Structure, cured product, epoxy resin composition, sealing material, and semiconductor package

Abstract

To provide a structure having a cured product which is excellent in heat resistance, suppresses occurrence of voids, and has high reliability.SOLUTION: A structure has a first layer, a second layer, and a plurality of copper pillars for connecting between the first layer and the second layer, wherein the first layer and the second layer each has at least one kind selected from the group consisting of a resin, silicon, ceramics, a compound semiconductor, and glass, a distance between the adjacent copper pillars among the plurality of copper pillars is 150 μm or less, a third layer contacting each of the first layer and the second layer is provided between the first layer and the second layer, the third layer is a cured product of an epoxy resin composition containing an epoxy resin, a polyimide resin and an inorganic filler, and an area ratio of voids to the area of the surface of the third layer is 1% or less.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a structure, a cured product, an epoxy resin composition, an encapsulant, and a semiconductor package. [Background technology]

[0002] Epoxy resins have been used in a wide range of applications, such as coating materials, electrical and electronic insulating materials, and adhesives, because their cured products have a variety of properties.

[0003] For example, Patent Document 1 discloses a semiconductor device bonded with a cured product of an adhesive containing a thermosetting resin such as an epoxy resin and a curing agent. Furthermore, Patent Document 2 discloses a laminate for a mounting substrate having copper pillars on a predetermined plastic film. Furthermore, Patent Document 3 discloses a laminate using an epoxy resin composition containing (A) a solvent-soluble polyimide resin, (B) an epoxy resin having an anthracene skeleton, (C) a curing catalyst, and (D) an inorganic filler, and a semiconductor device using the laminate. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2016 / 143815 [Patent Document 2] Japanese Patent Application Laid-Open No. 2015-230934 [Patent Document 3] Japanese Patent Application Publication No. 2018-90664 Summary of the Invention [Problem to be solved by the invention]

[0005] Recent demands for electronic devices are diverse. Examples of such demands include miniaturization, high functionality, weight reduction, and multi-functionality. More specifically, when mounting semiconductor chips, high reliability against temperature changes, i.e., no peeling, cracking, warping, etc., is required. To meet these demands, underfills have traditionally been used as adhesives placed in the gap between the chip and the substrate to protect the bump connections and the circuit surface of the chip, and to ensure reliability. On the other hand, in recent years, there has been an increasing demand for finer pitches and larger semiconductor chips in the electronic device equipment, and problems have arisen such as improper filling of the underfill used as an adhesive due to the finer pitch, causing peeling or cracking of the semiconductor chip, and increased warping due to the larger area.

[0006] As mentioned above, high reliability is required for the cured resin that is placed in the gap between the chip and substrate of an electronic device to protect the connection, and further improvements in reliability will be required in the future.

[0007] The adhesive disclosed in Patent Document 1 does not contain an inorganic filler, and therefore has the problem that there is room for improvement in the linear expansion coefficient.

[0008] The laminate for mounting substrates disclosed in Patent Document 2 is formed using an organic solvent in the adhesive portion, and there is a risk of voids being generated due to evaporation of the remaining solvent during the curing reaction, which leads to a deterioration in reliability, and therefore has a problem that there is room for improvement.

[0009] The epoxy resin composition disclosed in Patent Document 3 contains an inorganic filler and a solvent-soluble polyimide resin with excellent heat resistance, and is therefore expected to produce a cured product with high reliability. However, the composition requires the use of an organic solvent, which volatilizes during the curing reaction, which may result in the generation of voids and lead to a deterioration in reliability, and therefore has the problem that there is room for improvement.

[0010] Therefore, an object of the present invention is to provide a structure having a highly reliable cured product that has excellent heat resistance and suppresses the generation of voids. [Means for solving the problem]

[0011] The present inventors have conducted extensive research in light of the above-mentioned problems of the conventional technology, and have found that in a structure having first and second layers made of a predetermined material and a plurality of copper pillars arranged at a predetermined interval connecting the first and second layers, the above-mentioned problems of the conventional technology can be solved by providing a third layer made of a cured product of a predetermined epoxy resin composition between the first and second layers, and specifying the number of voids in the third layer to be within a predetermined numerical range, thereby completing the present invention. That is, the present invention is as follows.

[0012] [1] a first layer, a second layer, and a plurality of copper pillars connecting the first layer and the second layer; the first layer and the second layer each contain at least one material selected from the group consisting of resin, silicon, ceramics, a compound semiconductor, and glass; Among the plurality of copper pillars, the distance between adjacent copper pillars is 150 μm or less, a third layer is disposed between the first layer and the second layer and is in contact with each of the first layer and the second layer; the third layer is a cured product of an epoxy resin composition containing an epoxy resin, a polyimide resin, and an inorganic filler, The area ratio of voids to the surface area of ​​the third layer is 1% or less. structure. [2] the epoxy resin composition contains an organic solvent in an amount of 1% by mass or less; The structure described in [1] above. [3] The third layer is 1,700-1,800 cm in the infrared (IR) absorption spectrum -1The maximum peak intensity Ia exists in the range of 1,450 to 1,550 cm -1 and the maximum peak intensity Ib present in the range satisfies the following formula (i): The structure according to [1] or [2] above. 0.1≦Ia / Ib≦0.5 (i) [4] A cured product used for a third layer between a first layer and a second layer connected by a plurality of copper pillars, the distance between adjacent copper pillars being 150 μm or less, the cured product constituting the third layer is a cured product of an epoxy resin composition containing an epoxy resin, a polyimide resin, and an inorganic filler, The area ratio of voids to the surface area of ​​the third layer is 1% or less. cured product. [5] the epoxy resin composition contains an organic solvent in an amount of 1% by mass or less; The cured product described in [4] above. [6] 1,700-1,800 cm in the infrared (IR) absorption spectrum -1 The maximum peak intensity Ia exists in the range of 1,450 to 1,550 cm -1 and the maximum peak intensity Ib present in the range satisfies the following formula (i): The cured product according to [4] or [5] above. 0.1≦Ia / Ib≦0.5 (i) [7] An epoxy resin composition for use in the cured product according to any one of [4] to [6] above, Epoxy resin, polyimide resin, and inorganic filler, Epoxy resin composition. [8] A sealing material comprising the cured product according to any one of [4] to [6] above. [9] The encapsulant according to [8] above, which is used for encapsulating a semiconductor.

[10] A semiconductor package comprising the encapsulant described in [8].

[11] A semiconductor package including the structure according to any one of [1] to [3]. [Effects of the Invention]

[0013] According to the present invention, it is possible to provide a structure having a highly reliable cured product that has excellent heat resistance and suppresses the occurrence of voids. [Brief explanation of the drawings]

[0014] [Figure 1] This shows an example of an image of a cured product of an epoxy resin composition injected into a TEG (Test Element Group) that has voids. [Figure 2] This shows an example of an image of a void-free cured product of an epoxy resin composition injected into a TEG (Test Element Group). DETAILED DESCRIPTION OF THE INVENTION

[0015] Hereinafter, an embodiment of the present invention (hereinafter simply referred to as "the present embodiment") will be described in detail. The following embodiments are merely examples for explaining the present invention, and are not intended to limit the present invention to the following content. The present invention can be implemented by appropriately modifying it within the scope of the gist thereof. In this specification, when "~" is used to express a numerical value or a physical property value, the values ​​before and after the "~" are included. In the present specification, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range. In addition, in the present specification, the upper or lower limit of a numerical range may be replaced with a value shown in the examples. In the description of groups (atomic groups) in this specification, when a notation does not specify whether the group is substituted or unsubstituted, it encompasses both unsubstituted and substituted groups. For example, the term "alkyl group" encompasses not only alkyl groups without a substituent (unsubstituted alkyl groups) but also alkyl groups with a substituent (substituted alkyl groups).

[0016] [Structure] The structure of this embodiment has a first layer, a second layer, and a plurality of copper pillars connecting the first layer and the second layer, the first layer and the second layer each containing at least one material selected from the group consisting of resin, silicon, ceramics, compound semiconductor, and glass, the distance between adjacent copper pillars among the plurality of copper pillars is 150 μm or less, a third layer is provided between the first layer and the second layer and is in contact with each of the first layer and the second layer, the third layer is a cured product of an epoxy resin composition containing an epoxy resin, a polyimide resin, and an inorganic filler, and the area ratio of voids to the surface area of ​​the third layer is 1% or less.

[0017] According to the above-mentioned configuration, a highly reliable structure having excellent heat resistance and suppressing the occurrence of voids can be obtained. Each component of the structure of this embodiment will be described below.

[0018] (First and second layers) The first layer and the second layer contain at least one material selected from the group consisting of resin, silicon, ceramics, compound semiconductor, and glass. The first layer and the second layer may be made of different materials from these materials, the same material, or a combination of these materials. Examples of resins include, but are not limited to, polyacetal, polyamide (PA), polycarbonate (PC), modified polyphenylene ether, polybutylene terephthalate, glass fiber (GF) reinforced polyethylene terephthalate, ultra-high molecular weight polyethylene, syndiotactic polystyrene, epoxy, glass epoxy (FR-4), phenol, silicone, amorphous polyarylate, polysulfone, polyethersulfone, polyphenylene sulfide, polyetheretherketone, polyimide (PI), polyetherimide, fluororesin, and LCP (Liquid Crystal Polymer).

[0019] Examples of ceramics include, but are not limited to, alumina (Al2O3), aluminum nitride (AlN), silicon carbide (SiC), boron nitride (BN), and silicon nitride (SiN).

[0020] Examples of compound semiconductors include, but are not limited to, gallium nitride, indium phosphide, gallium arsenide, and gallium phosphide.

[0021] The area of ​​the first layer is not limited to the following, but may be, for example, 100 to 22,500 mm 2 The thickness is not limited to the following, but may be, for example, 500 to 1,000 μm. The area of ​​the second layer is not limited to the following, but may be, for example, 100 to 250,000 mm 2 The thickness is, but not limited to, 500 to 10,000 μm.

[0022] (copper pillar) The structure of this embodiment has multiple copper pillars connecting the first layer and the second layer. The copper pillars serve as metal wiring for electrical connection. The copper pillars may be connected between the first layer and the second layer by solder. The metal wiring referred to here refers to a metal region for electrical connection, and the shape of the metal region when viewed vertically from the horizontal surface of the mounting substrate may be, for example, dot-like, round, rectangular, or linear, or may be a combination of two or more of these.

[0023] The distance between adjacent copper pillars among the plurality of copper pillars is set to 150 μm or less, preferably 140 μm or less, and more preferably 130 μm or less, from the viewpoint of good electrical connection and increasing the capacity of electronic devices. In the structure of this embodiment, the distances between adjacent copper pillars among the plurality of copper pillars may all be the same or may be in different combinations. In the structure of this embodiment, the number of copper pillars is set to 1 mm 2 Preferably, there are 10 to 50 strands per unit area, more preferably 15 to 50 strands per unit area, and even more preferably 20 to 50 strands per unit area. The distance between the first and second layers connected by the copper pillar corresponds to the vertical length of the copper pillar and the thickness of the third layer described below, and is preferably 1 μm or more and 100 μm or less.

[0024] (Epoxy resin composition, third layer, cured product) The structure of this embodiment has a third layer between the first layer and the second layer, the third layer being in contact with both the first layer and the second layer. The third layer is a cured product (hereinafter, sometimes referred to as the cured product of the present embodiment) of an epoxy resin composition containing an epoxy resin, a polyimide resin, and an inorganic filler (hereinafter, sometimes referred to as the epoxy resin composition of the present embodiment). That is, the epoxy resin composition of the present embodiment is an epoxy resin composition used for the cured product of the present embodiment, and contains an epoxy resin, a polyimide resin, and an inorganic filler. The cured product of this embodiment is used for a third layer between a first layer and a second layer connected by a plurality of copper pillars, with the distance between adjacent copper pillars being 150 μm or less. From the viewpoint of reliability, in the third layer and the cured product of this embodiment, the area ratio of voids to the surface area of ​​the third layer and the cured product is 1% or less, preferably 0.8% or less, and more preferably 0.5% or less. The epoxy resin composition used in the third layer constituting the structure of this embodiment and the epoxy resin composition used in the cured product of this embodiment preferably contains an organic solvent in an amount of 1% by mass or less, more preferably 0.7% by mass or less, and even more preferably 0.5% by mass or less. This can prevent voids from being generated in the cured product due to evaporation of the organic solvent. The content of the organic solvent in the epoxy resin composition can be measured using a GC (gas chromatograph), and can be controlled to fall within the above-mentioned range by carrying out a drying treatment in the purification step of the polyimide resin. Furthermore, the area ratio of voids can be controlled by adjusting the content of polyimide resin. Reducing the content of polyimide resin tends to reduce the area ratio of voids. Specifically, by adjusting the content of polyimide resin to 1 to 20% by mass of the entire cured product, the area ratio of voids in the cured product can be controlled to 1% or less. From this perspective, the content of polyimide is preferably 1 to 20% by mass of the entire cured product, more preferably 1 to 15% by mass, and even more preferably 2 to 10.5% by mass. The area ratio of voids on the surface of the cured product of this embodiment can be obtained by taking an image of the cured product observed from a direction perpendicular to the surface and calculating the area ratio of the voids. Specifically, it can be measured by the method described in the Examples below.

[0025] <Peak intensity ratio in infrared absorption spectrum> The third layer constituting the structure of the present embodiment and the cured product of the present embodiment exhibit a peak in the infrared (IR) absorption spectrum of 1,700 to 1,800 cm originating from C═O of polyimide. -1The maximum intensity of the peak in the range of Ia is defined as the peak at 1,450–1,550 cm−1 due to the C=C in the aromatic ring. 1 It is preferable that the maximum intensity of the peak present in the range Ib satisfies the following formula (i): 0.1≦Ia / Ib≦0.5 (i) From the viewpoint of reducing the CTE (coefficient of thermal expansion) of the third layer constituting the structure of this embodiment and the cured product of this embodiment, the ratio Ia / Ib is preferably 0.1 or more, more preferably 0.105 or more, and even more preferably 0.11 or more. From the viewpoint of suppressing void generation, the ratio Ia / Ib is preferably 0.5 or less, more preferably 0.495 or less, and even more preferably 0.49 or less. The ratio Ia / Ib in the formula (i) can be controlled to fall within the above-mentioned range by adjusting the content of the polyimide resin in the epoxy resin composition used for the cured product.

[0026] <Epoxy resin> The epoxy resin composition used in the third layer constituting the structure of the present embodiment and in the cured product of the present embodiment contains an epoxy resin. The epoxy resin is not particularly limited, and any commonly used epoxy resin can be used. For example, an epoxy resin having two or more epoxy groups in one molecule is preferred. The epoxy resin may be solid or liquid at room temperature, but is preferably liquid at room temperature from the viewpoint of the filling property of the epoxy resin composition of the present embodiment. The epoxy resin may particularly be an epoxy resin that is liquid at room temperature (hereinafter also referred to as a "liquid epoxy resin"), and a commonly used liquid epoxy resin may be used. The liquid epoxy resin preferably has a viscosity of, for example, 0.0001 to 10 Pa·s as measured with an E-type viscometer at room temperature.

[0027] Examples of epoxy resins include, but are not limited to, diglycidyl ether epoxy resins such as bisphenol-type epoxy resins (e.g., bisphenol A, bisphenol F, bisphenol AD, bisphenol S, and hydrogenated bisphenol A); naphthalene-type epoxy resins; epoxy resins obtained by epoxidizing novolac resins obtained from phenols and aldehydes (e.g., orthocresol novolac-type epoxy resins); glycidyl ester-type epoxy resins obtained by reacting polybasic acids (e.g., phthalic acid, dimer acid) with epichlorohydrin; glycidylamine-type epoxy resins obtained by reacting amine compounds (e.g., p-aminophenol, diaminodiphenylmethane, and isocyanuric acid) with epichlorohydrin; and linear aliphatic epoxy resins and alicyclic epoxy resins obtained by oxidizing olefin bonds with peracids (e.g., peracetic acid). These epoxy resins may be used singly or in combination.

[0028] Among these, for example, bisphenol-type epoxy resins are preferred from the viewpoint of the fluidity of the epoxy resin composition, and for example, glycidylamine-type epoxy resins are preferred from the viewpoints of the heat resistance and adhesiveness of the epoxy resin composition and the cured product, and the fluidity of the epoxy resin composition.

[0029] As described above, the epoxy resin is preferably at least one selected from the group consisting of bisphenol-type epoxy resins and glycidylamine-type epoxy resins. As the bisphenol type epoxy resin, from the viewpoint of the fluidity of the epoxy resin composition, one or more types selected from the group consisting of diglycidyl ether type epoxy resins of bisphenol A (bisphenol A type epoxy resins) and diglycidyl ether type epoxy resins of bisphenol F (bisphenol F type epoxy resins) are preferred. When a bisphenol A type epoxy resin and a bisphenol F type epoxy resin are used in combination, their mass ratio (bisphenol A type epoxy resin:bisphenol F type epoxy resin) is not particularly limited, but from the viewpoints of the heat resistance and adhesiveness of the epoxy resin composition and the cured product, and the fluidity of the epoxy resin composition, it is preferably, for example, 5:95 to 50:50, more preferably 10:90 to 40:60, and even more preferably 20:80 to 40:60. From the viewpoint of the fluidity of the epoxy resin composition, it is preferable that both the bisphenol type epoxy resin and the glycidyl amine type epoxy resin are liquid at room temperature. The bisphenol-type epoxy resin and the glycidylamine-type epoxy resin may be used alone or in combination of two or more. From the viewpoints of the heat resistance and adhesiveness of the epoxy resin composition and the cured product, and the flowability of the epoxy resin composition, it is preferable to use a bisphenol-type epoxy resin and a glycidylamine-type epoxy resin in combination. The total content of the bisphenol-type epoxy resin and the glycidylamine-type epoxy resin is not particularly limited, but from the viewpoints of the heat resistance and adhesiveness of the epoxy resin composition and the cured product, and the fluidity of the epoxy resin composition, it is, for example, preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 50% by mass or more, and even more preferably 80% by mass or more, based on the total amount of epoxy resin. There is no particular upper limit to the total content, and it can be determined within a range in which desired properties and characteristics are obtained from the viewpoints of viscosity, glass transition temperature, heat resistance, etc., and may be 100% by mass.

[0030] When a bisphenol-type epoxy resin and a glycidylamine-type epoxy are used in combination, their mass ratio (bisphenol-type epoxy resin:glycidylamine-type epoxy) is not particularly limited, but from the viewpoints of the heat resistance and adhesiveness of the epoxy resin composition and the cured product, and the fluidity of the epoxy resin composition, it is preferably, for example, 20:80 to 95:5, more preferably 40:60 to 90:10, and even more preferably 60:40 to 80:20.

[0031] In this embodiment, an epoxy resin that is solid at room temperature can also be used. From the viewpoint of the fluidity of the epoxy resin composition, the content of the epoxy resin that is solid at room temperature is, for example, preferably 0 to 20 mass%, more preferably 0 to 10 mass%, and even more preferably 0 to 5 mass%, relative to the total amount of epoxy resin.

[0032] The epoxy equivalent of the epoxy resin is not particularly limited, but from the viewpoint of the heat resistance of the epoxy resin composition and the cured product, it is preferably 60 to 400 g / mol, more preferably 70 to 300 g / mol, and even more preferably 80 to 250 g / mol. Here, the epoxy equivalent is the mass of resin per epoxy group (g / eq) and can be measured according to the method specified in JIS K 7236. Specifically, using a Mitsubishi Chemical Analytech Corporation automatic titrator "GT-200 Model," 2 g of epoxy resin is weighed into a 200 mL beaker, 90 mL of methyl ethyl ketone is added dropwise, and the resin is dissolved in an ultrasonic cleaner. Then, 10 mL of glacial acetic acid and 1.5 g of cetyltrimethylammonium bromide are added, and the resin is titrated with a 0.1 mol / L perchloric acid / acetic acid solution to determine the epoxy equivalent.

[0033] The epoxy resin preferably has a high purity. In particular, the amount of hydrolyzable chlorine is preferably small because it is involved in corrosion of aluminum wiring on elements such as ICs (Integrated Circuits). From the viewpoint of excellent moisture resistance, the amount of hydrolyzable chlorine is preferably, for example, 500 ppm or less. Here, the amount of hydrolyzable chlorine is measured by dissolving 1 g of a sample epoxy resin in 30 mL of dioxane, adding 5 mL of 1N-KOH (potassium hydroxide) methanol solution, refluxing for 30 minutes, and then measuring the value obtained by potentiometric titration.

[0034] The content of the epoxy resin in the third layer, the cured product of the present embodiment, and the epoxy resin composition of the present embodiment is not particularly limited, but from the viewpoints of heat resistance and adhesiveness, it is preferably 1 to 50 mass %, more preferably 10 to 45 mass %, and even more preferably 20 to 40 mass %, based on the total amount of the third layer and the cured product.

[0035] <Polyimide resin> Examples of polyimide resins include, but are not limited to, those obtained by condensation reaction of tetracarboxylic dianhydride and diamine by a known method. Such polyimide resins can be obtained, for example, by addition reaction of tetracarboxylic dianhydride and diamine in an organic solvent at a reaction temperature of 80°C or less, preferably 0 to 60°C. As the reaction proceeds, the viscosity of the reaction solution gradually increases, and polyamic acid, a polyimide precursor, is produced. Polyimide resins can be obtained by dehydration ring-closing this polyamic acid. Dehydration ring-closing can be performed by a thermal ring-closing method using heat treatment or a chemical ring-closing method using a dehydrating agent.

[0036] In the condensation reaction, the blending ratio of the tetracarboxylic dianhydride to the diamine (tetracarboxylic dianhydride:diamine) is usually 1.00:1.00 to 1.00:2.00 in terms of molar ratio. From the viewpoints of increasing compatibility with the epoxy resin when made into an epoxy resin composition and improving the flowability of the epoxy resin composition, the blending ratio of the tetracarboxylic dianhydride to the diamine is preferably 1.00:1.00 to 1.00:2.00, more preferably 1.00:1.20 to 1.00:2.00, and even more preferably 1.00:1.50 to 1.00:2.00. The ratio of diamine to tetracarboxylic dianhydride can be 2.00 or more, but since tetracarboxylic dianhydride can only react with a maximum of two diamines, the upper limit of the ratio is 2.00.

[0037] Examples of tetracarboxylic dianhydrides that are raw materials for polyimide resins include, but are not limited to, 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride (hereinafter also referred to as BISDA), 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-cyclohexene-1,2dicarboxylic anhydride, pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2', 3,3'-Benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, methylene-4,4-diphthalic dianhydride, 1,1-ethylidene-4,4'-diphthalic dianhydride, 2,2-propylidene-4,4'-diphthalic dianhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-di Phthalic dianhydride, 1,5-pentamethylene-4,4'-diphthalic dianhydride, 4,4'-oxydiphthalic dianhydride (hereinafter also referred to as ODPA), p-phenylenebis(trimellitate anhydride), sulfonyl-4,4'-diphthalic dianhydride, 1,3-bis(3,-dicarboxyphenyl)benzene dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,3-bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzene dianhydride, 1, 4-Bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzene dianhydride, bis[3-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, bis[4-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, 2,2-bis[3-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, bis(3,4-dicarboxyphenoxy)dimethylsilane dianhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride, etc.

[0038] In addition, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid)=1,1'-biphenyl-4,4'-diyl, 2,2',3,3',5,5'-hexamethyl[1,1'-biphenyl] phenyl]-4,4'-diyl bis(1,3-dioxo-1,3-dihydro-2-benzofuran-5-carboxylate), 1,2,3,4-cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, cyclopentanone bisspironorbornanetetracarboxylic dianhydride, 3,3',4,4'-bicyclohexyltetracarboxylic dianhydride, carbonyl-4,4'-bis(cyclohexane-1,2- Dicarboxylic acid) dianhydride, methylene-4,4'-bis(cyclohexane-12-dicarboxylic acid) dianhydride, 1,2-ethylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-ethylidene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 2,2-propylidene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, oxy-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, sulfonyl 4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, REL-[1S,5R,6R]-3-oxabicyclo[3,2]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride, ethylene glycol-bis-3,4-dicarboxylic acid anhydride (phenyl) ether, and the like.

[0039] Diamines that are raw materials for polyimide resins include, but are not limited to, 4-aminophenyl-4-aminobenzoate (APAB), 2-methyl-4-aminophenyl-4-aminobenzoate, 3-methyl-4-aminophenyl-4-aminobenzoate, 2-fluoro-4-aminophenyl-4-aminobenzoate, 3-fluoro-4-aminophenyl-4-aminobenzoate, 3-methyl-4-aminophenyl-3-methyl-4-aminobenzoate, and the like. benzoate, 4,4'-diaminobenzanilide, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10 -bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, m-tolidine, 2,2'-bis(trifluoromethyl)benzidine, and the like.

[0040] Further, for example, 4,4'-diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, bis(4-amino-3,5-dimethylphenyl)methane, 4,4'-diamino-3,3'-5,5'-tetraethyldiphenylmethane, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, bis(4-amino-3,5-diisopropylphenyl) Methane, 3,3'-diaminodiphenyl difluoromethane, 3,4'-diaminodiphenyl difluoromethane, 4,4'-diaminodiphenyl difluoromethane, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl ketone, 3,4'-diaminodiphenyl ketone, 4,4'-diaminodiphenyl ketone, 2,2-bis(3-aminophenyl)propane, 2,2'-(3,4'-diaminodiphenyl) Propane, 2,2-bis(3-aminophenyl)hexafluoropropane, 2,2-(3,4'-diaminodiphenyl)hexafluoropropane, 1,4-bis(3-aminophenoxy)benzene, 3,3'-(1,4-phenylenebis(1-methylethylidene))bisaniline, 3,4'-(1,4-phenylenebis(1-methylethylidene))bisaniline, 4,4'-(1,4-phenylenebis(1-methylethylidene))bisaniline, 2,2-bis(4-(3-aminophenoxy)phenyl)propane, 2,2-bis(4-(3-aminophenoxy)phenyl) 2,2-bis(4-(4-aminophenoxy)phenyl)hexafluoropropane, 2,2-bis(4-(4-aminophenoxy)phenyl)hexafluoropropane, bis(4-(3-aminoenoxy)phenyl)sulfide, bis(4-(4-aminoenoxy)phenyl)sulfide, bis(4-(3-aminoenoxy)phenyl)sulfone, bis(4-(4-aminoenoxy)phenyl)sulfone, 3,5-diaminobenzoic acid, 1,3-bis(aminomethyl)cyclohexane, 2,2-bis(4-aminophenoxyphenyl)propane, diethyltoluenediamine(2,4-diamino-3,5-diethyltoluene, 2,6-diamino-3,5-diethyltoluene, dimethylthiotoluenediamine, etc.

[0041] When synthesizing a polyimide resin using the compound by the above-mentioned method, the organic solvent is preferably one capable of dissolving or dispersing the polyimide resin, but is not limited to the following. Examples of such organic solvents include, but are not limited to, alcohols such as methanol, ethanol, 1-propanol, 2-propanol, butanol, and t-butyl alcohol; halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, and o-dichlorobenzene; halogenated phenols such as p-chlorophenol, pentachlorophenol, and pentafluorophenol; ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, and diethylene glycol dimethyl ether; ketones such as acetone, cyclohexanone, and methyl ethyl ketone; ethyl acetate, γ-butyrolactone, and the like. nitriles such as acetonitrile and succinonitrile; amide solvents (organic solvents having an amide bond in the molecule) such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone (NMP); urea compounds such as tetramethylurea; nitro compounds such as nitromethane and nitrobenzene; sulfur compounds such as dimethyl sulfoxide and sulfolane; and phosphorus compounds such as hexamethylphosphoramide and tri-n-butylphosphate. These organic solvents may be used alone or in combination of two or more.

[0042] The content of polyimide resin in the third layer, the cured product of this embodiment, and the epoxy resin composition of this embodiment is not particularly limited, but from the viewpoint of lowering the CTE of the cured product of this embodiment and suppressing voids, the content is preferably 1 to 20 mass %, more preferably 1 to 15 mass %, and even more preferably 2 to 10.5 mass %, relative to the total amount of the third layer and the cured product.

[0043] <Inorganic fillers> Examples of inorganic fillers include, but are not limited to, silica such as fused silica and crystalline silica, calcium carbonate, clay, alumina such as alumina oxide, silicon nitride, silicon carbide, boron nitride, calcium silicate, potassium titanate, aluminum nitride, beryllia, zirconia, zircon, forsterite, steatite, spinel, mullite, titania, and other powders, as well as beads obtained by spheronizing these, and glass fiber. The inorganic filler may be an inorganic filler having a flame retardant effect, and examples of the inorganic filler having a flame retardant effect include, but are not limited to, aluminum hydroxide, magnesium hydroxide, zinc borate, and zinc molybdate. The inorganic fillers may be used alone or in combination of two or more. Among these, from the viewpoints of availability, chemical stability, and material cost, for example, silica is preferred, and fused silica is more preferred. The particle shape of the inorganic filler is not particularly limited, and may be either amorphous or spherical. From the viewpoint of flowability and permeability into fine gaps in the epoxy resin composition, however, spherical silica, particularly spherical fused silica, is preferred.

[0044] The inorganic filler may also be surface-treated. Specifically, the inorganic filler may be surface-treated with a silane coupling agent. Examples of silane coupling agents include, but are not limited to, aminosilane coupling agents, epoxysilane coupling agents, phenylsilane coupling agents, alkylsilane coupling agents, alkenylsilane coupling agents, alkynylsilane coupling agents, haloalkylsilane coupling agents, siloxane coupling agents, hydrosilane coupling agents, silazane coupling agents, alkoxysilane coupling agents, chlorosilane coupling agents, (meth)acrylsilane coupling agents, aminosilane coupling agents, isocyanurate silane coupling agents, ureido silane coupling agents, mercaptosilane coupling agents, sulfide silane coupling agents, and isocyanate silane coupling agents.

[0045] The volume average particle size of the inorganic filler is not limited to the following, but is preferably 0.1 to 10 μm, more preferably 0.3 to 5 μm, and even more preferably 0.5 to 3 μm. By making the volume average particle diameter of the inorganic filler 0.1 μm or more, the dispersibility in the epoxy resin tends to be improved, while by making it 10 μm or less, the settling of the inorganic filler in the epoxy resin composition tends to be easily suppressed, and the permeability and fluidity of the epoxy resin composition into fine gaps tend to be improved, which tends to suppress the occurrence of voids and unfilled portions. The volume-average particle size is the particle size at the point corresponding to 50% volume when a cumulative frequency distribution curve is calculated based on particle size, with the total volume of the particles being 100%, and can be measured using a particle size distribution measuring device using a laser diffraction scattering method.

[0046] The content of the inorganic filler in the third layer, the cured product of the present embodiment, and the epoxy resin composition of the present embodiment is not particularly limited, but is preferably 50% by mass to 70% by mass relative to the total amount of the third layer, the cured product, and the epoxy resin composition. By setting the content of the inorganic filler to 50% by mass or more, it is likely that the effect of reducing the thermal expansion coefficient and the effect of improving resistance to temperature cycles will be easily obtained. By setting the content of the inorganic filler to 70% by mass or less, the permeability and fluidity of the epoxy resin composition into fine gaps will be improved, and the occurrence of voids and unfilled portions will tend to be suppressed. In particular, from the viewpoint of the effect of improving resistance to temperature cycles, the higher the lower limit of the content of the inorganic filler, the better.

[0047] <Epoxy resin curing agent> The third layer and the cured product of this embodiment can be produced using a curing agent for epoxy resins. Examples of the epoxy resin curing agent used to obtain the third layer and the cured product of the present embodiment include, but are not limited to, aromatic amine curing agents, aromatic amine adduct curing agents, acid anhydride curing agents, phenolic curing agents, and thiol curing agents.

[0048] Examples of aromatic amine curing agents include, but are not limited to, diaminodiphenylmethane, m-phenylenediamine, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, diethyltoluenediamine, trimethylenebis(4-aminobenzoate), polytetramethylene oxide-di-p-aminobenzoate, 4-aminophenyl 4-aminobenzoate, KAYAHARDA-A (manufactured by Nippon Kayaku Co., Ltd.), and Ethacure 100 (manufactured by Mitsui Chemicals Fine Co., Ltd.). These may be used alone or in combination of two or more.

[0049] Examples of aromatic amine adduct curing agents include, but are not limited to, compounds obtained by reacting a compound having one and / or multiple reactive groups with an amine compound. Examples of compounds having one and / or multiple reactive groups include, but are not limited to, epoxy resins, epoxy-based reactive diluents, alcohol compounds, alkyl halide compounds, isocyanate compounds, and ester compounds.

[0050] Examples of acid anhydride curing agents include, but are not limited to, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride.

[0051] Examples of phenol-based curing agents include, but are not limited to, phenol novolac resin, cresol novolac resin, phenol aralkyl resin, cresol aralkyl resin, naphthol aralkyl resin, biphenyl-modified phenol resin, biphenyl-modified phenol aralkyl resin, dicyclopentadiene-modified phenol resin, aminotriazine-modified phenol resin, naphthol novolac resin, naphthol-phenol co-condensed novolac resin, naphthol-cresol co-condensed novolac resin, and allyl acrylic phenol resin.

[0052] Examples of thiol-based curing agents include, but are not limited to, thiol compounds obtained by an esterification reaction between a polyol, such as trimethylolpropane tris(thioglycolate), pentaerythritol tetrakis(thioglycolate), ethylene glycol dithioglycolate, trimethylolpropane tris(β-thiopropionate), pentaerythritol tetrakis(β-thiopropionate), or dipentaerythritol poly(β-thiopropionate), and a thiol organic acid; alkyl polythiol compounds, such as 1,4-butanedithiol, 1,6-hexanedithiol, or 1,10-decanedithiol; terminal thiol group-containing polyethers; terminal thiol group-containing polythioethers; thiol compounds obtained by the reaction of an epoxy compound with hydrogen sulfide; and thiol compounds having terminal thiol groups obtained by the reaction of a polythiol with an epoxy compound.

[0053] Here, with regard to the aromatic amine compounds used in the aromatic amine adduct curing agent, amine compounds having electron-withdrawing properties and amine compounds having multiple functional groups on the side chain are inferior in reactivity as amines but are excellent in stability when made into amine adducts, and therefore examples of the aromatic amine compounds include 4,4'-diaminodiphenyl sulfone, diethyltoluenediamine (2,4-diamino-3,5-diethyltoluene, 2,6-diamino-3,5-diethyltoluene), and dimethylthiotoluenediamine.

[0054] On the other hand, with regard to the aromatic amine compounds used in the aromatic amine adduct curing agents, amine compounds that do not have electron-withdrawing properties and amine compounds that do not have functional groups in the side chain are highly reactive as amines and exhibit excellent curing properties when formed into amine adducts. Therefore, aromatic amines having a -CO-, -C(=O)O-, -, or -C(=O)NH- bond are preferred as the aromatic amine compound, and aromatic amines having a -C(=O)O- bond are particularly preferred. Examples of the aromatic amine compound include 4-aminophenyl-4-aminobenzoate (APAB), 3,4'-diaminodiphenyl ether (34ODA), and 1,3-bis(3-aminophenoxy)benzene (TPE-M), with 4-aminophenyl-4-aminobenzoate (APAB) being particularly preferred.

[0055] <Organic solvents> As described above, the polyimide resin is obtained by the condensation reaction of a tetracarboxylic dianhydride and a diamine. The organic solvent used in synthesizing the polyimide resin is not particularly limited, but is preferably one that can dissolve or disperse the polyimide resin. Examples of the organic solvent include, but are not limited to, alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and t-butyl alcohol; halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, and o-dichlorobenzene; halogenated phenols such as p-chlorophenol, pentachlorophenol, and pentafluorophenol; ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, and diethylene glycol dimethyl ether; ketones such as acetone, cyclohexanone, and methyl ethyl ketone; ethyl acetate, γ-butyrolactone, and the like. Examples of suitable organic solvents include esters such as methacrylate, carbonates such as ethylene carbonate and propylene carbonate, amines such as triethylamine, aromatic compounds such as toluene and xylene, nitrogen-containing heterocyclic aromatic compounds such as pyridine, nitriles such as acetonitrile and succinonitrile, amide solvents (organic solvents having an amide bond in the molecule) such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone (NMP), urea compounds such as tetramethylurea, nitro compounds such as nitromethane and nitrobenzene, sulfur compounds such as dimethyl sulfoxide and sulfolane, and phosphorus compounds such as hexamethylphosphoramide and tri-n-butylphosphate. These organic solvents may be used singly or in combination of two or more.

[0056] The epoxy resin composition of this embodiment may contain the organic solvent used in synthesizing the polyimide resin described above. The content of the organic solvent in the epoxy resin composition is preferably 1% by mass or less, from the viewpoint of suppressing the generation of voids when the composition is cured. The content of the organic solvent in the epoxy resin composition is more preferably 0.7% by mass or less, and even more preferably 0.5% by mass or less. The lower limit of the organic solvent content is not particularly limited, and may be below the detection limit, which is 1 ppm or more. Furthermore, from the viewpoint of improving compatibility with the epoxy resin, curing agent, and polyimide resin, and improving the flowability of the epoxy resin composition, the content of the organic solvent is preferably 0.01% by mass or more. The organic solvent may contain organic solvents other than those used in the synthesis of the polyimide resin, as long as the content is within the above range.

[0057] [Method for producing cured product] The third layer constituting the structure of the present embodiment and the cured product of the present embodiment can be obtained by curing the epoxy resin composition of the present embodiment, which contains an epoxy resin, a polyimide resin, an inorganic filler, and, as needed, a curing agent. That is, the epoxy resin composition of the present embodiment is used for the cured product of the present embodiment, and contains an epoxy resin, a polyimide resin, and an inorganic filler. The epoxy resin composition of the present embodiment can be obtained by mixing the components, for example, by stirring and mixing them in a planetary centrifugal mixer (for example, "ARE-310" manufactured by Thinky Corporation), followed by kneading with a three-roll mill.

[0058] [Method for forming the third layer] The third layer constituting the structure of the present embodiment can be formed by injecting the above-described epoxy resin composition of the present embodiment between the first layer and the second layer, molding it, and then heat-curing it. Specifically, the first and second layers connected by copper pillars can be obtained by aligning the semiconductor chip and substrate using a connecting device such as a flip-chip bonder, then pressing the semiconductor chip and substrate together while heating them at a temperature above the melting point of the solder bumps to connect the semiconductor chip and substrate, or by aligning the semiconductor chip and substrate and pressing them together at a temperature below the melting point of the solder bumps to temporarily fix them, and then heating them in a reflow furnace to melt the solder bumps and connect the semiconductor chip and substrate. The epoxy resin composition is then injected between the first and second layers using a casting machine, transfer molding machine, compression molding machine, injection molding machine, jet dispenser, or the like, appropriately molded, and heated at 80°C to 180°C for 1 to 10 hours. Examples of the heating method include a method using a heating oven, a clean oven, a pressure oven, or the like.

[0059] [Sealing materials, etc.] The cured product of this embodiment is useful as a sealing material, a filling material, an insulating material, a sealing material, and the like. As a sealing material, it is useful as a solid sealing material, a liquid sealing material, a film sealing material, etc. As a liquid sealing material, it is useful as an underfill material, a potting material, a dam material, etc. As an insulating material, it is useful as an insulating adhesive film, an insulating adhesive paste, a solder resist, etc. The cured product of this embodiment can be suitably used as a sealant, and the sealant is preferably a semiconductor sealant. The sealing material of this embodiment includes the cured product of this embodiment.

[0060] [Semiconductor Package] The structure of this embodiment can also be suitably used as a semiconductor package. The semiconductor package of this embodiment includes the sealing material of this embodiment. The method for manufacturing a semiconductor package of this embodiment includes a step of manufacturing a semiconductor package using the cured product of this embodiment. [Example]

[0061] The present embodiment will be described below with reference to specific examples and comparative examples, but the present invention is not limited to the following examples and comparative examples. In other words, a person skilled in the art can practice the present invention by making various modifications to the examples shown below. In the following, unless otherwise specified, "parts" are based on mass.

[0062] [Methods for measuring and evaluating physical properties and characteristics of cured products of epoxy resin compositions] Cured products were prepared as follows using the epoxy resin compositions prepared in the examples and comparative examples described below, and the physical properties of the cured products were measured as follows.

[0063] (Preparation of cured product) A TEG (Test Element Group) with Cu pillar bumps, a silicon chip size of 10 mm x 10 mm, and an organic resin substrate of 30 mm x 30 mm was used. The epoxy resin compositions prepared in the examples and comparative examples were injected into the TEG and heated to 165°C for 2 hours to cure, yielding a cured product.

[0064] (Measurement and evaluation of IR spectrum intensity ratio) The intensity ratio (Ia / Ib) of the IR spectrum of the cured product was measured by the following method. Equipment: LUMOS FT-IR microscope (manufactured by Bruker Japan Co., Ltd.) Condition: Attenuated Total Reflection (Ge) Incident angle: 30° Aperture size: 124 x 124 μm Resolution: 4cm -1 Accumulation count: 32 times Contact pressure: High Measurement range: 600~5000cm -1 Spectral vertical axis: absorbance <Procedure> 1.2000~2500cm -1 Draw a baseline based on this. 2. 1,450~1,550cm -1 Normalize to the maximum peak present in the range. 3. 1,700~1,800cm -1 The maximum peak intensity present in the range is read. 4. IR spectrum: 1,700-1,800 cm -1 The maximum peak intensity in the range of Ia, 1,450 to 1,550 cm -1 The peak intensity ratio was calculated from the following formula, assuming that the maximum peak intensity present in the range was Ib. Peak intensity ratio = Ia / Ib <Evaluation criteria> The peak intensity ratio calculated as described above was evaluated according to the following criteria. A: Ia / Ib was greater than or equal to 0.1 and less than or equal to 0.5. B: Ia / Ib was less than 0.1 or greater than 0.5.

[0065] (Boyd's evaluation) Using the measuring device described below, an image was obtained by observing the surface of the cured product from a direction perpendicular to the surface, and the area ratio of the void portion was calculated and evaluated according to the following criteria. The voids are the white areas observed in Figure 1. Also, Figure 2 shows an image in the case where there are no voids (0%). Measuring device: Fine SAT FS300II (Hitachi Construction Machinery Finetech) Probe frequency: 200MHz <Evaluation criteria> ○: The area occupied by voids is 1% or less of the chip area ×: The area occupied by voids is greater than 1% of the chip area

[0066] (Measurement and evaluation of coefficient of linear expansion (CTE)) The cured epoxy resin composition was cured at 165°C for 2 hours and cut into a size of 5 mm x 5 mm to prepare a test piece. Using a test piece and a thermomechanical analyzer (product name: TMA450, manufactured by TA Instruments), the temperature was raised from -30 to 250°C at a rate of 5°C / min in compression mode, then cooled to -30°C and again raised to 250°C at a rate of 5°C / min for measurement. The slope of the tangent line at 10 to 30°C of the second measurement result was taken as the CTE, and was evaluated according to the following criteria. <Evaluation criteria> A: The CTE was less than 30 ppm / K. B: CTE was 30 ppm / K or more and less than 35 ppm / K. C:CTE was 35 ppm / K or more.

[0067] [Preparation of Epoxy Resin Composition] In the examples and comparative examples, an epoxy resin composition was prepared using (A) an epoxy resin, (B) a polyimide resin, (C) a curing agent, (D) an inorganic filler, (E) a curing accelerator, and (F) a solvent.

[0068] The abbreviations of the components used in the examples and comparative examples have the following meanings: In addition, the materials used in the preparation of the components are also shown below. ((A) Epoxy resin) EXA-850CRP (DIC Corporation) EXA-830CRP (DIC Corporation) JER-630LSD (Mitsubishi Chemical Corporation) HP4032D (DIC Corporation)

[0069] (Acid dianhydride: (B) Material for preparing polyimide resin) BPDA: Biphenyltetracarboxylic dianhydride ODPA: 4,4'-oxydiphthalic anhydride TAHQ: p-phenylenebis(trimellitate anhydride) BPAF: 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride

[0070] (Diamine: (B) Material for preparing polyimide resin) APAB: 4-aminophenyl-4'-aminobenzoate 44DAS: 4,4'-diaminodiphenyl sulfone 33DAS: 3,3'-diaminodiphenyl sulfone TPE-M: 1,3-bis(3-aminophenoxy)benzene 34ODA: 3,4'-diaminodiphenyl ether m-TB: m-Tolidine BAPP: 2,2-bis[4-(4-aminophenoxy)phenyl]propane BAFL: 9,9-bis(4-aminophenyl)fluorene Ethacure 100 Plus (+): A hardener containing diethyltoluenediamine (manufactured by Mitsui Fine Chemicals, Inc.) Ethacure 300: A hardener containing diethylthiotoluenediamine (manufactured by Mitsui Fine Chemicals, Inc.)

[0071] (Aromatic amine: (C) Material for preparing curing agent) APAB: 4-aminophenyl-4'-aminobenzoate 44DAS: 4,4'-diaminodiphenyl sulfone 34ODA: 3,4'-diaminodiphenyl ether TPE-M: 1,3-bis(3-aminophenoxy)benzene Ethacure 300: A hardener containing diethylthiotoluenediamine (manufactured by Mitsui Fine Chemicals, Inc.) Ethacure 100 Plus (+): A hardener containing diethyltoluenediamine (manufactured by Mitsui Fine Chemicals, Inc.) Kayahard AA: A hardener containing 3,3'-diethyl-4,4'-jaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd.)

[0072] (Reactive Compound: (C) Material for Preparing Curing Agent) 2-EH: 2-ethylhexyl glycidyl ether BGE: butyl glycidyl ether ph-GE: phenyl glycidyl ether

[0073] ((D) Inorganic filler) SE203G-SEJ (manufactured by Admatechs Co., Ltd.)

[0074] ((E) Curing accelerator) 2P4MHZ-PW (manufactured by Shikoku Chemicals Corporation) Compounds E-1A / E-1B: as described below. Compound E-1C: See below. Compound E-1D: See below.

[0075] ((B) Polyimide resin) <Preparation of polyimide resin (PI)> [Synthesis example 1-1: PI-1] A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen. Then, 21 g of N-methyl-2-pyrrolidone (NMP) and 14.62 g (50 mmol) of 1,3-bis(3-aminophenoxy)benzene (TPE-M) were added and stirred until homogenous. Then, 7.36 g (25 mmol) of biphenyltetracarboxylic dianhydride (BPDA), 20 g of NMP, 21.6 g of 1-butanol, and 174 μL of triethylamine were added. The mixture was heated to 180 °C under a nitrogen flow. After reaching 180 °C, the polymerization reaction was carried out for 4 hours. One hour after reaching 180 °C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to 80 °C, and NMP was added to obtain a 20% by mass solution of polyimide resin (PI) in NMP. The NMP solution was dropped into ethanol to reprecipitate the polyimide resin (PI), and the resin powder was collected by suction filtration. The collected powder was washed with water and vacuum-dried in an oven at 80°C to obtain a powder of polyimide resin (PI-1).

[0076] [Synthesis example 1-2: PI-2] A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen. 30 g of N-methyl-2-pyrrolidone (NMP) and 20.53 g (50 mmol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) were added and stirred until homogenous. 7.36 g (25 mmol) of biphenyltetracarboxylic dianhydride (BPDA), 22 g of NMP, 23.3 g of 1-butanol, and 174 μL of triethylamine were then added. The mixture was heated to 180 °C under nitrogen flow. After reaching 180 °C, the polymerization reaction was allowed to proceed for 4 hours. One hour after reaching 180 °C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to 80 °C, and NMP was added to obtain a 20% by weight NMP solution of polyimide resin (PI). The NMP solution was dropped into ethanol to reprecipitate the polyimide resin (PI), and the resin powder was collected by suction filtration. The collected powder was washed with water and vacuum-dried in an oven at 80°C to obtain polyimide resin (PI-2) powder.

[0077] [Synthesis example 1-3: PI-3] A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen. 26 g of N-methyl-2-pyrrolidone (NMP) and 17.43 g (50 mmol) of 9,9-bis(4-aminophenyl)fluorene (BAFL) were added and stirred until homogenous. 7.36 g (25 mmol) of biphenyltetracarboxylic dianhydride (BPDA), 20 g of NMP, 22.6 g of 1-butanol, and 174 μL of triethylamine were added. The mixture was heated to 180 °C under nitrogen flow. After reaching 180 °C, the polymerization reaction was allowed to proceed for 4 hours. One hour after reaching 180 °C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to 80 °C, and NMP was added to obtain a 20% by weight NMP solution of polyimide resin (PI). The NMP solution was dropped into ethanol to reprecipitate the polyimide resin (PI), and the resin powder was collected by suction filtration. The collected powder was washed with water and vacuum-dried in an oven at 80°C to obtain polyimide resin (PI-3) powder.

[0078] [Synthesis example 1-4: PI-4] A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen. Then, 15 g of N-methyl-2-pyrrolidone (NMP) and 8.91 g (50 mmol) of Ethacure 100 Plus were added and stirred until homogenous. Then, 7.36 g (25 mmol) of biphenyltetracarboxylic dianhydride (BPDA), 15 g of NMP, 19.9 g of 1-butanol, and 174 μL of triethylamine were added. The mixture was heated to 180 °C under a nitrogen flow. After reaching 180 °C, the polymerization reaction was carried out for 4 hours. One hour after reaching 180 °C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to 80 °C, and NMP was added to obtain a 20% by mass NMP solution of polyimide resin (PI). This NMP solution was added dropwise to ethanol to reprecipitate the polyimide resin (PI), and the resin powder was collected by suction filtration. The collected powder was washed with water and dried in a vacuum oven at 80°C to obtain a powder of polyimide resin (PI-4).

[0079] [Synthesis example 1-5: PI-5] A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen. Then, 20 g of N-methyl-2-pyrrolidone (NMP) and 10.72 g (50 mmol) of Ethacure 300 were added and stirred until homogenous. Then, 7.36 g (25 mmol) of biphenyltetracarboxylic dianhydride (BPDA), 14 g of NMP, 20.5 g of 1-butanol, and 174 μL of triethylamine were added. The mixture was heated to 180 °C under nitrogen flow. After reaching 180 °C, the polymerization reaction was carried out for 4 hours. One hour after reaching 180 °C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to 80 °C, and NMP was added to obtain a 20% by mass NMP solution of polyimide resin (PI). This NMP solution was added dropwise to ethanol to reprecipitate the polyimide resin (PI), and the resin powder was collected by suction filtration. The collected powder was washed with water and dried in a vacuum oven at 80°C to obtain a powder of polyimide resin (PI-5).

[0080] [Synthesis example 1-6: PI-6] A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen. 22 g of N-methyl-2-pyrrolidone (NMP) and 14.62 g (50 mmol) of 1,3-bis(3-aminophenoxy)benzene (TPE-M) were added and stirred until homogenous. 7.76 g (25 mmol) of 4,4'-oxydiphthalic anhydride (ODPA), 20 g of NMP, 22 g of 1-butanol, and 174 μL of triethylamine were then added. The mixture was heated to 180 °C under nitrogen flow. After reaching 180 °C, the polymerization reaction was allowed to proceed for 4 hours. One hour after reaching 180 °C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to 80 °C, and NMP was added to obtain a 20% by weight NMP solution of polyimide resin (PI). The NMP solution was dropped into ethanol to reprecipitate the polyimide resin (PI), and the resulting powder was collected by suction filtration. The collected powder was washed with water and vacuum-dried in an oven at 80°C to obtain a powder of polyimide resin (PI-6).

[0081] [Synthesis example 1-7: PI-7] A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen. 30 g of N-methyl-2-pyrrolidone (NMP) and 20.53 g (50 mmol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) were added and stirred until homogenous. 7.76 g (25 mmol) of 4,4'-oxydiphthalic anhydride (ODPA), 23 g of NMP, 23.6 g of 1-butanol, and 174 μL of triethylamine were then added. The mixture was heated to 180 °C under nitrogen flow. After reaching 180 °C, the polymerization reaction was allowed to proceed for 4 hours. One hour after reaching 180 °C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to 80 °C, and NMP was added to obtain a 20% by weight NMP solution of polyimide resin (PI). The NMP solution was dropped into ethanol to reprecipitate the polyimide resin (PI), and the resulting powder was collected by suction filtration. The collected powder was washed with water and vacuum-dried in an oven at 80°C to obtain a powder of polyimide resin (PI-7).

[0082] [Synthesis example 1-8:PI-8] A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen. 27 g of N-methyl-2-pyrrolidone (NMP) and 17.43 g (50 mmol) of 9,9-bis(4-aminophenyl)fluorene (BAFL) were added and stirred until homogenous. 7.76 g (25 mmol) of 4,4'-oxydiphthalic anhydride (ODPA), 20 g of NMP, 22.9 g of 1-butanol, and 174 μL of triethylamine were added. The mixture was heated to 180 °C under nitrogen flow. After reaching 180 °C, the polymerization reaction was allowed to proceed for 4 hours. One hour after reaching 180 °C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to 80 °C, and NMP was added to obtain a 20% by weight NMP solution of polyimide resin (PI). The NMP solution was dropped into ethanol to reprecipitate the polyimide resin (PI), and the resulting powder was collected by suction filtration. The collected powder was washed with water and dried in a vacuum oven at 80°C to obtain a powder of polyimide resin (PI-8).

[0083] [Synthesis example 1-9: PI-9] A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen. Then, 15 g of N-methyl-2-pyrrolidone (NMP) and 8.91 g (50 mmol) of Ethacure 100 Plus were added and stirred until homogenous. Then, 7.76 g (25 mmol) of 4,4'-oxydiphthalic anhydride (ODPA), 15 g of NMP, 20 g of 1-butanol, and 174 μL of triethylamine were added. The mixture was heated to 180 °C under nitrogen flow. After reaching 180 °C, the polymerization reaction was carried out for 4 hours. One hour after reaching 180 °C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to 80 °C, and NMP was added to obtain a 20% by weight NMP solution of polyimide resin (PI). The NMP solution was dropped into ethanol to reprecipitate the polyimide resin (PI), and the resulting powder was collected by suction filtration. The collected powder was washed with water and vacuum-dried in an oven at 80°C to obtain a powder of polyimide resin (PI-9).

[0084] [Synthesis example 1-10: PI-10] A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen. 20 g of N-methyl-2-pyrrolidone (NMP) and 10.72 g (50 mmol) of Ethacure 300 were added and stirred until homogenous. 7.76 g (25 mmol) of 4,4'-oxydiphthalic anhydride (ODPA), 14 g of NMP, 20.6 g of 1-butanol, and 174 μL of triethylamine were then added. The mixture was heated to 180 °C under nitrogen flow. After reaching 180 °C, the polymerization reaction was allowed to proceed for 4 hours. One hour after reaching 180 °C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to 80 °C, and NMP was added to obtain a 20% by weight NMP solution of polyimide resin (PI). The NMP solution was dropped into ethanol to reprecipitate the polyimide resin (PI), and the resulting powder was collected by suction filtration. The collected powder was washed with water and vacuum-dried in an oven at 80°C to obtain a powder of polyimide resin (PI-10).

[0085] [Synthesis example 1-11: PI-11] A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen. Then, 28 g of N-methyl-2-pyrrolidone (NMP) and 14.62 g (50 mmol) of 1,3-bis(3-aminophenoxy)benzene (TPE-M) were added and stirred until homogenous. Then, 11.46 g (25 mmol) of p-phenylenebis(trimellitate anhydride) (TAHQ), 20 g of NMP, 22.8 g of 1-butanol, and 174 μL of triethylamine were added. The mixture was heated to 180 °C under nitrogen flow. After reaching 180 °C, the polymerization reaction was carried out for 4 hours. One hour after reaching 180 °C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to 80 °C, and NMP was added to obtain a 20% by mass NMP solution of polyimide resin (PI). The NMP solution was dropped into ethanol to reprecipitate the polyimide resin (PI), and the resulting powder was collected by suction filtration. The collected powder was washed with water and dried in a vacuum oven at 80°C to obtain a powder of polyimide resin (PI-11).

[0086] [Synthesis example 1-12: PI-12] A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen. 30 g of N-methyl-2-pyrrolidone (NMP) and 20.53 g (50 mmol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) were added and stirred until homogenous. 11.46 g (25 mmol) of p-phenylenebis(trimellitate anhydride) (TAHQ), 29 g of NMP, 25 g of 1-butanol, and 174 μL of triethylamine were then added. The mixture was heated to 180 °C under nitrogen flow. After reaching 180 °C, the polymerization reaction was allowed to proceed for 4 hours. One hour after reaching 180 °C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to 80 °C, and NMP was added to obtain a 20% by weight NMP solution of polyimide resin (PI). The NMP solution was dropped into ethanol to reprecipitate the polyimide resin (PI), and the resulting powder was collected by suction filtration. The collected powder was washed with water and vacuum-dried in an oven at 80°C to obtain a powder of polyimide resin (PI-12).

[0087] [Synthesis example 1-13: PI-13] A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen. Then, 34 g of N-methyl-2-pyrrolidone (NMP) and 17.43 g (50 mmol) of 9,9-bis(4-aminophenyl)fluorene (BAFL) were added and stirred until homogenous. Then, 11.46 g (25 mmol) of p-phenylenebis(trimellitate anhydride) (TAHQ), 20 g of NMP, 23.6 g of 1-butanol, and 174 μL of triethylamine were added. The mixture was heated to 180 °C under nitrogen flow. After reaching 180 °C, the polymerization reaction was carried out for 4 hours. One hour after reaching 180 °C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to 80 °C, and NMP was added to obtain a 20% by mass solution of polyimide resin (PI) in NMP. The NMP solution was dropped into ethanol to reprecipitate the polyimide resin (PI), and the resulting powder was collected by suction filtration. The collected powder was washed with water and dried in a vacuum oven at 80°C to obtain a powder of polyimide resin (PI-13).

[0088] [Synthesis example 1-14: PI-14] A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen. Then, 20 g of N-methyl-2-pyrrolidone (NMP) and 8.91 g (50 mmol) of Ethacure 100 Plus were added and stirred until homogenous. Then, 11.46 g (25 mmol) of p-phenylenebis(trimellitate anhydride) (TAHQ), 18 g of NMP, 21.2 g of 1-butanol, and 174 μL of triethylamine were added. The mixture was heated to 180 °C under a nitrogen flow. After reaching 180 °C, the polymerization reaction was carried out for 4 hours. One hour after reaching 180 °C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to 80 °C, and NMP was added to obtain a 20% by mass NMP solution of polyimide resin (PI). The NMP solution was dropped into ethanol to reprecipitate the polyimide resin (PI), and the resulting powder was collected by suction filtration. The collected powder was washed with water and vacuum-dried in an oven at 80°C to obtain a powder of polyimide resin (PI-14).

[0089] [Synthesis example 1-15: PI-15] A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen, and then 21 g of N-methyl-2-pyrrolidone (NMP) and 10.72 g (50 mmol) of Ethacure 300 were added and stirred until homogenous. Then, 11.46 g (25 mmol) of p-phenylenebis(trimellitate anhydride) (TAHQ), 20 g of NMP, 21.8 g of 1-butanol, and 174 μL of triethylamine were added. The mixture was heated to 180 °C under a nitrogen flow. After reaching 180 °C, the polymerization reaction was carried out for 4 hours. One hour after reaching 180 °C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to 80 °C, and NMP was added to obtain a 20% by mass NMP solution of polyimide resin (PI). The NMP solution was dropped into ethanol to reprecipitate the polyimide resin (PI), and the resulting powder was collected by suction filtration. The collected powder was washed with water and vacuum-dried in an oven at 80°C to obtain a powder of polyimide resin (PI-15).

[0090] [Synthesis example 1-16: PI-16] A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen. Then, 22 g of N-methyl-2-pyrrolidone (NMP) and 11.41 g (50 mmol) of 4-aminophenyl-4'-aminobenzoate (APAB) were added and stirred until homogenous. Then, 11.46 g (25 mmol) of 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BPAF), 20 g of NMP, 22.1 g of 1-butanol, and 174 μL of triethylamine were added. The mixture was heated to 180 °C under a nitrogen flow. After reaching 180 °C, the polymerization reaction was carried out for 4 hours. One hour after reaching 180 °C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to 80 °C, and NMP was added to obtain a 20% by mass solution of polyimide resin (PI) in NMP. The NMP solution was dropped into ethanol to reprecipitate the polyimide resin (PI), and the resulting powder was collected by suction filtration. The collected powder was washed with water and vacuum-dried in an oven at 80°C to obtain a powder of polyimide resin (PI-16).

[0091] [Synthesis example 1-17:PI-17] A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen. Then, 24 g of N-methyl-2-pyrrolidone (NMP) and 12.42 g (50 mmol) of 4,4'-diaminodiphenyl sulfone (44DAS) were added and stirred until homogenous. Then, 11.46 g (25 mmol) of 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BPAF), 20 g of NMP, 22.2 g of 1-butanol, and 174 μL of triethylamine were added. The mixture was heated to 180 °C under nitrogen flow. After reaching 180 °C, the polymerization reaction was carried out for 4 hours. One hour after reaching 180 °C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to 80 °C, and NMP was added to obtain a 20% by mass NMP solution of polyimide resin (PI). The NMP solution was dropped into ethanol to reprecipitate the polyimide resin (PI), and the resulting powder was collected by suction filtration. The collected powder was washed with water and dried in a vacuum oven at 80°C to obtain a powder of polyimide resin (PI-17).

[0092] [Synthesis example 1-18:PI-18] A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen. Then, 24 g of N-methyl-2-pyrrolidone (NMP) and 12.42 g (50 mmol) of 3,3'-diaminodiphenyl sulfone (33DAS) were added and stirred until homogenous. Then, 11.46 g (25 mmol) of 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BPAF), 20 g of NMP, 22.2 g of 1-butanol, and 174 μL of triethylamine were added. The mixture was heated to 180 °C under nitrogen flow. After reaching 180 °C, the polymerization reaction was carried out for 4 hours. One hour after reaching 180 °C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to 80 °C, and NMP was added to obtain a 20% by mass solution of polyimide resin (PI) in NMP. The NMP solution was dropped into ethanol to reprecipitate the polyimide resin (PI), and the resulting powder was collected by suction filtration. The collected powder was washed with water and dried in a vacuum oven at 80°C to obtain a powder of polyimide resin (PI-18).

[0093] [Synthesis example 1-19:PI-19] A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen. Then, 28 g of N-methyl-2-pyrrolidone (NMP) and 14.62 g (50 mmol) of 1,3-bis(3-aminophenoxy)benzene (TPE-M) were added and stirred until homogenous. Then, 11.46 g (25 mmol) of 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BPAF), 20 g of NMP, 22.8 g of 1-butanol, and 174 μL of triethylamine were added. The mixture was heated to 180 °C under nitrogen flow. After reaching 180 °C, the polymerization reaction was carried out for 4 hours. One hour after reaching 180 °C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to 80 °C, and NMP was added to obtain a 20% by mass solution of polyimide resin (PI) in NMP. The NMP solution was dropped into ethanol to reprecipitate the polyimide resin (PI), and the resulting powder was collected by suction filtration. The collected powder was washed with water and dried in a vacuum oven at 80°C to obtain a powder of polyimide resin (PI-19).

[0094] [Synthesis example 1-20: PI-20] A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen. Then, 20 g of N-methyl-2-pyrrolidone (NMP) and 10.01 g (50 mmol) of 3,4'-diaminodiphenyl ether (34ODA) were added and stirred until homogenous. Then, 11.46 g (25 mmol) of 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BPAF), 20 g of NMP, 21.5 g of 1-butanol, and 174 μL of triethylamine were added. The mixture was heated to 180 °C under nitrogen flow. After reaching 180 °C, the polymerization reaction was carried out for 4 hours. One hour after reaching 180 °C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to 80 °C, and NMP was added to obtain a 20% by mass solution of polyimide resin (PI) in NMP. The NMP solution was dropped into ethanol to reprecipitate the polyimide resin (PI), and the resin powder was collected by suction filtration. The collected powder was washed with water and vacuum dried in an oven at 80°C to obtain polyimide resin (PI-20) powder.

[0095] [Synthesis example 1-21: PI-21] A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen. Then, 21 g of N-methyl-2-pyrrolidone (NMP) and 10.62 g (50 mmol) of m-tolidine (m-TB) were added and stirred until homogenous. Then, 11.46 g (25 mmol) of 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BPAF), 20 g of NMP, 21.7 g of 1-butanol, and 174 μL of triethylamine were added. The mixture was heated to 180 °C under nitrogen flow. After reaching 180 °C, the polymerization reaction was carried out for 4 hours. One hour after reaching 180 °C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to 80 °C, and NMP was added to obtain a 20% by mass solution of polyimide resin (PI) in NMP. The NMP solution was dropped into ethanol to reprecipitate the polyimide resin (PI), and the resulting powder was collected by suction filtration. The collected powder was washed with water and dried in a vacuum oven at 80°C to obtain a powder of polyimide resin (PI-21).

[0096] [Synthesis example 1-22: PI-22] A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen. Then, 30 g of N-methyl-2-pyrrolidone (NMP) and 20.53 g (50 mmol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) were added and stirred until homogenous. Then, 11.46 g (25 mmol) of 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BPAF), 29 g of NMP, 25 g of 1-butanol, and 174 μL of triethylamine were added. The mixture was heated to 180 °C under nitrogen flow. After reaching 180 °C, the polymerization reaction was carried out for 4 hours. One hour after reaching 180 °C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to 80 °C, and NMP was added to obtain a 20% by weight NMP solution of polyimide resin (PI). The NMP solution was dropped into ethanol to reprecipitate the polyimide resin (PI), and the resin powder was collected by suction filtration. The collected powder was washed with water and vacuum dried in an oven at 80°C to obtain polyimide resin (PI-22) powder.

[0097] [Synthesis example 1-23: PI-23] A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen. Then, 34 g of N-methyl-2-pyrrolidone (NMP) and 17.43 g (50 mmol) of 9,9-bis(4-aminophenyl)fluorene (BAFL) were added and stirred until homogenous. Then, 11.46 g (25 mmol) of 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BPAF), 20 g of NMP, 23.6 g of 1-butanol, and 174 μL of triethylamine were added. The mixture was heated to 180 °C under nitrogen flow. After reaching 180 °C, the polymerization reaction was carried out for 4 hours. One hour after reaching 180 °C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to 80 °C, and NMP was added to obtain a 20% by weight NMP solution of polyimide resin (PI). The NMP solution was dropped into ethanol to reprecipitate the polyimide resin (PI), and the resulting powder was collected by suction filtration. The collected powder was washed with water and vacuum-dried in an oven at 80°C to obtain a powder of polyimide resin (PI-23).

[0098] [Synthesis example 1-24: PI-24] A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen. Then, 20 g of N-methyl-2-pyrrolidone (NMP) and 8.91 g (50 mmol) of Ethacure 100 Plus were added and stirred until homogenous. Then, 11.46 g (25 mmol) of 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BPAF), 18 g of NMP, 21.2 g of 1-butanol, and 174 μL of triethylamine were added. The mixture was heated to 180 °C under nitrogen flow. After reaching 180 °C, the polymerization reaction was carried out for 4 hours. One hour after reaching 180 °C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to 80 °C, and NMP was added to obtain a 20% by weight NMP solution of polyimide resin (PI). The NMP solution was dropped into ethanol to reprecipitate the polyimide resin (PI), and the resulting powder was collected by suction filtration. The collected powder was washed with water and dried in a vacuum oven at 80°C to obtain a powder of polyimide resin (PI-24).

[0099] [Synthesis example 1-25: PI-25] A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen, and then 21 g of N-methyl-2-pyrrolidone (NMP) and 10.72 g (50 mmol) of Ethacure 300 were added and stirred until homogenous. Then, 11.46 g (25 mmol) of 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BPAF), 20 g of NMP, 21.8 g of 1-butanol, and 174 μL of triethylamine were added. The mixture was heated to 180 °C under a nitrogen flow. After reaching 180 °C, the polymerization reaction was carried out for 4 hours. One hour after reaching 180 °C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to 80 °C, and NMP was added to obtain a 20% by mass NMP solution of polyimide resin (PI). The NMP solution was dropped into ethanol to reprecipitate the polyimide resin (PI), and the resulting powder was collected by suction filtration. The collected powder was washed with water and vacuum-dried in an oven at 80°C to obtain a powder of polyimide resin (PI-25).

[0100] [Synthesis example 1-26: PI-26] A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen, and then 15 g of N-methyl-2-pyrrolidone (NMP) and 6.42 g (36 mmol) of Ethacure® 100 Plus were added and stirred until homogenous. Next, 8.83 g (30 mmol) of biphenyltetracarboxylic dianhydride (BPDA), 13 g of NMP, 19.5 g of 1-butanol, and 209 μL of triethylamine were added. The mixture was stirred at room temperature for 1 hour under a nitrogen flow to carry out an addition reaction. The mixture was then heated to 180°C, and after reaching 180°C, dehydration ring closure was carried out for 4 hours. One hour after reaching 180°C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to an internal temperature of 80°C, and NMP was added to obtain a 20% by mass NMP solution of polyimide resin (PI). The NMP solution was dropped into ethanol to reprecipitate the polyimide resin (PI), and the resulting powder was collected by suction filtration. The collected powder was washed with water and then vacuum-dried in an oven at 80°C for 4 hours to obtain a powder of polyimide resin (PI-26).

[0101] [Synthesis example 1-27:PI-27] A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen, and then 15 g of N-methyl-2-pyrrolidone (NMP) and 8.02 g (45 mmol) of Ethacure® 100 Plus were added and stirred until homogenous. Next, 8.83 g (30 mmol) of biphenyltetracarboxylic dianhydride (BPDA), 16 g of NMP, 20.0 g of 1-butanol, and 209 μL of triethylamine were added. The mixture was stirred at room temperature for 1 hour under a nitrogen flow to carry out an addition reaction. The mixture was then heated to 180°C, and after reaching 180°C, dehydration ring closure was carried out for 4 hours. One hour after reaching 180°C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to an internal temperature of 80°C, and NMP was added to obtain a 20% by mass NMP solution of polyimide resin (PI). The NMP solution was dropped into ethanol to reprecipitate the polyimide resin (PI), and the resulting powder was collected by suction filtration. The collected powder was washed with water and then vacuum-dried in an oven at 80°C for 4 hours to obtain a powder of polyimide resin (PI-27).

[0102] [Synthesis example 1-28:PI-28] A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen, and then 15 g of N-methyl-2-pyrrolidone (NMP) and 6.42 g (36 mmol) of Ethacure® 100 Plus were added and stirred until homogenous. Next, 9.31 g (30 mmol) of 4,4'-oxydiphthalic anhydride (ODPA), 14 g of NMP, 19.9 g of 1-butanol, and 209 μL of triethylamine were added. The mixture was stirred at room temperature for 1 hour under a nitrogen flow to carry out an addition reaction. The mixture was then heated to 180°C, and after reaching 180°C, dehydration ring closure was carried out for 4 hours. One hour after reaching 180°C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to an internal temperature of 80°C, and NMP was added to obtain a 20% by mass NMP solution of polyimide resin (PI). The NMP solution was dropped into ethanol to reprecipitate the polyimide resin (PI), and the resulting powder was collected by suction filtration. The collected powder was washed with water and then vacuum-dried in an oven at 80°C for 4 hours to obtain a powder of polyimide resin (PI-28).

[0103] [Synthesis example 1-29:PI-29] A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen, and then 15 g of N-methyl-2-pyrrolidone (NMP) and 8.02 g (45 mmol) of Ethacure® 100 Plus were added and stirred until homogenous. Next, 9.31 g (30 mmol) of 4,4'-oxydiphthalic anhydride (ODPA), 17 g of NMP, 20.3 g of 1-butanol, and 209 μL of triethylamine were added. The mixture was stirred at room temperature for 1 hour under a nitrogen flow to carry out an addition reaction. The mixture was then heated to 180°C, and after reaching 180°C, dehydration ring closure was carried out for 4 hours. One hour after reaching 180°C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to an internal temperature of 80°C, and NMP was added to obtain a 20% by mass NMP solution of polyimide resin (PI). The NMP solution was dropped into ethanol to reprecipitate the polyimide resin (PI), and the resulting powder was collected by suction filtration. The collected powder was washed with water and then vacuum-dried in an oven at 80°C for 4 hours to obtain a powder of polyimide resin (PI-29).

[0104] (Synthesis Example 1-30) A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen, and then 15 g of N-methyl-2-pyrrolidone (NMP) and 6.15 g (34.5 mmol) of Ethacure® 100 Plus were added and stirred until homogenous. Next, 8.83 g (30 mmol) of biphenyltetracarboxylic dianhydride (BPDA), 12 g of NMP, 19.5 g of 1-butanol, and 209 μL of triethylamine were added. The mixture was stirred at room temperature for 1 hour under a nitrogen flow to carry out an addition reaction. The mixture was then heated to 180°C, and after reaching 180°C, dehydration ring closure was carried out for 4 hours. One hour after reaching 180°C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to an internal temperature of 80°C, and NMP was added to obtain a 20% by mass NMP solution of polyimide resin (PI). The NMP solution was dropped into ethanol to reprecipitate the polyimide resin (PI), and the resulting powder was collected by suction filtration. The collected powder was washed with water and then vacuum-dried in an oven at 80°C for 4 hours to obtain a powder of polyimide resin (PI-30).

[0105] Table 1 below shows polyimides PI-1 to PI-30 of Synthesis Examples 1-1 to 1-30, along with the acid dianhydrides and diamines used and the molar ratio of diamine / acid dianhydride.

[0106] [Table 1]

[0107] ((C) Hardener) <Preparation of Curing Agent> [Synthesis Example 2-1: Curing Agent (A-1)] A 500 ml four-neck flask equipped with a reflux condenser and stirring blade was purged with nitrogen, and then 20 g of 1-butanol and 0.05 mol of 4,4'-diaminodiphenyl sulfone (44DAS) were added and heated to an internal temperature of 120°C. Then, using a dropping funnel, 0.03 mol of 2-ethylhexyl glycidyl ether (2-EH) was added dropwise over 30 minutes. After the dropwise addition was complete, the reaction solution was heated at 120°C for 6 hours while stirring to complete the reaction. The resulting solution was distilled off 1-butanol over 2 hours using an evaporator, maintaining the temperature at 80°C and the pressure at 15 mmHg or less, to obtain epoxy resin curing agent (A-1).

[0108] [Synthesis Example 2-2: Curing agent (A-2)] Synthesis and purification were carried out under the same conditions as in Synthesis Example 2-1, except that 0.03 mol of 2-ethylhexyl glycidyl ether (2-EH) was changed to 0.035 mol of butyl glycidyl ether (BGE), to obtain a curing agent (A-2) for epoxy resins.

[0109] [Synthesis Example 2-3: Amine Adduct (B)] Synthesis and purification were carried out under the same conditions as in Synthesis Example 2-1, except that 4,4'-diaminodiphenyl sulfone (44DAS) was changed to 1,3-bis(3-aminophenoxy)benzene (TPE-M), to obtain an amine adduct (B).

[0110] [Synthesis Example 2-4: Amine adduct (C-1)] Synthesis and purification were carried out under the same conditions as in Synthesis Example 2-1, except that 4,4'-diaminodiphenyl sulfone (44DAS) was changed to 4-aminophenyl-4'-aminobenzoate (APAB) and 2-ethylhexyl glycidyl ether (2-EH) was changed from 0.03 mol to 0.05 mol, to obtain an amine adduct (C-1).

[0111] [Synthesis Example 2-5: Amine adduct (C-2)] Synthesis and purification were carried out under the same conditions as in Synthesis Example 2-4, except that 2-ethylhexyl glycidyl ether (2-EH) was changed to butyl glycidyl ether (BGE), to obtain an amine adduct (C-2).

[0112] [Synthesis Example 2-6: Amine adduct (D-1)] Synthesis and purification were carried out under the same conditions as in Synthesis Example 2-1, except that 4,4'-diaminodiphenyl sulfone (44DAS) was changed to 3,4'-oxydianiline (34ODA) and 2-ethylhexyl glycidyl ether (2-EH) was changed from 0.03 mol to 0.05 mol, to obtain an amine adduct (D-1).

[0113] [Synthesis Example 2-7: Amine adduct (D-2)] Synthesis and purification were carried out under the same conditions as in Synthesis Example 2-6, except that 2-ethylhexyl glycidyl ether (2-EH) was changed to butyl glycidyl ether (BGE), to obtain an amine adduct (D-2).

[0114] [Synthesis Example 2-8: Amine adduct (E-1)] Synthesis and purification were carried out under the same conditions as in Synthesis Example 2-1, except that 4,4'-diaminodiphenyl sulfone (44DAS) was changed to Kayahard AA and 2-ethylhexyl glycidyl ether (2-EH) was changed from 0.03 mol to 0.04 mol, to obtain an amine adduct (E-1).

[0115] [Synthesis Example 2-9: Amine adduct (E-2)] Synthesis and purification were carried out under the same conditions as in Synthesis Example 2-8, except that 2-ethylhexyl glycidyl ether (2-EH) was changed to phenyl glycidyl ether (ph-GE), to obtain an amine adduct (E-2).

[0116] [Synthesis Example 2-10: Amine adduct (F-1)] Synthesis and purification were carried out under the same conditions as in Synthesis Example 2-1, except that 4,4'-diaminodiphenyl sulfone (44DAS) was changed to Ethacure 100 Plus and 2-ethylhexyl glycidyl ether (2-EH) was changed from 0.03 mol to 0.025 mol, to obtain an amine adduct (F-1).

[0117] [Synthesis Example 2-11: Amine adduct (F-2)] Synthesis and purification were carried out under the same conditions as in Synthesis Example 2-10, except that 0.025 mol of 2-ethylhexyl glycidyl ether (2-EH) was changed to 0.03 mol of butyl glycidyl ether (BGE), to obtain an amine adduct (F-2).

[0118] [Synthesis Example 2-12: Amine adduct (F-3)] Synthesis and purification were carried out under the same conditions as in Synthesis Example 2-10, except that 0.025 mol of 2-ethylhexyl glycidyl ether (2-EH) was changed to 0.035 mol of phenyl glycidyl ether (ph-GE), to obtain an amine adduct (F-3).

[0119] [Synthesis Example 2-13: Amine adduct (G)] Synthesis and purification were carried out under the same conditions as in Synthesis Example 2-1, except that 4,4'-diaminodiphenyl sulfone (44DAS) was changed to Ethacure 300, to obtain an amine adduct (G).

[0120] Table 2 below shows the curing agents of Synthesis Examples 2-1 to 2-13, along with the aromatic amines and reactive compounds used.

[0121] [Table 2]

[0122] ((E) Curing accelerator) <Preparation of Curing Accelerator> [Compound: Preparation of a mixture containing compound (E-1A) and compound (E-1B)] 7.20 g (0.07 mol) of ethyl propionate, 13.17 g (0.0245 mol) of Denacol EX-830, and 1.67 g (0.0105 mol) of EX-830CRP were weighed into a recovery flask, and the flask was heated in an oil bath to 90 ° C. Next, 6.00 g (0.06 mol) of 1-aminopiperidine was added dropwise over 15 minutes. After the completion of the addition, the mixture was stirred for 4 hours while maintaining the temperature at 90 ° C., and the reaction was completed. The resulting reaction solution was concentrated under reduced pressure at 80 ° C. to remove the by-product alcohol and unreacted raw materials, and a mixture containing the liquid product compounds: Compound (E-1A) and Compound (E-1B) was obtained. In the table below, such a mixture is designated as compound E-1A / E-1B. The structures of compound (E-1A) and compound (E-1B) are shown below.

[0123] [ka]

[0124] [Preparation of Compound (E-1C)] 3.93 g (0.038 mol) of ethyl propionate and 5.00 g (0.038 mol) of butyl glycidyl ether were weighed into a recovery flask, and the flask was heated in an oil bath to 90 ° C. Next, 3.85 g (0.038 mol) of 1-aminopiperidine was added dropwise over 15 minutes. After the completion of the addition, the mixture was stirred for 4 hours while maintaining the temperature at 90 ° C., and the reaction was completed. The resulting reaction solution was concentrated under reduced pressure at 80 ° C. to remove the by-product alcohol and unreacted raw materials, and a liquid product, compound (E-1C), was obtained. The structure of compound (E-1C) is shown below.

[0125] [ka]

[0126] [Preparation of Compound (E-1D)] 1.94 g (0.019 mol) of ethyl propionate and 5.00 g (0.009 mol) of polyethylene glycol diglycidyl ether were weighed into a recovery flask, and the flask was heated in an oil bath to 90 °C. Next, 1.62 g (0.016 mol) of 1-aminopiperidine was added dropwise over 15 minutes. After the completion of the addition, the mixture was stirred for 4 hours while maintaining the temperature at 90 °C, and the reaction was completed. The resulting reaction solution was concentrated under reduced pressure at 80 °C to remove the by-product alcohol and unreacted raw materials, yielding the liquid product, Compound (E-1D). The structure of compound (E-1D) is shown below.

[0127] [ka]

[0128] [Examples 1 to 56], [Comparative Example 1] Each component shown in Tables 3 to 8 below was placed in a plastic stirring vessel in the amount shown in the table, and the mixture was stirred and mixed using a planetary centrifugal mixer ("ARE-310" manufactured by Thinky Corporation), followed by kneading using a three-roll mill to prepare an epoxy resin composition. The PI powder may be dispersed or dissolved in advance in an epoxy resin or a hardener.

[0129] [Table 3]

[0130] [Table 4]

[0131] [Table 5]

[0132] [Table 6]

[0133] [Table 7]

[0134] [Table 8]

[0135] As shown in the table above, all of the examples were cured products containing polyimide resins with excellent thermal properties, and therefore exhibited low coefficients of linear expansion (CTE). Furthermore, in the examples, the content of organic solvent in the epoxy resin composition was 1% by mass or less, so no voids were generated during the curing reaction. Furthermore, since the peak intensity of the IR spectrum correlates with the polyimide ratio, the effect of a low CTE was realized as long as it was within a preferred range. Therefore, the cured products of the examples were found to have excellent reliability due to the absence of voids that could be the starting point for cracks and the low CTE. Comparative Example 1 contained a large amount of organic solvent, which evaporated during the curing reaction, resulting in the generation of numerous voids, with the void area ratio exceeding 1%. Furthermore, even though polyimide resin was included, the residual organic solvent increased the CTE. When such a material was used, cracks and other problems were more likely to occur from the voids, resulting in reduced reliability. Furthermore, as the CTE increased, the stress applied due to CTE mismatch during thermal expansion and contraction increased, reducing reliability. [Industrial Applicability]

[0136] The structure of the present invention has industrial applicability as a semiconductor chip.

Claims

1. a first layer, a second layer, and a plurality of copper pillars connecting the first layer and the second layer; the first layer and the second layer each contain at least one material selected from the group consisting of resin, silicon, ceramics, a compound semiconductor, and glass; Among the plurality of copper pillars, the distance between adjacent copper pillars is 150 μm or less, a third layer is disposed between the first layer and the second layer and is in contact with each of the first layer and the second layer; the third layer is a cured product of an epoxy resin composition containing an epoxy resin, a polyimide resin, and an inorganic filler, the area ratio of voids to the surface area of ​​the third layer is 1% or less; structure.

2. the epoxy resin composition contains an organic solvent in an amount of 1% by mass or less; The structure of claim 1 .

3. The third layer is Infrared (IR) absorption spectrum: 1,700 to 1,800 cm -1 The maximum peak intensity Ia present in the range of 1,450 to 1,550 cm -1 and the maximum peak intensity Ib present in the range satisfies the following formula (i): The structure of claim 1 . 0.1≦Ia / Ib≦0.5...(i)

4. A cured product used for a third layer between a first layer and a second layer connected by a plurality of copper pillars, the distance between adjacent copper pillars being 150 μm or less, the cured product constituting the third layer is a cured product of an epoxy resin composition containing an epoxy resin, a polyimide resin, and an inorganic filler, the area ratio of voids to the surface area of ​​the third layer is 1% or less; cured product.

5. the epoxy resin composition contains an organic solvent in an amount of 1% by mass or less; The cured product according to claim 4.

6. Infrared (IR) absorption spectrum: 1,700 to 1,800 cm -1 The maximum peak intensity Ia present in the range of 1,450 to 1,550 cm -1 and the maximum peak intensity Ib present in the range satisfies the following formula (i): The cured product according to claim 4. 0.1≦Ia / Ib≦0.5...(i)

7. An epoxy resin composition used for the cured product according to claim 4, Epoxy resin, polyimide resin, and inorganic filler, Epoxy resin composition.

8. A sealing material comprising the cured product according to claim 4 .

9. The encapsulant according to claim 8, which is used for encapsulating a semiconductor.

10. A semiconductor package comprising the encapsulant of claim 8.

11. A semiconductor package comprising the structure of any one of claims 1 to 3.

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