Manufacturing method of semiconductor chip package

Abstract

The present invention addresses the problem of providing a method for manufacturing a semiconductor chip package capable of providing a semiconductor chip package in which generation of voids is suppressed. The invention provides a manufacturing method of a semiconductor chip package. The method for manufacturing a semiconductor chip package includes, in the following order: (I) a step of laminating a resin composition layer of a resin sheet including a support and a resin composition layer provided on the support on a semiconductor chip package in which at least one semiconductor chip is mounted on a circuit board, and performing mold underfill; and (II) a step for thermally curing the resin composition layer, wherein the loss tangent of the resin composition layer at the temperature at which the molding underfill is performed is 0.05-1.3 (inclusive).

Description

Technical Field

[0001] The invention relates to a method for manufacturing semiconductor chip packaging. Background Art

[0002] The demand for semiconductor chip packages, which include semiconductor chips bonded to circuit boards, has increased with the popularity of smartphones and the like. In order to protect the bonding and wiring parts between the circuit board and the semiconductor chip from the external environment, semiconductor chip packages have the following process: after bottom filling with a sealing material that fills the gap (gap) between the circuit board and the semiconductor chip, the semiconductor chip package is overmolded with another sealing material.

[0003] This method has the problem of many steps and time-consuming. In addition, due to the use of different sealing materials, stress and other pressures are generated at the resin interface, which also has the problem of reduced reliability. Therefore, for example, as shown in Patent Document 1, a molded underfill is proposed in which overmolding and underfilling are performed simultaneously using a molded underfill sealing material.

[0004] Prior art literature Patent Literature Patent Document 1: Japanese Patent No. 6894077 Summary of the invention

[0005] Technical problem to be solved by the invention In recent years, in order to make electronic components more dense, the gap between the circuit substrate and the semiconductor chip and the gap between the electrodes have become narrower and narrower. The inventors have confirmed that the previous mold bottom filling sealing material is not sufficiently immersed in the gap or between the electrodes. If the immersion in the gap or between the electrodes is insufficient, the filling property of the mold bottom filling sealing material into the gap or between the electrodes is poor, resulting in voids. If voids are generated, the sealing material may expand or reduce reliability when thermally curing it.

[0006] The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a method for manufacturing a semiconductor chip package, which can provide a semiconductor chip package in which generation of voids is suppressed.

[0007] Means of solving technical problems The present inventors have conducted intensive studies and have found that the above-mentioned problems can be solved by a method for manufacturing a semiconductor chip package having the following structure, thereby completing the present invention.

[0008] That is, the present invention includes the following contents. [1] A method for manufacturing a semiconductor chip package, the method comprising: (I) laminating a resin composition layer of a resin sheet having a support and a resin composition layer provided on the support on a semiconductor chip package having at least one semiconductor chip mounted on a circuit board, and performing under-mold filling; and (II) thermally curing the resin composition layer, The resin composition layer has a loss tangent of 0.05 or more and 1.3 or less at a temperature at which the mold underfill is performed. [2] The method for manufacturing a semiconductor chip package according to [1], wherein in step (I), the temperature for performing the mold underfill is 70° C. or higher and 180° C. or lower. [3] The method for manufacturing a semiconductor chip package according to [1] or [2], wherein in step (II), after the resin composition layer is subjected to a heat treatment maintained at a temperature T1, it is subjected to a heat treatment maintained at a temperature T2 higher than temperature T1. [4] The method for manufacturing a semiconductor chip package according to any one of [1] to [3], wherein the resin composition layer contains (A) an inorganic filler. [5] The method for manufacturing a semiconductor chip package according to [4], wherein the content of the (A) inorganic filler is 65% by mass or more when the nonvolatile component of the resin composition layer is 100% by mass. [6] The method for manufacturing a semiconductor chip package according to any one of [1] to [5], wherein the melt viscosity of the resin composition layer is 1000 poise or more and 10000 poise or less. [7] The method for manufacturing a semiconductor chip package according to any one of [1] to [6], wherein the gap between the circuit substrate and the semiconductor chip is 60 μm or less. [8] The method for manufacturing a semiconductor chip package according to any one of [3] to [7], wherein the temperature T2 is 150° C. or higher. [9] The method for manufacturing a semiconductor chip package according to any one of [3] to [8], wherein a difference T2-T1 between the temperature T2 and the temperature T1 is 20°C or more.

[10] The method for manufacturing a semiconductor chip package according to any one of [3] to [9], wherein the temperature T1 is 50° C. or higher. Effects of the Invention

[0009] According to the present invention, it is possible to provide a method for manufacturing a semiconductor chip package capable of providing a semiconductor chip package in which generation of voids is suppressed. DETAILED DESCRIPTION

[0010] Hereinafter, the present invention will be described in detail based on its preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and can be implemented with arbitrary changes within the scope of the claims and their equivalents.

[0011] Before describing in detail the method for manufacturing a semiconductor chip package of the present invention, a resin sheet used in the manufacturing method will be described.

[0012] [Resin sheet] The resin sheet has a support and a resin composition layer provided on the support, wherein the resin composition layer has a loss tangent (tan δ) of 0.05 or more and 1.3 or less at a temperature for performing underfill molding.

[0013] <Support body> The resin sheet has a support. Examples of the support include films made of plastic materials, metal foils, and release papers, and films made of plastic materials and metal foils are preferred.

[0014] When a film formed of a plastic material is used as a support, the plastic material includes polyesters such as polyethylene terephthalate (hereinafter sometimes referred to as "PET") and polyethylene naphthalate (hereinafter sometimes referred to as "PEN"), polycarbonate (hereinafter sometimes referred to as "PC"), acrylic polymers such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0015] When a metal foil is used as a support, examples of the metal foil include copper foil and aluminum foil, preferably copper foil. The copper foil may be a foil made of a single metal such as copper or an alloy of copper and other metals (such as tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.).

[0016] The surface of the support to be in contact with the resin composition layer may be subjected to matte treatment, corona treatment, or antistatic treatment.

[0017] In addition, as a support, a protective film with a release layer having a release layer on the surface bonded to the resin composition layer can be used. As a release agent used in the release layer of the support with a release layer, for example, one or more release agents selected from alkyd resins, polyolefin resins, polyurethane resins and silicone resins can be cited. The support with a release layer can use commercial products, for example, PET film having a release layer with an alkyd resin-based release agent as the main component, such as "SK-1", "AL-5", and "AL-7" manufactured by Lintec, "Lumirror T60" manufactured by Toray Industries, "Purex" manufactured by Teijin, and "Unipeel" manufactured by Unitika.

[0018] The thickness of the support is not particularly limited, but is preferably 1 μm or more, more preferably 5 μm or more, further preferably 10 μm or more, and preferably 75 μm or less, more preferably 60 μm or less, further preferably 50 μm or less. When a support with a release layer is used, the overall thickness of the support with the release layer is preferably within the above range.

[0019] <Resin Composition Layer> The resin sheet includes a resin composition layer formed by a resin composition. The resin composition layer is a material for filling the gap (gap) between the circuit substrate and the semiconductor chip and sealing the semiconductor chip. The resin composition layer is bonded to the support to form a resin sheet. The resin composition layer can be 1 layer or more than 2 layers. From the viewpoint of significantly obtaining the effect of the present invention, the resin composition layer is preferably 1 layer.

[0020] The loss tangent (tan δ) of the resin composition layer at the temperature of the molded bottom filling is 0.05 or more and 1.3 or less. The inventors found that by adjusting the loss tangent at the temperature of the molded bottom filling to the range described, the pressure from the outside applied when the molded bottom filling is performed, the resin composition layer is effectively applied with force, and the resin composition layer is easy to flow. Thus, even if the gap between the circuit substrate and the semiconductor chip or the gap between the electrodes is narrowed, the resin composition layer becomes easy to immerse and fill. As a result, the generation of gaps is suppressed.

[0021] The loss tangent (tanδ) is a value obtained by dividing the loss elastic modulus by the storage elastic modulus (loss elastic modulus / storage elastic modulus). The temperature for performing the mold bottom filling is the temperature for performing the mold bottom filling in the step (I) described later. Specifically, when the resin composition layer is laminated in a manner bonded to the semiconductor chip package for mold bottom filling, it refers to the heating and pressing temperature during lamination. When the mold bottom filling is performed by hot pressing, it refers to the temperature of the mold during hot pressing. Hereinafter, the temperature for performing the mold bottom filling is sometimes referred to as the "molding temperature".

[0022] From the viewpoint of filling the resin composition layer in the gap between the circuit substrate and the semiconductor chip or the gap between the electrodes, the loss tangent at the molding temperature is more than 0.05, preferably more than 0.1, more preferably more than 0.15, more than 0.2, more than 0.25, more than 0.3, more than 0.35, more than 0.4 or more than 0.45. The upper limit is less than 1.3, preferably less than 1.28, more preferably less than 1.25, and more preferably less than 1.23. The loss tangent can be measured by the method described in the embodiments described later.

[0023] The melt viscosity of the resin composition layer is preferably 1000 poise or more, more preferably 2000 poise or more, further preferably 3000 poise or more, or 4000 poise or more, preferably 10000 poise or less, more preferably 9000 poise or less, further preferably 8000 poise or less, 7000 poise or less, or 6000 poise or less. By adjusting the melt viscosity of the resin composition layer to within the range described above, it is possible to fill the resin composition layer in the gap between the circuit substrate and the semiconductor chip. The melt viscosity is the melt viscosity at the molding temperature, and can be measured by the method described in the embodiments described later.

[0024] As the component contained in the resin composition layer, as long as the loss tangent is within the above range, the cured product has sufficient hardness and insulation. As the component contained in the resin composition layer, for example (A) inorganic filler can be cited. As needed, the resin composition layer may further include (B) epoxy resin, (C) curing agent, (D) elastomer, (E) thermoplastic resin, (F) curing accelerator, (G) free radical polymerizable resin, (H) free radical polymerization initiator, (I) flame retardant, (J) other additives and (K) solvent.

[0025] -(A) Inorganic filler materials- The resin composition layer contains (A) an inorganic filler as the (A) component. By making the resin composition layer contain the (A) inorganic filler, a cured product with a low dielectric loss tangent can be obtained, and the loss tangent can be made to be greater than 0.05 and less than 1.3. The (A) inorganic filler is usually contained in the resin composition layer in the form of particles. The (A) component can be used alone or in combination of two or more.

[0026] As the material of (A) inorganic filler, an inorganic compound is used. As the material of (A) inorganic filler, for example, silicon dioxide, aluminum oxide, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, 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, calcium zirconate, zirconium phosphate and zirconium tungstate phosphate, etc. can be cited. Among them, silicon dioxide is particularly preferred. As silicon dioxide, for example, amorphous silicon dioxide, fused silica, crystalline silicon dioxide, synthetic silicon dioxide, hollow silica, etc. can be cited. In addition, as silicon dioxide, spherical silicon dioxide is preferred.

[0027] (A) Commercially available products of the inorganic filler include, for example, "SP60-05" and "SP507-05" manufactured by Nippon Steel Chemical Materials Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", "YA010C", "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1" manufactured by Yaduma Co., Ltd.; "UFP-30", "DAW-03", and "FB-105FD" manufactured by Denka Co., Ltd.; "Silfil NSS-3N", "Silfil NSS-4N", and "Silfil NSS-5N" manufactured by Tokuyama Co., Ltd.; "CellSpheres" and "MGH-005" manufactured by Pacific Cement Co., Ltd., etc.

[0028] From the viewpoint of making it easier for the resin composition layer to infiltrate the gap or fill between electrodes, the average particle size of the inorganic filler (A) is preferably smaller. Specifically, it is preferably 0.01 μm or more, more preferably 0.1 μm or more, further preferably 0.3 μm or more, preferably 10 μm or less, more preferably 5 μm or less, and further preferably 3 μm or less.

[0029] (A) 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 can be made on a volume basis by a laser diffraction scattering particle size distribution measuring device, and the median particle size can be measured as the average particle size. The sample can be measured using a sample obtained by weighing 100 mg of inorganic filler and 10 g of methyl ethyl ketone in a vial and dispersing it with ultrasound for 10 minutes. The sample is measured using a laser diffraction particle size distribution measuring device, and the wavelength of the light source is set to blue and red. The particle size distribution of the volume basis of the inorganic filler is measured by a flow cell method, and the average particle size is calculated as the median particle size according to the obtained particle size distribution. As a laser diffraction particle size distribution measuring device, for example, "LA-960" made by Horiba, Ltd. can be cited.

[0030] (A) The BET specific surface area of ​​the inorganic filler is preferably 0.1 m 2 / g or more, more preferably 0.5m 2 / g or more, more preferably 1m 2 / g or more, preferably 100m 2 / g or less, more preferably 70m 2 / g or less, more preferably 40m 2 / g or less.

[0031] (A) The specific surface area of ​​the inorganic filler can be measured by the BET method, by adsorbing nitrogen gas on the surface of a sample using a specific surface area measuring apparatus (Macsorb HM-1210 manufactured by Mountech Co., Ltd.), and calculating the specific surface area using the BET multipoint method.

[0032] From the viewpoint of improving moisture resistance and dispersibility, (A) inorganic filler material is preferably treated with a surface treatment agent. As the surface treatment agent, for example, fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, titanate coupling agents, etc. can be cited. The surface treatment agent can be used alone or in any combination of two or more.

[0033] Commercially available products of the surface treatment agent include, for example, “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBE903” (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM573” (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “SZ-31” (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM103” (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM-4803” (long-chain epoxy-type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., and “KBM-7103” (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.

[0034] From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment using the surface treatment agent is preferably within a specific range. Specifically, 100% by mass of the inorganic filler is preferably surface treated with 0.2% by mass to 5% by mass of the surface treatment agent, more preferably with 0.2% by mass to 3% by mass of the surface treatment agent, and further preferably with 0.3% by mass to 2% by mass of the surface treatment agent.

[0035] The degree of surface treatment by the surface treatment agent can be evaluated by the carbon content per unit surface area of ​​the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the carbon content per unit surface area of ​​the inorganic filler is preferably 0.02 mg / m 2 More preferably 0.1 mg / m 2 More preferably, 0.2 mg / m 2 On the other hand, from the viewpoint of preventing the increase in the melt viscosity of the resin composition layer, it is preferably 1.0 mg / m 2 Below, more preferably 0.8 mg / m 2 Below, more preferably 0.5 mg / m 2 the following.

[0036] (A) The amount of carbon per unit surface area of ​​the inorganic filler can be measured after the surface-treated inorganic filler is cleaned with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK is added as a solvent to the inorganic filler surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid component, the amount of carbon per unit surface area of ​​the inorganic filler can be measured using a carbon analyzer. As a carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. can be used.

[0037] In addition, the degree of surface treatment performed by the surface treatment agent can be evaluated by the carbon amount per unit mass of the inorganic filler. The carbon amount per unit mass of the inorganic filler is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, in addition, preferably 1.0% by mass or less, more preferably 0.8% by mass or less, and further preferably 0.5% by mass or less. (A) The carbon amount per unit mass of the inorganic filler can be measured using a carbon analyzer in the same manner as the carbon amount per unit surface area of ​​the inorganic filler (A).

[0038] The content of the (A) inorganic filler is preferably 65% ​​by mass or more, more preferably 70% by mass or more, further preferably 75% by mass or more, or 80% by mass or more, preferably 95% by mass or less, more preferably 90% by mass or less, and further preferably 85% by mass or less, when the non-volatile component in the resin composition layer is set to 100% by mass. By adjusting the content of the (A) inorganic filler within such a range, it is easy to adjust the loss tangent within the above range.

[0039] It should be noted that in the present invention, unless otherwise expressly stated, the content of each component in the resin composition layer is the value when the non-volatile component in the resin composition layer is set to 100% by mass, and the so-called non-volatile component refers to the components constituting the resin composition layer except for the (K) solvent described later.

[0040] -(B) Epoxy resin- The resin composition layer may contain (B) an epoxy resin as the (B) component. By containing the (B) epoxy resin, a cured product having good mechanical strength and insulation reliability can be obtained. The (B) epoxy resins may be used alone or in combination of two or more.

[0041] Examples of the epoxy resin (B) include bixylene type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol novolac type epoxy resins, phenol novolac type epoxy resins, tert-butyl-catechol type epoxy resins, naphthalene type epoxy resins, naphthol type epoxy resins, anthracene type epoxy resins, glycidylamine type epoxy resins, glycidyl ester type epoxy resins, glycidylcyclohexane type epoxy resins. Resins, alkyl diglycidyl ether type epoxy resins, cresol novolac type epoxy resins, biphenyl type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, epoxy resins containing spiro rings, cyclohexane type epoxy resins, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resins, trimethylol type epoxy resins, tetraphenylethane type epoxy resins, phenolphthalimidine type epoxy resins, etc. The epoxy resins may be used alone or in combination of two or more.

[0042] In the resin composition layer, as component (B), an epoxy resin having two or more epoxy groups in one molecule is preferably included. From the viewpoint of significantly obtaining the desired effect of the present invention, the proportion of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more, relative to 100% by mass of the epoxy resin (A).

[0043] The epoxy resin includes an epoxy resin that is liquid at a temperature of 20° C. (hereinafter sometimes referred to as “liquid epoxy resin”) and an epoxy resin that is solid at a temperature of 20° C. (hereinafter sometimes referred to as “solid epoxy resin”). The resin composition layer may contain only a liquid epoxy resin or only a solid epoxy resin as the component (B), and preferably contains a combination of a liquid epoxy resin and a solid epoxy resin.

[0044] As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferred.

[0045] As the liquid epoxy resin, preferred are bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, glycidyl amine type epoxy resin, and epoxy resin having a butadiene structure, glycidyl cyclohexane type epoxy resin, phenol benzopyrrolone type epoxy resin, and alkyl diglycidyl ether type epoxy resin, and more preferred are bisphenol A type epoxy resin, bisphenol F type epoxy resin, and epoxy resin having a butadiene structure.

[0046] Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resins) manufactured by DIC Corporation; "828US", "jER828EL", "825", and "EPIKOTE828EL" (bisphenol A-type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "jER807" and "1750" (bisphenol F-type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630" and "630LSD" (glycidylamine-type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "ZX1059" (a mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin) manufactured by Nippon Steel Chemical Materials Co., Ltd.; "EX-721" (glycidyl ester-type epoxy resin) manufactured by Nagase ChemteX Corporation; and "CELLOXIDE "2021P" (alicyclic epoxy resin with an ester skeleton); "PB-3600" manufactured by Daicel Corporation (epoxy resin with a butadiene structure); "ZX1658" and "ZX1658GS" manufactured by Nippon Steel Chemical Materials Co., Ltd. (liquid 1,4-glycidylcyclohexane type epoxy resin); "YED216D" (alkyl diglycidyl ether type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YD-8125G" (bisphenol A type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., etc. They can be used alone or in combination of two or more.

[0047] The solid epoxy resin is preferably a solid epoxy resin having two or more epoxy groups in one molecule, more preferably a solid epoxy resin having three or more epoxy groups in one molecule, and more preferably an aromatic solid epoxy resin having three or more epoxy groups in one molecule.

[0048] As the solid epoxy resin, preferred are biphenylol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, and tetraphenylethane type epoxy resin, and more preferred are biphenylol type epoxy resin, naphthylene ether type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, and naphthol type epoxy resin.

[0049] Specific examples of solid epoxy resins include “HP4032H” (naphthalene type epoxy resin), “HP-4700”, “HP-4710” (naphthalene type tetrafunctional epoxy resin), “N-690” (cresol novolac type epoxy resin), “N-695” (cresol novolac type epoxy resin), “HP-7200”, “HP-7200HH”, “HP-7200H” (dicyclopentadiene type epoxy resin), “EXA-7311”, “EXA-7311-G3”, “EXA-7311-G4”, “EXA-7311-G4S”, “HP6000”, “HP6000L” (naphthylene ether type epoxy resin) manufactured by DIC Corporation; “EPPN-502H” (trisphenol type epoxy resin), “NC7000L” (naphthol novolac type epoxy resin), “NC3000H”, “NC3000L” (naphthylene ether type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. 000", "NC3000L", "NC3100" (biphenyl epoxy resin); "ESN475V" (naphthalene epoxy resin), "ESN485" (naphthol novolac epoxy resin) made by Nippon Steel Chemical Materials Co., Ltd.; "YX4000H", "YL6121" (biphenyl epoxy resin), "YX4000HK" (biphenyl epoxy resin), "YX8800" (anthracene epoxy resin) made by Mitsubishi Chemical Corporation. "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., "YL7760" (bisphenol AF type epoxy resin), "YL7800" (fluorene type epoxy resin), "jER1010" (solid bisphenol A type epoxy resin), "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "WHR-991S" (phenol benzopyrrolidone type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. These may be used alone or in combination of two or more.

[0050] When a liquid epoxy resin and a solid epoxy resin are used in combination as the component (B), the mass ratio of these (liquid epoxy resin:solid epoxy resin) is preferably 1:0.1 to 1:20, more preferably 1:0.15 to 1:10, and particularly preferably 1:0.2 to 1:5.

[0051] The epoxy equivalent of component (B) is preferably 50 g / eq. to 5000 g / eq., more preferably 50 g / eq. to 3000 g / eq., further preferably 80 g / eq. to 2000 g / eq., and further more preferably 110 g / eq. to 1000 g / eq. Within this range, a cured product having a sufficient crosslinking density of the cured product of the resin composition layer can be obtained. The epoxy equivalent is the mass of an epoxy resin containing 1 equivalent of epoxy groups. The epoxy equivalent can be measured according to JIS K7236.

[0052] The weight average molecular weight (Mw) of the component (B) is preferably 100 to 5000, more preferably 150 to 3000, and even more preferably 200 to 1500 from the viewpoint of significantly obtaining the desired effects of the present invention. The weight average molecular weight of the epoxy resin is a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC).

[0053] From the viewpoint of obtaining a cured product showing good mechanical strength and insulation reliability, when the non-volatile component in the resin composition layer is set to 100% by mass, the content of component (B) is preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more. The upper limit is preferably below 25% by mass, more preferably below 20% by mass, and particularly preferably below 15% by mass.

[0054] From the viewpoint of obtaining a cured product showing good mechanical strength and insulation reliability, when the resin component in the resin composition layer is set to 100% by mass, the content of component (B) is preferably 35% by mass or more, more preferably 40% by mass or more, and further preferably 45% by mass or more. The upper limit is preferably 75% by mass or less, more preferably 70% by mass or less, and particularly preferably 65% ​​by mass or less.

[0055] The resin component in the resin composition layer refers to the component excluding the (A) inorganic filler from the non-volatile components in the resin composition layer.

[0056] -(C) Curing agent- The resin composition layer may contain a (C) curing agent as the (C) component. The (C) curing agent as the (C) component does not include a substance belonging to the above-mentioned (B) component. The (C) component generally has a function of reacting with the (B) component to cure the resin composition layer. The (C) component may be used alone or in combination of two or more in any ratio.

[0057] As component (C), a compound that can react with component (B) to cure the resin composition layer can be used. As such a curing agent, for example, active ester curing agents, phenolic curing agents, carbodiimide curing agents, benzoxazine curing agents, anhydride curing agents, amine curing agents, cyanate curing agents, etc. can be cited. Among them, as component (C), it is preferred to include any one of active ester curing agents, phenolic curing agents and carbodiimide curing agents, more preferably any one of active ester curing agents and phenolic curing agents, and further preferably active ester curing agents.

[0058] As active ester curing agent, curing agent with more than one active ester group in one molecule can be enumerated. Wherein, as active ester curing agent, preferably esters of phenolic esters, thiophenolic esters, N-hydroxylamine esters, heterocyclic hydroxy compounds, etc. have more than two compounds with high reactive ester groups in one molecule. The active ester curing agent is preferably obtained by the condensation reaction of carboxylic acid compounds and / or thiocarboxylic acid compounds with hydroxy compounds and / or thiol compounds. In particular, from the viewpoint of heat resistance improvement, the active ester curing agent preferably obtained by carboxylic acid compounds and hydroxy compounds, more preferably the active ester curing agent obtained by carboxylic acid compounds and phenol compounds and / or naphthol compounds.

[0059] Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.

[0060] Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, 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, phloroglucinol, pyrogallol, dicyclopentadiene-type diphenol compounds, and novolac resins. Here, the so-called "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

[0061] Preferred specific examples of active ester curing agents include active ester compounds containing dicyclopentadiene diphenol structures, active ester compounds containing naphthalene structures, active ester compounds containing acetylated products of novolac resins, and active ester compounds containing benzoylated products of novolac resins. Among them, active ester compounds containing naphthalene structures and active ester compounds containing dicyclopentadiene diphenol structures are more preferred. "Dicyclopentadiene diphenol structure" means a divalent structure formed by phenylene-dicyclopentylene-phenylene.

[0062] As commercially available active ester curing agents, as active ester compounds containing a dicyclopentadiene-type diphenol structure, there are "EXB-9451", "EXB-9460", "EXB-9460S", "HPC-8000", "HPC-8000H", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L", "EXB-8000L-65TM" (manufactured by DIC Corporation); as commercially available active ester compounds containing a naphthalene structure, there are "HPC-8150-60T", "HPC-8150-62T", "EXB-8150L-65T", "EXB-8100L-65T", "EXB-8150L-65 T", "EXB9416-70BK", "EXB-8151-62T" (manufactured by DIC Corporation); as an active ester compound containing an acetylated product of a linear phenolic resin, "DC808" (manufactured by Mitsubishi Chemical Corporation) can be cited; as an active ester compound containing a benzoylated product of a linear phenolic resin, "YLH1026" (manufactured by Mitsubishi Chemical Corporation) can be cited; as an active ester curing agent that is an acetylated product of a linear phenolic resin, "DC808" (manufactured by Mitsubishi Chemical Corporation) can be cited; as an active ester curing agent that is a benzoylated product of a linear phenolic resin, "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation) and the like can be cited.

[0063] As phenolic curing agents, curing agents having one or more, preferably two or more, hydroxyl groups bonded to aromatic rings (benzene rings, naphthalene rings, etc.) in one molecule can be cited. Among them, compounds having hydroxyl groups bonded to benzene rings are preferred. In addition, from the viewpoints of heat resistance and water resistance, phenolic curing agents having a phenolic structure are preferred. Furthermore, from the viewpoint of filling properties, nitrogen-containing phenolic curing agents are preferred, phenolic curing agents containing a triazine skeleton are more preferred, and linear phenolic resin curing agents containing a triazine skeleton are further preferred.

[0064] Specific examples of phenolic curing agents and naphthol curing agents include "MEH-7700", "MEH-7810", "MEH-7851", and "MEH-8000H" manufactured by Meiwa Chemicals; "NHN", "CBN", and "GPH" manufactured by Nippon Kayaku Co., Ltd.; and "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-495V", and "SN-375" manufactured by Nippon Steel Chemicals Co., Ltd. , "SN-395"; "TD-2090", "TD-2090-60M", "LA-7052", "LA-7054", "LA-1356", "LA-3018", "LA-3018-50P", "EXB-9500", "HPC-9500", "KA-1160", "KA-1163", "KA-1165" manufactured by DIC; "GDP-6115L", "GDP-6115H", "ELPC 75" and so on manufactured by Qunrong Chemical Co., Ltd.

[0065] Specific examples of the benzoxazine-based curing agent include “ODA-BOZ” manufactured by JFE Chemical Co., Ltd., “HFB2006M” manufactured by Showa High Molecular Co., Ltd., and “Pd” and “Fa” manufactured by Shikoku Chemical Industry Co., Ltd.

[0066] Specific examples of the carbodiimide-based curing agent include "V-03", "V-05", and "V-07" manufactured by Nisshinbo Chemical Co., Ltd. and Stabaxol (registered trademark) P manufactured by Lanxess Co., Ltd.

[0067] Examples of the acid anhydride curing agent include curing agents having one or more acid anhydride groups in one molecule. Specific examples of the acid anhydride curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, and homophenylene. Tetracarboxylic anhydride, benzophenonetetracarboxylic anhydride, biphenyltetracarboxylic anhydride, naphthalenetetracarboxylic anhydride, oxydiphthalic anhydride, 3,3'-4,4'-diphenylsulfonetetracarboxylic anhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(trimellitic anhydride ester), styrene-maleic acid resin obtained by copolymerization of styrene and maleic acid, etc. Polymer-type acid anhydrides, etc. Commercially available products of acid anhydride-based curing agents include, for example, "MH-700" manufactured by Shin Nippon Rika Co., Ltd.

[0068] As the amine curing agent, there can be mentioned a curing agent having one or more amino groups in one molecule, for example, aliphatic amines, polyether amines, alicyclic amines, aromatic amines, etc. Among them, from the viewpoint of achieving the desired effect of the present invention, aromatic amines are preferred. The amine curing agent is preferably a primary amine or a secondary amine, and more preferably a primary amine. Specific examples of the amine curing agent include 4,4'-methylenebis(2,6-dimethylaniline), diphenyldiaminosulfone, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, metaphenylenediamine, metaphenylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino- 4-hydroxyphenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, etc. As the amine curing agent, commercially available products can be used, for example, "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD AA", "KAYAHARD AB", "KAYAHARD AS" manufactured by Nippon Kayaku Co., Ltd., "EPICURE W" manufactured by Mitsubishi Chemical Corporation, etc.

[0069] Examples of the cyanate curing agent include difunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis(2,6-dimethylphenylcyanate), 4,4'-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyano)phenylpropane, 1,1-bis(4-cyanophenylmethane), bis(4-cyano-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanophenyl-1-(methylethylidene))benzene, bis(4-cyanophenyl)sulfide and bis(4-cyanophenyl)ether; polyfunctional cyanate resins derived from phenol novolac resins and cresol novolac resins; and prepolymers obtained by triazinization of a portion of these cyanate resins. Specific examples of cyanate curing agents include "PT30" and "PT60" manufactured by Arxada (both are linear phenolic resin-type multifunctional cyanate resins), "ULL-950S" (multifunctional cyanate resin), "BA230", "BA230S75" (prepolymers obtained by triazine-forming a trimer of part or all of bisphenol A dicyanate), etc.

[0070] The range of the weight average molecular weight of the (C) curing agent may be the same as the range of the weight average molecular weight of the (B) epoxy resin.

[0071] When the number of epoxy groups of component (B) is set to 1, the active radical number of the curing agent (C) is preferably 0.01 or more, more preferably 0.05 or more, further preferably 0.1 or more, preferably 10 or less, more preferably 5 or less, and further preferably 3 or less. Here, the so-called "number of epoxy groups of component (B)" refers to the value obtained by adding up all the values ​​obtained by dividing the mass of the non-volatile components of component (B) present in the resin composition by the epoxy equivalent. In addition, the so-called "active radical number of the curing agent (C)" refers to the value obtained by adding up all the values ​​obtained by dividing the mass of the non-volatile components of the curing agent (C) present in the resin composition by the active radical equivalent. By setting the active radical number of the curing agent (C) when the number of epoxy groups of component (B) is 1 within the above range, the desired effect of the present invention can be significantly obtained.

[0072] The content of the (C) curing agent is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, and is preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, when the non-volatile component in the resin composition layer is 100% by mass.

[0073] (C) The content of the curing agent is preferably 20% by mass or more, more preferably 25% by mass or more, and further preferably 30% by mass or more, when the resin component in the resin composition layer is 100% by mass. The upper limit is preferably 50% by mass or less, more preferably 45% by mass or less, and particularly preferably 40% by mass or less.

[0074] When the curing agent (C) includes an active ester curing agent, the content of the active ester curing agent is preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more, and preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass or less, when the non-volatile component in the resin composition layer is 100% by mass. By adjusting the content of the active ester curing agent within the above range, it is easy to adjust the loss tangent within the above range.

[0075] When the curing agent (C) includes an active ester curing agent, from the viewpoint of significantly obtaining the effect of the present invention, the content of the active ester curing agent is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 15% by mass or more, when the resin component in the resin composition layer is set to 100% by mass. The upper limit is preferably 50% by mass or less, more preferably 45% by mass or less, and particularly preferably 40% by mass or less. By adjusting the content of the active ester curing agent to the above range, it is easy to adjust the loss tangent to the above range.

[0076] -(D) Elastomer- The resin composition layer may contain an elastomer (D) as the component (D). The elastomer (D) as the component (D) does not include the elastomers belonging to the above-mentioned components (B) to (C). The component (D) may be used alone or in combination of two or more in any ratio.

[0077] In the present invention, (D) elastomer refers to a resin having flexibility, and is an amorphous resin component dissolved in an organic solvent, preferably a resin having rubber elasticity or a resin that exhibits rubber elasticity by polymerization with other components. Examples of rubber elasticity include resins that exhibit an elastic modulus of 1 GPa or less when subjected to a tensile test at 25°C and 40%RH according to Japanese Industrial Standards (JIS K7161).

[0078] In one embodiment, the component (D) is preferably a resin having one or more structures selected from a polybutadiene structure, a polysiloxane structure, a poly(meth)acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure in the molecule. From the viewpoint of obtaining a material having flexibility, a resin having one or more structures selected from a polybutadiene structure and a polycarbonate structure is more preferred. It should be noted that "(meth)acrylate" refers to methacrylate and acrylate.

[0079] In addition, in another embodiment, the component (D) is preferably one or more selected from a resin having a glass transition temperature (Tg) of 25°C or less and a resin that is liquid at 25°C or less. The glass transition temperature of the resin having a glass transition temperature (Tg) of 25°C or less is preferably 20°C or less, and more preferably 15°C or less. The lower limit of the glass transition temperature is not particularly limited, and may generally be -15°C or more. In addition, as the resin that is liquid at 25°C, a resin that is liquid at 20°C or less is preferably a resin that is liquid at 15°C or less, and more preferably a resin that is liquid at 15°C or less.

[0080] As a more preferred embodiment, component (D) is preferably one or more selected from resins having a glass transition temperature of 25°C or less and being liquid at 25°C, and having in the molecule one or more structures selected from polybutadiene structure, polysiloxane structure, poly(meth)acrylate structure, polyalkylene oxide structure, polyisoprene structure, polyisobutylene structure and polycarbonate structure.

[0081] The polybutadiene structure includes not only a structure formed by polymerizing butadiene, but also a structure formed by hydrogenating the structure. In addition, the butadiene structure may be hydrogenated in part or in its entirety. Furthermore, in the component (D), the polybutadiene structure may be contained in the main chain or in the side chain.

[0082] Preferred examples of polybutadiene resins include resins containing hydrogenated polybutadiene skeletons, polybutadiene resins containing hydroxyl groups, polybutadiene resins containing phenolic hydroxyl groups, polybutadiene resins containing carboxyl groups, polybutadiene resins containing acid anhydride groups, polybutadiene resins containing epoxy groups, polybutadiene resins containing isocyanate groups, polybutadiene resins containing carbamate groups, etc. Among them, polybutadiene resins containing phenolic hydroxyl groups are further preferred. Here, the so-called "resin containing hydrogenated polybutadiene skeleton" refers to a resin in which at least a part of the polybutadiene skeleton is hydrogenated, and it is not necessarily a resin in which the polybutadiene skeleton is completely hydrogenated. As resins containing hydrogenated polybutadiene skeletons, for example, epoxy resins containing hydrogenated polybutadiene skeletons can be cited. In addition, as polybutadiene resins containing phenolic hydroxyl groups, resins having a polybutadiene structure and having phenolic hydroxyl groups can be cited.

[0083] Specific examples of the resin having a polybutadiene structure in the molecule, i.e., the polybutadiene resin, include "Ricon 657" (polybutadiene containing an epoxy group), "Ricon 130MA8", "Ricon 130MA13", "Ricon 130MA20", "Ricon 131MA5", "Ricon 131MA10", "Ricon 131MA17", "Ricon 131MA20", "Ricon 184MA6" (polybutadiene containing an acid anhydride group), "GQ-1000" (polybutadiene introduced with a hydroxyl group or a carboxyl group), "G-1000", "G-2000", "G-3000" (polybutadiene containing hydroxyl groups at both ends), "GI-1000", "GI-2000", "GI-3000" (polybutadiene containing hydroxyl groups at both ends), "PB3600", "PB4700" (polybutadiene skeleton epoxy compound), "Epofriend" (polybutadiene containing hydroxyl groups at both ends) and "GQ-1000" (polybutadiene containing hydroxyl groups at both ends) manufactured by Daicel Corporation. A1005", "Epofriend A1010", "Epofriend A1020" (epoxide compounds of styrene, butadiene and styrene block copolymers), "FCA-061L" (hydrogenated polybutadiene skeleton epoxy compound) and "R-45EPT" (polybutadiene skeleton epoxy compound) manufactured by Nagase ChemteX Co., Ltd.

[0084] In addition, as an example of a preferred polybutadiene resin, a linear polyimide (polyimide described in Japanese Unexamined Patent Publication No. 2006-37083 and International Publication No. 2008 / 153208) made of hydroxyl-terminated polybutadiene, a diisocyanate compound and a polyacid or its anhydride can also be cited. The content of the polybutadiene structure of the polyimide resin is preferably 60% to 95% by mass, more preferably 75% to 85% by mass. The details of the polyimide resin can be referred to the records of Japanese Unexamined Patent Publication No. 2006-37083 and International Publication No. 2008 / 153208, and the contents are incorporated into this specification.

[0085] The number average molecular weight of the hydroxyl-terminated polybutadiene is preferably 500 to 5,000, more preferably 1,000 to 3,000. The hydroxyl equivalent of the hydroxyl-terminated polybutadiene is preferably 250 to 1,250.

[0086] Examples of the diisocyanate compound include aromatic diisocyanates such as toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, xylene diisocyanate, and diphenylmethane diisocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate; and alicyclic diisocyanates such as isophorone diisocyanate. Among these, aromatic diisocyanates are preferred, and toluene-2,4-diisocyanate is more preferred.

[0087] Examples of the polybasic acid or its anhydride include ethylene glycol ditrimellitate, pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, naphthalenetetracarboxylic acid, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-cyclohexene-1,2-dicarboxylic acid, 3,3'-4,4'-diphenylsulfonetetracarboxylic acid and other tetrabasic acids and their anhydrides, trimellitic acid, cyclohexanetricarboxylic acid and other tribasic acids and their anhydrides, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho(1,2-C)furan-1,3-dione and the like.

[0088] The polybutadiene structure includes a polystyrene structure having a structure obtained by polymerizing styrene.

[0089] Specific examples of resins having a polystyrene structure in their molecules, i.e., polystyrene resins, include styrene-butadiene-styrene block copolymers (SBS), styrene-isoprene-styrene block copolymers (SIS), styrene-ethylene-butylene-styrene block copolymers (SEBS), styrene-ethylene-propylene-styrene block copolymers (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymers (SEEPS), styrene-butadiene-butylene-styrene block copolymers (SBBS), styrene-butadiene diblock copolymers, hydrogenated styrene-butadiene block copolymers, hydrogenated styrene-isoprene block copolymers, and hydrogenated styrene-butadiene random copolymers.

[0090] The polystyrene resin may be a commercially available product, for example, hydrogenated styrene-based thermoplastic elastomers "H1041", "Tuftec H1043", "Tuftec P2000", "Tuftec MP10" (manufactured by Asahi Kasei Corporation); epoxidized styrene-butadiene thermoplastic elastomers "Epofriend AT501", "CT310" (manufactured by Daicel Corporation); modified styrene-based elastomer "SEPTON HG252" (manufactured by Kuraray Co., Ltd.) having a hydroxyl group; modified styrene-based elastomer "Tuftec N503M" having a carboxyl group, modified styrene-based elastomer "Tuftec N501" having an amino group, and modified styrene-based elastomer "Tuftec M1913" having an acid anhydride group (manufactured by Asahi Kasei Corporation); unmodified styrene-based elastomer "SEPTON S8104" (manufactured by Kuraray Co., Ltd.), etc.

[0091] The polysiloxane structure is a structure including a siloxane bond, and is included in, for example, silicone rubber. The component (D) may include a polysiloxane structure in the main chain or in the side chain.

[0092] Specific examples of the resin having a polysiloxane structure in the molecule, i.e., the polysiloxane resin, include: "SMP-2006", "SMP-2003PGMEA", "SMP-5005PGMEA" manufactured by Shin-Etsu Silicone Co., Ltd., and linear polyimide made of amino-terminated polysiloxane and tetrabasic acid anhydride as raw materials (International Publication No. 2010 / 053185).

[0093] The poly(meth)acrylate structure is a structure formed by polymerizing acrylic acid or acrylic acid ester, and also includes a structure formed by polymerizing methacrylic acid or methacrylic acid ester. The component (D) may contain a (meth)acrylate structure in the main chain or in the side chain.

[0094] Preferred examples of the resin having a poly(meth)acrylate structure in the molecule, i.e., the poly(meth)acrylate resin, include: a poly(meth)acrylate resin containing a hydroxyl group, a poly(meth)acrylate resin containing a phenolic hydroxyl group, a poly(meth)acrylate resin containing a carboxyl group, a poly(meth)acrylate resin containing an acid anhydride group, a poly(meth)acrylate resin containing an epoxy group, a poly(meth)acrylate resin containing an isocyanate group, a poly(meth)acrylate resin containing a carbamate group, and the like.

[0095] Specific examples of poly(meth)acrylate resins include: TEISANRESIN "SG-70L", "SG-708-6", "WS-023", "SG-700AS", "SG-280TEA" (carboxyl-containing acrylate copolymer resins, acid value of 5 to 34 mgKOH / g, weight average molecular weight of 400,000 to 900,000, Tg of -30°C to 5°C), "SG-80H", "SG-80H-3", "SG-P3" (epoxy-containing acrylate copolymer resins, epoxy equivalent of 4761 to 14285 g / eq, weight average molecular weight of 350,000) manufactured by Nagase ChemteX Co., Ltd. ~850,000, Tg is 11°C~12°C), "SG-600TEA", "SG-790" (hydroxyl-containing acrylate copolymer resin, hydroxyl value is 20~40mgKOH / g, weight average molecular weight is 500,000~1.2 million, Tg is -37°C~-32°C), "ME-2000", "W-116.3" (carboxyl-containing acrylate copolymer resin), "W-197C" (hydroxyl-containing acrylate copolymer resin), "KG-25", "KG-3000" (epoxy-containing acrylate copolymer resin) made by Negami Industries, Ltd., etc.

[0096] The polyalkylene structure preferably has a predetermined number of carbon atoms. The specific number of carbon atoms in the polyalkylene structure is preferably 2 or more, more preferably 3 or more, particularly preferably 5 or more, preferably 15 or less, more preferably 10 or less, particularly preferably 6 or less. In addition, in the component (D), the polyalkylene structure may be contained in the main chain or in the side chain.

[0097] The polyalkyleneoxy structure preferably has a predetermined number of carbon atoms. The specific number of carbon atoms in the polyalkyleneoxy structure is preferably 2 or more, preferably 3 or more, more preferably 5 or more, preferably 15 or less, more preferably 10 or less, and particularly preferably 6 or less. In the component (D), the polyalkyleneoxy structure may be contained in the main chain or in the side chain.

[0098] Specific examples of resins having a polyalkylene structure in their molecules, i.e., polyalkylene resins, and resins having a polyalkyleneoxy structure in their molecules, i.e., polyalkyleneoxy resins, include: "PTXG-1000" and "PTXG-1800" manufactured by Asahi Kasei Fibers Corporation, "YX-7180" (a resin having an ether bond and containing an alkylene structure) manufactured by Mitsubishi Chemical Corporation, "EXA-4850-150", "EXA-4816", and "EXA-4822" manufactured by DIC Corporation, "EP-4000", "EP-4003", "EP-4010", and "EP-4011" manufactured by ADEKA Corporation, "BEO-60E" and "BPO-20E" manufactured by Shin Nippon Rika Co., Ltd., and "YL7175" and "YL7410" manufactured by Mitsubishi Chemical Corporation.

[0099] The component (D) may contain a polyisoprene structure in the main chain or in the side chain. Specific examples of the polyisoprene resin having a polyisoprene structure in the molecule include "KL-610" and "KL-613" manufactured by Kuraray Co., Ltd.

[0100] The component (D) may contain a polyisobutylene structure in the main chain or in the side chain. Specific examples of the resin having a polyisobutylene structure in the molecule, i.e., the polyisobutylene resin, include "SIBSTAR-073T" (styrene-isobutylene-styrene triblock copolymer) and "SIBSTAR-042D" (styrene-isobutylene diblock copolymer) manufactured by KANEKA Corporation.

[0101] The component (D) may contain a polycarbonate structure in the main chain or in the side chain.

[0102] Preferred examples of resins having a polycarbonate structure in their molecules, i.e., polycarbonate resins, include: polycarbonate resins containing hydroxyl groups, polycarbonate resins containing phenolic hydroxyl groups, polycarbonate resins containing carboxyl groups, polycarbonate resins containing acid anhydride groups, polycarbonate resins containing epoxy groups, polycarbonate resins containing isocyanate groups, polycarbonate resins containing carbamate groups, and the like.

[0103] Specific examples of the polycarbonate resin include "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemicals Corporation, and "C-1090", "C-2090" and "C-3090" (polycarbonate diol) manufactured by Kuraray Corporation.

[0104] In addition, as an example of a preferred polycarbonate resin, a linear polyimide made of a hydroxyl-terminated polycarbonate, a diisocyanate compound, and a polyacid or its anhydride as a raw material can also be cited. The linear polyimide has a carbamate structure and a polycarbonate structure. The content of the polycarbonate structure of the polyimide resin is preferably 60% to 95% by mass, and more preferably 75% to 85% by mass. The details of the polyimide resin can be referred to the record of International Publication No. 2016 / 129541, and its content is incorporated into this specification.

[0105] The number average molecular weight of the hydroxyl-terminated polycarbonate is preferably 500 to 5,000, more preferably 1,000 to 3,000. The hydroxyl equivalent of the hydroxyl-terminated polycarbonate is preferably 250 to 1,250.

[0106] The component (D) preferably has an imide structure. The imide structure can improve the heat resistance of the component (D) and effectively improve the crack resistance.

[0107] The component (D) may have any structure of linear, branched, or cyclic, but is preferably linear.

[0108] The component (D) preferably further has a functional group that can react with the component (B). The functional group also includes a reactive group that is developed by heating. The component (D) having a functional group can improve the mechanical strength of the cured product of the resin composition layer.

[0109] Examples of the functional group include a carboxyl group, a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group, and a carbamate group, etc. Among them, from the viewpoint of significantly obtaining the effect of the present invention, it is preferred that the functional group has one or more functional groups selected from a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group, and a carbamate group, and a phenolic hydroxyl group is particularly preferred.

[0110] From the viewpoint of exerting flexibility, component (D) is preferably a high molecular weight. The specific number average molecular weight Mn of component (D) is preferably 4000 or more, more preferably 4500 or more, further preferably 5000 or more, further preferably greater than 5000, particularly preferably 5500 or more, preferably 100000 or less, more preferably 95000 or less, particularly preferably 90000 or less. The number average molecular weight Mn of component (D) is a polystyrene-converted number average molecular weight measured using GPC (gel permeation chromatography).

[0111] From the viewpoint of obtaining flexibility, the weight average molecular weight of the component (D) is preferably 5,500 to 100,000, more preferably 10,000 to 90,000, and even more preferably 15,000 to 80,000. The weight average molecular weight of the component (D) is a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC).

[0112] When the component (D) has a functional group, the functional group equivalent of the component (D) is preferably 100 or more, more preferably 200 or more, further preferably 1000 or more, particularly preferably 2500 or more, preferably 50000 or less, more preferably 30000 or less, further preferably 10000 or less, particularly preferably 5000 or less. The functional group equivalent is the number of grams of the resin containing 1 gram equivalent of the functional group. For example, the epoxy equivalent can be measured according to JIS K 7236. In addition, for example, the hydroxyl equivalent can be calculated by dividing the molecular weight of KOH by the hydroxyl value measured according to JIS K1557-1.

[0113] The content of the elastomer (D) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, and is preferably 5% by mass or less, more preferably 3% by mass or less, further preferably 2% by mass or less, when the non-volatile component in the resin composition layer is 100% by mass.

[0114] The content of the elastomer (D) is preferably 3% by mass or more, more preferably 5% by mass or more, further preferably 8% by mass or more, and is preferably 25% by mass or less, more preferably 20% by mass or less, further preferably 15% by mass or less, when the resin component in the resin composition layer is 100% by mass.

[0115] -(E) Thermoplastic resin- The resin composition layer may contain (E) a thermoplastic resin as the (E) component. The (E) thermoplastic resin as the (E) component does not include the substances belonging to the above-mentioned (B) to (D) components. The (E) component may be used alone or in combination of two or more.

[0116] The weight average molecular weight (Mw) of the component (E) is preferably 5000 or more, more preferably greater than 5000, more preferably 8000 or more, and further preferably 10000 or more. The upper limit of the Mw is not particularly limited, but is preferably 100000 or less, more preferably 80000 or less, and further preferably 50000 or less. The Mw of the component (E) can be measured as a polystyrene-converted value by gel permeation chromatography (GPC).

[0117] As the component (E), for example, thermoplastic resins such as phenoxy resins, polyimide resins, polycarbonate resins, polyvinyl acetal resins, polyolefin resins, polyamide-imide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polyetheretherketone resins, polystyrene resins, and polyester resins can be cited. Among them, as the component (E), from the viewpoint of significantly obtaining the effects of the present invention, it is preferred that at least one selected from the group consisting of phenoxy resins, polyimide resins, and polycarbonate resins is included, and a phenoxy resin is more preferred.

[0118] Examples of the phenoxy resin include phenoxy resins having one or more skeletons selected from the group consisting of bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, phenolic skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, and trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group.

[0119] Commercially available products of phenoxy resins include, for example, "1256" and "4250" manufactured by Mitsubishi Chemical Corporation (both are phenoxy resins containing a bisphenol A skeleton); "YX8100" manufactured by Mitsubishi Chemical Corporation (a phenoxy resin containing a bisphenol S skeleton); "YX6954" manufactured by Mitsubishi Chemical Corporation (a phenoxy resin containing a bisphenol acetophenone skeleton); "FX280" and "FX293" manufactured by Nippon Steel Chemical Materials Co., Ltd.; "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290" and "YL7482" manufactured by Mitsubishi Chemical Corporation.

[0120] The polyimide resin may be a resin having an imide structure. The polyimide resin may be generally obtained by an imidization reaction of a diamine compound and an acid anhydride. The polyimide resin may be a commercially available product, such as "RIKACOAT SN20" and "RIKACOAT PN20" manufactured by Shin Nippon Chemical Co., Ltd.

[0121] Polycarbonate resin is a resin having a carbonate structure. As such resin, carbonate resins without reactive groups, carbonate resins containing hydroxyl groups, carbonate resins containing phenolic hydroxyl groups, carbonate resins containing carboxyl groups, carbonate resins containing anhydride groups, carbonate resins containing isocyanate groups, carbonate resins containing carbamate groups, carbonate resins containing epoxy groups, etc. can be cited. Here, the so-called reactive group refers to a functional group that can react with other components such as hydroxyl groups, phenolic hydroxyl groups, carboxyl groups, anhydride groups, isocyanate groups, carbamate groups and epoxy groups.

[0122] Commercially available polycarbonate resins may be used, such as "FPC0220" and "FPC2136" manufactured by Mitsubishi Gas Chemical Co., Ltd., "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Corporation, and "C-1090", "C-2090" and "C-3090" (polycarbonate diol) manufactured by Kuraray Co., Ltd.

[0123] The content of the component (E) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, and is preferably 5% by mass or less, more preferably 3% by mass or less, further preferably 2% by mass or less, when the non-volatile component in the resin composition layer is set to 100% by mass.

[0124] The content of the component (E) is preferably 0.3% by mass or more, more preferably 0.5% by mass or more, further preferably 0.8% by mass or more, and is preferably 10% by mass or less, more preferably 9% by mass or less, further preferably 8% by mass or less, when the resin component in the resin composition layer is 100% by mass.

[0125] If an active ester curing agent is contained in the resin composition layer as the (C) curing agent, the value of the loss tangent may become large. In the present invention, when an active ester curing agent is used as the curing agent, the value of the loss tangent can be easily adjusted to the above range by containing any of (D) an elastomer and (E) a thermoplastic resin in addition to (A) an inorganic filler and (B) an epoxy resin in the resin composition layer.

[0126] The ratio of the content of the active ester curing agent to the total content of the elastomer (D) and the thermoplastic resin (E) {(the content of the active ester curing agent when the non-volatile component is 100% by mass) / (the total content of the elastomer (D) and the thermoplastic resin (E) when the non-volatile component is 100% by mass)} is preferably 0.5 or more, more preferably 1 or more, further preferably 1.5 or more, more preferably 40 or less, more preferably 30 or less, particularly preferably 20 or less, 10 or less, or 5 or less.

[0127] The total content of the components (B), (C), (D) and (E) is preferably 5% by mass or more, more preferably 8% by mass or more, further preferably 10% by mass or more, or 15% by mass or more, and is preferably 35% by mass or less, more preferably 30% by mass or less, and further preferably 25% by mass or less, when the non-volatile component in the resin composition layer is taken as 100% by mass.

[0128] -(F) Curing accelerator- The resin composition layer may contain (F) a curing accelerator as the (F) component. The (F) curing accelerator as the (F) component does not include substances belonging to the above-mentioned (B) to (E) components. By containing the (F) component, the curing of the (B) component can be further accelerated. The (F) component can be used alone or in combination of two or more.

[0129] As the component (F), for example, amine curing accelerators, imidazole curing accelerators, phosphorus curing accelerators, urea curing accelerators, guanidine curing accelerators, metal curing accelerators, etc. Among them, a curing accelerator selected from amine curing accelerators and imidazole curing accelerators is preferred, and an amine curing accelerator is particularly preferred.

[0130] Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene.

[0131] As the amine-based curing accelerator, a commercially available product may be used, and examples thereof include "MY-25" manufactured by Ajinomoto Fine-Techno Co., Ltd.

[0132] As the imidazole-based curing accelerator, a commercially available product may be used, and examples thereof include "1B2PZ", "2MZA-PW", "2PHZ-PW", and "C11Z-A" manufactured by Shikoku Chemical Industries, Ltd., and "P200-H50" manufactured by Mitsubishi Chemical Corporation.

[0133] Phosphorus curing accelerators include, for example, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium)pyromellitate, tetrabutylphosphonium hexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, di-tert-butyldimethylphosphonium tetraphenylborate and other aliphatic phosphonium salts; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetraphenylphosphonium; Aromatic phosphonium salts such as p-tolyl borate, tetraphenylphosphonium tetraphenyl borate, tetraphenylphosphonium tetra-p-tolyl borate, triphenylethylphosphonium tetraphenyl borate, tris(3-methylphenyl)ethylphosphonium tetraphenyl borate, tris(2-methoxyphenyl)ethylphosphonium tetraphenyl borate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; aromatic phosphine-quinone addition reactants such as triphenylphosphine-p-benzoquinone addition reactants; tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butyl)phosphine aliphatic phosphines such as dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tri(4-ethylphenyl)phosphine, tri(4-propylphenyl)phosphine, tri(4-isopropylphenyl)phosphine, tri(4-butylphenyl)phosphine, tri(4-tert-butylphenyl)phosphine, tri(2,4-dimethylphenyl)phosphine, tri(2,5-dimethylphenyl)phosphine, tri(2,6-dimethylphenyl)phosphine Aromatic phosphines such as tris(diphenyl)phosphine, tris(3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, and 2,2'-bis(diphenylphosphino)diphenyl ether.

[0134] Examples of the urea curing accelerator include 1,1-dimethylurea; aliphatic dimethylureas such as 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, and 3-cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, 3-(3,4-dimethylphenyl)-1,1 -dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea), N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluenebisdimethylurea] and the like.

[0135] Examples of the guanidine-based curing accelerator include 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-methylbiguanidine, 1-ethylbiguanidine, 1-n-butylbiguanidine, 1-n-octadecylbiguanidine, 1,1-dimethylbiguanidine, 1,1-diethylbiguanidine, 1-cyclohexylbiguanidine, 1-allylbiguanidine, 1-phenylbiguanidine, and 1-(o-tolyl)biguanidine.

[0136] Examples of the imidazole curing accelerator 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-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazole trimellitate, 2,4-diamino-6-[2′-methylimidazolyl-(1′)]-ethyl imidazole compounds such as 2,4-diamino-6-[2'-undecylimidazolyl-(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, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, and adducts of imidazole compounds with epoxy resins.

[0137] As metal curing accelerators, organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin can be cited. Specific examples of organic metal complexes include organic cobalt complexes such as cobalt acetylacetonate (II) and cobalt acetylacetonate (III); organic copper complexes such as copper acetylacetonate (II); organic zinc complexes such as zinc acetylacetonate (II); organic iron complexes such as iron acetylacetonate (III); organic nickel complexes such as nickel acetylacetonate (II); organic manganese complexes such as manganese acetylacetonate (II). As organic metal salts, for example, zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, etc. can be cited.

[0138] When the non-volatile component in the resin composition layer is set to 100 mass %, the content of the component (F) is preferably 0.01 mass % or more, more preferably 0.02 mass % or more, further preferably 0.03 mass % or more, preferably 1 mass % or less, more preferably 0.5 mass % or less, further preferably 0.1 mass % or less.

[0139] When the resin component in the resin composition layer is set to 100 mass%, the content of the component (F) is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, further preferably 0.1 mass% or more, preferably 5 mass% or less, more preferably 3 mass% or less, further preferably 1 mass% or less.

[0140] -(G) Radical polymerizable resin- The resin composition layer may contain (G) a radical polymerizable resin as the (G) component. The (G) radical polymerizable resin as the (G) component excludes the resins belonging to the (B) to (F) components. The (G) component may be used alone or in combination of two or more.

[0141] (G) The radical polymerizable resin may contain an ethylenically unsaturated bond. Therefore, the radical polymerizable resin (G) may have a radical polymerizable group containing an ethylenically unsaturated bond. Examples of the radical polymerizable group include unsaturated hydrocarbon groups such as vinyl, allyl, styryl, 1-propenyl, 3-cyclohexenyl, 3-cyclopentenyl, 2-vinylphenyl, 3-vinylphenyl, and 4-vinylphenyl; and α,β-unsaturated carbonyl groups such as acryloyl and methacryloyl. Among them, as the ethylenically unsaturated bond, preferably one or more selected from allyl, styryl, vinylphenyl, acryloyl, and methacryloyl. The radical polymerizable resin (G) preferably has two or more radical polymerizable groups.

[0142] (G) The radical polymerizable resin includes, for example, a (meth)acrylic radical polymerizable resin, a styrene radical polymerizable resin, an allyl radical polymerizable resin, and the like, and a (meth)acrylic radical polymerizable resin is preferred.

[0143] The (meth)acrylic radical polymerizable resin is, for example, a compound having one or more, preferably two or more, acryloyl groups and / or methacryloyl groups. Examples of the (meth)acrylic radical polymerizable resin include low molecular weight (molecular weight less than 1000) aliphatic (meth)acrylate compounds such as cyclohexane-1,4-dimethanol di(meth)acrylate, cyclohexane-1,3-dimethanol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, glycerol tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate; and dioxanediol di(meth)acrylate, 3,6-dioxa-1,8-octanediol di(meth)acrylate, and 1,10-decanediol di(meth)acrylate. Ether-containing (meth)acrylate compounds having a low molecular weight (molecular weight less than 1000) such as glycol di(meth)acrylate, 3,6,9-trioxaundecane-1,11-diol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, etc.; isocyanurate-containing (meth)acrylate compounds having a low molecular weight (molecular weight less than 1000) such as tris(3-hydroxypropyl)isocyanurate tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate, etc.; and high molecular weight (molecular weight 1000 or more) acrylate compounds such as (meth)acrylic acid-modified polyphenylene ether resin, etc. Examples of commercially available (meth)acrylic radical polymerizable resins include “A-DOG” (dioxanediol diacrylate) manufactured by Shin-Nakamura Chemical Industry Co., Ltd., “DCP-A” (tricyclodecane dimethanol diacrylate) and “DCP” (tricyclodecane dimethanol dimethacrylate) manufactured by Kyoeisha Chemical Co., Ltd., “KAYARAD R-684” (tricyclodecane dimethanol diacrylate) and “KAYARAD R-604” (dioxanediol diacrylate) manufactured by Nippon Kayaku Co., Ltd., and “SA9000” and “SA9000-111” (methacrylic acid-modified polyphenylene ether) manufactured by SABIC.

[0144] Styrene-based free radical polymerizable resins are compounds having one or more, preferably two or more, vinyl groups directly bonded to aromatic carbon atoms. Examples of styrene-based free radical polymerizable resins include low molecular weight (molecular weight less than 1000) styrene-based compounds such as divinylbenzene, 2,4-divinyltoluene, 2,6-divinylnaphthalene, 1,4-divinylnaphthalene, 4,4'-divinylbiphenyl, 1,2-bis(4-vinylphenyl)ethane, 2,2-bis(4-vinylphenyl)propane, and bis(4-vinylphenyl)ether; and high molecular weight (molecular weight greater than 1000) styrene-based compounds such as vinylbenzyl-modified polyphenylene ether resins and styrene-divinylbenzene copolymers. Examples of commercially available styrene-based radical polymerizable resins include “ODV-XET (X03)”, “ODV-XET (X04)”, and “ODV-XET (X05)” (styrene-divinylbenzene copolymers) manufactured by Nippon Steel Chemical Materials Co., Ltd. and “OPE-2St 1200” and “OPE-2St 2200” (vinyl benzyl-modified polyphenylene ether resins) manufactured by Mitsubishi Gas Chemical Co., Ltd.

[0145] Allyl radical polymerizable resins are, for example, compounds having one or more, preferably two or more, allyl groups. Examples of allyl radical polymerizable resins include aromatic carboxylic acid allyl ester compounds such as diallyl diphenate, triallyl trimellitate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl 2,6-naphthalene dicarboxylate, and diallyl 2,3-naphthalene dicarboxylate; 1,3,5-triallyl isocyanurate, 1,3-diallyl-5-glycidyl isocyanurate, etc. isocyanuric acid allyl ester compounds; 2,2-bis[3-allyl-4-(glycidyloxy)phenyl]propane and other epoxy-containing aromatic allyl compounds; bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)phenyl]methane and other benzoxazine-containing aromatic allyl compounds; 1,3,5-triallyl ether benzene and other ether-containing aromatic allyl compounds; diallyldiphenylsilane and other allyl silane compounds. Commercially available allyl radical polymerizable resins include, for example, "TAIC" (1,3,5-triallyl isocyanurate) manufactured by Nippon Chemical Industry Co., Ltd., Nisshoku TechnoFine Chemicals Co., Ltd., and Nisshoku TechnoFine Chemicals Co., Ltd. "DAD" (diallyl biphenyldicarboxylate) manufactured by Fujifilm Wako Pure Chemical Co., Ltd., "TRIAM-705" (triallyl trimellitate) manufactured by Fujifilm Wako Pure Chemical Co., Ltd., "DAND" (diallyl 2,3-naphthoate) manufactured by Nichikyu Techno Fine Chemicals Co., Ltd., "ALP-d" (bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)phenyl]methane) manufactured by Shikoku Chemical Co., Ltd., "RE-810NM" (2,2-bis[3-allyl-4-(glycidyloxy)phenyl]propane) manufactured by Nippon Kayaku Co., Ltd., "DA-MGIC" (1,3-diallyl-5-glycidyl isocyanurate) manufactured by Shikoku Chemical Co., Ltd., and "NE-V-1100-70T" (a compound containing a plurality of allyl groups and a plurality of benzene rings) manufactured by DIC Corporation.

[0146] (G) The ethylenic unsaturated bond equivalent of the radical polymerizable resin is preferably 20 g / eq. to 3,000 g / eq., more preferably 50 g / eq. to 2,500 g / eq., further preferably 70 g / eq. to 2,000 g / eq., and particularly preferably 90 g / eq. to 1,500 g / eq. The ethylenic unsaturated bond equivalent refers to the mass of the radical polymerizable resin per 1 equivalent of ethylenic unsaturated bonds.

[0147] (G) The weight average molecular weight (Mw) of the radical polymerizable resin is preferably 40,000 or less, more preferably 10,000 or less, further preferably 5,000 or less, and particularly preferably 3,000 or less. The lower limit is not particularly limited, and may be, for example, 150 or more. The weight average molecular weight can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC).

[0148] When the non-volatile component in the resin composition layer is set to 100 mass %, the content of the component (G) is preferably 1 mass % or more, more preferably 2 mass % or more, further preferably 3 mass % or more, preferably 7 mass % or less, more preferably 6 mass % or less, further preferably 5 mass % or less.

[0149] When the resin component in the resin composition layer is set to 100 mass%, the content of the component (G) is preferably 1 mass% or more, more preferably 5 mass% or more, further preferably 10 mass% or more, preferably 20 mass% or less, more preferably 18 mass% or less, further preferably 15 mass% or less.

[0150] -(H) Radical Polymerization Initiator- The resin composition layer may contain a (H) radical polymerization initiator as the (H) component. The (H) radical polymerization initiator as the (H) component excludes substances belonging to the (B) to (G) components. The (H) radical polymerization initiator may be, for example, a thermal polymerization initiator that generates free radicals when heated. In addition, the (H) radical polymerization initiator may be a polymerization initiator of a radical reactive group. The (H) radical polymerization initiator may be used alone or in any combination of two or more.

[0151] (H) As a radical polymerization initiator, a peroxide radical polymerization initiator, an azo radical polymerization initiator, etc. are mentioned, for example. Among them, a peroxide radical polymerization initiator is preferable.

[0152] Examples of the peroxide-based radical polymerization initiator include hydroperoxide compounds such as 1,1,3,3-tetramethylbutyl hydroperoxide; dialkyl peroxide compounds such as tert-butyl isopropyl peroxide, di-tert-butyl peroxide, di-tert-hexyl peroxide, dicumyl peroxide, 1,4-bis(1-tert-butylperoxy-1-methylethyl)benzene, and 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane; dilauroyl peroxide, didecanoyl peroxide, dicyclohexyl peroxydicarbonate, bis(4-tert-butylcyclohexyl)peroxide; Peroxy diacyl compounds such as oxidized dicarbonates; peroxy ester compounds such as tert-butyl peroxyacetate, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl monocarbonate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyneodecanoate, tert-hexyl peroxyisopropyl monocarbonate, tert-butyl peroxylaurate, 1,1-dimethylpropyl 2-ethylperoxyhexanoate, tert-butyl 2-ethylperoxyhexanoate, tert-butyl 3,5,5-trimethylperoxyhexanoate, tert-butyl peroxy-2-ethylhexyl monocarbonate, tert-butyl peroxymaleate, etc.; etc.

[0153] Examples of the azo radical polymerization initiator include azo nitrile compounds such as 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 1-[(1-cyano-1-methylethyl)azo]formamide, and 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile; 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide], 2,2'-azobis[2-methyl-N-[1,1-bis( Azo amide compounds such as 2,2'-azobis[2-methyl-N-[2-(1-hydroxybutyl)]-propionamide], 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)-propionamide], 2,2'-azobis(2-methylpropionamide) dihydrate, 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide], 2,2'-azobis(N-butyl-2-methylpropionamide), 2,2'-azobis(N-cyclohexyl-2-methylpropionamide); alkylazo compounds such as 2,2'-azobis(2,4,4-trimethylpentane) and 2,2'-azobis(2-methylpropane); etc.

[0154] (G) Examples of commercially available products of the radical polymerization initiator include “PERBUTYL C”, “PERBUTYL A”, “PERBUTYL P”, “PERBUTYL L”, “PERBUTYL O”, “PERBUTYL ND”, “PERBUTYL Z”, “PERBUTYL I”, “PERCUMYL P”, “PERCUMYL D”, “PERHEXYL D”, “PERHEXYL A”, “PERHEXYL I”, “PERHEXYL Z”, “PERHEXYL ND”, “PERHEXYL O”, and “PERHEXYL PV” manufactured by NOF Corporation.

[0155] The content of the (H) radical polymerization initiator is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, further preferably 0.05% by mass or more, and is preferably 0.5% by mass or less, more preferably 0.3% by mass or less, further preferably 0.1% by mass or less, when the non-volatile component in the resin composition layer is 100% by mass.

[0156] The content of the (H) radical polymerization initiator is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, preferably 1% by mass or less, more preferably 0.5% by mass or less, further preferably 0.3% by mass or less, when the resin component in the resin composition layer is set to 100% by mass.

[0157] -(I) Flame retardant- The resin composition layer may contain (I) a flame retardant as the component (I). The flame retardant as the component (I) excludes those belonging to the components (B) to (H). The component (I) may be used alone or in combination of two or more.

[0158] (I) As flame retardants, for example, organic phosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, organic silicon flame retardants, metal hydroxides and the like are mentioned.

[0159] As the (I) flame retardant, a commercially available item may be used, and examples thereof include "HCA-HQ" manufactured by Sanko Corporation.

[0160] The content of the component (I) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, further preferably 0.5% by mass or more, and is preferably 5% by mass or less, more preferably 3% by mass or less, further preferably 1% by mass or less, when the non-volatile component in the resin composition layer is 100% by mass.

[0161] The content of the component (I) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, and is preferably 5% by mass or less, more preferably 4% by mass or less, further preferably 3% by mass or less, when the resin component in the resin composition layer is 100% by mass.

[0162] -(J) Other additives- In addition to the above-mentioned components, the resin composition layer may further contain other additives as arbitrary components. Examples of (J) other additives include: organic fillers; organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; thickeners such as Benton (bentonite) and montmorillonite; defoamers such as silicone-based defoamers, acrylic-based defoamers, fluorine-based defoamers, and vinyl resin-based defoamers; ultraviolet light absorbers such as benzotriazole-based ultraviolet light absorbers; adhesion enhancers such as urea silane; triazole-based adhesion imparting agents, tetrazole-based Adhesion-imparting agents, such as triazine-based adhesion-imparting agents; antioxidants such as hindered phenol-based antioxidants; fluorescent whitening agents such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; dispersants such as phosphate-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, silicone-based dispersants, anionic dispersants, and cationic dispersants; stabilizers such as borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic anhydride-based stabilizers; photopolymerization initiation aids such as tertiary amines; photosensitizers such as pyrazolines, anthracenes, coumarins, xanthones, and thioxanthones. (J) Other additives may be used alone or in combination of two or more.

[0163] -(K)Solvent- In addition to the non-volatile components mentioned above, the resin composition layer may further contain any solvent as a volatile component. As the (K) solvent, a known solvent may be used appropriately, and its type is not particularly limited, and an organic solvent is preferred. As the (K) solvent, for example: ketone solvents such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, and anisole; alcohol solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, carbitol acetate (ethyl diglycol Ether ester solvents such as acetate, γ-butyrolactone, and methyl methoxypropionate; ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butyl carbitol); amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene; solvent naphtha, etc. (K) The solvent may be used alone or in combination of two or more in any ratio.

[0164] Usually, all or most of the (K) solvent is removed by drying during the manufacture of the resin composition layer. Therefore, the resin composition layer may also be free of the (K) solvent. In addition, when the resin composition layer includes the (K) solvent, sometimes a void is generated during the thermal curing of the step (II) due to the volatilization of the solvent. Therefore, from the viewpoint of suppressing the generation of the void, when the resin composition layer is formed using a resin varnish, it is preferably fully dried during the manufacture of the resin composition layer to reduce the amount of the (K) solvent remaining in the resin composition layer.

[0165] From the viewpoint of thinning the printed wiring board and providing a cured product with excellent insulation even if the cured product of the resin composition layer is a thin film, the thickness of the resin composition layer is preferably 500 μm or less, more preferably 300 μm or less, and further preferably 250 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, and for example, it can be 1 μm or more, 3 μm or more, 5 μm or more, etc.

[0166] <Other layers> The resin sheet may also be further laminated with a protective film based on the support on the surface of the resin composition layer that is not bonded to the support, that is, on the surface opposite to the support. The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress the adhesion of garbage or the like on the surface of the resin composition layer or the generation of damage.

[0167] <Method for producing resin sheet> The resin sheet can be produced, for example, by a method comprising forming a resin composition layer on a support. As a specific example, the resin sheet can also be produced by a production method comprising the following steps in sequence: a step of preparing a resin varnish containing a resin composition, a step of applying the resin varnish on a support, and a step of drying the applied resin varnish to form a resin composition layer.

[0168] The resin varnish can be produced by mixing the components and solvents that can be contained in the resin composition layer. As the solvent of the resin varnish, the above-mentioned (K) solvent can be used. The components can be mixed in part or in whole at the same time, or can be mixed in sequence. In the process of mixing the components, the temperature can be appropriately set, so that heating and / or cooling can be performed temporarily or all the time. In addition, stirring or shaking can be performed in the process of mixing the components.

[0169] The coating of the resin varnish can be carried out using a coating device such as a die coater. Drying can be carried out by known methods such as heating and hot air blowing. The drying conditions are not particularly limited, and the drying is carried out in a manner such that the content of the solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. It also varies depending on the boiling point of the solvent in the resin varnish. For example, when a resin varnish containing 30% to 60% by mass of a solvent is used, a resin composition layer can be formed by drying at 50°C to 150°C for 3 minutes to 10 minutes.

[0170] The resin sheet can be stored by being wound into a roll. When the resin sheet has a protective film, it can be used by peeling off the protective film.

[0171] [Manufacturing method of semiconductor chip package] The manufacturing method of the semiconductor chip package of the present invention sequentially comprises: (I) laminating a resin composition layer of a resin sheet having a support and a resin composition layer provided on the support on a semiconductor chip package having at least one semiconductor chip mounted on a circuit board, and performing under-mold filling; and (II) thermally curing the resin composition layer.

[0172] In the present invention, a resin composition layer having a loss tangent of 0.05 or more and 1.3 or less at a molding temperature is used for molding bottom filling. Therefore, even if a semiconductor chip package has a plurality of semiconductor chips, and even if the semiconductor chip package is large in area, the resin composition layer is effectively applied with external pressure during molding bottom filling, and even if the gap or the gap between electrodes is narrow, the resin composition layer can be filled in the gap or between electrodes. Thus, the generation of gaps in the gap or between electrodes can be suppressed.

[0173] <Step (I)> In step (I), a resin sheet including a support and a resin composition layer provided on the support is laminated on a semiconductor chip package in which at least one semiconductor chip is mounted on a circuit board so that the resin composition layer is bonded to the semiconductor chip package, and mold underfill is performed.

[0174] Step (I) may include: (I-1) Step of preparing a resin sheet, (I-2) a step of preparing a semiconductor chip package in which at least one semiconductor chip is mounted on a circuit board, and (I-3) a step of laminating a resin composition layer of a resin sheet on the semiconductor chip package. Generally, in the lamination in step (I-3), the resin composition layer is pressed onto the semiconductor chip package at a molding temperature to achieve mold underfill. In step (I), if necessary, a step (I-4) of pressing and smoothing the resin composition layer may be included as an optional step after step (I-3).

[0175] The resin sheet prepared in step (I-1) is as described in the above-mentioned column [Resin sheet]. When the resin sheet has a protective film, the protective film is peeled off to expose the resin composition layer.

[0176] In the present invention, a resin composition layer having a loss tangent of 0.05 or more and 1.3 or less at a temperature (molding temperature) for performing molding bottom filling, i.e., a temperature for performing step (I-3) is used. Therefore, even if it is a semiconductor chip package having multiple semiconductor chips, and even if the semiconductor chip package is a large area, for the pressure from the outside in the molding bottom filling, force is effectively applied to the resin composition layer, and even if the gap between the gap or the electrode is narrow, the resin composition layer can be filled in the gap or between the electrodes. Thus, it is possible to suppress the generation of gaps in the gap or between the electrodes.

[0177] In step (I-2), at least one semiconductor chip is bonded and mounted on a circuit substrate to obtain a semiconductor chip package. The circuit substrate can use a conventionally known circuit substrate used to form a semiconductor chip package. The circuit substrate can have any of a conductor layer and an insulating layer on one or both sides thereof, and any of the conductor layer and the insulating layer can be patterned.

[0178] The circuit substrate and the semiconductor chip can be bonded together by, for example, forming bumps on the circuit substrate or the semiconductor chip. The bump formation method can be implemented by a method known to those skilled in the art used in the manufacture of semiconductor chip packages.

[0179] The bonding conditions between the circuit substrate and the semiconductor chip may be any conditions that can connect the terminal electrodes of the semiconductor chip to the circuit wiring of the circuit substrate by conductor connection. For example, the conditions used in flip-chip mounting of the semiconductor chip may be used.

[0180] As a bonding method, for example, a method of crimping a semiconductor chip onto a circuit substrate can be cited. As a crimping condition, the crimping temperature is usually in the range of 120°C to 240°C (preferably in the range of 130°C to 200°C, more preferably in the range of 140°C to 180°C), and the crimping time is usually in the range of 1 second to 60 seconds (preferably 5 seconds to 30 seconds). In addition, as a bonding method, for example, a method of placing a semiconductor chip on a circuit substrate for reflow soldering and bonding can also be cited. The reflow soldering conditions can be in the range of 120°C to 300°C.

[0181] The number of semiconductor chips bonded to the circuit substrate can be at least one. In the present invention, since a resin composition layer having a loss tangent of 0.05 or more and 1.3 or less is used for molding bottom filling, the number of semiconductor chips can be multiple, and even if the semiconductor chip is packaged in a large area, the resin composition layer can be filled in the gap. The number of specific semiconductor chips varies depending on the semiconductor device with the semiconductor chip package, for example, preferably more than 2, more preferably more than 5, more preferably more than 10, preferably less than 500, more preferably less than 400, and more preferably less than 300.

[0182] In the present invention, a resin composition layer having a loss tangent of 0.05 or more and 1.3 or less at a temperature for performing step (I-3) is used. Therefore, even if the gap between the circuit substrate and the semiconductor chip is narrow, the resin composition layer can be filled in the gap. As the gap, it is preferably 60 μm or less, more preferably 50 μm or less, and further preferably 40 μm or less. The lower limit is not particularly limited, and may be 1 μm or more.

[0183] In step (I-3), the resin composition layer of the resin sheet is stacked on the semiconductor chip package. Usually, the resin composition layer is pressed at a molding temperature in a manner that the resin composition layer is bonded to the semiconductor chip package, and the resin composition layer is stacked with the semiconductor chip package. Through this stacking, the resin composition layer is filled between the semiconductor chip and the circuit substrate to achieve molded bottom filling.

[0184] In step (I-3), as a first embodiment, the resin composition layer may be laminated so as to be bonded to the semiconductor chip package to perform underfill molding. Alternatively, in step (I-3), as a second embodiment, hot pressing may be used.

[0185] -First Embodiment- In the step (I-3) of the first embodiment, the semiconductor chip package is laminated in such a way that the resin composition layer of the resin sheet is in contact with each other. Since the laminated resin composition layer and the semiconductor chip package are heated and pressed, the gap between the circuit board and the semiconductor chip can be filled and the semiconductor chip can be sealed at the same time.

[0186] The semiconductor chip package in the first embodiment and the stacking of the resin composition layer of the resin sheet can be performed by heating and pressing the resin sheet to the inner substrate from the support body side. As a component for heating and pressing the resin sheet to the semiconductor chip package (hereinafter also referred to as "heating and pressing component"), for example, a heated metal plate (SUS end plate, etc.) or a metal roller (SUS roller) can be cited. It should be noted that the heating and pressing component is not directly pressed on the resin sheet, and it is preferred that it is pressed via an elastic material such as heat-resistant rubber so that the resin sheet fully follows the surface unevenness of the semiconductor chip package.

[0187] Lamination can be performed by a commercially available vacuum laminator. Examples of the commercially available vacuum laminator include a vacuum pressure laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum laminator manufactured by Nikko-Materials Co., Ltd., and a batch vacuum pressure laminator.

[0188] The heating and pressing temperature, i.e., the molding temperature, is preferably carried out under the condition that the loss tangent of the resin composition layer is 0.05 or more and 1.3 or less. The heating and pressing temperature varies depending on the composition of the resin composition layer, and is, for example, preferably 70°C or more, more preferably 80°C or more, further preferably 90°C or more, 100°C or more, 110°C or more, 120°C or more, or 130°C or more, preferably 180°C or less, more preferably 170°C or less, further preferably 160°C or less, 150°C or less, or 140°C or less.

[0189] The heating and compression bonding pressure is preferably in the range of 0.098 MPa to 1.77 MPa, and more preferably in the range of 0.29 MPa to 1.47 MPa.

[0190] The heating and pressing time is preferably in the range of 20 seconds to 400 seconds, and more preferably in the range of 30 seconds to 300 seconds. In the first embodiment, the step (I-3) is preferably carried out under reduced pressure conditions of 26.7 hPa or less.

[0191] After lamination, the laminated resin sheet can be smoothed by, for example, performing a step (I-4) of pressing the heating and pressing member from the support body side under normal pressure (atmospheric pressure). The pressing conditions for the smoothing treatment can be the same as the heating and pressing conditions for the above-mentioned lamination. The smoothing treatment can be performed using a commercially available laminator. It should be noted that the lamination and smoothing treatment can be performed continuously using the above-mentioned commercially available vacuum laminator.

[0192] The peeling of the support may be performed between the step (I) and the step (II) or after the step (II).

[0193] - Second Embodiment - In the second embodiment, in step (I-3), the semiconductor chip package and the resin sheet are laminated by heat pressing. Typically, the resin composition layer and the semiconductor chip package are laminated by pressing in a mold at a molding temperature so that the resin composition layer and the semiconductor chip package are bonded.

[0194] Regarding the details of the operation (I-3) in the second embodiment, for example, a semiconductor chip package can be placed on the lower mold of the mold for hot pressing, and a resin sheet can be placed on the surface of the semiconductor chip package, and then the mold is closed to make it stacked. In addition, for example, a resin sheet can be placed on the lower mold of the mold for hot pressing, and a semiconductor chip package can be installed on the upper mold, and then the mold is closed to make it stacked. In either case, the resin composition layer in the mold is heated and pressed with the semiconductor chip package by closing the mold, so that the gap between the circuit substrate and the semiconductor chip using the resin composition layer can be filled and the semiconductor chip can be sealed.

[0195] The molding bottom filling in the second embodiment is usually carried out by hot pressing. As the specific operation of molding bottom filling, for example, it is carried out as follows. As the mold used for hot pressing, a heatable upper mold and lower mold are prepared. In step (I-3), the laminated product laminated with the resin composition layer and the semiconductor chip package is arranged on the lower mold, and the upper mold and the lower mold are heated and hot pressed so that the resin composition layer is filled in the gap, and the semiconductor chip is sealed at the same time.

[0196] When hot pressing is used for molding bottom filling, the temperature of the mold during hot pressing, that is, the molding temperature, varies depending on the composition of the resin composition layer, and is, for example, preferably above 70°C, more preferably above 80°C, further preferably above 90°C, above 100°C, above 110°C, above 120°C, or above 130°C, preferably below 180°C, more preferably below 170°C, further preferably below 160°C, below 150°C, or below 140°C.

[0197] In addition, from the viewpoint of filling the gap with the resin composition layer and sealing the semiconductor chip at the same time, the pressure applied during hot pressing is preferably 1 MPa or more, more preferably 3 MPa or more, particularly preferably 5 MPa or more, preferably 50 MPa or less, more preferably 30 MPa or less, and particularly preferably 20 MPa or less.

[0198] From the viewpoint of improving the adhesion of the resin composition layer to the semiconductor chip package, the hot pressing is preferably performed under reduced pressure conditions. As reduced pressure conditions, the pressure is preferably 5 to 10 Torr, and the reduced pressure holding time (the time from the start of reduced pressure to the start of hot pressing) is 5 to 600 seconds.

[0199] After the gap is filled and the semiconductor chip is sealed, the upper mold and the upper mold are removed. The removal of the mold can be performed after the end of process (I) or after process (II). In addition, the peeling of the support body can be performed between process (I) and process (II) or after process (II).

[0200] <Step (II)> In step (II), the resin composition layer filling the gap and the resin composition layer formed on the semiconductor chip are thermally cured so that the gap is filled with the cured product of the resin composition layer and a sealing layer is formed on the semiconductor chip package.

[0201] The heat curing method of the resin composition layer in step (II) includes a two-stage heating method and a one-stage heating method. The two-stage heating method is a method in which the resin composition layer is subjected to a heat treatment maintained at a temperature T1 and then subjected to a heat treatment maintained at a temperature T2 higher than the temperature T1. Hereinafter, the heat treatment maintained at the temperature T1 is referred to as a "pre-curing step", and the heat treatment maintained at the temperature T2 is referred to as a "post-curing step".

[0202] The one-step heating method is a method of subjecting the resin composition layer to a heat treatment in which the resin composition layer is kept at a temperature T2 instead of at a temperature T1, that is, a method of subjecting the resin composition layer to a heat treatment in which the resin composition layer is kept at a temperature T2 without performing a pre-curing step.

[0203] If a pre-curing step is performed, the generation of voids generated when the solvent that may be contained in the resin composition layer evaporates can be suppressed. Therefore, in step (II), it is preferred to perform thermal curing by a two-stage heating method. It should be noted that the unit of temperature T1 and temperature T2 is "°C", and T1<T2.

[0204] -Pre-curing process (heating treatment at temperature T1) Usually, before the pre-curing process, the resin composition layer is at a heating start temperature T0 (°C) lower than the temperature T1. The heating start temperature T0 may be, for example, room temperature. Therefore, process (II) may include a process of heating the resin composition layer from the heating start temperature T0 to the temperature T1 before the pre-curing process. From the viewpoint of significantly obtaining the effect of the present invention, the heating rate in the heating process is preferably 0.5°C / minute or more, more preferably 1°C / minute or more, further preferably 1.5°C / minute or more, further more preferably 2°C / minute or more, particularly preferably 2.5°C / minute or more, and the upper limit is preferably 30°C / minute or less, more preferably 25°C / minute or less, further preferably 20°C / minute or less, further more preferably 15°C / minute or less, and particularly preferably 10°C / minute or less. The heating rate in the heating process may be constant or variable.

[0205] In the pre-curing process, the resin composition layer is subjected to a heat treatment maintained at a temperature T1. The heating temperature T1 in the pre-curing process is set within a temperature range higher than room temperature and lower than temperature T2. From the viewpoint of significantly obtaining the effect of the present invention, the specific range of the heating temperature T1 is preferably 50°C or more, more preferably 60°C or more, further preferably 70°C or more, further more preferably 80°C or more, and its upper limit is preferably less than 150°C, more preferably 140°C or less, and further preferably 130°C or less. In the pre-curing process, keeping the resin composition layer at temperature T1 is not limited to maintaining the temperature of the resin composition layer at a constant temperature, but also includes the temperature of the resin composition layer changing within a range that does not significantly impair the effect of the present invention. For example, in the pre-curing process, the temperature of the resin composition layer can change within a range of ±10°C, a range of ±8°C, or a range of ±5°C. However, even in the case where the temperature of the resin composition layer changes, in the pre-curing process, the temperature of the resin composition layer is preferably within the above-mentioned preferred range, for example, within a range of 50°C or more and less than 150°C. Among them, in the pre-curing step, it is particularly preferred that the temperature of the resin composition layer does not fluctuate but remains constant.

[0206] The time for which the resin composition layer is maintained at the heating temperature T1 in the pre-curing process depends on the composition of the resin composition layer and the value of the heating temperature T1. From the viewpoint of significantly obtaining the effects of the present invention, the time is preferably 10 minutes or more, more preferably 15 minutes or more, and further preferably 20 minutes or more. The upper limit is preferably 150 minutes or less, more preferably 120 minutes or less, and further preferably 120 minutes or less.

[0207] -Post-curing process (heating treatment at temperature T2)- Typically, before the post-curing process, the resin composition layer is at a temperature lower than temperature T2. Therefore, process (II) may include a process of heating the resin composition layer to temperature T2 after the pre-curing process and before the post-curing process. From the viewpoint of significantly obtaining the effect of the present invention, the heating rate in the heating process is preferably 0.5°C / minute or more, more preferably 1°C / minute or more, further preferably 1.5°C / minute or more, further more preferably 2°C / minute or more, particularly preferably 2.5°C / minute or more, and its upper limit is preferably 30°C / minute or less, more preferably 25°C / minute or less, further preferably 20°C / minute or less, further more preferably 15°C / minute or less, particularly preferably 10°C / minute or less. Therefore, in one embodiment, in process (II), the resin composition layer is heated to temperature T2 at a heating rate of 0.5°C / minute or more and 30°C / minute or less. The heating rate in the heating process may be constant or variable.

[0208] In the post-curing process, the resin composition layer is subjected to a heating treatment maintained at a temperature T2. The heating temperature T2 in the post-curing process is set to a temperature higher than the temperature T1. From the viewpoint of significantly obtaining the effect of the present invention, the specific range of the heating temperature T2 is preferably 150°C or more, more preferably 155°C or more, further preferably 160°C or more, and particularly preferably 170°C or more, and its upper limit is preferably 250°C or less, more preferably 230°C or less, further preferably 220°C or less, further more preferably 210°C or less, and particularly preferably 200°C or less. In the post-curing process, maintaining the resin composition layer at temperature T2 includes not only maintaining the temperature of the resin composition layer at a constant temperature, but also including the temperature of the resin composition layer changing within a range that does not significantly impair the effect of the present invention. For example, in the post-curing process, the temperature of the resin composition layer can change within a range of ±10°C, a range of ±8°C, or a range of ±5°C. However, even in the case where the temperature of the resin composition layer changes in this way, in the post-curing process, the temperature of the resin composition layer is preferably within the above-mentioned preferred range, for example, within a range of 150°C or more and 250°C or less. Among them, in the post-curing step, it is particularly preferred that the temperature of the resin composition layer does not fluctuate but remains constant.

[0209] The difference T2-T1 between the heating temperature T2 in the post-curing process and the heating temperature T1 in the pre-curing process is preferably within a specific range from the viewpoint of significantly obtaining the effect of the present invention. Specifically, the difference T2-T1 is preferably 20°C or more, more preferably 30°C or more, and further preferably 40°C or more, and its upper limit is preferably 150°C or less, more preferably 140°C or less, further preferably 130°C or less, and particularly preferably 120°C or less. In the case where the temperature of the resin composition layer changes in the pre-curing process and / or the post-curing process, the difference between the central value of the temperature of the resin composition in the post-curing process and the central value of the temperature of the resin composition in the pre-curing process is preferably within the above range.

[0210] The time for which the resin composition layer is maintained at the heating temperature T2 in the post-curing process depends on the composition of the resin composition layer and the value of the heating temperature T2. From the viewpoint of significantly obtaining the effects of the present invention, it is preferably 10 minutes or more, more preferably 15 minutes or more, and further preferably 20 minutes or more. The upper limit is preferably 150 minutes or less, and more preferably 120 minutes or less.

[0211] After the heat treatment at temperature T1 in the pre-curing process, the resin composition layer may be temporarily cooled, and then the heat treatment at heating temperature T2 in the post-curing process may be performed. Alternatively, after the heat treatment at temperature T1 in the pre-curing process, the resin composition layer may be heated without cooling, and the heat treatment at temperature T2 in the post-curing process may be performed.

[0212] The heating treatment in the pre-curing process and the heating treatment in the post-curing process can be implemented using the same heating treatment device. In addition, the first heating treatment device can be used to implement the heating treatment in the pre-curing process, and the second heating treatment device different from the first heating treatment device can be used to implement the heating treatment in the post-curing process. The heating treatment device is not particularly limited as long as it can thermally cure the resin composition layer. As a heating treatment device, for example, an oven, a hot press, etc. can be used. For example, after using an oven adjusted to temperature T1 to implement the heating treatment in the pre-curing process, the laminate of the substrate and the resin sheet can be transferred to an oven adjusted to temperature T2, and the heating treatment in the post-curing process can be implemented. Alternatively, a heating treatment device capable of performing programmed temperature increase can be used, and after implementing the heating treatment in the pre-curing process, the temperature is increased from temperature T1 to temperature T2, and the heating treatment in the post-curing process is implemented.

[0213] In addition to the above-mentioned pre-curing step or post-curing step, and the heating step before them, step (II) may also include any step. For example, step (II) may include heating the resin composition layer at a temperature other than temperature T1 and T2. That is, step (II) is not limited to a heating treatment of one step or two steps, and may also include a heating treatment of three or more steps.

[0214] Step (II) is preferably performed under a nitrogen atmosphere. When the nitrogen atmosphere contains oxygen, the oxygen concentration in the nitrogen atmosphere is preferably 5 mass % or less, more preferably 3 mass % or less, further preferably 1 mass % or less, and may be 0 mass %.

[0215] The pressure condition of the nitrogen atmosphere for carrying out step (II) may be normal pressure or reduced pressure. In one example, the specific pressure condition of the nitrogen atmosphere is preferably 0.1 hPa or more, more preferably 1.3 hPa or more, and the upper limit is preferably 5000 hPa or less, more preferably 2500 hPa or less.

[0216] The production method of the present invention may include other steps as long as it includes the above-mentioned step (I) and step (II) in order.

[0217] The semiconductor chip package manufactured by the manufacturing method of the present invention can be any of a fan-in package and a fan-out package. In the case where the semiconductor package is a fan-out package, the original feature of the fan-out package, such as the ability to form a rewiring layer in a large area, can form a conductor circuit in a large area with a fine pattern.

[0218] The semiconductor chip package manufactured by the manufacturing method of the present invention, because it contains a cured product of a resin composition layer having a loss tangent of 0.05 or more and 1.3 or less at a temperature for molding bottom filling, shows the characteristic of a low dielectric loss tangent of the cured product. The resin composition layer having a thickness of 40 μm is thermally cured at 130° C. for 30 minutes and then thermally cured at 200° C. for 90 minutes to obtain a cured product for evaluation. The cured product for evaluation is cut into a specified size, and the dielectric loss tangent is measured three times at a measurement frequency of 5.8 GHz and a measurement temperature of 23° C. by a resonant cavity perturbation method. The average value of the dielectric loss tangent at this time is preferably less than 0.01, more preferably less than 0.008, and further preferably less than 0.005. The lower limit is not particularly limited, and may be 0.0001 or more. The determination of the dielectric loss tangent can be determined by the method described in the embodiments described later.

[0219] The semiconductor chip package manufactured by the manufacturing method of the present invention, due to the use of a resin composition layer having a loss tangent of more than 0.05 and less than 1.3 at a temperature for performing molding bottom filling, it is shown that even if the resin composition layer is stacked on the semiconductor chip package, the characteristics of the generation of the void can be suppressed before the resin composition layer is cured. For example, in a manner where 4 vertical and 3 horizontal layers are 12 in total on a glass substrate, the chip spacing is 400 μm, and the gap between the glass substrate and the semiconductor chip is 30 μm, a resin composition layer is laminated on a semiconductor chip connected with a gold bump (gold bump), and an evaluation substrate is obtained. If the number of semiconductor chips having a void is generated in the resin composition between the semiconductor chip and the glass substrate of the evaluation substrate, the number of voids is preferably less than 2, and more preferably there is no void. The evaluation of the void can be measured by the method described in the embodiment described later.

[0220] The semiconductor chip package manufactured by the manufacturing method of the present invention uses a resin composition layer having a loss tangent of more than 0.05 and less than 1.3 at a temperature for performing molding bottom filling, so that even if the resin composition layer is laminated on the semiconductor chip package, the resin composition layer can be thermally cured to suppress the generation of voids. For example, a resin composition layer is laminated on a semiconductor chip connected with a gold bump in a manner that 4 vertical and 3 horizontal layers are 12 in total, the chip distance is 400 μm, and the gap between the glass substrate and the semiconductor chip is 30 μm, and the resin composition layer is thermally cured to obtain an evaluation substrate. If the number of semiconductor chips having voids is counted in the resin composition between the semiconductor chip and the glass substrate of the evaluation substrate, the number of voids is preferably less than 3, more preferably less than 2, and more preferably there is no void. The evaluation of the void can be measured by the method described in the embodiment described later. Example

[0221] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. It should be noted that in the following description, "parts" refer to "parts by mass" unless otherwise expressly stated. It should be noted that, unless otherwise expressly stated, the description is carried out at room temperature and atmospheric pressure.

[0222] [Synthesis of Elastomer A] In a reaction container, 69 g of a bifunctional hydroxy-terminated polybutadiene ("G-3000" manufactured by Nippon Soda Co., Ltd., number average molecular weight = 3000, hydroxyl equivalent = 1800 g / eq.), 40 g of an aromatic hydrocarbon mixed solvent ("Ipzole 150" manufactured by Idemitsu Petrochemical Co., Ltd.), and 0.005 g of dibutyltin laurate were added and mixed to be uniformly dissolved. After becoming uniform, the temperature was raised to 60° C., and 8 g of isophorone diisocyanate ("IPDI" manufactured by Evonik Degussa Japan Co., Ltd., isocyanate equivalent = 113 g / eq.) was added while stirring, and the reaction was carried out for about 3 hours.

[0223] Then, 23 g of cresol novolac resin ("KA-1160" manufactured by DIC Corporation, hydroxyl equivalent = 117 g / eq.) and 60 g of ethyl diglycol acetate (manufactured by Daicel Corporation) were added to the reactant, and the temperature was raised to 150°C while stirring, and the reaction was carried out for about 10 hours. FT-IR was used to measure the reaction temperature at 2250 cm -1 The disappearance of the NCO peak was confirmed. The disappearance of the NCO peak was regarded as the end point of the reaction, and the reactants were cooled to room temperature. Then, the reactants were filtered with a 100-mesh filter cloth to obtain an elastomer having a butadiene structure and phenolic hydroxyl groups (butadiene resin containing phenolic hydroxyl groups: non-volatile components 50% by mass). The number average molecular weight of elastomer A is 5900, and the glass transition temperature is -7°C.

[0224] [Inorganic fillers used] Inorganic filler A: average particle size 3 μm, specific surface area 3.5 m 2 / g, and a material surface-treated with KBM573 (manufactured by Shin-Etsu Chemical Co., Ltd.). Inorganic filler B: average particle size 0.5 μm, specific surface area 5.9 m 2 / g, and a material surface-treated with KBM573 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0225] [Examples 1-2, Comparative Example 1] 30 parts of a biphenyl type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185 g / eq.), 20 parts of a biphenyl type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 272 g / eq.), and 10 parts of a naphthyl ether type epoxy resin ("HP-6000L" manufactured by DIC Corporation, epoxy equivalent of 215 g / eq.) were dissolved in a mixed solvent of 20 parts of solvent naphtha and 30 parts of cyclohexanone while stirring and heating. The mixture was cooled to room temperature to prepare a dissolved composition of epoxy resin. In the epoxy resin dissolving composition, 30 parts of elastomer A, 20 parts of a phenolic curing agent having a triazine skeleton and a phenolic structure ("LA3018-50P" manufactured by DIC Corporation, a 2-methoxypropanol solution containing 50% of nonvolatile components, 50 parts of an active ester curing agent ("HPC-8000-65T" manufactured by DIC Corporation, a toluene solution containing 65% of nonvolatile components, and 50 parts of a carbodiimide curing agent were mixed. 10 parts of (V-03 manufactured by Nisshinbo Chemical Co., Ltd., carbodiimide group equivalent 216 g / eq., toluene solution with 50% by mass of non-volatile components), 1 part of a curing accelerator (1-benzyl-2-phenylimidazole (1B2PZ), MEK solution with 10% by mass of non-volatile components), 10 parts of a curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution with 2.5% by mass of solid content), and 650 parts of an inorganic filler A are uniformly dispersed using a high-speed rotary mixer to prepare a resin varnish.

[0226] As a support, a polyethylene terephthalate film ("AL5" manufactured by Lintec Corporation, thickness 38 μm) having a release layer was prepared. The above-mentioned resin varnish was evenly applied on the release layer of the support so that the thickness of the resin composition layer after drying was 200 μm. Then, the resin varnish was dried at 80°C to 120°C (average 100°C) for 6 minutes to prepare a resin sheet comprising a support and a resin composition layer (thickness 200 μm). In addition, except that the thickness of the resin composition layer after drying was 40 μm, a resin sheet comprising a support and a resin composition layer (thickness 40 μm) was prepared in the same manner.

[0227] [Examples 3-4, Comparative Example 2] 2 parts of bisphenol A epoxy resin ("YD-8125G" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., epoxy equivalent of about 174 g / eq.), 5 parts of dimethylol epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185 g / eq.), 5 parts of naphthyl ether epoxy resin ("EXA-7311-G4" manufactured by DIC Corporation, epoxy equivalent of about 213 g / eq.), 5 parts of biphenyl epoxy resin ("N- C3000L", epoxy equivalent of about 272 g / eq.), 15 parts of epoxidized polybutadiene ("PB3600" manufactured by Daicel Corporation, epoxy equivalent of about 193 g / eq.), and 10 parts of phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, a 1:1 solution of cyclohexanone:methyl ethyl ketone (MEK) with a solid content of 30% by mass) were dissolved in a mixed solvent of 15 parts of solvent naphtha and 10 parts of cyclohexanone while stirring and heating. After cooling to room temperature, 5 parts of a cresol novolac curing agent containing a triazine skeleton ("LA3018-50P" manufactured by DIC Corporation, a hydroxyl equivalent of about 151 g / eq., a 2-methoxypropanol solution of 50% solid content), 12 parts of an active ester curing agent ("HPC-8000-65T" manufactured by DIC Corporation, an active group equivalent of about 223 g / eq., a toluene solution of 65% by mass of non-volatile components), and a carbodiimide resin (Nisshinbo Chemical Co., Ltd.) were mixed therein. 10 parts of "V-03", a toluene solution with a carbodiimide equivalent of about 216 g / eq. and a non-volatile component of 50% by mass), 3 parts of a curing accelerator (4-dimethylaminopyridine (DMAP), a MEK solution with a solid content of 2.5% by mass), 2 parts of a flame retardant ("HCA-HQ" manufactured by Sanko Co., Ltd., 10-(2,5-dihydroxyphenyl)-10-hydrogen-9-oxa-10-phosphaphenanthrene-10-oxide, with an average particle size of 1.2 μm), and 180 parts of an inorganic filler B were uniformly dispersed using a high-speed rotary mixer to prepare a resin varnish.

[0228] As a support, a polyethylene terephthalate film ("AL5" manufactured by Lintec Corporation, thickness 38 μm) having a release layer was prepared. The above-mentioned resin varnish was evenly applied on the release layer of the support so that the thickness of the resin composition layer after drying was 200 μm. Then, the resin varnish was dried at 80°C to 120°C (average 100°C) for 6 minutes to prepare a resin sheet comprising a support and a resin composition layer. In addition, except that the thickness of the resin composition layer after drying was 40 μm, a resin sheet comprising a support and a resin composition layer (thickness 40 μm) was prepared in the same manner.

[0229] [Example 5] 30 parts of a biphenyl type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185 g / eq.), 20 parts of a biphenyl type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 272 g / eq.), and 10 parts of a naphthyl ether type epoxy resin ("HP-6000L" manufactured by DIC Corporation, epoxy equivalent of 215 g / eq.) were dissolved in a mixed solvent of 20 parts of solvent naphtha and 30 parts of cyclohexanone while stirring and heating. The mixture was cooled to room temperature to prepare a dissolved composition of epoxy resin. In the dissolved composition of the epoxy resin, 30 parts of the elastomer A, 20 parts of a phenolic curing agent having a triazine skeleton and a phenolic structure ("LA3018-50P" manufactured by DIC Corporation, a 2-methoxypropanol solution containing 50% of a reactive group equivalent, 151 g / eq., and a non-volatile component), 10 parts of a carbodiimide curing agent ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., a toluene solution containing 50% of a non-volatile component by mass), 1 part of a curing accelerator (a MEK solution containing 10% of a non-volatile component by mass), 10 parts of a curing accelerator (a MEK solution containing 2.5% of a solid content by mass of 4-dimethylaminopyridine (DMAP), and 10 parts of an inorganic filler A6 were mixed and uniformly dispersed using a high-speed rotary mixer to prepare a resin varnish 3.

[0230] As a support, a polyethylene terephthalate film ("AL5" manufactured by Lintec Corporation, thickness 38 μm) having a release layer was prepared. The above-mentioned resin varnish was evenly applied on the release layer of the support so that the thickness of the resin composition layer after drying was 200 μm. Then, the resin varnish was dried at 80°C to 120°C (average 100°C) for 6 minutes to prepare a resin sheet comprising a support and a resin composition layer. In addition, except that the thickness of the resin composition layer after drying was 40 μm, a resin sheet comprising a support and a resin composition layer (thickness 40 μm) was prepared in the same manner.

[0231] [Examples 6 to 7, Comparative Example 3] 10 parts of bisphenol epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., a 1:1 mixture of bisphenol A and bisphenol F, epoxy equivalent 169 g / eq.) and 50 parts of naphthol epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., epoxy equivalent about 330 g / eq.) were dissolved in 40 parts of solvent naphtha while stirring and heating. The mixture was cooled to room temperature to prepare a dissolved composition of epoxy resin. In the epoxy resin dissolving composition, 5 parts of phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, a 1:1 solution of MEK and cyclohexanone with a nonvolatile content of 30% by mass), 5 parts of a phenolic curing agent having a triazine skeleton and a phenolic structure ("LA3018-50P" manufactured by DIC Corporation, a 2-methoxypropanol solution with a reactive group equivalent of about 151 g / eq., and a nonvolatile content of 50%), and an active ester curing agent ("HPC-8000-65T" manufactured by DIC Corporation, a reactive group equivalent of about 223 g / eq., 70 parts of a toluene solution containing 65% by mass of nonvolatile components), 20 parts of a (meth)acrylate ("A-DOG" manufactured by Shin-Nakamura Chemical Co., Ltd., (meth)acryloyl equivalent 156 g / eq.), 15 parts of a carbodiimide curing agent ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., carbodiimide group equivalent 216 g / eq., a toluene solution containing 50% by mass of nonvolatile components), 6 parts of a curing accelerator (1-benzyl-2-phenylimidazole (1B2PZ), a MEK solution containing 10% by mass of nonvolatile components), 2 parts of a polymerization initiator (PERCUMYL D (manufactured by NOF Corporation, a MEK solution containing 20% ​​by mass of nonvolatile components)), 470 parts of an inorganic filler B, 10 parts of cyclohexanone, and 10 parts of MEK were uniformly dispersed using a high-speed rotary mixer to prepare a resin varnish.

[0232] As a support, a polyethylene terephthalate film ("AL5" manufactured by Lintec Corporation, thickness 38 μm) having a release layer was prepared. The above-mentioned resin varnish was evenly applied on the release layer of the support so that the thickness of the resin composition layer after drying was 200 μm. Then, the resin varnish was dried at 80°C to 120°C (average 100°C) for 6 minutes to prepare a resin sheet comprising a support and a resin composition layer. In addition, except that the thickness of the resin composition layer after drying was 40 μm, a resin sheet comprising a support and a resin composition layer (thickness 40 μm) was prepared in the same manner.

[0233] [Determination of melt viscosity and loss tangent] Using a resin sheet having a resin composition layer thickness of 200 μm, only the resin composition layer was peeled off from a release PET (support), and compressed with a mold to prepare pellets for measurement (diameter 18 mm, 1.2 to 1.3 g).

[0234] Using a dynamic viscoelasticity measuring device ("Rheosol-G3000" manufactured by UBM), for 1 g of the sample resin composition layer, a parallel plate with a diameter of 18 mm was used, and the temperature was raised from the starting temperature of 70°C to 180°C at a heating rate of 5°C / min, and the dynamic viscoelastic modulus was measured under the measurement conditions of a measurement temperature interval of 2.5°C, a vibration frequency of 1 Hz, and a deformation of 1 degree. After measuring the dynamic viscoelastic modulus, a graph with the horizontal axis being the temperature and the vertical axis being the melt viscosity or the loss tangent was prepared, and the melt viscosity (poise) and the loss tangent (tanδ) at the molding temperature were calculated.

[0235] [Determination of dielectric loss tangent of cured product] The untreated surface of a release PET film ("501010" manufactured by Lintec, 38 μm thick, 240 mm square) was placed on a glass cloth-based epoxy resin double-sided copper-clad laminate ("R5715ES" manufactured by Matsushita Electric Works, 0.7 mm thick, 255 mm square) in contact with a glass cloth-based epoxy resin double-sided copper-clad laminate, and the four sides of the release PET film were fixed with polyimide adhesive tape (10 mm width).

[0236] The resin sheets (200 mm square) having a resin composition layer thickness of 40 μm prepared in the examples and comparative examples were laminated in the center using a batch vacuum pressurizing laminator (Nikko-materials, 2-stage stacking laminator "CVP700") so that the resin composition layer was in contact with the release surface of a release PET film (Lintec, "501010") . The lamination process was performed by reducing the pressure for 30 seconds to 13 hPa or less, and then pressing at 100° C. and a pressure of 0.74 MPa for 30 seconds.

[0237] Next, the release PET (support) was peeled off from the resin sheet, and the mixture was placed in an oven at 130°C for 30 minutes and then transferred to an oven at 200°C for 90 minutes for thermal curing to obtain a cured product for evaluation.

[0238] The above-mentioned "cured product for evaluation" was cut into a test piece with a width of 1.5 mm and a length of 80 mm. The dielectric loss tangent (Df) of the test piece was measured by the resonant cavity perturbation method at a measurement frequency of 5.8 GHz and a measurement temperature of 23° C. using "HP8362B" manufactured by Agilent Technologies. The measurement was performed on three test pieces, and the average value was calculated.

[0239] [Evaluation of the generation of gaps] <Preparation of Samples for Evaluation of Mold Underfilling Properties> (1) Preparation of evaluation substrate An evaluation substrate was prepared in which a semiconductor chip (960 μm in length, 1350 μm in width, and 200 μm in thickness) was flip-chip connected to a glass substrate (38 mm square, 1 mm in thickness). The semiconductor chips were connected using gold bumps (60 μm in diameter and 240 μm in pitch) in a manner of 4 vertical and 3 horizontal semiconductor chips on the glass substrate, a total of 12 chips, with a distance of 400 μm between chips and a gap of 30 μm between the glass substrate and the semiconductor chip.

[0240] (2) Molding bottom filling of resin sheet A batch vacuum pressurizing laminator (Nikko-materials two-stage stacking laminator "CVP700") was used to arrange a resin composition layer with a thickness of 200 μm so as to cover the semiconductor chip of the evaluation substrate, and laminated to obtain an evaluation substrate A. The lamination was performed by reducing the pressure to 13 hPa or less for 30 seconds, and then pressing at a molding temperature of 100 to 140°C and a pressure of 0.74 MPa for 30 seconds.

[0241] (3) Curing of resin sheet The evaluation substrate A of Examples 2, 4, 7, and Comparative Examples 2 and 3 was placed in an oven at 130°C for a pre-curing step for 30 minutes, and then transferred to an oven at 200°C for a post-curing step for 90 minutes, thereby thermally curing the resin composition layer to obtain an evaluation substrate B.

[0242] The evaluation substrate A of Examples 1, 3, 5, 6 and Comparative Example 1 was placed in an oven at 200° C. without a pre-curing step and then subjected to a post-curing step for 90 minutes to thermally cure the resin composition layer, thereby obtaining an evaluation substrate B.

[0243] <Evaluation of the gap> The number of semiconductor chips in which voids were generated in the resin composition between the semiconductor chip and the glass substrate was counted using a digital microscope (Keyence Corporation "VHX-7000") in evaluation substrate A and evaluation substrate B. In addition, the generation of voids in evaluation substrate B was evaluated according to the following criteria. 0: The number of gaps is 0 △: The number of gaps is 1 or more and 3 or less ×: The number of gaps is 4 or more

[0244] [Table 1]

Claims

1. A method for manufacturing a semiconductor chip package, the method for manufacturing a semiconductor chip package comprising: (I) laminating a resin composition layer of a resin sheet having a support and a resin composition layer provided on the support on a semiconductor chip package having at least one semiconductor chip mounted on a circuit board, and performing a mold underfill; and (II) a step of thermally curing the resin composition layer, The resin composition layer has a loss tangent of 0.05 or more and 1.3 or less at a temperature at which the mold underfill is performed.

2. The method for manufacturing a semiconductor chip package according to claim 1, wherein: In the step (I), the temperature for performing the mold underfill is 70° C. or higher and 180° C. or lower.

3. The method for manufacturing a semiconductor chip package according to claim 1, wherein: In the step (II), the resin composition layer is subjected to a heat treatment while being maintained at a temperature T1, and then subjected to a heat treatment while being maintained at a temperature T2 higher than the temperature T1.

4. The method for manufacturing a semiconductor chip package according to claim 1, wherein: The resin composition layer contains (A) an inorganic filler.

5. The method for manufacturing a semiconductor chip package according to claim 4, wherein: When the nonvolatile component of the resin composition layer is 100 mass %, the content of the (A) inorganic filler is 65 mass % or more.

6. The method for manufacturing a semiconductor chip package according to claim 1, wherein: The melt viscosity of the resin composition layer is 1000 poise or more and 10000 poise or less.

7. The method for manufacturing a semiconductor chip package according to claim 1, wherein: The gap between the circuit board and the semiconductor chip is 60 μm or less.

8. The method for manufacturing a semiconductor chip package according to claim 3, wherein: The temperature T2 is 150° C. or higher.

9. The method for manufacturing a semiconductor chip package according to claim 3, wherein: The difference T2-T1 between the temperature T2 and the temperature T1 is 20°C or more.

10. The method for manufacturing a semiconductor chip package according to claim 3, wherein: The temperature T1 is 50° C. or higher.

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