JP2020147758A - Resin composition - Google Patents

Abstract

To provide a resin composition having suppressed generation of warpage and suppressed expansion after curing, low in average linear thermal expansion coefficient and elastic modulus, an adhesive film, a circuit board with components, a semiconductor device using the resin composition and a manufacturing method of a sheet-like resin composition.SOLUTION: There is provided a resin composition containing (a) an elastomer, (b1) a liquid epoxy resin having an aromatic structure, (b2) a solid epoxy resin having the aromatic structure and (c) an inorganic filler, the content of (c) component is 50 mass% to 95 mass% based on 100 mass% of a nonvolatile component of the resin composition, elastic modulus at 23°C of a thermal cured article after thermally curing the resin composition at 180°C for 1 hour is 18 GPa or less and moisture permeability coefficient of a thermal cured article is 3 (g/mm/m2/24h) or more.SELECTED DRAWING: None

Description

The present invention relates to resin compositions. Further, the present invention relates to an adhesive film, a circuit board with built-in components, a semiconductor device, and a method for producing a sheet-like resin composition.

In recent years, the demand for small high-performance mobile terminals such as smartphones and tablet terminals (tablet PCs) has been increasing. Further miniaturization and higher functionality are required for semiconductor devices and the like used to make such high-performance mobile terminals function. As the structure of such a semiconductor device, for example, a multi-chip package in which two or more parts such as a semiconductor chip are encapsulated, or a plurality of multi-chip packages are bonded to each other and further integrally sealed. Package-on-package (PoP) composed of, wafer level package (WLP) or panel level package (PLP) that performs wiring, electrode formation, resin encapsulation, and packaging in the wafer / panel state, and further, chips. Attention is being paid to structures such as system-in-package (SiP) that are sealed in one package.

Further, a component-embedded circuit board has been proposed as a printed wiring board capable of miniaturization while increasing the mounting amount of components by incorporating components such as a semiconductor chip and a capacitor in an inner layer circuit board.

A resin that is a sealing material on a support in order to seal a component contained in a multi-chip package, a package-on package, a wafer level package, a panel level package, a system-in package, or a circuit board with a built-in component as described above. A sheet material provided with a composition layer may be used.

In such a conventional sheet material, the thickness of the resin composition layer may be insufficient to sufficiently seal the parts. Therefore, in order to increase the thickness of the resin composition layer, the resin composition layer is used. A method has been proposed in which the resin composition layers of the provided sheet materials are bonded to each other or the coating is repeated a plurality of times (for example, Patent Documents 1 and 2).

Japanese Unexamined Patent Publication No. 2012-25907 Japanese Unexamined Patent Publication No. 2015-61720

However, due to the thicker resin composition layer, swelling may occur between the resin composition layer and the substrate or the like after curing.

Further, in order to prevent the substrate from warping, the resin composition layer is required to have characteristics such as a low average linear thermal expansion coefficient (CTE) and a low elastic modulus, and all of these characteristics are satisfied. However, it was difficult to eliminate the swelling after curing. Further, if a large amount of an inorganic filler is contained in order to obtain these characteristics, the resin varnish may become unstable.

The present invention has been made to solve the above problems, and is a resin composition in which the generation of warpage and swelling after curing are suppressed, and the average linear thermal expansion coefficient and elastic coefficient are low; the resin composition is used. Provided are adhesive films, circuit boards with built-in components, semiconductor devices (particularly, multi-chip packages, package-on-packages, wafer-level packages, panel-level packages, system-in-packages, etc.), and methods for producing sheet-like resin compositions. There is.

That is, the present invention includes the following contents.
[1] A resin composition containing (a) an elastomer, (b1) a liquid epoxy resin having an aromatic structure, (b2) a solid epoxy resin having an aromatic structure, and (c) an inorganic filler.
The content of the component (c) is 50% by mass to 95% by mass when the non-volatile component of the resin composition is 100% by mass.
The elastic modulus of the thermosetting product obtained by thermally curing the resin composition at 180 ° C. for 1 hour at 23 ° C. is 18 GPa or less.
A resin composition having a moisture permeability coefficient of a thermosetting product of 3 (g / mm / m ² / 24h) or more.
[2] The resin according to [1], wherein the content of the component (a) is 30% by mass to 85% by mass when the non-volatile component of the resin composition excluding the component (c) is 100% by mass. Composition.
[3] In the powder rheometer measurement, the basic fluid energy (mJ / g) per 1 g of the component (c) is 6 to 6 under the condition C1 where the tip speed of the rotor blade is 100 mm / sec and the approach angle of the rotor blade is 5 °. 20. The resin composition according to [1] or [2].
[4] In the powder rheometer measurement, the basic fluid energy (mJ / g) per 1 g of the component (c) is 12 to 12 under the condition C2 where the tip speed of the rotor is 40 mm / sec and the approach angle of the rotor is 5 °. 27. The resin composition according to any one of [1] to [3].
[5] The component (a) is selected from a butadiene structural unit, a polysiloxane structural unit, a (meth) acrylate structural unit, an alkylene structural unit, an alkyleneoxy structural unit, an isoprene structural unit, an isobutylene structural unit, and a polycarbonate structural unit. The resin composition according to any one of [1] to [4], which has one or more structural units.
[6] The composition according to any one of [1] to [5], wherein the component (a) is at least one selected from a resin having a glass transition temperature of 25 ° C. or lower and a resin liquid at 25 ° C. Resin composition.
[7] The resin composition according to any one of [1] to [6], wherein the component (a) has a functional group capable of reacting with the component (b).
[8] The resin composition according to any one of [1] to [7], wherein the component (a) has an imide structural unit.
[9] The resin composition according to any one of [1] to [8], wherein the component (a) has a phenolic hydroxyl group.
[10] When the content of the component (b1) is B1 (mass%) and the content of the component (b2) is B2 (mass%), the relationship of B1> B2 is satisfied, according to [1] to [9]. The resin composition according to any one.
[11] The resin composition according to any one of [1] to [10], wherein the thermosetting product has a moisture permeability coefficient of 3 to 10 (g / mm / m ² / 24h).
[12] An adhesive film comprising a support and a temporary resin composition layer provided on the support and containing the resin composition according to any one of [1] to [11].
[13] A component-embedded circuit board including a sealing layer formed of a cured product of the resin composition according to any one of [1] to [11].
[14] A semiconductor device including a sealing layer formed of a cured product of the resin composition according to any one of [1] to [11].
[15] An adhesive film having (A) a support and a temporary resin composition layer containing the resin composition according to any one of [1] to [11] provided on the support. The process to prepare above and
(B) The step of superimposing the temporary resin composition layers of the adhesive film so as to be in contact with each other is included.
A method for producing a sheet-like resin composition, wherein the step (B) is performed only once or repeated two or more times to form a resin composition layer having a thickness of 400 μm to 900 μm.

According to the present invention, a resin composition in which warpage and swelling after curing are suppressed and the average linear thermal expansion coefficient and elastic modulus are low, an adhesive film using the resin composition, a circuit board with built-in components, and a semiconductor An apparatus and a method for producing a sheet-like resin composition can be provided.

Hereinafter, the resin composition of the present invention, a method for producing an adhesive film, a circuit board with built-in components, a semiconductor device, and a sheet-like resin composition using the resin composition will be described in detail.

[Resin composition]
The resin composition of the present invention contains (a) an elastomer, (b1) a liquid epoxy resin having an aromatic structure, (b2) a solid epoxy resin having an aromatic structure, and (c) an inorganic filler. The content of the component (c) is 50% by mass to 95% by mass when the non-volatile component of the resin composition is 100% by mass, and the resin composition is heat-cured at 180 ° C. for 1 hour. The elasticity of the heat-cured product at 23 ° C. is 18 GPa or less, and the moisture permeability coefficient of the heat-cured product is 3 (g / mm / m ² / 24h) or more.

From the viewpoint of suppressing the generation of warpage and swelling after curing, and lowering the average linear thermal expansion coefficient and elastic coefficient, the resin composition of the present invention comprises (a) an elastomer and (b1) an aromatic. It contains a liquid epoxy resin having a structure, (b2) a solid epoxy resin having an aromatic structure, and (c) an inorganic filler. The resin composition may further contain (d) a curing agent, (e) a curing accelerator, (f) a flame retardant, and (g) other additives, if necessary. Hereinafter, each component contained in the resin composition will be described in detail.

<(A) Elastomer>
The resin composition comprises (a) an elastomer. In the present invention, the elastomer means a flexible resin, and is not particularly limited, but for example, in the molecule, a butadiene structural unit, a polysiloxane structural unit, a (meth) acrylate structural unit, an alkylene structural unit, and an alkyleneoxy structural unit. , An isoprene structural unit, an isobutylene structural unit, and a resin that exhibits flexibility by having one or more structures selected from the polycarbonate structural unit. By including a flexible resin such as the component (a), the plating peel strength against copper and the like can be improved, and the occurrence of warpage and the like can be suppressed.

More specifically, the component (a) is a butadiene structural unit such as polybutadiene and hydrogenated polybutadiene, a polysiloxane structural unit such as silicone rubber, a (meth) acrylate structural unit, and an alkylene structural unit (preferably 2 to 2 carbon atoms). 15, more preferably 3 to 10 carbon atoms, still more preferably 5 to 6 carbon atoms), an alkyleneoxy structural unit (preferably 2 to 15 carbon atoms, more preferably 3 to 10 carbon atoms, even more preferably. It is preferable to have one or more structural units selected from 5 to 6 carbon atoms), isoprene structural unit, isoprene structural unit, and polycarbonate structural unit, and butadiene structural unit, polysiloxane structural unit, (meth). ) It is preferable to have one or more structural units selected from an acrylate structural unit, an isoprene structural unit, an isoprene structural unit, or a polycarbonate structural unit, and is selected from a butadiene structural unit and a (meth) acrylate structural unit. It is more preferable to have one or more structural units. In addition, "(meth) acrylate" refers to methacrylate and acrylate.

The component (a) preferably has a high molecular weight in order to exhibit flexibility, and the number average molecular weight (Mn) is preferably 1,000 to 1,000,000, more preferably 5,000 to 9,00,000. It is 000. The number average molecular weight (Mn) is a polystyrene-equivalent number average molecular weight measured using GPC (gel permeation chromatography).

The component (a) is preferably one or more resins selected from a resin having a glass transition temperature of 25 ° C. or lower and a resin liquid at 25 ° C. in order to exhibit flexibility.

The glass transition temperature of the resin having a glass transition temperature (Tg) of 25 ° C. or lower is preferably 20 ° C. or lower, more preferably 15 ° C. or lower. The lower limit of the glass transition temperature is not particularly limited, but can usually be −15 ° C. or higher. The resin that is liquid at 25 ° C. is preferably a resin that is liquid at 20 ° C. or lower, and more preferably a resin that is liquid at 15 ° C. or lower.

The component (a) is not particularly limited as long as it is a flexible resin, but it is preferable to have a functional group capable of reacting with the component (b) described later. The functional groups that can react with the component (b) include functional groups that appear by heating.

In one preferred embodiment, the functional group capable of reacting with component (b) comprises the group consisting of a hydroxy group (more preferably a phenolic hydroxyl group), a carboxy group, an acid anhydride group, an epoxy group, an isocyanate group and a urethane group. One or more functional groups of choice. Among them, as the functional group, a hydroxy group, an acid anhydride group, an epoxy group and an isocyanate group are preferable, and a hydroxy group, an acid anhydride group and an epoxy group are more preferable. However, when an epoxy group is contained as a functional group, the component (a) does not have an aromatic structure.

A preferred embodiment of the component (a) is a butadiene resin. The butadiene resin is preferably a butadiene resin that is liquid at 25 ° C. or has a glass transition temperature of 25 ° C. or lower, and is preferably a hydride polybutadiene skeleton-containing resin (for example, a hydride polybutadiene skeleton-containing epoxy resin) or a hydroxy group-containing butadiene resin (more preferably phenolic). One or more resins selected from the group consisting of hydroxyl group-containing butadiene resin), carboxy group-containing butadiene resin, acid anhydride group-containing butadiene resin, epoxy group-containing butadiene resin, isocyanate group-containing butadiene resin, and urethane group-containing butadiene resin. More preferable. Here, the "butadiene resin" refers to a resin containing a butadiene structure, and in these resins, the butadiene structure may be contained in the main chain or the side chain. The butadiene structure may be partially or wholly hydrogenated. Here, the "hydrogenated polybutadiene skeleton-containing resin" means a resin in which at least a part of the polybutadiene skeleton is hydrogenated, and the polybutadiene skeleton does not necessarily have to be a completely hydrogenated resin.

The number average molecular weight (Mn) of the butadiene resin is preferably 1,000 to 100,000, more preferably 5,000 to 50,000, more preferably 7,500 to 30,000, still more preferably 10,000 to 10,000. It is 15,000. Is. Here, the number average molecular weight (Mn) of the resin is a polystyrene-equivalent number average molecular weight measured by using GPC (gel permeation chromatography).

When the butadiene resin has a functional group, the functional group equivalent is preferably 100 to 10000, more preferably 200 to 5000. The functional group equivalent is the number of grams of the resin containing 1 gram equivalent of the functional group. For example, the epoxy group equivalent can be measured according to JIS K7236. The hydroxyl group equivalent can be calculated by dividing the molecular weight of KOH by the hydroxyl value measured according to JIS K1557-1.

Specific examples of the butadiene resin include "Ricon 657" (polybutadiene containing an epoxy group), "Ricon 130MA8", "Ricon 130MA13", "Ricon 130MA20", "Ricon 131MA5", "Ricon 131MA10", and "Ricon 131MA10" manufactured by Clay Valley. "Ricon 131MA17", "Ricon 131MA20", "Ricon 184MA6" (polybutadiene containing acid anhydride group), "JP-100", "JP-200" (epoxidized polybutadiene), "GQ-1000" manufactured by Nippon Soda Co., Ltd. (Polybutadiene with hydroxyl group and carboxyl group introduced), "G-1000", "G-2000", "G-3000" (polybutadiene with hydroxyl groups at both ends), "GI-1000", "GI-2000", "GI-3000" (Both-terminal hydroxyl-hydrogenated polybutadiene), "PB3600", "PB4700" (polybutadiene skeleton epoxy resin), "Epofriend A1005", "Epofriend A1010", "Epofriend A1020" (with styrene) manufactured by Daicel Co., Ltd. (Epoxidized product of butadiene and styrene block copolymer), "FCA-061L" (hydrogenated polybutadiene skeleton epoxy resin), "R-45EPT" (polybutadiene skeleton epoxy resin), etc. manufactured by Nagase ChemteX Corporation. ..

Further, as another preferable embodiment of the component (a), a linear polyimide using a hydroxy group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride as raw materials (Japanese Patent Laid-Open No. 2006-37083, International Publication No. 2008/153208) The polyimide described in No.) can also be used. The content of the butadiene structure of the polyimide resin is preferably 60% by mass to 95% by mass, and more preferably 75% by mass to 85% by mass. For details of the polyimide resin, the description of JP-A-2006-37083 and International Publication No. 2008/153208 can be referred to, and the contents thereof are incorporated in the present specification.

Another preferred embodiment of the component (a) is an acrylic resin. As the acrylic resin, an acrylic resin having a Tg of 25 ° C. or lower is preferable, and a hydroxy group-containing acrylic resin (more preferably a phenolic hydroxyl group-containing acrylic resin), a carboxy group-containing acrylic resin, an acid anhydride group-containing acrylic resin, and an epoxy group-containing acrylic resin are preferable. More preferably, one or more resins selected from the group consisting of acrylic resins, isocyanate group-containing acrylic resins and urethane group-containing acrylic resins. Here, the "acrylic resin" refers to a resin containing a (meth) acrylate structure, and in these resins, the (meth) acrylate structure may be contained in the main chain or the side chain.

The number average molecular weight (Mn) of the acrylic resin is preferably 10,000 to 1,000,000, more preferably 30,000 to 900,000. Here, the number average molecular weight (Mn) of the resin is a polystyrene-equivalent number average molecular weight measured by using GPC (gel permeation chromatography).

When the acrylic resin has a functional group, the functional group equivalent is preferably 1000 to 50,000, more preferably 2500 to 30000.

Specific examples of the acrylic resin include Teisan resins "SG-70L", "SG-708-6", "WS-023", "SG-700AS", and "SG-280TEA" (carboxy group) manufactured by Nagase ChemteX Corporation. Containing acrylic acid ester copolymer resin, acid value 5 to 34 mgKOH / g, weight average molecular weight 400,000 to 900,000, Tg-30 to 5 ° C), "SG-80H", "SG-80H-3", "SG" -P3 "(epoxy group-containing acrylic acid ester copolymer resin, epoxy equivalent 4761 to 14285 g / eq, weight average molecular weight 350,000 to 850,000, Tg 11 to 12 ° C.)," SG-600TEA "," SG-790 "( Hydroxy group-containing acrylic acid ester copolymer resin, hydroxyl value 20-40 mgKOH / g, weight average molecular weight 500,000-1.2 million, Tg-37-32 ° C), "ME-2000" manufactured by Negami Kogyo Co., Ltd., "W-116.3" (carboxy group-containing acrylic acid ester copolymer resin), "W-197C" (hydroxyl group-containing acrylic acid ester copolymer resin), "KG-25", "KG-3000" (epoxy) Group-containing acrylic acid ester copolymer resin) and the like.

Moreover, one preferable embodiment of the component (a) is a carbonate resin. The carbonate resin preferably has a glass transition temperature of 25 ° C. or lower, and is preferably a hydroxy group-containing carbonate resin (more preferably a phenolic hydroxyl group-containing carbonate resin), a carboxy group-containing carbonate resin, an acid anhydride group-containing carbonate resin, or an epoxy group. One or more resins selected from the group consisting of a carbonate-containing resin, an isocyanate group-containing carbonate resin, and a urethane group-containing carbonate resin are preferable. Here, the "carbonate resin" refers to a resin containing a carbonate structure, and in these resins, the carbonate structure may be contained in the main chain or the side chain.

The number average molecular weight (Mn) and functional group equivalent of the carbonate resin are the same as those of the butadiene resin, and the preferable ranges are also the same.

Specific examples of the carbonate resin include "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemicals Co., Ltd., and "C-1090", "C-2090" and "C-3090" manufactured by Kuraray Co., Ltd. (Polycarbonate diol) and the like.

Further, a linear polyimide (PCT / JP2016 / 053609) made from a hydroxy group-terminated polycarbonate, a diisocyanate compound and a tetrabasic acid anhydride can also be used. The content of the carbonate structure of the polyimide resin is preferably 60% by mass to 95% by mass, and more preferably 75% by mass to 85% by mass. For details of the polyimide resin, the description of PCT / JP2016 / 053609 can be referred to, and this content is incorporated in the present specification.

Further, a preferred embodiment of the component (a) is a polysiloxane resin, an alkylene resin, an alkyleneoxy resin, an isoprene resin, and an isobutylene resin.

Specific examples of the polysiloxane resin are "SMP-2006", "SMP-2003PGMEA", and "SMP-5005PGMEA" manufactured by Shinetsu Silicone Co., Ltd. Examples thereof include amine group-terminated polysiloxane and linear polyimide using tetrabasic acid anhydride as a raw material (International Publication No. 2010/053185). Specific examples of the alkylene resin include "PTXG-1000" and "PTXG-1800" manufactured by Asahi Kasei Fibers Corporation. Specific examples of the isoprene resin include "KL-610" and "KL613" manufactured by Kuraray Co., Ltd. Specific examples of the isobutylene resin include "SIBSTAR-073T" (styrene-isobutylene-styrene triblock copolymer) and "SIBSTAR-042D" (styrene-isobutylene block copolymer) manufactured by Kaneka Co., Ltd. ..

Further, preferred embodiments of the component (a) include acrylic rubber particles, polyamide fine particles, silicone particles and the like. Specific examples of the acrylic rubber particles include fine particles of a resin that is insoluble and insoluble in an organic solvent by chemically cross-linking a resin exhibiting rubber elasticity such as acrylonitrile butadiene rubber, butadiene rubber, and acrylic rubber. Specifically, XER-91 (manufactured by Nippon Synthetic Rubber Co., Ltd.), Staphyroid AC3355, AC3816, AC3832, AC4030, AC3364, IM101 (above, manufactured by Ganz Kasei Co., Ltd.), Pararoid EXL2655, EXL2602 (above, Kureha). (Made by Chemical Industry Co., Ltd.) and the like. Specific examples of the polyamide fine particles may be any aliphatic polyamide such as nylon, and any flexible skeleton such as polyamide-imide. Specifically, VESTOSINT 2070 (Daiselhurus Co., Ltd.) ), SP500 (manufactured by Toray Industries, Inc.) and the like.

The content of the component (a) in the resin composition is 30% by mass to 85% by mass when the non-volatile component of the resin composition excluding the component (c) is 100% by mass from the viewpoint of imparting flexibility. It is preferably 80% by mass or less, more preferably 70% by mass or less, and further preferably 60% by mass or less. The lower limit is preferably 35% by mass or more, more preferably 45% by mass or more, and further preferably 55% by mass or more.

<(B1) Liquid epoxy resin having an aromatic structure and (b2) Solid epoxy resin having an aromatic structure>
The resin composition includes (b1) a liquid epoxy resin having an aromatic structure and (b2) a solid epoxy resin having an aromatic structure. (B1) A liquid epoxy resin having an aromatic structure (hereinafter, also simply referred to as “liquid epoxy resin”) has an aromatic structure having two or more epoxy groups in one molecule and is liquid at a temperature of 20 ° C. (B2) A solid epoxy resin having an aromatic structure (hereinafter, also simply referred to as "solid epoxy resin") has three or more epoxy groups in one molecule. Refers to an epoxy resin having an aromatic structure, which is solid at a temperature of 20 ° C. The aromatic structure is a chemical structure generally defined as aromatic, and also includes polycyclic aromatics and aromatic heterocycles. In the present invention, a resin composition having excellent flexibility can be obtained by using a liquid epoxy resin and a solid epoxy resin in combination.

Examples of the liquid epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin having an aromatic structure, and glycidylamine type epoxy resin having an aromatic structure. , Phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton having an aromatic structure, cyclohexanedimethanol type epoxy resin having an aromatic structure, and epoxy resin having a butadiene structure having an aromatic structure are preferable, and bisphenol A Type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin and naphthalene type epoxy resin are more preferable, and bisphenol A type epoxy resin and bisphenol F type epoxy resin are further preferable. Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC Co., Ltd., "828US", "jER828EL" (bisphenol A) manufactured by Mitsubishi Chemical Corporation. Type epoxy resin), "JER806", "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolac type epoxy resin), "630", "630LSD" (glycidylamine type epoxy resin), Nippon Steel & Sumitomo Metal Chemical ( "ZX1059" (mixed product of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nagase ChemteX Corporation, "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Corporation, manufactured by Daicel Co., Ltd. "Ceroxide 2021P" (alicyclic epoxy resin having an ester skeleton), "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane) manufactured by Nippon Steel Chemical Co., Ltd. can be mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type.

The content of the liquid epoxy resin in the resin composition is preferably 1% by mass or more, more preferably 2% by mass or more, from the viewpoint of adjusting the tackiness when the non-volatile component in the resin composition is 100% by mass. , More preferably 2.5% by mass or more. The upper limit of the content of the epoxy resin is not particularly limited as long as the effect of the present invention is exhibited, but is preferably 15% by mass or less, more preferably 10% by mass or less, and further preferably 8% by mass or less.

The epoxy equivalent of the liquid epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, and even more preferably 110 to 1000. Within this range, the crosslink density of the cured product of the resin composition becomes sufficient, and when the cured product is used as the sealing layer, a sealing layer having a small surface roughness can be obtained. The epoxy equivalent of the liquid epoxy resin can be measured according to JIS K7236, and is the mass of the resin containing 1 equivalent of the epoxy group.

The weight average molecular weight of the liquid epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and even more preferably 400 to 1500. Here, the weight average molecular weight of the liquid epoxy resin is a polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) method.

Examples of the solid epoxy resin include naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin having an aromatic structure, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, and naphthylene. Ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin are preferable, and naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, and naphthic are preferable. Lene ether type epoxy resin is more preferable, and naphthalene type tetrafunctional epoxy resin and naphthylene ether type epoxy resin are further preferable. Specific examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin), "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin), and "N-690" manufactured by DIC Co., Ltd. (Cresol novolac type epoxy resin), "N-695" (cresol novolac type epoxy resin), "HP-7200", "HP-7200L", "HP-7200HH", "HP-7200H", "HP-7200HHH" (Dicyclopentadiene type epoxy resin), "EXA7311", "EXA7311-G3", "EXA7311-G4", "EXA7311-G4S", "HP6000" (naphthylene ether type epoxy resin), Nippon Kayaku Co., Ltd. "EPPN-502H" (trisphenol type epoxy resin), "NC7000L" (naphthol novolac type epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin), Nippon Steel & Sumitomo Metal "ESN475V" (naphthol type epoxy resin), "ESN485" (naphthol novolac type epoxy resin) manufactured by Kagaku Co., Ltd., "YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000HK" manufactured by Mitsubishi Chemical Co., Ltd. (Bixylenol type epoxy resin), "YL7760" (bisphenol AF type epoxy resin), "YX8800" (anthracene type epoxy resin), "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd., "jER1031S" (tetraphenylethane type epoxy resin), " 157S70 ”(bisphenol novolac type epoxy resin), Mitsubishi Chemical Co., Ltd.“ YX4000HK ”(bixilenol type epoxy resin),“ YX8800 ”(anthracene type epoxy resin), Osaka Gas Chemical Co., Ltd.“ PG-100 ” , "CG-500", "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation, and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.

The content of the solid epoxy resin in the resin composition is preferably 0.1% by mass or more from the viewpoint of adjusting the viscosity of the resin composition when the non-volatile component in the resin composition is 100% by mass. It is preferably 0.2% by mass or more, and more preferably 0.5% by mass or more. The upper limit of the content of the epoxy resin is not particularly limited as long as the effect of the present invention is exhibited, but is preferably 10% by mass or less, more preferably 8% by mass or less, and further preferably 5% by mass or less.

The epoxy equivalent of the solid epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, and even more preferably 110 to 1000. Within this range, the crosslink density of the cured product becomes sufficient, and a sealing layer having a small surface roughness can be obtained. The epoxy equivalent of the solid epoxy resin can be measured according to JIS K7236, and is the mass of the resin containing 1 equivalent of the epoxy group.

The weight average molecular weight of the solid epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and even more preferably 400 to 1500. Here, the weight average molecular weight of the solid epoxy resin is a polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) method.

When the content of the liquid epoxy resin is B1 (mass%) and the content of the solid epoxy resin is B2 (mass%), it is preferable to satisfy the relationship of B1> B2 from the viewpoint of adjusting the melt viscosity. The difference between B1 and B2 (B1-B2) is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.3% by mass or more, 0.5% by mass or more. Or it is 1% by mass or more. The upper limit of the difference (B1-B2) is not particularly limited, but may be usually 10% by mass or less, 5% by mass or less, or the like.

The amount ratio of the liquid epoxy resin to the solid epoxy resin (solid epoxy resin / liquid epoxy resin) is preferably in the range of 0.01 to 1 in terms of mass ratio. By setting the amount ratio of the liquid epoxy resin to the solid epoxy resin within such a range, i) appropriate adhesiveness is provided when used in the form of an adhesive film, and ii) when used in the form of an adhesive film. Sufficient flexibility can be obtained, handleability is improved, and iii) a cured product having sufficient breaking strength can be obtained. From the viewpoint of the effects of i) to iii) above, the amount ratio of the liquid epoxy resin to the solid epoxy resin (solid epoxy resin / liquid epoxy resin) is more in the range of 0.05 to 0.8 in terms of mass ratio. The range of 0.1 to 0.5 is preferable, and the range of 0.1 to 0.5 is more preferable.

<(C) Inorganic filler>
The resin composition comprises (c) an inorganic filler. The material of the inorganic filler is not particularly limited, but for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, water. Aluminum oxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide , Zirconate oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconate titanate, zirconate titnate phosphate and the like. Of these, silica is particularly suitable. Further, as silica, spherical silica is preferable. The inorganic filler may be used alone or in combination of two or more.

The average particle size of the inorganic filler is preferably 5 μm or less, more preferably 4 μm or less, still more preferably 3 μm or less, and more preferably 2.5 μm or less from the viewpoint of improving the circuit embedding property. The lower limit of the average particle size is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.1 μm or more. Commercially available products of inorganic fillers having such an average particle size include, for example, "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by Admatex Co., Ltd., and manufactured by Electrochemical Industry Co., Ltd. "UFP-30", Tokuyama Co., Ltd. "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS-5N", Admatex Co., Ltd. "SC2500SQ", "SO-C6", "SO" -C4 "," SO-C2 "," SO-C1 ", Admatex Co., Ltd." Admafine "," Admanano ", Denki Kagaku Kogyo Co., Ltd." SFP Series ", Nippon Steel & Sumitomo Metal Materials Co., Ltd. Examples include "SP (H) series" manufactured by Sakai Chemical Industry Co., Ltd., "Sciqas series" manufactured by Sakai Chemical Industry Co., Ltd., and "Seahoster series" manufactured by Nippon Catalyst Co., Ltd.

The average particle size of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, it can be measured by creating a particle size distribution of the inorganic filler on a volume basis with a laser diffraction / scattering type particle size distribution measuring device and using the median diameter as the average particle size. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As the laser diffraction / scattering type particle size distribution measuring device, "LA-500" manufactured by HORIBA, Ltd. or the like can be used.

From the viewpoint of enhancing moisture resistance and dispersibility, the inorganic filler is an aminosilane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane-based coupling agent, a silane-based coupling agent, an organosilazane compound, and a titanate-based coupling agent. It is preferable that the treatment is performed with one or more surface treatment agents such as. Commercially available surface treatment agents include, for example, "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. and "KBM803" (3-mercaptopropyltrimethoxy) manufactured by Shin-Etsu Chemical Co., Ltd. Silane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical Co., Ltd. "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" (long-chain epoxy type) manufactured by Shin-Etsu Chemical Co., Ltd. Silane coupling agent) and the like.

The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. Carbon content per unit surface area of the inorganic filler, from the viewpoint of improving dispersibility of the inorganic filler is preferably 0.02 mg / ^{m 2} or more, 0.1 mg / ^{m 2} or more preferably, 0.2 mg / ^{m 2} The above is more preferable. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin varnish and the melt viscosity in the sheet form, 1 mg / m ² or less is preferable, 0.8 mg / m ² or less is more preferable, and 0.5 mg / m ² or less is further preferable. preferable.

The amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by HORIBA, Ltd. or the like can be used.

The basic fluid energy per 1 g of the component (c) in the powder leometer measurement is under the condition C1 of the tip speed of the rotor blade of 100 mm / sec and the approach angle of the rotor blade of 5 ° from the viewpoint of improving the stability of the resin varnish. It is preferably 6 mJ / g or more, more preferably 7 mJ / g or more, and further preferably 8 mJ / g or more. The upper limit is preferably 20 mJ / g or less, more preferably 15 mJ / g or less, still more preferably 13 mJ / g or less. The powder rheometer measurement under the condition C1 can be measured according to the following (powder rheometer measurement under the condition C1).

The basic fluid energy per 1 g of the component (c) in the powder leometer measurement is under the condition C2 of the tip speed of the rotor blade of 40 mm / sec and the approach angle of the rotor blade of 5 ° from the viewpoint of improving the stability of the resin varnish. , Preferably 12 mJ / g or more, more preferably 13 mJ / g or more, still more preferably 14 mJ / g or more. The upper limit is preferably 27 mJ / g or less, more preferably 25 mJ / g or less, still more preferably 20 mJ / g or less. The powder rheometer measurement under the condition C2 can be measured according to the following (powder rheometer measurement under the condition C2).

The content of the inorganic filler in the resin composition is 50% by mass to 95% by mass when the non-volatile component in the resin composition is 100% by mass from the viewpoint of obtaining a sealing layer having a low coefficient of thermal expansion. .. It is preferably 55% by mass or more, more preferably 60% by mass or more, and further preferably 65% by mass or more. The upper limit is preferably 90% by mass or less, more preferably 88% by mass or less, still more preferably 85% by mass or less, from the viewpoint of mechanical strength of the sealing layer, particularly elongation.

<(D) Hardener>
The resin composition may contain (d) a curing agent. The curing agent is not particularly limited as long as it has a function of curing the resin such as the component (b). For example, a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, a benzoxazine-based curing agent, and a cyanate ester. Examples thereof include a system curing agent and a carbodiimide system curing agent. The curing agent may be used alone or in combination of two or more. The component (d) is preferably one or more selected from a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, and a cyanate ester-based curing agent.

As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable from the viewpoint of heat resistance and water resistance. Further, from the viewpoint of adhesion to the wiring layer, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable. Of these, a triazine skeleton-containing phenol novolac hardener is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion to the wiring layer.

Specific examples of the phenol-based curing agent and the naphthol-based curing agent include "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., and Nippon Kayaku Co., Ltd. "NHN", "CBN", "GPH", "SN170", "SN180", "SN190", "SN475", "SN485", "SN495V", "SN375", "SN395" manufactured by Nippon Steel & Sumitomo Metal Corporation , DIC Co., Ltd. "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500", "HPC-9500" , "KA-1160", "KA-1163", "KA-1165", "GDP-6115L", "GDP-6115H" manufactured by Gunei Chemical Co., Ltd. and the like.

The active ester-based curing agent is not particularly limited, but generally contains an ester group having high reactive activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds in one molecule. A compound having two or more esters is preferably used. The active ester-based curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid and the like. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-. Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenol, trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglusin, Examples thereof include benzenetriol, dicyclopentadiene-type diphenol compounds, and phenol novolac. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two phenol molecules with one dicyclopentadiene molecule.

Specifically, an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and an active ester compound containing a benzoylated product of phenol novolac are preferable. Of these, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferable. The "dicyclopentadiene-type diphenol structure" represents a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

Commercially available products of active ester-based curing agents include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", and "HPC-8000H-" as active ester compounds containing a dicyclopentadiene type diphenol structure. "65TM", "EXB-8000L-65TM" (manufactured by DIC Co., Ltd.), "EXB9416-70BK" (manufactured by DIC Co., Ltd.) as an active ester compound containing a naphthalene structure, as an active ester compound containing an acetylated product of phenol novolac. "DC808" (manufactured by Mitsubishi Chemical Corporation), "YLH1026" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing a benzoyl compound of phenol novolac, and "DC808" as an active ester-based curing agent which is an acetylated product of phenol novolac. (Made by Mitsubishi Chemical Co., Ltd.), "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1030" (manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1048" as active ester-based curing agents that are benzoyl compounds of phenol novolac. (Manufactured by Mitsubishi Chemical Co., Ltd.) and the like.

Specific examples of the benzoxazine-based curing agent include "HFB2006M" manufactured by Showa Polymer Co., Ltd., "Pd" and "FA" manufactured by Shikoku Kasei Kogyo Co., Ltd.

Examples of the cyanate ester-based curing agent include bisphenol A disicianate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis (2,6-dimethylphenylcyanate), and 4,4. '-Etilidene diphenyl disianate, hexafluorobisphenol A disyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanate phenylmethane), bis (4-cyanate-3,5-dimethyl) Bifunctional cyanate resins such as phenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether, phenol Examples thereof include polyfunctional cyanate resins derived from novolak and cresol novolak, and prepolymers in which these cyanate resins are partially triazined. Specific examples of the cyanate ester-based curing agent include "PT30" and "PT60" (both phenol novolac type polyfunctional cyanate ester resins), "BA230", and "BA230S75" (bisphenol A disicanate) manufactured by Lonza Japan Co., Ltd. Prepolymers in which some or all of them are triazined to form a trimer) and the like.

Specific examples of the carbodiimide-based curing agent include "V-03" and "V-07" manufactured by Nisshinbo Chemical Co., Ltd.

The content of the curing agent in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 10% by mass or less, more preferably 8% by mass or less, still more preferably 5. It is mass% or less. The lower limit is not particularly limited, but is preferably 1% by mass or more.

<(E) Curing accelerator>
The resin composition may contain (e) a curing accelerator. Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, and the like, and phosphorus-based curing accelerators and amine-based curing accelerators. A curing accelerator, an imidazole-based curing accelerator, and a metal-based curing accelerator are preferable, and an amine-based curing accelerator, an imidazole-based curing accelerator, and a metal-based curing accelerator are more preferable. The curing accelerator may be used alone or in combination of two or more.

Examples of the phosphorus-based curing accelerator include triphenylphosphine, phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, and (4-methylphenyl) triphenylphosphonium thiocyanate. , Tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like, and triphenylphosphine and tetrabutylphosphonium decanoate are preferable.

Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) phenol, and 1,8-diazabicyclo. Examples thereof include (5,4,0) -undecene, and 4-dimethylaminopyridine and 1,8-diazabicyclo (5,4,5) -undecene are preferable.

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 1,2-dimethyl imidazole, 2-ethyl-4-methyl imidazole, 1,2-dimethyl imidazole, and the like. 2-Ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-Cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimerite, 1-cyanoethyl- 2-Phenylimidazolium trimerite, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecyl Imidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4- Diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline , 2-Phenylimidazoline and other imidazole compounds and adducts of the imidazole compound and an epoxy resin are mentioned, with 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole being preferred.

As the imidazole-based curing accelerator, a commercially available product may be used, and examples thereof include "P200-H50" manufactured by Mitsubishi Chemical Corporation.

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, and trimethylguanidine. Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadesylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 Examples thereof include −allyl biguanide, 1-phenylbiguanide, 1- (o-tolyl) biganide, and dicyandiamide, 1,5,7-triazabicyclo [4.4.0] deca-5-ene is preferable.

Examples of the metal-based curing accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organic metal complex include an organic cobalt complex such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, an organic copper complex such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Examples thereof include organic zinc complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate and the like.

The content of the curing accelerator in the resin composition is not particularly limited, but is preferably 0.01% by mass to 3% by mass when the total amount of the non-volatile component of the component (b) and the curing agent is 100% by mass.

<(F) Flame retardant>
The resin composition may contain (f) a flame retardant. Examples of the flame retardant include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, and a metal hydroxide. The flame retardant may be used alone or in combination of two or more.

As the flame retardant, a commercially available product may be used, and examples thereof include "HCA-HQ" manufactured by Sanko Co., Ltd.

When the resin composition contains a flame retardant, the content of the flame retardant is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 0.5% by mass to 20% by mass. It is preferably 0.5% by mass to 15% by mass, more preferably 0.5% by mass to 10% by mass.

<(G) Arbitrary additive>
The resin composition may further contain other additives, if necessary, and such other additives include, for example, organometallic compounds such as organocopper compounds, organozinc compounds and organocobalt compounds. In addition, resin additives such as binders, thickeners, defoaming agents, leveling agents, adhesion imparting agents, and colorants can be mentioned.

From the viewpoint of suppressing warpage, the resin composition (or temporary resin composition layer) of the present invention usually has an elastic modulus of 18 GPa or less at 23 ° C. of a thermosetting product that has been thermoset at 180 ° C. for 1 hour. It is preferably 15 GPa or less, and more preferably 13 GPa or less, 11 GPa or less, 10 GPa or less, 9 GPa or less, or 8 GPa or less. The lower limit is not particularly limited, but may be, for example, 0.01 GPa or more, 0.5 GPa or more, 1 GPa or more, and the like. The elastic modulus can be measured according to the method described in <Measurement of elastic modulus> described later.

The resin composition (or temporary resin composition layer) of the present invention exhibits a characteristic that the occurrence of warpage is suppressed. The size of the warp is preferably 2 cm or less, more preferably 1 cm or less. The lower limit is not particularly limited, but is 0.01 cm or more. The warpage can be measured according to the method described in <Confirmation of Warpage Amount> described later.

The moisture permeability coefficient of the thermosetting product obtained by thermosetting the resin composition (or temporary resin composition layer) of the present invention at 180 ° C. for 1 hour is usually 3 from the viewpoint of suppressing swelling and warpage after curing. (G / mm / m ² / 24h) or more, preferably 3.5 (g / mm / m ² / 24h) or more, more preferably 4 (g / mm / m ² / 24h) or more, still more preferably. It can be 5, 6, or 7 (g / mm / m ² / 24h) or more. The upper limit is not particularly limited, but is preferably 10 (g / mm / m ² / 24h) or less, more preferably 9 (g / mm / m ² / 24h) or less, still more preferably 8 (g / mm / m ² ) or less. / 24h) or less. The moisture permeability coefficient can be measured according to the method described in <Measurement of moisture permeability coefficient> described later.

The average coefficient of linear thermal expansion (CTE) of the thermosetting product obtained by thermally curing the resin composition (or temporary resin composition layer) of the present invention at 180 ° C. for 1 hour is preferably 20 ppm from the viewpoint of suppressing warpage. / ° C. or lower, more preferably 15 ppm / ° C. or lower, still more preferably 10 ppm / ° C. or lower. The lower limit is not particularly limited, but may be 1 ppm / ° C. or higher. The average coefficient of linear thermal expansion can be measured according to the procedure of <Measurement of average coefficient of linear thermal expansion (CTE)> described later.

The resin varnish made of the resin composition of the present invention exhibits a characteristic of excellent stability. The resin varnish made of the resin composition of the present invention does not cause precipitation of the resin varnish component on the bottom of the container even if it is left to stand for 4 days, and more preferably the resin varnish on the bottom of the container even if it is left to stand for 5 days. No precipitation of components occurs. The stability of the resin varnish can be measured according to the procedure of <Stability of the resin varnish> described later.

The thermosetting product of the resin composition (or temporary resin composition layer) of the present invention shows the result that swelling after curing is suppressed. That is, the thermosetting product obtained by thermally curing the resin composition (or temporary resin composition layer) of the present invention at 180 ° C. for 1 hour does not cause swelling after curing. The swelling after curing can be measured according to the procedure of <presence or absence of swelling after curing> described later.

[Adhesive film, sheet-shaped resin composition and method for producing sheet-shaped resin composition]
The method for producing the sheet-shaped resin composition is as follows.
(A) A step of preparing two or more adhesive films having a support and a temporary resin composition layer containing the resin composition of the present invention provided on the support.
(B) Including a step of superimposing the temporary resin composition layers of the adhesive film so as to be in contact with each other.
The step (B) is performed only once or repeated two or more times to form a resin composition layer having a thickness of 400 μm to 900 μm. Further, the sheet-shaped resin composition is produced by the above-mentioned production method.

Hereinafter, each step will be described.

<Process (A)>
The step (A) is a step of preparing two or more adhesive films having a support and a temporary resin composition layer containing the resin composition of the present invention provided on the support, that is, 2 This is the process of preparing the above adhesive film. The two or more adhesive films to be prepared may be the same adhesive film or different adhesive films.

(Adhesive film)
The adhesive film has a support and a temporary resin composition layer containing the resin composition of the present invention provided on the support.

The thickness of the temporary resin composition layer is preferably 50 μm or more, more preferably 100 μm or more, from the viewpoint of improving the yield and the accuracy of the thickness. The upper limit of the thickness of the temporary resin composition layer is not particularly limited, but may be preferably 700 μm or less, more preferably 600 μm or less, and the like.

Examples of the support include a film made of a plastic material, a metal foil, and a paper pattern, and a film made of a plastic material and a metal foil are preferable.

When a film made of a plastic material is used as the support, the plastic material may be, for example, polyethylene terephthalate (hereinafter abbreviated as "PET") or polyethylene naphthalate (hereinafter abbreviated as "PEN"). ) Etc., polyester, polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylic polymer such as polymethylmethacrylate (PMMA), cyclic polyolefin, triacetylcellulose (TAC), polyethersulfide (PES), poly. Examples thereof include ether ketone and polyethylene. Of these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, and copper foil is preferable. As the copper foil, a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. You may use it.

In the support, the surface to be joined to the temporary resin composition layer may be matted or corona treated.

Further, as the support, a support with a release layer having a release layer on the surface to be joined with the temporary resin composition layer may be used. Examples of the release agent used for the release layer of the support with the release layer include one or more release agents selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. .. As the support with a release layer, a commercially available product may be used. For example, "SK-1" manufactured by Lintec Co., Ltd., which is a PET film having a release layer containing an alkyd resin-based release agent as a main component. , "AL-5", "AL-7", "Lumirror T6AM" manufactured by Toray Industries, Inc., and the like.

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. When a support with a release layer is used, the thickness of the entire support with a release layer is preferably in the above range.

For the adhesive film, for example, a resin varnish in which a resin composition is dissolved in an organic solvent is prepared, the resin varnish is applied onto a support using a die coater or the like, and further dried to form a temporary resin composition layer. It can be manufactured by making it.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, cellosolve and butyl carbitol and the like. Examples thereof include carbitols, aromatic hydrocarbons such as toluene and xylene, and amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. The organic solvent may be used alone or in combination of two or more.

Drying may be carried out by a known method such as heating or blowing hot air. The drying conditions are not particularly limited, but the temporary resin composition layer is dried so that the content of the organic solvent is 10% by mass or less, preferably 5% by mass or less. Although it depends on the boiling point of the organic solvent in the resin varnish, for example, when a resin varnish containing 30% by mass to 60% by mass of an organic solvent is used, it is dried at 50 ° C. to 150 ° C. for 3 to 10 minutes to prepare a temporary resin. A composition layer can be formed.

In the adhesive film, a protective film similar to the support can be further laminated on the surface of the temporary resin composition layer that is not bonded to the support (that is, the surface opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to prevent dust and the like from adhering to the surface of the temporary resin composition layer and scratches. The adhesive film can be rolled up and stored. If the adhesive film has a protective film, it can be used by peeling off the protective film.

<Process (B)>
Next, the temporary resin composition layers of the adhesive film prepared in the step (A) are overlapped so as to be in contact with each other (step (B)). In that case, a roll-to-roll method can be used, and for example, the linear pressure at the time of superimposition may be 0.02 to 1 MPa / mm ² .

The step (B) is performed only once or repeated two or more times to form a resin composition layer so that the thickness (total) is 400 μm to 900 μm. By setting the thickness of the resin composition layer to 400 μm to 900 μm in this way, the parts can be preferably sealed. The thickness of the resin composition layer is preferably 450 μm or more, more preferably 500 μm or more, or 550 μm or more. The upper limit is preferably 850 μm or less, more preferably 700 μm or less, still more preferably 650 μm or less, or 600 μm or less.

In the production of the sheet-shaped resin composition of the present invention, from the viewpoint of improving the yield, reducing the number of coatings to reduce the risk of foreign matter adhesion, etc., and improving the accuracy of the thickness of the resin composition layer. The step (B) is preferably performed only once or repeated only twice.

(1) When the step (B) is performed only once In this case, the temporary resin composition layers of the adhesive film are overlapped so as to be in contact with each other and integrated with the temporary resin composition layer to have a predetermined thickness. Resin composition layer is formed.

The two or more adhesive films prepared in the step (A) may be the same adhesive film or different adhesive films. That is, the composition of the resin composition forming the temporary resin composition layer in the two types of adhesive films may be the same or different, and the thickness of the temporary resin composition layer in the two types of adhesive films is the same. It may be different.

(2) When the step (B) is repeated twice or more An example of the case where the step (B) is repeated twice is as follows. First, in the step (A), the first to third adhesive films are prepared, and the temporary resin composition layers of the first and second adhesive films are overlapped so as to be in contact with each other. Then, after peeling off one of the supports, the temporary resin composition layer of the third adhesive film and the temporary resin composition layer in which the temporary resin composition layers of the first and second adhesive films are integrated are brought into contact with each other. Overlay on. In this way, a resin composition layer having a predetermined thickness is formed. The same can be performed when the step (B) is repeated three or more times.

When the step (B) is repeated two or more times, the "temporary resin composition" is also applied to the layer structure in the middle of production in which the step (B) is performed once or more but the final predetermined thickness is not reached. It is called "material layer".

At this time, the composition of the resin composition forming the temporary resin composition layer of each adhesive film prepared in the step (A) and the thickness of the temporary resin composition layer may be the same or different. Further, the thickness of the temporary resin composition layer of the portion added by each of the steps (B) repeated two or more times may be the same or different.

When the drying treatment under the drying conditions in the step (A) is performed while transporting a long roll-shaped support, the drying treatment is continuously performed on the moving exposed region. As a result, the long temporary resin composition layer and the resin composition layer are uniformly dried. Further, the residual solvent ratio of the formed resin composition layer is preferably 0.5% by mass to 5% by mass. The residual solvent ratio is preferably 5% by mass or less from the viewpoint of preventing voids from being generated in the resin composition layer (cured body) during curing. Further, from the viewpoint of improving the handleability of the resin composition layer, the residual solvent ratio is preferably 0.5% by mass or more.

The above-mentioned step of forming the temporary resin composition layer and / or the step of forming the resin composition layer sequentially determines whether the thickness of the formed temporary resin composition layer and / or the resin composition layer is a predetermined thickness. It is preferable to measure and control the thickness. By doing so, the uniformity of the thickness of the resin composition layer can be further improved, and the quality of the sheet-shaped resin composition can be further improved.

It is preferable that either one or both of the step (A) and the step (B) is performed by a roll-to-roll method using a long support as a support. Either one or both of the step (A) and the step (B) may be performed by a batch method, and the step (A) and the step (B) performed once or more are each performed by a roll-to-roll method. It may be performed in combination with the batch method.

The process of forming the temporary resin composition layer and / or the resin composition layer by the roll-to-roll method involves a long support (substrate, film) stretched between at least two rolls including a take-up roll and a take-up roll. ) Is continuously conveyed, the resin composition is applied to one main surface of the support exposed between the unwinding roll and the winding roll to form a coating film, and the coating film is continuously dried. This is performed by forming a temporary resin composition layer or a resin composition layer, and further measuring the thickness of the continuously formed layers.

The step (A) and the step (B) that is performed once or repeated twice or more can also be carried out as a series of steps in a roll-to-roll system. If these steps are carried out by a roll-to-roll method, the yield can be further improved.

The sheet-shaped resin composition of the present invention may further include a protective film that covers the surface of the resin composition layer. The protective film contributes to the prevention of dust and the like and scratches on the resin composition layer. As the material of the protective film, the same material as that described for the temporary resin composition layer and the support can be used. The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. In particular, the thickness of the protective film is preferably thinner than the thickness of the support because it is possible to prevent unwinding and wrinkles when producing the roll-shaped sheet-shaped resin composition.

The sheet-shaped resin composition can be suitably used as a film for sealing parts, and when the sheet-shaped resin composition is used as a film for sealing parts, the protective film is peeled off when the sealing step is performed. It can be used by exposing the resin composition layer.

(Usage mode of film for sealing parts)
When the sheet-shaped resin composition is used as a film for sealing parts, the parts that can be sealed by the film for sealing parts are not particularly limited, and any suitable parts according to a desired function can be mentioned. Examples of components that can be sealed by the component sealing film include passive components such as capacitors, inductors, and resistors, as well as active components such as semiconductor chips and semiconductor chip packages. The component sealing film according to the present invention can be suitably used, for example, in a component sealing step of a component built-in circuit board. The component encapsulation film according to the present invention is a sealing process (underfill molding) for semiconductor devices such as semiconductor chips and semiconductor chip packages (multi-chip package, package-on-package, wafer-level package, panel-level package, system-in-package). , Overmolding) and the like. That is, the component-embedded circuit board of the present invention includes a sealing layer formed of a cured product of the resin composition of the present invention, and the semiconductor device of the present invention (preferably a multi-chip package, a package-on-package, a wafer-level package, etc.) The panel level package (or system in package) includes a sealing layer formed by a cured product of the resin composition of the present invention.

If the sealing process is carried out using a component sealing film, the difference in the height of the unevenness of the sealing surface on which the sealing layer (sealing portion) is formed will be different when a thicker component is mounted. Even if it is large, it can be effectively embedded to form a sealing layer (sealing portion) with high accuracy. By this sealing process, it is possible to efficiently manufacture a circuit board with built-in components and a semiconductor device of higher quality with high yield.

Applications of component-embedded circuit boards and semiconductor devices in which component encapsulation films are used include, for example, electrical products (for example, computers, mobile phones, digital cameras and televisions, etc.) and vehicles (for example, motorcycles, automobiles, trains, etc.). Examples thereof include circuit boards with built-in components and semiconductor devices of various forms used for controlling the operation of (ships, aircraft, etc.) and the like.

An example of a sealing process using a component sealing film will be described. First, a component-embedded circuit board and a semiconductor device on which the components to be sealed are mounted are prepared. The resin composition layer of the component sealing film is placed so as to be in contact with the surface of the component to be sealed. Then, for example, by carrying out a press forming step or a vacuum laminating step, the component is embedded and coated in the resin composition layer.

The press forming step or the vacuum laminating step can be performed under arbitrary suitable conditions on the condition that the functions of the sealed parts are not impaired. The temperature condition and the pressurizing condition at this time may be determined in consideration of the minimum melt viscosity of the resin composition layer. Such a press forming step or a vacuum laminating step can be carried out by using a commercially available vacuum press device or vacuum laminator device. Since the semiconductor chip generally may be deteriorated by stress and heat treatment, it is preferable to embed it by a vacuum lamination step using a vacuum laminator device. Such vacuum lamination conditions can be performed, for example, under conditions of a pressure of 1 to 11 kgf / cm ² , a temperature of 70 to 140 ° C., and a time of 5 to 180 seconds.

The support may be peeled off from the resin composition layer after such a press forming step or a vacuum laminating step, or may be peeled off after a thermosetting step. The support is preferably peeled off after the thermosetting step. For example, when a heat dissipation function, a protective function, or the like is added by the support, the support may be used as it is without being peeled from the resin composition layer or the cured product.

Next, a thermosetting step is performed in which the resin composition layer in which the parts are embedded is heat-treated and heat-cured. By this thermosetting step, the resin composition layer is cured to form a sealing layer.

The conditions for the heat treatment in the thermosetting step are not particularly limited, and may be determined in consideration of the minimum melt viscosity of the resin composition layer and the like on the condition that the functions of the sealed parts are not impaired. Further, it is preferable that the thermosetting step is performed under atmospheric pressure (under normal pressure).

By the above sealing step, the resin composition layer becomes a cured product that seals the parts, that is, a sealing layer.

If desired, an individualization step of cutting the structure provided with the sealing layer into two or more pieces may be carried out. This individualization step can be performed, for example, by grinding and cutting the margin region with a conventionally known dicing device provided with a rotary blade. By this individualization step, the structure in which the sealing layer is formed is individualized into a plurality of functional elements each including a sealing portion that encloses and seals the component.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. In the following description, "parts" and "%" mean "parts by mass" and "% by mass", respectively, unless otherwise specified.

(Inorganic filler used)
"Adma Fine" and "Admanano" manufactured by Admatex Co., Ltd., "SFP series" and "UFP series" manufactured by Denki Kagaku Kogyo Co., Ltd., "SP (H) series" manufactured by Nippon Steel & Sumitomo Metal Materials Co., Ltd., Sakai Chemical Co., Ltd. The following inorganic fillers 1 to 5 were prepared by surface-treating the "Sciqas series" manufactured by Kogyo Co., Ltd. and the "Seahoster series" manufactured by Nippon Shokubai Co., Ltd. alone or in combination.
Inorganic filler 1:
Average particle size: 2.1 μm, aminosilane coupling agent: “KBM573” manufactured by Shin-Etsu Chemical Co., Ltd., basic fluid energy under measurement condition C1: 10.1 mJ / g, basic fluid energy under measurement condition C2: 14 .2mJ / g
Inorganic filler 2:
Average particle size: 2.1 μm, aminosilane coupling agent: “KBM573” manufactured by Shin-Etsu Chemical Co., Ltd., basic fluid energy under measurement condition C1: 9.2 mJ / g, basic fluid energy under measurement condition C2: 14 .1mJ / g
Inorganic filler 3:
Average particle size: 2.4 μm, aminosilane coupling agent: “KBM573” manufactured by Shin-Etsu Chemical Co., Ltd., basic fluid energy under measurement condition C1: 13 mJ / g, basic fluid energy under measurement condition C2: 21.3 mJ / G
Inorganic filler 4:
Average particle size: 1.6 μm, aminosilane coupling agent: “KBM573” manufactured by Shin-Etsu Chemical Co., Ltd., basic fluid energy under measurement condition C1: 18.4 mJ / g, basic fluid energy under measurement condition C2: 26 mJ / G
Inorganic filler 5:
Average particle size: 2.8 μm, aminosilane coupling agent: “KBM573” manufactured by Shin-Etsu Chemical Co., Ltd., basic fluid energy under measurement condition C1: 5.7 mJ / g, basic fluid energy under measurement condition C2: 11 .2mJ / g

(Powder rheometer measurement under condition C1)
Using a powder rheometer FT4 (manufactured by freeman technology), using a container with an inner diameter of 50 mm and a capacity of 160 ml, measurement was performed under the conditions of a rotary blade (diameter: 48 mm) tip speed of 100 mm / sec and a rotary blade approach angle of 5 °. did.

(Powder rheometer measurement under condition C2)
Using a powder rheometer FT4 (manufactured by freeman technology), using a container with an inner diameter of 50 mm and a capacity of 160 ml, measurement was performed under the conditions of a rotary blade (diameter: 48 mm) tip speed of 40 mm / sec and a rotary blade approach angle of 5 °. did.

(Synthesis of Elastomer A)
In a flask equipped with a stirrer, a thermometer and a condenser, 292.09 g of ethyldiglycol acetate and 292.09 g of Solbesso 150 (aromatic solvent, manufactured by ExxonMobil) were placed as solvents, and 100.1 g of diphenylmethane diisocyanate (100.1 g). (0.4 mol) and 426.6 g (0.2 mol) of polybutadiene diol (hydroxyl value 52.6 KOHmg / g, molecular weight 2133) were charged and reacted at 70 ° C. for 4 hours. Next, nonylphenol novolak resin (hydroxyl equivalent 229.4 g / eq, average 4.27 functionality, average calculated molecular weight 979.5 g / mol) 195.9 g (0.2 mol) and ethylene glycol bisamhydrotrimerite 41.0 g ( 0.1 mol) was charged, the temperature was raised to 150 ° C. over 2 hours, and the reaction was carried out for 12 hours.

After the reaction, it became a transparent brown liquid, and a polyimide resin solution having a non-volatile content of 55% and a viscosity of 14 Pa · s (25 ° C.) was obtained. As a result of coating the obtained polyimide resin solution on the KBr plate and measuring the infrared absorption spectrum of the sample in which the solvent component was volatilized, the characteristic absorption of the isocyanate group, 2270 cm ^-1, was completely eliminated, and 725 cm. Absorption of the imide ring was confirmed at ^-1 and 1780 cm ^-1 and 1720 cm ^-1 . In addition, absorption of urethane bonds was confirmed at 1540 cm- ¹ . The amount of carbon dioxide generated with the progress of imidization was 8.8 g (0.2 mol), which was tracked by the change in the weight charged in the flask. The functional group equivalent of the acid anhydride of ethylene glycol bisanhydrotrimeritate is 0.2 mol, the amount of carbon dioxide gas generated is also 0.2 mol, all the acid anhydrides are used for imide formation, and the carboxylic acid. It is concluded that the anhydride is not present. As a result, 0.2 mol of the isocyanate groups are converted into imide bonds, and the remaining isocyanate groups form urethane bonds together with the hydroxyl groups of the polybutadiene diol and the phenolic hydroxyl groups in the nonylphenol novolac resin, whereby phenol novolac is formed in the resin. An polyimide urethane resin (epolymer A) having a phenolic hydroxyl group of the resin and having some phenolic hydroxyl groups modified by a urethane bond was obtained.

<Measurement of moisture permeability coefficient>
(Preparation of cured product for evaluation)
A glass cloth base material epoxy resin double-sided copper-clad laminate (Matsushita Electric Works Co., Ltd.) on the release agent-treated PET film (“501010” manufactured by Lintec Co., Ltd., thickness 38 μm, 240 mm square) "R5715ES" manufactured by R5715ES, thickness 0.7 mm, 255 mm square) was overlapped and the four sides were fixed with polyimide adhesive tape (width 10 mm) (hereinafter, "fixed PET film").
PET film (“Lumilar R80” manufactured by Toray Co., Ltd., thickness 38 μm,” obtained by mold-releasing the resin varnish produced in Examples and Comparative Examples with an alkyd resin-based mold release agent (“AL-5” manufactured by Lintec Co., Ltd.). A softening point of 130 ° C. (hereinafter referred to as “release PET”) is coated with a die coater so that the thickness of the temporary resin composition layer after drying is 40 μm, and the temperature is 80 ° C. to 120 ° C. (average 100 ° C.). It was dried for 10 minutes to obtain an adhesive film. Each adhesive film (thickness 40 μm, 200 mm square) is fixed with a temporary resin composition layer using a batch type vacuum pressure laminator (2-stage build-up laminator manufactured by Nikko Materials Co., Ltd., CVP700). A resin sheet with a support was obtained by laminating in the center so as to be in contact with the mold release surface. The laminating treatment was carried out by reducing the pressure for 30 seconds to reduce the atmospheric pressure to 13 hPa or less, and then crimping at 100 ° C. and a pressure of 0.74 MPa for 30 seconds.

Then, under a temperature condition of 100 ° C., the mixture was placed in an oven at 100 ° C. for 30 minutes, and then transferred to an oven at 175 ° C. for 30 minutes and then thermoset. Then, the substrate was taken out under a room temperature atmosphere, the release PET was peeled off from the resin sheet with a support, and then the substrate was further put into an oven at 190 ° C. and then heat-cured under curing conditions for 90 minutes.

After thermosetting, the polyimide adhesive tape is peeled off, the cured product is removed from the glass cloth base material epoxy resin double-sided copper-clad laminate, and the PET film (“501010” manufactured by Lintec Co., Ltd.) is also peeled off to form a sheet-shaped cured product. Got The obtained cured product is referred to as an "evaluation cured product".

The cured product for evaluation (thickness 40 μm) was cut into a circle having a diameter of 70 mm, and the moisture permeability was measured according to the moisture permeability test method (cup method) of JIS Z0208. Specifically, 60 ℃, 85% RH, 24 hours determine the moisture permeability ^(g / m 2 · 24h) by measuring the moisture weight transmitted through the sample, permeance by dividing a film thickness (g · ^mm / m 2 · 24h) was calculated. The average values of the three test pieces are shown in the table below.

<Measurement of average coefficient of linear thermal expansion (CTE)>
The cured product for evaluation was cut into test pieces having a width of 5 mm and a length of 15 mm, and thermomechanical analysis was performed by a thermomechanical weighting method using a thermomechanical analyzer (“Thermo Plus TMA8310” manufactured by Rigaku Co., Ltd.). Specifically, after the test piece was attached to the thermomechanical analyzer, measurements were taken twice in succession under the measurement conditions of a load of 1 g and a heating rate of 5 ° C./min. Then, in the two measurements, the average linear thermal expansion coefficient (ppm / ° C.) in the plane direction in the range of 25 ° C. to 150 ° C. was calculated.

<Measurement of elastic modulus>
The cured product for evaluation was cut into a dumbbell-shaped No. 1 shape to obtain a test piece. The test piece was subjected to tensile strength measurement using a tensile tester "RTC-1250A" manufactured by Orientec, and the elastic modulus at 23 ° C. was determined. The measurement was carried out in accordance with JIS K7127. This operation was performed 3 times and the average value is shown in the table.

<Presence or absence of swelling after curing>
The resin composition varnish produced in Examples and Comparative Examples was placed on a polyethylene terephthalate (PET) film (thickness 38 μm) so that the thickness of the resin composition layer after drying was 400 μm. It is applied with a die coater and dried at 80 to 120 ° C. (average 100 ° C.) for 10 minutes to obtain an adhesive film, and then an adhesive film made of the same resin varnish is attached to obtain a sheet-like resin composition having a thickness of 800 μm. Obtained, one of the supports was peeled off. Next, the PET film was removed after laminating the surface side from which the support of the sheet-shaped resin composition had been peeled off on a copper foil (“JTC foil” manufactured by JX Nippon Mining & Metals Co., Ltd., copper foil thickness 18 μm). The obtained copper foil with a sheet-like resin composition was applied to both sides of a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.3 mm, R5715ES manufactured by Matsushita Electric Works Co., Ltd.). Batch type vacuum pressurizing laminator (2-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.) to 1 μm with a roughening treatment agent (CZ8100) manufactured by Nikko Materials Co., Ltd. ”). The size of the substrate and the sheet-shaped resin composition was 255 mm × 340 mm. Then, after heating at 100 ° C. for 30 minutes, it is heat-cured at 180 ° C. for 90 minutes, and it is confirmed whether or not there is swelling between the substrate and the sheet-shaped resin composition or between the sheet-shaped resin composition and the copper foil. "○" was used, and those with swelling were designated as "x".

<Confirmation of warpage amount>
The resin varnish produced in Examples and Comparative Examples was placed on a polyethylene terephthalate (PET) film (thickness 38 μm), and the obtained resin varnish was placed on a polyethylene terephthalate (PET) film (thickness 38 μm) so that the thickness of the temporary resin composition layer after drying was 400 μm. It is applied with a ter and dried at 80 ° C. to 120 ° C. (average 100 ° C.) for 10 minutes to obtain an adhesive film, and then an adhesive film made of the same resin varnish is attached to obtain a sheet-like resin composition having a thickness of 800 μm. Obtained, one of the supports was peeled off. Batch type vacuum pressurization on one side of glass cloth base material BT resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.15 mm, Mitsubishi Gas Chemical Company's "HL832NSF LCA", size 15 cm x 18 cm) A laminator (2-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.) was used to laminate the surface side from which the support of the sheet-shaped resin composition was peeled off, and after removing the PET film, the temperature was 100 ° C. for 30 minutes. After heating, it was heat-cured at 180 ° C. for 90 minutes and placed on a flat surface to check the amount of warpage. The average value of the amount of warpage of each of the four corners was defined as "◯", "Δ" for 1 cm or more and less than 2 cm, and "x" for 2 cm or more.

<Stability of resin varnish>
The resin varnishes produced in Examples and Comparative Examples were placed in a plastic container and allowed to stand in a refrigerator at 5 ° C. for 1 to 5 days to confirm the stability of the resin varnish. “○” indicates that the resin varnish component does not precipitate on the bottom of the container after standing for 5 days, and the resin varnish component does not precipitate on the bottom of the container after standing for 4 days. Those in which the varnish component was precipitated were marked with "Δ", and those in which the resin varnish component was precipitated on the bottom of the container after being allowed to stand by the 4th day were marked with "x".

<Example 1>
Liquid epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq), 30 parts, biphenyl type Epoxy resin ("NC-3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 288 g / eq) 8 parts, aminophenol type epoxy resin ("630 LSD" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent: 90-105 g / eq) ) 5 parts, curing accelerator ("2P4MZ" manufactured by Shikoku Kasei Co., Ltd., imidazole derivative), 1 part, acrylic acid ester copolymer ("Taisan Resin SG-P3" manufactured by Nagase ChemteX Corporation, solid content 15% Methyl ethyl ketone solution, Tg 12 ° C., functional group equal amount 4762 g / eq, weight average molecular weight Mw 850,000) 1,000 parts, cresol novolac resin ("KA-1163" manufactured by DIC Co., Ltd., phenolic hydroxyl group equivalent: 118 g / eq) ) 12 parts, spherical silica surface-treated with an inorganic filler 1 (aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Industry Co., Ltd.) (basic fluid energy: 10.1 mJ / g, average particle size 2. 1 μm)) 950 parts and 20 parts of methyl ethyl ketone were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish 1.

<Example 2>
Liquid epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq), 30 parts, biphenyl type Epoxy resin ("NC-3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 288 g / eq) 8 parts, aminophenol type epoxy resin ("630 LSD" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent: 90-105 g / eq) ) 5 parts, curing accelerator ("2P4MZ" manufactured by Shikoku Kasei Co., Ltd., imidazole derivative), 300 parts of epoxy A, cresol novolac resin ("KA-1163" manufactured by DIC Co., Ltd., phenolic hydroxyl group equivalent: 118 g) / Ep) 12 parts, spherical silica (basic fluid energy: 9.2 mJ / g) surface-treated with inorganic filler 2 (aminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Industry Co., Ltd.), average grain 950 parts (diameter 2.1 μm) and 20 parts of methyl ethyl ketone were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish 2.

<Example 3>
Liquid epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq), 30 parts, biphenyl type Epoxy resin ("NC-3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 288 g / eq) 8 parts, aminophenol type epoxy resin ("630 LSD" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent: 90-105 g / eq) ) 5 parts, curing accelerator ("2P4MZ" manufactured by Shikoku Kasei Co., Ltd., imidazole derivative), 300 parts of epoxy A varnish, cresol novolac resin ("KA-1163" manufactured by DIC Co., Ltd., phenolic hydroxyl group equivalent: 118 g / eq) 12 parts, spherical silica (basic fluid energy: 13 mJ / g) surface-treated with inorganic filler 3 (aminosilane coupling agent (“KBM573” manufactured by Shinetsu Chemical Industry Co., Ltd.), average particle size 2.4 μm) 950 parts and 20 parts of methyl ethyl ketone were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish 3.

<Example 4>
Liquid epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq), 30 parts, biphenyl type Epoxy resin ("NC-3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 288 g / eq) 8 parts, aminophenol type epoxy resin ("630 LSD" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent: 90-105 g / eq) ) 5 parts, curing accelerator ("2P4MZ" manufactured by Shikoku Kasei Co., Ltd., imidazole derivative), 300 parts of epoxy A, cresol novolac resin ("KA-1163" manufactured by DIC Co., Ltd., phenolic hydroxyl group equivalent: 118 g) / Ep) 12 parts, spherical silica (basic fluid energy: 18.4 mJ / g) average particle size surface-treated with inorganic filler 4 (aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Industry Co., Ltd.)) 950 parts of 1.6 μm) and 20 parts of methyl ethyl ketone were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish 4.

<Example 5>
Liquid epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq) 45 parts, biphenyl type Epoxy resin ("NC-3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 288 g / eq) 12 parts, aminophenol type epoxy resin ("630 LSD" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent: 90-105 g / eq) ) 8 parts, curing accelerator ("2P4MZ" manufactured by Shikoku Kasei Co., Ltd., imidazole derivative), 240 parts of epoxy A, cresol novolac resin ("KA-1163" manufactured by DIC Co., Ltd., phenolic hydroxyl group equivalent: 118 g) / Ep) 20 parts, spherical silica (basic fluid energy: 10.1 mJ / g) surface-treated with inorganic filler 1 (aminosilane coupling agent (“KBM573” manufactured by Shinetsu Chemical Industry Co., Ltd.), average grain 950 parts (diameter 2.1 μm) and 20 parts of methyl ethyl ketone were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish 5.

<Example 6>
Liquid epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq) 18 parts, biphenyl type Epoxy resin ("NC-3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 288 g / eq) 5 parts, aminophenol type epoxy resin ("630 LSD" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent: 90-105 g / eq) ) 3 parts, curing accelerator ("2P4MZ" manufactured by Shikoku Kasei Co., Ltd., imidazole derivative) 1 part, acrylic acid ester copolymer ("Taisan Resin SG-P3" manufactured by Nagase ChemteX Corporation, solid content 15% Methyl ethyl ketone solution, weight average molecular weight of acrylic acid ester copolymer: 850,000) 1,133 parts, cresol novolac resin ("KA-1163" manufactured by DIC Co., Ltd., phenolic hydroxyl group equivalent: 118 g / eq) 9 parts , Spherical silica (basic fluid energy: 10.1 mJ / g) surface-treated with inorganic filler 3 (aminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Industry Co., Ltd.), average particle size 2.4 μm) 950 parts and 20 parts of methyl ethyl ketone were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish 6.

<Example 7>
Liquid epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq) 66 parts, biphenyl type Epoxy resin ("NC-3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 288 g / eq) 30 parts, aminophenol type epoxy resin ("630 LSD" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent: 90-105 g / eq) ) 15 parts, curing accelerator ("2P4MZ" manufactured by Shikoku Kasei Co., Ltd., imidazole derivative), 140 parts of epoxy A, cresol novolac resin ("KA-1163" manufactured by DIC Co., Ltd., phenolic hydroxyl group equivalent: 118 g) / Ep) 30 parts, spherical silica (basic fluid energy: 10.1 mJ / g) surface-treated with inorganic filler 3 (aminosilane coupling agent (“KBM573” manufactured by Shinetsu Chemical Industry Co., Ltd.), average grain 1100 parts (diameter 2.4 μm) and 40 parts of methyl ethyl ketone were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish 7.

<Example 8>
Liquid epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., 1: 1 mixture (mass ratio) of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy equivalent: 169 g / eq), 30 parts, biphenyl type Epoxy resin ("NC-3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 288 g / eq) 8 parts, aminophenol type epoxy resin ("630 LSD" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent: 90-105 g / eq) ) 5 parts, curing accelerator ("2P4MZ" manufactured by Shikoku Kasei Co., Ltd., imidazole derivative), 1 part, acrylic acid ester copolymer ("Taisan Resin SG-P3" manufactured by Nagase ChemteX Corporation, solid content 15% Methyl ethyl ketone solution, weight average molecular weight of acrylic acid ester copolymer: 850,000) 1,000 parts, cresol novolac resin ("KA-1163" manufactured by DIC Co., Ltd., phenolic hydroxyl group equivalent: 118 g / eq) 12 parts , Spherical silica surface-treated with inorganic filler 5 (aminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Industry Co., Ltd.) (basic fluid energy: 5.7 mJ / g, average particle size 2.8 μm)) 950 parts and 20 parts of methyl ethyl ketone were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish 8.

<Comparative example 1>
Liquid epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., 1: 1 mixture (mass ratio) of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy equivalent: 169 g / eq) 76 parts, biphenyl type Epoxy resin ("NC-3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 288 g / eq) 25 parts, naphthalene type epoxy resin ("HP4032" manufactured by DIC Co., Ltd., epoxy equivalent 140-150 g / eq) 20 parts , Aminophenol type epoxy resin ("630LSD" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent: 90 to 105 g / eq) 13 parts, curing accelerator ("2P4MZ" manufactured by Shikoku Kasei Co., Ltd., imidazole derivative) 1 part, polyester 40 parts of resin (manufactured by Unitika Co., Ltd., "UE3400"), 30 parts of cresol novolac resin (manufactured by DIC Co., Ltd. "KA-1163", phenolic hydroxyl group equivalent: 118 g / eq), inorganic filler 3 (aminosilane cup) Spherical silica (basic fluid energy: 13 mJ / g) surface-treated with a ring agent (“KBM573” manufactured by Shin-Etsu Chemical Industry Co., Ltd.), 950 parts with an average particle size of 2.4 μm), and 20 parts of methyl ethyl ketone are mixed. The resin varnish 9 was produced by uniformly dispersing it with a high-speed rotating mixer.

表中、「（ｃ）成分の含有量（質量％）」は、樹脂組成物の不揮発成分を１００質量％とした場合の（ｃ）成分の含有量を表し、「（ａ）成分の含油量（質量％）」は、（ｃ）成分を除いた樹脂組成物の不揮発成分を１００質量％とした場合の（ａ）成分の含有量を表す。

In the table, "content of component (c) (% by mass)" represents the content of component (c) when the non-volatile component of the resin composition is 100% by mass, and "content of component (a)". "(Mass%)" represents the content of the component (a) when the non-volatile component of the resin composition excluding the component (c) is 100% by mass.

Claims (14)

A resin composition containing (a) an elastomer, (b1) a liquid epoxy resin having an aromatic structure, (b2) a solid epoxy resin having an aromatic structure, and (c) an inorganic filler.
The content of the component (c) is 50% by mass to 95% by mass when the non-volatile component of the resin composition is 100% by mass.
A resin composition in which the content of the component (a) is 33% by mass to 85% by mass when the non-volatile component of the resin composition excluding the component (c) is 100% by mass. The basic fluid energy (mJ / g) per 1 g of the component (c) in the powder rheometer measurement is 6 to 20 under the condition C1 of the tip speed of the rotor blade of 100 mm / sec and the approach angle of the rotor blade of 5 °. , The resin composition according to claim 1. The basic fluid energy (mJ / g) per 1 g of the component (c) in the powder rheometer measurement is 12 to 27 under the condition C2 of the tip speed of the rotor blade of 40 mm / sec and the approach angle of the rotor blade of 5 °. , The resin composition according to claim 1 or 2. One or more of the components (a) selected from a butadiene structural unit, a polysiloxane structural unit, a (meth) acrylate structural unit, an alkylene structural unit, an alkyleneoxy structural unit, an isoprene structural unit, an isobutylene structural unit, and a polycarbonate structural unit. The resin composition according to any one of claims 1 to 3, which has the structural unit of. The resin composition according to any one of claims 1 to 4, wherein the component (a) is at least one selected from a resin having a glass transition temperature of 25 ° C. or lower and a resin liquid at 25 ° C. .. The resin composition according to any one of claims 1 to 5, wherein the component (a) has a functional group capable of reacting with the component (b). The resin composition according to any one of claims 1 to 6, wherein the component (a) has an imide structural unit. The resin composition according to any one of claims 1 to 7, wherein the component (a) has a phenolic hydroxyl group. According to any one of claims 1 to 8, when the content of the component (b1) is B1 (mass%) and the content of the component (b2) is B2 (mass%), the relationship of B1> B2 is satisfied. The resin composition described. The resin composition according to any one of claims 1 to 9, wherein the thermosetting product has a moisture permeability coefficient of 3 to 10 (g / mm / m ² / 24h). An adhesive film comprising a support and a temporary resin composition layer provided on the support and containing the resin composition according to any one of claims 1 to 10. A component-embedded circuit board including a sealing layer formed of a cured product of the resin composition according to any one of claims 1 to 10. A semiconductor device including a sealing layer formed of a cured product of the resin composition according to any one of claims 1 to 10. (A) Prepare two or more adhesive films having a support and a temporary resin composition layer containing the resin composition according to any one of claims 1 to 10 provided on the support. Process and
(B) The step of superimposing the temporary resin composition layers of the adhesive film so as to be in contact with each other is included.
A method for producing a sheet-like resin composition, wherein the step (B) is performed only once or repeated two or more times to form a resin composition layer having a thickness of 400 μm to 900 μm.