JP7156335B2 - RESIN COMPOSITION, ADHESIVE FILM, COMPONENT-BUILDING CIRCUIT BOARD, SEMICONDUCTOR DEVICE, AND METHOD FOR MANUFACTURING SHEET-LIKE RESIN COMPOSITION - Google Patents

Description

The present invention relates to resin compositions. Furthermore, it relates to a method for producing an adhesive film, a component-embedded circuit board, a semiconductor device, and a sheet-shaped resin composition.

In recent years, there has been an increasing demand for small, highly functional mobile terminals such as smart phones and tablet terminals (tablet PCs). Semiconductor devices and the like used to function such highly functional mobile terminals are required to be further miniaturized and highly functional. As a structure of such a semiconductor device, for example, a multi-chip package in which two or more parts such as semiconductor chips are encapsulated, and a plurality of multi-chip packages are bonded together and then integrally sealed. Package-on-Package (PoP) consisting of, Wafer-Level Package (WLP) or Panel-Level Package (PLP) that performs wiring, electrode formation, resin sealing, and packaging in the wafer/panel state, and furthermore, chips A structure such as a system-in-package (SiP), which is sealed in one package, has attracted attention.

In addition, a component-embedded circuit board has been proposed as a printed wiring board in which components such as a semiconductor chip and a capacitor are embedded in an inner layer circuit board, thereby increasing the amount of components to be mounted and reducing the size of the board.

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

With such a conventional sheet material, the thickness of the resin composition layer may be insufficient to sufficiently seal the parts. A method of laminating the resin composition layers of the provided sheet material together or repeating the application a plurality of times has been proposed (for example, Patent Documents 1 and 2).

JP 2012-25907 A JP 2015-61720 A

However, increasing the thickness of the resin composition layer may cause swelling between the resin composition layer and the substrate or the like after curing.

In addition, in order to prevent the substrate from warping, the resin composition layer is required to have characteristics such as a low average coefficient of linear thermal expansion (CTE) and a low elastic modulus. However, it was difficult to eliminate swelling after curing. Moreover, when a large amount of inorganic filler is added to obtain these properties, the resin varnish may become unstable.

The present invention has been made to solve the above problems, and provides a resin composition that suppresses the occurrence of warpage and swelling after curing and has a low average linear thermal expansion coefficient and elastic modulus; The present invention provides an adhesive film, a component-embedded circuit board, a semiconductor device (in particular, a multi-chip package, a package-on-package, a wafer-level package, a panel-level package, or a system-in-package, etc.), and a method for producing a sheet-shaped resin composition. That's what it 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 at 23° C. of a thermoset product obtained by thermosetting the resin composition at 180° C. for 1 hour is 18 GPa or less,
A resin composition, a thermoset of which has a moisture permeability coefficient of 3 (g/mm/m ² /24h) or more.
[2] The resin according to [1], wherein the content of component (a) is 30% by mass to 85% by mass when the non-volatile component of the resin composition excluding component (c) is taken as 100% by mass. Composition.
[3] In the powder rheometer measurement, the basic fluidity energy (mJ/g) per 1 g of the component (c) is 6 to 6 under condition C1 with a rotor blade tip speed of 100 mm/sec and a rotor blade approach angle of 5°. 20, the resin composition according to [1] or [2].
[4] In the powder rheometer measurement, the basic fluidity energy (mJ/g) per 1 g of the component (c) is 12 to 12 under condition C2 with a rotor blade tip speed of 40 mm/sec and a rotor blade approach angle of 5°. 27, the resin composition according to any one of [1] to [3].
[5] Component (a) is selected from butadiene structural units, polysiloxane structural units, (meth)acrylate structural units, alkylene structural units, alkyleneoxy structural units, isoprene structural units, isobutylene structural units, and polycarbonate structural units. The resin composition according to any one of [1] to [4], which has one or more structural units.
[6] The component (a) according to any one of [1] to [5], wherein the component (a) is one or more selected from resins having a glass transition temperature of 25°C or less and resins that are liquid at 25°C. Resin composition.
[7] The resin composition according to any one of [1] to [6], wherein component (a) has a functional group capable of reacting with component (b).
[8] The resin composition according to any one of [1] to [7], wherein component (a) has an imide structural unit.
[9] The resin composition according to any one of [1] to [8], wherein component (a) has a phenolic hydroxyl group.
[10] When the content of the component (b1) is B1 (% by mass) and the content of the component (b2) is B2 (% by mass), the relationship of B1>B2 is satisfied, [1] to [9] The resin composition according to any one of the above.
[11] The resin composition according to any one of [1] to [10], wherein the thermoset 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 containing the resin composition according to any one of [1] to [11] provided on the support.
[13] A component-embedded circuit board, comprising a sealing layer formed from a cured product of the resin composition according to any one of [1] to [11].
[14] A semiconductor device comprising a sealing layer formed from a cured product of the resin composition according to any one of [1] to [11].
[15] (A) Two adhesive films each having 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,
(B) a step of overlapping the temporary resin composition layers of the adhesive film so that they are in contact with each other,
A method for producing a sheet-shaped 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.

INDUSTRIAL APPLICABILITY According to the present invention, there is provided a resin composition that suppresses warpage and swelling after curing and has a low average linear thermal expansion coefficient and elastic modulus, an adhesive film, a component-embedded circuit board, and a semiconductor that use the resin composition. An apparatus and a method for producing a sheet-shaped resin composition can be provided.

The resin composition of the present invention and methods for producing adhesive films, component-embedded circuit boards, semiconductor devices, and sheet-like resin compositions using the resin composition are described in detail below.

[Resin composition]
The resin composition of the present invention comprises (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 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 thermoset material has an elastic modulus at 23° C. of 18 GPa or less, and a moisture permeability coefficient of the thermoset material of 3 (g/mm/m ² /24 h) or more.

The resin composition of the present invention suppresses the occurrence of warpage and swelling after curing, and from the viewpoint of lowering the average linear thermal expansion coefficient and elastic modulus, the resin composition contains (a) an elastomer, (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. Each component contained in the resin composition will be described in detail below.

<(a) Elastomer>
The resin composition contains (a) an elastomer. In the present invention, the elastomer means a resin having flexibility, and is not particularly limited. , an isoprene structural unit, an isobutylene structural unit, and a polycarbonate structural unit. By including a flexible resin such as the component (a), the peel strength of the plating against copper or the like is improved, and the occurrence of warpage or the like can be suppressed.

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

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

Component (a) is preferably one or more resins selected from resins having a glass transition temperature of 25°C or lower and resins that are 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. Although the lower limit of the glass transition temperature is not particularly limited, it is usually −15° C. or higher. The resin that is liquid at 25°C is preferably a resin that is liquid at 20°C or lower, more preferably a resin that is liquid at 15°C or lower.

Component (a) is not particularly limited as long as it is a flexible resin, but it preferably has a functional group capable of reacting with component (b), which will be described later. The functional group capable of reacting with the component (b) includes a functional group that appears upon heating.

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

A preferred embodiment of component (a) is butadiene resin. As the butadiene resin, a butadiene resin that is liquid at 25°C or has a glass transition temperature of 25°C or less is preferable. 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 preferred. Here, "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 in the side chain. The butadiene structure may be partially or wholly hydrogenated. Here, the "hydrogenated polybutadiene skeleton-containing resin" refers to a resin in which at least a portion of the polybutadiene skeleton is hydrogenated, and does not necessarily have to be a resin in which the polybutadiene skeleton is completely hydrogenated.

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 15,000. is. Here, the number average molecular weight (Mn) of the resin is the polystyrene equivalent number average molecular weight measured using GPC (gel permeation chromatography).

When the butadiene resin has a functional group, the functional group equivalent is preferably 100-10,000, more preferably 200-5,000. Note that the functional group equivalent is the number of grams of resin containing 1 gram equivalent of functional group. For example, the epoxy group equivalent can be measured according to JIS K7236. The hydroxyl equivalent can be calculated by dividing the molecular weight of KOH by the hydroxyl value measured according to JIS K1557-1.

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

In addition, as another preferred embodiment of the component (a), a linear polyimide made from hydroxy group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (Japanese Patent Laid-Open No. 2006-37083, International Publication No. 2008/153208 Polyimide described in No.) can also be used. The butadiene structure content of the polyimide resin is preferably 60% to 95% by mass, more preferably 75% to 85% by mass. Details of the polyimide resin can be referred to in JP-A-2006-37083 and WO 2008/153208, the contents of which are incorporated herein.

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

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

When the acrylic resin has a functional group, the functional group equivalent is preferably 1,000 to 50,000, more preferably 2,500 to 30,000.

Specific examples of acrylic resins include Teisan Resin "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 5-34 mgKOH/g, weight average molecular weight 400,000-900,000, Tg-30-5°C), "SG-80H", "SG-80H-3", "SG -P3" (epoxy group-containing acrylate copolymer resin, epoxy equivalent 4761-14285 g/eq, weight average molecular weight 350,000-850,000, Tg 11-12°C), "SG-600TEA", "SG-790" ( Hydroxy group-containing acrylic acid ester copolymer resin, hydroxyl value 20-40 mgKOH/g, weight average molecular weight 500,000-1,200,000, Tg -37--32°C), "ME-2000" manufactured by Negami Kogyo Co., Ltd., "W-116.3" (carboxy group-containing acrylic ester copolymer resin), "W-197C" (hydroxyl group-containing acrylic ester copolymer resin), "KG-25", "KG-3000" (epoxy group-containing acrylic acid ester copolymer resin) and the like.

A preferred embodiment of component (a) is a carbonate resin. As the carbonate resin, a carbonate resin having a glass transition temperature of 25° C. or less is preferable, and a hydroxyl 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, an epoxy group-containing carbonate resin, or a One or more resins selected from the group consisting of containing carbonate resins, isocyanate group-containing carbonate resins and urethane group-containing carbonate resins are preferred. Here, "carbonate resin" means a resin containing a carbonate structure, and in these resins, the carbonate structure may be contained in the main chain or in the side chain.

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

Specific examples of carbonate resins include "T6002" and "T6001" (polycarbonate diols) 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.

Linear polyimides (PCT/JP2016/053609) made from hydroxyl-terminated polycarbonates, diisocyanate compounds and tetrabasic acid anhydrides can also be used. The carbonate structure content of the polyimide resin is preferably 60% to 95% by mass, more preferably 75% to 85% by mass. Details of the polyimide resin can be referred to the description of PCT/JP2016/053609, the content of which is incorporated herein.

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

Specific examples of polysiloxane resins are "SMP-2006", "SMP-2003PGMEA" and "SMP-5005PGMEA" manufactured by Shin-Etsu Silicone Co., Ltd. Further, amine group-terminated polysiloxanes, linear polyimides made from tetrabasic acid anhydride (International Publication No. 2010/053185), and the like can be mentioned. Specific examples of the alkylene resin include "PTXG-1000" and "PTXG-1800" manufactured by Asahi Kasei Fibers Co., Ltd. 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 diblock copolymer) manufactured by Kaneka Corporation. .

Furthermore, preferred embodiments of component (a) include acrylic rubber particles, polyamide fine particles, silicone particles, and the like. Specific examples of acrylic rubber particles include fine particles of resins made insoluble and infusible in organic solvents by chemically cross-linking resins exhibiting rubber elasticity such as acrylonitrile-butadiene rubber, butadiene rubber, and acrylic rubber. Specifically, XER-91 (manufactured by Japan Synthetic Rubber Co., Ltd.), Staphyloid AC3355, AC3816, AC3832, AC4030, AC3364, IM101 (manufactured by Ganz Kasei Co., Ltd.), Pararoid EXL2655, EXL2602 (manufactured by Kureha manufactured by Kagaku Kogyo Co., Ltd.) and the like. Specific examples of the polyamide fine particles include aliphatic polyamides such as nylon, and polyamideimides, as long as they have flexible skeletons. )) and SP500 (manufactured by Toray Industries, Inc.).

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 taken as 100% by mass from the viewpoint of imparting flexibility. , preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less. Also, the lower limit is preferably 35% by mass or more, more preferably 45% by mass or more, and even more preferably 55% by mass or more.

<(b1) Liquid Epoxy Resin Having Aromatic Structure, and (b2) Solid Epoxy Resin Having Aromatic Structure>
The resin composition contains (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 a "liquid epoxy resin") has two or more epoxy groups in one molecule and is liquid at a temperature of 20°C and has an aromatic structure. (b2) 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 , an epoxy resin having an aromatic structure that is solid at a temperature of 20°C. Aromatic structures are chemical structures generally defined as aromatic and also include polycyclic aromatic and heteroaromatic rings. In the present invention, by using a liquid epoxy resin and a solid epoxy resin together, a resin composition having excellent flexibility can be obtained.

Liquid epoxy resins 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 resins, alicyclic epoxy resins having an ester skeleton having an aromatic structure, cyclohexane dimethanol type epoxy resins having an aromatic structure, and epoxy resins having a butadiene structure having an aromatic structure are preferred, 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 more preferable. Specific examples of liquid epoxy resins include "HP4032", "HP4032D" and "HP4032SS" (naphthalene type epoxy resins) manufactured by DIC Corporation, "828US" and "jER828EL" manufactured by Mitsubishi Chemical Corporation (bisphenol A type epoxy resin), "JER806", "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolac type epoxy resin), "630", "630LSD" (glycidylamine type epoxy resin), Nippon Steel & Sumikin Chemical ( Co., Ltd. "ZX1059" (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin), Nagase ChemteX Co., Ltd. "EX-721" (glycidyl ester type epoxy resin), Daicel Co., Ltd. "Celoxide 2021P" (alicyclic epoxy resin having an ester skeleton) of Nippon Steel Chemical Co., Ltd. "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane). 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 epoxy resin content 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 still more preferably 8% by mass or less.

The epoxy equivalent of the liquid epoxy resin is preferably 50-5000, more preferably 50-3000, even more preferably 80-2000, still more preferably 110-1000. Within this range, the crosslink density of the cured product of the resin composition is sufficient, and when the cured product is used as a sealing layer, a sealing layer with 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 one equivalent of epoxy groups.

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

Solid epoxy resins 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 preferred, naphthalene-type tetrafunctional epoxy resin, naphthol-type epoxy resin, biphenyl-type epoxy resin, naphthyl A lene ether type epoxy resin is more preferable, and a naphthalene type tetrafunctional epoxy resin and a naphthylene ether type epoxy resin are more preferable. Specific examples of solid epoxy resins include "HP4032H" (naphthalene-type epoxy resin), "HP-4700", "HP-4710" (naphthalene-type tetrafunctional epoxy resin), and "N-690" manufactured by DIC Corporation. ” (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 novolak type epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin), Nippon Steel & Sumitomo Metal Corporation Chemical Co., Ltd. "ESN475V" (naphthol type epoxy resin), "ESN485" (naphthol novolac type epoxy resin), Mitsubishi Chemical Corporation "YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000HK ” (Bixylenol type epoxy resin), “YL7760” (bisphenol AF type epoxy resin), “YX8800” (anthracene type epoxy resin), “PG-100”, “CG-500” manufactured by Osaka Gas Chemicals Co., Ltd., "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "jER1031S" (tetraphenylethane type epoxy resin), " 157S70” (bisphenol novolac type epoxy resin), Mitsubishi Chemical Co., Ltd. “YX4000HK” (bixylenol 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.

From the viewpoint of adjusting the viscosity of the resin composition, the content of the solid epoxy resin in the resin composition is preferably 0.1% by mass or more, when the non-volatile component in the resin composition is 100% by mass. It is preferably 0.2% by mass or more, more preferably 0.5% by mass or more. The upper limit of the epoxy resin content 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 still more preferably 5% by mass or less.

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

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

When the content of the liquid epoxy resin is B1 (% by mass) and the content of the solid epoxy resin is B2 (% by mass), it is preferable to satisfy the relationship B1>B2 from the viewpoint of adjusting the melt viscosity. Further, 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. Although the upper limit of the difference (B1-B2) is not particularly limited, it can usually be 10% by mass or less, 5% by mass or less, or the like.

The mass 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. By setting the amount ratio of the liquid epoxy resin to the solid epoxy resin in such a range, i) when used in the form of an adhesive film, moderate tackiness is brought about, and ii) when used in the form of an adhesive film. iii) a cured product having sufficient breaking strength can be obtained. From the viewpoint of the above effects i) to iii), the mass ratio of the liquid epoxy resin to the solid epoxy resin (solid epoxy resin/liquid epoxy resin) is preferably in the range of 0.05 to 0.8. Preferably, the range of 0.1 to 0.5 is more preferable.

<(c) Inorganic filler>
The resin composition contains (c) an inorganic filler. The material of the inorganic filler is not particularly limited, but examples include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, and 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 , zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly suitable. As silica, spherical silica is preferable. An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.

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 circuit embedding properties. Although the lower limit of the average particle size is not particularly limited, it is preferably 0.01 μm or more, more preferably 0.05 μm or more, and still more preferably 0.1 μm or more. Examples of commercially available inorganic fillers having such an average particle size include “YC100C”, “YA050C”, “YA050C-MJE” and “YA010C” manufactured by Admatechs Co., Ltd., manufactured by Denki Kagaku Kogyo Co., Ltd. "UFP-30", Tokuyama Co., Ltd. "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS-5N", Admatechs Co., Ltd. "SC2500SQ", "SO-C6", "SO -C4", "SO-C2", "SO-C1", "ADMAFINE" and "ADMANANO" manufactured by Admatechs Co., Ltd., "SFP Series" manufactured by Denki Kagaku Kogyo Co., Ltd., Nippon Steel & Sumikin Materials Co., Ltd. "SP (H) Series" manufactured by Sakai Chemical Industry Co., Ltd., "Sciqas Series" manufactured by Sakai Chemical Industry Co., Ltd., "Seahoster Series" manufactured by Nippon Shokubai Co., Ltd., and the like.

The average particle size of the inorganic filler can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is prepared on a volume basis using a laser diffraction/scattering particle size distribution analyzer, and the median diameter thereof can be used as the average particle size for measurement. As the measurement sample, one obtained by ultrasonically dispersing an inorganic filler in water can be preferably used. As a laser diffraction scattering type particle size distribution analyzer, "LA-500" manufactured by HORIBA, Ltd. can be used.

Inorganic fillers include aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, organosilazane compounds, and titanate coupling agents from the viewpoint of improving moisture resistance and dispersibility. It is preferably treated with one or more surface treatment agents such as. Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. silane), Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd. "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM-4803" (long chain epoxy type silane coupling agents) and the like.

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m ² or more, more preferably 0.1 mg/m ² or more, and more preferably 0.2 mg/m ² from the viewpoint of improving the dispersibility of the inorganic filler. 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, it is preferably 1 mg/m ² or less, more preferably 0.8 mg/m ² or less, and further preferably 0.5 mg/m ² or less. 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 (eg, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treatment agent, and ultrasonic cleaning is performed at 25° C. for 5 minutes. After removing the supernatant liquid and drying the solid content, a carbon analyzer can be used to measure the amount of carbon per unit surface area of the inorganic filler. As a carbon analyzer, "EMIA-320V" manufactured by Horiba Ltd. can be used.

From the viewpoint of improving the stability of the resin varnish, the basic fluidity energy per 1 g of the component (c) measured by the powder rheometer was measured under condition C1 with a rotor blade tip speed of 100 mm/sec and a rotor blade approach angle of 5°. , preferably 6 mJ/g or more, more preferably 7 mJ/g or more, still more 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 condition C1 can be performed according to (powder rheometer measurement under condition C1) described later.

From the viewpoint of improving the stability of the resin varnish, the basic fluidity energy per 1 g of the component (c) measured by the powder rheometer was measured under condition C2 with a rotor blade tip speed of 40 mm/sec and a rotor blade approach angle of 5°. , 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 condition C2 can be measured according to (powder rheometer measurement under condition C2) described later.

From the viewpoint of obtaining a sealing layer with a low coefficient of thermal expansion, 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. . It is preferably 55% by mass or more, more preferably 60% by mass or more, and still more preferably 65% by mass or more. The upper limit is preferably 90% by mass or less, more preferably 88% by mass or less, and even more preferably 85% by mass or less, from the viewpoint of mechanical strength, particularly elongation, of the sealing layer.

<(d) Curing agent>
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 component (b). Examples include phenolic curing agents, naphthol curing agents, active ester curing agents, benzoxazine curing agents, and cyanate esters curing agents, carbodiimide curing agents, and the like. A single curing agent may be used alone, or two or more curing agents may be used in combination. Component (d) is preferably one or more selected from phenol-based curing agents, naphthol-based curing agents, active ester-based curing agents, and cyanate ester-based curing agents.

As the phenolic curing agent and the naphtholic curing agent, a phenolic curing agent having a novolac structure or a naphtholic curing agent having a novolac structure is preferable from the viewpoint of heat resistance and water resistance. From the viewpoint of adhesion to the wiring layer, a nitrogen-containing phenolic curing agent is preferable, and a triazine skeleton-containing phenolic curing agent is more preferable. Among them, a triazine skeleton-containing phenol novolac curing agent is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion to the wiring layer.

Specific examples of phenol-based curing agents and naphthol-based curing agents include, for example, “MEH-7700”, “MEH-7810” and “MEH-7851” manufactured by Meiwa Kasei Co., Ltd., manufactured by Nippon Kayaku Co., Ltd. "NHN", "CBN", "GPH", Nippon Steel & Sumikin Co., Ltd. "SN170", "SN180", "SN190", "SN475", "SN485", "SN495V", "SN375", "SN395" , DIC Corporation "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500", "HPC-9500" , “KA-1160”, “KA-1163”, “KA-1165”, and “GDP-6115L” and “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 with high reaction activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds in one molecule. A compound having two or more is preferably used. The active ester 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 curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred. Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, 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, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, Benzenetriol, dicyclopentadiene-type diphenol compound, phenol novolak, and the like. Here, the term "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

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 novolak are preferred. Among them, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferable. "Dicyclopentadiene-type diphenol structure" represents a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

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

Specific examples of benzoxazine-based curing agents include "HFB2006M" manufactured by Showa High Polymer Co., Ltd., and "Pd" and "Fa" manufactured by Shikoku Kasei Kogyo Co., Ltd.

Examples of cyanate ester curing agents include bisphenol A dicyanate, polyphenolcyanate, oligo(3-methylene-1,5-phenylenecyanate), 4,4′-methylenebis(2,6-dimethylphenylcyanate), 4,4 '-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatophenylmethane), bis(4-cyanate-3,5-dimethyl Bifunctional cyanate resins such as phenyl)methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl)thioether, and bis(4-cyanatophenyl)ether, phenol Polyfunctional cyanate resins derived from novolacs, cresol novolaks, etc., and prepolymers obtained by partially triazine-forming these cyanate resins. Specific examples of cyanate ester curing agents include "PT30" and "PT60" (both phenol novolac type polyfunctional cyanate ester resins), "BA230" and "BA230S75" (bisphenol A dicyanate) manufactured by Lonza Japan Co., Ltd. a prepolymer that is partially or wholly triazined to form a trimer), and the like.

Specific examples of carbodiimide-based curing agents include “V-03” and “V-07” manufactured by Nisshinbo Chemical Co., Ltd., and the like.

The content of the curing agent in the resin composition is not particularly limited. % by mass or less. Moreover, the lower limit is not particularly limited, but 1% by mass or more is preferable.

<(e) Curing accelerator>
The resin composition may contain (e) a curing accelerator. Examples of curing accelerators include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators. Curing accelerators, imidazole-based curing accelerators, and metallic curing accelerators are preferred, and amine-based curing accelerators, imidazole-based curing accelerators, and metallic curing accelerators are more preferred. A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type.

Phosphorus curing accelerators include, for example, triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate. , tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate, and triphenylphosphine and tetrabutylphosphonium decanoate are preferred.

Examples of amine curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo (5,4,0)-undecene and the like, with 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene being preferred.

Examples of imidazole curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 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 trimellitate, 1-cyanoethyl- 2-phenylimidazolium trimellitate, 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 isocyanurate, 2-phenylimidazole isocyanurate, 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 the like, and adducts of imidazole compounds and epoxy resins, 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, such as "P200-H50" manufactured by Mitsubishi Chemical Corporation.

Guanidine curing accelerators include, for example, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, Pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0] Dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide and the like, with dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene being preferred.

Metal-based curing accelerators include, for example, organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organocopper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. organic zinc complexes such as iron (III) acetylacetonate; organic nickel complexes such as nickel (II) acetylacetonate; organic manganese complexes such as manganese (II) acetylacetonate; Examples of organic metal salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

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 non-volatile components 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 flame retardants include organic phosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants, and metal hydroxides. A flame retardant may be used individually by 1 type, or may use 2 or more types together.

As the flame retardant, a commercially available product such as "HCA-HQ" manufactured by Sanko Co., Ltd. may be used.

When the resin composition contains a flame retardant, the content of the flame retardant is not particularly limited. It is preferably 0.5% by mass to 15% by mass, more preferably 0.5% by mass to 10% by mass.

<(g) optional additive>
The resin composition may further contain other additives as necessary, such other additives as, for example, organometallic compounds such as organocopper compounds, organozinc compounds and organocobalt compounds, and resin additives such as binders, thickeners, antifoaming agents, leveling agents, adhesion imparting agents, and coloring agents.

From the viewpoint of suppressing warping, the resin composition (or temporary resin composition layer) of the present invention has an elastic modulus at 23 ° C. of a thermoset product obtained by heat curing at 180 ° C. for 1 hour is usually 18 GPa or less, It is preferably 15 GPa or less, more preferably 13 GPa or less, 11 GPa or less, 10 GPa or less, 9 GPa or less, or 8 GPa or less. Although the lower limit is not particularly limited, it can be, for example, 0.01 GPa or more, 0.5 GPa or more, or 1 GPa or more. The elastic modulus can be measured according to the method described in <Measurement of Elastic Modulus> below.

The resin composition (or temporary resin composition layer) of the present invention exhibits the property of suppressing the occurrence of warpage. The amount of warp is preferably 2 cm or less, more preferably 1 cm or less. Although the lower limit is not particularly limited, it is 0.01 cm or more. The warp can be measured according to the method described in <Confirmation of Warp Amount> described later.

The moisture permeability coefficient of the thermoset 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 warping 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. Although the upper limit is not particularly limited, it 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 /24h) or less. The moisture permeability coefficient can be measured according to the method described in <Measurement of Moisture Permeability Coefficient> below.

The average linear thermal expansion coefficient (CTE) of the thermoset obtained by thermosetting 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 less, more preferably 15 ppm/°C or less, still more preferably 10 ppm/°C or less. Although the lower limit is not particularly limited, it may be 1 ppm/° C. or more. 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.

A resin varnish made of the resin composition of the present invention exhibits excellent stability. The resin varnish made of the resin composition of the present invention preferably does not cause sedimentation of the resin varnish component on the bottom of the container even after standing still for 4 days, and more preferably does not cause the resin varnish to remain on the bottom of the container even after standing still for 5 days. No precipitation of ingredients occurs. The stability of the resin varnish can be measured according to the procedure of <Stability of 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 thermoset obtained by thermosetting the resin composition (or temporary resin composition layer) of the present invention at 180° C. for 1 hour does not swell after curing. Blistering 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 a sheet-like resin composition comprises:
(A) a step of preparing two or more adhesive films each having a support and a temporary resin composition layer containing the resin composition of the present invention provided on the support;
(B) a step of superimposing the temporary resin composition layers of the adhesive film so that they are 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. Moreover, a sheet-shaped resin composition is manufactured by the said manufacturing method.

Each step will be described below.

<Step (A)>
The step (A) is a step of preparing two or more adhesive films each having a support and a temporary resin composition layer containing the resin composition of the present invention provided on the support. This is the step of preparing the above adhesive film. The two or more adhesive films 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 improving the precision of the thickness. Although the upper limit of the thickness of the temporary resin composition layer is not particularly limited, it is preferably 700 μm or less, more preferably 600 μm or less.

Examples of the support include a film made of a plastic material, a metal foil, and a release paper, 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, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"). ), polyesters such as polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylic polymers such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), poly Ether ketone, polyimide and the like can be mentioned. Among them, 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, with copper foil being preferred. 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 other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. may be used.

The support may be subjected to matte treatment or corona treatment on the surface to be bonded to the temporary resin composition layer.

Further, as the support, a support with a release layer having a release layer on the surface to be bonded to the temporary resin composition layer may be used. The release agent used in the release layer of the release layer-attached support includes, for example, one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . As the support with a release layer, a commercially available product may be used, for example, "SK-1" manufactured by Lintec Corporation, which is a PET film having a release layer containing an alkyd resin 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, more preferably in the range of 10 μm to 60 μm. When a release layer-attached support is used, the thickness of the release layer-attached support as a whole is preferably within the above range.

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

Examples of organic solvents include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate and other acetates, cellosolve and butyl carbitol. carbitols, aromatic hydrocarbons such as toluene and xylene, amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

Drying may be carried out by a known method such as heating or blowing hot air. Although the drying conditions are not particularly limited, drying is performed so that the content of the organic solvent in the temporary resin composition layer is 10% by mass or less, preferably 5% by mass or less. Although it varies depending on the boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing 30% to 60% by mass of the organic solvent, the temporary resin A composition layer can be formed.

In the adhesive film, a protective film conforming 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). Although the thickness of the protective film is not particularly limited, it is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to prevent the surface of the temporary resin composition layer from being dusted or scratched. The adhesive film can be wound into a roll and stored. When the adhesive film has a protective film, it can be used by peeling off the protective film.

<Step (B)>
Next, the temporary resin composition layers of the adhesive films prepared in step (A) are superimposed so that they are in contact with each other (step (B)). In that case, a roll-to-roll method can be used, and for example, a linear pressure of 0.02 to 1 MPa/mm ² may be applied when overlapping.

The step (B) is performed only once or repeated two or more times to form a resin composition layer having a (total) thickness of 400 μm to 900 μm. By setting the thickness of the resin composition layer to 400 μm to 900 μm in this manner, the parts can be suitably 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-like resin composition of the present invention, from the viewpoint of improving yield, reducing the risk of foreign matter adhesion by suppressing the number of coatings, and improving the accuracy of the thickness of the resin composition layer, the above Step (B) is preferably performed only once or repeated only twice.

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

The two or more adhesive films prepared in 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 may be the same. may be different.

(2) Case of Repeating Step (B) Twice or More An example of repeating step (B) twice is as follows. First, in step (A), first to third adhesive films are prepared and superimposed so that the temporary resin composition layers of the first and second adhesive films are in contact with each other. After that, after peeling one of the supports, the temporary resin composition layer of the third adhesive film and the temporary resin composition layer obtained by integrating the temporary resin composition layers of the first and second adhesive films are in contact. superimposed on the Thus, a resin composition layer having a predetermined thickness is formed. The same can be done when the step (B) is repeated three times or more.

In addition, when the step (B) is repeated two or more times, the layer structure in the middle of production in which the step (B) has been performed one or more times but has not reached the final predetermined thickness is also "temporary resin composition "Monolayer".

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

In addition, when the drying treatment related to the drying conditions in step (A) is performed while transporting the long roll-shaped support, the drying treatment is continuously performed on the exposed area that is moving. As a result, the long temporary resin composition layer and the resin composition layer are uniformly dried. Further, the resin composition layer formed preferably has a residual solvent content of 0.5% by mass to 5% by mass. From the viewpoint of preventing the generation of voids in the resin composition layer (cured body) during curing, the residual solvent content is preferably 5% by mass or less. Moreover, from the viewpoint of improving the handleability of the resin composition layer, the residual solvent rate is preferably 0.5% by mass or more.

In the step of forming the temporary resin composition layer and/or the step of forming the resin composition layer, it is sequentially checked whether the thickness of the temporary resin composition layer and/or the resin composition layer to be formed is a predetermined thickness. It is preferable to carry out while measuring and controlling 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-like resin composition can be further improved.

Either or both of step (A) and step (B) are preferably carried out by a roll-to-roll method using a long support as the support. Either one or both of step (A) and step (B) may be performed in a batch mode, and each of step (A) and step (B) performed one or more times may be performed in a roll-to-roll method. It may be performed in combination with a batch method.

The step of forming a temporary resin composition layer and / or a resin composition layer by a roll-to-roll method includes a long support (substrate, film ) is continuously conveyed, a 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. It is carried out by forming a temporary resin composition layer or a resin composition layer with a thin film, and measuring the thickness of the continuously formed layer.

Step (A) and step (B), which is performed once or repeated two or more times, can also be performed as a series of steps in a roll-to-roll manner. 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 covering the surface of the resin composition layer. The protective film contributes to prevention of adhesion of dust and the like to the resin composition layer and prevention of scratches. As materials for the protective film, the same materials as those described for the temporary resin composition layer and the support can be used. Although the thickness of the protective film is not particularly limited, it is, for example, 1 μm to 40 μm. In particular, it is preferable that the thickness of the protective film is thinner than the thickness of the support, because it is possible to prevent slippage and wrinkles when producing a roll-shaped sheet-like 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 performing the sealing step. It can be used by exposing the resin composition layer with a

(Mode of use of film for sealing parts)
When the sheet-like resin composition is used as a component-sealing film, the component that can be sealed with the component-sealing film is not particularly limited, and may be any suitable component depending on the desired function. Examples of components that can be sealed with a component sealing film include active components such as semiconductor chips and semiconductor chip packages, in addition to passive components such as capacitors, inductors and resistors. The component-sealing film according to the present invention can be suitably used, for example, in a component-sealing process for a component-embedded circuit board. The component sealing film according to the present invention is used in the sealing process (underfill molding) of 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 from a cured product of the resin composition of the present invention, and the semiconductor device of the present invention (preferably, multi-chip package, package-on-package, wafer-level package, A panel level package (or system-in package) includes a sealing layer formed from a cured product of the resin composition of the present invention.

If the sealing process is performed using a component sealing film, when a component with a greater thickness is mounted, the difference in the height of the unevenness of the sealing surface on which the sealing layer (sealing portion) is formed will increase. Even if it is large, it can be embedded effectively and a sealing layer (sealing portion) can be formed with high precision. By this sealing process, it is possible to efficiently manufacture high-quality component-embedded circuit boards and semiconductor devices with high yields.

Applications of component-embedded circuit boards and semiconductor devices to which the component-sealing film is used include, for example, electrical appliances (e.g., computers, mobile phones, digital cameras, televisions, etc.) and vehicles (e.g., motorcycles, automobiles, trains, etc.). Various forms of component-embedded circuit boards and semiconductor devices used for controlling the operation of ships, aircraft, etc., can be mentioned.

An example of the sealing process using the component sealing film will be described. First, a component-embedded circuit board on which a component to be sealed is mounted and a semiconductor device are prepared. The component to be sealed is placed so that the resin composition layer of the component sealing film is in contact with the surface of the component. Components are then embedded and coated in the resin composition layer, for example, by performing a press molding process or a vacuum lamination process.

Such press molding process or vacuum lamination process can be carried out under arbitrary and suitable conditions provided that the functions of the parts to be sealed are not impaired. The temperature conditions and pressure conditions at this time may be determined in consideration of the minimum melt viscosity of the resin composition layer. Such a press molding process or vacuum lamination process can be carried out using a commercially available vacuum press machine or vacuum laminator machine. A semiconductor chip is generally likely to be deteriorated by stress and heat treatment, so it is preferable to embed it by a vacuum lamination process using a vacuum laminator device. Such vacuum lamination conditions can be, for example, 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 the press molding process or the vacuum lamination process, or may be peeled off after the thermosetting process. The support is preferably peeled off after the heat curing step. In addition, for example, when the support has a heat radiation function, a protection function, or the like, the support may be used as it is without being separated 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 thermally cured. Through 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, etc., provided that the functions of the parts to be sealed are not impaired. Moreover, it is preferable to perform this thermosetting process under atmospheric pressure (normal pressure).

Through the above sealing process, the resin composition layer becomes a cured body that seals the parts, that is, a sealing layer.

If desired, a singulation step of cutting the structure provided with the sealing layer into two or more pieces may be performed. This singulation step can be performed by grinding and cutting the margin region by a conventionally known dicing device equipped with a rotary blade, for example. By this singulation process, the structure with the sealing layer formed thereon is singulated into a plurality of functional elements, each of which has a sealing portion that encloses and seals the component.

EXAMPLES The present invention will be specifically described below by way of examples, but the present invention is not limited to these examples. In the following description, "parts" and "%" mean "mass parts" and "mass%", respectively, unless otherwise specified. Example 7 shall be read as Reference Example 7. The same applies to Table 1 below.

(Inorganic filler used)
"ADMAFINE" and "ADMANANO" manufactured by Admatechs Co., Ltd., "SFP series" and "UFP series" manufactured by Denki Kagaku Kogyo Co., Ltd., "SP (H) series" manufactured by Nippon Steel & Sumikin Materials Co., Ltd., Sakai Chemical "Sciqas series" manufactured by Kogyo Co., Ltd. and "Seahoster series" manufactured by Nippon Shokubai Co., Ltd. were subjected to surface treatment alone or in combination to prepare inorganic fillers 1 to 5 below.
Inorganic filler 1:
Average particle size: 2.1 μm, aminosilane-based 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 .2 mJ/g
Inorganic filler 2:
Average particle size: 2.1 μm, aminosilane-based coupling agent: “KBM573” manufactured by Shin-Etsu Chemical Co., Ltd., basic flow energy under measurement condition C1: 9.2 mJ/g, basic flow energy under measurement condition C2: 14 .1mJ/g
Inorganic filler 3:
Average particle diameter: 2.4 μm, aminosilane-based coupling agent: “KBM573” manufactured by Shin-Etsu Chemical Co., Ltd., basic fluidity energy under measurement condition C1: 13 mJ/g, basic fluidity energy under measurement condition C2: 21.3 mJ /g
Inorganic filler 4:
Average particle diameter: 1.6 μm, aminosilane-based 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 diameter: 2.8 μm, aminosilane-based 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 .2 mJ/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 rotor blade (diameter: 48 mm) tip speed of 100 mm/sec and a rotor 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 rotor blade (diameter: 48 mm) tip speed of 40 mm/sec and a rotor blade approach angle of 5°. did.

(Synthesis of Elastomer A)
A flask equipped with a stirrer, thermometer and condenser was charged with 292.09 g of ethyl diglycol acetate and 292.09 g of Solvesso 150 (aromatic solvent, manufactured by Exxon Mobil) as solvents, and 100.1 g of diphenylmethane diisocyanate ( 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. Then, 195.9 g (0.2 mol) of nonylphenol novolak resin (hydroxyl equivalent 229.4 g/eq, average 4.27 functionality, average calculated molecular weight 979.5 g/mol) and 41.0 g ( 0.1 mol) was charged, the temperature was raised to 150° C. over 2 hours, and the reaction was allowed to proceed for 12 hours.

After the reaction, a transparent brown liquid was obtained, and a polyimide resin solution with a non-volatile content of 55% and a viscosity of 14 Pa·s (25° C.) was obtained. The obtained polyimide resin solution was applied to a ^KBr plate, and the infrared absorption spectrum of the sample after volatilizing the solvent component was measured. Absorption of the imide ring was confirmed at ⁻¹ , 1780 cm ⁻¹ and 1720 cm ⁻¹ . Also, absorption of urethane bonds was confirmed at 1540 cm ⁻¹ . Further, the amount of carbon dioxide gas generated with the progress of imidization was tracked by the change in the weight charged in the flask and found to be 8.8 g (0.2 mol). The functional group equivalent of the acid anhydride of ethylene glycol bisanhydrotrimellitate is 0.2 mol, the amount of carbon dioxide generated is also 0.2 mol, all the acid anhydride is used for imide formation, and the carboxylic acid It is concluded that no anhydride is present. As a result, 0.2 mol of the isocyanate groups are converted to imide bonds, and the remaining isocyanate groups form urethane bonds with the hydroxyl groups of polybutadiene diol and the phenolic hydroxyl groups in the nonylphenol novolac resin, thereby forming phenol novolac resins in the resin. A polyimide urethane resin (elastomer A) was obtained which had phenolic hydroxyl groups in the resin and had some of the phenolic hydroxyl groups modified with urethane bonds.

<Measurement of Moisture Permeability Coefficient>
(Preparation of cured product for evaluation)
A glass cloth-based epoxy resin double-sided copper clad laminate (Matsushita Electric Works Co., Ltd.) was applied to the untreated side of a release agent-treated PET film (“501010” manufactured by Lintec Co., Ltd., thickness 38 μm, 240 mm square). "R5715ES" (thickness: 0.7 mm, 255 mm square) were overlapped and fixed on four sides with a polyimide adhesive tape (width: 10 mm) (hereinafter referred to as "fixed PET film").
PET film ("Lumirror R80" manufactured by Toray Industries, Inc., thickness 38 μm, PET film obtained by releasing the resin varnishes prepared in Examples and Comparative Examples with an alkyd resin release agent ("AL-5" manufactured by Lintec Corporation), A softening point of 130 ° C., hereinafter referred to as “releasing PET”) is coated with a die coater so that the thickness of the temporary resin composition layer after drying is 40 μm, and is applied at 80 ° C. to 120 ° C. (average 100 ° C.). After drying for 10 minutes, an adhesive film was obtained. Each adhesive film (thickness 40 μm, 200 mm square) is separated from the fixed PET film by using a batch type vacuum pressure laminator (Nikko Materials Co., Ltd. 2-stage build-up laminator, CVP700). A resin sheet with a support was obtained by laminating in the center so as to be in contact with the stencil-treated surface. The lamination process was carried out by pressure bonding for 30 seconds at 100° C. and pressure of 0.74 MPa after reducing the pressure to 13 hPa or less for 30 seconds.

Next, under the temperature condition of 100°C, the film was placed in an oven at 100°C for 30 minutes, and then under the temperature condition of 175°C, it was transferred to an oven at 175°C and then heat-cured for 30 minutes. After that, the substrate was taken out in an atmosphere of room temperature, the release PET was peeled off from the resin sheet with the support, and the substrate was placed in an oven at 190° C. and thermally cured under curing conditions for 90 minutes.

After thermal curing, the polyimide adhesive tape is peeled off, the cured product is removed from the glass cloth-based epoxy resin double-sided copper clad laminate, and the PET film ("501010" manufactured by Lintec Co., Ltd.) is also peeled off to obtain a sheet-like cured product. got The resulting cured product is referred to as "evaluation cured product".

The cured product for evaluation (40 μm thick) was cut into a circle with a diameter of 70 mm, and the moisture permeability was measured according to the moisture permeability test method (cup method) of JIS Z0208. Specifically, the moisture permeability (g/m ² · 24 h) is obtained by measuring the weight of water that has permeated the sample at 60 ° C., 85% RH, 24 hours, and the moisture permeability coefficient (g・mm/m ²・24h) was calculated. The average values of the three specimens are shown in the table below.

<Measurement of average coefficient of linear thermal expansion (CTE)>
The cured product for evaluation was cut into a test piece having a width of 5 mm and a length of 15 mm, and thermomechanical analysis was performed by a tensile load method using a thermomechanical analyzer (“Thermo Plus TMA8310” manufactured by Rigaku Corporation). Specifically, after mounting the test piece on the thermomechanical analyzer, the measurement was performed twice continuously under the measurement conditions of a load of 1 g and a temperature increase 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 from 25°C to 150°C was calculated.

<Measurement of elastic modulus>
The cured product for evaluation was cut into a dumbbell-shaped No. 1 specimen to obtain a test piece. The tensile strength of the test piece was measured using a tensile tester "RTC-1250A" manufactured by Orientec Co., Ltd., and the elastic modulus at 23°C was obtained. The measurement was carried out according to 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 varnishes prepared in Examples and Comparative Examples were coated on a polyethylene terephthalate (PET) film (thickness: 38 μm) so that the thickness of the resin composition layer after drying was 400 μm. After coating with a die coater and drying for 10 minutes at 80 to 120° C. (average 100° C.) to obtain an adhesive film, an adhesive film made of the same resin varnish is attached to form a sheet-shaped resin composition having a thickness of 800 μm. obtained, and one of the supports was peeled off. Next, after laminating the side of the sheet-like resin composition from which the support was peeled off to a copper foil (“JTC foil” manufactured by JX Nippon Mining & Metals Co., Ltd., copper foil thickness 18 μm), the PET film was removed. The obtained copper foil with the sheet-like resin composition was placed on both sides of a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.3 mm, Matsushita Electric Works Co., Ltd. R5715ES). 1 μm with a roughening treatment agent (CZ8100) manufactured by Co., Ltd.) to a batch type vacuum pressure laminator (2-stage build-up laminator “CVP700” 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, heat curing at 180 ° C. for 90 minutes, check for swelling between the substrate and the sheet-shaped resin composition or between the sheet-shaped resin composition and the copper foil. It was evaluated as "○", and those with swelling were evaluated as "X".

<Checking the amount of warpage>
The resin varnishes prepared in Examples and Comparative Examples were coated on a polyethylene terephthalate (PET) film (thickness 38 μm) so that the thickness of the temporary resin composition layer after drying was 400 μm. After coating with a tar and drying at 80° C. to 120° C. (average 100° C.) for 10 minutes to obtain an adhesive film, an adhesive film made of the same resin varnish is laminated to form a sheet-shaped resin composition having a thickness of 800 μm. obtained, and one of the supports was peeled off. Batch-type vacuum pressurization was applied to one side of a double-sided copper-clad laminate (copper foil thickness: 18 μm, substrate thickness: 0.15 mm, manufactured by Mitsubishi Gas Chemical Co., Ltd., size: 15 cm x 18 cm) made of glass cloth base material BT resin. Laminating the side of the sheet-shaped resin composition from which the support is peeled off with a laminator (2-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.), removing the PET film, and then 100 ° C. for 30 minutes After heating, it was thermally cured at 180° C. for 90 minutes, placed on a flat surface, and the amount of warpage was confirmed. The average value of the amount of warpage at each of the four corners was evaluated as "◯" when less than 1 cm, "Δ" when 1 cm or more and less than 2 cm, and "x" when 2 cm or more.

<Stability of resin varnish>
The resin varnishes prepared 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. "O" indicates that the resin varnish component did not precipitate at the bottom of the container after standing for 5 days. A case in which the varnish component precipitated was indicated as "Δ", and a case in which the resin varnish component precipitated on the bottom of the container by the 4th day was indicated as "x".

<Example 1>
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) 30 parts, biphenyl type Epoxy resin (Nippon Kayaku Co., Ltd. "NC-3000H", epoxy equivalent: 288 g / eq) 8 parts, aminophenol type epoxy resin (Mitsubishi Chemical Co., Ltd. "630LSD", epoxy equivalent: 90 to 105 g / eq ) 5 parts, curing accelerator ("2P4MZ" manufactured by Shikoku Kasei Co., Ltd., imidazole derivative) 1 part, acrylic acid ester copolymer (manufactured by Nagase ChemteX Co., Ltd. "Teisan Resin SG-P3", solid content 15% of methyl ethyl ketone solution, Tg 12 ° C., functional group equivalent weight 4762 g / eq, weight average molecular weight Mw 850,000) 1,000 parts, cresol novolac resin (manufactured by DIC Corporation "KA-1163", phenolic hydroxyl group equivalent: 118 g / eq ), 12 parts of inorganic filler 1 (spherical silica surface-treated with an aminosilane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573") (basic fluidity energy: 10.1 mJ/g, average particle diameter: 2.0). 950 parts of 1 μm)) and 20 parts of methyl ethyl ketone were mixed and uniformly dispersed in a high-speed rotating mixer to prepare a resin varnish 1.

<Example 2>
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) 30 parts, biphenyl type Epoxy resin (Nippon Kayaku Co., Ltd. "NC-3000H", epoxy equivalent: 288 g / eq) 8 parts, aminophenol type epoxy resin (Mitsubishi Chemical Co., Ltd. "630LSD", epoxy equivalent: 90 to 105 g / eq ) 5 parts, curing accelerator (“2P4MZ” manufactured by Shikoku Kasei Co., Ltd., imidazole derivative) 1 part, elastomer A 300 parts, cresol novolak resin (manufactured by DIC Corporation “KA-1163”, phenolic hydroxyl group equivalent: 118 g / eq) 12 parts, inorganic filler 2 (spherical silica surface-treated with aminosilane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) (basic fluidity energy: 9.2 mJ / g), average grain A resin varnish 2 was prepared by mixing 950 parts of a diameter of 2.1 μm) and 20 parts of methyl ethyl ketone and uniformly dispersing the mixture with a high-speed rotating mixer.

<Example 3>
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) 30 parts, biphenyl type Epoxy resin (Nippon Kayaku Co., Ltd. "NC-3000H", epoxy equivalent: 288 g / eq) 8 parts, aminophenol type epoxy resin (Mitsubishi Chemical Co., Ltd. "630LSD", epoxy equivalent: 90 to 105 g / eq ) 5 parts, curing accelerator (manufactured by Shikoku Kasei Co., Ltd. "2P4MZ", imidazole derivative) 1 part, elastomer A varnish 300 parts, cresol novolak resin (manufactured by DIC Corporation "KA-1163", phenolic hydroxyl group equivalent: 118 g/eq) 12 parts, inorganic filler 3 (spherical silica surface-treated with aminosilane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) (basic fluidity energy: 13 mJ/g), average particle size 2.4 μm) and 20 parts of methyl ethyl ketone were mixed and uniformly dispersed in a high-speed rotating mixer to prepare a resin varnish 3.

<Example 4>
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) 30 parts, biphenyl type Epoxy resin (Nippon Kayaku Co., Ltd. "NC-3000H", epoxy equivalent: 288 g / eq) 8 parts, aminophenol type epoxy resin (Mitsubishi Chemical Co., Ltd. "630LSD", epoxy equivalent: 90 to 105 g / eq ) 5 parts, curing accelerator (“2P4MZ” manufactured by Shikoku Kasei Co., Ltd., imidazole derivative) 1 part, elastomer A 300 parts, cresol novolak resin (manufactured by DIC Corporation “KA-1163”, phenolic hydroxyl group equivalent: 118 g / eq) 12 parts, inorganic filler 4 (spherical silica surface-treated with aminosilane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) (basic fluidity energy: 18.4 mJ / g) average particle size 1.6 μm) and 20 parts of methyl ethyl ketone were mixed and uniformly dispersed in a high-speed rotating 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 (Nippon Kayaku Co., Ltd. "NC-3000H", epoxy equivalent: 288 g / eq) 12 parts, aminophenol type epoxy resin (Mitsubishi Chemical Co., Ltd. "630LSD", epoxy equivalent: 90 to 105 g / eq ) 8 parts, curing accelerator ("2P4MZ" manufactured by Shikoku Kasei Co., Ltd., imidazole derivative) 1 part, elastomer A 240 parts, cresol novolak resin (manufactured by DIC Corporation "KA-1163", phenolic hydroxyl group equivalent: 118 g / eq) 20 parts, inorganic filler 1 (spherical silica surface-treated with aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (basic fluidity energy: 10.1 mJ / g), average grain A resin varnish 5 was prepared by mixing 950 parts of a diameter of 2.1 μm) and 20 parts of methyl ethyl ketone and uniformly dispersing the mixture with a high-speed rotating mixer.

<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 (Nippon Kayaku Co., Ltd. "NC-3000H", epoxy equivalent: 288 g / eq) 5 parts, aminophenol type epoxy resin (Mitsubishi Chemical Co., Ltd. "630LSD", epoxy equivalent: 90 to 105 g / eq ) 3 parts, curing accelerator ("2P4MZ" manufactured by Shikoku Kasei Co., Ltd., imidazole derivative) 1 part, acrylic acid ester copolymer (manufactured by Nagase ChemteX Co., Ltd. "Teisan Resin SG-P3", solid content 15% methyl ethyl ketone solution, weight average molecular weight of acrylic acid ester copolymer: 850,000) 1,133 parts, cresol novolac resin (DIC Corporation "KA-1163", phenolic hydroxyl group equivalent: 118 g / eq) 9 parts , Inorganic filler 3 (spherical silica surface-treated with an aminosilane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) (basic fluidity energy: 10.1 mJ / g), average particle size 2.4 μm) 950 parts of the mixture and 20 parts of methyl ethyl ketone were mixed and uniformly dispersed with a high-speed rotating 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 (Nippon Kayaku Co., Ltd. "NC-3000H", epoxy equivalent: 288 g / eq) 30 parts, aminophenol type epoxy resin (Mitsubishi Chemical Co., Ltd. "630LSD", epoxy equivalent: 90 to 105 g / eq ) 15 parts, curing accelerator ("2P4MZ" manufactured by Shikoku Kasei Co., Ltd., imidazole derivative) 1 part, elastomer A 140 parts, cresol novolak resin (manufactured by DIC Corporation "KA-1163", phenolic hydroxyl group equivalent: 118 g / eq) 30 parts, inorganic filler 3 (spherical silica surface-treated with aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (basic fluidity energy: 10.1 mJ / g), average grain A resin varnish 7 was prepared by mixing 1100 parts of a diameter of 2.4 μm) and 40 parts of methyl ethyl ketone and dispersing them uniformly with a high-speed rotating mixer.

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

<Comparative Example 1>
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) 76 parts, biphenyl type Epoxy resin (manufactured by Nippon Kayaku Co., Ltd. "NC-3000H", epoxy equivalent: 288 g / eq) 25 parts, naphthalene type epoxy resin (manufactured by DIC Corporation "HP4032", epoxy equivalent 140-150 g / eq) 20 parts , Aminophenol type epoxy resin (manufactured by Mitsubishi Chemical Corporation "630LSD", epoxy equivalent: 90 ~ 105 g / eq) 13 parts, curing accelerator (manufactured by Shikoku Kasei Co., Ltd. "2P4MZ", imidazole derivative) 1 part, polyester Resin (manufactured by Unitika Ltd., "UE3400") 40 parts, cresol novolak resin (manufactured by DIC Corporation "KA-1163", phenolic hydroxyl group equivalent: 118 g / eq) 30 parts, inorganic filler 3 (aminosilane-based cup 950 parts of spherical silica (basic fluidity energy: 13 mJ / g), average particle size 2.4 μm) surface-treated with a ring agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.), and 20 parts of methyl ethyl ketone are mixed, A resin varnish 9 was prepared by dispersing uniformly 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 (% by mass) of component (c)" represents the content of component (c) when the non-volatile component of the resin composition is 100% by mass, and "oil content of component (a) (% by mass)” represents the content of the component (a) when the non-volatile component of the resin composition excluding the component (c) is taken as 100% by mass.

Claims (15)

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 component (c) is 81.6% 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 55 % by mass to 85% by mass when the non-volatile components of the resin composition excluding the component (c) are taken as 100% by mass. Component (a) is at least one selected from butadiene structural units, polysiloxane structural units, (meth)acrylate structural units, alkylene structural units, alkyleneoxy structural units, isoprene structural units, isobutylene structural units, and polycarbonate structural units. The resin composition according to claim 1, having a structural unit of 3. The resin composition according to claim 1, wherein component (a) has a butadiene structural unit. The resin composition according to any one of claims 1 to 3, wherein component (a) is one or more selected from resins having a glass transition temperature of 25°C or less and resins that are liquid at 25°C. . The resin composition according to any one of claims 1 to 4, wherein component (a) has a functional group capable of reacting with component (b). The resin composition according to any one of claims 1 to 5, wherein component (a) has an imide structural unit. The resin composition according to any one of claims 1 to 6, wherein component (a) has a phenolic hydroxyl group. The resin composition according to any one of claims 1 to 7, wherein the component (b1) comprises a glycidylamine type epoxy resin having an aromatic structure. The resin composition according to any one of claims 1 to 8, wherein the content of component (c) is 90% by mass or less when the non-volatile component of the resin composition is 100% by mass. When the content of the component (b1) is B1 (% by mass) and the content of the component (b2) is B2 (% by mass), the relationship of B1>B2 is satisfied. The described resin composition. The resin composition according to any one of claims 1 to 10, wherein the thermoset 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 containing the resin composition according to any one of claims 1 to 11 provided on the support. A component-embedded circuit board, comprising a sealing layer formed from a cured product of the resin composition according to any one of claims 1 to 11. A semiconductor device comprising a sealing layer formed from a cured product of the resin composition according to any one of claims 1 to 11. (A) preparing two or more adhesive films each having a support and a temporary resin composition layer containing the resin composition according to any one of claims 1 to 11 provided on the support; process and
(B) a step of overlapping the temporary resin composition layers of the adhesive film so that they are in contact with each other,
A method for producing a sheet-shaped 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.