TW201703207A - Sealing film and electronic component device using same - Google Patents

Abstract

This sealing film contains (A) an epoxy resin, (B) a curing agent, (C) one or more elastomers selected from the group consisting of butadiene rubber and silicone rubber, and (D) an inorganic filler, wherein the content of constituent (C) is 0.5-7.0 mass% inclusive based on the total mass of constituent (A), constituent (B), constituent (C), and constituent (D).

Description

Sealing film and electronic component device using the same

The present invention relates to a film for sealing and an electronic component device using the film for sealing.

With the miniaturization and thinning of electronic devices, the miniaturization and thinning of semiconductor devices are also progressing. For example, a semiconductor device having almost the same size as a semiconductor element, and a package on package in which a semiconductor device is stacked on a semiconductor device are also popular. Therefore, in the future, it is expected that the miniaturization and thinning of semiconductor devices will progress.

There are also problems to be solved in terms of miniaturization and thinning of a semiconductor device. For example, as the miniaturization of semiconductor elements progresses, the number of terminals increases, and it is difficult to provide all external connection terminals on the semiconductor elements. When the external connection terminal is reluctantly provided, as the pitch between the terminals is narrowed and the height of the terminal is lowered, it is difficult to ensure connection reliability after the semiconductor device is mounted.

Therefore, in recent years, new construction methods have been proposed. For example, Patent Literatures 1 to 3 listed below disclose a mounting method and a semiconductor device fabricated by using the mounting method, and the method includes the steps of: manufacturing and cutting each of the semiconductor wafers Semiconductor element After reconfiguring at a moderate interval, the semiconductor elements are sealed using a solid or liquid sealing resin. In this embodiment, the sealing molded article in which a plurality of semiconductor elements are sealed is subjected to a step of arranging wiring for external connection terminals and forming external connection terminals. Therefore, the number of semiconductor elements to be rearranged is increased once. The number of semiconductor devices that can be fabricated in the step increases.

Therefore, research into increasing the size of the sealed molded article has continued. At present, since a semiconductor manufacturing apparatus is used in the formation of wiring, it is desired to increase the diameter of a sealing molded article formed into a wafer shape. As another shape, the panelization of a seal molded product which can be increased in size has been continuously studied, and the panel formation of the seal molded product can use a printed wiring board manufacturing apparatus which is cheaper than a semiconductor manufacturing apparatus.

[Previous Technical Literature] (Patent Literature)

Patent Document 1: Japanese Patent Laid-Open No. 3616615

Patent Document 2: Japanese Laid-Open Patent Publication No. 2001-244372

Patent Document 3: Japanese Laid-Open Patent Publication No. 2001-127095

The sealing of the reconfigured semiconductor element is carried out by molding, which molds a liquid or solid resin encapsulating material by a mold. Previously, a transfer molding was used in which a pellet-shaped resin sealing material was melted and then poured into a mold to perform sealing. Of course On the other hand, since the transfer molding is performed by flowing the molten resin, it is possible to form an unfilled portion when a large-area sealing is desired.

As another molding method, there is a compression molding which is a method in which a resin sealing material is supplied to a mold or a sealed body in advance and then molded. In the compression molding, since the sealing material is directly supplied to the sealed body or the mold, there is an advantage that the unfilled portion hardly occurs even in a large-area seal. However, even in such a molding method, when the sealed body is enlarged, the liquid resin sealing material may be in a state in which the liquid flow is unbalanced, and thus it is easy to become a resin sealing material which is difficult to uniformly supply the liquid to the sealed body. . On the other hand, the particulate solid resin sealing material is difficult to uniformly supply to the object to be sealed, and the pellet and powdery resin sealing material may become a dust source to contaminate the device and the clean room.

On the other hand, there is a problem that occurs as the size of the mold increases. Since a large-sized mold requires high mold precision, there is a problem that the manufacturing cost is greatly increased as the technical difficulty is increased.

In view of the above circumstances, the present inventors have studied a technique of laminating or pressing a film-like sealing resin as a sealing method, which can also correspond to a sealing molding method that does not require a mold, and is less likely to be dusted. Further, it is also expected to achieve the panel formation of the above-described sealed molded article. When a film-shaped sealing resin is used, the semiconductor element placed on the temporary fixing material is sealed with a sealing resin, and then the sealing molded article is peeled off from the temporary fixing material to be cured, and then enters the redistribution layer. Form the process. At this time, if the hardened body after curing is warped, the line redistribution layer cannot be formed horizontally, so The hardened body is sucked with a sorber to make it level. However, if the warpage is large, the sorbent cannot sufficiently absorb the hardened body, and the formation of the wiring redistribution layer tends to be difficult.

An object of the present invention is to provide a film for sealing and an electronic component device using the film for sealing, which can seal an electronic component such as a semiconductor element well, and can also form a cured body in which the amount of warpage is sufficiently suppressed.

The inventors of the present invention attempted to reduce the warpage by increasing the content of the filler in the film so that the CTE (coefficient of thermal expansion) of the film for sealing is close to the CTE of the semiconductor wafer. However, when the content of the filler in the film is increased, there is another problem that the fluidity is deteriorated, the resin flow marks, and the unfilled portions occur. Therefore, the inventors of the present invention have estimated that the stress and the amount of hardening shrinkage which occur during the hardening of the molded product after sealing have an influence on the warpage after hardening, and review the preparation of the stress relieving component and the hardened body of the sealed molded product. The relationship between the amount of warpage. Further, the inventors of the present invention have found that the sealing body obtained by sealing the tantalum wafer by using a sealing film prepared by blending a specific amount of a specific elastomer component has a very small amount of warpage even after hardening, based on The above findings complete the present invention.

That is, the present invention provides a film for sealing comprising: (A) an epoxy resin; (B) a hardener; (C) an elastomer selected from the group consisting of butadiene rubber and neodymium rubber. One or more of the group; and, (D) an inorganic filler; wherein, (A) component, (B) The content of the component (C) is 0.5 to 7.0% by mass based on the total mass of the component (C) and the component (D).

According to the film for sealing of the present invention, the electronic component such as a semiconductor element can be satisfactorily sealed, and a hardened body in which the amount of warpage is sufficiently suppressed can be formed, so that formation of a subsequent wiring redistribution layer becomes possible.

In the film for sealing of the present invention, the component (A) may be contained in an amount of 5% by mass or more based on the total mass of the component (A), the component (B), the component (C), and the component (D). A liquid epoxy resin at 25 ° C. At this time, the warpage of the hardened body can be further suppressed.

The film for sealing of the present invention may further contain (E) a curing accelerator.

The film for sealing of the present invention may contain 0.2 to 1.5% by mass of the organic solvent (F) based on the total mass of the film for sealing. When the content of the organic solvent is within the above range, it is possible to suppress cracking of the film for sealing and generation of bubbles, and it is possible to obtain better embedding property.

In the film for sealing of the present invention, the content of the component (D) may be 65 mass% or more based on the total mass of the component (A), the component (B), the component (C) and the component (D). When the content of the component (D) is within the above range, the difference in thermal expansion coefficient between the film for sealing and the body to be sealed can be reduced, and the warpage of the cured body can be made smaller.

In the film for sealing of the present invention, the thickness of the film can be set to 50 to 250 μm.

The present invention also provides an electronic component device including an electronic component, and a cured body of the sealing film, which seals the electronic component.

According to the present invention, there is provided a film for sealing and an electronic component device using the film for sealing, which can seal a good electronic component such as a semiconductor element and can form a cured body in which the amount of warpage is sufficiently suppressed.

1‧‧‧Support

2‧‧‧Seal film

2a‧‧‧hardened body

10‧‧‧film for sealing with support

20‧‧‧Semiconductor components

30‧‧‧Substrate

40‧‧‧ Temporary fixing materials

50‧‧‧Stainless steel plate

60‧‧‧ 7.3mm square wafer

70‧‧‧3mm square wafer

Fig. 1 is a schematic cross-sectional view for explaining an embodiment of a method of manufacturing an electronic component device.

Fig. 2 is a view showing an example of arrangement of germanium wafers.

Hereinafter, a mode for carrying out the invention (hereinafter referred to as "this embodiment") will be described in detail. Further, the present invention is not limited to the following embodiments.

The film for sealing of the present embodiment contains (A) an epoxy resin (hereinafter also referred to as component (A)), (B) a curing agent (hereinafter also referred to as component (B)), and (C) an elastomer. It is one or more selected from the group consisting of a butadiene-based rubber and a ruthenium-based rubber (hereinafter also referred to as (C) component); and, (D) an inorganic filler (hereinafter also referred to as (D) The component (C) has a content of (C) component of 0.5 to 7.0% by mass based on the total mass of the component (A), the component (B), the component (C), and the component (D). Also, this implementation The film for sealing of the aspect may further contain (E) a curing accelerator (hereinafter also referred to as (E) component). When the film for sealing contains (E) a hardening accelerator, the content of (C) component is based on the total mass of (A) component, (B) component, (C) component, and (D) component and (E) component. It can also be 0.5 to 7.0% by mass.

(A) Epoxy resin

The (A) epoxy resin is not particularly limited as long as it has two or more epoxy propyl groups per molecule. The (A) component may, for example, be a bisphenol A epoxy resin, a bisphenol AP epoxy resin, a bisphenol AF epoxy resin, a bisphenol B epoxy resin, or a bisphenol BP 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, double Bisphenol S type epoxy resin such as phenol P type epoxy resin, bisphenol PH type epoxy resin, bisphenol TMC type epoxy resin, bisphenol Z type epoxy resin, hexanediol bisphenol S diglycidyl ether , a novolac type epoxy resin such as a phenolic phenol epoxy resin, a biphenyl type epoxy resin, a naphthalene type epoxy resin, a dicyclopentadiene type epoxy resin, or a dixylenol diglycidyl ether, A hydrogenated bisphenol A type epoxy resin such as hydrogenated bisphenol A glycidyl ether, and such a dibasic acid modified diglycidyl ether type epoxy resin or an aliphatic epoxy resin. (A) The components may be used singly or in combination of two or more.

A commercially available epoxy resin can also be used for the component (A). The commercially available epoxy resin may, for example, be a trade name of DIC Corporation: EXA4700 (4-functional naphthalene type epoxy resin), and a Japanese chemical company Trade name: N-type epoxy resin such as NC-7000 (polyfunctional solid epoxy resin containing naphthalene skeleton); Trade name: EPPN-502H (trisphenol epoxy resin) manufactured by Nippon Kayaku Co., Ltd. An epoxide such as a condensate of a phenol and an aromatic hydrazine having a phenolic hydroxyl group (trisphenol type epoxy resin); trade name of DIC Corporation: EPICLON HP-7200H (containing a dicyclopentadiene skeleton) Dicyclopentadiene aralkyl type epoxy resin such as polyfunctional solid epoxy resin; trade name of Nippon Chemical Co., Ltd.: NC-3000H (multifunctional solid epoxy resin containing biphenyl skeleton) Biphenyl aralkyl type epoxy resin; trade name of EPICLON N660, EPICLON N690, manufactured by Nippon Kayaku Co., Ltd., and phenolic varnish type epoxy resin such as EOCN-104S; Nissan Chemical Industry Co., Ltd. Trade name of the company: tris(2,3-epoxypropyl)isocyanurate such as TEPIC, trade name of DIC Corporation: EPICLON 860, EPICLON 900-IM, EPICLON EXA-4816, EPICLON EXA-4822, Asahi CHIBA Co., Ltd. trade name: A Product name: Epotot YD-134, manufactured by Mitsubishi Chemical Co., Ltd.: JER834, JER872, Sumitomo Chemical Co., Ltd., trade name: ELA-134, Mitsubishi Chemical Co., Ltd. Product names of the company: Epikote 807, 815, 825, 827, 828, 834, 1001, 1004, 1007, 1009, trade names of Dow Chemical Co., Ltd.: DER-330, 301, 361, manufactured by Dongdu Chemical Co., Ltd. Trade name: bisphenol A type epoxy resin such as YD8125, YDF8170; Trade name of Mitsubishi Chemical Co., Ltd.: bisphenol F type epoxy resin such as JER806; trade name of DIC Corporation: naphthalene type epoxy resin such as EPICLON HP-4032; trade name of DIC Corporation A phenol novolak type epoxy resin such as EPICLON N-740 or an aliphatic epoxy resin such as Denacol DLC301 manufactured by Nagase ChemteX Co., Ltd., or the like. These epoxy resins may be used alone or in combination of two or more.

As the component (A), an epoxy resin which is liquid at 25 ° C can also be used. The liquid epoxy resin is not particularly limited as long as it is a liquid epoxy resin at 25 ° C. Examples of the liquid epoxy resin include bisphenol A-based, bisphenol F-based, biphenyl-based, novolak-based, dicyclopentadiene-based, polyfunctional phenol-based, naphthalene-based, and aralkyl-modified systems. An alicyclic system, a glycidyl ether (glycidyl ether) such as an alcohol, a glycidylamine-based or a glycidyl ester-based resin. These resins may be used alone or in combination of two or more. The liquid epoxy resin may be a bisphenol F-type epoxy resin from the viewpoint of imparting handleability.

In the present specification, the epoxy resin which is liquid at 25 ° C means an epoxy resin having a viscosity of 400 Pa·s or less as measured by an E-type viscosity meter or a B-type viscosity meter at 25 ° C. .

From the viewpoint of imparting good handleability to the film for sealing, the content of the component (A) may be 5 based on the total mass of the component (A), the component (B), the component (C), and the component (D). ~20% by mass, may be 5 to 15% by mass, or may be 6 to 11% by mass. Again, when sealed When the film contains the component (E), the total of the (A) component, the (B) component, the (C) component, the (D) component, and the (E) component is obtained from the viewpoint of imparting good handleability to the film for sealing. The mass of the component (A) may be 5 to 20% by mass, may be 5 to 15% by mass, or may be 6 to 11% by mass.

When the film for sealing of the present embodiment contains an epoxy resin which is liquid at 25 ° C, the component (A), the component (B), and the component (C) are used from the viewpoint of imparting good handleability to the film for sealing. The content of the epoxy resin may be 5% by mass or more, or may be 6% by mass or more, based on the total mass of the component (D). On the other hand, from the viewpoint of suppressing excessive stickiness on the surface of the film, the total mass of the components (A), (B), (C) and (D) is used as a reference at 25 ° C. The content of the liquid epoxy resin may be 20% by mass or less, may be 15% by mass or less, or may be 11% by mass or less. In addition, when the film for sealing contains the component (E), the component (A), the component (B), the component (C), the component (D), and (E) are provided from the viewpoint of imparting good handleability to the film for sealing. The content of the epoxy resin which is liquid at 25 ° C may be 5% by mass or more, or may be 6% by mass or more based on the total mass of the components. On the other hand, from the viewpoint of suppressing excessive adhesion of the surface of the film, based on the total mass of the component (A), the component (B), the component (C), the component (D), and the component (E), The content of the epoxy resin which is liquid at 25 ° C may be 20% by mass or less, may be 15% by mass or less, or may be 11% by mass or less.

(B) hardener

The curing agent is not particularly limited as long as it is a curing agent having two or more functional groups capable of reacting with a glycidyl group in one molecule. Examples of the functional group reactive with the propylene group include a phenolic hydroxyl group, an amine group, and an acid anhydride (phthalic anhydride or the like). Examples of the component (B) include a phenol resin, an acid anhydride, an imidazole compound, and an aliphatic amine. (B) The components may be used singly or in combination of two or more.

The phenol resin is not particularly limited as long as it is a phenol resin having two or more phenolic hydroxyl groups in one molecule, and a known phenol resin can be used. Examples of the phenol resin include phenols such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A, and bisphenol F; or α-naphthol and β-naphthol. a resin obtained by condensation or co-condensation of a naphthol such as dihydroxynaphthalene with an aldehyde such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde or salicylaldehyde under an acidic catalyst; a biphenyl skeleton type phenol resin; P-xylylene modified phenol resin, m-xylylene-p-xylylene modified phenol resin, melamine modified phenol resin, terpene modified phenol resin, dicyclopentadiene modified phenol resin, cyclopentane Diene modified phenol resin, polycyclic aromatic ring modified phenol resin, benzene dimethyl modified naphthol resin. The phenol resin may be used singly or in combination of two or more.

As the phenol resin, a commercially available phenol resin can also be used. Commercially available phenol resins include, for example, Phenolite LF2882, Phenolite TD-2090, Phenolite TD-2149, Phenolite VH-4150, Phenolite VH-4170, and products manufactured by Mitsui Chemicals, Inc. Name: XLC-LL, XLC-4L, Nippon Steel & Sumitomo Metal Chemical Co., Ltd. Trade name: SN-100, SN-300, SN-400, and the product name of Air-Water Co., Ltd.: SKResin HE910. These phenol resins may be used alone or in combination of two or more.

From the viewpoint of reducing the unreacted (A) component and (B) component, the content of the (B) component may be 50 to 75 parts by mass, and may be 55 to 60 mass, relative to 100 parts by mass of the component (A). The portion may also be 60 to 65 parts by mass.

The ratio of the component (A) to the component (B) as the ratio of the equivalent of the epoxy group of the component (A) to the equivalent of the functional group capable of reacting with the epoxypropyl group in the component (B) (in the epoxy The equivalent of the epoxy propyl group in the resin / the equivalent of the functional group capable of reacting with the epoxy propyl group in the curing agent may be 0.7 to 2.0, and may be 0.8 to 1.8 or 0.9 to 1.7. When the ratio is in the above range, the unreacted component (A) or component (B) is reduced, and when the film for sealing is cured, the physical properties of the desired cured film tend to be easily obtained.

(C) Elastomer

The (C) elastomer is preferably one or more elastomers selected from the group consisting of butadiene rubber and silicone rubber from the viewpoint of dispersibility and solubility. Examples of the component (C) include styrene-butadiene particles, an anthracene oxygen powder, a ruthenium oxide oligomer, and a ruthenium oxide rubber obtained by modifying a resin with a polyoxyxylene resin. These may be used alone or in combination of two or more. In the present embodiment, It is preferred to contain a core-shell type particle which has a skeleton derived from butadiene or helium oxygen as a block copolymer or a graft copolymer.

Among the commercially available (C) components, there are also products which are not elastomer monomers but are previously dispersed in a liquid epoxy resin, and these can be used without problems. The product in which the elastomer is dispersed in the liquid epoxy resin in advance is, for example, a product name: MX-136, MX-217, MX-267, MX-965, etc., manufactured by KANEKA CORPORATION.

The content of the component (C) may be 0.5 to 7.0% by mass, and may be 1.0 to 6.0% by mass based on the total mass of the component (A), the component (B), the component (C), and the component (D). It is 1.0 to 5.7 mass%, and may be 1.0 to 4.6% by mass. When the content of the component (C) is within the above range, when the electronic component such as a semiconductor element is sealed by the sealing film to form a sealed molded article and cured, the amount of warpage of the cured body can be sufficiently suppressed, and the electronic component can be continuously continued. Form a line redistribution layer. When the resin film for sealing contains the component (E), the component (A), (B), (C), (D) and (E) are based on the total mass of the component (C). The content may be 0.5 to 7.0% by mass, may be 1.0 to 6.0% by mass, may be 1.0 to 5.7% by mass, or may be 1.0 to 4.6% by mass. When the content of the component (C) is within the above range, when the electronic component such as a semiconductor element is sealed by the sealing film and the sealed molded article is cured, the amount of warpage of the cured body can be sufficiently suppressed, and Continue to form a line redistribution layer.

When the component (C) is a particle, the average particle diameter thereof is not particularly limited and can be used. On eWLB (embedded wafer level ball gate array, In the use of the embedded wafer level ball grid array or the like, the average particle diameter of the component (C) may be 50 μm or less, or may be 20 μm or less, or 5.0 μm or less. Further, from the viewpoint of dispersibility, the average particle diameter of the component (C) may be 0.05 μm or more, may be 0.1 μm or more, may be 0.5 μm or more, or may be 1.0 μm or more.

(D) Inorganic filler

As the (D) inorganic filler, a conventional inorganic filler can be used, and it is not limited to a specific material. Examples of the component (D) include barium sulfate, barium titanate, amorphous ceria, crystalline ceria, molten ceria, spheroidal ceria, talc, clay, magnesium carbonate, and calcium carbonate. , alumina, aluminum hydroxide, tantalum nitride, aluminum nitride. As the component (D), it is easy to improve the dispersibility in the resin and to easily control the precipitation in the varnish depending on the surface modification, and since it has a small coefficient of thermal expansion, it is easy to obtain desired properties of the cured film. It can also be cerium oxide.

(D) The composition may also be surface-modified, and the manner of surface modification is not particularly limited. For example, the surface modification is simple, and the types of functional groups are abundant, and the desired characteristics can be easily imparted. The way of mixing. Examples of the decane coupling agent include alkyl decane, alkoxy decane, vinyl decane, epoxy decane, amino decane, acryl decane, methacryl decane, thiodecane, and thioether. Decane, isocyanatodecane, thiodecane, styryldecane, alkylchlorodecane, and the like.

Examples of the decane coupling agent include methyltrimethoxydecane, dimethyldimethoxydecane, trimethylmethoxydecane, and methyltriethyl. Oxydecane, methyltriphenoxydecane, ethyltrimethoxydecane, n-propyltrimethoxydecane, diisopropyldimethoxydecane, isobutyltrimethoxydecane, diisobutyl Dimethoxydecane, isobutyltriethoxydecane, n-hexyltrimethoxydecane, n-hexyltriethoxydecane, cyclohexylmethyldimethoxydecane, n-octyltriethoxy Decane, n-dodecylmethoxydecane, phenyltrimethoxydecane, diphenyldimethoxydecane, triphenylstanol, methyltrichlorodecane, dimethyldichlorodecane, trimethyl Chlorodecane, n-octyldimethylchlorodecane, tetraethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-(2-amino group Ethyl)aminopropyltrimethoxydecane, 3-(2-aminoethyl)aminopropylmethyldimethoxydecane, 3-phenylaminopropyltrimethoxydecane, 3-ring Oxypropoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 3-glycidoxypropyltriethoxydecane, 3-epoxypropoxy Propylmethyldiethoxydecane, bis(3-(triethoxy) Alkyl)propyl)disulfide, bis(3-(triethoxydecyl)propyl)tetrasulfide, vinyltriethoxydecane, vinyltrimethoxydecane, vinyltriethoxy Base decane, vinyl triisopropoxy, allyl trimethoxy decane, diallyldimethyl decane, 3-methyl propylene methoxy propyl trimethoxy decane, 3-methyl propylene oxime Propyl propyl dimethoxy decane, 3-methyl propylene methoxy propyl triethoxy decane, 3-hydrothiopropyl trimethoxy decane, 3-hydrothiopropyl methyl dimethyl Oxydecane, 3-hydrothiopropyltriethoxydecane, N-(1,3-dimethylbutylidene)-3-aminopropyltriethoxydecane, aminodecane, and the like. These decane coupling agents may be used alone or in combination of two or more.

The content of the component (D) may be 65 to 95% by mass, and may be 75 to 90% by mass based on the total mass of the component (A), the component (B), the component (C), and the component (D). It can be 80 to 90% by mass. When the content of the component (D) is 65 mass% or more, the thermal expansion coefficient of the film for sealing can be effectively reduced, and the warpage of the semiconductor device or the electronic component device tends to be small. When the content of the component (D) is 95% by mass or less, the cracking of the film for sealing or the increase in the melt viscosity of the film for sealing tends to be suppressed in the drying step at the time of coating. This tendency is more intense when the content of the component (D) is 90% by mass or less. In addition, the content of the component (D) may be 65 mass% or more, and may be 70 masses, from the viewpoint of reducing the difference in the thermal expansion ratio between the film for sealing and the body to be sealed and making the warpage of the hardened body smaller. % or more may be 80% by mass or more. Further, when the film for sealing contains the component (E), based on the total mass of the component (A), the component (B), the component (C), the component (D) and the component (E), the component (D) The content may be 65 to 95% by mass, may be 75 to 90% by mass, or may be 80 to 90% by mass. When the content of the component (D) is 65 mass% or more, the thermal expansion coefficient of the film for sealing can be effectively reduced, and the warpage of the semiconductor device or the electronic component device tends to be small. When the content of the component (D) is 95% by mass or less, in the drying step at the time of coating, the crack of the sealing film or the increase in the melt viscosity of the film for sealing tends to be suppressed. This tendency is more intense when the content of the component (D) is 90% by mass or less. Moreover, from the viewpoint of reducing the difference in the thermal expansion ratio between the film for sealing and the body to be sealed, and making the warpage of the hardened body smaller, (D) component The content may be 65 mass% or more, may be 70 mass% or more, or may be 80 mass% or more.

The average particle diameter of the component (D) may be from 0.01 μm to 50 μm, may be from 0.1 μm to 25 μm, or may be from 0.3 μm to 10 μm. When the average particle diameter is 0.01 μm or more, aggregation of the inorganic filler is suppressed, and dispersion of the inorganic filler tends to be easy. On the other hand, when the average particle diameter is 50 μm or less, the precipitation of the inorganic filler in the varnish is suppressed, and the production of the film for sealing tends to be easy. The average particle diameter is a particle diameter of 50% when the total volume of the particles is set to 100%, and when the cumulative frequency distribution curve is generated based on the particle diameter, the laser refraction method can be used. The measurement is performed by a particle size distribution measuring apparatus or the like which is carried out.

(E) hardening accelerator

The film for sealing of the present embodiment may further contain (E) a curing accelerator. The (E) hardening accelerator may be used without particular limitation, and may be an amine-based or phosphorus-based hardening accelerator. Examples of the amine-based curing accelerator include an imidazole compound, an aliphatic amine, an aromatic amine, a modified amine, and a polyamide resin. Examples of the phosphorus-based hardening accelerator include organic phosphorus compounds such as a phosphine oxide, a phosphonium salt, and a diphosphine. Among these hardening accelerators, the component (E) may be an imidazole compound from the viewpoint of having a large number of derivatives and easily obtaining a desired activation temperature.

The content of the (E) component may be 0.01% by mass to 5% by mass based on the total mass of the component (A) and the component (B), and may be 0.1% by mass to 3% by mass, and may be 0.3% by mass to 1.5% by mass. quality%, It may be 0.3% by mass to 1.5% by mass. When the content of the component (E) is 0.01% by mass or more, a sufficient hardening promoting effect is easily obtained. On the other hand, when the content of the component (E) is 5% by mass or less, the progress of the curing during the drying step at the time of application or during storage is suppressed, and the film for sealing is broken or the viscosity of the film is increased. The occurrence of molding failure tends to decrease.

(F) organic solvent

The film for sealing of the present embodiment can further contain (F) an organic solvent (hereinafter referred to as a component (F)). The (F) component can use a conventional organic solvent. The component (F) is preferably an organic solvent capable of dissolving components other than the component (D), and examples thereof include aliphatic hydrocarbons, aromatic hydrocarbons, terpenes, halogens, esters, ketones, and alcohols. , aldehydes. The component (F) may be an ester, a ketone or an alcohol from the viewpoint of a small environmental load and easy dissolution of the component (A) and the component (B). As the component (F), among these components, a ketone may be used from the viewpoint of particularly easily dissolving the component (A) and the component (B). The ketones may be acetone, methyl ethyl ketone or methyl isobutyl ketone from the viewpoint of less volatilization at room temperature and easy removal during drying.

The content of the component (F) contained in the film for sealing may be 0.2% by mass to 1.5% by mass, or may be 0.3% by mass to 1% by mass based on the total mass of the film for sealing. The content of the component (F) is based on the total mass of the film for sealing, and when it is 0.2% by mass or more, the occurrence of defects such as film breakage can be suppressed, and the lowest melt viscosity can be suppressed to a low level. Can get good embedding Sexual tendency. On the other hand, when the content of the component (F) is less than 1.5% by mass based on the total mass of the film for sealing, the adhesion of the film for sealing is suppressed, and good film handleability can be obtained. It is difficult to cause a problem such as foaming due to volatilization of an organic solvent during thermal curing. The content of the component (F) contained in the film for sealing can be calculated by the method in the examples of the present specification.

The film for sealing of the present embodiment can further use other additives insofar as the effects of the present invention are not impaired. Specific examples of such an additive include a pigment, a dye, a releasing agent, an oxidation preventing agent, and a surface tension adjusting agent. Further, in order to improve the dispersibility and solubility of each of the above components, eucalyptus oil may be contained.

The film for sealing of this embodiment can be manufactured in the following manner. The above-mentioned (A) component, (B) component, (C) component and (D) component, and (E) component and additive are added as needed, and mixed into (F) an organic solvent to prepare a varnish. The method of mixing is not particularly limited, and for example, a mill, a stirrer, or a stirring blade can be used. The component (F) can dissolve or disperse the component (A), the component (B), the component (C) and the component (D) in the present embodiment to form a varnish, or can assist the above component to become a varnish. Further, when the film for sealing contains the component (E), the component (F) can dissolve or disperse the component (A), the component (B), the component (C), the component (D) and the component (E) in the present embodiment. It becomes a varnish or can be used as a varnish to assist the above ingredients.

The varnish produced in the above manner is applied to a film-shaped support and then dried by heating by a hot air drying method or the like.

As the film-shaped support, for example, a polymer film, a metal foil, or the like can be used.

Examples of the polymer film include a polyolefin film such as a polyethylene film, a polypropylene film, or a polyvinyl chloride film; a polyester film such as a polyethylene terephthalate film; a polycarbonate film and cellulose acetate. Film, tetrafluoroethylene film, etc. Examples of the metal foil include copper foil and aluminum foil.

The thickness of the film-shaped support is not particularly limited, and may be 2 to 200 μm from the viewpoint of workability and dryness. When the thickness of the film-shaped support is 2 μm or more, it is possible to suppress the occurrence of breakage during coating or to suppress the occurrence of defects due to the weight of the varnish. When the thickness of the support is 200 μm or less, it is mainly in a dryer capable of hot-air drying both the coated surface and the back surface, and it is easy to suppress the occurrence of a problem that the drying of the solvent in the varnish is inhibited.

The method of coating used at the time of coating is not particularly limited, and for example, a comma coater (comma coater), a bar coater, a staple coater, and a roller coater can be used ( A coating device such as a roll coater, a gravure coater, or a die coater.

The method of heating and drying the varnish applied to the support is not particularly limited, and examples thereof include a hot air drying method. The conditions for heat drying include heating at 100 to 140 ° C for 5 to 20 minutes.

In the step of drying the applied varnish, the component (F) is removed to form the film for sealing of the present embodiment. Also, when the film for sealing is used When the component (F) is contained, the varnish can be dried so that the component (F) remaining in the film has the above content.

The film for sealing of the present embodiment may have a film thickness of 50 to 250 μm. In addition, the sealing film of the present embodiment can be laminated with a plurality of sheets to produce a film for sealing of more than 250 μm.

A layer for protection may be formed on the film for sealing which has been formed on the film-shaped support. The formation of a layer for protection on the film for sealing tends to improve handleability. When a layer for protection is formed on the film for sealing, for example, even if the film for sealing is wound up, it is possible to avoid the problem that the film for sealing adheres to the back surface of the film-shaped support.

As a layer for protection, for example, a polymer film or a metal film can be used. Examples of the polymer film include a polyolefin film such as a polyethylene film, a polypropylene film, or a polyvinyl chloride film; a polyester film such as a polyethylene terephthalate film; a polycarbonate film and cellulose acetate. Film, tetrafluoroethylene film, etc. Examples of the metal foil include copper foil and aluminum foil.

Next, a method of manufacturing the electronic component device using the film for sealing of the present 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 showing an embodiment of a method of manufacturing a semiconductor device. The method of the present embodiment includes an embedding step (Fig. 1(a) and Fig. 1(b)) in which the semiconductor element 20 is embedded in the sealing film 2, and a sealing in which the semiconductor element is embedded. a hardening step using a film hardening (Fig. 1(c)); the embedding step, The sealing film 10 with a support is opposed to the semiconductor element 20 (face to face), and the sealing film 2 is pressed onto the semiconductor element 20 while being heated, and the semiconductor element 20 is embedded in the sealing film 2 The film 10 for sealing with the support includes a support 1 and a film 2 for sealing provided on the support 1, and the semiconductor element 20, that is, the object to be embedded, is arranged and disposed on the temporary fixing material 40. On the substrate 30. In the present embodiment, the sealing element is obtained by sealing the semiconductor element by a lamination method, and further, an electronic component device including the semiconductor element 20 is obtained, and the semiconductor element is embedded in the sealing molding. The hardened body 2a formed by heat curing of the object. In addition to the above methods, the sealed molded article can also be obtained by compression molding.

The laminating machine to be used is not particularly limited, and examples thereof include a laminating machine such as a roller type or a balloon type. Among them, a vacuum-pressure air bag type laminator can be used from the viewpoint of embedding property.

The lamination temperature is usually carried out below the softening temperature of the support. The lamination temperature is preferably in the vicinity of the lowest melt viscosity of the film for sealing. The pressure at the time of lamination may vary depending on the size and density of the semiconductor element or the electronic component to be embedded, and may be performed 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 and may be 20 to 600 seconds, and may be 30 to 300 seconds or 40 to 120 seconds.

The hardening can be carried out, for example, under an atmospheric environment or an inert gas atmosphere. The curing temperature is not particularly limited and may be 80 to 280 ° C, and may be 100 to 240 ° C or 120 to 200 ° C. When the curing temperature is 80° C. or higher, the curing of the film for sealing can be sufficiently performed, and the occurrence of defects can be more effectively suppressed. When the hardening temperature is 280 ° C or lower, there is a tendency to more effectively suppress thermal damage to other materials. The hardening time is not particularly limited and may be 30 to 600 minutes, and may be 45 to 300 minutes or 60 to 240 minutes. As long as the hardening time is within these ranges, the hardening of the film for sealing can be sufficiently performed, and better production efficiency can be obtained. Further, the curing conditions may be combined with a plurality of conditions.

As described above, a suitable embodiment of the film for sealing and the electronic component device of the present invention has been described. However, the present invention is not limited to the above-described embodiments, and may be appropriately changed without departing from the spirit and scope of the invention. As an electronic component other than a semiconductor element, for example, it can also be applied to a circuit board material.

[Examples]

Hereinafter, the present invention will be described in more detail based on the examples, but the present invention is not limited to the examples.

In order to produce a film for sealing, the following components were prepared.

(Component A: Epoxy resin)

Epoxy Resin A1: Bisphenol F-type epoxy resin (trade name: Grade 806, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 160, liquid at 25 ° C)

Epoxy Resin A2: a polyfunctional solid epoxy resin containing a naphthalene skeleton (trade name: EXA-4750, manufactured by DIC Corporation, epoxy equivalent: 182)

Epoxy resin A3 (elastomer C4): bisphenol F-type epoxy resin containing butadiene elastomer (trade name: MX-136, butadiene elastomer, manufactured by KANEKA Co., Ltd.) Content of 25% by mass, liquid at 25 ° C)

Epoxy resin A4 (elastomer C5): bisphenol F type epoxy resin containing a butadiene elastomer and bisphenol A type epoxy resin (trade name: MX-made by KANEKA Co., Ltd.) having an average particle diameter of 0.2 μm 267, butadiene elastomer content of 37%, liquid at 25 ° C)

Epoxy resin A5 (elastomer C6): bisphenol F type epoxy resin containing cerium oxide elastomer and bisphenol A type epoxy resin (trade name: MX-965, manufactured by KANEKA Co., Ltd.) , 矽 oxygen elastomer content of 25%, liquid at 25 ° C)

Epoxy resin A6 (elastomer C7): phenol novolac type epoxy resin containing butadiene elastomer (trade name: MX-217, manufactured by KANEKA Co., Ltd., butadiene elastomer content) 25 mass%, liquid at 25 ° C)

(Component B: hardener)

Hardener B1: phenol novolac (trade name: Asahi Organic Materials Co., Ltd.: PAPS-PN2, phenolic hydroxyl equivalent: 104)

Hardener B2: Naphthalene glycol novolac (trade name: SN-395, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.)

(Component C: Elastomer)

Elastomer C1: 矽 oxygen powder (trade name: Shin-Etsu Chemical Co., Ltd., trade name: KMP-605, average particle size 2 μm)

Elastomer C2: 矽 oxygen powder (trade name: Shin-Etsu Chemical Co., Ltd., trade name: KMP-600, average particle size 5 μm)

Elastomer C3: 矽 oxygen powder (trade name: Shin-Etsu Chemical Co., Ltd., trade name: KMP-602, average particle size 30 μm)

(D component: inorganic filler)

Inorganic filler D1: cerium oxide (trade name: FB-5SDC, manufactured by Denki Kagaku Kogyo Co., Ltd., phenylamino decane treatment, average particle diameter: 5.0 μm).

Inorganic filler D2: cerium oxide (trade name: SFP-20M, manufactured by Electric Chemical Industry Co., Ltd., phenylamino decane treatment, average particle diameter: 0.5 μm).

Inorganic filler D3: cerium oxide (trade name: SX-E2, manufactured by Admatech Co., Ltd., phenylamino decane treatment, average particle diameter: 5.8 μm).

(E component: hardening accelerator)

Hardening accelerator E: imidazole (trade name: 2P4MZ, manufactured by Shikoku Chemical Industry Co., Ltd.).

(F component: organic solvent)

Organic solvent F: methyl ethyl ketone

[Production of film for sealing]

(Example 1)

673.2 g of the organic solvent F was placed in a 10 L polyethylene container, and 3962 g of the inorganic filler D3 was further added, and the inorganic filler D3 was dispersed by a stirring blade. In this dispersion, add 100g Epoxy resin A1, 70g which is liquid at 25 ° C, liquid epoxy resin A2 at 180 ° C, 180 g of bisphenol F epoxy resin A3 containing 0.1 μm butadiene elastomer And 183 g of the hardener B1 which is not liquid at 25 ° C, and is stirred. When it was visually confirmed that the hardener B1 which was not liquid at 25 ° C was dissolved, 2.1 g of the hardening accelerator E was added to the dispersion, and the stirring was further continued for 1 hour. This dispersion liquid was filtered through a sieve made of nylon #200 (mesh opening 75 μm), and the filtrate was taken up to obtain a varnish-like epoxy resin composition. This varnish-like epoxy resin composition was applied onto a support (polyethylene terephthalate having a thickness of 38 μm) under the following conditions using a coater to prepare a seal having a film thickness of 185 μm, 200 μm, and 225 μm. film.

‧ Coating head style: comma

‧ Coating and drying speed: 1m / minute

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

Then, the film for sealing having a film thickness of 185 μm and 225 μm was superposed by connecting the films for sealing of the two sheets, and bonded by a vacuum press laminator under the following conditions.

‧Laminating machine device: Vacuum pressure laminating machine (trade name: MVLP-500, manufactured by Co., Ltd.)

‧Lamination temperature: 90 ° C

‧Lamination pressure: 0.15MPa

‧ Vacuum time: 10 seconds

‧Lamination time: 5 seconds

A film for sealing having a film thickness of 370 μm and 450 μm was prepared in the above manner.

(Example 2)

1945 g of the organic solvent F was placed in a 10 L polyethylene container, and then 9700 g of inorganic filler D1, 1712 g of D2 was added, and the inorganic fillers D1 and D2 were dispersed by a stirring blade. To the dispersion, 134 g of an epoxy resin A2 which was not liquid at 25 ° C, and 1,206 g of a bisphenol F type epoxy resin A3 and 106 g of a butadiene elastomer having a particle diameter of 0.1 μm were added. C1 and 684 g were not liquid hardener B2 at 25 ° C and were stirred. After visually confirming that the hardener B2 which was not liquid at 25 ° C was dissolved, 5.4 g of the hardening accelerator E was added to the dispersion, and the stirring was further continued for 1 hour. This dispersion liquid was filtered through a sieve made of nylon #200 (mesh opening 75 μm), and the filtrate was taken up to obtain a varnish-like epoxy resin composition. This varnish-like epoxy resin composition was applied onto a support (polyethylene terephthalate having a thickness of 38 μm) under the following conditions using a coater to prepare a seal having a film thickness of 185 μm, 200 μm, and 225 μm. film.

‧ Coating head style: comma

‧ Coating and drying speed: 1m / minute

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

Thereafter, in the same manner as in Example 1, a film for sealing having a film thickness of 370 μm and 450 μm was prepared.

(Example 3)

1217 g of the organic solvent F was placed in a 10 L polyethylene container, 6070 g of inorganic filler D1, 1071 g of D2 was further added, and the inorganic fillers D1 and D2 were dispersed by a stirring blade. To the dispersion, 808 g of a bisphenol F-type epoxy resin A3 having a particle diameter of 0.2 μm butadiene elastomer, and 90 g of a styrene-based phenol novolak-type epoxy resin A6 and 66 g of ruthenium were added. The oxygen powders C1 and 369g were not in the form of a liquid hardener B2 at 25 ° C and were stirred. When it was visually confirmed that the hardener B2 which was not liquid at 25 ° C was dissolved, 2.7 g of the hardening accelerator E was added to the dispersion, and the stirring was further continued for 1 hour. This dispersion liquid was filtered through a sieve made of nylon #200 (mesh opening 75 μm), and the filtrate was taken up to obtain a varnish-like epoxy resin composition. This varnish-like epoxy resin composition was applied onto a support (polyethylene terephthalate having a thickness of 38 μm) under the following conditions using a coater to prepare a seal having a film thickness of 185 μm, 200 μm, and 225 μm. film.

‧ Coating head style: comma

‧ Coating and drying speed: 1m / minute

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

Thereafter, in the same manner as in Example 1, a film for sealing having a film thickness of 370 μm and 450 μm was prepared.

(Example 4)

100 g of the organic solvent F was placed in a 1 L polyethylene container, 713 g of inorganic filler D1, 126 g of D2 was further added, and the inorganic fillers D1 and D2 were dispersed by a stirring blade. In this dispersion Among them, 104 g of a bisphenol F-type epoxy resin A3 containing a particle diameter of 0.1 μm butadiene elastomer and 52 g of a hardener B2 which was not liquid at 25 ° C were added and stirred. After visually confirming that the hardener B2 which was not liquid at 25 ° C was dissolved, 0.4 g of the hardening accelerator E was added to the dispersion, and the stirring was further continued for 1 hour. This dispersion liquid was filtered through a sieve made of nylon #200 (mesh opening 75 μm), and the filtrate was taken up to obtain a varnish-like epoxy resin composition. This varnish-like epoxy resin composition was applied onto a support (polyethylene terephthalate having a thickness of 38 μm) under the following conditions using a coater to prepare a seal having a film thickness of 185 μm, 200 μm, and 225 μm. film.

‧ Coating head style: comma

‧ Coating and drying speed: 1m / minute

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

Thereafter, as in Example 1, a film for sealing having a film thickness of 370 μm and 450 μm was prepared.

(Example 5)

100 g of the organic solvent F was placed in a 1 L polyethylene container, 713 g of inorganic filler D1, 126 g of D2 was further added, and the inorganic fillers D1 and D2 were dispersed by a stirring blade. To the dispersion, 34 g of an epoxy resin A1 which was liquid at 25 ° C and 71 g of a bisphenol F-type epoxy resin A4 containing a butadiene elastomer having a particle diameter of 0.2 μm were added and stirred. When it was visually confirmed that the hardener B2 which was not liquid at 25 ° C was dissolved, 0.4 g of a hardening accelerator was added to the dispersion. E, further stirring was continued for 1 hour. This dispersion liquid was filtered through a sieve made of nylon #200 (mesh opening 75 μm), and the filtrate was taken up to obtain a varnish-like epoxy resin composition. This varnish-like epoxy resin composition was applied onto a support (polyethylene terephthalate having a thickness of 38 μm) under the following conditions using a coater to prepare a seal having a film thickness of 185 μm, 200 μm, and 225 μm. film.

‧ Coating head style: comma

‧ Coating and drying speed: 1m / minute

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

3.3m, 140°C/3.3m.

Thereafter, in the same manner as in Example 1, a film for sealing having a film thickness of 370 μm and 450 μm was prepared.

(Example 6)

41 g of the organic solvent F was placed in a 1 L polyethylene container, 204 g of inorganic filler D1, 36 g of D2 was further added, and the inorganic fillers D1 and D2 were dispersed by a stirring blade. To this dispersion, 0.2 g of epoxy resin A1, 30 g of a bisphenol F-type epoxy resin containing a silicone elastomer at 25 ° C and a bisphenol A type epoxy resin (epoxy resin) were added. A5), and 15 g of the hardener B2 which is not liquid at 25 ° C, and stirred. After visually confirming that the hardener B2 which was not liquid at 25 ° C was dissolved, 0.1 g of the hardening accelerator E was added to the dispersion, and stirring was further continued for 1 hour. The dispersion was filtered through a sieve made of nylon #200 (mesh 75 μm), and the filtrate was taken to obtain a varnish-like ring. Oxygen resin composition. This varnish-like epoxy resin composition was applied onto a support (polyethylene terephthalate having a thickness of 38 μm) under the following conditions using a coater to prepare a seal having a film thickness of 185 μm, 200 μm, and 225 μm. film.

‧ Coating head style: comma

‧ Coating and drying speed: 1m / minute

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

Thereafter, in the same manner as in Example 1, a film for sealing having a film thickness of 370 μm and 450 μm was prepared.

(Example 7)

100 g of the organic solvent F was placed in a 1 L polyethylene container, 713 g of inorganic filler D1, 126 g of D2 was further added, and the inorganic fillers D1 and D2 were dispersed by a stirring blade. To the dispersion, 78 g of an epoxy resin A1 and 26 g of a liquid epoxy resin C2 at 25 ° C and 53 g of a hardener B2 which was not liquid at 25 ° C were added and stirred. When it was visually confirmed that the hardener B2 which was not liquid at 25 ° C was dissolved, 0.3 g of the hardening accelerator E was added to the dispersion, and the stirring was further continued for 1 hour. This dispersion liquid was filtered through a sieve made of nylon #200 (mesh opening 75 μm), and the filtrate was taken up to obtain a varnish-like epoxy resin composition. This varnish-like epoxy resin composition was applied onto a support (polyethylene terephthalate having a thickness of 38 μm) under the following conditions using a coater to prepare a seal having a film thickness of 185 μm, 200 μm, and 225 μm. film.

‧ Coating head style: comma

‧ Coating and drying speed: 1m / minute

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

Thereafter, in the same manner as in Example 1, a film for sealing having a film thickness of 370 μm and 450 μm was prepared.

(Example 8)

100 g of the organic solvent F was placed in a 1 L polyethylene container, 713 g of inorganic filler D1, 126 g of D2 was further added, and the inorganic fillers D1 and D2 were dispersed by a stirring blade. To the dispersion, 78 g of epoxy resin A1 and 26 g of liquid epoxy resin C3 at 25 ° C and 53 g of a hardener B2 which was not liquid at 25 ° C were added and stirred. When it was visually confirmed that the hardener B2 which was not liquid at 25 ° C was dissolved, 0.3 g of the hardening accelerator E was added to the dispersion, and the stirring was further continued for 1 hour. This dispersion liquid was filtered through a sieve made of nylon #200 (mesh opening 75 μm), and the filtrate was taken up to obtain a varnish-like epoxy resin composition. This varnish-like epoxy resin composition was applied onto a support (polyethylene terephthalate having a thickness of 38 μm) under the following conditions using a coater to prepare a seal having a film thickness of 185 μm, 200 μm, and 225 μm. film.

‧ Coating head style: comma

‧ Coating and drying speed: 1m / minute

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

Thereafter, in the same manner as in Example 1, a film for sealing having a film thickness of 370 μm and 450 μm was prepared.

(Example 9)

100 g of the organic solvent F was placed in a 1 L polyethylene container, 713 g of inorganic filler D1, 126 g of D2 was further added, and the inorganic fillers D1 and D2 were dispersed by a stirring blade. To the dispersion, 78 g of the epoxy resins C1 and 53 g of the epoxy resins A1 and 26 g which were liquid at 25 ° C were added without a liquid hardener B2 at 25 ° C, and stirred. When it was visually confirmed that the hardener B2 which was not liquid at 25 ° C was dissolved, 0.3 g of the hardening accelerator E was added to the dispersion, and the stirring was further continued for 1 hour. This dispersion liquid was filtered through a sieve made of nylon #200 (mesh opening 75 μm), and the filtrate was taken up to obtain a varnish-like epoxy resin composition. This varnish-like epoxy resin composition was applied onto a support (polyethylene terephthalate having a thickness of 38 μm) under the following conditions using a coater to prepare a seal having a film thickness of 185 μm, 200 μm, and 225 μm. film.

‧ Coating head style: comma

‧ Coating and drying speed: 1m / minute

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

Thereafter, in the same manner as in Example 1, a film for sealing having a film thickness of 370 μm and 450 μm was prepared.

(Comparative Example 1)

406.8 g of the organic solvent F was placed in a 10 L polyethylene container, 2394 g of the inorganic filler D3 was further added, and the inorganic filler D3 was dispersed by a stirring blade. In this dispersion, 160 g of epoxy resin A1 and 40 g which were liquid at 25 ° C were added, and the epoxy resins A 2 and 122 g which were not liquid at 25 ° C were not liquid hardened at 25 ° C. Agent B1 and stirred. When it was visually confirmed that the hardener B1 which was not liquid at 25 ° C was dissolved, 1.2 g of the hardening accelerator E was added to the dispersion, and the stirring was further continued for 1 hour. This dispersion liquid was filtered through a sieve made of nylon #200 (mesh opening 75 μm), and the filtrate was taken up to obtain a varnish-like epoxy resin composition. This varnish-like epoxy resin composition was applied onto a support (polyethylene terephthalate having a thickness of 38 μm) under the following conditions using a coater to prepare a seal having a film thickness of 185 μm, 200 μm, and 225 μm. film.

‧ Coating head style: comma

‧ Coating and drying speed: 1m / minute

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

Thereafter, in the same manner as in Example 1, a film for sealing having a film thickness of 370 μm and 450 μm was prepared.

(Comparative Example 2)

1329 g of the organic solvent F was placed in a 10 L polyethylene container, and then 7821 g of the inorganic filler D3 was added, and the inorganic filler D3 was dispersed by a stirring blade. In this dispersion, 382 g of epoxy resin A1, 134g which was liquid at 25 ° C was not present at 25 ° C. Liquid epoxy resin A2, 111g bisphenol F type epoxy resin containing a bisphenol F type epoxy resin A3 and 43 g of a butadiene elastomer having a particle diameter of 0.1 μm, and a bisphenol F type epoxy resin containing a siloxane elastomer and a bisphenol A type The epoxy resin (epoxy resin A5) and 382 g of the hardener B1 which is not liquid at 25 ° C were stirred. After visually confirming that the hardener B1 which was not liquid at 25 ° C was dissolved, 4.0 g of the hardening accelerator E was added to the dispersion, and stirring was further continued for 1 hour. This dispersion liquid was filtered through a sieve made of nylon #200 (mesh opening 75 μm), and the filtrate was taken up to obtain a varnish-like epoxy resin composition. This varnish-like epoxy resin composition was applied onto a support (polyethylene terephthalate having a thickness of 38 μm) under the following conditions using a coater to prepare a seal having a film thickness of 185 μm, 200 μm, and 225 μm. film.

‧ Coating head style: comma

‧ Coating and drying speed: 1m / minute

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

Thereafter, in the same manner as in Example 1, a film for sealing having a film thickness of 370 μm and 450 μm was prepared.

(Comparative Example 3)

100 g of the organic solvent F was placed in a 1 L polyethylene container, 713 g of inorganic filler D1, 126 g of D2 was further added, and the inorganic fillers D1 and D2 were dispersed by a stirring blade. To the dispersion, 93 g of an epoxy resin A1 which was liquid at 25 ° C and 64 g of a hardener B2 which was not liquid at 25 ° C were added and stirred. When After confirming that the hardener B2 which was not liquid at 25 ° C was dissolved, 0.4 g of the hardening accelerator E was added to the dispersion, and stirring was further continued for 1 hour. This dispersion liquid was filtered through a sieve made of nylon #200 (mesh opening 75 μm), and the filtrate was taken up to obtain a varnish-like epoxy resin composition. This varnish-like epoxy resin composition was applied onto a support (polyethylene terephthalate having a thickness of 38 μm) under the following conditions using a coater to prepare a seal having a film thickness of 185 μm, 200 μm, and 225 μm. film.

‧ Coating head style: comma

‧ Coating and drying speed: 1m / minute

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

Thereafter, in the same manner as in Example 1, a film for sealing having a film thickness of 370 μm and 450 μm was prepared.

The compositions of the films for sealing of the examples and the comparative examples are shown in Table 1.

Further, the content of the component (F) in the film for sealing was calculated in the following manner. The obtained film for sealing with a support was cut into a square sample having a side length of 5 cm. The sample was placed in an aluminum cup of pre-measured quality to measure the mass of the aluminum cup that had been placed in the sample. Next, the aluminum cup on which the sample was placed was placed in an oven at 180 ° C for 10 minutes, left at room temperature for 10 minutes, and then the mass of the aluminum cup on which the sample was placed was measured again. Next, according to the mass of the aluminum cup on which the sample is placed before or after heating, the mass of the square support body cut into a side length of 5 cm and the mass of the aluminum cup are separately subtracted, and the heat is obtained before heating and The quality of the film for sealing after heating. Then, the quality of the film for sealing before heating is reduced. The value obtained by the mass of the film for sealing after heating is the amount of the organic solvent contained in the film for sealing. Then, the ratio of the amount of the organic solvent to the mass of the film for sealing before heating is set to the content of the organic solvent.

[Table 1]

<Evaluation method>

(1) A method of evaluating the warpage of a cured product when the tantalum wafer is sealed by using a sealing film to form an eWLB package.

As the film for sealing, a film having a thickness of 370 μm which was formed by laminating two films for sealing having a thickness of 185 μm was used. A ruthenium wafer having a thickness of 350 μm on a stainless steel plate was packaged by a film for sealing in the following order to prepare an eWLB package having a size of 8 Å. The film for sealing produced by the method shown in the example was cut into a circular shape having a diameter of 20 cm. The support was entirely peeled off and placed on a crucible wafer on a stainless steel plate, and then the wafer was packaged under the following conditions using a compression molding apparatus to produce a sealed body. Fig. 2 is a view showing the arrangement of a germanium wafer in the present measurement system. On the stainless steel plate 50, a square tantalum wafer 60 having a side length of 7.3 mm and a square tantalum wafer 70 having a side length of 3 mm were disposed as shown in Fig. 2 .

‧Compression molding device: APIC YAMADA Co., Ltd. Trade name: WCM-300

‧Compression molding temperature: 140 ° C

‧Compression molding pressure: 2.5MPa

‧Compression molding time: 10 minutes

The resulting sealed body was cured under the following conditions to prepare a cured body.

‧Oven: Trade name made by ESPEC Co., Ltd.: SAFETY OVEN SPH-201

‧Oven temperature: 140 ° C

‧Time: 120 minutes

The amount of warpage of the completed hardened body was measured using the following apparatus.

‧ Warpage measuring machine name: COMS Co., Ltd. Product name: CP-500

‧ Warpage measurement laser light device name: KEYENCE Co., Ltd. trade name: LK-030

The center portion of the surface of the hardened body was set to 0 (reference point), and the height of the end portion was measured as the amount of warpage, and evaluated based on the following evaluation criteria.

○: Warpage amount ≦ 2.0mm

×: warpage amount>2.0 mm

(2) A method of attaching a film for sealing to a 12-inch silicon wafer and evaluating the warpage of the cured body during curing.

As the film for sealing, a film having a thickness of 200 μm was used. The film for sealing was laminated on a 12-inch tantalum wafer having a thickness of 800 μm according to the following procedure, and then the film for sealing was cured to obtain a sealed body. The lamination step was carried out under the following conditions.

‧Laminating machine device: Vacuum pressure laminating machine (trade name: MVLP-500, manufactured by Co., Ltd.)

‧Lamination temperature: 90 ° C

‧Lamination pressure: 0.5MPa

‧ Vacuum time: 30 seconds

‧Lamination time: 40 seconds

The resulting sealed body was cured under the following conditions to prepare a cured body.

‧Oven: Trade name made by ESPEC Co., Ltd.: SAFETY OVEN SPH-201

‧Oven temperature: 140 ° C

‧Time: 120 minutes

The amount of warpage of the produced hardened body was measured by a device below.

‧ Warpage measuring machine name: COMS Co., Ltd. Product name: CP-500

‧ Warpage measurement laser light device name: KEYENCE Co., Ltd. trade name: LK-030

The center portion of the surface of the hardened body was set to 0 (reference point), and the height of the end portion was measured as the amount of warpage, and evaluated based on the following evaluation criteria.

○: Warpage amount ≦ 2.0mm

×: warpage amount>2.0 mm

(3) Method for evaluating warpage of a hardened body formed by press-molding a film for sealing onto a tantalum wafer after press-forming and hardening the film for sealing

As the film for sealing, a film having a thickness of 450 μm which was formed by laminating two films for sealing having a thickness of 225 μm was used. The film for sealing was cut into a size of 120 mm × 10 mm, and placed on a tantalum wafer cut to a size of 120 mm × 10 mm and having a thickness of 725 μm, and pressed by press molding to obtain a sealed body. Press molding was carried out under the following conditions.

‧Repression device: MASADA Manufacturing Co., Ltd. Trade name: MH-50Y

‧ Pressing temperature: 140 ° C

‧ Fit pressure: 1.0Mpa

‧ suppression time: 20 minutes

The resulting sealed body was cured under the following conditions to prepare a cured body.

‧Oven: Trade name made by ESPEC Co., Ltd.: SAFETY OVEN SPH-201

‧Oven temperature: 140 ° C

‧Time: 120 minutes

The amount of warpage of the produced hardened body was measured by a device below.

‧ Warpage measuring machine name: COMS Co., Ltd. Product name: CP-500

‧ Warpage measurement laser light device name: KEYENCE Co., Ltd. trade name: LK-030

The center portion of the surface of the hardened body was set to 0 (reference point), and the height of the end portion was measured as the amount of warpage, and evaluated based on the following evaluation criteria.

○: Warpage amount ≦1.5mm

×: warpage amount>1.5 mm

<evaluation result>

From the results of Example 1 and Comparative Examples 1 and 2 shown in Table 2, it can be seen that as the elastomer component increases, the desired result can be obtained by evaluating the warpage of the cured body by the eWLB package. Again, from the results of Examples 2, 3 and Comparative Example 2, 12 twins The evaluation of the warpage of the hardened body by rounding can also obtain desired results by increasing the amount of the elastomer added.

From the results of Examples 4 to 9 and Comparative Example 3 shown in Table 3, the warpage of the hardened body can be improved regardless of the addition of any of the components of the elastomer. Also, we know that the oxygenated elastomer is more effective in reducing warpage than the butadiene elastomer. It is also known that in the oxirane elastomer, the smaller the particle size, the better the effect of lowering the warpage.

From the above results, it is known that 0.5 to 7.0% by mass of the elastomer component is added to the film for sealing based on the total mass of the component (A), the component (B), the component (C), and the component (D). Thereby, the amount of warpage of the hardened body can be suppressed.

Claims (7)

A film for sealing comprising: (A) an epoxy resin; (B) a hardener; (C) an elastomer selected from the group consisting of butadiene rubber and silicone rubber And (D) an inorganic filler; wherein the component (C) is based on the total mass of the component (A), the component (B), the component (C), and the component (D) The content is from 0.5 to 7.0% by mass. The film for sealing according to claim 1, wherein the component (A) is based on the total mass of the component (A), the component (B), the component (C), and the component (D). It contains 5% by mass or more of an epoxy resin which is liquid at 25 ° C. The film for sealing according to claim 1 or 2, further comprising (E) a curing accelerator. The film for sealing according to any one of claims 1 to 3, which contains 0.2 to 1.5% by mass of the organic solvent (F) based on the total mass of the film for sealing. The film for sealing according to any one of claims 1 to 4, wherein the total mass of the component (A), the component (B), the component (C), and the component (D) is used as a reference. The content of the component (D) is 65 mass% or more. The film for sealing according to any one of claims 1 to 5, wherein the film for sealing has a thickness of 50 to 250 μm. An electronic component device comprising: an electronic component; and a cured body of the film for sealing according to any one of claims 1 to 6, which seals the electronic component.