JP7302496B2 - resin composition - Google Patents

Description

The present invention relates to resin compositions containing epoxy resins. Furthermore, the present invention relates to a cured product, a resin sheet, a circuit board, a semiconductor chip package, and a semiconductor device obtained using the resin composition.

In recent years, the demand for compact, high-performance electronic devices such as smartphones and tablet devices has increased, and along with this, the encapsulants for semiconductor chip packages used in these small electronic devices are required to have even higher functionality. ing. As such a sealing material, one formed by curing a resin composition is known (Patent Document 1).

Moreover, a resin composition containing a polyether skeleton-containing epoxy compound has been known so far (Patent Document 2). A resin composition containing a polyether skeleton-containing non-epoxy compound containing butylene oxide units is also known (Patent Document 3).

JP 2017-008312 A WO2018/221681 JP 2018-168354 A

Materials with a low linear thermal expansion coefficient and excellent dimensional stability are required for sealing materials used in semiconductor chip packages. As a technique for keeping the coefficient of linear thermal expansion low, a method of filling a resin composition with a high amount of an inorganic filler is known.

However, when the resin material is highly filled with an inorganic filler, the resin composition tends to become brittle, which generally lowers the mechanical strength and increases the melt viscosity. is likely to decrease, the elastic modulus increases, and it may become difficult to suppress warpage.

Accordingly, an object of the present invention is to provide a resin composition that has excellent embeddability, can suppress warpage during curing, and can yield a cured product with excellent mechanical strength.

In order to achieve the object of the present invention, the present inventors have made intensive studies, and as a result, (B) even a resin composition highly filled with an inorganic filler (D) composed of predetermined monomer units To obtain a cured product having excellent embeddability, suppressing warpage during curing, and having excellent mechanical strength by using a resin composition containing an ether skeleton-containing non-epoxy compound and satisfying other predetermined conditions. The present inventors have found that it is possible to complete the present invention.

That is, the present invention includes the following contents.
[1] A resin composition comprising (A) an epoxy resin, (B) an inorganic filler, (C) a curing agent, and (D) a polyether skeleton-containing non-epoxy compound,
The polyether skeleton contained in component (D) is a polyoxyalkylene skeleton composed of one or more monomer units selected from ethylene oxide units and propylene oxide units,
The content of component (B) is 70% by mass or more when all non-volatile components in the resin composition are 100% by mass,
A resin composition in which the content of component (D) is 1% by mass or more and 30% by mass or less when non-volatile components other than component (B) in the resin composition are taken as 100% by mass.
[2] The resin composition according to [1] above, wherein component (D) is one or more compounds selected from the group consisting of polyalkylene glycol and polyoxyalkylene-modified silicone.
[3] The resin composition according to [2] above, wherein the polyalkylene glycol is polyoxyethylene-polyoxypropylene glycol.
[4] The resin composition according to any one of [1] to [3] above, wherein the component (D) has a number average molecular weight of 500 to 10,000.
[5] The resin composition according to any one of [1] to [4] above, wherein the viscosity of component (D) at 25° C. is 3000 mPa·s or less.
[6] The content of component (B) is 78% by mass or more when all non-volatile components in the resin composition are 100% by mass. Resin composition.
[7] The resin composition according to any one of [1] to [6] above, wherein the component (B) is silica.
[8] The resin composition according to any one of [1] to [7] above, wherein component (A) contains an epoxy resin containing a condensed ring structure.
[9] The resin composition according to [8] above, wherein the content of the epoxy resin containing a condensed ring structure in component (A) is 50% by mass or more when the total amount of component (A) is 100% by mass. .
[10] The resin composition according to any one of [1] to [9] above, wherein the component (A) contains a glycidylamine type epoxy resin.
[11] The resin composition according to any one of [1] to [10] above, wherein component (A) contains a liquid epoxy resin.
[12] The resin composition according to [11] above, wherein the content of the liquid epoxy resin in component (A) is 50% by mass or more when the total amount of component (A) is 100% by mass.
[13] Any of the above [1] to [12], wherein the content of component (A) is 40% by mass or more when non-volatile components other than component (B) in the resin composition are 100% by mass. The resin composition according to .
[14] Any one of [1] to [13] above, wherein component (C) contains one or more curing agents selected from the group consisting of acid anhydride curing agents and amine curing agents. Resin composition.
[15] The resin composition according to any one of [1] to [14] above for forming an insulating layer of a semiconductor chip package.
[16] The resin composition according to any one of [1] to [14] above for forming an insulating layer of a circuit board.
[17] The resin composition according to any one of the above [1] to [14] for encapsulating a semiconductor chip in a semiconductor chip package.
[18] A cured product of the resin composition according to any one of [1] to [17] above.
[19] A resin sheet comprising a support and a resin composition layer containing the resin composition according to any one of [1] to [17] provided on the support.
[20] A circuit board comprising an insulating layer formed from a cured product of the resin composition according to any one of [1] to [17] above.
[21] A semiconductor chip package including the circuit board according to [20] above and a semiconductor chip mounted on the circuit board.
[22] A semiconductor chip package comprising a semiconductor chip and a cured product of the resin composition according to any one of [1] to [17] for encapsulating the semiconductor chip.
[23] A semiconductor device comprising the semiconductor chip package according to [21] or [22] above.

According to the present invention, it is possible to provide a resin composition that has excellent embeddability, can suppress warpage during curing, and can give a cured product with excellent mechanical strength.

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will now be described in detail with reference to its preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily modified without departing from the scope of the claims of the present invention and their equivalents.

<Resin composition>
The resin composition of the present invention contains (A) an epoxy resin, (B) an inorganic filler, (C) a curing agent, and (D) a non-epoxy compound containing a polyether skeleton, and the polyether contained in the component (D) The skeleton is a polyoxyalkylene skeleton composed of one or more monomer units selected from ethylene oxide units and propylene oxide units, and the content of component (B) is 100 mass of all non-volatile components in the resin composition. %, it is 70% by mass or more, and the content of component (D) is 1% by mass or more and 30% by mass or less when non-volatile components other than component (B) in the resin composition are 100% by mass. is.

Such a resin composition has excellent embeddability, can suppress warpage during curing, and can provide a cured product with excellent mechanical strength.

The resin composition of the present invention comprises (A) an epoxy resin, (B) an inorganic filler, (C) a curing agent, and (D) a non-epoxy compound containing a polyether skeleton, and (E) a curing accelerator, (F) Other additives and (G) an organic solvent may be included. Each component contained in the resin composition will be described in detail below.

<(A) Epoxy resin>
The resin composition of the present invention contains (A) an epoxy resin. (A) Epoxy resin means a resin having an epoxy group.

(A) Epoxy resins include, for example, bixylenol 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, and trisphenol type epoxy resins. Epoxy resin, naphthol novolak type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin , cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexane Dimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, isocyanurate type epoxy resin and the like can be mentioned. (A) Epoxy resins may be used singly or in combination of two or more.

(A) The epoxy resin preferably contains a glycidylamine type epoxy resin from the viewpoint of further improving the heat resistance and copper adhesion of the cured product.

In addition, (A) the epoxy resin preferably contains a condensed ring structure-containing epoxy resin from the viewpoint of imparting excellent heat resistance. Examples of the condensed ring in the epoxy resin containing a condensed ring structure include naphthalene ring, anthracene ring, phenanthrene ring and the like, and naphthalene ring is particularly preferred. Therefore, (A) the epoxy resin particularly preferably contains a naphthalene ring structure-containing epoxy resin. Epoxy resins containing a naphthalene ring structure include, for example, 1,6-bis(glycidyloxy)naphthalene, 1,5-bis(glycidyloxy)naphthalene, 2,7-bis(glycidyloxy)naphthalene and the like. Epoxy resins having a naphthalene ring structure; Epoxy resins having two naphthalene ring structures in one molecule such as glycidyloxy)-1-naphthyl][2-(glycidyloxy)-1-naphthyl]methane; naphthol novolac type epoxy resins, naphthol-phenol cocondensed novolacs type epoxy resin, naphthol-cresol cocondensed novolac type epoxy resin, naphthol aralkyl type epoxy resin, naphthalene diol aralkyl type epoxy resin, naphthylene ether type epoxy resin, etc., having two or three or more naphthalene ring structures in one molecule. polymer-type epoxy resins having Among them, an epoxy resin having one naphthalene ring structure in one molecule is preferable. The content of the epoxy resin containing a condensed ring structure in the epoxy resin (A) is not particularly limited. is 40% by mass or more, particularly preferably 50% by mass or more.

The resin composition preferably contains an epoxy resin having two or more epoxy groups in one molecule as (A) the epoxy resin. (A) The ratio of the epoxy resin having two or more epoxy groups in one molecule to 100% by mass of the non-volatile components of the epoxy resin is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably is 70% by mass or more.

Epoxy resins include liquid epoxy resins at a temperature of 20° C. (hereinafter sometimes referred to as “liquid epoxy resins”) and solid epoxy resins at a temperature of 20° C. (hereinafter sometimes referred to as “solid epoxy resins”). ). As the epoxy resin, the resin composition of the present invention may contain only a liquid epoxy resin, may contain only a solid epoxy resin, or may contain a combination of a liquid epoxy resin and a solid epoxy resin. Although it may contain only a liquid epoxy resin, it is preferred.

A liquid epoxy resin having two or more epoxy groups in one molecule is preferable as the liquid epoxy resin.

Examples of liquid epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, and an ester skeleton. An alicyclic epoxy resin, a cyclohexane type epoxy resin, a cyclohexanedimethanol type epoxy resin, and an epoxy resin having a butadiene structure are preferred.

Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resins) manufactured by DIC; "828US", "828EL", "jER828EL", and "825" manufactured by Mitsubishi Chemical Corporation; ", "Epikote 828EL" (bisphenol A type epoxy resin); "jER807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630", "630LSD", "604" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ED-523T" (glycirrol type epoxy resin) manufactured by ADEKA; "EP-3950L" manufactured by ADEKA; "EP-3980S" (glycidylamine type epoxy resin); "EP-4088S" (dicyclopentadiene type epoxy resin) manufactured by ADEKA; "ZX1059" manufactured by Nippon Steel & Sumikin Chemical (bisphenol A type epoxy resin and bisphenol F type Epoxy resin mixture); "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX; "Celoxide 2021P" manufactured by Daicel (alicyclic epoxy resin having an ester skeleton); "PB-3600", Nippon Soda Co., Ltd. "JP-100", "JP-200" (epoxy resin having a butadiene structure); glycidylcyclohexane type epoxy resin) and the like. These may be used individually by 1 type, and may be used in combination of 2 or more types.

The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups per molecule, more preferably an aromatic solid epoxy resin having 3 or more epoxy groups per molecule.

Solid epoxy resins include bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolak 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.

Specific examples of solid epoxy resins include "HP4032H" (naphthalene-type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resin) manufactured by DIC; "N-690" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolak type epoxy resin) manufactured by DIC Corporation; "HP-7200", "HP-7200HH", "HP -7200H" (dicyclopentadiene type epoxy resin); DIC's "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" ( Naphthylene ether type epoxy resin); Nippon Kayaku Co., Ltd. "EPPN-502H" (trisphenol type epoxy resin); Nippon Kayaku Co., Ltd. "NC7000L" (naphthol novolac type epoxy resin); "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin); "ESN475V" (naphthol type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; type epoxy resin); "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX4000HK" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation; YX8800" (anthracene type epoxy resin); "YX7700" (xylene structure-containing novolac type epoxy resin) manufactured by Mitsubishi Chemical; "PG-100" and "CG-500" manufactured by Osaka Gas Chemicals; "YL7760" (bisphenol AF type epoxy resin); "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; jER1031S" (tetraphenylethane type epoxy resin) and the like. These may be used individually by 1 type, and may be used in combination of 2 or more types.

In one embodiment, (A) the epoxy resin preferably contains a liquid condensed ring structure-containing epoxy resin, and particularly preferably a liquid naphthalene ring structure-containing epoxy resin. Examples of the liquid epoxy resin containing a condensed ring (naphthalene ring) structure include those having a condensed ring (naphthalene ring) structure among those exemplified as liquid epoxy resins.

The content of the liquid epoxy resin in (A) the epoxy resin is not particularly limited. More preferably 70% by mass or more, 75% by mass or more, still more preferably 80% by mass or more, 85% by mass or more, still more preferably 90% by mass or more, 95% by mass or more, 98% by mass or more, particularly preferably 100% by mass %.

(A) The epoxy equivalent of the epoxy resin is preferably 50 g/eq. ~5000g/eq. , more preferably 50 g/eq. ~2000g/eq. , more preferably 80 g/eq. ~1000 g/eq. , even more preferably 80 g/eq. ~500 g/eq. is. Epoxy equivalent weight is the mass of resin containing one equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

(A) The weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5,000, more preferably 200 to 3,000, still more preferably 250 to 1,500. The weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.

The content of the (A) epoxy resin in the resin composition is not particularly limited, but is preferably 10% when the non-volatile components other than the (B) inorganic filler in the resin composition are 100% by mass. % by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, and particularly preferably 50% by mass or more. The upper limit of the content of (A) the epoxy resin in the resin composition is not particularly limited. , 98% by mass or less, 95% by mass or less, 90% by mass or less, and the like.

<(B) Inorganic filler>
The resin composition of the present invention contains (B) an inorganic filler.

(B) The material of the inorganic filler is not particularly limited, but examples include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, Boehmite, 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 titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate, with silica and alumina being particularly preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. As silica, spherical silica is preferable. (B) The inorganic filler may be used singly or in combination of two or more.

(B) Commercially available inorganic fillers include, for example, “UFP-30” manufactured by Denka Kagaku Kogyo; “SP60-05” and “SP507-05” manufactured by Nippon Steel & Sumikin Materials; "YC100C", "YA050C", "YA050C-MJE", "YA010C"; "UFP-30" manufactured by Denka; 5N”; “SC2500SQ”, “SO-C4”, “SO-C2” and “SO-C1” manufactured by Admatechs, “DAW-03” and “FB-105FD” manufactured by Denka.

The average particle size of the inorganic filler (B) is not particularly limited, but is preferably 40 µm or less, more preferably 20 µm or less, still more preferably 10 µm or less, even more preferably 5 µm or less, and particularly preferably 3 µm or less. is. The lower limit of the average particle size of the inorganic filler is not particularly limited, but is preferably 0.01 µm or more, more preferably 0.05 µm or more, still more preferably 0.1 µm or more, and still more preferably 0.5 µm or more. , more preferably 1 μm or more, and particularly preferably 1.5 μm or more. The average particle size of the inorganic filler can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is prepared on a volume basis using a laser diffraction/scattering type particle size distribution measuring device, and the median diameter can be used as the average particle size for measurement. A measurement sample can be obtained by weighing 100 mg of an inorganic filler and 10 g of methyl ethyl ketone in a vial and dispersing them with ultrasonic waves for 10 minutes. A measurement sample is measured using a laser diffraction particle size distribution measuring device, the wavelengths of the light source used are blue and red, the volume-based particle size distribution of the inorganic filler is measured by the flow cell method, and from the obtained particle size distribution The average particle diameter was calculated as the median diameter. Examples of the laser diffraction particle size distribution analyzer include "LA-960" manufactured by Horiba, Ltd., and the like.

(B) The specific surface area of the inorganic filler is not particularly limited, but is preferably 0.01 m ² /g or more, 0.1 m ² /g or more, 0.5 m ² /g or more, more preferably 1 m ² /g or more, more preferably 2 m ² /g or more, and particularly preferably 3 m ² /g or more. Although there is no particular upper limit, it is preferably 50 m ² /g or less, more preferably 20 m ² /g or less, 10 m ² /g or less, or 5 m ² /g or less. The specific surface area of the inorganic filler is calculated using a BET multi-point method using a BET fully automatic specific surface area measuring device (Macsorb HM-1210 manufactured by Mountec) to adsorb nitrogen gas on the sample surface according to the BET method. obtained by doing

(B) Inorganic fillers include aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, alkoxysilane compounds, organosilazane compounds, titanate-based coupling agents, from the viewpoint of improving moisture resistance and dispersibility. It is preferably treated with one or more surface treatment agents such as agents. Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical Industry Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "SZ-31" ( Hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd. "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM-4803" (long-chain epoxy type silane coupling agent), Shin-Etsu Chemical Co., Ltd. "KBM- 7103” (3,3,3-trifluoropropyltrimethoxysilane), “KBM503” (3-methacryloxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM5783” manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment with the surface treatment agent is preferably within a predetermined range. Specifically, 100% by mass of the inorganic filler is preferably surface-treated with a surface treatment agent of 0.2% to 5% by mass, and is surface-treated with 0.2% to 3% by mass. preferably 0.3 mass % to 2 mass % of the surface treatment.

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m ² or more, more preferably 0.1 mg/m ² or more, and more preferably 0.2 mg/m ² from the viewpoint of improving the dispersibility of the inorganic filler. The above is more preferable. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin composition and the melt viscosity in the form of a sheet, it is preferably 1.0 mg/m ² or less, more preferably 0.8 mg/m ² or less, and 0.5 mg/m ^{2 or less} . More preferred are:

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

The content of the inorganic filler (B) in the resin composition is 70% by mass or more, preferably 72% by mass or more, and 73% by mass when all non-volatile components in the resin composition are 100% by mass. Above, more preferably 74% by mass or more, 75% by mass or more, still more preferably 76% by mass or more, 77% by mass or more, particularly preferably 78% by mass or more, 79% by mass or more, or 80% by mass or more. The upper limit of the content of the inorganic filler (B) in the resin composition is not particularly limited, but when all non-volatile components in the resin composition are 100% by mass, for example, 98% by mass or less. , 95% by mass or less, 90% by mass or less, 85% by mass or less, or the like.

<(C) Curing agent>
The resin composition of the present invention contains (C) a curing agent. (C) The curing agent has a function of curing the (A) epoxy resin. The (C) curing agent referred to here is a component that does not correspond to (D) the polyether skeleton-containing non-epoxy compound.

(C) The curing agent is not particularly limited, but for example, phenol-based curing agent, naphthol-based curing agent, acid anhydride-based curing agent, amine-based curing agent, active ester-based curing agent, benzoxazine-based curing agent Curing agents and cyanate ester curing agents are included. The curing agent may be used singly or in combination of two or more.

In one embodiment, (C) the curing agent preferably contains one or more curing agents selected from the group consisting of acid anhydride curing agents and amine curing agents.

As the phenolic curing agent and the naphtholic curing agent, a phenolic curing agent having a novolac structure or a naphtholic curing agent having a novolac structure is preferable from the viewpoint of heat resistance and water resistance. From the viewpoint of adhesion to adherends, a nitrogen-containing phenolic curing agent or a nitrogen-containing naphthol curing agent is preferable, and a triazine skeleton-containing phenolic curing agent or a triazine skeleton-containing naphthol curing agent is more preferable. Among them, a triazine skeleton-containing phenol novolak resin is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion. Specific examples of phenol-based curing agents and naphthol-based curing agents include "MEH-7700", "MEH-7810" and "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., "NHN" manufactured by Nippon Kayaku Co., Ltd., "CBN", "GPH", Nippon Steel Chemical & Materials "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495" ”, “SN-375”, “SN-395”, DIC “LA-7052”, “LA-7054”, “LA-3018”, “LA-3018-50P”, “LA-1356”, "TD2090", "TD-2090-60M" and the like.

Acid anhydride curing agents include curing agents having one or more acid anhydride groups in one molecule, and curing agents having two or more acid anhydride groups in one molecule are preferred. Specific examples of acid anhydride curing agents include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, and hydrogenated methylnadic acid. anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trianhydride mellitic acid, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'- Diphenylsulfonetetracarboxylic dianhydride, 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(anhydrotrimellitate), polymer-type acid anhydrides such as styrene/maleic acid resin obtained by copolymerizing styrene and maleic acid. Commercially available acid anhydride-based curing agents include "HNA-100", "MH-700", "MTA-15", "DDSA" and "OSA" manufactured by Shin Nippon Rika Co., Ltd., and " YH-306”, “YH-307”, “HN-2200” and “HN-5500” manufactured by Hitachi Chemical Co., Ltd., and the like.

Amine-based curing agents include curing agents having one or more, preferably two or more amino groups in one molecule. Examples include aliphatic amines, polyether amines, alicyclic amines, Aromatic amines and the like can be mentioned, and among them, aromatic amines are preferable from the viewpoint of achieving the desired effects of the present invention. Amine-based curing agents are preferably primary amines or secondary amines, more preferably primary amines. Specific examples of amine curing agents include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, and 3,3'-diaminodiphenylsulfone. , m-phenylenediamine, m-xylylenediamine, 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, and the like. Commercially available amine-based curing agents may be used, for example, Seika "SEIKACURE-S", Nippon Kayaku "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD AA". , “Kayahard AB”, “Kayahard AS”, “Epicure W” manufactured by Mitsubishi Chemical Corporation, and the like.

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

Specifically, an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and an active ester compound containing a benzoylated product of phenol novolak are preferred. Among them, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferable. "Dicyclopentadiene-type diphenol structure" represents a divalent structural unit consisting of phenylene-dicyclopentalene-phenylene.

Commercially available active ester curing agents include, as active ester compounds containing a dicyclopentadiene type diphenol structure, "EXB9451", "EXB9460", "EXB9460S", "HPC-8000", "HPC-8000H", " HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L", "EXB-8000L-65M", "EXB-8000L-65TM" (manufactured by DIC); active ester compounds containing a naphthalene structure "EXB-9416-70BK", "EXB-8150-65T", "EXB-8100L-65T", "EXB-8150L-65T" (manufactured by DIC Corporation); "DC808" (manufactured by Mitsubishi Chemical Corporation); "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation) and "YLH1048" (manufactured by Mitsubishi Chemical Corporation) as active ester curing agents that are benzoyl compounds of phenol novolak manufactured by); and the like.

Specific examples of benzoxazine-based curing agents include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Co., Ltd.; "HFB2006M" manufactured by Showa Polymer Co., Ltd.; Examples include "Fa".

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

When the resin composition contains (A) an epoxy resin and (C) a curing agent, the ratio between (A) the epoxy resin and (C) the curing agent is [the number of epoxy groups of (A) the epoxy resin]:[(C ) The ratio of the number of reactive groups of the curing agent] is preferably 1:0.2 to 1:2, more preferably 1:0.3 to 1:1.5, and 1:0.4 to 1:1.4. More preferred. Here, the reactive group of the curing agent (C) is, for example, an aromatic hydroxyl group in the case of a phenol-based curing agent or a naphthol-based curing agent, or an active ester group in the case of an active ester-based curing agent. different.

(C) The reactive group equivalent of the curing agent is preferably 50 g/eq. ~3000g/eq. , more preferably 100 g/eq. ~1000g/eq. , more preferably 100 g/eq. ~500 g/eq. , particularly preferably 100 g/eq. ~300 g/eq. is. Reactive group equivalent weight is the mass of curing agent per equivalent of reactive group.

The content of the (C) curing agent in the resin composition is not particularly limited, but is preferably 80% when the non-volatile components other than the (B) inorganic filler in the resin composition are 100% by mass. % by mass or less, more preferably 60% by mass or less, even more preferably 50% by mass or less, and particularly preferably 40% by mass or less. The lower limit of the content of the curing agent (C) in the resin composition is not particularly limited. , 0.001% by mass or more, 0.01% by mass or more, 0.1% by mass or more, 1% by mass or more, and 2% by mass or more.

<(D) Polyether skeleton-containing non-epoxy compound>
The resin composition of the present invention contains (D) a polyether skeleton-containing non-epoxy compound.

(D) polyether skeleton-containing non-epoxy compound means a polymer compound having a polyether skeleton containing no epoxy group, and the polyether skeleton contained in (D) polyether skeleton-containing non-epoxy compound contains ethylene oxide units and propylene It is a polyoxyalkylene skeleton composed of one or more monomer units selected from oxide units, and does not contain a polyether skeleton containing monomer units having 4 or more carbon atoms such as butylene oxide units and phenylene oxide units. (D) The polyether skeleton contained in the polyether skeleton-containing non-epoxy compound is particularly preferably composed of a polyoxyalkylene skeleton composed of ethylene oxide units, or composed of two types of monomer units: ethylene oxide units and propylene oxide units. It is a polyoxyalkylene skeleton.

The average degree of polymerization of the monomer units in the polyether skeleton contained in the polyether skeleton-containing non-epoxy compound (D) is preferably 300 or less, more preferably 200 or less, even more preferably 100 or less, and particularly preferably 80 or less.

In one embodiment, (D) the polyether skeleton-containing non-epoxy compound may contain a silicone skeleton. Examples of the silicone skeleton include, but are not limited to, polydialkylsiloxane skeletons such as polydimethylsiloxane skeletons; polydiarylsiloxane skeletons such as polydiphenylsiloxane skeletons; and polyalkylarylsiloxane skeletons such as polymethylphenylsiloxane skeletons. a polydialkyl-diarylsiloxane skeleton such as a polydimethyl-diphenylsiloxane skeleton; a polydialkyl-alkylarylsiloxane skeleton such as a polydimethyl-methylphenylsiloxane skeleton; a polydiaryl-alkylarylsiloxane skeleton such as a polydiphenyl-methylphenylsiloxane skeleton; A polydialkylsiloxane skeleton is preferred, and a polydimethylsiloxane skeleton is particularly preferred. Component (D) containing a silicone skeleton may be polyoxyalkylene-modified silicone, alkyl-etherified polyoxyalkylene-modified silicone (polyoxyalkylene-modified silicone in which at least a portion of the ends of the polyether skeleton are alkoxy groups), or the like. In one embodiment, (D) the polyether skeleton-containing non-epoxy compound may contain a hydroxy group.

Examples of (D) polyether skeleton-containing non-epoxy compounds include linear polyoxyalkylene glycols (linear polyalkylene glycols) such as polyethylene glycol, polypropylene glycol, and polyoxyethylene polyoxypropylene glycol; polyoxyethylene glyceryl Ether, Polyoxypropylene Glyceryl Ether, Polyoxyethylene Polyoxypropylene Glyceryl Ether, Polyoxyethylene Trimethylolpropane Ether, Polyoxypropylene Trimethylolpropane Ether, Polyoxyethylene Polyoxypropylene Trimethylolpropane Ether, Polyoxyethylene Diglyceryl Ether , polyoxypropylene diglyceryl ether, polyoxyethylene polyoxypropylene diglyceryl ether, polyoxyethylene topentaerythritol ether, polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene sorbitol, polyoxy Polyoxyalkylene glycols (polyalkylene glycols) such as multi-chain polyoxyalkylene glycols (poly-chain polyalkylene glycols) such as propylene sorbitol and polyoxyethylene polyoxypropylene sorbitol; polyoxyethylene monoalkyl ethers, polyoxyethylene dialkyl Polyoxyalkylene alkyl ether such as ether, polyoxypropylene monoalkyl ether, polyoxypropylene dialkyl ether, polyoxyethylene polyoxypropylene monoalkyl ether, polyoxyethylene polyoxypropylene dialkyl ether; polyoxyethylene monoester, polyoxyethylene Polyoxyalkylene esters such as diesters, polypropylene glycol monoesters, polypropylene glycol diesters, polyoxyethylene polyoxypropylene monoesters, polyoxyethylene polyoxypropylene diesters (acetic esters, propionic acid esters, butyric acid esters, (meth)acrylic acid esters) etc.); polyoxyethylene monoester, polyoxyethylene diester, polyoxypropylene monoester, polyoxypropylene diester, polyoxyethylene polyoxypropylene monoester, polyoxyethylene polyoxypropylene diester, polyoxyethylene alkyl ether ester , polyoxypropylene alkyl ether ester, polyoxyethylene polyoxypropylene alkyl ether ester (including acetate, propionate, butyrate, (meth)acrylic acid ester, etc.); polyoxyethylene Polyoxyalkylenealkylamines such as alkylamines, polyoxypropylenealkylamines and polyoxyethylenepolyoxypropylenealkylamines; Polyoxyalkylenes such as polyoxyethylenealkylamides, polyoxypropylenealkylamides and polyoxyethylenepolyoxypropylenealkylamides Alkylamide; polyoxyethylene dimethicone, polyoxypropylene dimethicone, polyoxyethylene polyoxypropylene dimethicone, polyoxyethylene polydimethylsiloxyalkyl dimethicone, polyoxypropylene polydimethylsiloxyalkyl dimethicone, polyoxyethylene polyoxypropylene polydimethylsiloxyalkyl dimethicone Polyoxyalkylene-modified silicones such as polyoxyethylene alkyl ether dimethicone, polyoxypropylene alkyl ether dimethicone, polyoxyethylene polyoxypropylene alkyl ether dimethicone, polyoxyethylene alkyl ether polydimethylsiloxyalkyl dimethicone, polyoxypropylene alkyl ether polydimethyl Alkyl-etherified polyoxyalkylene-modified silicones such as siloxyalkyl dimethicone, polyoxyethylene polyoxypropylene alkyl ether polydimethylsiloxyalkyl dimethicone (polyoxyalkylene-modified silicone in which at least a portion of the polyether skeleton ends are alkoxy groups), and the like. .

(D) The polyether skeleton-containing non-epoxy compound is preferably one or more compounds selected from the group consisting of polyoxyalkylene glycol (polyalkylene glycol) and polyoxyalkylene-modified silicone.

In one embodiment, the polyoxyalkylene glycol (polyalkylene glycol) is preferably a linear polyoxyalkylene glycol (linear polyalkylene glycol).

The average degree of polymerization of the monomer units in polyoxyalkylene glycol (polyalkylene glycol) is preferably 300 or less, more preferably 200 or less, even more preferably 100 or less, and particularly preferably 80 or less. The lower limit is preferably 5 or more, more preferably 10 or more, even more preferably 20 or more, and particularly preferably 30 or more.

Polyoxyalkylene glycol (polyalkylene glycol) is particularly preferably polyoxyethylene polyoxypropylene glycol. Polyoxyethylene polyoxypropylene glycol includes polyoxyethylene-polyoxypropylene block copolymer, polyoxyethylene-polyoxypropylene-polyoxyethylene block copolymer, polyoxypropylene-polyoxyethylene-polyoxypropylene block Copolymers and the like are included.

The average degree of polymerization of ethylene oxide units in polyoxyethylene polyoxypropylene glycol is preferably 200 or less, more preferably 100 or less, even more preferably 50 or less, and particularly preferably 30 or less. The lower limit is preferably 3 or more, more preferably 5 or more, even more preferably 10 or more, and particularly preferably 15 or more. The average degree of polymerization of propylene oxide units in polyoxyethylene polyoxypropylene glycol is preferably 200 or less, more preferably 100 or less, even more preferably 50 or less, and particularly preferably 40 or less. The lower limit is preferably 3 or more, more preferably 5 or more, even more preferably 10 or more, and particularly preferably 15 or more.

In one embodiment, (D) the polyether backbone-containing non-epoxy compound has the formula (1):

It is preferably a compound represented by the formula (1 '):

(a block copolymer of x1 units, x2 units and x3 units) represented by the following is particularly preferred.

In formula (1), two R ¹ are each independently a hydrogen atom, an alkyl group (preferably having 1 to 6 carbon atoms), an alkenyl group (preferably having 2 to 6 carbon atoms), alkyl-carbonyl group (preferably having 2 to 7 carbon atoms) or alkenyl-carbonyl group (preferably having 3 to 7 carbon atoms). Two R ¹ are particularly preferably hydrogen atoms. Alkyl (group) refers to a linear, branched and/or cyclic monovalent aliphatic saturated hydrocarbon group. Examples of alkyl (group) include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group and sec-pentyl group. , tert-pentyl group, cyclopentyl group, cyclohexyl group and the like. Alkenyl (group) refers to linear, branched and/or cyclic monovalent unsaturated aliphatic hydrocarbon groups having at least one carbon-carbon double bond. Examples of alkenyl (group) include vinyl group, 1-propenyl group, 2-propenyl group and the like.

In Formula (1), each n is 2 or 3 independently.

In formula (1), x represents an integer of 5-300. x is preferably an integer of 5-200, particularly preferably an integer of 10-100.

In formula (1'), x1 and x3 are each independently an integer of 3 to 200. x1 and x3 are preferably each independently an integer of 3-100.

In formula (1'), x2 is an integer of 3-200. x2 is preferably an integer of 5-100.

In one embodiment, the polyoxyalkylene-modified silicone is, for example, a linear or branched dimethylpolysiloxane (dimethicone) having one or more polyoxyalkylene chains, preferably polyoxyethylene dimethicone, Polyoxyethylene polydimethylsiloxyalkyl dimethicone.

The average degree of polymerization of the monomer units of one polyoxyalkylene chain in the polyoxyalkylene-modified silicone is preferably 30 or less, more preferably 20 or less, even more preferably 15 or less, and particularly preferably 10 or less. The lower limit is preferably 2 or more.

In one embodiment, (D) the polyether backbone-containing non-epoxy compound has the formula (2):

It is preferably a polyoxyalkylene-modified silicone represented by.

In formula (2), a represents an integer of 2 to 10,000. a is preferably an integer of 2-5000, more preferably an integer of 2-1000, even more preferably an integer of 2-500, and particularly preferably an integer of 2-200.

In formula (2), 4+a R ² are each independently an alkyl group (preferably having 1 to 6 carbon atoms), an aralkyl group (preferably having 7 to 15 carbon atoms), or an aryl group (preferably 6 to 14 carbon atoms). Each of the 4+a R ² is independently preferably an alkyl group (preferably having 1 to 6 carbon atoms), particularly preferably a methyl group. An aryl group refers to a monovalent aromatic hydrocarbon group. The aryl group includes, for example, phenyl group, 1-naphthyl group, 2-naphthyl group and the like, preferably phenyl group. An aralkyl group refers to an alkyl group substituted with one or more aryl groups. Aralkyl groups include, for example, benzyl, phenethyl and 2-naphthylmethyl groups.

In formula (2), two R ³ and a R ⁴ are each independently an alkyl group (preferably having 1 to 6 carbon atoms), an aralkyl group (preferably having 7 to 15 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), formula (X):

A group represented by or formula (Y):

and at least one of the two R ³ and a R ⁴ is a group represented by the formula (X). Preferably, two R ³ are each independently an alkyl group (preferably having 1 to 6 carbon atoms), an aralkyl group (preferably having 7 to 15 carbon atoms), or an aryl group (preferably having 6 to 14), and a R ⁴ is each independently an alkyl group (preferably having 1 to 6 carbon atoms), an aralkyl group (preferably having 7 to 15 carbon atoms), an aryl group (preferably 6 to 14 carbon atoms), a group represented by formula (X), or a group represented by formula (Y), and at least one of a R ⁴ is represented by formula (X) It is a group that is More preferably, two R ³ are each independently a methyl group, and a R ⁴ are each independently a methyl group, a group represented by the formula (X), or a group represented by the formula (Y ), and at least one of a R ⁴ is a group represented by formula (X).

In formula (2), the number of groups represented by formula (X) is preferably 1 to 20, more preferably 1 to 10, particularly preferably 1 to 5. In formula (2), the number of groups represented by formula (Y) is preferably 0 to 20, more preferably 0 to 10, particularly preferably 0 to 5.

In formulas (X) and (Y), * indicates a bond.

In formula (X), R ¹ and n are the same as defined for R ¹ and n in formula (1), respectively.

In formula (X), X represents a single bond or an alkylene group (preferably having 1 to 6 carbon atoms). An alkylene group refers to a linear, branched and/or cyclic divalent saturated aliphatic hydrocarbon group. Examples of the alkylene group include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group and the like.

In formula (X), y represents an integer of 2-300. y is preferably an integer of 2-100, more preferably an integer of 2-50, particularly preferably an integer of 2-20.

In formula (Y), b represents an integer of 1-10,000. b is preferably an integer of 1-1000, more preferably an integer of 1-500, still more preferably an integer of 1-200, and particularly preferably an integer of 1-100.

In formula (Y), 3+2b R ⁵ are each independently an alkyl group (preferably having 1 to 6 carbon atoms), an aralkyl group (preferably having 7 to 15 carbon atoms), or an aryl group (preferably 6 to 14 carbon atoms). The 3+2b R ⁵ are each independently preferably an alkyl group (preferably having 1 to 6 carbon atoms), particularly preferably a methyl group.

In formula (Y), Y represents an alkylene group (preferably having 1 to 6 carbon atoms).

(D) The polyether skeleton-containing non-epoxy compound preferably has a number average molecular weight of 500 to 40,000, more preferably 500 to 20,000, and even more preferably 500 to 10,000. (D) The weight average molecular weight of the polyether skeleton-containing non-epoxy compound is preferably 500 to 40,000, more preferably 500 to 20,000, still more preferably 500 to 10,000. The number average molecular weight and weight average molecular weight can be measured as polystyrene-equivalent values by gel permeation chromatography (GPC).

(D) The polyether skeleton-containing non-epoxy compound is preferably liquid at 25°C. (D) The viscosity of the polyether skeleton-containing non-epoxy compound at 25° C. is preferably 100000 mPa s or less, more preferably 50000 mPa s or less, or 30000 mPa s or less, still more preferably 10000 mPa s or less, or 5000 mPa s. Below, it is more preferably 4000 mPa·s or less, or 3000 mPa·s or less, and particularly preferably 2000 mPa·s or less, or 1500 mPa·s or less. (D) The lower limit of the viscosity at 25°C of the polyether skeleton-containing non-epoxy compound is preferably 10 mPa s or more, more preferably 20 mPa s or more, still more preferably 30 mPa s or more, and even more preferably 40 mPa s or more. , and particularly preferably 50 mPa·s or more. The viscosity may be a viscosity (mPa·s) obtained by measuring with a Brookfield viscometer.

(D) Examples of polyether skeleton-containing non-epoxy compounds include NOF Corporation's "Pronon #102", "Pronon #104", "Pronon #201", "Pronon #202B", "Pronon #204", "Pronon #208", "Unilube 70DP-600B", "Unilube 70DP-950B" (polyoxyethylene polyoxypropylene glycol); "Pluronic L-23", "Pluronic L-31", "Pluronic L" manufactured by ADEKA -44”, “Pluronic L-61”, “ADEKA Pluronic L-62”, “Pluronic L-64”, “Pluronic L-71”, “Pluronic L-72”, “Pluronic L-101”, “Pluronic L -121”, “Pluronic P-84”, “Pluronic P-85”, “Pluronic P-103”, “Pluronic F-68”, “Pluronic F-88”, “Pluronic F-108”, “Pluronic 25R-” 1”, “Pluronic 25R-2”, “Pluronic 17R-2”, “Pluronic 17R-3”, “Pluronic 17R-4” (polyoxyethylene polyoxypropylene glycol); “KF-6011” manufactured by Shin-Etsu Silicone Co., Ltd. , "KF-6011P", "KF-6012", "KF-6013", "KF-6015", "KF-6016", "KF-6017", "KF-6017P", "KF-6043", " KF-6004", "KF351A", "KF352A", "KF353", "KF354L", "KF355A", "KF615A", "KF945", "KF-640", "KF-642", "KF-643" , "KF-644", "KF-6020", "KF-6204", "X22-4515", "KF-6028", "KF-6028P", "KF-6038", "KF-6048", " KF-6025” (polyoxyalkylene-modified silicone) and the like.

The content of the (D) polyether skeleton-containing non-epoxy compound in the resin composition is 1% by mass or more when the non-volatile components other than the (B) inorganic filler in the resin composition is 100% by mass, It is preferably 2% by mass or more, more preferably 3% by mass or more, still more preferably 4% by mass or more, and particularly preferably 5% by mass or more. The upper limit of the content of the (D) polyether skeleton-containing non-epoxy compound in the resin composition is 30% by mass or less when the non-volatile components other than the (B) inorganic filler in the resin composition are 100% by mass. It is preferably 27% by mass or less, more preferably 25% by mass or less, still more preferably 23% by mass or less, and particularly preferably 22% by mass or less.

<(E) Curing accelerator>
The resin composition of the present invention may contain (E) a curing accelerator as an optional nonvolatile component. (E) The curing accelerator has a function of accelerating the curing of (A) the epoxy resin. The (E) curing accelerator referred to here is a component that does not correspond to (D) the polyether skeleton-containing non-epoxy compound.

(E) the curing accelerator contains at least one selected from the group consisting of phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators, Preferably, an imidazole curing accelerator is included.

Phosphorus curing accelerators include, for example, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium) pyromellitate, tetrabutylphosphonium hydro Aliphatic phosphonium salts such as genhexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, di-tert-butylmethylphosphonium tetraphenylborate; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, tetraphenyl phosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4 -methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, aromatic phosphonium salts such as butyltriphenylphosphonium thiocyanate; aromatic phosphine/borane complexes such as triphenylphosphine/triphenylborane; triphenylphosphine/p-benzoquinone Aromatic phosphine/quinone addition reaction products such as addition reaction products; 2-butenyl)phosphine, aliphatic phosphines such as tricyclohexylphosphine; -tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropylphenyl)phosphine, tris(4-butyl) phenyl)phosphine, tris(4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,5-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)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, 2,2′-bis(diphenylphosphino)diphenyl ether, and other aromatic phosphines. be done.

Urea-based curing accelerators include, for example, 1,1-dimethylurea; 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, 3- Aliphatic dimethylurea such as 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) Aromatic dimethylurea such as bis(N',N'-dimethylurea), N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluenebisdimethylurea] etc.

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

Examples of imidazole curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecyl imidazolyl-(1′)]-ethyl-s-triazine, 2,4-diamino-6-[2′-ethyl-4′-methylimidazolyl-(1′)]-ethyl-s-triazine, 2,4- Diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanurate, 2-phenylimidazole isocyanurate, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline , 2-phenylimidazoline and other imidazole compounds, and adducts of imidazole compounds and epoxy resins.

The molecular weight of the imidazole-based curing accelerator is not particularly limited, but is preferably 1,000 or less, more preferably 1,000 or less, more preferably from the viewpoint of improving workability (fluidity) and suppressing undissolved residue during heat molding. It is 600 or less, more preferably 400 or less, and particularly preferably 300 or less.

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

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

The content of (E) the curing accelerator in the resin composition is not particularly limited, but when non-volatile components other than the component (B) in the resin composition are 100% by mass, it is preferably 10% by mass. % or less, more preferably 5 mass % or less, still more preferably 3 mass % or less, and particularly preferably 1 mass % or less. The lower limit of the content of the curing accelerator (E) in the resin composition is not particularly limited, but when the non-volatile components other than the component (B) in the resin composition are 100% by mass, for example, 0% by mass or more, 0.001% by mass or more, 0.01% by mass or more, 0.1% by mass or more, 0.2% by mass or more, 0.3% by mass or more, 0.4% by mass or more, etc. .

<(F) Other additives>
The resin composition of the present invention may further contain optional additives as non-volatile components. Examples of such additives include organic fillers such as rubber particles, polyamide fine particles and silicone particles; thermoplastic resins such as polycarbonate resins, phenoxy resins, polyvinyl acetal resins, polyolefin resins, polysulfone resins and polyester resins; compounds, organozinc compounds, organometallic compounds such as organocobalt compounds; coloring agents such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black; hydroquinone, catechol, pyrogallol, phenothiazine, etc. Polymerization inhibitors; leveling agents such as silicone leveling agents and acrylic polymer leveling agents; thickeners such as bentone and montmorillonite; Defoamers such as foaming agents; UV absorbers such as benzotriazole UV absorbers; Adhesion improvers such as urea silane; Triazole adhesion imparting agents, tetrazole adhesion imparting agents, triazine adhesion imparting agents, etc. Anti-oxidants such as hindered phenol-based antioxidants and hindered amine-based antioxidants; fluorescent brighteners such as stilbene derivatives; surfactants such as fluorine-based surfactants; phosphorus-based flame retardants ( Examples include flame retardants such as phosphate ester compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus), nitrogen-based flame retardants (e.g. melamine sulfate), halogen-based flame retardants, and inorganic flame retardants (e.g. antimony trioxide). . One of the additives may be used alone, or two or more of them may be used in combination at an arbitrary ratio. (F) The content of other additives can be appropriately set by those skilled in the art.

<(G) Organic solvent>
The resin composition of the present invention may further contain an arbitrary organic solvent as a volatile component in addition to the non-volatile component described above. As the (G) organic solvent, a known one can be used as appropriate, and the type thereof is not particularly limited. (G) Examples of organic solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, and diphenyl ether; alcohol solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; Ether ester solvents such as 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, methyl methoxypropionate; methyl lactate, ethyl lactate, 2-hydroxyisobutyric acid ester alcohol solvents such as methyl; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, diethylene glycol monobutyl ether (butyl carbitol); N,N-dimethylformamide, Amide solvents such as N,N-dimethylacetamide and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethylsulfoxide; nitrile solvents such as acetonitrile and propionitrile; hexane, cyclopentane, cyclohexane, methylcyclohexane and the like Aliphatic hydrocarbon solvents; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, and the like can be mentioned. (G) The organic solvent may be used singly or in combination of two or more at any ratio. In one embodiment, the amount of (F) the organic solvent is preferably as small as possible (for example, when the non-volatile component in the resin composition is 100% by mass, 3% by mass or less, 1% by mass or less, 0.5% by mass or less , 0.1% by mass or less, 0.01% by mass or less).

<Method for producing resin composition>
The resin composition of the present invention is, for example, placed in an arbitrary reaction vessel (A) an epoxy resin, (B) an inorganic filler, (C) a curing agent, (D) a polyether skeleton-containing non-epoxy compound, and optionally ( E) a curing accelerator, optionally (F) other additives, and optionally (G) an organic solvent are added in any order and/or partially or wholly at the same time and mixed. can do. Also, during the process of adding and mixing each component, the temperature can be set appropriately, and heating and/or cooling may be performed temporarily or over time. Moreover, you may stir or shake in the process of adding and mixing each component. In addition, during or after the addition and mixing, the resin composition may be stirred using a stirring device such as a mixer to uniformly disperse.

<Characteristics of resin composition>
The resin composition of the present invention contains (A) an epoxy resin, (B) an inorganic filler, (C) a curing agent, and (D) a non-epoxy compound containing a polyether skeleton, and the polyether contained in the component (D) The skeleton is a polyoxyalkylene skeleton composed of one or more monomer units selected from ethylene oxide units and propylene oxide units, and the content of (B) the inorganic filler is such that all non-volatile components in the resin composition are When 100% by mass, it is 70% by mass or more, and the content of (D) polyether skeleton-containing non-epoxy compound is 100% by mass of non-volatile components other than (B) inorganic filler in the resin composition. In this case, since it is 1% by mass or more and 30% by mass or less, it is possible to obtain a cured product having excellent embeddability, suppressing warping during curing, and having excellent mechanical strength.

In one embodiment, since the resin composition of the present invention has excellent embeddability, for example, when the melt viscosity is measured as in Test Example 5 below, the minimum melt viscosity is preferably 100 poise or less, more It can be preferably 50 poise or less, more preferably 20 poise or less, and particularly preferably 10 poise or less.

In one embodiment, the resin composition of the present invention can suppress warping during curing. The amount of warpage can be preferably less than 20 mm, more preferably less than 10 mm, even more preferably less than 5 mm, particularly preferably less than 3 mm.

In one embodiment, the resin composition of the present invention can obtain a cured product having excellent mechanical strength. Therefore, for example, as in Test Example 3 below, the three-point bending strength of the cured product at 23 ° C. is measured. If so, the three-point bending strength can be preferably greater than 10 MPa, more preferably greater than 30 MPa, even more preferably greater than 40 MPa, and particularly preferably greater than 50 MPa.

In one embodiment, when the elastic modulus of the cured product of the resin composition of the present invention at 25° C. is measured, for example, according to JIS K7127 as in Test Example 2 below, it is particularly preferably 25 GPa or less, more preferably It can be 20 GPa or less, more preferably 17 GPa or less, and particularly preferably 15 GPa or less.

In one embodiment, the gelation time of the resin composition of the present invention is preferably 500 seconds or less, more preferably 400 seconds or less, when measured according to JIS C6521, for example, as in Test Example 4 below. It can be preferably 350 seconds or less, particularly preferably 300 seconds or less.

<Application of resin composition>
Due to the advantages described above, the cured product of the resin composition of the present invention is particularly useful for sealing layers and insulating layers of semiconductors. Therefore, this resin composition can be used as a resin composition for semiconductor encapsulation or an insulating layer.

For example, the resin composition of the present invention is a resin composition for forming an insulating layer of a semiconductor chip package (a resin composition for an insulating layer of a semiconductor chip package), and a circuit board (including a printed wiring board). It can be suitably used as a resin composition for forming an insulating layer (resin composition for an insulating layer of a circuit board).

Further, for example, the resin composition of the present invention can be suitably used as a resin composition for sealing a semiconductor chip of a semiconductor chip package (resin composition for semiconductor chip sealing).

Semiconductor chip packages to which the sealing layer or insulating layer formed of the cured product of the resin composition of the present invention can be applied include, for example, FC-CSP, MIS-BGA package, ETS-BGA package, Fan-out type WLP ( Wafer Level Package), Fan-in type WLP, Fan-out type PLP (Panel Level Package), and Fan-in type PLP.

The resin composition of the present invention may also be used as an underfill material, for example, as a material for MUF (Molding Under Filling) used after connecting a semiconductor chip to a substrate.

Furthermore, the resin composition of the present invention includes resin sheets, sheet-like laminated materials such as prepreg, liquid materials such as resin inks for solder resists, die bonding materials, hole-filling resins, component-embedding resins, and the like. It can be used for a wide range of applications.

<Resin sheet>
The resin sheet of the present invention has a support and a resin composition layer provided on the support. The resin composition layer is a layer containing the resin composition of the present invention, and is usually formed of the resin composition.

The thickness of the resin composition layer is preferably 600 µm or less, more preferably 500 µm or less, from the viewpoint of thinning. The lower limit of the thickness of the resin composition layer is preferably 1 µm or more, 5 µm or more, more preferably 10 µm or more, still more preferably 50 µm or more, and particularly preferably 100 µm or more.

The thickness of the cured product obtained by curing the resin composition layer is preferably 600 μm or less, more preferably 500 μm or less. The lower limit of the thickness of the cured product is preferably 1 µm or more, 5 µm or more, more preferably 10 µm or more, still more preferably 50 µm or more, and particularly preferably 100 µm or more.

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

When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"). Polycarbonate (hereinafter sometimes abbreviated as "PC"); Acrylic polymers such as polymethyl methacrylate (hereinafter sometimes abbreviated as "PMMA"); Cyclic polyolefins; Triacetyl cellulose (hereinafter polyether sulfide (hereinafter sometimes abbreviated as "PES"); polyether ketone; polyimide; Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

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

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

Further, as the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. The release agent used in the release layer of the release layer-attached support includes, for example, one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . Examples of commercially available release agents include alkyd resin-based release agents such as “SK-1”, “AL-5” and “AL-7” manufactured by Lintec. Examples of the release layer-attached support include "Lumirror T60" manufactured by Toray Industries, Inc.; "Purex" manufactured by Teijin Limited; and "Unipeel" manufactured by Unitika.

The thickness of the support is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. When a release layer-attached support is used, the thickness of the release layer-attached support as a whole is preferably within the above range.

The resin sheet can be produced, for example, by coating a resin composition on a support using a coating device such as a die coater. If necessary, the resin composition may be dissolved in an organic solvent to prepare a resin varnish, and this resin varnish may be applied to produce a resin sheet. By using an organic solvent, the viscosity can be adjusted and the coatability can be improved. When a resin composition or resin varnish containing an organic solvent is used, the resin composition or resin varnish is usually dried after coating to form a resin composition layer.

Drying may be carried out by a known method such as heating or blowing hot air. The drying conditions are such that the content of the organic solvent in the resin composition layer is usually 10% by mass or less, preferably 5% by mass or less. Depending on the boiling point of the organic solvent in the resin composition or resin varnish, for example, when using a resin composition or resin varnish containing 30% by mass to 60% by mass of an organic solvent, the temperature is 50° C. to 150° C. for 3 minutes to 10 minutes. A resin composition layer can be formed by drying for minutes.

The resin sheet may contain arbitrary layers other than the support and the resin composition layer, if necessary. For example, in the resin sheet, the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support) may be provided with a protective film conforming to the support. The thickness of the protective film is, for example, 1 μm to 40 μm. The protective film can prevent dust from adhering to the surface of the resin composition layer and scratches on the surface of the resin composition layer. When the resin sheet has a protective film, the resin sheet can be used by peeling off the protective film. In addition, the resin sheet can be wound into a roll and stored.

A resin sheet can be suitably used for forming an insulating layer in the manufacture of a semiconductor chip package (an insulating resin sheet for a semiconductor chip package). For example, the resin sheet can be used to form an insulating layer of a circuit board (resin sheet for insulating layer of circuit board). Examples of packages using such substrates include FC-CSP, MIS-BGA packages, and ETS-BGA packages.

In addition, the resin sheet can be suitably used for sealing semiconductor chips (semiconductor chip sealing resin sheet). Applicable semiconductor chip packages include, for example, Fan-out type WLP, Fan-in type WLP, Fan-out type PLP, Fan-in type PLP and the like.

Also, the resin sheet may be used as a material for the MUF that is used after connecting the semiconductor chip to the substrate.

Furthermore, the resin sheet can be used in a wide range of other applications that require high insulation reliability. For example, a resin sheet can be suitably used to form an insulating layer of a circuit board such as a printed wiring board.

<Circuit board>
The circuit board of the present invention includes an insulating layer formed from a cured product of the resin composition of the present invention. This circuit board can be manufactured, for example, by a manufacturing method including the following steps (1) and (2).
(1) A step of forming a resin composition layer on a substrate.
(2) A step of thermosetting the resin composition layer to form an insulating layer.

In step (1), a substrate is prepared. Examples of base materials include substrates such as glass epoxy substrates, metal substrates (stainless steel, cold-rolled steel plate (SPCC), etc.), polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. Moreover, the base material may have a metal layer such as a copper foil on the surface as part of the base material. For example, a substrate having peelable first and second metal layers on both surfaces may be used. When such a substrate is used, a conductor layer as a wiring layer capable of functioning as circuit wiring is usually formed on the surface of the second metal layer opposite to the first metal layer. As a substrate having such a metal layer, for example, an ultra-thin copper foil with a carrier copper foil "Micro Thin" manufactured by Mitsui Kinzoku Mining Co., Ltd. can be used.

Also, a conductor layer may be formed on one or both surfaces of the substrate. In the following description, a member including a base material and a conductor layer formed on the surface of the base material may be referred to as a "wiring layer-attached base material" as appropriate. The conductor material contained in the conductor layer is, for example, one selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Materials containing the above metals can be mentioned. As the conductor material, a single metal may be used, or an alloy may be used. Examples of alloys include alloys of two or more metals selected from the above group (eg, nickel-chromium alloys, copper-nickel alloys and copper-titanium alloys). Among them, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper as single metals; and nickel-chromium alloys as alloys , a copper-nickel alloy, and a copper-titanium alloy; are preferred. Among them, single metals of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper; and nickel-chromium alloys; are more preferred, and single metals of copper are particularly preferred.

The conductor layer may be patterned, for example, to function as a wiring layer. At this time, the line (circuit width) / space (width between circuits) ratio of the conductor layer is not particularly limited, but is preferably 20/20 μm or less (that is, the pitch is 40 μm or less), more preferably 10/10 μm or less, and further It is preferably 5/5 μm or less, more preferably 1/1 μm or less, and particularly preferably 0.5/0.5 μm or more. The pitch need not be the same throughout the conductor layer. The minimum pitch of the conductor layers may be, for example, 40 μm or less, 36 μm or less, or 30 μm or less.

The thickness of the conductor layer is preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm, even more preferably 10 μm to 20 μm, particularly preferably 15 μm to 20 μm, depending on the design of the circuit board.

The conductor layer is formed by, for example, a process of laminating a dry film (photosensitive resist film) on a base material, and performing pattern drying by exposing and developing the dry film under predetermined conditions using a photomask to form a pattern. It can be formed by a method including a step of obtaining a film, a step of forming a conductor layer by a plating method such as electroplating using the developed patterned dry film as a plating mask, and a step of peeling off the patterned dry film. As the dry film, a photosensitive dry film made of a photoresist composition can be used. For example, a dry film made of a resin such as a novolak resin or an acrylic resin can be used. The conditions for laminating the substrate and the dry film may be the same as the conditions for laminating the substrate and the resin sheet, which will be described later. Stripping of the dry film can be carried out using, for example, an alkaline stripping solution such as sodium hydroxide solution.

After preparing the substrate, a resin composition layer is formed on the substrate. When a conductor layer is formed on the surface of the substrate, the resin composition layer is preferably formed so that the conductor layer is embedded in the resin composition layer.

Formation of the resin composition layer is performed, for example, by laminating a resin sheet and a substrate. This lamination can be performed, for example, by bonding the resin composition layer to the substrate by thermocompression bonding the resin sheet to the substrate from the support side. Examples of the member for thermocompression bonding the resin sheet to the substrate (hereinafter sometimes referred to as "thermocompression member") include heated metal plates (such as SUS end plates) and metal rolls (such as SUS rolls). be done. Instead of pressing the thermocompression member directly onto the resin sheet, it is preferable to press the resin sheet through an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently follow the uneven surface of the substrate.

Lamination of the base material and the resin sheet may be carried out, for example, by a vacuum lamination method. In the vacuum lamination method, the thermocompression bonding temperature is preferably in the range of 60°C to 160°C, more preferably 80°C to 140°C. The thermocompression pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably 0.29 MPa to 1.47 MPa. The thermocompression bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions of 13 hPa or less.

After lamination, the laminated resin sheets may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression member from the support side. Pressing conditions for the smoothing treatment may be the same as the thermocompression bonding conditions for the lamination described above. Lamination and smoothing may be performed continuously using a vacuum laminator.

Formation of the resin composition layer can be performed by, for example, a compression molding method. As the molding conditions, the same conditions as in the method of forming the resin composition layer in the step of forming the sealing layer of the semiconductor chip package, which will be described later, may be adopted.

After forming the resin composition layer on the substrate, the resin composition layer is thermally cured to form an insulating layer. The thermosetting conditions for the resin composition layer vary depending on the type of resin composition, but the curing temperature is usually in the range of 120°C to 240°C (preferably in the range of 150°C to 220°C, more preferably in the range of 170°C to 200°C). ), and the curing time is in the range of 5 minutes to 120 minutes (preferably in the range of 10 minutes to 100 minutes, more preferably in the range of 15 minutes to 90 minutes).

Prior to thermal curing of the resin composition layer, the resin composition layer may be subjected to a preheating treatment of heating at a temperature lower than the curing temperature. For example, prior to thermosetting the resin composition layer, the resin composition layer is usually heated at a temperature of 50 ° C. or higher and lower than 120 ° C. (preferably 60 ° C. or higher and 110 ° C. or lower, more preferably 70 ° C. or higher and 100 ° C. or lower). may be preheated for usually 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

A circuit board having an insulating layer can be manufactured in the manner described above. Moreover, the method for manufacturing the circuit board may further include an arbitrary step.
For example, when a circuit board is manufactured using a resin sheet, the method for manufacturing the circuit board may include a step of peeling off the support of the resin sheet. The support may be peeled off before heat curing of the resin composition layer, or may be peeled off after heat curing of the resin composition layer.

The method of manufacturing the circuit board may include, for example, a step of polishing the surface of the insulating layer after forming the insulating layer. A polishing method is not particularly limited. For example, the surface of the insulating layer can be polished using a surface grinder.

The method of manufacturing the circuit board may include, for example, the step (3) of connecting the conductor layers between layers, for example, the step of drilling holes in the insulating layer. As a result, holes such as via holes and through holes can be formed in the insulating layer. Examples of methods for forming via holes include laser irradiation, etching, and mechanical drilling. The size and shape of the via hole may be appropriately determined according to the design of the circuit board. In step (3), interlayer connection may be performed by polishing or grinding the insulating layer.

After forming the via hole, it is preferable to perform a step of removing smear in the via hole. This process is sometimes called a desmear process. For example, when the conductive layer is formed on the insulating layer by a plating process, the via holes may be subjected to a wet desmear treatment. Further, when the conductor layer is formed on the insulating layer by a sputtering process, a dry desmear process such as a plasma treatment process may be performed. Furthermore, the insulating layer may be roughened by a desmear process.

Further, the insulating layer may be roughened before forming the conductor layer on the insulating layer. According to this roughening treatment, the surface of the insulating layer including the inside of the via hole is usually roughened. As the roughening treatment, either dry or wet roughening treatment may be performed. Examples of dry roughening treatment include plasma treatment and the like. Moreover, examples of wet roughening treatment include a method in which swelling treatment with a swelling liquid, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing liquid are performed in this order.

After forming the via holes, a conductor layer may be formed on the insulating layer. By forming a conductor layer at the position where the via hole is formed, the newly formed conductor layer and the conductor layer on the surface of the base material are electrically connected to each other, thereby performing interlayer connection. Methods for forming the conductor layer include, for example, plating, sputtering, vapor deposition, etc. Among them, plating is preferable. In a preferred embodiment, the surface of the insulating layer is plated by an appropriate method such as a semi-additive method or a full-additive method to form a conductor layer having a desired wiring pattern. Moreover, when the support in the resin sheet is a metal foil, a conductor layer having a desired wiring pattern can be formed by a subtractive method. The material of the conductor layer to be formed may be a single metal or an alloy. Moreover, this conductor layer may have a single layer structure, or may have a multi-layer structure including two or more layers of different kinds of materials.

An example embodiment of forming a conductor layer on an insulating layer will now be described in detail. A plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer to expose a portion of the plating seed layer corresponding to a desired wiring pattern. After forming an electrolytic plating layer on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. After that, the unnecessary plating seed layer is removed by a treatment such as etching to form a conductor layer having a desired wiring pattern. The dry film used for forming the mask pattern when forming the conductor layer is the same as the dry film described above.

The circuit board manufacturing method may include a step (4) of removing the base material. By removing the substrate, a circuit board having an insulating layer and a conductor layer embedded in this insulating layer is obtained. This step (4) can be performed, for example, when a base material having a peelable metal layer is used.

<Semiconductor chip package>
A semiconductor chip package according to a first embodiment of the present invention includes the circuit board described above and a semiconductor chip mounted on the circuit board. This semiconductor chip package can be manufactured by bonding a semiconductor chip to a circuit board.

Any condition that allows conductor connection between the terminal electrodes of the semiconductor chip and the circuit wiring of the circuit board can be adopted as the bonding condition of the circuit board and the semiconductor chip. For example, conditions used in flip-chip mounting of semiconductor chips can be employed. Alternatively, for example, the semiconductor chip and the circuit board may be bonded via an insulating adhesive.

As an example of the bonding method, there is a method of crimping the semiconductor chip to the circuit board. As for the crimping conditions, the crimping temperature is usually in the range of 120° C. to 240° C. (preferably 130° C. to 200° C., more preferably 140° C. to 180° C.), and the crimping time is usually in the range of 1 second to 60 seconds. (preferably in the range of 5 seconds to 30 seconds).

Another example of the bonding method is a method of reflowing and bonding a semiconductor chip to a circuit board. The reflow conditions may range from 120.degree. C. to 300.degree.

After bonding the semiconductor chip to the circuit board, the semiconductor chip may be filled with a mold underfill material. As the mold underfill material, the resin composition described above may be used, or the resin sheet described above may be used.

A semiconductor chip package according to a second embodiment of the present invention includes a semiconductor chip and a cured product of the resin composition sealing the semiconductor chip. In such a semiconductor chip package, the cured resin composition usually functions as a sealing layer. As a semiconductor chip package according to the second embodiment, for example, a fan-out type WLP can be used.

A method for manufacturing such a semiconductor chip package includes:
(A) a step of laminating a temporary fixing film on a substrate;
(B) temporarily fixing the semiconductor chip on the temporary fixing film;
(C) forming a sealing layer on the semiconductor chip;
(D) a step of peeling the substrate and the temporary fixing film from the semiconductor chip;
(E) forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the substrate and the temporary fixing film have been removed;
(F) forming a rewiring layer as a conductor layer on the rewiring forming layer;
(G) forming a solder resist layer on the rewiring layer;
including. Further, the method for manufacturing the semiconductor chip package includes:
(H) A step of dicing the plurality of semiconductor chip packages into individual semiconductor chip packages to individualize them.

(Step (A))
Step (A) is a step of laminating a temporary fixing film on a substrate. The conditions for laminating the base material and the temporary fixing film may be the same as the conditions for laminating the base material and the resin sheet in the method for manufacturing a circuit board.

Examples of substrates include silicon wafers; glass wafers; glass substrates; metal substrates such as copper, titanium, stainless steel and cold-rolled steel plate (SPCC); FR-4 substrates and the like; A heat-cured substrate; a substrate made of bismaleimide triazine resin such as BT resin; and the like.

Any material that can be peeled off from the semiconductor chip and that can temporarily fix the semiconductor chip can be used for the temporary fixing film. Commercially available products include "Riva Alpha" manufactured by Nitto Denko Corporation.

(Step (B))
Step (B) is a step of temporarily fixing the semiconductor chip on the temporary fixing film. Temporary fixing of the semiconductor chip can be performed using a device such as a flip chip bonder, a die bonder, or the like. The layout and the number of semiconductor chips to be arranged can be appropriately set according to the shape and size of the temporary fixing film, the target production number of semiconductor chip packages, and the like. For example, the semiconductor chips may be arranged in a matrix of multiple rows and multiple columns and temporarily fixed.

(Step (C))
Step (C) is a step of forming a sealing layer on the semiconductor chip. The sealing layer is formed from a cured product of the resin composition described above. The encapsulation layer is usually formed by a method including the steps of forming a resin composition layer on the semiconductor chip and thermosetting the resin composition layer to form the encapsulation layer.

Formation of the resin composition layer is preferably carried out by a compression molding method. In the compression molding method, a semiconductor chip and a resin composition are usually placed in a mold, and pressure and, if necessary, heat are applied to the resin composition in the mold to form a resin composition layer covering the semiconductor chip.

A specific operation of the compression molding method can be, for example, as follows. An upper mold and a lower mold are prepared as molds for compression molding. Also, the resin composition is applied to the semiconductor chip temporarily fixed on the temporary fixing film as described above. The semiconductor chip coated with the resin composition is attached to the lower mold together with the substrate and the temporary fixing film. After that, the upper mold and the lower mold are clamped, and heat and pressure are applied to the resin composition for compression molding.

Further, the specific operation of the compression molding method may be, for example, as follows. An upper mold and a lower mold are prepared as molds for compression molding. A resin composition is placed on the lower mold. Also, the semiconductor chip is attached to the upper mold together with the base material and the temporary fixing film. Thereafter, the upper mold and the lower mold are clamped so that the resin composition placed on the lower mold is in contact with the semiconductor chip attached to the upper mold, and heat and pressure are applied to perform compression molding.

Molding conditions vary depending on the composition of the resin composition, and suitable conditions can be adopted so as to achieve good sealing. For example, the temperature of the mold during molding is preferably 70°C or higher, more preferably 80°C or higher, particularly preferably 90°C or higher, preferably 200°C or lower, more preferably 170°C or lower, and particularly preferably 150°C. It is below. The pressure applied during molding is preferably 1 MPa or higher, more preferably 3 MPa or higher, particularly preferably 5 MPa or higher, and preferably 50 MPa or lower, more preferably 30 MPa or lower, and particularly preferably 20 MPa or lower. The cure time is preferably 1 minute or more, more preferably 2 minutes or more, particularly preferably 3 minutes or more, and preferably 60 minutes or less, more preferably 30 minutes or less, and particularly preferably 20 minutes or less. After formation of the resin composition layer, the mold is usually removed. The mold may be removed before or after heat curing of the resin composition layer.

The resin composition layer may be formed by laminating a resin sheet and a semiconductor chip. For example, the resin composition layer can be formed on the semiconductor chip by thermocompression bonding the resin composition layer of the resin sheet and the semiconductor chip. The lamination of the resin sheet and the semiconductor chip can be carried out in the same manner as the lamination of the resin sheet and the base material in the circuit board manufacturing method, using the semiconductor chip instead of the base material.

After forming the resin composition layer on the semiconductor chip, the resin composition layer is thermally cured to obtain a sealing layer covering the semiconductor chip. As a result, the semiconductor chip is sealed with the cured product of the resin composition. The thermosetting conditions for the resin composition layer may be the same as the thermosetting conditions for the resin composition layer in the circuit board manufacturing method. Furthermore, before thermally curing the resin composition layer, the resin composition layer may be subjected to a preheating treatment of heating at a temperature lower than the curing temperature. As the processing conditions for this preheating treatment, the same conditions as those for the preheating treatment in the circuit board manufacturing method may be employed.

(Step (D))
Step (D) is a step of peeling off the substrate and the temporary fixing film from the semiconductor chip. As for the peeling method, it is desirable to employ an appropriate method according to the material of the temporary fixing film. Examples of the peeling method include a method of heating, foaming, or expanding the temporary fixing film to peel it. Moreover, as a peeling method, for example, a method of irradiating the temporary fixing film with ultraviolet rays through the base material to reduce the adhesive strength of the temporary fixing film and peel it off can be used.

In the method of peeling by heating, foaming or expanding the temporary fixing film, the heating conditions are usually 100° C. to 250° C. for 1 second to 90 seconds or 5 minutes to 15 minutes. In the method of peeling off the temporary fixing film by irradiating it with ultraviolet rays to reduce its adhesive strength, the irradiation dose of ultraviolet rays is usually 10 mJ/cm ² to 1000 mJ/cm ² .

(Step (E))
Step (E) is a step of forming a rewiring forming layer as an insulating layer on the surface of the semiconductor chip from which the substrate and the temporary fixing film have been removed.

Any insulating material can be used as the material of the rewiring formation layer. Among them, photosensitive resins and thermosetting resins are preferable from the viewpoint of easiness in manufacturing semiconductor chip packages. Moreover, you may use the resin composition of this invention as this thermosetting resin.

After the rewiring formation layer is formed, via holes may be formed in the rewiring formation layer for interlayer connection between the semiconductor chip and the rewiring layer.

In the method of forming a via hole when the material of the rewiring layer is a photosensitive resin, the surface of the rewiring layer is usually irradiated with an active energy ray through a mask pattern to irradiate the rewiring layer in the irradiated portion with light. Harden. Examples of active energy rays include ultraviolet rays, visible rays, electron beams, and X-rays, and ultraviolet rays are particularly preferred. The irradiation amount and irradiation time of ultraviolet rays can be appropriately set according to the photosensitive resin. The exposure method includes, for example, a contact exposure method in which the mask pattern is brought into close contact with the rewiring layer and exposed, and a non-contact exposure method in which the mask pattern is not brought into close contact with the rewiring layer and is exposed using parallel light rays. is mentioned.

After the rewiring layer is photo-cured, the rewiring layer is developed to remove the unexposed portions to form via holes. The development may be either wet development or dry development. The development method includes, for example, a dipping method, a paddle method, a spray method, a brushing method, a scraping method, and the like, and the paddle method is preferable from the viewpoint of resolution.

When the material of the rewiring formation layer is a thermosetting resin, the method of forming via holes includes, for example, laser irradiation, etching, mechanical drilling, and the like. Among them, laser irradiation is preferable. Laser irradiation can be performed using an appropriate laser processing machine using a light source such as a carbon dioxide laser, a UV-YAG laser, an excimer laser, or the like.

Although the shape of the via hole is not particularly limited, it is generally circular (substantially circular). The top diameter of the via hole is preferably 50 μm or less, more preferably 30 μm or less, still more preferably 20 μm or less. Here, the top diameter of the via hole means the diameter of the opening of the via hole on the surface of the rewiring layer.

(Step (F))
Step (F) is a step of forming a rewiring layer as a conductor layer on the rewiring formation layer. The method of forming the rewiring layer on the rewiring forming layer can be the same as the method of forming the conductor layer on the insulating layer in the method of manufacturing the circuit board. Alternatively, the steps (E) and (F) may be repeated to alternately build up the rewiring layers and the rewiring formation layers (build-up).

(Step (G))
Step (G) is a step of forming a solder resist layer on the rewiring layer. Any insulating material can be used as the material of the solder resist layer. Among them, photosensitive resins and thermosetting resins are preferable from the viewpoint of easiness in manufacturing semiconductor chip packages. Moreover, you may use the resin composition of this invention as a thermosetting resin.

Moreover, in the step (G), a bumping process for forming bumps may be performed as necessary. Bumping can be performed by a method such as solder balls or solder plating. Formation of via holes in the bumping process can be performed in the same manner as in step (E).

(Step (H))
The method for manufacturing a semiconductor chip package may include step (H) in addition to steps (A) to (G). Step (H) is a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages to separate them into pieces. The method of dicing the semiconductor chip package into individual semiconductor chip packages is not particularly limited.

<Semiconductor device>
A semiconductor device includes a semiconductor chip package. Examples of semiconductor devices include electrical products (e.g., computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical equipment, televisions, etc.) and vehicles (e.g., motorcycles, automobiles, trains, ships, etc.). and aircraft, etc.).

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. The invention is not limited to these examples. In the following, "parts" and "%" representing amounts mean "parts by mass" and "% by mass", respectively, unless otherwise specified.

<Example 1>
Amine curing agent (“SEIKACURE-S” manufactured by Seika) 0.5 parts, glycidylamine type epoxy resin (“630” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 95 g / eq.) 7 parts, naphthalene type epoxy resin (DIC Corporation manufactured by "HP-4032D", epoxy equivalent of about 143 g / eq.) 8 parts, imidazole-based curing accelerator ("2E4-MZ" manufactured by Shikoku Kasei Kogyo Co., Ltd.) 0.1 parts, polyoxyethylene polyoxypropylene glycol (ADEKA Co., Ltd. “L-44” manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts, inorganic filler (average particle size 1.8 μm, specific surface area 3.6 m ² /g, KBM573 (N-phenyl-3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) 70 parts of spherical silica treated with was uniformly dispersed using a mixer to prepare a resin composition.

<Example 2>
Example except that 2 parts of polyoxyethylene polyoxypropylene glycol (ADEKA "L-64") was used instead of 2 parts of polyoxyethylene polyoxypropylene glycol (ADEKA "L-44") A resin composition was prepared in the same manner as in 1.

<Example 3>
Example except that 4 parts of polyoxyethylene polyoxypropylene glycol (ADEKA "L-64") was used instead of 2 parts of polyoxyethylene polyoxypropylene glycol (ADEKA "L-44") A resin composition was prepared in the same manner as in 1.

<Example 4>
Acid anhydride curing agent ("MH-700" manufactured by Shin Nippon Rika Co., Ltd., equivalent weight of acid anhydride: 163 g/eq.) 7 parts, glycidylamine type epoxy resin ("630" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight: about 95 g/eq.). ) 5 parts, naphthalene type epoxy resin (manufactured by DIC "HP-4032D", epoxy equivalent of about 143 g / eq.) 6 parts, imidazole-based curing accelerator (manufactured by Shikoku Kasei Kogyo Co., Ltd. "2MA-OK-PW") 0. 1 part, polyoxyalkylene-modified silicone (“KF-6028” manufactured by Shin-Etsu Chemical Co., Ltd.) 3 parts, inorganic filler (average particle size 1.8 μm, specific surface area 3.6 m ² / g, KBM573 (N-phenyl-3 85 parts of spherical silica treated with -aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) were uniformly dispersed using a mixer to prepare a resin composition.

<Example 5>
Instead of 3 parts of polyoxyalkylene-modified silicone (manufactured by Shin-Etsu Chemical Co., Ltd. "KF-6028"), except for using 3 parts of polyoxyalkylene-modified silicone (manufactured by Shin-Etsu Chemical Co., Ltd. "KF-6015") Examples A resin composition was prepared in the same manner as in 4.

<Example 6>
Instead of 3 parts of polyoxyalkylene-modified silicone (manufactured by Shin-Etsu Chemical Co., Ltd. "KF-6028"), except for using 1 part of polyoxyalkylene-modified silicone (manufactured by Shin-Etsu Chemical Co., Ltd. "KF-6015") Examples A resin composition was prepared in the same manner as in 4.

<Comparative Example 1>
A resin composition was prepared in the same manner as in Example 1, except that polyoxyethylene polyoxypropylene glycol ("L-44" manufactured by ADEKA) was not used.

<Comparative Example 2>
A resin composition was prepared in the same manner as in Example 1, except that the amount of polyoxyethylene polyoxypropylene glycol ("L-44" manufactured by ADEKA) was changed from 2 parts to 7 parts.

<Comparative Example 3>
A resin composition was prepared in the same manner as in Example 4, except that the polyoxyalkylene-modified silicone (“KF-6028” manufactured by Shin-Etsu Chemical Co., Ltd.) was not used.

<Comparative Example 4>
A resin composition was prepared in the same manner as in Example 4, except that the amount of polyoxyalkylene-modified silicone (“KF-6028” manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 3 parts to 8 parts.

<Comparative Example 5>
8 parts of the polyoxyalkylene-modified silicone of Comparative Example 4 (“KF-6028” manufactured by Shin-Etsu Chemical Co., Ltd.) was added to an amphiphilic polyether block copolymer (“Fortegra 100” manufactured by Dow Chemical Co., a polyether compound containing a polybutylene oxide block) 8 A resin composition was prepared in the same manner as in Comparative Example 4, except that the amount was changed to .

<Test Example 1: Evaluation of warpage>
On a 12-inch silicon wafer, the resin compositions prepared in Examples and Comparative Examples were compression-molded using a compression molding apparatus (mold temperature: 130°C, pressure: 6 MPa, cure time: 10 minutes) to obtain a thickness. A resin composition layer having a thickness of 300 μm was formed. After that, the resin composition layer was thermally cured by heating at 180° C. for 90 minutes. As a result, a sample substrate including a silicon wafer and a cured product layer of the resin composition was obtained. Using a shadow moiré measuring device (“Thermoire AXP” manufactured by Akorometrics), the amount of warpage at 25° C. of the sample substrate was measured. The measurement was performed in accordance with JEITA EDX-7311-24 of the Japan Electronics and Information Technology Industries Association standard. Specifically, a virtual plane calculated by the method of least squares of all data of the substrate surface in the measurement area is used as a reference plane, and the difference between the minimum value and the maximum value in the direction perpendicular to the reference plane is obtained as the amount of warpage. evaluated according to the standard.
"○": Warp amount less than 3 mm "×": Warp amount 3 mm or more

<Test Example 2: Measurement of elastic modulus (GPa)>
The resin compositions prepared in Examples and Comparative Examples were applied onto a SUS plate whose surface had been subjected to mold release treatment, using a compression molding apparatus (mold temperature: 130°C, pressure: 6 MPa, cure time: 10 minutes). The resin composition layer having a thickness of 300 μm was formed by compression molding. The SUS plate was peeled off, and the resin composition layer was thermally cured by heating at 180° C. for 90 minutes to obtain a cured product layer of the resin composition. This cured product layer was cut into dumbbell-shaped No. 1 specimens to obtain test pieces. The test piece was subjected to tensile strength measurement using a tensile tester "RTC-1250A" manufactured by Orientec Co., Ltd., and the elastic modulus (GPa) at 25°C was obtained. The measurement was carried out according to JIS K7127. This operation was performed 3 times and the average value is shown in the table.

<Test Example 3: Evaluation of 3-point bending strength>
The resin compositions prepared in Examples and Comparative Examples were compression-molded using a release-treated SUS plate compression molding apparatus (mold temperature: 130°C, pressure: 6 MPa, cure time: 10 minutes) to obtain a thickness. A resin composition layer having a thickness of 300 μm was formed. After that, the resin composition was peeled off from the SUS plate and thermally cured at 150° C. for 60 minutes to obtain a test piece for measuring three-point bending strength. Three-point bending strength (MPa) at 23° C. was determined using a tensile tester “RTC-1250A” manufactured by Orientec. The test was performed 5 times and the average value was used. A sample with a three-point bending strength of 50 MPa or less was rated as "x", and a sample with a three-point bending strength of greater than 50 MPa was rated as "o".

<Test Example 4: Measurement of gel time (gelling time) (seconds)>
The gel time (gelling time) was measured according to JIS C6521 for the resin compositions prepared in Examples and Comparative Examples. Specifically, first, using a hot plate gelation tester (GT-D: manufactured by Nisshin Kagaku Co., Ltd.), the time (seconds) at which the resin compositions of Examples and Comparative Examples stopped drawing strings at 130 ° C. was measured. It was measured. More specifically, about 0.5 g of sample (resin composition) was placed on a hot plate gelation tester. Starting from the point of 130° C. (130° C. gel time), a spatula with a tip width of 5 mm is applied to the resin composition so that the resin composition stays within a range of 25 mm in diameter on the hot plate. was repeated (1 rotation per second). The resin composition was lifted vertically from the hot plate by 30 mm, and the end point was set when the thread-like material became cut, and the time from the start point to the end point was regarded as the time until gelation, and the measurement was performed. The spatula was not lifted while the viscosity of the resin was low, and when the viscosity increased, the spatula was lifted vertically by about 30 mm from the hot plate, and this up-and-down motion was repeated until the string was cut. The measurement was repeated twice and the average value was used as the result.

<Test Example 5: Evaluation of minimum melt viscosity>
The melt viscosities of the resin compositions prepared in Examples and Comparative Examples were measured using a dynamic viscoelasticity measuring device ("Rheosol-G3000" manufactured by UBM Co., Ltd.). This measurement was performed on a 1 g sample taken from the resin composition using a parallel plate with a diameter of 18 mm. The measurement conditions were a starting temperature of 60° C. to 200° C., a temperature increase rate of 5° C./min, a measurement temperature interval of 2.5° C., and a vibration of 1 Hz/deg. The lowest melt viscosity was obtained from the measured values of the obtained melt viscosities. A minimum melt viscosity of 10 poise or less was evaluated as "◯", a minimum melt viscosity of more than 10 poise and less than or equal to 100 poise was evaluated as "Δ", and a minimum melt viscosity of more than 100 poise was evaluated as "X".

Table 1 below shows the non-volatile components and amounts used in the resin compositions of Examples and Comparative Examples, as well as the measurement results and evaluation results of Test Examples.

From the above results, the resin composition to be used contains (A) an epoxy resin, (B) an inorganic filler, (C) a curing agent, and (D) a polyether skeleton-containing non-epoxy compound, and component (D) The contained polyether skeleton is a polyoxyalkylene skeleton composed of one or more monomer units selected from ethylene oxide units and propylene oxide units, and (B) the content of the inorganic filler is the total content of the resin composition. is 70% by mass or more, and the content of the (D) polyether skeleton-containing non-epoxy compound is 100% by mass of the non-volatile components other than the (B) inorganic filler in the resin composition. In terms of % by mass, when it is 1% by mass or more and 30% by mass or less, it is possible to obtain a cured product that has excellent embeddability, can suppress warping during curing, and has excellent mechanical strength. have understood.

Claims (21)

A resin composition comprising (A) an epoxy resin, (B) an inorganic filler, (C) a curing agent, and (D) a polyether skeleton-containing non-epoxy compound,
The polyether skeleton contained in component (D) is a polyoxyalkylene skeleton composed of one or more monomer units selected from ethylene oxide units and propylene oxide units,
(D) component does not contain a polyether skeleton containing a monomer unit having 4 or more carbon atoms,
The content of component (B) is 70% by mass or more when all non-volatile components in the resin composition are 100% by mass,
(D) component is one or more compounds selected from the group consisting of polyalkylene glycol and polyoxyalkylene-modified silicone, the polyalkylene glycol is polyoxyethylene polyoxypropylene glycol,
A resin composition in which the content of component (D) is 1% by mass or more and 30% by mass or less when non-volatile components other than component (B) in the resin composition are taken as 100% by mass. 2. The resin composition according to claim 1 , wherein component (D) has a number average molecular weight of 500 to 10,000. 3. The resin composition according to claim 1, wherein the viscosity of component (D) at 25° C. is 3000 mPa·s or less. The resin composition according to any one of claims 1 to 3 , wherein the content of component (B) is 78% by mass or more when all non-volatile components in the resin composition are taken as 100% by mass. The resin composition according to any one of claims 1 to 4 , wherein component (B) is silica. 6. The resin composition according to any one of claims 1 to 5 , wherein component (A) comprises an epoxy resin containing a condensed ring structure. 7. The resin composition according to claim 6 , wherein the content of the condensed ring structure-containing epoxy resin in component (A) is 50% by mass or more when the total amount of component (A) is 100% by mass. The resin composition according to any one of claims 1 to 7 , wherein component (A) comprises a glycidylamine type epoxy resin. The resin composition according to any one of claims 1 to 8 , wherein component (A) contains a liquid epoxy resin. 10. The resin composition according to claim 9 , wherein the content of the liquid epoxy resin in component (A) is 50% by mass or more when the total amount of component (A) is 100% by mass. The content of component (A) is 40% by mass or more when non-volatile components other than component (B) in the resin composition are 100 % by mass. of the resin composition. The resin composition according to any one of claims 1 to 11 , wherein component (C) contains one or more curing agents selected from the group consisting of acid anhydride curing agents and amine curing agents. . The resin composition according to any one of claims 1 to 12 , for forming an insulating layer of a semiconductor chip package. The resin composition according to any one of claims 1 to 12 , for forming an insulating layer of a circuit board. The resin composition according to any one of claims 1 to 12 , for encapsulating a semiconductor chip in a semiconductor chip package. A cured product of the resin composition according to any one of claims 1 to 15 . A resin sheet comprising a support and a resin composition layer containing the resin composition according to any one of claims 1 to 15 provided on the support. A circuit board comprising an insulating layer formed from a cured product of the resin composition according to any one of claims 1 to 15 . A semiconductor chip package comprising the circuit board according to claim 18 and a semiconductor chip mounted on the circuit board. A semiconductor chip package comprising a semiconductor chip and a cured product of the resin composition according to any one of claims 1 to 15 for sealing the semiconductor chip. A semiconductor device comprising the semiconductor chip package according to claim 19 or 20 .