-be-sealed body, 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, it is necessary to increase the size of the mold when increasing the size of the sealing structure. 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.

On the other hand, the resin composition of the present invention can be made into a film for sealing for sealing a body to be sealed, and is in the form of a film. The sealing film of the present invention contains the resin composition of the present invention. In this case, the resin can be uniformly supplied to the sealed body and dust generation can be reduced. In addition, a landfill capability can be obtained, 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 body to be sealed 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. In addition, according to the present invention, it is possible to provide a sealing film and a sealing structure obtained by using the aforementioned resin composition.

1: Support

2: Film for sealing

2a: Hardened object

10: Sealing film with supporting body

20: Semiconductor components

30: substrate

40: Temporarily fix the material

50: stainless steel plate

60: 7.3mm square silicon wafer

70: 3mm square silicon chip

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.

In this manual, the numerical range represented by "~" means the range that includes the numerical values 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 lower limit of the numerical range may be replaced with the value disclosed in the examples. The so-called "A or B", as long as it includes any one of A and B, and may include both A and B. The materials exemplified in this specification may be used alone, or two or more of them may be used in combination, unless otherwise specified. In this 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.

Hereinafter, an embodiment of the present invention will be described.

<Resin composition and hardened material>

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, (C) curing accelerators, and the like. 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 (D) the 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]

Examples of thermosetting resins include epoxy resins, phenoxy resins, cyanate ester resins, thermosetting polyimides, melamine resins, urea resins, unsaturated polyesters, alkyd resins, and polyurethanes. Wait. From the standpoint of easily obtaining a cured product with 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 ring Oxygen resin, bisphenol AF type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol 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, phenol novolak type epoxy resin (o-cresol novolak type epoxy resin, etc.), biphenyl type epoxy resin, naphthalene Type epoxy resin, dicyclopentadiene type epoxy resin, dixylenol type epoxy resin (dixylenol diglycidyl ether, etc.), hydrogenated bisphenol A type epoxy resin (hydrogenated bisphenol A glycidyl Diglycidyl ether type epoxy resin, aliphatic epoxy resin, etc. The 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 ether Base ether, trifunctional or tetrafunctional glycidylamine, etc.

Examples of commercially available epoxy resins include "EXA-4700 (trade name, the same hereinafter)" (tetrafunctional naphthalene type epoxy resin) manufactured by DIC Co., Ltd., "EPICLON HP-4032" and "EXA- 4750'' (multifunctional solid epoxy resin containing naphthalene skeleton), Japan Naphthalene type epoxy resins such as "NC-7000" (multifunctional solid epoxy resin containing naphthalene skeleton) manufactured by Kayaku Pharmaceutical Co., Ltd.; "EPPN-502H" (ginsengphenol epoxy resin) manufactured by Nippon Kayaku Co., Ltd. The epoxide of the condensate of other phenols and aromatic aldehydes with phenolic hydroxyl groups (phenol epoxy resin); "EPICLON HP-7200H" manufactured by DIC Co., Ltd. (containing dicyclopentadiene skeleton multifunctional Solid epoxy resin) and other dicyclopentadiene aralkyl type epoxy resin; Nippon Kayaku Co., Ltd. "NC-3000H" (multifunctional solid epoxy resin containing biphenyl skeleton) and other biphenyl aralkyl type epoxy resin Epoxy resin; "EPICLON N-660", "EPICLON N-690", "EPICLON N-740" (phenol novolak type epoxy resin) and "N500P-1" (ortho-cresol phenolic resin) manufactured by DIC Co., Ltd. Varnish-type epoxy resin), novolac-type epoxy resin such as "EOCN-104S" manufactured by Nippon Kayaku Co., Ltd.; "TEPIC" and other ginseng (2,3-epoxypropane Base) isocyanurate; "EPICLON 860", "EPICLON 900-IM", "EPICLON EXA-4816" and "EPICLON EXA-4822" manufactured by DIC Co., Ltd., "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.), manufactured by Japan Epoxy Resins Co., Ltd. (Mitsubishi Chemical Co., Ltd.) "JER834", "jER872", "jER807", "jER815", "jER825", "jER827", "JER828", "jER1001", "jER1004", "jER1007" and "jER1009", "ELA-134" manufactured by Sumitomo Chemical Co., Ltd., "DER-330", "DER-301" manufactured by DOW Chemical, and Bisphenol A type epoxy resin such as "DER-361"; Bisphenol F type epoxy resin such as "jER806" manufactured by Japan Epoxy Resins Co., Ltd. (Mitsubishi Chemical Co., Ltd.); "Denacol" manufactured by Nagase ChemteX Co., Ltd. Aliphatic epoxy resins such as DLC301". 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 , Further 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 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 One step is 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, and still more preferably 13% by mass or less.

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

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) Total quality of ingredients 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, particularly preferably 5% by mass or more, and extremely preferably 7 Mass% or more, 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 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.

[(B) Ingredient: Hardener]

The curing agent is not particularly limited, and examples thereof 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 singly, or two or more of them may be used in combination.

The phenol resin is not particularly limited as long as it has two or more phenolic hydroxyl groups in one molecule, and conventional phenol resins can be used. Examples of phenol resins include: resins obtained by condensation or co-condensation of phenols and/or naphthols and aldehydes using acidic catalysts, biphenyl skeleton type phenol resins, p-xylene modified phenol resins, and m-benzene Dimethyl-p-xylylene modified phenol resin, melamine modified phenol resin, terpene modified phenol resin, dicyclopentadiene modified phenol resin, cyclopentadiene modified phenol resin, polycyclic aromatic Cyclo-modified 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, dihydroxynaphthalene, and the like. 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 Industry Co., Ltd., Qunrong Chemical Industry Co., Ltd. "ELP40" and so on.

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 glycidyl group (epoxy equivalent) of epoxy resin and the functional group (phenolic hydroxyl group, etc.) that can react with glycidyl group in the hardener )of The ratio of equivalent (phenolic hydroxyl equivalent, etc.) (equivalent of glycidyl group of epoxy resin/functional group that can react with glycidyl group in hardener), preferably 0.7~2.0, more preferably 0.8~1.8 , Further 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 desired properties of the cured product are easily obtained.

[Component (C): Hardening accelerator]

As the hardening accelerator, it can be used without particular limitation, and it is preferably at least one selected from the group consisting of an amine-based hardening accelerator and a phosphorus-based hardening accelerator. In particular, from the standpoint of easily obtaining a cured product with excellent thermal conductivity, the standpoint of abundant derivatives, and the standpoint 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 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 accelerating 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 in It is not easy to harden during the steps (such as coating and drying) of 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. From the viewpoint of promoting hardening The content of the agent 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 material, 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, aluminum nitride, and the like. Examples of the inorganic filler containing silicon oxide include amorphous silicon oxide, crystalline silicon oxide, fused silica, spherical silicon oxide, and the like. 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 because of the relatively small thermal expansion rate. As a constituent material other than alumina, silicon oxide is preferred. Examples of commercially available inorganic fillers containing silicon oxide include "SC2500-SXJ", "SC5500-SXE" and "SC2050-KC" manufactured by Admatechs Co., Ltd. Constituent materials other than alumina may be used singly, or two or more of them may be used in combination.

The inorganic filler material can undergo surface modification. The method of surface modification is not particularly limited. From the viewpoints of simple 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 the 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, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, and methyltriphenoxy. Silane, Ethyl Trimethoxy Silane, n-Propyl Trimethoxy Silane, Diisopropyl Dimethoxy Silane, Isobutyl Trimethoxy Silane, Diisobutyl Dimethoxy Silane, Isobutyl Triethyl Oxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, cyclohexylmethyldimethoxysilane, n-octyltriethoxysilane, n-dodecylmethoxysilane, 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 triacetoxysilane, vinyl trimethoxysilane, vinyl triethoxy Silane, vinyl triisopropoxy silane, allyl trimethoxy silane, diallyl dimethyl silane, 3-methacryloxy propyl trimethoxy silane, 3-methacryloxy silane Propylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, N-(1, 3-Dimethylbutyryl)-3-amine Propyl propyl triethoxy silane, amino silane (phenyl amino silane, etc.), etc. The silane coupling agent may be used singly, or two or more of them may be used in combination.

From the viewpoint of easily inhibiting aggregation of the inorganic filler and easily dispersing the inorganic filler, the average particle diameter 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. Preferably, it is 0.5 μm or more. From the viewpoint of easily suppressing the deposition of the inorganic filler in the varnish and easily producing a homogeneous sealing film, the average particle size of the inorganic filler is preferably 25 μm or less, more preferably 10 μm or less, and still more preferably 5 μm or less. 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 extremely preferably 0.5 to 5 μm. The average particle size of the inorganic filler can 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 size is preferably 15-25 μm. Preferably, it is used in combination: an inorganic filler with an average particle size of 15-25 μm, an inorganic filler with an average particle size of 0.5-2.5 μm, and an inorganic filler with an average particle size 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 combined inorganic The average particle diameter of the filler 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 used 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 mass% or more, more preferably 73 mass% or more. From the viewpoint that it is easy to suppress the cracking of the sealing film during the drying step when the sealing film is made, and the viewpoint that the melt viscosity of the sealing film increases and the fluidity is reduced, and the sealed body (electronic parts, etc.) is easily sealed. 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% by mass, more preferably 72 to 90% by mass, and still more preferably It is 72 to 85% by mass, particularly preferably 72 to 84.5% by mass, extremely preferably 72.5 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 landfill properties, 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) 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 sealing films are 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, and 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 ingredients)

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.

<Film for sealing>

The sealing film 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 the film is composed of the resin composition of the present embodiment. The sealing film of this 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, still more preferably 50 μm or more, and particularly preferably Above 100μm. From the viewpoint of easily obtaining a certain degree of 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 having a thickness of more than 250 μm.

Relative to the total mass of the sealing film after excluding the solvent, 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 The amount is preferably within the following range. From the viewpoint of further improving the thermal conductivity and easily suppressing the increase in 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 Above mass%. 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 object to be sealed (electronic parts, etc.) easily, it is preferably 93% by mass or less, more preferably 90% by mass or less, and furthermore 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 ~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 extremely preferably 0.7 to 1% by mass.

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

First, the 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 that 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 the varnish prepared in the above manner is applied to a support (a 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; Acetyl cellulose film; tetrafluoroethylene film, etc. Examples of metal foils 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, the inconvenience of bending of the support due to the weight of the varnish, and the like. 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 disadvantage of preventing the solvent in the varnish from drying.

A protective layer can be arranged on the sealing film formed on the support 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; Cellulose film; tetrafluoroethylene film, etc. As metal foil, copper foil, aluminum foil, etc. can be illustrated, for example.

The sealing film prepared in the above manner can obtain a cured product of the sealing film by the following steps, and thereby manufacture a sealing structure (for example, an electronic component device such as a semiconductor device): Landfill target) Step toward the state of the sealing film; heat the sealing film to melt and apply pressure to fill the sealed body Step; and, the step of thermally hardening the sealing film with landfill capability by heating.

<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 (in the sealing film of this embodiment) Cured products of the contained resin composition, etc.). 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 the present 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 part 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 and arranging a plurality of semiconductor elements 20 as sealed objects (to be filled) on a substrate 30 having a temporary fixing material 40 (Figure 1(a)) ; Make the sealing film with support body 10 (with The support 1 and the sealing film 2 provided on the support 1 are opposed to the semiconductor element 20, and then the sealing film 2 is pressed (laminated) on the semiconductor element 20 under heating, thereby embedding the semiconductor element 20 The step to the sealing film 2 (Fig. 1(b)); and the step of curing the sealing film 2 in which the semiconductor element 20 is embedded to obtain a cured product 2a (Fig. 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 components such as semiconductor elements) to be filled. The pressure during stacking, 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 can 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 sealing film The hardening 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 hardening time (heating time) is not particularly limited, and it can 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 hardening 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 can be appropriately modified within the scope not departing from the gist of the present invention.

[Example]

Examples are listed below to more specifically illustrate the present invention, 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 type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name jER806, epoxy equivalent 160g/eq, epoxy resin showing liquid state at 25°C)

A2: Multifunctional solid epoxy resin containing naphthalene skeleton (manufactured by DIC Co., Ltd., trade name EXA-4700, epoxy equivalent 182g/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, and the content of elastomer particles is 25% by mass , Epoxy equivalent 226g/eq, the average particle size of the elastomer particles is 0.1μm, and contains the epoxy resin component that shows liquid at 25°C)

A4: Epoxy resin containing silicone elastomer particles (a mixture of bisphenol F type liquid epoxy resin and bisphenol A type liquid epoxy resin, manufactured by Kaneka Co., Ltd., trade name MX-965, liquid ring The content of the oxygen resin is 75% by mass, and the content of the elastomer particles is 25% by mass, including the epoxy resin that is liquid at 25°C)

A5: o-cresol novolac epoxy resin (manufactured by DIC Co., Ltd., trade name N500P-1, epoxy equivalent of 201 g/eq, epoxy resin that does not show liquid at 25°C)

A6: Bisphenol A epoxy resin containing a flexible skeleton (manufactured by DIC Co., Ltd., trade name EPICLON EXA-4816, epoxy equivalent 403g/eq, liquid epoxy resin at 25°C)

(B)Component: Hardener (phenol resin)

B1: Phenolic novolac resin (manufactured by Asahi Organic Materials Co., Ltd., trade name PAPS-PN2, phenolic hydroxyl equivalent 104g/eq, phenol resin that does not show liquid at 25°C)

B2: Alkylphenol novolac resin (manufactured by Qunrong Chemical Industry Co., Ltd., trade name ELP40, phenolic hydroxyl equivalent 140g/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 (manufactured by Shikoku 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 1.5μm)

D2: Alumina particles (manufactured by Denka Co., Ltd., trade name DAW20, average particle size 20μm)

D3: Silica particles (manufactured by Admatechs Co., Ltd., trade name SC2500-SXJ, aniline silane treatment, average particle size 0.5μm)

D4: Silicon oxide particles (manufactured by Admatechs Co., Ltd., trade name SC5500-SXE, aniline silane treatment, average particle size 1.6μm)

D5: Silica slurry (manufactured by Admatechs Co., Ltd., trade name SC2050-KC, treated with silicone oligomer, average particle size 0.5μm, diluted with methyl isobutyl ketone solvent (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 sealing film>

(Example 1)

Add 172g of organic solvent E1 into a 10L polyethylene container. 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. To this dispersion, 48 g of thermosetting resin A1, 12 g of thermosetting resin A2, and 38 g of curing agent B1 were added and stirred. After confirming that the curing agent B1 was dissolved, 0.8 g of the curing 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. Use a coater to coat this varnish-like epoxy resin composition on the following film-like support under the following conditions, and produce a sealing film (film-like epoxy resin) with a film thickness of 100 μm on the support. Composition).

‧Coating head style: missing angle wheel coater

‧Coating and drying speed: 1m/min

‧Drying conditions (temperature/furnace length): 110℃/3.3m, 130℃/3.3m, 140℃/3.3m

‧Film-like support: Polyethylene terephthalate film after 38μm

The surface of the sealing film is protected by arranging a protective layer (12μm thick polyethylene terephthalate film) 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)

Put 141g of organic solvent E1 into a 10L 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 liquid. 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 that the curing agent B1 was dissolved, 1.4 g of the curing accelerator C1 was added, and the mixture was 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 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 100 μm.

(Example 3)

Put 114g of organic solvent E1 into a 10L polyethylene container. 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 liquid. To this dispersion, 48 g of thermosetting resin A1, 12 g of thermosetting resin A2, and 38 g of curing agent B1 were added and stirred. After confirming that the curing agent B1 was dissolved, 0.8 g of the curing 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 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 100 μm.

(Example 4)

Add 149g of organic solvent E1 into a 10L 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. To this dispersion, 48 g of thermosetting resin A1, 12 g of thermosetting resin A2, and 38 g of curing agent B1 were added and stirred. After confirming that the curing agent B1 was dissolved, 0.8 g of the curing 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 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 100 μm.

(Comparative example 1)

Add 96 g of organic solvent E1 into a 10L 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. To this dispersion, 144 g of thermosetting resin A1, 36 g of thermosetting resin A2, and 114 g of hardener B1 were added and stirred. After confirming that the hardening agent B1 was dissolved, 2.3 g of the hardening accelerator C1 was added, and the mixture was 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 set this varnish-like epoxy resin in the same manner as in Example 1. The finished product was coated on a film-shaped support to produce a sealing film (film-shaped epoxy resin composition) with a film thickness of 100 μm.

(Comparative example 2)

Add 4629g of organic solvent E1 into a 10L 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 liquid. 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 curing agent B1 is dissolved, 15 g of the curing 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 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 100 μm.

(Comparative example 3)

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

(Example 5)

Put 83 g of organic solvent E1 in a 10L polyethylene container. Put 151g of inorganic filler D5 into the aforementioned container, and add 660g of inorganic filler D2 and 53g of inorganic filler D4, then use stirring The wings disperse the inorganic fillers D2, D4, and D5 to obtain a dispersion liquid. The average particle size of the inorganic fillers D2, D4, and D5 is 16 μm. To this dispersion, 34 g of thermosetting resin A5, 11 g of thermosetting resin A6, and 28 g of hardener B2 were added 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 #150 mesh (opening 106 μm) made by nylon, 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) having a film thickness of 125 μm.

(Example 6)

Put 83 g of organic solvent E1 in a 10L polyethylene container. 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 that the curing agent B2 was dissolved, 8 g of the elastomer F1 and 0.14 g of the curing accelerator C1 were added, and the mixture was further stirred for 1 hour to obtain a mixed solution. This mixed liquid was filtered with #150 mesh (opening 106 μm) made by nylon, 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. Then, a sealing film (film-like epoxy resin composition) having a film thickness of 125 μm was produced.

(Example 7)

Put 83 g of organic solvent E1 in a 10L polyethylene container. 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 the inorganic filler D2, D3, and D4 were dispersed using a stirring blade to obtain a dispersion liquid. The average particle size of the inorganic fillers D2, D3, and D4 is 18 μm. To 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 curing agent B2 was dissolved, 5.6 g of the elastomer F1 and 0.11 g of the curing accelerator C1 were added, and the mixture was further stirred for 1 hour to obtain a mixed solution. This mixed liquid was filtered with #150 mesh (opening 106 μm) made by nylon, 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) having a film thickness of 125 μm.

(Example 8)

Put 83 g of organic solvent E1 in a 10L polyethylene container. 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 the inorganic filler D2, D3, and D4 were dispersed using a stirring blade to obtain a dispersion liquid. The average particle size of the inorganic fillers D2, D3, and D4 is 18 μm. Add 17.9g of thermosetting resin A5, 4.5 to this dispersion g thermosetting resin A6, 14 g hardener B2 and stirring. After confirming that the curing agent B2 was dissolved, 6.4 g of the elastomer F1 and 0.11 g of the curing accelerator C1 were added, and the mixture was further stirred for 1 hour to obtain a mixed solution. This mixed liquid was filtered with #150 mesh (opening 106 μm) made by nylon, 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) having a film thickness of 125 μm.

<evaluation>

(1) Thermal conductivity A of the cured product of the sealing film

Under the following conditions, the two sides of the sealing films (thickness 100 μm or 125 μm) of Examples 1 to 8 and Comparative Examples 1 to 3 were laminated with copper foil to obtain a sealing film with copper foil on both sides.

‧Laminator: Vacuum pressurized laminator manufactured by Meiki Mfg. Co., Ltd., trade name "MVLP-500"

‧Laminating temperature: 90℃

‧Building pressure: 0.5MPa

‧Vacuum suction time: 30 seconds

‧Layer time: 40 seconds

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℃

‧Heating time: 120 minutes

The produced copper foil with a copper foil hardened epoxy resin is removed by etching to obtain a hardened epoxy resin (hardened film for sealing). The obtained cured epoxy resin was cut into 1 cm square, and the thermal diffusivity was measured using the following apparatus.

‧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: The product name "SD200L" 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: product 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 (constant)

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. Furthermore, the thermal conductivity of Examples 5 to 8 is the same as 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>2.5W/m‧K

"B": Thermal conductivity≦2.5W/m‧K

(2) Thermal conductivity B of the cured product of the sealing film

The sealing films (125 μm in thickness) of Examples 5 to 8 were stacked on 4 sheets each, 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: Brand name "BIG HEART" manufactured by Imoto Manufacturing Co., Ltd.

‧Hand pressure molding temperature: 140℃

‧Hand pressure forming time: 30 minutes

‧Forming load: 20kN

The obtained laminated film having 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>2.5W/m‧K

"B": Thermal conductivity≦2.5W/m‧K

(3) Solvent content of sealing film

The obtained sealing film was cut into a sample of 5 cm square, and the sample was added to an aluminum cup whose mass was measured in advance, and then the mass of the aluminum cup containing the sample was 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) Landfill

Four sealing films each having a thickness of 100 μm or 125 μm are stacked to obtain a laminated film having 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 silicon wafer (a 7.3 mm square silicon wafer 60 and a 3 mm square silicon wafer 70) with a thickness of 350 μm is placed on the stainless steel plate 50. Then, the laminated film was cut into a circle with a diameter of 20 cm, and then 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: 25MPa

‧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℃

‧Heating time: 120 minutes

According to the following evaluation criteria, the landfillability of the hardened material produced is evaluated. 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 Results>

As shown in Table 1 and Table 2, it can be seen that a resin composition contains a thermosetting component and an inorganic filler, where the inorganic filler contains alumina, and the total mass of the resin composition after excluding the solvent is taken as By reference, the content of the inorganic filler is 72% by mass or more. In this case, the thermal conductivity of the hardened product can achieve an excellent effect. From Example 4 shown in Table 1, it can be seen 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 is based on the mass excluding the solvent. As a reference, the content of the inorganic filler 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: Sealing film with supporting body

20: Semiconductor components

30: substrate

40: Temporarily fix the material

Claims (16)

A resin composition containing a thermosetting component and an inorganic filler, and, The aforementioned thermosetting component further includes epoxy resin, hardener, and hardening accelerator, The aforementioned inorganic filler material contains alumina, and further contains silicon oxide, And based on the total mass of the resin composition after excluding the mass of the solvent, the content of the inorganic filler is 72% by mass or more, The content of alumina in the aforementioned 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, wherein the hardening accelerator is an imidazole compound. 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% by 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, 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. 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 after 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 after excluding the mass of the solvent. The resin composition according to claim 1, wherein the average particle diameter 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 10. A film for sealing comprising the resin composition according to any one of claims 1 to 10. The sealing film according to claim 12, wherein the content of the solvent is 0.2 to 1.5% by mass. The sealing film described in claim 12 or 13 has a thickness of 20 to 250 μm. A sealed structure including a body to be sealed and a sealing part, the sealing part sealing the body to be sealed, and, The aforementioned sealing portion includes a cured product of the resin composition according to any one of claims 1 to 10. The sealed structure according to claim 15, wherein the sealed body is an electronic component.

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