WO2017038941A1

WO2017038941A1 - Resin composition, cured product, sealing film, and sealing structure

Info

Publication number: WO2017038941A1
Application number: PCT/JP2016/075688
Authority: WO
Inventors: 裕介渡瀬; 藤本　大輔; 野村　豊; 弘邦荻原; 知世金子; 正也鳥羽; 鈴木　雅彦
Original assignee: 日立化成株式会社
Priority date: 2015-09-02
Filing date: 2016-09-01
Publication date: 2017-03-09
Also published as: JP6763391B2; TW201718692A; KR20180048674A; TWI825365B; TW202126719A; KR102486893B1; JP7115520B2; JP2020200478A; TWI714625B; JPWO2017038941A1; CN107924886A; JP2022136188A

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

As electronic devices become lighter, thinner and smaller, electronic component devices (semiconductor devices, etc.) are becoming smaller and thinner. A form using a semiconductor device of almost the same size as a semiconductor element (a semiconductor chip such as a silicon chip), or a mounting form (package-on-package) in which a semiconductor device is stacked on a semiconductor device has been actively performed. In the future, it is expected that electronic component devices will be further reduced in size and thickness.

As the miniaturization of semiconductor elements progresses and the number of terminals increases, it becomes difficult to provide all the external connection terminals (external connection terminals) on the semiconductor elements. For example, when the external connection terminals are forcibly provided, the pitch between the terminals is reduced and the height of the terminals is reduced, and it is difficult to ensure connection reliability after the semiconductor device is mounted. Therefore, many new mounting methods have been proposed in order to realize a reduction in size and thickness of electronic component devices.

For example, after rearranging a semiconductor element manufactured by dividing a semiconductor wafer into pieces having an appropriate interval, the semiconductor element is sealed using a solid or liquid resin (sealing resin). A mounting method in which an external connection terminal can be provided on a sealing portion for sealing a semiconductor element outside the semiconductor device and a semiconductor device manufactured using the mounting method have been proposed (for example, Patent Documents 1 to 3 below) reference).

Japanese Patent No. 3616615 JP 2001-244372 A Japanese Patent Laid-Open No. 2001-127095

However, when the thermal conductivity of the sealing part (cured product of the sealing resin) that seals the object to be sealed is low, the heat dissipation is poor. For this reason, the low thermal conductivity causes deterioration of the apparatus, ignition of the apparatus, and the like. In this case, it is conceivable to increase heat dissipation by reducing the thickness (sealing thickness) of the sealing portion on the object to be sealed. However, for example, a package form such as PoP (Package on Package) has the merit that the mounting area can be reduced by stacking the CPU and the memory that are normally mounted separately, while the thickness of the entire apparatus increases. Therefore, it is easy to worry about a decrease in heat dissipation. Therefore, there is a limit to improving heat dissipation by reducing the thickness of the sealing portion.

This invention is made | formed in view of the said subject, and it aims at providing the resin composition which can obtain the hardened | cured material which has the outstanding heat conductivity, and its hardened | cured material. Another object of the present invention is to provide a sealing film and a sealing structure using the resin composition.

The thermal conductivity of a cured product of a conventional sealing resin composition (film epoxy resin composition or the like) is about 1.2 W / m · K. On the other hand, the present inventors obtain a cured product having excellent thermal conductivity by using a resin composition containing a thermosetting component and a specific amount of an inorganic filler containing aluminum oxide. The present invention has been found to be possible.

The resin composition according to the present invention is a resin composition containing a thermosetting component and an inorganic filler, wherein the inorganic filler contains aluminum oxide, and the content of the inorganic filler is the total mass of the resin composition. 72% by mass or more based on (excluding the mass of the solvent).

According to the resin composition of the present invention, it is possible to obtain a cured product having excellent thermal conductivity, for example, thermal conductivity exceeding 2.5 W / m · K (preferably 2.7 W / A cured product having a thermal conductivity of m · K or more can be obtained. If the thermal conductivity of the cured product of the sealing resin composition can be improved, the heat dissipation of an electronic component device (semiconductor device or the like) including a sealing part containing the cured product of the resin composition is improved. It is possible to suppress the progress of deterioration and ignition of the device. In particular, according to the resin composition according to the present invention, it is possible to improve heat dissipation, which is a problem in a package form (PoP or the like) having an increased thickness. According to the resin composition of the present invention, a cured product having excellent thermal conductivity can be obtained while ensuring the embedding property of the resin composition.

The thermosetting component may contain a thermosetting resin. The thermosetting resin preferably contains an epoxy resin.

The thermosetting component may further contain a curing agent. The curing agent preferably contains a phenol resin.

The thermosetting component may further contain a curing accelerator. The curing accelerator preferably contains an imidazole compound.

The content of the epoxy resin that is liquid at 25 ° C. is preferably 5% by mass or more and more preferably 7% by mass or more based on the total mass of the resin composition (excluding the mass of the solvent).

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

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

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

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

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

By the way, normally, sealing of electronic components such as semiconductor elements (sealing process in the packaging method) is often performed at the final stage when manufacturing an electronic component device such as a semiconductor device. In the mounting method in this case, for the sealing structure (sealed molded product) produced by sealing the electronic component, there is a step of forming the wiring for arranging the external connection terminals and the external connection terminals. To be implemented.

In the conventional mounting method, a plurality of electronic component devices (semiconductor devices, etc.) may be obtained by dicing a sealing structure obtained by sealing a plurality of electronic components (semiconductor elements, etc.). In this case, the more electronic components that are rearranged, the more electronic component devices that can be manufactured in a single process. In view of this, studies have been conducted to enlarge the sealing structure. At present, for example, since a semiconductor manufacturing apparatus is used for wiring formation, the sealing structure is formed into a wafer shape, and the diameter of the wafer shape tends to increase. Furthermore, the use of a sealing structure as a panel is also being studied so that a printed wiring board manufacturing apparatus or the like that can be made larger and cheaper than a semiconductor manufacturing apparatus can be used.

For the sealing of electronic parts, there is a case where a mold molding in which a solid or liquid resin sealing material is molded with a mold may be used. For example, transfer molding may be used in which a pellet-shaped resin sealing material is melted and sealed by pouring the resin into a mold. However, since transfer molding is performed by pouring molten resin, when filling a large area, an unfilled portion may occur. Therefore, in recent years, compression molding has started to be performed in which molding is performed after supplying a resin sealing material to a mold or a sealed body in advance. In compression molding, since the resin sealing material is directly supplied to the mold or the object to be sealed, there is an advantage that an unfilled portion is hardly generated even when sealing a large area.

In compression molding, a solid or liquid resin sealing material is used as in transfer molding. However, when the encapsulated body is increased in size, a liquid resin encapsulant may cause a liquid flow or the like, and it may be difficult to uniformly supply the encapsulated body onto the encapsulated body. Further, since it is necessary to supply the resin uniformly onto the object to be sealed, a solid or resin sealing material is not a conventional pellet-shaped resin, but a granular or powder resin sealing material. There is a case. However, it is difficult to uniformly supply the resin sealing material onto the mold or the object to be sealed in the granule or powder resin sealing material, and since it is a granule or powder, the resin sealing material is It becomes a source of dust generation, and there is concern about contamination of equipment or clean rooms.

Also, in molding, since the resin is molded in the mold, it is essential to increase the size of the mold in order to increase the size of the sealing structure. However, increasing the size of the mold requires high mold accuracy, which increases the technical difficulty and greatly increases the manufacturing cost of the mold.

On the other hand, the resin composition according to the present invention may be in the form of a film as a sealing film for sealing an object to be sealed. The sealing film according to the present invention includes the resin composition according to the present invention. In this case, it is possible to uniformly supply the resin onto the object to be sealed and reduce dust generation. In addition, it is possible to obtain an embedding ability capable of sealing not only by molding but also by a molding method (laminate, press, etc.) that does not require a mold (such as a mold for high pressure).

In the sealing film according to the present invention, the content of the solvent is preferably 0.2 to 1.5% by mass. The minimum melt viscosity of a film-like resin composition important for embedding an object to be sealed (for example, an electronic component such as a semiconductor element) decreases as the content of a solvent (such as an organic solvent) increases. This is considered because a solvent improves the fluidity | liquidity of a film-form resin composition. Further, an appropriate amount of the solvent gives the film-like resin composition stickiness and easily prevents peeling from the film-like support, cracking of the film-like resin composition itself, and the like. These effects are easily exerted to the maximum when the solvent is 0.2 to 1.5% by mass without causing other problems.

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

The sealing structure which concerns on this invention is equipped with the to-be-sealed body and the sealing part which seals the said to-be-sealed body, The said sealing part is the hardened | cured material of the resin composition which concerns on this invention. Including. The sealed object may be an electronic component.

According to the present invention, it is possible to provide a resin composition capable of obtaining a cured product having excellent thermal conductivity, and a cured product thereof. Moreover, according to this invention, the film for sealing and the sealing structure using the said resin composition can be provided.

It is a schematic cross section for demonstrating one Embodiment of the manufacturing method of a sealing structure. It is a figure which shows the example of arrangement | positioning of the silicon chip used in order to evaluate the embedding property in the Example.

In this specification, a numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively. In the numerical ranges described stepwise in the present specification, the upper limit value or lower limit value of a numerical range of a certain step may be replaced with the upper limit value or lower limit value of the numerical range of another step. In the numerical range described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples. “A or B” only needs to include either A or B, and may include both. Unless otherwise specified, the materials exemplified in the present specification may be used alone or in combination of two or more. In the present specification, the content of each component in the composition is the sum of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. Means quantity.

“Liquid epoxy resin” is an epoxy resin that is liquid at 25 ° C. “Liquid at 25 ° C.” means that the viscosity at 25 ° C. measured with an E-type viscometer is 400 Pa · s or less.

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

<Resin composition and cured product>
The resin composition according to this embodiment is a resin composition containing a thermosetting component and an inorganic filler. Examples of the thermosetting component include (A) thermosetting resins (excluding compounds corresponding 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. The resin composition according to the present embodiment contains (D) an inorganic filler in addition to the thermosetting component, and (D) the inorganic filler contains aluminum oxide. The resin composition according to the present embodiment may be in the form of a varnish or a film (a sealing film). The cured product according to the present embodiment is a cured product of the resin composition according to the present embodiment.

(Thermosetting component)
[(A) component: thermosetting resin]
Examples of the thermosetting resin include epoxy resin, phenoxy resin, cyanate resin, thermosetting polyimide, melamine resin, urea resin, unsaturated polyester, alkyd resin, polyurethane and the like. As the thermosetting resin, an epoxy resin is preferable from the viewpoint of easily obtaining a cured product having excellent thermal conductivity. 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. Examples of the epoxy resin include 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, bisphenol C type epoxy resin, bisphenol E type epoxy resin, and bisphenol. F type epoxy resin, bisphenol G type epoxy resin, bisphenol M type epoxy resin, bisphenol S type epoxy resin (hexanediol 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 (orthocresol novolak type epoxy resin, etc.), biff Nyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, bixylenol type epoxy resin (bixylenol diglycidyl ether, etc.), hydrogenated bisphenol A type epoxy resin (hydrogenated bisphenol A glycidyl ether, etc.), these Examples of the resin include dibasic acid-modified diglycidyl ether type epoxy resins and aliphatic epoxy resins. 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, bisphenol F type glycidyl ether, water-added bisphenol A type glycidyl ether, and ethylene oxide adduct bisphenol A type. Examples thereof include glycidyl ether, propylene oxide adduct bisphenol A-type glycidyl ether, naphthalene resin glycidyl ether, trifunctional or tetrafunctional glycidylamine, and the like.

Commercially available epoxy resins include “EXA-4700” (tetrafunctional naphthalene type epoxy resin), “Epiclon HP-4032” and “EXA-4750” (polyfunctional solid epoxy resin containing naphthalene skeleton) manufactured by DIC Corporation, Japan. Naphthalene type epoxy resins such as “NC-7000” (Naphthalene skeleton-containing polyfunctional solid epoxy resin) manufactured by Kayaku Co., Ltd .; phenols such as “EPPN-502H” (Trisphenol epoxy resin) manufactured by Nippon Kayaku Co., Ltd. And epoxidized products of condensation products of aromatic aldehydes having phenolic hydroxyl groups (Trisphenol type epoxy resin); “Epiclon HP-7200H” (dicyclopentadiene skeleton-containing polyfunctional solid epoxy resin) manufactured by DIC Corporation, etc. Dicyclopentadiene aralkyl epoxy resin; Biphenyl aralkyl type epoxy resins such as “NC-3000H” (bifunctional skeleton-containing polyfunctional solid epoxy resin) manufactured by Kayaku Co., Ltd .; “Epicron N-660”, “Epicron N-690”, “Epicron” manufactured by DIC Corporation Novolak type epoxy resins such as “N-740” (phenol novolac type epoxy resin) and “N500P-1” (orthocresol novolak type epoxy resin), “EOCN-104S” manufactured by Nippon Kayaku Co., Ltd .; Nissan Chemical Industries, Ltd. Tris (2,3-epoxypropyl) isocyanurate such as “TEPIC” manufactured by DIC Corporation; “Epicron 860”, “Epicron 900-IM”, “Epicron EXA-4816” and “Epicron EXA-4822” manufactured by DIC Corporation, "Araldite AER280" manufactured by Asahi Ciba Co., Ltd. "Epototo YD-134", "YD-8125" and "YDF8170" manufactured by Toto Kasei Co., Ltd. (Nippon Steel & Sumikin Chemical Co., Ltd.), "jER834" and "jER872" manufactured by Japan Epoxy Resin Co., Ltd. (Mitsubishi Chemical Corporation) ”,“ JER807 ”,“ jER815 ”,“ jER825 ”,“ jER827 ”,“ jER828 ”,“ jER1001 ”,“ jER1004 ”,“ jER1007 ”and“ jER1009 ”,“ ELA-134 ”manufactured by Sumitomo Chemical Co., Ltd. Bisphenol A type epoxy resins such as “DER-330”, “DER-301” and “DER-361” manufactured by Dow Chemical Company; bisphenol F such as “jER806” manufactured by Japan Epoxy Resin Co., Ltd. (Mitsubishi Chemical Corporation) Type epoxy resin; Nagase ChemteX Corporation Examples thereof include aliphatic epoxy resins such as “Nadecor DLC301” manufactured by the manufacturer. These epoxy resins may be used individually by 1 type, and may use 2 or more types together.

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 (excluding the mass of the solvent) from the viewpoint of easily obtaining excellent fluidity. Preferably, 4% by mass or more is more preferable, 4% by mass or more is particularly preferable, 5% by mass or more is extremely preferable, 10% by mass or more is very preferable, and 15% by mass or more is even more preferable. The content of the thermosetting resin is preferably 30% by mass or less, based on the total mass of the resin composition (excluding the mass of the solvent), from the viewpoint of easily suppressing the occurrence of cracks and cracks on the film surface, and 25% by mass. % Or less is more preferable, and 20% by mass or less is still more preferable.

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

The content of the liquid epoxy resin is preferably 0.5% by mass or more based on the total mass of the resin composition (excluding the mass of the solvent) from the viewpoint of easily suppressing the occurrence of cracks and cracks on the film surface. More preferably 3% by weight or more, still more preferably 5% by weight or more, particularly preferably 7% by weight or more, and very preferably 9% by weight or more. The content of the liquid epoxy resin is based on the total mass of the resin composition (excluding the mass of the solvent) from the viewpoint of easily suppressing the increase in the tackiness of the film and from the viewpoint of easily suppressing edge fusion. 20 mass% or less is preferable, 15 mass% or less is more preferable, and 13 mass% or less is still more preferable.

The content of the liquid epoxy resin is preferably 20% by mass or more, more preferably 30% by mass or more, based on the total mass of the thermosetting resin, from the viewpoint of easily suppressing the occurrence of cracks and cracks on the film surface. More preferably, it is more than mass%. The content of the liquid epoxy resin is 95% by mass or less based on the total mass of the thermosetting resin, from the viewpoint of easily suppressing an excessive increase in the tackiness of the film and from the viewpoint of easily suppressing edge fusion. Preferably, 90 mass% or less is more preferable, and 80 mass% or less is still more preferable. 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 the component (A) (epoxy resin, etc.), the component (B), the component (C) and the component (D), the content of the liquid epoxy resin causes cracks and cracks on the film surface. From the viewpoint of easy suppression, it is preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 3% by mass or more, and more preferably 5% by mass or more, based on the total mass of the components (A) to (D). Is particularly preferable, 7% by mass or more is very preferable and 9% by mass or more is very preferable. The content of the liquid epoxy resin is 20 on the basis of the total mass of the components (A) to (D) from the viewpoint of easily suppressing an excessive increase in the tackiness of the film and from the viewpoint of easily suppressing the edge fusion. % By mass or less is preferred, 15% by mass or less is more preferred, and 13% by mass or less is still more preferred.

[(B) component: curing agent]
Although it does not specifically limit as a hardening | curing agent, A phenol type hardening | curing agent (phenol resin etc.), an acid anhydride type hardening | curing agent, an active ester type hardening | curing agent, a cyanate ester type hardening | curing agent etc. are mentioned. When the component (A) contains an epoxy resin, the curing agent (B) can be used without particular limitation as long as it is a compound having two or more functional groups that react with a glycidyl group in one molecule. Examples of such curing agents include phenol resins and acid anhydrides. As the curing agent, a phenol resin is preferable from the viewpoint of easily obtaining a cured product having excellent thermal conductivity. A hardening | curing agent may be used individually by 1 type, and may use 2 or more types together.

As long as the phenol resin is a resin having two or more phenolic hydroxyl groups in one molecule, a known phenol resin can be used without particular limitation. Examples of phenol resins include resins obtained by condensation or cocondensation of phenols and / or naphthols and aldehydes in the presence of an acidic catalyst, biphenyl skeleton type phenol resins, paraxylylene-modified phenol resins, metaxylylene / paraxylylene-modified phenol resins, melamine Examples thereof include a modified phenol resin, a terpene modified phenol resin, a dicyclopentadiene modified phenol resin, a cyclopentadiene modified phenol resin, a polycyclic aromatic ring modified phenol resin, and a xylylene modified naphthol resin. Examples of phenols include phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, and the like. Examples of naphthols include α-naphthol, β-naphthol, dihydroxynaphthalene and the like. Examples of aldehydes include formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde and the like.

Commercially available phenol resins include “Phenolite LF2882”, “Phenolite LF2822”, “Phenolite TD-2090”, “Phenolite TD-2149”, “Phenolite VH-4150” and “Phenolite” manufactured by DIC Corporation. "Light VH4170", "XLC-LL" and "XLC-4L" manufactured by Mitsui Chemicals, Inc. "SN-100", "SN-300", "SN-395" and "SN-" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. 400 ”,“ SK Resin HE910 ”manufactured by Air Water Co., Ltd.,“ PAPS-PN2 ”(molecular weight distribution intensive novolak resin) manufactured by Asahi Organic Materials Co., Ltd.,“ ELP40 ”manufactured by Gunei Chemical Industry Co., Ltd. Is mentioned.

The content of the curing agent is preferably 1 to 20% by mass, preferably 2 to 15% by mass based on the total mass of the resin composition (excluding the mass of the solvent) from the viewpoint of excellent curability of the thermosetting resin. More preferred is 3 to 10% by mass.

As the blending ratio of the epoxy resin and the curing agent (such as phenol resin), the equivalent of the glycidyl group (epoxy equivalent) of the epoxy resin and the equivalent of the functional group (such as phenolic hydroxyl group) that reacts with the glycidyl group in the curing agent (phenolic) (Equivalent of hydroxyl group equivalent) (equivalent of glycidyl group of epoxy resin / equivalent of functional group reacting with glycidyl group in curing agent) is preferably 0.7 to 2.0, more preferably 0.8 to 1.8 0.9 to 1.7 is more preferable. When the ratio is 0.7 or more or 2.0 or less, unreacted epoxy resin and / or unreacted curing agent hardly remains, and desired cured product characteristics are easily obtained.

[(C) component: curing accelerator]
Although it can use without a restriction | limiting especially as a hardening accelerator, At least 1 sort (s) chosen from the group which consists of an amine type hardening accelerator and a phosphorus type hardening accelerator is preferable. As the curing accelerator, in particular, from the viewpoint of easily obtaining a cured product having excellent thermal conductivity, the viewpoint that a derivative is abundant, and the viewpoint that a desired active temperature is easily obtained, an amine-based curing accelerator is used. Preferably, at least one selected from the group consisting of imidazole compounds, aliphatic amines and alicyclic amines is more preferable, and imidazole compounds are more preferable. Examples of the imidazole compound include 2-phenyl-4-methylimidazole and 1-benzyl-2-methylimidazole. A hardening accelerator may be used individually by 1 type, and may use 2 or more types together. Examples of commercially available curing accelerators include “2P4MZ” and “1B2MZ” manufactured by Shikoku Kasei Kogyo Co., Ltd.

The content of the curing accelerator is preferably in the following range based on the total amount of the thermosetting resin (epoxy resin or the like) and the curing agent (phenol resin or the like). The content of the curing 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 viewpoint that a sufficient curing acceleration effect can be easily obtained. The content of the curing accelerator is such that curing does not easily proceed during the process (for example, coating and drying) at the time of producing the sealing film, or during the storage of the sealing film, And from a viewpoint of being easy to prevent the molding defect accompanying a raise of melt viscosity, 5 mass% or less is preferable, 3 mass% or less is more preferable, and 1.5 mass% or less is still more preferable. From these viewpoints, the content of the curing 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.

((D) component: inorganic filler)
The inorganic filler contains aluminum oxide (such as aluminum oxide particles). Examples of commercially available inorganic fillers containing aluminum oxide include “AA-1.5” manufactured by Sumitomo Chemical Co., Ltd. and “DAW20” manufactured by Denka Co., Ltd.

The inorganic filler may contain a constituent material other than aluminum oxide (such as aluminum oxide particles). That is, the resin composition according to this embodiment may contain particles containing aluminum oxide and a constituent material other than aluminum oxide, and contains aluminum oxide particles and particles containing components other than aluminum oxide. You may do it.

The content of aluminum oxide in the inorganic filler is preferably 50% by mass or more, more preferably 70% by mass or more, more preferably 80% by mass, based on the total mass of the inorganic filler, from the viewpoint of further improving the thermal conductivity improvement effect. % Or more is more preferable, and 90 mass% or more is particularly preferable. The content of aluminum oxide may be 100% by mass based on the total mass of the inorganic filler.

As the constituent material other than aluminum oxide, constituent materials contained in conventionally known inorganic fillers can be used, and are not limited to specific ones. Examples of constituent materials other than aluminum oxide include barium sulfate, barium titanate, silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum hydroxide, silicon nitride, and aluminum nitride. Examples of the inorganic filler containing silica include amorphous silica, crystalline silica, fused silica, and spherical silica. As a constituent material other than aluminum oxide, it has a relatively small thermal expansion coefficient as well as a viewpoint of easily obtaining a dispersibility improving effect in a resin and a sedimentation suppressing effect in a varnish by surface modification or the like. From the viewpoint of easily obtaining desired cured product characteristics, silica is preferable. Examples of commercially available inorganic fillers containing silica include “SC2500-SXJ”, “SC5500-SXE” and “SC2050-KC” manufactured by Admatechs Co., Ltd. As the constituent material other than aluminum oxide, one type may be used alone, or two or more types may be used in combination.

The surface of the inorganic filler may be modified. The method of surface modification is not particularly limited. Surface modification using a silane coupling agent is preferable from the viewpoint of simple treatment, rich types of functional groups, and easy provision of desired characteristics.

Examples of the silane coupling agent include alkyl silane, alkoxy silane, vinyl silane, epoxy silane, amino silane, acrylic silane, methacryl silane, mercapto silane, sulfide silane, isocyanate silane, sulfur silane, styryl silane, alkyl chlorosilane, and the like.

Specific examples of the silane coupling agent include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, diisopropyldimethoxysilane, isobutyl. Trimethoxysilane, diisobutyldimethoxysilane, isobutyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, cyclohexylmethyldimethoxysilane, n-octyltriethoxysilane, n-dodecylmethoxysilane, phenyltrimethoxysilane, Diphenyldimethoxysilane, triphenylsilanol, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, -Octyldimethylchlorosilane, tetraethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropylmethyl Dimethoxysilane, 3-phenylaminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldi Ethoxysilane, bis (3- (triethoxysilyl) propyl) disulfide, bis (3- (triethoxysilyl) propyl) tetrasulfide, vinyltriacetoxysilane, vinyltrimethoxysilane, vinyltriet Sisilane, vinyltriisopropoxysilane, allyltrimethoxysilane, diallyldimethylsilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-mercaptopropyltrimethoxy Examples thereof include silane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, N- (1,3-dimethylbutylidene) -3-aminopropyltriethoxysilane, aminosilane (phenylaminosilane and the like), and the like. A silane coupling agent may be used individually by 1 type, and may use 2 or more types together.

The average particle diameter of the inorganic filler is preferably 0.01 μm or more, more preferably 0.1 μm or more, and more preferably 0.3 μm or more from the viewpoint of easily suppressing the aggregation of the inorganic filler and easy dispersion of the inorganic filler. Is more preferable, and 0.5 μm or more is particularly preferable. The average particle diameter of the inorganic filler is preferably 25 μm or less, more preferably 10 μm or less, and more preferably 5 μm or less from the viewpoint of easily suppressing the precipitation of the inorganic filler in the varnish and easy to produce a uniform sealing film. Is more preferable. 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, still more preferably 0.1 to 10 μm, particularly preferably 0.3 to 5 μm, and 0 Very preferably 5 to 5 μm. The average particle diameter of the inorganic filler may be 10 to 18 μm.

From the viewpoint of excellent fluidity of the resin composition, it is preferable to use a combination of a plurality of inorganic fillers having different average particle diameters. Among the combinations of inorganic fillers, the largest average particle size is preferably 15 to 25 μm. A combination of an inorganic filler having an average particle diameter of 15 to 25 μm, an inorganic filler having an average particle diameter of 0.5 to 2.5 μm, and an inorganic filler having an average particle diameter of 0.1 to 1.0 μm. It is preferable to use it.

The “average particle size” is the particle size at a point corresponding to a volume of 50% when the cumulative frequency distribution curve by the particle size is obtained with the total volume of the particles being 100%, and the particle size distribution using the laser diffraction scattering method It can be measured with a measuring device or the like. The average particle diameter of each combined inorganic 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.

The content of the inorganic filler (the total amount of the inorganic filler containing aluminum oxide and the inorganic filler not containing aluminum oxide) is a viewpoint of improving the thermal conductivity and the coefficient of thermal expansion with the object to be sealed. 72% by mass based on the total mass of the resin composition (excluding the mass of the solvent) from the viewpoint of easily suppressing an increase in warpage of the sealing structure (for example, an electronic component device such as a semiconductor device) due to the difference in That's it. The content of the inorganic filler is the total mass of the resin composition (excluding the mass of the solvent) from the viewpoint of further improving the thermal conductivity and from the viewpoint of further suppressing the warpage of the sealing structure. Is preferably at least 72.5% by mass, more preferably at least 73% by mass. The content of the inorganic filler is such that the sealing film is easily cracked in the drying step when the sealing film is produced, and the fluidity is increased due to an increase in the melt viscosity of the sealing film. From the viewpoint of suppressing the reduction and easily sealing the object to be sealed (such as an electronic component), 93% by mass or less is preferable based on the total mass of the resin composition (excluding the mass of the solvent), 90 mass% or less is more preferable, 85 mass% or less is further more preferable, 84.5 mass% or less is especially preferable, 81 mass% or less is very preferable, and 80 mass% or less is very preferable. From these viewpoints, the content of the inorganic filler is preferably 72 to 93% by mass, more preferably 72 to 90% by mass, and more preferably 72 to 85% based on the total mass of the resin composition (excluding the mass of the solvent). More preferably, it is more preferably from 72 to 84.5% by weight, very particularly preferably from 72.5 to 81% by weight and very particularly preferably from 73 to 80% by weight.

The content of the inorganic filler containing aluminum oxide (such as aluminum oxide particles) is preferably in the following range based on the total mass of the resin composition (excluding the mass of the solvent). From the viewpoint of further improving the thermal conductivity, the content of the inorganic filler containing aluminum oxide is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 70% by mass or more. The content of the inorganic filler containing aluminum oxide is preferably 85% by mass or less, more preferably 80% by mass or less, and still more preferably 75% by mass or less, from the viewpoint of ensuring sufficient embedding properties.

((E) component: solvent)
The resin composition according to the present embodiment may contain (E) a solvent or may not contain (E) a solvent. A conventionally well-known organic solvent can be used as a solvent. As the organic solvent, a solvent capable of dissolving components other than the inorganic filler is preferable, and examples thereof include aliphatic hydrocarbons, aromatic hydrocarbons, terpenes, halogens, esters, ketones, alcohols, aldehydes, and the like. It is done. A solvent may be used individually by 1 type and may use 2 or more types together.

The solvent is selected from the group consisting of esters, ketones, and alcohols from the viewpoint of low environmental burden and the ability to easily dissolve thermosetting resins (such as epoxy resins) and curing agents (such as phenolic resins). At least one is preferred. Among these, ketones are preferable from the viewpoint of easily dissolving a thermosetting resin (such as an epoxy resin) and a curing agent (such as a phenol resin). The solvent is preferably at least one selected from the group consisting of acetone, methyl ethyl ketone and methyl isobutyl ketone, from the viewpoint of low volatilization at room temperature (25 ° C.) and easy removal during drying.

((F) component: elastomer)
The resin composition according to the present embodiment may contain (F) an elastomer (flexible agent) as necessary. From the viewpoint of excellent dispersibility and solubility, it is preferable to use at least one elastomer selected from the group consisting of polybutadiene particles, styrene butadiene particles, acrylic elastomers, silicone powders, silicone oils, and silicone oligomers. One type of elastomer may be used alone, or two or more types may be used in combination.

When the elastomer is particulate, there is no particular limitation on the average particle diameter of the elastomer. In eWLB (Embedded Wafer-Level Ball Grid Array) applications, it is necessary to embed between semiconductor elements, so when using a sealing film for eWLB applications, the average particle size of the elastomer may be 50 μm or less. preferable. The average particle diameter of the elastomer is preferably 0.1 μm or more from the viewpoint of excellent dispersibility of the elastomer.

Examples of commercially available elastomers include “HTR280” manufactured by Nagase ChemteX Corporation. Also, some commercially available elastomer components are dispersed in advance in a liquid resin (for example, a liquid epoxy resin) instead of the elastomer alone, but can be used without any problem. Examples of such commercially available products include “MX-136” and “MX-965” manufactured by Kaneka Corporation.

(Other ingredients)
The resin composition according to the present embodiment can further contain other additives. Specific examples of such additives include pigments, dyes, mold release agents, antioxidants, surface tension adjusting agents and the like.

<Sealing film>
The sealing film according to the present embodiment includes the resin composition according to the present embodiment. The sealing film according to the present embodiment may be obtained by molding the resin composition according to the present embodiment into a film shape and may be formed of the resin composition according to the present embodiment. The sealing film according to this embodiment can be used, for example, for sealing a semiconductor device, embedding an electronic component arranged on a printed wiring board, and the like.

The thickness (film thickness) of the sealing film is preferably 20 μm or more, more preferably 30 μm or more, further preferably 50 μm or more, and more preferably 100 μm or more, from the viewpoint of easily suppressing in-plane thickness variation during coating. Particularly preferred. The thickness of the sealing film is preferably 250 μm or less, more preferably 200 μm or less, and even more preferably 150 μm or less, from the viewpoint that a certain drying property can be easily obtained in the depth direction during coating. 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. Further, a plurality of sealing films can be laminated to produce a sealing film having a thickness exceeding 250 μm.

The content of the inorganic filler in the sealing film (total amount of inorganic filler including aluminum oxide and inorganic filler not including aluminum oxide) is the total mass of the sealing film (excluding the mass of the solvent) On the other hand, the following ranges are preferable. The content of the inorganic filler is preferably 72% by mass or more, more preferably 72.5% by mass or more from the viewpoint of further improving the thermal conductivity and from the viewpoint of easily suppressing the warpage of the sealing structure. More preferably, 73 mass% or more is still more preferable. The content of the inorganic filler is 93% by mass from the viewpoint that the fluidity is suppressed from lowering due to the increase in the melt viscosity of the sealing film, and the object to be sealed (electronic parts, etc.) is easily sealed. The following is preferable, 90% by mass or less is more preferable, 85% by mass or less is further preferable, 84.5% by mass or less is particularly preferable, 81% by mass or less is extremely preferable, and 80% by mass or less is very preferable. From these viewpoints, the content of the inorganic filler is preferably 72 to 93% by mass, more preferably 72 to 90% by mass, further preferably 72 to 85% by mass, particularly preferably 72 to 84.5% by mass, 72.5 to 81% by mass is very preferable, and 73 to 80% by mass is very preferable.

It is preferable that content of the solvent (organic solvent etc.) contained in the sealing film is in the following range with respect to the total mass (including the mass of the solvent) of the sealing film. The content of the solvent is from the viewpoint of easily suppressing the sealing film from becoming brittle and causing problems such as cracking of the sealing film, and the minimum melt viscosity to be increased and the embedding property to be lowered. 2 mass% or more is preferable, 0.3 mass% or more is more preferable, 0.5 mass% or more is further preferable, 0.6 mass% or more is particularly preferable, and 0.7 mass% or more is extremely preferable. The content of the solvent is a problem that the adhesiveness of the sealing film becomes too strong and the handleability is lowered, and a problem such as foaming due to the volatilization of the solvent (organic solvent, etc.) during thermal curing of the sealing film. 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, further preferably 0.5 to 1% by mass, and 0.6 to 1%. % By weight is particularly preferred, and 0.7 to 1% by weight is very particularly preferred.

Specifically, the sealing film according to the present embodiment can be produced as follows.

First, the components of the resin composition according to the present embodiment ((A) thermosetting resin, (B) curing agent, (C) curing accelerator, (D) inorganic filler, (E) solvent, etc.) are mixed. By doing so, a varnish (varnish-like resin composition) is produced. The mixing method is not particularly limited, and a mill, a mixer, and a stirring blade can be used. A solvent (such as an organic solvent) can be used to dissolve and disperse the constituents of the resin composition, which is a material for the sealing film, to prepare a varnish, or to assist in preparing the varnish. . Most of the solvent can be removed in the drying step after coating.

The sealing varnish can be produced by applying the varnish thus produced to a support (film-like support etc.) and then drying by heating with hot air blowing or the like. Although it does not specifically limit as a coating (coating) method, For example, coating apparatuses, such as a comma coater, a bar coater, a kiss coater, a roll coater, a gravure coater, a die coater, can be used.

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

The thickness of the support is not particularly limited, but is preferably 2 to 200 μm from the viewpoint of excellent workability and drying properties. When the thickness of the support is 2 μm or more, it is easy to suppress problems such as breakage of the support during coating, 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, it is easy to suppress problems that prevent solvent drying in the varnish when hot air is blown from both the coating surface and the back surface in the drying step.

A protective layer for the purpose of protecting the sealing film may be disposed on the sealing film formed on the support. By forming the protective layer, the handleability is improved, and the problem that the sealing film sticks to the back surface of the support can be avoided when the film is wound.

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

The sealing film produced as described above includes a step of placing the object to be sealed (embedded object) facing the sealing film, and heating and melting the sealing film to obtain a pressure. A sealing structure (e.g., a semiconductor) by obtaining a cured body of the sealing film by applying the step of embedding the object to be sealed and the step of thermally curing the sealing film having an embedding ability by heating. It can be used to manufacture an electronic component device such as a device.

<Sealing structure>
The sealing structure which concerns on this embodiment is provided with the to-be-sealed body and the sealing part which seals the said to-be-sealed body, and the sealing part is the hardened | cured material of the resin composition which concerns on this embodiment. (A cured product of the resin composition contained in the sealing film according to the present embodiment). An electronic component device etc. are mentioned as a sealing structure. 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 according to the present embodiment. Examples of the electronic component include a semiconductor element; a semiconductor wafer; an integrated circuit; a semiconductor device; a filter such as a SAW filter; a passive component such as a sensor. A semiconductor element obtained by separating a semiconductor wafer may be used. The electronic component device may be a semiconductor device including a semiconductor element or a semiconductor wafer as an electronic component; a printed wiring board or the like. The sealing structure according to the present embodiment may include a plurality of objects to be sealed. The plurality of objects to be sealed may be of the same type or different types.

Next, a method for manufacturing an electronic component device using the sealing film according to this embodiment will be described. Here, a case where the electronic component is a semiconductor element will be described. FIG. 1 is a schematic cross-sectional view for explaining an embodiment of a manufacturing method of a semiconductor device which is an electronic component device as an embodiment of a manufacturing method of a sealing structure. The manufacturing method according to the present embodiment includes a step (FIG. 1A) of arranging a plurality of semiconductor elements 20 side by side on a substrate 30 having a temporary fixing material 40 as an object to be sealed (a target to be embedded), and a support. The sealing film 2 with the support provided with the body 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 heated on the semiconductor element 20. The step of embedding the semiconductor element 20 in the sealing film 2 by pressing (laminating) (FIG. 1B) and the sealing film 2 embedded with the semiconductor element 20 are cured to obtain a cured product 2a. And a step of obtaining (FIG. 1C). In the present embodiment, after sealing the semiconductor element 20 with the sealing film 2 by a laminating method, the sealing film 2 is thermally cured to provide the semiconductor element 20 embedded in the cured product 2a. Although the structure (electronic component device) is obtained, the sealing structure may be obtained by a compression mold.

The laminator used in the laminating method is not particularly limited, and examples thereof include roll type and balloon type laminators. The laminator may be a balloon type capable of vacuum pressurization from the viewpoint of excellent embeddability.

Lamination is usually performed below the softening point of the support. The laminating temperature is preferably around the minimum melt viscosity of the sealing film. The pressure at the time of laminating varies depending on the size, density, etc. of an object to be sealed (for example, an electronic component such as a semiconductor element). The pressure during lamination may be, for example, in the range of 0.2 to 1.5 MPa, or in the range of 0.3 to 1.0 MPa. The lamination time is not particularly limited, but may be 20 to 600 seconds, 30 to 300 seconds, or 40 to 120 seconds.

The sealing film can be cured, for example, in the air or under 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. When the curing temperature is 80 ° C. or higher, the curing of the sealing film proceeds sufficiently, and the occurrence of defects can be suppressed. When the curing temperature is 280 ° C. or lower, the occurrence of heat damage to other materials tends to be suppressed. 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, curing of the sealing film proceeds sufficiently, and better production efficiency can be obtained. Moreover, you may combine several conditions for hardening conditions.

The preferred embodiments of the present invention have been described above, but the present invention is not necessarily limited to the above-described embodiments, and modifications may be made as appropriate without departing from the spirit of the present invention.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

The following components were used as components of a varnish-like epoxy resin composition (varnish) for obtaining a 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: 160 g / eq, epoxy resin which shows liquid at 25 ° C.)
A2: Naphthalene skeleton-containing polyfunctional solid epoxy resin (manufactured by DIC Corporation, trade name: EXA-4750, epoxy equivalent: 182 g / eq, epoxy resin not showing liquid at 25 ° C.)
A3: Polybutadiene elastomer particle-containing bisphenol F type epoxy resin (manufactured by Kaneka Corporation, trade name: MX-136, liquid epoxy resin content: 75 mass%, elastomer particle content: 25 mass%, epoxy equivalent: 226 g / eq, average particle diameter of elastomer particles: 0.1 μm, a component containing an epoxy resin that is liquid at 25 ° C.)
A4: Epoxy resin containing silicone elastomer particles (mixture of bisphenol F type liquid epoxy resin and bisphenol A type liquid epoxy resin, manufactured by Kaneka Corporation, trade name: MX-965, liquid epoxy resin content: 75% by mass, elastomer particles Content: 25 mass%, a component containing an epoxy resin that is liquid at 25 ° C.)
A5: Ortho-cresol novolac type epoxy resin (manufactured by DIC Corporation, trade name: N500P-1, epoxy equivalent: 201 g / eq, epoxy resin not showing liquid at 25 ° C.)
A6: Flexible skeleton-containing bisphenol A type epoxy resin (manufactured by DIC Corporation, trade name: Epicron EXA-4816, epoxy equivalent: 403 g / eq, epoxy resin that shows liquid at 25 ° C.)

(B) component; curing agent (phenolic resin)
B1: Phenol novolac resin (manufactured by Asahi Organic Materials Co., Ltd., trade name: PAPS-PN2, phenolic hydroxyl group equivalent: 104 g / eq, phenol resin not showing liquid at 25 ° C.)
B2: Alkylphenol novolak resin (manufactured by Gunei Chemical Industry Co., Ltd., trade name: ELP40, phenolic hydroxyl group equivalent: 140 g / eq)

Component (C): Curing accelerator C1: 2-phenyl-4-methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name: 2P4MZ)
C2: 1-benzyl-2-methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name: 1B2MZ)

Component (D): Inorganic filler D1: Aluminum oxide particles (manufactured by Sumitomo Chemical Co., Ltd., trade name: AA-1.5, average particle size: 1.5 μm)
D2: Aluminum oxide particles (Denka Co., Ltd., trade name: DAW20, average particle size: 20 μm)
D3: Silica particles (manufactured by Admatechs Co., Ltd., trade name: SC2500-SXJ, phenylaminosilane treatment, average particle size: 0.5 μm)
D4: Silica particles (manufactured by Admatechs Co., Ltd., trade name: SC5500-SXE, phenylaminosilane 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 cut (silica filler content: 70 mass%))

(E) component; solvent E1: methyl ethyl ketone

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

<Preparation of sealing film>
Example 1
172 g of organic solvent E1 was put in a 10 L polyethylene container. After adding 542 g of the inorganic filler D1 to the container, the inorganic filler D1 was dispersed with a stirring blade 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 further stirred for 1 hour to obtain a mixed solution. This mixed solution was filtered through nylon # 200 mesh (opening 75 μm), and the filtrate was collected to prepare a varnish-like epoxy resin composition. Using a coating machine, this varnish-like epoxy resin composition is coated on the following film-like support under the following conditions, and a sealing film (film-like epoxy resin composition) having a film thickness of 100 μm is supported. Made above.
・ Coating head method: Comma coater ・ Coating and drying speed: 1 m / min ・ Drying conditions (temperature / furnace length): 110 ° C./3.3 m, 130 ° C./3.3 m, 140 ° C./3.3 m
-Film-like support: polyethylene terephthalate film with a thickness of 38 μm

The surface of the sealing film was protected by disposing a protective layer (12 μm thick polyethylene terephthalate film) on the side opposite to the support in the sealing film. In addition, in each following evaluation, it evaluated, after peeling a support body and a protective layer. The same applies to the following examples and comparative examples.

(Example 2)
141 g of organic solvent E1 was put in a 10 L polyethylene container. After adding 493 g of the inorganic filler D1 to the container, the inorganic filler D1 was dispersed with a stirring blade to obtain a dispersion. To this dispersion, 88 g of thermosetting resin A1, 22 g of thermosetting resin A2, and 70 g of curing agent 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 further stirred for 1 hour to obtain a mixed solution. This mixed solution was filtered through nylon # 200 mesh (opening 75 μm), and the filtrate was collected to prepare a varnish-like epoxy resin composition. Using a coating machine, this varnish-like epoxy resin composition was applied onto a film-like support in the same manner as in Example 1, and a film for sealing (film-like epoxy resin composition) having a film thickness of 100 μm was obtained. Produced.

(Example 3)
114 g of organic solvent E1 was put in a 10 L polyethylene container. After adding 401 g of the inorganic filler D1 to the container, the inorganic filler D1 was dispersed with a stirring blade 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 further stirred for 1 hour to obtain a mixed solution. This mixed solution was filtered through nylon # 200 mesh (opening 75 μm), and the filtrate was collected to prepare a varnish-like epoxy resin composition. Using a coating machine, this varnish-like epoxy resin composition was applied onto a film-like support in the same manner as in Example 1, and a film for sealing (film-like epoxy resin composition) having a film thickness of 100 μm was obtained. Produced.

Example 4
149 g of organic solvent E1 was put in a 10 L polyethylene container. After adding 423 g of the inorganic filler D1 to the container, 104 g of the inorganic filler D3 was added, and the inorganic fillers D1 and D3 were dispersed with a stirring blade to obtain a dispersion. The average particle diameter of the inorganic fillers D1 and D3 was 1.0 μm. 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 further stirred for 1 hour to obtain a mixed solution. This mixed solution was filtered through nylon # 200 mesh (opening 75 μm), and the filtrate was collected to prepare a varnish-like epoxy resin composition. Using a coating machine, this varnish-like epoxy resin composition was applied onto a film-like support in the same manner as in Example 1, and a film for sealing (film-like epoxy resin composition) having a film thickness of 100 μm was obtained. Produced.

(Comparative Example 1)
96 g of the organic solvent E1 was put in a 10 L polyethylene container. After adding 328 g of the inorganic filler D1 to the container, the inorganic filler D1 was dispersed with a stirring blade to obtain a dispersion. To this dispersion, 144 g of thermosetting resin A1, 36 g of thermosetting resin A2, and 114 g of curing agent B1 were added and stirred. After confirming that the curing agent B1 was dissolved, 2.3 g of the curing accelerator C1 was added and further stirred for 1 hour to obtain a mixed solution. This mixed solution was filtered through nylon # 200 mesh (opening 75 μm), and the filtrate was collected to prepare a varnish-like epoxy resin composition. Using a coating machine, this varnish-like epoxy resin composition was applied onto a film-like support in the same manner as in Example 1, and a film for sealing (film-like epoxy resin composition) having a film thickness of 100 μm was obtained. Produced.

(Comparative Example 2)
4629 g of organic solvent E1 was placed in a 10 L polyethylene container. After adding 6622 g of inorganic filler D3 to the container, the inorganic filler D3 was dispersed with a stirring blade 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 curing agent B1 were added and stirred. After confirming that the curing agent B1 was dissolved, 15 g of the curing accelerator C1 was added, and the mixture was further stirred for 1 hour to obtain a mixed solution. This mixed solution was filtered through nylon # 200 mesh (opening 75 μm), and the filtrate was collected to prepare a varnish-like epoxy resin composition. Using a coating machine, this varnish-like epoxy resin composition was applied onto a film-like support in the same manner as in Example 1, and a film for sealing (film-like epoxy resin composition) having a film thickness of 100 μm was obtained. Produced.

(Comparative Example 3)
A sealing film (film epoxy resin composition) having a film thickness of 100 μm was prepared in the same manner as in Comparative Example 1 except that the coating and drying speed of Comparative Example 1 were changed from 1 m / min to 0.5 m / min. .

(Example 5)
83 g of organic solvent E1 was put in a 10 L polyethylene container. After adding 151 g of the inorganic filler D5 to the container, 660 g of the inorganic filler D2 and 53 g of the inorganic filler D4 are added, and the inorganic fillers D2, D4, and D5 are dispersed with a stirring blade to obtain a dispersion. It was. The average particle diameter of the inorganic fillers D2, D4 and D5 was 16 μm. To this dispersion, 34 g of thermosetting resin A5, 11 g of thermosetting resin A6, and 28 g of curing agent B2 were added and stirred. After confirming that the curing agent B2 was dissolved, 7 g of the elastomer F1 and 0.5 g of the curing accelerator C2 were added and further stirred for 1 hour to obtain a mixed solution. The mixture was filtered through nylon # 150 mesh (opening 106 μm), and the filtrate was collected to prepare a varnish-like epoxy resin composition. Using a coating machine, this varnish-like epoxy resin composition was applied onto a film-like support in the same manner as in Example 1, and a film for sealing (film-like epoxy resin composition) having a film thickness of 125 μm was obtained. Produced.

(Example 6)
83 g of organic solvent E1 was put in a 10 L polyethylene container. After adding 98 g of inorganic filler D5 to the container, add 430 g of inorganic filler D2 and 34 g of inorganic filler D4, and disperse the inorganic fillers D2, D4 and D5 with a stirring blade to obtain a dispersion. It was. The average particle diameter of the inorganic fillers D2, D4 and D5 was 18 μm. To this dispersion, 21 g of thermosetting resin A5, 7 g of thermosetting resin A6, and 17 g of curing agent B2 were added 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 further stirred for 1 hour to obtain a mixed solution. The mixture was filtered through nylon # 150 mesh (opening 106 μm), and the filtrate was collected to prepare a varnish-like epoxy resin composition. Using a coating machine, this varnish-like epoxy resin composition was applied onto a film-like support in the same manner as in Example 1, and a film for sealing (film-like epoxy resin composition) having a film thickness of 125 μm was obtained. Produced.

(Example 7)
83 g of organic solvent E1 was put in a 10 L polyethylene container. After adding 68.6 g of inorganic filler D3 to the container, add 463 g of inorganic filler D2 and 34.3 g of inorganic filler D4, and disperse inorganic fillers D2, D3, and D4 with a stirring blade. A dispersion was obtained. The average particle diameter of the inorganic fillers D2, D3 and D4 was 18 μm. To this dispersion, 18.3 g of thermosetting resin A5, 4.6 g of thermosetting resin A6, and 14.4 g of curing agent B2 were added and stirred. After confirming that curing agent B2 was dissolved, 5.6 g of elastomer F1 and 0.11 g of curing accelerator C1 were added, and the mixture was further stirred for 1 hour to obtain a mixed solution. The mixture was filtered through nylon # 150 mesh (opening 106 μm), and the filtrate was collected to prepare a varnish-like epoxy resin composition. Using a coating machine, this varnish-like epoxy resin composition was applied onto a film-like support in the same manner as in Example 1, and a film for sealing (film-like epoxy resin composition) having a film thickness of 125 μm was obtained. Produced.

(Example 8)
83 g of organic solvent E1 was put in a 10 L polyethylene container. After adding 68.6 g of inorganic filler D3 to the container, add 463 g of inorganic filler D2 and 34.3 g of inorganic filler D4, and disperse inorganic fillers D2, D3, and D4 with a stirring blade. A dispersion was obtained. The average particle diameter of the inorganic fillers D2, D3 and D4 was 18 μm. To this dispersion, 17.9 g of thermosetting resin A5, 4.5 g of thermosetting resin A6, and 14 g of curing agent B2 were added and stirred. After confirming that curing agent B2 was dissolved, 6.4 g of elastomer F1 and 0.11 g of curing accelerator C1 were added and further stirred for 1 hour to obtain a mixed solution. The mixture was filtered through nylon # 150 mesh (opening 106 μm), and the filtrate was collected to prepare a varnish-like epoxy resin composition. Using a coating machine, this varnish-like epoxy resin composition was applied onto a film-like support in the same manner as in Example 1, and a film for sealing (film-like epoxy resin composition) having a film thickness of 125 μm was obtained. Produced.

<Evaluation>
(1) Thermal conductivity A of cured product of sealing film
Under the following conditions, both surfaces of the sealing films of Examples 1 to 8 and Comparative Examples 1 to 3 (thickness: 100 μm or 125 μm) were laminated with copper foil to obtain a sealing film with double-sided copper foil.
・ Laminator: Vacuum pressure laminator manufactured by Meiki Seisakusho Co., Ltd., trade name “MVLP-500”
・ Lamination temperature: 90 ℃
・ Lamination pressure: 0.5 MPa
・ Vacuum drawing time: 30 seconds ・ Lamination time: 40 seconds

The obtained film for sealing with double-sided copper foil was cured under the following conditions to produce a cured epoxy resin body with copper foil.
・ Oven: Espec Co., Ltd., trade name "SAFETY OPEN SPH-201"
・ Oven temperature: 140 ℃
・ Heating time: 120 minutes

The copper foil of the produced epoxy resin cured body with copper foil was removed by etching to obtain an epoxy resin cured body (cured product of sealing film). 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: Product name “LFA447” (Xenon Flash Analyzer) manufactured by NETZSCH

Moreover, the specific gravity of the obtained epoxy resin cured body was measured with the following specific gravity meter.
・ Hydrometer: Trade name “SD200L” manufactured by Alpha Mirage

The specific heat of the obtained cured epoxy resin was determined by differential scanning calorimetry under the following conditions.
・ Differential scanning calorimeter: 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 (constant)

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

And thermal conductivity was evaluated based on the following evaluation criteria. The results of Examples 1 to 4 are shown in Table 1. 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 was 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 cured product of sealing film
Four sealing films (thickness: 125 μm) of Examples 5 to 8 were respectively stacked, and a laminated film having a thickness of 500 μm was produced using a hand press under the following conditions.
・ Hand press machine: Product name “BIG HEART” manufactured by Imoto Seisakusho Co., Ltd.
・ Hand press molding temperature: 140 ℃
・ Hand press molding time: 30 minutes ・ Molding load: 20 kN

The obtained laminated film having a thickness of 500 μm was cured under the following conditions to prepare an epoxy resin cured body (cured product of sealing film).
・ Oven: Product name “SAFETY OPEN SPH-201” manufactured by ESPEC Corporation
・ 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 a temperature gradient method using a thermal resistivity meter. And thermal conductivity was 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 sealing film The obtained sealing film was cut into a 5 cm square sample. This sample was put in an aluminum cup whose mass was measured in advance, and the mass of the aluminum cup containing the sample was measured. Next, the sample was heated in an oven at 180 ° C. for 10 minutes while being placed in an aluminum cup, and then allowed to stand at room temperature (25 ° C.) for 10 minutes. Next, the mass of the aluminum cup containing the sample was measured again. Next, the mass of the aluminum cup separately measured was subtracted from the measured value of the mass of the aluminum cup containing the sample (before and after heating) to determine the mass of the sealing film before and after heating, respectively. And the value obtained by dividing the value obtained by subtracting the mass of the sealing film after heating from the mass of the sealing film before heating by the mass of the sealing film before heating was obtained as the solvent content. . The results are shown in Tables 1 and 2.

(4) Embeddability Four sealing films each having a thickness of 100 μm or 125 μm were stacked to obtain a laminated film having a thickness of 400 μm or 500 μm. An 8-inch sized eWLB package was produced using the laminated film by the following procedure. FIG. 2 shows a layout of silicon chips in this measurement. First, as shown in FIG. 2, silicon chips (7.3 mm square silicon chip 60 and 3 mm square silicon chip 70) having a thickness of 350 μm were arranged on the SUS plate 50. Next, the laminated film was cut into a circle having a diameter of 20 cm and placed on the silicon chip. Next, the silicon chip was sealed under the following conditions using a compression mold apparatus (manufactured by Apic Yamada Co., Ltd., trade name: WCM-300) to obtain a sealed body (sealed structure).
・ Compression molding temperature: 140 ℃
・ Compression mold pressure: 2.5MPa
・ Compression mold time: 10 minutes

Next, the produced sealing body was cured by heating under the following conditions to produce a cured body. Thereby, an eWLB package was obtained.
・ Oven: Product name “SAFETY OPEN SPH-201” manufactured by ESPEC Corporation
・ Oven temperature: 140 ℃
・ Heating time: 120 minutes

The embedding property of the produced cured body was evaluated based on the following evaluation criteria. The results are shown in Tables 1 and 2.
"A": Can be embedded without voids and has a smooth surface. "B": Some voids are seen and the surface is smooth. "C": Voids are found and the surface is inferior.

<Evaluation results>
As shown in Table 1 and Table 2, in the resin composition containing the thermosetting component and the inorganic filler, the inorganic filler contains aluminum oxide, and the content of the inorganic filler is that of the resin composition. It can be seen that when the total mass (excluding the mass of the solvent) is 72% by mass or more, an excellent effect can be obtained with respect to the thermal conductivity of the cured product. From Example 4 shown in Table 1, it can be seen that even when the inorganic filler contains silica, an excellent effect can be obtained regarding the thermal conductivity of the cured product.

From the above results, in the resin composition containing the thermosetting component and the inorganic filler, the inorganic filler contains aluminum oxide, and the content of the inorganic filler is the total mass of the resin composition (excluding the mass of the solvent). ) On the basis of 72% by mass or more, it was found that an excellent effect on the thermal conductivity of the cured product was obtained and the embedding property was excellent.

DESCRIPTION OF SYMBOLS 1 ... Support body, 2 ... Sealing film, 2a ... Hardened | cured material, 10 ... Sealing film with a support body, 20 ... Semiconductor element, 30 ... Board | substrate, 40 ... Temporary fixing material, 50 ... SUS board, 60 ... 7 3mm square silicon chip, 70 ... 3mm square silicon chip.

Claims

A resin composition containing a thermosetting component and an inorganic filler,
The inorganic filler comprises aluminum oxide;
The resin composition whose content of the said inorganic filler is 72 mass% or more on the basis of the total mass (except the mass of a solvent) of the said resin composition.
The resin composition according to claim 1, wherein the thermosetting component contains a thermosetting resin.
The resin composition according to claim 2, wherein the thermosetting resin contains an epoxy resin.
The resin composition according to claim 2 or 3, wherein the thermosetting component further contains a curing agent.
The resin composition according to claim 4, wherein the curing agent comprises a phenol resin.
6. The resin composition according to any one of claims 2 to 5, wherein the thermosetting component further contains a curing accelerator.
The resin composition according to claim 6, wherein the curing accelerator contains an imidazole compound.
The resin according to any one of claims 1 to 7, wherein the content of the epoxy resin that is liquid at 25 ° C is 5% by mass or more based on the total mass of the resin composition (excluding the mass of the solvent). Composition.
The resin according to any one of claims 1 to 7, wherein the content of the epoxy resin that is liquid at 25 ° C is 7% by mass or more based on the total mass of the resin composition (excluding the mass of the solvent). Composition.
The resin composition according to any one of claims 1 to 9, 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 any one of claims 1 to 9, wherein the content of the inorganic filler is 85% by mass or less based on the total mass (excluding the mass of the solvent) of the resin composition.
The resin composition according to any one of claims 1 to 11, wherein the inorganic filler has an average particle size of 0.01 to 25 µm.
The resin composition according to any one of claims 1 to 11, wherein the inorganic filler has an average particle size of 0.01 to 10 袖 m.
The resin composition according to any one of claims 1 to 13, wherein the content of aluminum oxide in the inorganic filler is 50% by mass or more.
The resin composition according to any one of claims 1 to 14, further comprising a solvent.
A cured product of the resin composition according to any one of claims 1 to 15.
A sealing film comprising the resin composition according to any one of claims 1 to 15.
The sealing film according to claim 17, wherein the content of the solvent is 0.2 to 1.5 mass%.
The sealing film according to claim 17 or 18, having a thickness of 20 to 250 µm.
A sealed body and a sealing portion for sealing the sealed body,
A sealing structure in which the sealing portion includes a cured product of the resin composition according to any one of claims 1 to 15.
The sealing structure according to claim 20, wherein the object to be sealed is an electronic component.