Resin composition, cured product, structure, encapsulation material, adhesive, semiconductor encapsulation body

Abstract

The invention provides a resin composition, a cured product, a structure, a sealing material, an adhesive, and a semiconductor package and a method for producing the same, the resin composition having excellent permeability despite the low content of an organic solvent, being capable of achieving both curability and storage stability, and not generating voids during curing. This resin composition contains an epoxy resin (A), a polyimide resin (B), a curing agent (C), and an inorganic filler (D), wherein the content of an organic solvent is 1% by mass or less in the resin composition.

Description

Technical Field

[0001] The present invention relates to a resin composition, a cured product, a structure, a packaging material, an adhesive, a semiconductor package and a method for manufacturing the same. Background Art

[0002] Epoxy resins are used in a wide range of applications, including coatings, electrical and electronic insulation materials, and adhesives, due to the various properties of their cured products.

[0003] Patent Document 1 describes an epoxy resin represented by a specific general formula.

[0004] Patent Document 2 describes an epoxy resin composition characterized in that it contains (A) an epoxy resin, (B) an aromatic amine-based curing agent, (C) a curing accelerator, and (D) a stabilizer, wherein the ratio of the equivalent of all amino groups in the aromatic amine-based curing agent (B) to 1 equivalent of all epoxy groups in the epoxy resin (A) is 0.7 to 1.5, the curing accelerator (C) is an organic boron compound selected from aryl borate salts or aryl borane complexes, and the stabilizer (D) contains an aryl phosphine.

[0005] Patent Document 3 describes a resin composition comprising (A) a solvent-soluble polyimide resin, (B) an epoxy resin having an anthracene skeleton, (C) a curing catalyst, and (D) an inorganic filler, wherein these components are dissolved or dispersed in an organic solvent. Furthermore, Patent Document 6 discloses a laminate obtained using the epoxy resin composition and a semiconductor device obtained using the laminate.

[0006] For example, Patent Document 4 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.

[0007] Patent Document 5 discloses a laminate for a mounting substrate having copper posts on a predetermined plastic film.

[0008] Prior art literature

[0009] Patent Literature

[0010] Patent Document 1: Japanese Patent Application Laid-Open No. 2015-199804

[0011] Patent Document 2: Japanese Patent Application Publication No. 2019-172738

[0012] Patent Document 3: Japanese Patent Application Laid-Open No. 2018-90664

[0013] Patent Document 4: International Publication No. 2016 / 143815

[0014] Patent Document 5: Japanese Patent Application Laid-Open No. 2015-230934 Summary of the Invention

[0015] Problems to be solved by the invention

[0016] Currently, as epoxy resin compositions generally used, there are so-called two-component epoxy resin compositions in which an epoxy resin and a curing agent are mixed before use.

[0017] Two-component epoxy resin compositions cure at room temperature, but the epoxy resin and curing agent are stored separately and then metered and mixed as needed before use. This complicates storage and handling. Furthermore, the limited usable time prevents pre-mixing of large quantities, increasing the frequency of mixing and inevitably reducing efficiency.

[0018] To solve the problems of two-component epoxy resin compositions, several one-component epoxy resin compositions have been proposed. For example, one example is an epoxy resin composition obtained by blending an epoxy resin curing agent with an epoxy resin.

[0019] However, recent demands on electronic devices are diverse. Examples of these demands include miniaturization, enhanced functionality, lightweighting, increased functionality, and multifunctionality. More specifically, in semiconductor chip mounting technology, there is a demand for further miniaturization, miniaturization, and increased density achieved through finer pitches between electrode pads and pad spacing.

[0020] Furthermore, underfill is used as an adhesive in the gap between the chip and the substrate to protect the bump connections and the chip's circuit surface. To meet the demand for higher-resolution pitches, underfill that can penetrate into narrower gaps is required.

[0021] Furthermore, as mentioned above, requirements for electronic devices include miniaturization, enhanced functionality, lightweighting, increased functionality, and multifunctionality. More specifically, semiconductor chip mounting requires high reliability against temperature fluctuations, i.e., no peeling, cracking, or warping. To meet these requirements, underfill has traditionally been used as an adhesive placed in the gap between the chip and the substrate to protect the bump connections and the chip's circuit surface and ensure reliability.

[0022] On the other hand, in recent years, the demand for finer pitch and larger area semiconductor chips in the aforementioned electronic equipment has increased. The finer pitch leads to poor filling of the bottom filler used as an adhesive, which causes the semiconductor chip to peel off and break, or the warping amount increases due to the larger area, which has become a problem.

[0023] As described above, a cured resin that is disposed in a gap between a chip and a substrate of an electronic device to protect a connection portion is required to have high reliability, and further improvement in reliability is being demanded in the future.

[0024] Furthermore, in recent years, demands for not only finer pitches but also larger areas of semiconductor chips have been increasing, which has the potential to increase the time it takes for underfill to penetrate. Consequently, underfills are also required to exhibit minimal viscosity changes in high-temperature environments during penetration and during storage.

[0025] As mentioned above, latent curing agents used in one-component epoxy resin compositions are required to achieve both good curability and storage stability after mixing with the epoxy resin. Furthermore, they are also required to have good penetration into fine areas, such as between densely packed fibers like carbon fibers and glass fibers, and in narrow gaps within electronic components.

[0026] The curing agent used in Patent Document 1 is in a solid state, and its permeability into narrow gaps still needs to be improved.

[0027] In Patent Document 2, a process such as adding additives is required to improve the storage stability and adhesiveness of the curing agent, and there is room for improvement from the viewpoint of storage and handling properties.

[0028] Patent documentation 3 is a resin combination comprising polyimide resin, but must be dissolved or dispersed in an organic solvent. Therefore, if used as bottom filler, then when solidifying, solvent also can volatilize, therefore, becomes the reason that produces void. In addition, when being coated on substrate and making film, fluidity is impaired, therefore, cannot be used as bottom filler. In addition, disclosed epoxy resin composition in patent documentation 3 comprises the solvent-soluble polyimide resin of inorganic filler and excellent heat resistance, therefore can think that the reliability of cured product becomes high, but must use organic solvent, when curing reaction, organic solvent can volatilize, therefore, likely produces void, causes reliability deterioration, therefore, has the problem that still has room for improvement.

[0029] The adhesive disclosed in Patent Document 4 does not contain an inorganic filler and therefore has a problem in that its linear expansion coefficient still needs to be improved.

[0030] The mounting substrate laminate disclosed in Patent Document 5 is formed using an organic solvent in the adhesive portion. This may cause voids to form due to volatilization of the residual solvent during the curing reaction, leading to reduced reliability. Therefore, there is still room for improvement.

[0031] The problem to be solved by the present invention is to provide a resin composition, a cured product, a packaging material, an adhesive, a semiconductor package and a method for manufacturing the same that have excellent permeability despite a low organic solvent content, can achieve both curability and storage stability, and does not generate voids during curing.

[0032] Another object of the present invention is to provide a structure having a cured product that is excellent in heat resistance, has suppressed void generation, and has high reliability.

[0033] Solutions for solving problems

[0034] In light of the aforementioned challenges of the prior art, the present inventors have conducted intensive research and have discovered that the aforementioned challenges of the prior art can be addressed by the following resin composition (hereinafter referred to as the "first resin composition" or "first epoxy resin composition") comprising an epoxy resin (A), a polyimide resin (B), a curing agent (C), and an inorganic filler (D), wherein the organic solvent content in the resin composition is 1% by mass or less, thereby completing the present invention. It should be noted that the "cured product of the first resin composition" and the "cured product of the first epoxy resin composition" are hereinafter referred to as the "first cured product."

[0035] Furthermore, the present inventors have conducted intensive research in view of the problems of the above-mentioned prior art and have discovered that, in a structure having a first layer and a second layer formed of specified materials, and a plurality of copper pillars arranged at specified intervals to connect the first and second layers, by providing a third layer formed from a cured product (hereinafter also referred to as a "second cured product") of an epoxy resin composition containing an epoxy resin, a polyimide resin, and an inorganic filler (hereinafter also referred to as a "second resin composition" or a "second epoxy resin composition") between the first and second layers, the pore volume of the third layer can be determined to be below a specified numerical range, thereby solving the problems of the above-mentioned prior art and completing the present invention.

[0036] The present invention includes the following technical solutions.

[0037] [1] A resin composition comprising an epoxy resin (A), a polyimide resin (B), a curing agent (C), and an inorganic filler (D), wherein the content of an organic solvent in the resin composition is 1% by mass or less.

[0038] [2] The resin composition according to [1], which has a viscosity at 25°C of 100 Pa·s or less.

[0039] [3] The resin composition according to [1] or [2], wherein the resin composition satisfies the following formula (I) at 110°C, where the viscosity at a shear rate of 10 / sec is V1 and the viscosity at a shear rate of 100 / sec is V2.

[0040] 0.8≤V1 / V2≤1.2…(I)

[0041] [4] The resin composition according to any one of [1] to [3], wherein the polyimide resin (B) comprises a condensate of tetracarboxylic dianhydride and a diamine, and the mixing ratio of the condensate (tetracarboxylic dianhydride:diamine) is 1.00:1.20 to 1.00:2.00 in terms of molar ratio.

[0042] [5] The resin composition according to any one of [1] to [4], wherein the curing agent (C) comprises an aromatic amine compound (C-1) and an aromatic amine adduct (C-2), wherein the aromatic amine adduct (C-2) is a reaction product of the aromatic amine compound (C-1) and a reactive compound having a functional group capable of reacting with the aromatic amine compound (C-1), and the aromatic amine adduct (C-2) comprises an aromatic amine adduct (C-2-1) obtained by adding one molecule of the reactive compound to one molecule of the aromatic amine compound (C-1).

[0043] [6] The resin composition according to [5], wherein the aromatic amine compound (C-1) is an aromatic amine compound represented by the following formula (1) or an aromatic amine compound represented by the following formula (2).

[0044]

[0045] (In formula (1), R1 and R2 each independently represent a monovalent organic group having 1 to 20 carbon atoms or a halogen atom, a and b each independently represent an integer of 0 to 4, and X represents a divalent organic group or a single bond.)

[0046]

[0047] (In formula (2), R3 each independently represents a monovalent organic group having 1 to 20 carbon atoms or a halogen atom, and c is an integer of 1 to 4.)

[0048] [7] The resin composition according to [5] or [6], wherein the reactive compound is an epoxy compound having one glycidyl group in the molecule.

[0049] [8] The resin composition according to any one of [1] to [7], further comprising a curing accelerator (E).

[0050] [9] The resin composition according to [8], wherein the viscosity after standing at 110°C for 60 minutes is 0.01 Pa·s to 4.50 Pa·s.

[0051]

[10] A cured product comprising the resin composition according to any one of [1] to [9].

[0052]

[11] A structure comprising a first layer, a second layer, and a plurality of copper pillars connecting the first layer and the second layer, wherein the first layer and the second layer each comprise at least one selected from the group consisting of resin, silicon, ceramic, compound semiconductor, and glass, wherein the distance between adjacent copper pillars is less than 150 μm, and a third layer is provided between the first layer and the second layer, the third layer being the cured product described in

[10] , and the ratio of the area of ​​the pores to the surface area of ​​the third layer is less than 1%.

[0053]

[12] The structure according to

[11] , wherein the third layer has an infrared (IR) absorption spectrum in the range of 1,700 to 1,800 cm -1 The maximum peak intensity Ia in the range of 1,450-1,550 cm -1 The maximum peak intensity Ib within the range satisfies the following formula (i).

[0054] 0.1≤Ia / Ib≤0.5…(i)

[0055]

[13] A cured product used to form a third layer between a first layer and a second layer connected by a plurality of copper pillars having a distance between adjacent copper pillars of 150 μm or less, wherein 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, and the ratio of the area of ​​the pores to the surface area of ​​the third layer is 1% or less.

[0056]

[14] A structure comprising a first layer, a second layer, and a plurality of copper pillars connecting the first layer and the second layer, wherein the first layer and the second layer each comprise at least one selected from the group consisting of resin, silicon, ceramic, compound semiconductor, and glass, wherein the distance between adjacent copper pillars is 150 μm or less, and a third layer is provided between the first layer and the second layer and in contact with each of the first and second layers.

[0057] The third layer is the cured product described in

[13] , and the ratio of the area of ​​the pores to the surface area of ​​the third layer is 1% or less.

[0058]

[15] The cured product according to

[13] or

[14] , wherein the organic solvent contained in the epoxy resin composition is 1% by mass or less.

[0059]

[16] The cured product according to

[10] ,

[13] or

[15] , wherein the infrared (IR) absorption spectrum has a wavelength of 1,700 to 1,800 cm -1 The maximum peak intensity Ia in the range of 1,450-1,550 cm -1 The maximum peak intensity Ib within the range satisfies the following formula (i).

[0060] 0.1≤Ia / Ib≤0.5…(i)

[0061]

[17] A packaging material comprising the cured product described in

[10] or

[13] .

[0062]

[18] The packaging material according to

[17] , which is a packaging material for semiconductors.

[0063]

[19] An adhesive comprising the resin composition according to any one of [1] to [9].

[0064]

[20] A semiconductor package comprising the cured product described in

[10] or

[13] .

[0065]

[21] A method for manufacturing a semiconductor package, comprising: using the resin composition according to any one of [1] to [9] to manufacture the semiconductor package.

[0066] Effects of the Invention

[0067] The present invention can provide a resin composition, a cured product, a packaging material, an adhesive, a semiconductor package, and a method for producing the same, which have excellent permeability despite a low organic solvent content, achieve both curability and storage stability, and do not generate voids during curing.

[0068] According to the present invention, a structure having a cured product that is excellent in heat resistance, has suppressed void generation, and has high reliability can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0069] Figure 1 1 shows an example of an image of a portion having pores of the second cured product of the second epoxy resin composition injected into a TEG (Test Element Group).

[0070] Figure 2 ] shows an example of an image of a portion without voids of the second cured product of the second epoxy resin composition injected into a TEG (Test Element Group). DETAILED DESCRIPTION

[0071] Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “this embodiment”) will be described in detail.

[0072] The following embodiments are examples for explaining the present invention and are not intended to limit the present invention to the following contents. The present invention can be implemented with appropriate modifications within the scope of the present invention.

[0073] In addition, when "to" is used in this specification and a numerical value or a physical property value is sandwiched before and after it, it is used as a form including the values ​​before and after it.

[0074] Within the numerical ranges described in this specification, the upper limit or lower limit of one numerical range may be replaced by the upper limit or lower limit of another numerical range described in another stage. In addition, within the numerical ranges described in this specification, the upper limit or lower limit of the numerical range may be replaced by the values ​​shown in the Examples.

[0075] In the description of groups (atomic groups) in this specification, the description without mentioning substitution and unsubstituted includes both the case of having no substituent and the case of having substituent. For example, "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups).

[0076] <<First Resin Composition>>

[0077] The first resin composition of this embodiment (hereinafter also referred to as the "first epoxy resin composition") contains an epoxy resin (A), a polyimide (B), a curing agent (C) and an inorganic filler (D), and the content of the organic solvent in the first resin composition is 1% by mass or less.

[0078] <Epoxy Resin (A)>

[0079] The first resin composition contains an epoxy resin (A).

[0080] As the epoxy resin, any commonly used epoxy resin can be used without particular limitation, but preferably, an epoxy resin has two or more epoxy groups in one molecule.

[0081] The epoxy resin may be solid or liquid at room temperature, but is preferably liquid at room temperature from the perspective of fillability. The epoxy resin may be particularly liquid at room temperature (hereinafter also referred to as "liquid epoxy resin"), and commonly used liquid epoxy resins may be used.

[0082] The viscosity of the liquid epoxy resin measured at room temperature using an E-type viscometer is preferably, for example, 0.0001 to 10 Pa·s.

[0083] Examples of epoxy resins include diglycidyl ether epoxy resins such as bisphenol-type epoxy resins, such as 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, such as o-cresol novolac epoxy resins; glycidyl ester epoxy resins obtained by reacting polyacids such as phthalic acid and dimer acid with epichlorohydrin; glycidyl amine epoxy resins obtained by reacting amine compounds such as p-aminophenol, diaminodiphenylmethane, and isocyanuric acid with epichlorohydrin; and linear aliphatic and cycloaliphatic epoxy resins obtained by oxidizing olefin bonds with peracids such as peracetic acid. The epoxy resins may be used alone or in combination of two or more.

[0084] Among these, bisphenol-type epoxy resins are preferred from the viewpoint of fluidity, and glycidylamine-type epoxy resins are preferred from the viewpoint of heat resistance, adhesion, and fluidity.

[0085] The epoxy resin is preferably at least one selected from the group consisting of bisphenol-type epoxy resins and glycidylamine-type epoxy resins.

[0086] The bisphenol epoxy resin is preferably at least one selected from the group consisting of diglycidyl ether epoxy resins of bisphenol A (bisphenol A epoxy resin) and diglycidyl ether epoxy resins of bisphenol F (bisphenol F epoxy resin) from the viewpoint of fluidity.

[0087] When a naphthalene-type epoxy resin and a glycidylamine-type epoxy resin are used in combination, the mass ratio (naphthalene-type epoxy resin:glycidylamine-type epoxy resin) is not particularly limited. From the viewpoint of heat resistance, adhesion and fluidity, for example, it is preferably 5:95 to 50:50, more preferably 10:90 to 40:60, and even more preferably 20:80 to 40:60.

[0088] From the viewpoint of fluidity, both the bisphenol-type epoxy resin and the glycidylamine-type epoxy resin are preferably liquid at room temperature.

[0089] The total content of the bisphenol-type epoxy resin and the glycidylamine-type epoxy resin is not particularly limited. From the perspectives of heat resistance, adhesion, and fluidity, it is preferably 20% by mass or greater, more preferably 30% by mass or greater, even more preferably 50% by mass or greater, and particularly preferably 80% by mass or greater, relative to the total amount of the epoxy resin. The upper limit of the total content is not particularly limited; from the perspectives of viscosity, glass transition temperature, and heat resistance, it can be determined within a range that achieves desired properties and characteristics, and may be 100% by mass.

[0090] When a bisphenol-type epoxy resin and a glycidylamine-type epoxy resin are used in combination, the mass ratio (bisphenol-type epoxy resin:glycidylamine-type epoxy resin) is not particularly limited. From the viewpoint of heat resistance, adhesion and fluidity, for example, it is preferably 20:80 to 95:5, more preferably 40:60 to 90:10, and even more preferably 60:40 to 80:20.

[0091] In addition, in this embodiment, an epoxy resin that is solid at room temperature can also be used.

[0092] From the viewpoint of fluidity, 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 the epoxy resin.

[0093] The epoxy equivalent of the epoxy resin is not particularly limited, but is preferably 60 to 400 g / mol, more preferably 70 to 300 g / mol, and even more preferably 80 to 250 g / mol from the viewpoint of heat resistance.

[0094] Here, the epoxy equivalent is the mass of the 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 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 after dissolution in an ultrasonic cleaner, 10 mL of glacial acetic acid and 1.5 g of cetyltrimethylammonium bromide are added, and the mixture is titrated with a 0.1 mol / L perchloric acid / acetic acid solution to obtain the epoxy equivalent.

[0095] The epoxy resin preferably has a high purity. In particular, the amount of hydrolyzable chlorine is associated with corrosion of aluminum wiring on components such as ICs (Integrated Circuits), so it is preferably as low as possible. For example, from the perspective of excellent moisture resistance, it is preferably 1500 ppm or less.

[0096] Here, the amount of hydrolyzable chlorine is determined by dissolving 1 g of a sample epoxy resin in 30 mL of dioxane, adding 5 mL of a 1N-KOH (potassium hydroxide) methanol solution, and refluxing the mixture for 30 minutes, followed by potentiometric titration.

[0097] The content of the epoxy resin (A) is not particularly limited, but is preferably 10 to 50% by mass, more preferably 15 to 45% by mass, and even more preferably 20 to 40% by mass, based on the total amount (100% by mass) of the first resin composition from the viewpoint of heat resistance, adhesion, and fluidity.

[0098] <Polyimide resin (B)>

[0099] The first resin composition contains a polyimide resin (B).

[0100] As polyimide resin (B), for example, a condensate of tetracarboxylic dianhydride and diamine is included. As polyimide resin (B), there is no particular limitation, and for example, it can be obtained by a known method by causing a condensation reaction between tetracarboxylic dianhydride and diamine. That is, in an organic solvent, tetracarboxylic dianhydride and diamine are subjected to an addition reaction under the circulation of an inert gas such as nitrogen at a reaction temperature of 80°C or less, preferably 0 to 60°C. The time of the addition reaction is generally about 1 minute to 24 hours. As the reaction proceeds, the viscosity of the reaction solution slowly increases, generating a polyamic acid as a polyimide precursor. By causing the polyamic acid to undergo dehydration ring closure, a polyimide resin can be obtained. Dehydration ring closure can be carried out by a thermal ring closure method in which a heat treatment is performed or a chemical ring closure method using a dehydrating agent. The heating temperature in the thermal ring closure method is generally 160 to 200°C, and the heating time is generally about 1 minute to 24 hours.

[0101] During the condensation reaction, the mixing ratio of tetracarboxylic dianhydride to diamine (tetracarboxylic dianhydride:diamine) is generally 1.00:1.00 to 1.00:2.00 in terms of molar ratio. From the perspective of further improving the compatibility between the polyimide resin (B) and the epoxy resin during composition formation and further improving the fluidity of the resulting composition, the mixing ratio of tetracarboxylic dianhydride to 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.

[0102] Although the mixing ratio of diamine to tetracarboxylic dianhydride can be 2.00 or more, tetracarboxylic dianhydride can react with only two diamines at most, and therefore the upper limit of the ratio is usually 2.00.

[0103] The condensation reaction can be carried out using an amine catalyst. Examples of such catalysts include triethylamine.

[0104] The tetracarboxylic dianhydride used as a raw material of the polyimide resin is not particularly limited, and examples thereof include 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 5-(2,5-dioxotetrahydro-3-furyl)-3-methyl-cyclohexene-1,2-dicarboxylic 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 (hereinafter also referred to as "BPDA"), 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, and 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-ethylidene-4,4'-diphthalic dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene-4,4'-diphthalic dianhydride, 4,4'-oxydiphthalic dianhydride (hereinafter also referred to as "ODPA"), p-phenylenebis(trimellitic anhydride) (hereinafter also referred to as "TAHQ"), 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (hereinafter also referred to as BPAF), sulfonyl-4,4'-diphthalic dianhydride, 1,3-bis(3,4-dicarboxyphenyl)phthalic dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)phthalic dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)phthalic dianhydride, 1,3-bis[2-(3,4-dicarboxyphenyl)-2-propyl]phthalic dianhydride, 1,4-bis[2-(3,4-dicarboxyphenyl)-2-propyl]phthalic 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, 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]-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, cyclopentanonebisspironorbornanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic 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 (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 and ethylene glycol-bis-3,4-dicarboxylic acid anhydride phenyl) ether, etc. Tetracarboxylic dianhydride may be used alone or in combination of two or more.

[0105] The diamine used as a raw material of the polyimide resin is not particularly limited, and examples thereof include 4-aminophenyl-4'-aminobenzoate (hereinafter also referred to as "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, 4,4'-diaminobenzanilide, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether (hereinafter also referred to as "34ODA"), 3,3'-diaminodiphenyl ether, 4,4'-diaminobenzanilide, 4,4'-diaminodiphenyl ether, 3,4 ... Diphenyl sulfone (hereinafter also referred to as "44DAS"), 3,3'-diaminodiphenyl sulfone (hereinafter also referred to as "33DAS"), 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 (hereinafter also referred to as "TPE-M"), 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-aminophenoxy)phenyl )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 (hereinafter also referred to as "BAPP"), 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, m-tolidine (hereinafter also referred to as "m-TB"), 9,9-bis(4-aminophenyl)fluorene (hereinafter also referred to as "BAFL"), 2,2'-bis(trifluoromethyl)benzidine, 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'-diaminodiphenyldifluoromethane, 3,4'-diaminodiphenyldifluoromethane, 4,4'-diaminodiphenyldifluoromethane, 3,4'-diaminodiphenylsulfone, 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))dianiline, 3,4'-(1,4-phenylenebis(1-methylethylidene))dianiline, 4,4'-(1,4-phenylenebis(1-methylethylidene))dianiline, 2,2-bis(4-(3-aminophenoxy)benzene Bis(4-(4-aminoethoxy)phenyl)sulfide, bis(4-(4-aminoethoxy)phenyl)sulfide, bis(4-(3-aminoethoxy)phenyl)sulfone, bis(4-(4-aminoethoxy)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), and dimethylthiotoluenediamine. The polyimide resin may be used alone or in combination of two or more.

[0106] In addition, as the raw material of the polyimide resin, a commercially available product can be used. Examples of such commercially available products include ETHACURE (registered trademark) 100 Plus (+) (trade name, a curing agent containing diethyltoluenediamine, manufactured by Mitsui Fine Chemicals) and ETHACURE (registered trademark) 300 (trade name, a curing agent containing diethylthiotoluenediamine, manufactured by Mitsui Fine Chemicals).

[0107] <Organic Solvents>

[0108] The organic solvent used in synthesizing the polyimide resin using the above-mentioned compound and the above-mentioned method is not particularly limited, but is preferably an organic solvent capable of dissolving or dispersing the polyimide resin (B). Examples of such organic solvents include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and tert-butanol; 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; esters such as ethyl acetate and γ-butyrolactone; ethylene carbonate and propylene carbonate; Carbonates; 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-butylphosphoric acid. The organic solvents may be used alone or in combination of two or more.

[0109] The first resin composition of the present embodiment may include an organic solvent for synthesizing the above-mentioned polyimide resin. From the viewpoint of being able to more suitably suppress the generation of voids when making the first cured product, the content of the organic solvent is preferably less than 1% by mass in the first resin composition. The content of the organic solvent is preferably less than 0.7% by mass in the first resin composition, more preferably less than 0.5% by mass. It should be noted that the lower limit of the content of the organic solvent is not particularly limited, and can be less than the detection limit, and the detection limit is more than 1ppm. In addition, from the viewpoint of further improving the compatibility of the epoxy resin, the curing agent and the polyimide, and further improving the fluidity of the composition, the content of the organic solvent is preferably more than 0.01% by mass. As an organic solvent, as long as it is the above-mentioned content range, an organic solvent other than the organic solvent for synthesizing the polyimide resin can be included.

[0110] The content of the organic solvent in the first resin composition can be controlled by, for example, appropriately setting the drying conditions when drying the powder of the polyimide resin obtained by reprecipitation. For drying, it is preferred to use a vacuum oven to heat the powder of the polyimide resin at a temperature of 50 to 100°C under reduced pressure for 1 to 12 hours. Alternatively, the content of the organic solvent can be controlled by adding the powder of the polyimide resin when mixing it with the epoxy resin and the curing agent. As for the specific control method, it is sufficient to refer to the examples.

[0111] The content of the polyimide resin (B) is not particularly limited, but is preferably 1 to 20% by mass, more preferably 1 to 15% by mass, and even more preferably 2 to 15% by mass, based on the total amount (100% by mass) of the first resin composition, from the perspective of improving the reliability and permeability.

[0112] <Curing Agent (C)>

[0113] The first resin composition contains a curing agent (C).

[0114] Examples of the curing agent of this embodiment include aromatic amine compounds (C-1), aromatic amine adducts (C-2), acid anhydride curing agents, phenolic curing agents, and thiol curing agents. The curing agent may be used alone or in combination of two or more.

[0115] Examples of the acid anhydride curing agent 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.

[0116] The phenolic curing agent is not limited to the following substances, and examples thereof include phenol novolac resin, cresol novolac resin, phenol aralkyl resin, cresol aralkyl resin, naphthol aralkyl resin, biphenyl-modified phenolic resin, biphenyl-modified phenolic aralkyl resin, dicyclopentadiene-modified phenolic resin, aminotriazine-modified phenolic resin, naphthol novolac resin, naphthol-phenol co-condensation novolac resin, naphthol-cresol co-condensation novolac resin, and allyl acryloyl phenolic resin.

[0117] Examples of thiol-based curing agents include, but are not limited to, trimethylolpropane tris(thioglycolate), pentaerythritol tetra(thioglycolate), ethylene glycol dimercaptoacetate, trimethylolpropane tris(β-thiopropionate), pentaerythritol tetra(β-thiopropionate), and dipentaerythritol poly(β-thiopropionate); thiol compounds obtained by esterification of polyols with thiol organic acids; alkyl polythiol compounds such as 1,4-butanedithiol, 1,6-hexanedithiol, and 1,10-decanedithiol; polyethers containing a terminal thiol group, polythioethers containing a terminal thiol group, thiol compounds obtained by reaction of an epoxy compound with hydrogen sulfide; and thiol compounds having a terminal thiol group obtained by reaction of a polythiol with an epoxy compound.

[0118] The curing agent of this embodiment includes an aromatic amine compound (C-1) and an aromatic amine adduct (C-2), wherein the aromatic amine adduct (C-2) is a reaction product of the aromatic amine compound (C-1) and a reactive compound having a functional group capable of reacting with the aromatic amine compound (C-1), and the aromatic amine adduct (C-2) preferably includes an aromatic amine adduct (C-2-1) obtained by adding one molecule of the reactive compound to one molecule of the aromatic amine compound (C-1).

[0119] The curing agent of the present embodiment includes the above-mentioned components, and thus has excellent permeability after being mixed with the epoxy resin, and can achieve both curability and storage stability.

[0120] When the curing agent of this embodiment includes an aromatic amine adduct (C-2), it may include an aromatic amine adduct (C-2-1) obtained by adding one molecule of a reactive compound to one molecule of an aromatic amine compound (C-1) and an aromatic amine adduct (C-2-2X) obtained by adding two or more molecules of a reactive compound to one molecule of an aromatic amine compound (C-1).

[0121] Here, as aromatic amine compounds, electron-withdrawing amine compounds and amine compounds with multiple functional groups on their side chains have poor amine reactivity and excellent stability when formed into amine adducts. Therefore, the ratio (C-1 / C-2-1) of aromatic amine (C-1) to aromatic amine adduct (C-2-1) can be increased. In other words, aromatic amine adduct (C-2) contains aromatic amine adduct (C-2-1) obtained by adding one molecule of the reactive compound to one molecule of aromatic amine compound (C-1). Examples of the aromatic amine compounds include 4,4'-diaminodiphenyl sulfone (hereinafter also referred to as "44DAS"), diethyltoluenediamine (2,4-diamino-3,5-diethyltoluene, 2,6-diamino-3,5-diethyltoluene), and dimethylthiotoluenediamine. These aromatic amine compounds may be used alone or in combination of two or more.

[0122] In addition, as an electron-withdrawing amine compound and an amine compound having multiple functional groups in a side chain, a commercially available product can be used. Examples of such commercially available products include ETHACURE (registered trademark) 100 Plus (+) (trade name, a curing agent comprising diethyltoluenediamine, manufactured by Mitsui Fine Chemicals), ETHACURE (registered trademark) 300 (trade name, a curing agent comprising diethylthiotoluenediamine, manufactured by Mitsui Fine Chemicals), and KAYAHARD (registered trademark) AA (a curing agent comprising 3,3'-diethyl-4,4'-diaminodiphenylmethane, manufactured by Nippon Kayaku Co., Ltd.).

[0123] On the other hand, since aromatic amine compounds that lack electron-withdrawing properties and amine compounds that lack functional groups in their side chains are highly reactive as amines and exhibit excellent curability when formed into amine adducts, the ratio of aromatic amine (C-1) to aromatic amine adduct (C-2-1) can be reduced. In other words, aromatic amine adduct (C-2) comprises aromatic amine adduct (C-2-1) obtained by adding one molecule of a reactive compound to one molecule of aromatic amine compound (C-1). Aromatic amine compounds preferably have an -O-, -O-C6H4-O-, -CH2-, -CO-, -C(=O)O-, or -C(=O)NH- bond, and particularly, aromatic amines having a -C(=O)O- bond are preferred. Preferred aromatic amine compounds include 4-aminophenyl-4-aminobenzoate (hereinafter also referred to as "APAB"), 3,4'-diaminodiphenyl ether (hereinafter also referred to as "34ODA"), and 1,3-bis(3-aminophenoxy)benzene (hereinafter also referred to as "TPE-M"). Among them, 4-aminophenyl-4-aminobenzoate (APAB) is preferred. The aromatic amine compounds may be used alone or in combination of two or more.

[0124] From the viewpoint of curability and storage stability, among the peak areas of the aromatic amine compound (C-1), the aromatic amine adduct (C-2-1), and the aromatic amine adduct (C-2-2X) obtained by component analysis in the epoxy resin curing agent described below, the ratio of the peak area of ​​the aromatic amine compound (C-1) to the peak area of ​​the aromatic amine adduct (C-2-1) (C-1 / C-2-1) is preferably 0.1 to 3.0, more preferably 0.2 to 2.5, and even more preferably 0.3 to 2.0.

[0125] [Analysis of components in epoxy resin curing agents]

[0126] The analysis method for each component in the epoxy resin curing agent is as follows.

[0127] The amine adduct synthesized in the synthesis example was adjusted to a concentration of 10% by mass with THF (tetrahydrofuran), and then a 1 mg / mL acetonitrile solution was prepared and subjected to LC-MS (liquid chromatography-mass spectrometry) analysis. The detailed conditions for the LC-MS analysis are as follows.

[0128] LC:

[0129] Apparatus: Ultra-high performance liquid chromatography (UPLC, manufactured by Waters),

[0130] Column: ACQUITY UPLC BEH C8 1.7 μm (2.1 mm ID × 50 mm, manufactured by Waters)

[0131] Detection: Absorbance detector (PDA, 200-400 nm)

[0132] Flow rate: 0.3 mL / min

[0133] Mobile phase: A = water (containing 0.1% formic acid)

[0134] B = acetonitrile (containing 0.1% formic acid)

[0135] Injection volume: 0.2 μL

[0136] [Table 1]

[0137]

[0138] MS:

[0139] Apparatus: Mass spectrometer (Synapt G2, manufactured by Waters)

[0140] Ionization: Electrospray ionization (ESI+)

[0141] Measuring range: m / z 50-2000

[0142] The peak areas of the PDA chromatogram at 300 nm obtained by the above-mentioned LC-MS measurement were determined, and based on the peak area ratio, the peak areas of the aromatic amine compound (C-1), aromatic amine adduct (C-2-1) and aromatic amine adduct (C-2-2X) were calculated according to the following calculation formula (1).

[0143] The ratio of each peak area was calculated from the sum of all the obtained peak areas using the following calculation formula (1).

[0144] Ratio of aromatic amine compound (%) = [(peak area of ​​aromatic amine compound) / {(peak area of ​​aromatic amine compound) + (peak area of ​​aromatic amine adduct (C-2-1)) + (peak area of ​​aromatic amine adduct (C-2-2X))}] × 100 (1)

[0145] <Aromatic Amine Compound (C-1)>

[0146] The curing agent of this embodiment preferably contains an aromatic amine compound (C-1). The aromatic amine compound (C-1) may be used alone or in combination of two or more.

[0147] The aromatic amine compound (C-1) is preferably an aromatic amine compound represented by the following formula (1) or an aromatic amine compound represented by the following formula (2).

[0148]

[0149] In formula (1), R1 and R2 each independently represent a monovalent organic group having 1 to 20 carbon atoms or a halogen atom, a and b each independently represent an integer of 0 to 4, and X represents a divalent organic group or a single bond.

[0150] In R1 and R2, the monovalent organic group having 1 to 20 carbon atoms is preferably a monovalent organic group having 1 to 10 carbon atoms, more preferably a monovalent organic group having 1 to 5 carbon atoms, and further preferably a monovalent organic group having 1 to 3 carbon atoms.

[0151] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0152] a and b are each independently preferably an integer of 0 to 2, more preferably 0 or 1.

[0153] In X, the divalent organic group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 6 carbon atoms.

[0154] Examples of the aromatic amine represented by formula (1) include 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, 4,4'-diaminobenzanilide, 4,4'-diaminodiphenyl ether, and 3,4'-diaminobenzanilide. -Diaminodiphenyl ether (34ODA), 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone (44DAS), 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 (TPE-M), bis[4-(4-aminophenoxy)phenyl]sulfone, 4,4-bis(4-aminophenoxy)phenyl]sulfone 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 Fluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, m-tolidine, 2,2'-bis(trifluoromethyl)benzidine, 4,4'-diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane, bis(4-amino-3,5-dimethylphenyl)methane, 4,4'-diamino-3,3'-5,5'-tetraethyldiphenylmethane, etc. The aromatic amine represented by formula (1) may be used alone or in combination of two or more, and preferably one or more selected from these may be used.

[0155] Among them, from the viewpoint of taking into account both curability and stability when forming a composition with an epoxy resin, X is preferably an aromatic amine having a -O-, -O-C6H4-O-, -CH2-, -CO-, -C(=O)O-, -SO2- or -C(=O)NH- bond, and among them, an aromatic amine having a -C(=O)O- bond is preferred.

[0156] The aromatic amine compound is preferably 4-aminophenyl-4-aminobenzoate (APAB), 3,4'-diaminodiphenyl ether (34ODA), 4,4'-diaminodiphenyl sulfone (44DAS), 1,3-bis(3-aminophenoxy)benzene (TPE-M) and 3,3'-diethyl-4,4'-diaminodiphenylmethane, and more preferably at least one selected from the group consisting of 4-aminophenyl-4-aminobenzoate (APAB).

[0157] Alternatively, an aromatic amine compound having a methanediyl group (—CH 2 —) which has high reactivity as an amine may be used.

[0158] In order to suppress the reactivity as an amine and improve the storage stability, it is preferable to use a compound other than an aromatic amine compound having a methanediyl group.

[0159] Examples of aromatic amine compounds having a methanediyl group include 3,3'-diethyl-4,4'-diaminodiphenylmethane (e.g., KAYAHARD (registered trademark) AA (trade name) manufactured by Nippon Kayaku Co., Ltd.), 4,4'-diaminodiphenylmethane, and 3,3'-diaminodiphenylmethane. Aromatic amine compounds having a methanediyl group may be used alone or in combination of two or more.

[0160]

[0161] In formula (2), R3 each independently represents a monovalent organic group having 1 to 20 carbon atoms or a halogen atom, and c is an integer of 1 to 4.

[0162] In R3, the monovalent organic group having 1 to 20 carbon atoms is preferably a monovalent organic group having 1 to 10 carbon atoms, more preferably a monovalent organic group having 1 to 5 carbon atoms, and further preferably a monovalent organic group having 1 to 3 carbon atoms.

[0163] c is preferably an integer of 1 to 3, and more preferably 1 or 2.

[0164] Examples of the aromatic amine represented by formula (2) include diethyltoluenediamine (2,4-diamino-3,5-diethyltoluene, 2,6-diamino-3,5-diethyltoluene), dimethylthiotoluenediamine, etc. The aromatic amine represented by formula (2) may be used alone or in combination of two or more, and preferably one or more selected from these may be used.

[0165] Among them, from the viewpoint of achieving both curability and stability when forming a composition with an epoxy resin, at least one selected from the group consisting of diethyltoluenediamine (2,4-diamino-3,5-diethyltoluene and 2,6-diamino-3,5-diethyltoluene) is preferred.

[0166] <Aromatic Amine Adduct (C-2)>

[0167] The aromatic amine adduct (C-2) is a reaction product of an aromatic amine compound (C-1) and a reactive compound having a functional group capable of reacting with the aromatic amine compound (C-1). The aromatic amine adduct (C-2) may be used alone or in combination of two or more.

[0168] (Reactive Compound)

[0169] The reactive compound has a functional group capable of reacting with the aromatic amine compound (C-1). The reactive compound may be used alone or in combination of two or more.

[0170] Examples of the functional group include -C(=O)OC(=O)-, carboxyl, sulfo, isocyanato, carbonyl, epoxy, fluoro, chloro, bromo, and iodo groups. Among these, epoxy is preferred as the functional group.

[0171] The reactive compound is preferably at least one compound selected from the group consisting of carboxylic acid compounds, acid anhydrides, acid dianhydrides, sulfonic acid compounds, isocyanate compounds, urea compounds, epoxy compounds, and alkyl halides.

[0172] Examples of the carboxylic acid compound include succinic acid, adipic acid, sebacic acid, phthalic acid, and dimer acid.

[0173] Examples of the acid anhydride include succinic anhydride, adipic anhydride, sebacic anhydride, and phthalic anhydride.

[0174] Examples of the acid dianhydride include tetracarboxylic dianhydride exemplified as the raw material of the polyimide resin.

[0175] Examples of the sulfonic acid compound include ethanesulfonic acid and p-toluenesulfonic acid.

[0176] Examples of the isocyanate compound include aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, aliphatic triisocyanate, and polyisocyanate.

[0177] Examples of the aliphatic diisocyanate include ethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate.

[0178] Examples of the alicyclic diisocyanate include isophorone diisocyanate, 4-4′-dicyclohexylmethane diisocyanate, norbornane diisocyanate, 1,4-isocyanatocyclohexane, 1,3-bis(isocyanatomethyl)cyclohexane, and 1,3-bis(2-isocyanatopropyl-2-yl)cyclohexane.

[0179] Examples of the aromatic diisocyanate include tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylene diisocyanate, and 1,5-naphthalene diisocyanate.

[0180] Examples of the aliphatic triisocyanate include 1,3,6-triisocyanatomethylhexane and 2-isocyanatoethyl 2,6-diisocyanatohexanoate.

[0181] Examples of the polyisocyanate include polymethylene polyphenyl polyisocyanate and polyisocyanates derived from the above-mentioned diisocyanate compounds.

[0182] Examples of the polyisocyanate derived from diisocyanate include isocyanurate-type polyisocyanate, biuret-type polyisocyanate, urethane-type polyisocyanate, allophanate-type polyisocyanate, and carbodiimide-type polyisocyanate.

[0183] Examples of the urea compound include urea, methylurea, dimethylurea, ethylurea, and tert-butylurea.

[0184] As the epoxy compound, for example, a monoepoxy compound, a polyepoxy compound, and a mixture thereof are used.

[0185] Examples of the monoepoxy compounds include butyl glycidyl ether (hereinafter also referred to as "BGE"), hexyl glycidyl ether, phenyl glycidyl ether (hereinafter also referred to as "ph-GE"), 2-ethylhexyl glycidyl ether (hereinafter also referred to as "2-EH"), dodecyl glycidyl ether, allyl glycidyl ether, p-tert-butylphenyl glycidyl ether, ethylene oxide, propylene oxide, p-xylyl glycidyl ether, glycidyl acetate, glycidyl butyrate, glycidyl hexanoate, and glycidyl benzoate.

[0186] Examples of the polyvalent epoxy compound include bisphenol-type epoxy compounds obtained by glycidating bisphenols such as bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol AD, tetramethylbisphenol S, tetrabromobisphenol A, tetrachlorobisphenol A, and tetrafluorobisphenol A; epoxy compounds obtained by glycidating diphenols such as biphenol, dihydroxynaphthalene, and 9,9-bis(4-hydroxyphenyl)fluorene; epoxy compounds obtained by glycidating triphenols such as 1,1,1-tris(4-hydroxyphenyl)methane and 4,4-(1-(4-(1-(4-hydroxyphenyl)-1-methylethyl)phenyl)ethylidene)bisphenol; epoxy compounds obtained by glycidating tetraphenols such as 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane; epoxy compounds obtained by glycidating phenol novolacs, cresol novolacs, and bisphenol Novolac-type epoxy compounds obtained by glycidylating novolacs such as A novolac, brominated phenol novolac, and brominated bisphenol A novolac; aliphatic ether-type epoxy compounds obtained by glycidylating polyols such as glycerol and polyethylene glycol; ether ester-type epoxy compounds obtained by glycidylating hydroxycarboxylic acids such as p-hydroxybenzoic acid and β-hydroxynaphthoic acid; ester-type epoxy compounds obtained by glycidylating polycarboxylic acids such as phthalic acid and terephthalic acid; glycidyl-type epoxy compounds such as epoxy compounds obtained by glycidylating amine compounds such as 4,4-diaminodiphenylmethane and m-aminophenol, and epoxy compounds obtained by glycidylating amine-type epoxy compounds such as triglycidyl isocyanurate; alicyclic epoxy compounds such as 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, etc.

[0187] Among the above, the reactive compound is preferably an epoxy compound, and more preferably an epoxy compound having one glycidyl group in the molecule (ie, a monoepoxy compound), from the viewpoint of excellent curability and storage stability.

[0188] The monoepoxy compound is preferably at least one selected from the group consisting of butyl glycidyl ether (BGE), phenyl glycidyl ether (ph-GE), and 2-ethylhexyl glycidyl ether (2-EH).

[0189] The aromatic amine adduct (C-2) is a reaction product of the aromatic amine compound (C-1) and a reactive compound having a functional group capable of reacting with the aromatic amine compound (C-1).

[0190] The aromatic amine adduct (C-2) used in this embodiment can be obtained by, for example, the following operation: reacting 1.0 to 5.0 moles of the aromatic amine compound (C-1) with a reactive compound (e.g., an epoxy compound) at a molar ratio of 0.2 to 5.0 for 0.1 to 10 hours in the presence of a solvent as needed, at a temperature of, for example, 50 to 250°C, and removing the unreacted aromatic amine compound (C-1) and the solvent as needed to obtain it.

[0191] The solvent used here is not particularly limited, and examples include hydrocarbons such as benzene, toluene, xylene, cyclohexane, mineral spirits, and naphtha; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as ethyl acetate, n-butyl acetate, and propylene glycol monomethyl ether acetate; alcohols such as methanol, isopropanol, 1-butanol, butyl cellosolve, and butyl carbitol; and water. These solvents can be used in combination.

[0192] The content of the curing agent (C) is not particularly limited, but is preferably 1 to 50% by mass, more preferably 3 to 40% by mass, and even more preferably 5 to 30% by mass, based on the total amount (100% by mass) of the first resin composition, from the viewpoint of curability and stability.

[0193] <Inorganic filler (D)>

[0194] The first resin composition contains an inorganic filler (D). The inorganic filler (D) may be used alone or in combination of two or more.

[0195] The inorganic filler is not particularly limited and includes, for example, silica such as fused silica and crystalline silica; aluminum oxide such as calcium carbonate, clay, aluminum oxide, silicon nitride, silicon carbide, boron nitride, calcium silicate, potassium titanate, aluminum nitride, beryllium oxide, zirconium oxide, zircon, forsterite, steatite, spinel, mullite, titanium dioxide and the like in powder form or beads obtained by spheroidizing them, glass fibers and the like.

[0196] As the inorganic filler, an inorganic filler having a flame retardant effect can be used. Examples of the inorganic filler having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, zinc borate, and zinc molybdate.

[0197] Among these, silica is preferred, and fused silica is more preferred, from the perspectives of availability, chemical stability, and material cost. The particle shape of the inorganic filler is not particularly limited and may be irregular or spherical. However, from the perspective of the fluidity and permeability of the first epoxy resin composition in fine gaps, spherical silica is preferred, and spherical fused silica is more preferred.

[0198] In addition, the inorganic filler may be surface treated.

[0199] Specifically, the inorganic filler may be surface-treated with a silane coupling agent.

[0200] Examples of the silane coupling agent include aminosilane coupling agents, epoxysilane coupling agents, phenylsilane coupling agents, alkylsilane coupling agents, alkenylsilane coupling agents, alkynylsilane coupling agents, haloalkylsilane coupling agents, siloxane coupling agents, hydrogensilane coupling agents, silazane coupling agents, alkoxysilane coupling agents, chlorosilane coupling agents, (meth)acrylic silane coupling agents, aminosilane coupling agents, isocyanurate silane coupling agents, ureide silane coupling agents, mercaptosilane coupling agents, sulfide silane coupling agents, and isocyanate silane coupling agents. Silane coupling agents may be used alone or in combination of two or more.

[0201] The volume average particle size of the inorganic filler is not particularly limited, but is preferably 0.1 to 10.0 μm, more preferably 0.2 to 5.0 μm, and even more preferably 0.3 to 3.0 μm. By setting the volume average particle size of the inorganic filler to 0.1 μm or more, there is a tendency for the dispersibility in the epoxy resin to be improved, the first epoxy resin composition to be less susceptible to thixotropy, and the flow properties of the first epoxy resin composition to be improved. On the other hand, by setting the volume average particle size to 10.0 μm or less, there is a tendency for the sedimentation of the inorganic filler in the first epoxy resin composition to be easily suppressed, and there is a tendency for the permeability and fluidity of the first epoxy resin composition in fine gaps to be improved, thereby suppressing the formation of voids and unfilled portions.

[0202] The volume average particle size refers to the particle size at a point corresponding to 50% volume when the cumulative number distribution curve is calculated based on the particle size, with the entire volume of the particles being 100%. This can be measured using a particle size distribution measuring device using a laser diffraction scattering method, for example.

[0203] The content of the inorganic filler (D) is not particularly limited, but is preferably 30 to 85 mass %, more preferably 40 to 80 mass %, and even more preferably 45 to 70 mass % relative to the total amount (100 mass %) of the first resin composition.

[0204] By setting the content of the inorganic filler to 30% by mass or more, there is a tendency to easily achieve the effect of reducing the thermal expansion coefficient and improving the effect of thermal cycling resistance. By setting the content of the inorganic filler to 85% by mass or less, there is a tendency to suppress the increase in viscosity of the first epoxy resin composition, and to improve fluidity, permeability, and dispensability. In particular, from the perspective of improving the effect of thermal cycling resistance, it is preferred that the lower limit of the content of the inorganic filler be higher.

[0205] In the present embodiment, even if the content of the inorganic filler is increased as described above, the first resin composition can be maintained at a low viscosity.

[0206] <Curing Accelerator (E)>

[0207] The first resin composition of the present embodiment preferably further contains a curing accelerator (E). The curing accelerator (E) may be used alone or in combination of two or more.

[0208] The curing accelerator is preferably at least one selected from the group consisting of the compound (E-1) and the imidazole compound (E-2).

[0209] (Compound (E-1))

[0210] The compound (E-1) is at least one selected from the group consisting of a compound represented by the following formula (4), a compound represented by the following formula (5), and a compound represented by the following formula (6).

[0211]

[0212] In formulas (4) to (6), R1 each independently represents a hydrogen atom or an n-valent organic group having 1 to 15 carbon atoms, optionally containing a hydroxyl group, a carbonyl group, an ester bond, or an ether bond; R2 and R3 each independently represent an unsubstituted or substituted alkyl group, an aryl group, or an aralkyl group having 1 to 12 carbon atoms, or are linked to form a heterocyclic ring having 7 or less carbon atoms; R4 each independently represents a hydrogen atom or an n-valent organic group having 1 to 30 carbon atoms, optionally containing an oxygen atom; and n represents an integer from 1 to 3. R5 represents a negatively charged nitrogen atom, and R6 represents a positively charged nitrogen atom.

[0213] It is speculated that in the compound represented by formula (4), the compound represented by formula (5), and the compound represented by formula (6), R1 contributes to lowering the energy of the cleavage of the N-N bond. It is speculated that R2 and R3 contribute to lowering the energy of the cleavage reaction due to destabilization due to steric hindrance. It is speculated that R4 contributes to the liquefaction of the compound and to suppressing the decrease in the glass transition temperature of the resulting first cured product.

[0214] Hereinafter, details of each group will be described.

[0215] In formulae (4), (5) and (6), R1 each independently represents a hydrogen atom, or an n-valent organic group having 1 to 15 carbon atoms which may have a hydroxyl group, a carbonyl group, an ester bond or an ether bond.

[0216] In R1, the organic group is not particularly limited, and examples thereof include hydrocarbon groups, groups in which hydrogen atoms bonded to carbon atoms in a hydrocarbon group are substituted with hydroxyl groups or carbonyl groups, or groups in which some carbon atoms in a hydrocarbon group are replaced with ester bonds or ether bonds.

[0217] Examples of the hydrocarbon group in R1 include linear, branched, or cyclic alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and ethylhexyl; alkenyl groups such as vinyl, propynyl, butynyl, pentynyl, hexynyl, octynyl, decynyl, dodecynyl, hexadecynyl, and octadecynyl; aryl groups such as phenyl; and aralkyl groups including combinations of alkyl and phenyl groups such as methylphenyl, ethylphenyl, and propylphenyl. Among these, R1 is preferably a linear, branched, or cyclic alkyl group, more preferably a linear alkyl group, and even more preferably a methyl, ethyl, or propyl group.

[0218] In R1, the organic group may have other substituents. The substituents are not particularly limited, and examples thereof include halogen atoms, alkoxy groups, carbonyl groups, cyano groups, azo groups, azido groups, thiol groups, sulfonyl groups, nitro groups, hydroxyl groups, acyl groups, and aldehyde groups.

[0219] In R1, the organic group has 1 to 15 carbon atoms, preferably 1 to 12, and more preferably 1 to 7. When the number of carbon atoms in the organic group is within this range, a liquid compound having an appropriate viscosity tends to be readily obtained, and the curing properties of the compound tend to be further improved. Furthermore, when the number of carbon atoms in the organic group is within this range, the availability of raw materials is further improved.

[0220] R2 and R3 each independently represent an unsubstituted or substituted alkyl group, aryl group or aralkyl group having 1 to 12 carbon atoms, or are linked to form a heterocyclic ring having 7 or less carbon atoms.

[0221] In R2 and R3, the alkyl group having 1 to 12 carbon atoms is not particularly limited, and examples thereof include straight-chain alkyl groups such as methyl, ethyl, propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, and n-dodecyl; branched-chain alkyl groups such as isopropyl, isobutyl, tert-butyl, neopentyl, 2-hexyl, 2-octyl, 2-decyl, and 2-dodecyl; and cyclic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclodecyl, and cyclododecyl.

[0222] The alkyl group may be a combination of a linear or branched alkyl group and a cyclic alkyl group. The alkyl group may also contain an unsaturated bond group.

[0223] Among them, R2 and R3 are preferably cyclic alkyl groups, and more preferably cyclohexyl groups.

[0224] In R2 and R3, the number of carbon atoms in the alkyl group is independently 1 to 12, preferably 2 to 10, and more preferably 5 to 10.

[0225] Asymmetric dialkylhydrazine compounds (e.g., dimethylhydrazine) with a small number of carbon atoms in the alkyl group may be toxic to humans, in addition to being explosive. By setting the number of carbon atoms in the alkyl groups in R2 and R3 to 2 or more, the use of raw materials with such toxic risks can be avoided.

[0226] Furthermore, by setting the number of carbon atoms of the alkyl group in R2 and R3 to 5 or more, a liquid compound having an appropriate viscosity tends to be easily obtained, and the curing performance of the compound tends to be further improved.

[0227] In R2 and R3, the aryl group is not particularly limited, and examples thereof include a phenyl group and a naphthyl group.

[0228] In R2 and R3, the aralkyl group is not particularly limited, and examples thereof include methylphenyl, ethylphenyl, methylnaphthyl, and dimethylnaphthyl.

[0229] Among them, R2 and R3 are preferably aralkyl groups, and more preferably methylphenyl (benzyl) groups.

[0230] In R2 and R3, the substituent of the alkyl group, aryl group or aralkyl group is not particularly limited, and examples thereof include halogen atoms, alkoxy groups, carbonyl groups, cyano groups, azo groups, azido groups, thiol groups, sulfon groups, nitro groups, hydroxyl groups, acyl groups, and aldehyde groups.

[0231] R2 and R3 may be optionally linked to form a heterocyclic ring having 7 or less carbon atoms together with R6 (positively charged nitrogen atom).

[0232] The heterocyclic ring is not particularly limited, and examples thereof include four-membered rings such as azetidine ring; five-membered rings such as pyrrolidine ring, pyrrole ring, morpholine ring, and thiazine ring; six-membered rings such as piperidine ring; and seven-membered rings such as hexamethyleneimine ring and azepine ring.

[0233] Wherein, as heterocycle, be preferably pyrrole ring, morpholine ring, thiazine ring, piperidine ring, hexamethyleneimine ring and azepine ring, more preferably six-membered ring and seven-membered ring.By having this group, thereby there is the tendency that the curing properties of liquid compound and compound are easily obtained and further improve.Among them, be preferably the hexamethyleneimine ring that R2, R3 and R6 are connected.

[0234] The substituent is not particularly limited and includes, for example, an alkyl group, an aryl group, or the substituents in R2 and R3. Furthermore, when the heterocyclic ring has an alkyl group as a substituent, examples thereof include a methyl group bonded to the carbon atom adjacent to R6.

[0235] In formulae (4), (5) and (6), R4 each independently represents a hydrogen atom or an n-valent organic group having 1 to 30 carbon atoms which may contain an oxygen atom.

[0236] In R4, the organic group is not particularly limited, and examples thereof include hydrocarbon groups, groups in which the hydrogen atoms bonded to carbon atoms in the hydrocarbon group are replaced by hydroxyl groups, carbonyl groups or groups containing silicon atoms, and groups in which part of the carbon atoms in the hydrocarbon group are replaced by ester bonds, ether bonds or silicon atoms.

[0237] In R4, as the hydrocarbon group, there can be listed a linear, branched or cyclic alkyl group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, ethylhexyl; an alkynyl group such as vinyl, propynyl, butynyl, pentynyl, hexynyl, octynyl, decynyl, dodecynyl, hexadecynyl, octadecynyl; an aryl group such as phenyl; an aralkyl group comprising a combination of an alkyl group and a phenyl group such as methylphenyl, ethylphenyl, propylphenyl, etc.; and the like.

[0238] In R4, the hydrocarbon group may include a bisphenol skeleton such as a bisphenol A skeleton, a bisphenol AP skeleton, a bisphenol B skeleton, a bisphenol C skeleton, a bisphenol E skeleton, or a bisphenol F skeleton.

[0239] The organic group containing a bisphenol skeleton is not particularly limited, and examples thereof include groups in which a polyoxyalkylene group is added to a hydroxyl group of each bisphenol skeleton.

[0240] In R4, the hydrocarbon group may have a polyoxyalkylene skeleton. Examples of the polyoxyalkylene skeleton include a polyoxyethylene skeleton.

[0241] Among these, the organic group shown in R4 in formula (4) or formula (5) is preferably an alkyl, alkenyl and aralkyl, more preferably an alkyl and alkenyl, further preferably an alkyl, and further preferably a branched alkyl. It should be noted that these preferred groups optionally have a substituent. By having such a group, there is a tendency to easily obtain a liquid compound with an appropriate viscosity and the curing performance of the compound is further improved. In addition, there is a tendency that the Tg of the first cured product obtained using the compound is further improved.

[0242] The number of carbon atoms in the organic group in R4 is preferably 1 to 50, more preferably 1 to 40, and even more preferably 1 to 30. By setting the number of carbon atoms in the organic group in R4 within this range, a liquid compound with an appropriate viscosity is easily obtained, and the curing performance of the compound tends to be further improved. Furthermore, the Tg of the first cured product obtained using this compound is further increased. Furthermore, by setting the number of carbon atoms in the organic group in R4 within the above range, the availability of raw materials is further improved.

[0243] Among the above, R4 in formula (4) or (5) is preferably a linear or branched alkyl group having 3 to 12 carbon atoms. The presence of such a group tends to facilitate obtaining a liquid compound having an appropriate viscosity and further improve the curing performance of the compound.

[0244] In formula (5) and formula (6), n is preferably 2 or 3. This increases the crosslinking density during curing, enables the production of a strong first cured product, and improves adhesiveness and reliability.

[0245] From the perspective of controlling the curing temperature or viscosity, compound (E-1) preferably contains multiple compounds represented by formula (4), compounds represented by formula (5), or compounds represented by formula (6). It should be noted that multiple compounds represented by the same formula but with different structures may be contained.

[0246] In particular, from the viewpoint of viscosity control, compound (E-1) preferably contains both the compound represented by formula (4) and the compound represented by formula (6). Regarding the content ratio in this case, the content of the compound represented by formula (4) is preferably 0.1 to 99.5% by mass relative to the total amount of the compound represented by formula (4) and the compound represented by formula (6). The content of the compound represented by formula (6) is preferably 0.5 to 99.9% by mass relative to the total amount of the compound represented by formula (4) and the compound represented by formula (6).

[0247] When a plurality of compounds represented by formula (4), compounds represented by formula (5), or compounds represented by formula (6) are contained, the content ratio of the compound represented by formula (4) is preferably 0.1 to 99.8% by mass relative to the total amount of the compounds represented by formula (4), the compounds represented by formula (5), and the compounds represented by formula (6). The content of the compound represented by formula (5) is preferably 0.1 to 99.8% by mass relative to the total amount of the compounds represented by formula (4), the compounds represented by formula (5), and the compounds represented by formula (6). The content of the compound represented by formula (6) is preferably 0.1 to 99.8% by mass relative to the total amount of the compounds represented by formula (4), the compounds represented by formula (5), and the compounds represented by formula (6). This makes it possible to easily control the viscosity.

[0248] A mixture containing a plurality of compounds represented by formula (4), (5) or (6) can be obtained by mixing the plurality of compounds or by simultaneously producing the plurality of compounds in the method for producing the compound described below.

[0249] The compound (E-1) preferably contains at least one selected from the group consisting of the compound represented by (E-1A) below (hereinafter also referred to as "compound (E-1A)"), the compound represented by (E-1B) below (hereinafter also referred to as "compound (E-1B)"), and the compound represented by (E-1C) below (hereinafter also referred to as "compound (E-1C)"). Use of these compounds makes it possible to more easily control the viscosity.

[0250]

[0251] It is also preferable that the compound (E-1) contains both the compound (E-1A) and the compound (E-1B).

[0252] The content of compound (E-1) is not particularly limited, but is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, and even more preferably 1 to 5% by mass, based on the total amount (100% by mass) of the first resin composition, since it tends to make it easier to control the viscosity.

[0253] The compound represented by formula (4), the compound represented by formula (5), or the compound represented by formula (6) is not limited to the following and can be produced by, for example, reacting an ester compound, a hydrazine compound, and a glycidyl ether compound.

[0254] The ester compound is not particularly limited, and examples thereof include monocarboxylic acid ester compounds and dicarboxylic acid ester compounds. The ester compound may be used alone or in combination of two or more.

[0255] Specific examples of the monocarboxylic acid ester compound include methyl lactate, ethyl lactate, methyl mandelate, methyl acetate, methyl propionate, ethyl propionate, methyl butyrate, methyl isobutyrate, methyl valerate, methyl isovalerate, methyl pivalate, methyl heptanoate, methyl octanoate, methyl acrylate, methyl methacrylate, methyl crotonate, methyl isocrotonic acid, methyl benzoylformate, 2-methoxybenzoylmethyl ester, 3-methoxybenzoylmethyl ester, 4-methoxybenzoylmethyl ester, 2-ethoxybenzoylmethyl ester, and 4-tert-butoxybenzoylmethyl ester.

[0256] In addition, ethyl esters, propyl esters, etc. can be used instead of them.

[0257] Specific examples of dicarboxylic acid ester compounds include dimethyl oxalate, dimethyl malonate, dimethyl succinate, dimethyl tartarate, dimethyl glutarate, dimethyl adipate, dimethyl pimelate, dimethyl suberate, dimethyl azelaic acid, dimethyl sebacate, dimethyl maleate, dimethyl fumarate, dimethyl itaconate, dimethyl phthalate, dimethyl isophthalate, dimethyl terephthalate, dimethyl 1,3-acetonedicarboxylate, and diethyl 1,3-acetonedicarboxylate. In addition, cyclic esters and the like may be used instead of these.

[0258] Specific examples of cyclic esters include α-acetone, β-propiolactone, γ-butyrolactone, δ-valerolactone, γ-valerolactone, ε-caprolactone, etc. In addition, diethyl esters, dipropyl esters, etc. can be used instead of these.

[0259] Among these, from the viewpoint of curability and liquidization, preferred ester compounds include ethyl lactate, methyl mandelate, methyl acetate, methyl propionate, ethyl propionate, methyl butyrate, methyl isobutyrate, methyl valerate, methyl isovalerate, methyl pivalate, methyl acrylate, methyl methacrylate, methyl crotonate, methyl isocrotonic acid, methyl benzoylformate, dimethyl oxalate, dimethyl malonate, dimethyl succinate, dimethyl tartaric acid, dimethyl glutarate, dimethyl adipate, dimethyl pimelate, dimethyl suberate, dimethyl azelate, dimethyl maleate, dimethyl fumarate, dimethyl phthalate, dimethyl isophthalate, dimethyl terephthalate, dimethyl 1,3-acetonedicarboxylate, diethyl 1,3-acetonedicarboxylate, γ-butyrolactone, δ-valerolactone, and γ-valerolactone.

[0260] The hydrazine compound is not particularly limited, and examples thereof include dimethylhydrazine, diethylhydrazine, methylethylhydrazine, methylpropylhydrazine, methylbutylhydrazine, methylpentylhydrazine, methylhexylhydrazine, ethylpropylhydrazine, ethylbutylhydrazine, ethylpentylhydrazine, ethylhexylhydrazine, dipropylhydrazine, dibutylhydrazine, dipentylhydrazine, dihexylhydrazine, methylphenylhydrazine, ethylphenylhydrazine, methyltolylhydrazine, ethyltolylhydrazine, diphenylhydrazine, benzylphenylhydrazine, dibenzylhydrazine, dinitrophenylhydrazine, 1-aminopiperidine, N-aminohomopiperidine, 1-amino-2,6-dimethylpiperidine, 1-aminopyrrolidine, 1-amino-2-methylpyrrolidine, 1-amino-2-phenylpyrrolidine, and 1-aminomorpholine.

[0261] Among these, from the viewpoints of curability and liquefaction, preferred hydrazine compounds are dimethylhydrazine, dibenzylhydrazine, 1-aminopiperidine, 1-aminopyrrolidine, and 1-aminomorpholine. Furthermore, among these, from the viewpoints of availability and safety, dibenzylhydrazine and 1-aminopiperidine are more preferred. The hydrazine compound may be used alone or in combination of two or more.

[0262] The glycidyl ether compound is not particularly limited, and examples thereof include monofunctional monoglycidyl ether compounds and difunctional or higher-functional polyglycidyl ether compounds. The glycidyl ether compound may be used alone or in combination of two or more.

[0263] Specific examples of the monoglycidyl ether compound include methyl glycidyl ether, ethyl glycidyl ether, n-butyl glycidyl ether, tert-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, dodecyl glycidyl ether, higher alcohol glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, o-phenylphenol glycidyl ether, benzyl glycidyl ether, biphenyl glycidyl ether, 4-tert-butylphenyl glycidyl ether, tert-butyldimethylsilyl glycidyl ether, and 3-[diethoxy(methyl)silyl]propyl glycidyl ether.

[0264] Specific examples of the polyglycidyl ether compound include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, butanediol glycidyl ether, hexanediol glycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, diglyceryl Aliphatic polyglycidyl ethers such as oil polyglycidyl ether, polyglycerol polyglycidyl ether, and sorbitol polyglycidyl ether; alicyclic polyglycidyl ether compounds such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, ethylene oxide addition type bisphenol A diglycidyl ether, propylene oxide addition type bisphenol A diglycidyl ether, and hydrogenated products of their condensates; aromatic polyglycidyl ether compounds such as resorcinol diglycidyl ether, etc.

[0265] Among these, from the viewpoint of curability and liquidization, preferred glycidyl ether compounds include methyl glycidyl ether, ethyl glycidyl ether, n-butyl glycidyl ether, tert-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, tert-butyldimethylsilyl glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, butanediol glycidyl ether, hexanediol glycidyl ether, trimethylolpropane polyglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, ethylene oxide-added bisphenol A diglycidyl ether, propylene oxide-added bisphenol A diglycidyl ether, polyethylene glycol diglycidyl ether, and 1-phenoxy-1,4-(oxiranylmethoxy)-3,6,9,12-tetraoxatetradecane.

[0266] Furthermore, from the viewpoint of adhesion, epoxy resins having an ether structure are preferred, and as specific examples, at least one selected from the group consisting of n-butyl glycidyl ether, polyethylene glycol diglycidyl ether, and 1-phenoxy-1,4-(oxiranylmethoxy)-3,6,9,12-tetraoxatetradecane is preferred.

[0267] The amounts of the ester compound, the hydrazine compound, and the glycidyl ether compound added to the reaction system can be set based on the molar ratio of the functional groups.

[0268] The amount of the ester group of the ester compound is preferably 0.8 mol to 3.0 mol, more preferably 0.9 mol to 2.8 mol, and even more preferably 0.95 mol to 2.5 mol, based on 1 mol of the primary amine of the hydrazine compound.

[0269] The amount of the glycidyl group in the glycidyl ether compound is preferably 0.80 mol to 2.00 mol, more preferably 0.90 mol to 1.50 mol, and even more preferably 0.95 mol to 1.40 mol, relative to 1 mol of the primary amine in the hydrazine compound.

[0270] By controlling the amount of glycidyl groups of the glycidyl ether compound added per 1 mol of the primary amine of the hydrazine compound, a mixture containing the compound represented by formula (4) and the compound represented by formula (6) can be produced simultaneously.

[0271] Specifically, the amount of the glycidyl group in the glycidyl ether compound is preferably 0.1 to 3.0 mol, more preferably 0.3 to 2.0 mol, and even more preferably 0.5 to 1.0 mol, per 1 mol of the primary amine in the hydrazine compound.

[0272] In the method for producing the above-mentioned compound or mixture, a solvent may be used from the viewpoint of uniformly progressing the reaction.

[0273] The solvent is not particularly limited, and examples thereof include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, butanol, and tert-butanol; and ethers such as tetrahydrofuran and diethyl ether.

[0274] The reaction temperature is preferably 10°C to 100°C, more preferably 40°C to 95°C. A reaction temperature of 10°C or higher tends to result in a rapid reaction, further improving the purity of the resulting compound. Furthermore, a reaction temperature of 95°C or lower effectively suppresses the polymerization reaction between glycidyl ether compounds, thereby further improving the purity of the compound.

[0275] The reaction time is preferably from 1 hour to 168 hours, more preferably from 1 hour to 96 hours, and even more preferably from 1 hour to 48 hours.

[0276] After the reaction is completed, the obtained reactant can be purified by known purification methods such as cleaning, extraction, recrystallization, column chromatography. For example, by utilizing water to clean the reaction solution dissolved in an organic solvent, the organic layer is heated under normal pressure or reduced pressure, thereby being able to remove unreacted raw materials and organic solvent from the reaction solution and recover the target compound. Purification by column chromatography can also recover the target compound. The solvent used in the above cleaning is not particularly limited as long as it can dissolve the residue of the raw material. From the viewpoint of yield, purity, and ease of removal, 1-hexane, 1-pentane and cyclohexane are preferably used.

[0277] The organic solvent used in the above extraction is not particularly limited as long as it can dissolve the target compound. From the viewpoint of yield, purity, and ease of removal, ethyl acetate, dichloromethane, chloroform, carbon tetrachloride, toluene, diethyl ether, and methyl isobutyl ketone are preferred, and ethyl acetate, chloroform, toluene, and methyl isobutyl ketone are more preferred.

[0278] The filler used in column chromatography can use known materials such as alumina and silica gel. In addition, the developing solvent can be used alone or in combination with known materials such as ethyl acetate, dichloromethane, chloroform, carbon tetrachloride, tetrahydrofuran, diethyl ether, acetone, methyl isobutyl ketone, acetonitrile, methanol, ethanol, and isopropanol.

[0279] (Imidazole compound (E-2))

[0280] The imidazole compound (E-2) can be used without limitation. The imidazole compound (E-2) can be used alone or in combination of two or more.

[0281] Examples of the imidazole compound (E-2) include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-undecyl-imidazole-trimellitate, imidazolylsuccinic acid, 2-methylimidazolesuccinic acid, 2-ethylimidazolesuccinic acid, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, and 1-cyanoethyl-2-phenylimidazole.

[0282] As the imidazole compound (E-2), 2-phenyl-4-methyl-5-hydroxymethylimidazole is preferred because it tends to make it easier to control the viscosity.

[0283] The content of the imidazole compound (E-2) is not particularly limited, but is preferably 1 to 10% by mass, more preferably 1 to 5% by mass, and even more preferably 1.5 to 5% by mass, based on the total amount (100% by mass) of the first resin composition, since it tends to make it easier to control the viscosity.

[0284] The content of the curing accelerator (E) is not particularly limited, but is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, and even more preferably 1 to 5% by mass, based on the total amount (100% by mass) of the first resin composition, since it tends to make it easier to control the viscosity.

[0285] <Viscosity of the First Resin Composition>

[0286] From the viewpoint of permeability, the viscosity of the first epoxy resin composition of the present embodiment at 25° C. is preferably 100 Pa·s or less, more preferably 97 Pa·s or less, and even more preferably 95 Pa·s or less.

[0287] From the viewpoint of curability, the viscosity of the first resin composition of the present embodiment at 25° C. is preferably 0.1 Pa·s or more, more preferably 1.0 Pa·s or more, and even more preferably 2.0 Pa·s or more.

[0288] The viscosity (Pa·s) of the first resin composition at 25°C can be measured by dropping the first epoxy resin composition into a measuring cup and, 5 minutes after the sample temperature reaches 25°C, using an E-type viscometer (e.g., "TV-20" (trade name) manufactured by Toki Sangyo Co., Ltd.) (measurement conditions: cone: No. 5, 3°, R = 12 mm). The specific measurement method can be found in the Examples.

[0289] The viscosity of the first resin composition of the present embodiment after being left at 110° C. for 60 minutes is preferably 0.01 Pa·s to 4.50 Pa·s, more preferably 0.01 Pa·s to 4.00 Pa·s, and even more preferably 0.01 Pa·s to 3.50 Pa·s.

[0290] The viscosity after standing at 110° C. for 60 minutes can be measured using a rheometer (for example, HAAKE (registered trademark) MARS (trade name), manufactured by Thermo Scientific). Specific measurement methods may be determined by referring to the Examples.

[0291] The first resin composition of the present embodiment preferably has a viscosity increase ratio after being left at 110° C. for 60 minutes of 1.0 to 50.0 times, more preferably 1.0 to 47.0 times, and even more preferably 1.0 to 45.0 times.

[0292] The thickening rate after standing at 110°C for 60 minutes was measured as follows: the first epoxy resin composition was dropped onto a measuring plate, and 5 minutes and 60 minutes after the sample temperature reached 110°C, the measurement was performed using a rheometer (HAAKE MARS, manufactured by Thermoscientific Co., Ltd.) (measurement conditions: aluminum cone plate, R = 20 mm, shear rate of 20 ( / s)).

[0293] The viscosity after 5 minutes is defined as "η1", the viscosity after 60 minutes is defined as "η2", and the value calculated by η2 / η1 is defined as the thickening rate. Specific measurement methods can be referred to in the Examples.

[0294] The first resin composition of the present embodiment preferably satisfies the following formula (I) at 110° C., where the viscosity at a shear rate of 10 / sec is V1 and the viscosity at a shear rate of 100 / sec is V2.

[0295] 0.8≤V1 / V2≤1.2…(I)

[0296] The viscosity (Pa·s) of the first epoxy resin composition at 110°C can be measured by dropping the resin composition onto a measuring plate. After the sample temperature reaches 110°C, the viscosity is measured using a rheometer (e.g., HAAKE (registered trademark) MARS (trade name), manufactured by Thermo Scientific) at a shear rate ranging from 10 ( / s) to 100 ( / s) (measurement conditions: aluminum cone plate R = 20 mm). The specific measurement method can be found in the Examples.

[0297] As a result, there is a tendency for the flow characteristics of the first resin composition of this embodiment to be improved. V1 / V2 is preferably 0.5 or more and 1.5 or less, more preferably 0.8 or more and 1.5 or less, and even more preferably 0.8 or more and 1.2 or less. V1 / V2 can be controlled by the molecular weight of the polyimide resin, and there is a tendency for the value to increase by increasing the molecular weight.

[0298] <Curing Rate of First Resin Composition>

[0299] The first resin composition of the present embodiment has a curing rate when cured at 165° C. of preferably 70% to 100%, more preferably 80% to 100%, and even more preferably 90% to 100%.

[0300] The curing rate when the first resin composition of this embodiment is cured at 165°C can be calculated as follows: for example, using EXSTER6000 (trade name, Hitachi High-Tech Sciences Co., Ltd.), the temperature is raised from 25°C to 300°C at 5°C / min, and the total amount of heat released observed in the temperature range of 100°C to 250°C is calculated.

[0301] Furthermore, after being placed in a small high-temperature chamber (manufactured by ESPEC) at 180°C for 2 hours, the same measurement can be performed, and the change in heat release within the same temperature range can be calculated as a percentage. Furthermore, after being placed in a small high-temperature chamber (manufactured by ESPEC) at 165°C for 2 hours, the same measurement can be performed, and the change in heat release within the same temperature range can be calculated as a percentage. The calculation formula is shown below. For specific measurement methods, please refer to the Examples.

[0302] Initial heat release A: DSC peak heat release of the first epoxy resin composition

[0303] Heat release after curing B: DSC peak heat release of the first epoxy resin composition after heating

[0304] Curing rate (%) = 100 × (initial heat release A - heat release after curing B) ÷ initial heat release A

[0305] <Method for Producing the First Resin Composition>

[0306] The first resin composition of the present embodiment can be manufactured by, for example, a method of dry-blending the components contained in the first resin composition of the present embodiment, a method of preparing the composition using an apparatus commonly used for mixing polymeric substances, etc. As a mixing apparatus, for example, a Banbury mixer, a LABO PLASTOMIL, a single-screw extruder, a twin-screw extruder, etc. can be cited.

[0307] The first resin composition is preferably obtained by stirring and mixing the components contained in the first resin composition of the present embodiment using a rotation / revolution stirrer (eg, "ARE-310" (trade name) manufactured by THINKY Corporation) and then kneading them using a three-roll mill.

[0308] In addition, the first resin composition is preferably obtained as follows: a solution is prepared by dissolving and dispersing the powder of the polyimide resin (B) in the epoxy resin (A) and the curing agent (C), and an inorganic filler (D) is dispersed in the solution to prepare a dispersion liquid, and then the dispersion liquid is stirred and mixed using a rotation / revolution stirrer, and then kneaded using a three-roll mill to obtain it.

[0309] <Purpose>

[0310] The first resin composition, the second resin composition, the first cured product and the second cured product of the present embodiment are useful as structures, adhesives, packaging materials, filling materials, insulating materials, conductive materials, anisotropic conductive materials, sealing (seal) materials, prepregs, etc. As adhesives, they are useful as liquid adhesives, film-like adhesives, chip bonding materials, etc. As packaging materials, they are useful as solid packaging materials, liquid packaging materials, film-like packaging materials, etc. As liquid packaging materials, they are useful as bottom filling materials, casting materials, barrier materials, etc. As insulating materials, they are useful as insulating adhesive films, insulating adhesive pastes, solder resists, etc. As conductive materials, they are useful as conductive films, conductive pastes, etc. As anisotropic conductive materials, they are useful as anisotropic conductive films, heterotropic conductive pastes, etc.

[0311] <<Cured product>>

[0312] The first cured product of the present embodiment comprises the first epoxy resin composition of the present embodiment. The first cured product is obtained by curing the first epoxy resin composition. The second cured product of the present embodiment comprises the second epoxy resin composition of the present embodiment. The second cured product is obtained by curing the second epoxy resin composition.

[0313] <<Structure>

[0314] The structure of this embodiment includes a first layer, a second layer, and a plurality of copper pillars connecting the first layer and the second layer, wherein the first layer and the second layer respectively contain at least one selected from the group consisting of resin, silicon, ceramics, compound semiconductors and glass, and the distance between adjacent copper pillars is less than 150 μm. A third layer is provided between the first layer and the second layer and is in contact with the first layer and the second layer respectively, wherein the third layer is a first cured product, and the ratio of the area of ​​the pores to the surface area of ​​the third layer is less than 1%.

[0315] The third layer of the structure may be the first cured product of the first epoxy resin composition of this embodiment.

[0316] The structure of this embodiment includes a first layer, a second layer, and a plurality of copper pillars connecting the first layer and the second layer, wherein the first layer and the second layer each contain at least one selected from the group consisting of resin, silicon, ceramics, compound semiconductors, and glass, wherein the distance between adjacent copper pillars is 150 μm or less, and a third layer is provided between the first layer and the second layer, the third layer being a second cured product of a second resin composition containing an epoxy resin, a polyimide resin, and an inorganic filler, and the ratio of the area of ​​the pores to the surface area of ​​the third layer is 1% or less.

[0317] The second cured product of this embodiment is used to form a third layer between the first layer and the second layer connected by multiple copper pillars with a distance between adjacent copper pillars of less than 150 μm. The cured product constituting the aforementioned third layer is a cured product of an epoxy resin composition containing an epoxy resin, a polyimide resin and an inorganic filler, and the ratio of the area of ​​the pores to the surface area of ​​the aforementioned third layer can be less than 1%.

[0318] According to the above configuration, a structure having excellent heat resistance, suppressed generation of voids, and high reliability can be obtained.

[0319] Hereinafter, each component of the structure of this embodiment will be described.

[0320] (First and second floors)

[0321] The first layer and the second layer include at least one selected from the group consisting of resin, silicon, ceramic, compound semiconductor, and glass. It should be noted that the first layer and the second layer may be composed of different materials among these materials, may be composed of the same material, or may be layers formed of materials obtained by combining these materials.

[0322] The resin is not limited to the following resins, and examples thereof include polyacetal, polyamide (PA), polycarbonate (PC), modified polyphenylene ether, polybutylene terephthalate, glass fiber (GF) reinforced polyethylene terephthalate, ultra-high molecular weight polyethylene, syndiotactic polystyrene, epoxy resin, glass epoxy resin (FR-4), phenol, silicon, amorphous polyarylate, polysulfone, polyethersulfone, polyphenylene sulfide, polyetheretherketone, polyimide (PI), polyetherimide, fluororesin, LCP (Liquid Crystal Polymer, liquid crystal polymer), etc.

[0323] Examples of ceramics include, but are not limited to, aluminum oxide (Al 2 O 3 ), aluminum nitride (AlN), silicon carbide (SiC), boron nitride (BN), and silicon nitride (SiN).

[0324] Examples of compound semiconductors include, but are not limited to, gallium nitride, indium phosphide, gallium arsenide, and gallium phosphide.

[0325] The area of ​​the first layer is not limited to the following areas, but can be, for example, 100 to 22,500 mm 2 The thickness is not limited to the following thicknesses, but may be, for example, 500 to 1,000 μm.

[0326] The area of ​​the second layer is not limited to the following areas, but can be, for example, 100 to 250,000 mm 2 The thickness is not limited to the following thicknesses, but may be 500 to 10,000 μm.

[0327] (Copper Pillar)

[0328] The structure of this embodiment has a plurality of copper pillars connecting the first layer and the second layer. The copper pillars play the role of metal wiring for electrical connection. The copper pillars can be connected between the first layer and the second layer by solder. In addition, the metal wiring mentioned here refers to a metal area for electrical connection. The shape of the metal area when viewed vertically from the horizontal surface of the mounting substrate can be, for example, any one of a dot shape, a circle shape, a square shape, and a line shape, or a combination of two or more thereof.

[0329] From the perspective of good electrical connection and increased capacity of electronic devices, the distance between adjacent copper pillars is set to 150 μm or less, preferably 140 μm or less, and more preferably 130 μm or less.

[0330] It should be noted that, in the structure of this embodiment, the distances between adjacent copper pillars among the plurality of copper pillars may be completely the same, or may be in different combinations.

[0331] In the structure of this embodiment, the number of copper pillars is 1 mm from the viewpoint of high density. 2 The number of the number of fibers is preferably 10 to 50, more preferably 15 to 50, and even more preferably 20 to 50.

[0332] The distance between the first layer and the second layer connected by the copper pillar corresponds to the longitudinal length of the copper pillar and the thickness of the third layer described later, and is preferably 1 μm to 100 μm.

[0333] (Second epoxy resin composition, third layer, second cured product)

[0334] In the structured body of the present embodiment, 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.

[0335] The third layer is a second cured product of a second epoxy resin composition containing an epoxy resin, a polyimide resin and an inorganic filler.

[0336] That is, the second epoxy resin composition of the present embodiment is an epoxy resin composition used for the second cured product of the present embodiment, and contains an epoxy resin, a polyimide resin, and an inorganic filler.

[0337] The second cured product of the present embodiment is a cured product of a third layer between the first layer and the second layer for connection using a plurality of copper pillars with a distance between adjacent copper pillars being 150 μm or less.

[0338] In the third layer and the second cured product of this embodiment, from the viewpoint of reliability, the ratio of the area of ​​pores to the surface area of ​​the third layer and the second cured product is 1% or less, preferably 0.8% or less, and more preferably 0.5% or less.

[0339] The organic solvent content in the second epoxy resin composition used in the third layer of the structure of this embodiment and the second epoxy resin composition used in the second cured product of this embodiment is preferably 1% by mass or less. More preferably, it is 0.7% by mass or less, and even more preferably, it is 0.5% by mass or less. This can suppress the formation of voids in the cured product caused by volatilization of the organic solvent during the production of the second cured product.

[0340] The content of the organic solvent in the second epoxy resin composition can be measured using GC (gas chromatography) and controlled to fall within the above-mentioned numerical range by performing a drying treatment in a purification step of the polyimide resin.

[0341] In addition, by adjusting the content of polyimide resin, the area ratio of the pores can be controlled. If the content of polyimide resin is reduced, there is a tendency that the area ratio of the pores becomes smaller. Specifically, by adjusting the content of polyimide resin to 1% to 20% by mass of the second cured product as a whole, the area ratio of the pores of the second cured product can be controlled to less than 1%. From this viewpoint, the content of polyimide is preferably 1% to 20% by mass of the second cured product as a whole, more preferably 1% to 15% by mass, and further preferably 2% to 10.5% by mass.

[0342] The area ratio of the pores on the surface of the second cured product of this embodiment can be obtained by obtaining an image observed from a direction perpendicular to the surface of the second cured product and calculating the area ratio of the pores. Specifically, it can be measured by the method described in the Examples below.

[0343] <Peak Intensity Ratio in Infrared Absorption Spectrum>

[0344] The third layer constituting the structure of the present embodiment, and the first and second cured products of the present embodiment have C=O derived from polyimide in the infrared (IR) absorption spectra and are present at 1,700 to 1,800 cm -1 The peak with the maximum intensity Ia in the range of 1,450 to 1,550 cm-1 is derived from C=C in the aromatic ring. -1 The maximum intensity Ib of the peak within the range of preferably satisfies the following formula (i).

[0345] 0.1≤Ia / Ib≤0.5…(i)

[0346] From the perspective of achieving low CTE (coefficient of thermal expansion) for the third layer constituting the structure of this embodiment, and the first and second cured products of this embodiment, the ratio Ia / Ib is preferably 0.1 or greater, more preferably 0.105 or greater, and even more preferably 0.11 or greater. Furthermore, from the perspective of suppressing void formation, the ratio Ia / Ib is preferably 0.5 or less, more preferably 0.495 or less, and even more preferably 0.49 or less.

[0347] The ratio Ia / Ib in the formula (i) can be controlled within the above numerical range by adjusting the content of the polyimide resin in the second epoxy resin composition used in the second cured product. Furthermore, the ratio Ia / Ib in the formula (i) can be controlled within the above numerical range by adjusting the content of the polyimide resin in the first epoxy resin composition used in the first cured product.

[0348] <Epoxy resin>

[0349] The second epoxy resin composition used in the third layer constituting the structured body of the present embodiment and the second cured product of the present embodiment contains an epoxy resin.

[0350] The epoxy resin is not particularly limited, and commonly used epoxy resins can be used. For example, an epoxy resin having two or more epoxy groups in one molecule is preferred.

[0351] The epoxy resin may be solid or liquid at room temperature. From the perspective of the filling properties of the second epoxy resin composition of this embodiment, the epoxy resin is preferably liquid at room temperature. The epoxy resin may be a liquid epoxy resin at room temperature (hereinafter also referred to as a "liquid epoxy resin"), and commonly used liquid epoxy resins may be used.

[0352] The viscosity of the liquid epoxy resin measured at room temperature using an E-type viscometer is preferably, for example, 0.0001 to 10 Pa·s.

[0353] As the epoxy resin, any of the epoxy resins exemplified as the epoxy resin (A) contained in the first resin composition may be used.

[0354] Among these, from the viewpoint of the fluidity of the second epoxy resin composition, for example, bisphenol-type epoxy resins are preferred. Furthermore, from the viewpoint of the heat resistance and adhesion of the second epoxy resin composition and the second cured product, and the fluidity of the second epoxy resin composition, for example, glycidylamine-type epoxy resins are preferred.

[0355] As described above, the epoxy resin is preferably one or more selected from the group consisting of bisphenol-type epoxy resins and glycidylamine-type epoxy resins.

[0356] From the viewpoint of the fluidity of the second epoxy resin composition, the bisphenol-type epoxy resin is preferably at least one 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).

[0357] When a bisphenol A epoxy resin and a bisphenol F epoxy resin are used in combination, the mass ratio (bisphenol A epoxy resin:bisphenol F epoxy resin) is not particularly limited. From the viewpoint of the heat resistance and adhesion of the second epoxy resin composition and the fluidity of the second epoxy resin composition, it is preferably 5:95 to 50:50, more preferably 10:90 to 40:60, and even more preferably 20:80 to 40:60.

[0358] From the viewpoint of the fluidity of the second epoxy resin composition, it is preferred that both the bisphenol-type epoxy resin and the glycidylamine-type epoxy resin be liquid at room temperature.

[0359] The bisphenol-type epoxy resin and the glycidylamine-type epoxy resin may be used alone or in combination of two or more. From the viewpoint of heat resistance and adhesion of the second epoxy resin composition and the second cured product, and the fluidity of the second epoxy resin composition, it is preferred to use a bisphenol-type epoxy resin and a glycidylamine-type epoxy resin in combination.

[0360] The total content of the bisphenol-type epoxy resin and the glycidylamine-type epoxy resin is not particularly limited. From the perspectives of heat resistance and adhesion of the second epoxy resin composition and the second cured product, as well as the fluidity of the second epoxy resin composition, the total content of the epoxy resin is preferably 20% by mass or greater, more preferably 30% by mass or greater, even more preferably 50% by mass or greater, and even more preferably 80% by mass or greater. The upper limit of the total content is not particularly limited; from the perspectives of viscosity, glass transition temperature, and heat resistance, it can be determined within a range that achieves desired properties and characteristics, and may be 100% by mass.

[0361] When a bisphenol-type epoxy resin and a glycidylamine-type epoxy resin are used in combination, the mass ratio (bisphenol-type epoxy resin:glycidylamine-type epoxy resin) is not particularly limited. From the viewpoint of heat resistance and adhesion of the second epoxy resin composition and the second cured product, and the fluidity of the second epoxy resin composition, for example, it is preferably 20:80 to 95:5, more preferably 40:60 to 90:10, and even more preferably 60:40 to 80:20.

[0362] In addition, in this embodiment, an epoxy resin that is solid at room temperature can also be used.

[0363] From the viewpoint of fluidity of the second 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 the epoxy resin.

[0364] The epoxy equivalent of the epoxy resin is not particularly limited, but is preferably 60 to 400 g / mol, more preferably 70 to 300 g / mol, and even more preferably 80 to 250 g / mol from the viewpoint of heat resistance of the second epoxy resin composition and the second cured product.

[0365] Here, the epoxy equivalent is the mass of the 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 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 after dissolution in an ultrasonic cleaner, 10 mL of glacial acetic acid and 1.5 g of cetyltrimethylammonium bromide are added, and the epoxy equivalent is determined by titrating with a 0.1 mol / L perchloric acid / acetic acid solution.

[0366] The epoxy resin preferably has a high purity. In particular, the amount of hydrolyzable chlorine is associated with corrosion of aluminum wiring on components such as ICs (Integrated Circuits), so it is preferably as low as possible. For example, from the perspective of excellent moisture resistance, it is preferably 500 ppm or less.

[0367] Here, the amount of hydrolyzable chlorine is determined by dissolving 1 g of a sample epoxy resin in 30 mL of dioxane, adding 5 mL of a 1N-KOH (potassium hydroxide) methanol solution, and refluxing the mixture for 30 minutes, followed by potentiometric titration.

[0368] The content of the epoxy resin in the third layer, the second cured product of the present embodiment, and the second epoxy resin composition of the present embodiment is not particularly limited. From the viewpoint of heat resistance and adhesion, it is preferably 1 to 50% by mass, more preferably 10 to 45% by mass, and even more preferably 20 to 40% by mass relative to the total amount of the third layer and the cured product.

[0369] <Polyimide resin>

[0370] The polyimide resin is not limited to the following substances, and examples thereof include resins obtained by condensing tetracarboxylic dianhydride with diamine by a known method. Such polyimide resins are obtained by, for example, reacting tetracarboxylic dianhydride with diamine in an organic solvent at a reaction temperature of 80°C or less, preferably 0-60°C. As the reaction proceeds, the viscosity of the reaction solution gradually increases, generating a polyamic acid as a polyimide precursor. The polyimide resin is obtained by subjecting the polyamic acid to dehydration ring closure. The dehydration ring closure can be performed by a thermal ring closure method using a heat treatment or a chemical ring closure method using a dehydrating agent.

[0371] During the condensation reaction, the mixing ratio of tetracarboxylic dianhydride to diamine (tetracarboxylic dianhydride:diamine) is generally 1.00:1.00 to 1.00:2.00 in terms of molar ratio. From the perspective of improving compatibility with the epoxy resin when forming the second epoxy resin composition and improving fluidity when the second epoxy resin composition is prepared, the mixing ratio of tetracarboxylic dianhydride to 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 1.0:2.0.

[0372] The mixing ratio of the diamine to the tetracarboxylic dianhydride can be 2.00 or more. However, since tetracarboxylic dianhydride can react with only two diamines at most, the upper limit of the ratio is 2.00.

[0373] Regarding tetracarboxylic dianhydride as a raw material of the polyimide resin, the same may be said of tetracarboxylic dianhydride used as a raw material of the polyimide resin (B) contained in the first resin composition.

[0374] The diamine used as a raw material of the polyimide resin may refer to the diamine used as a raw material of the polyimide resin (B) contained in the first resin composition. The polyimide resin may be used alone or in combination of two or more.

[0375] The organic solvent used in the synthesis of the polyimide resin contained in the second resin composition using the aforementioned compound by the above method is not limited to the following substances, and is preferably an organic solvent capable of dissolving or dispersing the polyimide resin. As such an organic solvent, reference may be made to the organic solvent used in the synthesis of the polyimide resin (B) contained in the first resin composition. One organic solvent may be used alone, or two or more organic solvents may be used in combination.

[0376] The content of the polyimide resin in the third layer, the second cured product of this embodiment, and the second epoxy resin composition of this embodiment is not particularly limited. From the perspective of lowering the CTE of the second cured product of this embodiment and suppressing voids, the content is preferably 1 to 20% by mass, more preferably 1 to 15% by mass, and even more preferably 2 to 10.5% by mass, relative to the total amount of the third layer and the second cured product.

[0377] <Inorganic filler>

[0378] As the inorganic filler, the inorganic filler (D) contained in the above-mentioned first resin composition may be referred to.

[0379] The inorganic filler may be a flame retardant. Examples of the flame retardant include, but are not limited to, aluminum hydroxide, magnesium hydroxide, zinc borate, and zinc molybdate.

[0380] The inorganic filler may be used alone or in combination of two or more.

[0381] Among these, from the viewpoint of easy availability, chemical stability, and material cost, for example, silica is preferred, and fused silica is more preferred.

[0382] The particle shape of the inorganic filler is not particularly limited and may be irregular or spherical. From the viewpoint of the fluidity and permeability of the epoxy resin composition into fine gaps, spherical silica is preferred, and spherical fused silica is particularly preferred.

[0383] In addition, the inorganic filler may be surface treated.

[0384] Specifically, the inorganic filler may be surface-treated with a silane coupling agent.

[0385] As the silane coupling agent, the silane coupling agents exemplified in the case of surface treatment of the inorganic filler (D) contained in the first resin composition may be used. Silane coupling agents may be used alone or in combination of two or more.

[0386] The volume average particle size of the inorganic filler is not limited to the following particle size, but is, for example, preferably 0.1 to 10 μm, more preferably 0.3 to 5 μm, and even more preferably 0.5 to 3 μm.

[0387] When the volume average particle size of the inorganic filler is 0.1 μm or larger, dispersibility in the epoxy resin tends to improve. On the other hand, when it is 10 μm or smaller, sedimentation of the inorganic filler in the second epoxy resin composition tends to be suppressed. Furthermore, the second epoxy resin composition has improved permeability and fluidity in fine gaps, thereby suppressing the formation of voids and unfilled areas.

[0388] The volume average particle size refers to the particle size at a point corresponding to 50% volume when the cumulative number distribution curve is calculated based on the particle size, with the total volume of the particles being 100%. This can be measured using a particle size distribution analyzer using a laser diffraction scattering method.

[0389] The content of the inorganic filler in the third layer, the second cured product of this embodiment, and the second epoxy resin composition of this embodiment is not particularly limited, but is preferably 50% to 70% by mass based on the total amount of the third layer, the second cured product, and the second epoxy resin composition.

[0390] By setting the inorganic filler content to 50% by mass or greater, the effect of reducing the thermal expansion coefficient and improving the thermal cycling resistance tends to be more easily achieved. By setting the inorganic filler content to 70% by mass or less, the second epoxy resin composition's permeability and fluidity in fine gaps tends to be improved, and the formation of voids and unfilled areas tends to be suppressed. In particular, from the perspective of improving the thermal cycling resistance, a higher lower limit of the inorganic filler content is preferred.

[0391] <Curing agent for epoxy resin>

[0392] The third layer and the second cured product of the present embodiment can be produced using a curing agent for epoxy resin.

[0393] The epoxy resin curing agent used to obtain the third layer and the second cured product of this embodiment is not limited to the following substances, and examples thereof include aromatic amine curing agents, aromatic amine adduct curing agents, acid anhydride curing agents, phenolic curing agents, and thiol curing agents. The curing agent may be used alone or in combination of two or more.

[0394] Examples of the aromatic amine curing agent include, but are not limited to, diaminodiphenylmethane, m-phenylenediamine, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, diethyltoluenediamine, trimethylenebis(4-aminobenzoate), polytetramethylene oxide-diparaaminobenzoate, 4-aminophenyl 4-benzoate, KAYAHARDA-A (manufactured by Nippon Kayaku Co., Ltd.), and ETHACURE 100 (manufactured by Mitsui Fine Chemicals Co., Ltd.).

[0395] These may be used alone or in combination of two or more.

[0396] Examples of the aromatic amine adduct-based curing agent include, but are not limited to, compounds obtained by reacting a compound having one and / or a plurality of reactive groups with an amine compound.

[0397] Examples of the compound having one and / or a plurality of reactive groups include, but are not limited to, epoxy resins, epoxy-based reactive diluents, alcohol compounds, alkyl halide compounds, isocyanate compounds, and ester compounds.

[0398] As the acid anhydride-based curing agent, the acid anhydride-based curing agent exemplified as the curing agent (C) contained in the above-mentioned first resin composition may be used.

[0399] As the phenolic curing agent, the phenolic curing agent exemplified as the curing agent (C) contained in the first resin composition may be used.

[0400] As the thiol-based curing agent, any of the thiol-based curing agents exemplified as the curing agent (C) contained in the first resin composition may be used.

[0401] Regarding the aromatic amine compounds used in the aforementioned aromatic amine adduct-based curing agents, electron-withdrawing amine compounds and amine compounds having multiple functional groups in their side chains have poor reactivity as amines and excellent stability when formed into amine adducts. Therefore, examples of the aforementioned aromatic amine compounds include 4,4'-diaminodiphenyl sulfone, diethyltoluenediamine (2,4-diamino-3,5-diethyltoluene, 2,6-diamino-3,5-diethyltoluene), and dimethylthiotoluenediamine.

[0402] On the other hand, regarding the aromatic amine compounds used in the aromatic amine adduct-based curing agents, amine compounds without electron-withdrawing properties and amine compounds without functional groups on their side chains are highly reactive as amines and exhibit excellent curability when formed into amine adducts. Therefore, the aromatic amine compounds are preferably aromatic amines having a -CO-, -C(=O)O-, or -C(=O)NH- bond, and particularly aromatic amines having a -C(=O)O- bond are particularly preferred. Examples of the aromatic amine compounds 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.

[0403] <Organic Solvents>

[0404] As described above, the polyimide resin is obtained by condensing tetracarboxylic dianhydride and diamine.

[0405] The organic solvent used in synthesizing the polyimide resin is not particularly limited, but is preferably an organic solvent capable of dissolving or dispersing the polyimide resin.

[0406] Examples of the organic solvent include, but are not limited to, alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and tert-butanol; 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; esters such as ethyl acetate and γ-butyrolactone; ethylene carbonate, carbonate Carbonates such as propylene glycol; 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 within 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-butylphosphoric acid. These organic solvents may be used alone or in combination.

[0407] The second epoxy resin composition of the present embodiment may include an organic solvent for synthesizing the above-mentioned polyimide resin. From the viewpoint of suppressing the generation of voids when making a cured product, the content of the organic solvent in the second epoxy resin composition is preferably 1% by mass or less. The content of the organic solvent in the second epoxy resin composition is more preferably 0.7% by mass or less, and further preferably 0.5% by mass or less. It should be noted that the lower limit of the content of the organic solvent is not particularly limited and may be below the detection limit, which is 1 ppm or more. In addition, from the viewpoint of improving compatibility with epoxy resin, curing agent, polyimide resin, and improving the fluidity of the second epoxy resin composition, the content of the organic solvent is preferably 0.01% by mass or more.

[0408] As the organic solvent, a solvent other than the organic solvent used for synthesizing the polyimide resin may be contained as long as the content falls within the above-mentioned range.

[0409] [Method for producing cured product]

[0410] The third layer constituting the structure of this embodiment and the second cured product of this embodiment can be obtained by curing the second epoxy resin composition of this embodiment containing an epoxy resin, a polyimide resin, an inorganic filler, and a curing agent as needed.

[0411] That is, the second epoxy resin composition of the present embodiment is used for the second cured product of the present embodiment, and contains an epoxy resin, a polyimide resin, and an inorganic filler.

[0412] The epoxy resin composition of the present embodiment can be obtained by mixing the components, for example, by stirring and mixing using a rotation / revolution stirrer (eg, "ARE-310" manufactured by THINKY Corporation), and then kneading using a three-roll mill.

[0413] [Method for forming the third layer]

[0414] The third layer constituting the structure of the present embodiment can be formed by using the second epoxy resin composition of the present embodiment, injecting it between the first layer and the second layer, and then heating and curing it after molding.

[0415] Specifically, the following methods are used to form a first layer and a second layer connected by copper pillars: a method wherein the semiconductor chip and substrate are aligned using a connection device such as a flip-chip bonder, and then the semiconductor chip and substrate are pressed while being heated at a temperature above the melting point of the solder bumps to connect the semiconductor chip and substrate; a method wherein the semiconductor chip and substrate are aligned, and the semiconductor chip and substrate are temporarily fixed by pressing the semiconductor chip and substrate at a temperature lower than the melting point of the solder bumps, and then the semiconductor chip and substrate are heated in a reflow furnace to melt the solder bumps and connect the semiconductor chip and substrate. Subsequently, a second epoxy resin composition is injected between the first and second layers using a mold, transfer molding machine, compression molding machine, injection molding machine, spray dispenser, etc., and appropriately molded, and then heated at 80°C to 180°C for 1 to 10 hours to form the second layer.

[0416] Examples of the heating method include methods using a heating oven, a clean oven, a pressurized oven, and the like.

[0417] Adhesives>>

[0418] The adhesive of the present embodiment includes the first epoxy resin composition or the second epoxy resin composition of the present embodiment.

[0419] The first epoxy resin composition or the second epoxy resin composition of the present embodiment can be suitably used as an adhesive.

[0420] Packaging Materials

[0421] The encapsulating material of this embodiment includes the first cured product or the second cured product of this embodiment. The first cured product or the second cured product of this embodiment can be suitably used as a sealant. The sealant is preferably a semiconductor encapsulating material.

[0422] The first cured product or the second cured product of the present embodiment is useful as a packaging material, a filling material, an insulating material, a sealing material, or the like.

[0423] As packaging materials, they are useful as solid packaging materials, liquid packaging materials, film-like packaging materials, etc. As liquid packaging materials, they are useful as underfill materials, casting materials, barrier materials, etc. As insulating materials, they are useful as insulating adhesive films, insulating adhesive pastes, solder resists, etc.

[0424] The first encapsulating material or the second encapsulating material of this embodiment includes the first cured product or the second cured product of this embodiment.

[0425] Semiconductor Package

[0426] The semiconductor package of this embodiment includes the first cured product or the second cured product of this embodiment.

[0427] The first cured product or the second cured product of this embodiment can be suitably used as a semiconductor package.

[0428] The method for manufacturing the first semiconductor package or the second semiconductor package of the present embodiment includes a step of manufacturing a semiconductor package using the first epoxy resin composition or the second epoxy resin composition of the present embodiment.

[0429] The process of manufacturing a semiconductor package using the first epoxy resin composition or the second epoxy resin composition of this embodiment may include a process of preparing the first epoxy resin composition or the second epoxy resin composition of this embodiment.

[0430] The process of manufacturing a semiconductor package using the first epoxy resin composition or the second epoxy resin composition of this embodiment may be a process of appropriately shaping the prepared first epoxy resin composition or the second epoxy resin composition, heating it at a specified temperature and time to cure it, and thereby manufacturing a semiconductor package.

[0431] Furthermore, the structure of this embodiment can be suitably used as a semiconductor package.

[0432] The semiconductor package of this embodiment includes the first packaging material or the second packaging material of this embodiment.

[0433] The method for manufacturing a semiconductor package according to the present embodiment includes a step of manufacturing a semiconductor package using the first cured product or the second cured product according to the present embodiment.

[0434] Example

[0435] Hereinafter, the present embodiment will be described with reference to specific examples and comparative examples, but the present invention is not limited to the following examples and comparative examples. That is, those skilled in the art can implement the present invention by adding various modifications to the following examples.

[0436] It should be noted that, unless otherwise specified, “portions” are used as a basis for quality.

[0437] [Examples and Comparative Examples of the First Epoxy Resin Composition and the First Cured Product]

[0438] [Analysis of Components in Epoxy Resin Curing Agents]

[0439] The analysis was performed by the method described in the above section [Analysis of components in epoxy resin curing agent] to calculate the peak areas of the aromatic amine compound (C-1), aromatic amine adduct (C-2-1), and aromatic amine adduct (C-2-2X).

[0440] [Method for measuring viscosity of epoxy resin composition at 25°C]

[0441] The viscosity (Pa·s) of the epoxy resin composition at 25°C was measured as follows: the resin composition (0.3 mL) obtained in the Examples and Comparative Examples was added dropwise to a measuring cup. Five minutes after the sample temperature reached 25°C, the viscosity was measured using an E-type viscometer ("TV-20" (trade name) manufactured by Toki Sangyo Co., Ltd.) (measurement conditions: cone: No. 5, 3°, R = 12 mm). The obtained viscosity was evaluated according to the following evaluation criteria.

[0442] [Evaluation Criteria]

[0443] A: The viscosity at 25°C is 20 Pa·s or less.

[0444] B: The viscosity at 25°C is more than 20 Pa·s and is 50 Pa·s or less.

[0445] C: The viscosity at 25° C. is more than 50 Pa·s and is 100 Pa·s or less.

[0446] D: The viscosity at 25°C exceeds 100 Pa·s.

[0447] [Method for measuring viscosity of epoxy resin composition at 110°C]

[0448] The viscosity (Pa·s) of the epoxy resin composition at 110°C was measured as follows: the resin composition obtained in the examples and comparative examples (0.2 mL) was dropped onto a measuring plate, and after the sample temperature reached 110°C, the viscosity was measured using a rheometer (HAAKE (registered trademark) MARS (trade name), manufactured by Thermo Scientific) by varying the shear rate within the range of 10 ( / s) to 100 ( / s) (measurement conditions: aluminum cone plate R = 20 mm).

[0449] The viscosity at a shear rate of 10 ( / sec) was defined as "V1" and the viscosity at a shear rate of 100 ( / sec) was defined as "V2". The value calculated by V1 / V2 was determined. The obtained values ​​were evaluated according to the following evaluation criteria.

[0450] [Evaluation Criteria]

[0451] A: V1 / V2 is a value of 0.8 or more and 1.2 or less.

[0452] B: V1 / V2 is less than 0.8 and greater than 1.2.

[0453] [Evaluation method for viscosity stability at 110°C (high temperature)]

[0454] Regarding the evaluation of the viscosity stability of the epoxy resin composition at 110°C, the resin composition (0.2 mL) obtained in the Examples and Comparative Examples was dropped onto a measuring plate, and 5 minutes and 60 minutes after the sample temperature reached 110°C, the viscosity was measured using a rheometer (HAAKE (registered trademark) MARS (trade name), manufactured by Thermo Scientific) under the condition that the measuring temperature was constant (110°C) using an oscillation mode (f = 1 Hz) (measuring conditions: aluminum cone plate R = 20 mm, shear rate 20 ( / s)).

[0455] The viscosity after 5 minutes is defined as "η1" and the viscosity after 60 minutes is defined as "η2." The value calculated as η2 / η1 is used as the thickening rate. The obtained thickening rate is evaluated according to the following evaluation criteria. Note that "η2" refers to the viscosity after standing at 110°C for 60 minutes.

[0456] In addition, the lower the thickening rate, the better the storage stability.

[0457] [Evaluation Criteria]

[0458] A: The thickening rate is less than 5.0 times.

[0459] B: The thickening ratio is 5.0 times or more and less than 10.0 times.

[0460] C: The thickening ratio is 10.0 times or more and less than 50.0 times.

[0461] D: The thickening rate is 50.0 times or more.

[0462] [Evaluation of liquidity]

[0463] A 25 μm gap was set on a glass substrate (26 mm wide x 75 mm long) to produce a test piece with a glass plate fixed in place of a semiconductor element. Next, the test piece was placed on a hot plate set at 110°C. The resin composition obtained in the Examples and Comparative Examples was applied to one end of the glass plate, and the time (in seconds) required for the resin to pass through the gap and reach the 20 mm point was measured. The obtained time was evaluated according to the following evaluation criteria.

[0464] It should be noted that the better the fluidity, the better the permeability.

[0465] [Evaluation Criteria]

[0466] A: The arrival time is less than 80 seconds.

[0467] B: The arrival time is more than 80 seconds and less than 120 seconds.

[0468] C: The arrival time is 120 seconds or more and less than 200 seconds.

[0469] D: Arrival time is more than 200 seconds.

[0470] [Curing rate when cured at 165°C]

[0471] The curing rate of the epoxy resin composition when cured at 165°C was determined by the following method. The resin composition obtained in the examples and comparative examples was placed in EXSTER6000 (trade name, Hitachi High-Tech Sciences Co., Ltd.), and the temperature was raised from 25°C to 300°C at 5°C / min. The total amount of heat released observed in the temperature range of 100°C to 250°C was calculated. After being placed in a small high-temperature chamber (manufactured by ESPEC) at 165°C for 2 hours, the same measurement was performed, and the change in heat release in the same temperature range was calculated as a percentage. The calculation formula is shown below.

[0472] Initial heat release A: DSC peak heat release of epoxy resin composition

[0473] Heat release after curing B: DSC peak heat release of the epoxy resin composition after heating

[0474] Curing rate (%) = 100 × (initial heat release A - heat release after curing B) ÷ initial heat release A

[0475] The obtained curing ratio was evaluated according to the following evaluation criteria.

[0476] [Evaluation Criteria]

[0477] A: The curing rate is 99% or more.

[0478] B: The curing rate is less than 99% and 95% or more.

[0479] C: The curing rate is less than 95% and 90% or more.

[0480] D: The curing rate is less than 90%.

[0481] [Solvent content]

[0482] GC-MS measurements were performed using the resin compositions obtained in the Examples and Comparative Examples as samples under the following measurement conditions. As a standard sample, the same solvent as the residual solvent contained in the resin composition was diluted with acetone to an appropriate concentration. Measurements were performed under the same measurement conditions as for the sample, and a calibration curve was created to quantify the solvent content (the amount of organic solvent in the resin composition).

[0483] (Measurement conditions)

[0484] Apparatus: Agilent 7890 / MSD5975C (trade name, gas chromatograph-mass spectrometer, manufactured by Agilent Technologies)

[0485] Column: DB1 (trade name, 30 m x 0.25 mm i.d., manufactured by Agilent Technologies, liquid phase thickness: 0.25 μm)

[0486] Column temperature: 40℃ / 5min~20℃ / min,

[0487] Heating temperature: 320℃ (maintain for 11 minutes)

[0488] Column flow rate: 1ml / min, constant flow

[0489] Inlet temperature: 300℃

[0490] Injection method: split method (split ratio is 200:1)

[0491] Interface temperature: 300°C

[0492] Ionization method: EI (ionization) method (temperature 230°C)

[0493] Determination method: Scan method

[0494] Thermal decomposition device: Frontier-lab PY-3030D (trade name, manufactured by Frontier lab)

[0495] Heating temperature (time): Sample (400°C (1 hour)), Standard sample (400°C (3 minutes))

[0496] Sample size: 0.2~5mg

[0497] [Evaluation Criteria]

[0498] A: The solvent content in the epoxy resin composition is 1% by mass or less.

[0499] B: The solvent content in the epoxy resin composition exceeds 1% by mass.

[0500] [empty hole]

[0501] The resin compositions obtained in Examples and Comparative Examples were poured into Teflon (registered trademark) molds, debubbled in a reduced pressure oven, and heated at 165° C. for 2 hours to produce cured products. The obtained cured products were evaluated according to the following evaluation criteria.

[0502] [Evaluation Criteria]

[0503] A: No voids were observed visually.

[0504] B: Generation of voids was visually observed.

[0505] The abbreviations of the components in the present examples have the following meanings. The abbreviations of the components in the following [Examples and Comparative Examples of the Structure, the Second Epoxy Resin Composition, and the Second Cured Product] are also described.

[0506] (Epoxy resin) or ((A) Epoxy resin)

[0507] EXA-850CRP (bisphenol A-type liquid epoxy resin, EPICLON (registered trademark) EXA-850CRP (trade name), 185 g / eq, manufactured by DIC Corporation)

[0508] EXA-830CRP (bisphenol F-type liquid epoxy resin, EPICLON (registered trademark) EXA-830CRP (trade name), 162 g / eq, manufactured by DIC Corporation)

[0509] jER (registered trademark)-630LSD (trade name, aminophenol-type epoxy resin, 95 g / eq, hydrolyzable chlorine content: 1200 ppm, manufactured by Mitsubishi Chemical Co., Ltd.)

[0510] HP4032D (naphthalene-type epoxy resin, EPICLON (registered trademark) HP4032D (trade name), 141 g / eq, hydrolyzable chlorine content: 100 ppm, manufactured by DIC Corporation)

[0511] (Tetracarboxylic dianhydride) or (acid dianhydride: material for preparing (B) polyimide resin)

[0512] BPDA: 4,4'-biphenyltetracarboxylic dianhydride

[0513] ODPA: 4,4'-oxydiphthalic anhydride

[0514] TAHQ: p-phenylene bis(trimellitic anhydride)

[0515] BPAF: 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride

[0516] (Diamine) or (Diamine: material for preparing (B) polyimide resin)

[0517] APAB: 4-aminophenyl-4'-aminobenzoate

[0518] 44DAS: 4,4'-diaminodiphenyl sulfone

[0519] 33DAS: 3,3'-diaminodiphenyl sulfone

[0520] TPE-M: 1,3-bis(3-aminophenoxy)benzene

[0521] 34ODA: 3,4'-diaminodiphenyl ether

[0522] m-TB: meta-Tolidine

[0523] BAPP: 2,2-bis[4-(4-aminophenoxy)phenyl]propane

[0524] BAFL: 9,9-bis(4-aminophenyl)fluorene

[0525] ETHACURE (registered trademark) 100 Plus (+): Curing agent containing diethyltoluenediamine (manufactured by Mitsui Fine Chemicals)

[0526] ETHACURE (registered trademark) 300: a curing agent containing diethylthiotoluenediamine (manufactured by Mitsui Fine Chemicals Co., Ltd.)

[0527] (Aromatic amine compound (C-1)) or (Aromatic amine: material for preparing (C) curing agent)

[0528] APAB: 4-aminophenyl-4'-aminobenzoate

[0529] 44DAS: 4,4'-diaminodiphenyl sulfone

[0530] 34ODA: 3,4'-diaminodiphenyl ether

[0531] TPE-M: 1,3-bis(3-aminophenoxy)benzene

[0532] ETHACURE (registered trademark) 300: a curing agent containing diethylthiotoluenediamine (manufactured by Mitsui Fine Chemicals Co., Ltd.)

[0533] ETHACURE (registered trademark) 100 Plus (+): Curing agent containing diethyltoluenediamine (manufactured by Mitsui Fine Chemicals)

[0534] KAYAHARD (registered trademark) AA: A curing agent containing 3,3'-diethyl-4,4'-diaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd.)

[0535] (Reactive compound) or (Reactive compound: material for preparing (C) curing agent)

[0536] 2-EH: 2-ethylhexyl glycidyl ether

[0537] BGE: Butyl Glycidyl Ether

[0538] ph-GE: phenyl glycidyl ether

[0539] (Curing Accelerator) or ((E)Curing Accelerator)

[0540] 2P4MHZ-PW (CUREZOL (registered trademark) 2P4MHZ-PW, 2-phenyl-4-methyl-5-hydroxymethylimidazole, manufactured by Shikoku Chemicals Co., Ltd.)

[0541] Compound E-1A / E-1B: described below.

[0542] Compound E-1C: described below.

[0543] Compound E-1D: described below.

[0544] (Inorganic filler) or ((D) Inorganic filler)

[0545] SE203G-SEJ (spherical fused silica, volume average particle size 0.5 μm, manufactured by ADMATECHS)

[0546] <Preparation of Polyimide (PI) Resin>

[0547] (Synthesis example A1-1)

[0548] After nitrogen purge, a 500 mL four-necked flask equipped with a reflux tube and a Dean-Stark tube was added with 21 g of N-methyl-2-pyrrolidone (NMP) and 14.62 g (50 mmol) of 1,3-bis(3-aminophenoxy)benzene (TPE-M) and stirred until homogeneous. Subsequently, 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. Under nitrogen flow, the mixture was stirred at room temperature for 1 hour to carry out an addition reaction. The temperature was then raised to 180°C, and after reaching 180°C, a polymerization reaction was carried out for 4 hours. One hour after reaching 180°C, the mixture of water and 1-butanol was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled until the internal temperature reached 80°C, and NMP was added to obtain an NMP solution of PI with a concentration of 20% by mass. The NMP solution was added dropwise to ethanol to reprecipitate PI, and the resin powder was recovered by suction filtration. The recovered powder was washed with water and then vacuum-dried in an oven at 80° C. for 4 hours to obtain PI1 powder.

[0549] (Synthesis example A1-2)

[0550] After nitrogen substitution in a 500 mL four-necked flask equipped with a reflux tube and a Dean-Stark tube, 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 uniform. Subsequently, 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 added and stirred at room temperature for 1 hour under nitrogen flow to carry out an addition reaction. Thereafter, the temperature was raised to 180°C, and after reaching 180°C, a dehydration ring closure was carried out for 4 hours. One hour after reaching 180°C, the mixture of water and 1-butanol was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled until the internal temperature reached 80°C, and NMP was added to obtain an NMP solution of PI with a concentration of 20% by mass. The NMP solution was added dropwise to ethanol to reprecipitate PI, and the resin powder was recovered by suction filtration. The recovered powder was washed with water and then vacuum-dried in an oven at 80° C. for 4 hours to obtain PI2 powder.

[0551] (Synthesis example A1-3)

[0552] After nitrogen substitution in a 500mL four-necked flask equipped with a reflux tube and a Dean Stark tube, 26g of N-methyl-2-pyrrolidone (NMP) and 17.43g (50mmol) of 9,9-bis(4-aminophenyl)fluorene (BAFL) were added and stirred until uniform. Subsequently, 7.36g (25mmol) of biphenyltetracarboxylic dianhydride (BPDA), 20g of NMP, 22.6g of 1-butanol, and 174μL of triethylamine were added and stirred at room temperature for 1 hour under nitrogen flow to carry out an addition reaction. Thereafter, the temperature was raised to 180°C, and after reaching 180°C, a dehydration ring closure was performed for 4 hours. One hour after reaching 180°C, a mixture of water and 1-butanol was taken out from the Dean Stark tube. After 4 hours, the mixture was cooled until the internal temperature reached 80°C, and NMP was added to obtain an NMP solution of PI with a concentration of 20% by mass. The NMP solution was added dropwise to ethanol to reprecipitate PI, and the resin powder was recovered by suction filtration. The recovered powder was washed with water and then vacuum-dried in an oven at 80° C. for 4 hours to obtain PI3 powder.

[0553] (Synthesis example A1-4)

[0554] After nitrogen replacement of a 500mL four-necked flask with a reflux tube and a Dean Stark tube, N-methyl-2-pyrrolidone (NMP) 15g, ETHACURE (registered trademark) 100Plus 8.91g (50mmol) were added and stirred until uniform. Thereafter, biphenyltetracarboxylic dianhydride (BPDA) 7.36g (25mmol), NMP 15g, 19.9g of 1-butanol, and 174 μL of triethylamine were added and stirred at room temperature for 1 hour under nitrogen flow for addition reaction. Thereafter, the temperature was raised to 180°C, and after reaching 180°C, a dehydration ring closure was performed for 4 hours. After 1 hour after reaching 180°C, a mixture of water and 1-butanol was taken out 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 an NMP solution of PI having a concentration of 20% by mass. The NMP solution was added dropwise to ethanol to reprecipitate PI, and the resin powder was recovered by suction filtration. The recovered powder was washed with water and then vacuum-dried in an oven at 80°C for 4 hours or 1 hour to obtain PI4 powder.

[0555] (Synthesis Example A1-5)

[0556] After nitrogen replacement of a 500mL four-necked flask with a reflux tube and a Dean Stark tube, 20g of N-methyl-2-pyrrolidone (NMP) and 10.72g (50mmol) of ETHACURE (registered trademark) 300 were added and stirred until uniform. Thereafter, 7.36g (25mmol) of biphenyltetracarboxylic dianhydride (BPDA), 14g of NMP, 20.5g of 1-butanol and 174 μL of triethylamine were added and stirred at room temperature for 1 hour under nitrogen flow for addition reaction. Thereafter, the temperature was raised to 180°C, and after reaching 180°C, a dehydration ring closure was performed for 4 hours. After 1 hour after reaching 180°C, a mixture of water and 1-butanol was taken out 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 an NMP solution of PI having a concentration of 20% by mass. The NMP solution was added dropwise to ethanol to reprecipitate PI, and the resin powder was recovered by suction filtration. The recovered powder was washed with water and then vacuum-dried in an oven at 80° C. for 4 hours to obtain PI5 powder.

[0557] (Synthesis example A1-6)

[0558] After nitrogen substitution in a 500mL four-necked flask equipped with a reflux tube and a Dean Stark tube, 22g of N-methyl-2-pyrrolidone (NMP) and 14.62g (50mmol) of 1,3-bis(3-aminophenoxy)benzene (TPE-M) were added and stirred until uniform. Subsequently, 7.76g (25mmol) of 4,4'-oxydiphthalic anhydride (ODPA), 20g of NMP, 22g of 1-butanol, and 174μL of triethylamine were added and stirred at room temperature for 1 hour under nitrogen flow to carry out the addition reaction. Thereafter, the temperature was raised to 180°C, and after reaching 180°C, a dehydration ring closure was performed for 4 hours. One hour after reaching 180°C, a mixture of water and 1-butanol was taken out from the Dean Stark tube. After 4 hours, the mixture was cooled until the internal temperature reached 80°C, and NMP was added to obtain an NMP solution of PI with a concentration of 20% by mass. The NMP solution was added dropwise to ethanol to reprecipitate PI, and the resin powder was recovered by suction filtration. The recovered powder was washed with water and then vacuum-dried in an oven at 80° C. for 4 hours to obtain PI6 powder.

[0559] (Synthesis Example A1-7)

[0560] After nitrogen purge, a 500 mL four-necked flask equipped with a reflux tube and a Dean-Stark tube was charged with 30 g of N-methyl-2-pyrrolidone (NMP) and 20.53 g (50 mmol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) and stirred until homogeneous. Subsequently, 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 added. Under a nitrogen flow, the mixture was stirred at room temperature for 1 hour to allow for an addition reaction. The temperature was then raised to 180°C, and after reaching 180°C, dehydration and ring closure were performed 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 until the internal temperature reached 80°C, and NMP was added to obtain a 20% by mass PI NMP solution. This NMP solution was added dropwise to ethanol to reprecipitate the PI, and the resin powder was recovered by suction filtration. The recovered powder was washed with water and then vacuum-dried in an 80°C oven for 4 hours to obtain PI7 powder.

[0561] (Synthesis example A1-8)

[0562] After nitrogen substitution in a 500mL four-necked flask equipped with a reflux tube and a Dean Stark tube, 27g of N-methyl-2-pyrrolidone (NMP) and 17.43g (50mmol) of 9,9-bis(4-aminophenyl)fluorene (BAFL) were added and stirred until uniform. Subsequently, 7.76g (25mmol) of 4,4'-oxydiphthalic anhydride (ODPA), 20g of NMP, 22.9g of 1-butanol, and 174μL of triethylamine were added and stirred at room temperature for 1 hour under nitrogen flow to carry out the addition reaction. Thereafter, the temperature was raised to 180°C, and after reaching 180°C, a dehydration ring closure was performed for 4 hours. One hour after reaching 180°C, a mixture of water and 1-butanol was taken out from the Dean Stark tube. After 4 hours, the mixture was cooled until the internal temperature reached 80°C, and NMP was added to obtain an NMP solution of PI with a concentration of 20% by mass. The NMP solution was added dropwise to ethanol to reprecipitate PI, and the resin powder was recovered by suction filtration. The recovered powder was washed with water and then vacuum-dried in an oven at 80° C. for 4 hours to obtain PI8 powder.

[0563] (Synthesis Example A1-9)

[0564] After nitrogen substitution in a 500mL four-necked flask equipped with a reflux tube and a Dean Stark tube, 15g of N-methyl-2-pyrrolidone (NMP) and 8.91g (50mmol) of ETHACURE (registered trademark) 100Plus were added and stirred until uniform. Subsequently, 7.76g (25mmol) of 4,4'-oxydiphthalic anhydride (ODPA), 15g of NMP, 20g of 1-butanol, and 174μL of triethylamine were added and stirred at room temperature for 1 hour under nitrogen flow to carry out an addition reaction. Thereafter, the temperature was raised to 180°C, and after reaching 180°C, a dehydration ring closure was performed for 4 hours. One hour after reaching 180°C, a mixture of water and 1-butanol was taken out from the Dean Stark tube. After 4 hours, the mixture was cooled until the internal temperature reached 80°C, and NMP was added to obtain an NMP solution of PI having a concentration of 20% by mass. The NMP solution was added dropwise to ethanol to reprecipitate PI, and the resin powder was recovered by suction filtration. The recovered powder was washed with water and then vacuum-dried in an oven at 80° C. for 4 hours to obtain PI9 powder.

[0565] (Synthesis example A1-10)

[0566] After nitrogen substitution in a 500mL four-necked flask equipped with a reflux tube and a Dean Stark tube, 20g of N-methyl-2-pyrrolidone (NMP) and 10.72g (50mmol) of ETHACURE (registered trademark) 300 were added and stirred until uniform. Thereafter, 7.76g (25mmol) of 4,4'-oxydiphthalic anhydride (ODPA), 14g of NMP, 20.6g of 1-butanol, and 174μL of triethylamine were added and stirred at room temperature for 1 hour under nitrogen flow to carry out the addition reaction. Thereafter, the temperature was raised to 180°C, and after reaching 180°C, a dehydration ring closure was performed for 4 hours. One hour after reaching 180°C, a mixture of water and 1-butanol was taken out from the Dean Stark tube. After 4 hours, the mixture was cooled until the internal temperature reached 80°C, and NMP was added to obtain an NMP solution of PI with a concentration of 20% by mass. The NMP solution was added dropwise to ethanol to reprecipitate PI, and the resin powder was recovered by suction filtration. The recovered powder was washed with water and then vacuum-dried in an oven at 80° C. for 4 hours to obtain PI10 powder.

[0567] (Synthesis example A1-11)

[0568] After nitrogen substitution in a 500mL four-necked flask equipped with a reflux tube and a Dean Stark tube, 28g of N-methyl-2-pyrrolidone (NMP) and 14.62g (50mmol) of 1,3-bis(3-aminophenoxy)benzene (TPE-M) were added and stirred until uniform. Subsequently, 11.46g (25mmol) of p-phenylene bis(trimellitic anhydride) (TAHQ), 20g of NMP, 22.8g of 1-butanol, and 174μL of triethylamine were added and stirred at room temperature for 1 hour under nitrogen flow to carry out the addition reaction. Thereafter, the temperature was raised to 180°C, and after reaching 180°C, a dehydration ring closure was carried out for 4 hours. One hour after reaching 180°C, the mixture of water and 1-butanol was removed from the Dean Stark tube. After 4 hours, the mixture was cooled until the internal temperature reached 80°C, and NMP was added to obtain an NMP solution of PI with a concentration of 20% by mass. The NMP solution was added dropwise to ethanol to reprecipitate PI, and the resin powder was recovered by suction filtration. The recovered powder was washed with water and then vacuum-dried in an oven at 80° C. for 4 hours to obtain PI11 powder.

[0569] (Synthesis example A1-12)

[0570] After nitrogen purge, a 500 mL four-necked flask equipped with a reflux tube and a Dean-Stark tube was added with 30 g of N-methyl-2-pyrrolidone (NMP) and 20.53 g (50 mmol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) and stirred until homogeneous. Subsequently, 11.46 g (25 mmol) of p-phenylenebis(trimellitic anhydride) (TAHQ), 29 g of NMP, 25 g of 1-butanol, and 174 μL of triethylamine were added, and the mixture was stirred at room temperature for 1 hour under a nitrogen flow to carry out an addition reaction. The temperature was then raised to 180°C, and after reaching 180°C, a dehydration ring closure was carried out for 4 hours. One hour after reaching 180°C, the mixture of water and 1-butanol was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled until the internal temperature reached 80°C, and NMP was added to obtain an NMP solution of PI with a concentration of 20% by mass. The NMP solution was added dropwise to ethanol to reprecipitate PI, and the resin powder was recovered by suction filtration. The recovered powder was washed with water and then vacuum-dried in an oven at 80° C. for 4 hours to obtain PI12 powder.

[0571] (Synthesis example A1-13)

[0572] After nitrogen substitution in a 500mL four-necked flask equipped with a reflux tube and a Dean Stark tube, 34g of N-methyl-2-pyrrolidone (NMP) and 17.43g (50mmol) of 9,9-bis(4-aminophenyl)fluorene (BAFL) were added and stirred until uniform. Subsequently, 11.46g (25mmol) of p-phenylenebis(trimellitic anhydride) (TAHQ), 20g of NMP, 23.6g of 1-butanol, and 174μL of triethylamine were added and stirred at room temperature for 1 hour under nitrogen flow to carry out the addition reaction. Thereafter, the temperature was raised to 180°C, and after reaching 180°C, a dehydration ring closure was performed for 4 hours. One hour after reaching 180°C, a mixture of water and 1-butanol was taken out from the Dean Stark tube. After 4 hours, the mixture was cooled until the internal temperature reached 80°C, and NMP was added to obtain an NMP solution of PI with a concentration of 20% by mass. The NMP solution was added dropwise to ethanol to reprecipitate PI, and the resin powder was recovered by suction filtration. The recovered powder was washed with water and then vacuum-dried in an oven at 80° C. for 4 hours to obtain PI13 powder.

[0573] (Synthesis example A1-14)

[0574] After nitrogen substitution in a 500mL four-necked flask equipped with a reflux tube and a Dean Stark tube, 20g of N-methyl-2-pyrrolidone (NMP) and 8.91g (50mmol) of ETHACURE (registered trademark) 100Plus were added and stirred until uniform. Subsequently, 11.46g (25mmol) of p-phenylene bis(trimellitic anhydride) (TAHQ), 18g of NMP, 21.2g of 1-butanol, and 174μL of triethylamine were added and stirred at room temperature for 1 hour under nitrogen flow to carry out an addition reaction. Thereafter, the temperature was raised to 180°C, and after reaching 180°C, a dehydration ring closure was performed for 4 hours. One hour after reaching 180°C, a mixture of water and 1-butanol was taken out from the Dean Stark tube. After 4 hours, the mixture was cooled until the internal temperature reached 80°C, and NMP was added to obtain an NMP solution of PI having a concentration of 20% by mass. The NMP solution was added dropwise to ethanol to reprecipitate PI, and the resin powder was recovered by suction filtration. The recovered powder was washed with water and then vacuum-dried in an oven at 80° C. for 4 hours to obtain PI14 powder.

[0575] (Synthesis example A1-15)

[0576] After nitrogen substitution in a 500mL four-necked flask equipped with a reflux tube and a Dean Stark tube, 21g of N-methyl-2-pyrrolidone (NMP) and 10.72g (50mmol) of ETHACURE (registered trademark) 300 were added and stirred until uniform. Thereafter, 11.46g (25mmol) of p-phenylene bis(trimellitic anhydride) (TAHQ), 20g of NMP, 21.8g of 1-butanol, and 174μL of triethylamine were added and stirred at room temperature for 1 hour under nitrogen flow to carry out an addition reaction. Thereafter, the temperature was raised to 180°C, and after reaching 180°C, a dehydration ring closure was performed for 4 hours. One hour after reaching 180°C, a mixture of water and 1-butanol was taken out from the Dean Stark tube. After 4 hours, the mixture was cooled until the internal temperature reached 80°C, and NMP was added to obtain an NMP solution of PI having a concentration of 20% by mass. The NMP solution was added dropwise to ethanol to reprecipitate PI, and the resin powder was recovered by suction filtration. The recovered powder was washed with water and then vacuum-dried in an oven at 80° C. for 4 hours to obtain PI15 powder.

[0577] (Synthesis example A1-16)

[0578] After nitrogen purge, a 500 mL four-necked flask equipped with a reflux tube and a Dean-Stark tube was charged with 22 g of N-methyl-2-pyrrolidone (NMP) and 11.41 g (50 mmol) of 4-aminophenyl-4'-aminobenzoate (APAB) and stirred until homogeneous. Subsequently, 11.46 g (25 mmol) of 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride (BPAF), 20 g of NMP, 22.1 g of 1-butanol, and 174 μL of triethylamine were added. Under a nitrogen flow, the mixture was stirred at room temperature for 1 hour to allow for an addition reaction. The temperature was then raised to 180°C, and after reaching 180°C, dehydration and ring closure were performed 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 until the internal temperature reached 80°C, and NMP was added to obtain a 20% by mass PI NMP solution. This NMP solution was added dropwise to ethanol to reprecipitate the PI, and the resin powder was recovered by suction filtration. The recovered powder was washed with water and then vacuum-dried in an 80°C oven for 4 hours to obtain PI16 powder.

[0579] (Synthesis example A1-17)

[0580] After nitrogen purge, a 500 mL four-necked flask equipped with a reflux tube and a Dean-Stark tube was charged with 24 g of N-methyl-2-pyrrolidone (NMP) and 12.42 g (50 mmol) of 4,4'-diaminodiphenylsulfone (44DAS) and stirred until homogeneous. Subsequently, 11.46 g (25 mmol) of 9,9-bis(3,4-dicarboxyphenyl)fluorene dicarboxylic anhydride (BPAF), 20 g of NMP, 22.2 g of 1-butanol, and 174 μL of triethylamine were added. Under a nitrogen flow, the mixture was stirred at room temperature for 1 hour to allow for an addition reaction. The temperature was then raised to 180°C, and after reaching 180°C, dehydration and ring closure were performed 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 until the internal temperature reached 80°C, and NMP was added to obtain a 20% by mass PI NMP solution. This NMP solution was added dropwise to ethanol to reprecipitate the PI, and the resin powder was recovered by suction filtration. The recovered powder was washed with water and then vacuum-dried in an 80°C oven for 4 hours to obtain a PI17 powder.

[0581] (Synthesis example A1-18)

[0582] After nitrogen purge, a 500 mL four-necked flask equipped with a reflux tube and a Dean-Stark tube was charged with 24 g of N-methyl-2-pyrrolidone (NMP) and 12.42 g (50 mmol) of 3,3'-diaminodiphenylsulfone (33DAS) and stirred until homogeneous. Subsequently, 11.46 g (25 mmol) of 9,9-bis(3,4-dicarboxyphenyl)fluorene dicarboxylic anhydride (BPAF), 20 g of NMP, 22.2 g of 1-butanol, and 174 μL of triethylamine were added. Under a nitrogen flow, the mixture was stirred at room temperature for 1 hour to allow for an addition reaction. The temperature was then raised to 180°C, and after reaching 180°C, dehydration and ring closure were performed 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 until the internal temperature reached 80°C, and NMP was added to obtain a 20% by mass PI NMP solution. This NMP solution was added dropwise to ethanol to reprecipitate the PI, and the resin powder was recovered by suction filtration. The recovered powder was washed with water and then vacuum-dried in an 80°C oven for 4 hours to obtain PI18 powder.

[0583] (Synthesis example A1-19)

[0584] After nitrogen purge, a 500 mL four-necked flask equipped with a reflux tube and a Dean-Stark tube was charged with 28 g of N-methyl-2-pyrrolidone (NMP) and 14.62 g (50 mmol) of 1,3-bis(3-aminophenoxy)benzene (TPE-M) and stirred until homogeneous. Subsequently, 11.46 g (25 mmol) of 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride (BPAF), 20 g of NMP, 22.8 g of 1-butanol, and 174 μL of triethylamine were added. The mixture was stirred at room temperature for 1 hour under a nitrogen flow to allow for an addition reaction. The temperature was then raised to 180°C, and after reaching 180°C, dehydration and ring closure were performed 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 until the internal temperature reached 80°C, and NMP was added to obtain a 20% by mass PI NMP solution. This NMP solution was added dropwise to ethanol to reprecipitate the PI, and the resin powder was recovered by suction filtration. The recovered powder was washed with water and then vacuum-dried in an 80°C oven for 4 hours to obtain PI19 powder.

[0585] (Synthesis example A1-20)

[0586] After nitrogen purge, a 500 mL four-necked flask equipped with a reflux tube and a Dean-Stark tube was charged with 20 g of N-methyl-2-pyrrolidone (NMP) and 10.01 g (50 mmol) of 3,4'-diaminodiphenyl ether (34ODA) and stirred until homogeneous. Subsequently, 11.46 g (25 mmol) of 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride (BPAF), 20 g of NMP, 21.5 g of 1-butanol, and 174 μL of triethylamine were added. The mixture was stirred at room temperature for 1 hour under a nitrogen flow to allow for an addition reaction. The temperature was then raised to 180°C, and after reaching 180°C, dehydration and ring closure were performed 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 until the internal temperature reached 80°C, and NMP was added to obtain a 20% by mass PI NMP solution. This NMP solution was added dropwise to ethanol to reprecipitate the PI, and the resin powder was recovered by suction filtration. The recovered powder was washed with water and then vacuum-dried in an 80°C oven for 4 hours to obtain PI20 powder.

[0587] (Synthesis example A1-21)

[0588] After nitrogen substitution in a 500mL four-necked flask equipped with a reflux tube and a Dean Stark tube, 21g of N-methyl-2-pyrrolidone (NMP) and 10.62g (50mmol) of m-tolidine (m-TB) were added and stirred until uniform. Subsequently, 11.46g (25mmol) of 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride (BPAF), 20g of NMP, 21.7g of 1-butanol, and 174μL of triethylamine were added and stirred at room temperature for 1 hour under nitrogen flow to carry out the addition reaction. Thereafter, the temperature was raised to 180°C, and after reaching 180°C, a dehydration ring closure was performed for 4 hours. One hour after reaching 180°C, a mixture of water and 1-butanol was removed from the Dean Stark tube. After 4 hours, the mixture was cooled until the internal temperature reached 80°C, and NMP was added to obtain an NMP solution of PI with a concentration of 20% by mass. The NMP solution was added dropwise to ethanol to reprecipitate PI, and the resin powder was recovered by suction filtration. The recovered powder was washed with water and then vacuum-dried in an oven at 80° C. for 4 hours to obtain PI21 powder.

[0589] (Synthesis example A1-22)

[0590] After nitrogen purge, a 500 mL four-necked flask equipped with a reflux tube and a Dean-Stark tube was charged with 30 g of N-methyl-2-pyrrolidone (NMP) and 20.53 g (50 mmol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) and stirred until homogeneous. Subsequently, 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 stirred at room temperature for one hour under a nitrogen flow to allow for an addition reaction. The temperature was then raised to 180°C, and after reaching 180°C, dehydration and ring closure were performed for four 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 until the internal temperature reached 80°C, and NMP was added to obtain a 20% by mass PI NMP solution. This NMP solution was added dropwise to ethanol to reprecipitate the PI, and the resin powder was recovered by suction filtration. The recovered powder was washed with water and then vacuum-dried in an 80°C oven for 4 hours to obtain a PI22 powder.

[0591] (Synthesis example A1-23)

[0592] After nitrogen purge, a 500 mL four-necked flask equipped with a reflux tube and a Dean-Stark tube was charged with 34 g of N-methyl-2-pyrrolidone (NMP) and 17.43 g (50 mmol) of 9,9-bis(4-aminophenyl)fluorene (BAFL) and stirred until homogeneous. Subsequently, 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 stirred at room temperature for one hour under a nitrogen flow to allow for an addition reaction. The temperature was then raised to 180°C, and after reaching 180°C, dehydration and ring closure were performed for four 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 until the internal temperature reached 80°C, and NMP was added to obtain a 20% by mass PI NMP solution. This NMP solution was added dropwise to ethanol to reprecipitate the PI, and the resin powder was recovered by suction filtration. The recovered powder was washed with water and then vacuum-dried in an 80°C oven for 4 hours to obtain a PI23 powder.

[0593] (Synthesis example A1-24)

[0594] After nitrogen substitution in a 500mL four-necked flask equipped with a reflux tube and a Dean Stark tube, 20g of N-methyl-2-pyrrolidone (NMP) and 8.91g (50mmol) of ETHACURE (registered trademark) 100Plus were added and stirred until uniform. Subsequently, 11.46g (25mmol) of 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride (BPAF), 18g of NMP, 21.2g of 1-butanol, and 174μL of triethylamine were added and stirred at room temperature for 1 hour under nitrogen flow to carry out the addition reaction. Thereafter, the temperature was raised to 180°C, and after reaching 180°C, a dehydration ring closure was performed for 4 hours. One hour after reaching 180°C, a mixture of water and 1-butanol was taken out from the Dean Stark tube. After 4 hours, the mixture was cooled until the internal temperature reached 80°C, and NMP was added to obtain an NMP solution of PI with a concentration of 20% by mass. The NMP solution was added dropwise to ethanol to reprecipitate PI, and the resin powder was recovered by suction filtration. The recovered powder was washed with water and then vacuum-dried in an oven at 80° C. for 4 hours to obtain PI24 powder.

[0595] (Synthesis example A1-25)

[0596] After nitrogen substitution in a 500mL four-necked flask equipped with a reflux tube and a Dean Stark tube, 21g of N-methyl-2-pyrrolidone (NMP) and 10.72g (50mmol) of ETHACURE (registered trademark) 300 were added and stirred until uniform. Subsequently, 11.46g (25mmol) of 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride (BPAF), 20g of NMP, 21.8g of 1-butanol, and 174μL of triethylamine were added and stirred at room temperature for 1 hour under nitrogen flow to carry out the addition reaction. Thereafter, the temperature was raised to 180°C, and after reaching 180°C, a dehydration ring closure was performed for 4 hours. One hour after reaching 180°C, a mixture of water and 1-butanol was removed from the Dean Stark tube. After 4 hours, the mixture was cooled until the internal temperature reached 80°C, and NMP was added to obtain an NMP solution of PI with a concentration of 20% by mass. The NMP solution was added dropwise to ethanol to reprecipitate PI, and the resin powder was recovered by suction filtration. The recovered powder was washed with water and then vacuum-dried in an oven at 80° C. for 4 hours to obtain PI25 powder.

[0597] (Synthesis example A1-26)

[0598] After nitrogen replacement of a 500mL four-necked flask with a reflux tube and a Dean Stark tube, N-methyl-2-pyrrolidone (NMP) 15g, ETHACURE (registered trademark) 100Plus 6.42g (36mmol) were added and stirred until uniform. Thereafter, biphenyltetracarboxylic dianhydride (BPDA) 8.83g (30mmol), NMP 13g, 1-butanol 19.5g, and triethylamine 209μL were added and stirred at room temperature for 1 hour under nitrogen flow for addition reaction. Thereafter, the temperature was raised to 180°C, and after reaching 180°C, a dehydration ring closure was performed for 4 hours. After 1 hour after reaching 180°C, a mixture of water and 1-butanol was taken out 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 an NMP solution of PI having a concentration of 20% by mass. The NMP solution was added dropwise to ethanol to reprecipitate PI, and the resin powder was recovered by suction filtration. The recovered powder was washed with water and then vacuum-dried in an oven at 80° C. for 4 hours to obtain PI26 powder.

[0599] (Synthesis example A1-27)

[0600] After nitrogen replacement of a 500mL four-necked flask with a reflux tube and a Dean Stark tube, N-methyl-2-pyrrolidone (NMP) 15g, ETHACURE (registered trademark) 100Plus 8.02g (45mmol) were added and stirred until uniform. Thereafter, biphenyltetracarboxylic dianhydride (BPDA) 8.83g (30mmol), NMP 16g, 1-butanol 20.0g, and triethylamine 209 μL were added and stirred at room temperature for 1 hour under nitrogen flow for addition reaction. Thereafter, the temperature was raised to 180°C, and after reaching 180°C, a dehydration ring closure was performed for 4 hours. After 1 hour after reaching 180°C, a mixture of water and 1-butanol was taken out 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 an NMP solution of PI having a concentration of 20% by mass. The NMP solution was added dropwise to ethanol to reprecipitate PI, and the resin powder was recovered by suction filtration. The recovered powder was washed with water and then vacuum-dried in an oven at 80° C. for 4 hours to obtain PI27 powder.

[0601] (Synthesis example A1-28)

[0602] After nitrogen substitution in a 500mL four-necked flask equipped with a reflux tube and a Dean Stark tube, 15g of N-methyl-2-pyrrolidone (NMP) and 6.42g (36mmol) of ETHACURE (registered trademark) 100Plus were added and stirred until uniform. Thereafter, 9.31g (30mmol) of 4,4'-oxydiphthalic anhydride (ODPA), 14g of NMP, 19.9g of 1-butanol, and 209μL of triethylamine were added and stirred at room temperature for 1 hour under nitrogen flow to carry out the addition reaction. Thereafter, the temperature was raised to 180°C, and after reaching 180°C, a dehydration ring closure was performed for 4 hours. One hour after reaching 180°C, a mixture of water and 1-butanol was taken out from the Dean Stark tube. After 4 hours, the mixture was cooled until the internal temperature reached 80°C, and NMP was added to obtain an NMP solution of PI having a concentration of 20% by mass. The NMP solution was added dropwise to ethanol to reprecipitate PI, and the resin powder was recovered by suction filtration. The recovered powder was washed with water and then vacuum-dried in an oven at 80° C. for 4 hours to obtain PI28 powder.

[0603] (Synthesis example A1-29)

[0604] After nitrogen substitution in a 500mL four-necked flask equipped with a reflux tube and a Dean Stark tube, 15g of N-methyl-2-pyrrolidone (NMP) and 8.02g (45mmol) of ETHACURE (registered trademark) 100Plus were added and stirred until uniform. Thereafter, 9.31g (30mmol) of 4,4'-oxydiphthalic anhydride (ODPA), 17g of NMP, 20.3g of 1-butanol, and 209μL of triethylamine were added and stirred at room temperature for 1 hour under nitrogen flow to carry out an addition reaction. Thereafter, the temperature was raised to 180°C, and after reaching 180°C, a dehydration ring closure was performed for 4 hours. One hour after reaching 180°C, a mixture of water and 1-butanol was taken out from the Dean Stark tube. After 4 hours, the mixture was cooled until the internal temperature reached 80°C, and NMP was added to obtain an NMP solution of PI having a concentration of 20% by mass. The NMP solution was added dropwise to ethanol to reprecipitate PI, and the resin powder was recovered by suction filtration. The recovered powder was washed with water and then vacuum-dried in an oven at 80° C. for 4 hours to obtain PI29 powder.

[0605] (Synthesis example A1-30)

[0606] After nitrogen replacement of a 500mL four-necked flask with a reflux tube and a Dean Stark tube, N-methyl-2-pyrrolidone (NMP) 15g, ETHACURE (registered trademark) 100Plus 6.15g (34.5mmol) were added and stirred until uniform. Thereafter, biphenyltetracarboxylic dianhydride (BPDA) 8.83g (30mmol), NMP 12g, 1-butanol 19.5g, and triethylamine 209μL were added and stirred at room temperature for 1 hour under nitrogen flow for addition reaction. Thereafter, the temperature was raised to 180°C, and after reaching 180°C, a dehydration ring closure was performed for 4 hours. After 1 hour after reaching 180°C, a mixture of water and 1-butanol was taken out 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 an NMP solution of PI having a concentration of 20% by mass. The NMP solution was added dropwise to ethanol to reprecipitate PI, and the resin powder was recovered by suction filtration. The recovered powder was washed with water and then vacuum-dried in an oven at 80° C. for 4 hours to obtain PI30 powder.

[0607] Table 2 shows the components used in Synthesis Examples A1-1 to A1-30.

[0608] [Table 2]

[0609]

[0610] <Preparation of Epoxy Resin Curing Agent>

[0611] (Synthesis Example A2-1)

[0612] After nitrogen purge, a 500 mL four-necked flask equipped with a reflux tube and a stirring blade was added with 20 g of 1-butanol and 0.05 mol of 4,4'-diaminodiphenyl sulfone (44DAS), and heated until the internal temperature reached 120°C. Subsequently, 0.03 mol of 2-ethylhexyl glycidyl ether (2-EH) was added dropwise using a dropping funnel over 30 minutes. After the addition was complete, the reaction solution was heated at 120°C for 6 hours while stirring to complete the reaction. Using a rotary evaporator, 1-butanol was distilled off from the resulting solution over 2 hours while maintaining the temperature at 80°C and the pressure below 15 mmHg to obtain epoxy resin curing agent (A-1). Here, the obtained epoxy resin curing agent (A-1) contains an amine adduct compound obtained by adding one molecule of 2-ethylhexyl glycidyl ether (2-EH) as a reactive compound to one molecule of 4,4'-diaminodiphenyl sulfone (44DAS) as an aromatic amine compound.

[0613] (Synthesis Example A2-2)

[0614] Synthesis and purification were performed under the same conditions as in Synthesis Example A2-1, except that 0.03 mol of 2-ethylhexyl glycidyl ether (2-EH) was replaced with 0.035 mol of butyl glycidyl ether (BGE). This epoxy resin curing agent (A-2) contained an amine adduct compound obtained by adding one molecule of butyl glycidyl ether (BGE) as a reactive compound to one molecule of 4,4'-diaminodiphenyl sulfone (44DAS) as an aromatic amine compound.

[0615] (Synthesis Example A2-3)

[0616] Amine adduct (B) was obtained by synthesis and purification under the same conditions as in Synthesis Example A2-1, except that 4,4'-diaminodiphenyl sulfone (44DAS) was replaced with 1,3-bis(3-aminophenoxy)benzene (TPE-M). The obtained amine adduct (B) comprised an amine adduct compound obtained by adding one molecule of 2-ethylhexyl glycidyl ether (2-EH) as a reactive compound to one molecule of 1,3-bis(3-aminophenoxy)benzene (TPE-M) as an aromatic amine compound.

[0617] (Synthesis Example A2-4)

[0618] Amine adduct (C-1) was synthesized and purified under the same conditions as in Synthesis Example A2-1, except that 4,4'-diaminodiphenyl sulfone (44DAS) was replaced with 4-aminophenyl-4'-aminobenzoate (APAB) and 0.05 mol of 2-ethylhexyl glycidyl ether (2-EH) was used instead of 0.03 mol. Here, the obtained amine adduct (C-1) contained an amine adduct compound obtained by adding one molecule of 2-ethylhexyl glycidyl ether (2-EH) as a reactive compound to one molecule of 4-aminophenyl-4'-aminobenzoate (APAB) as an aromatic amine compound.

[0619] (Synthesis Example A2-5)

[0620] Amine adduct (C-2) was obtained by synthesis and purification under the same conditions as in Synthesis Example A2-4, except that butyl glycidyl ether was used instead of 2-ethylhexyl glycidyl ether. The obtained amine adduct (C-2) comprised an amine adduct compound obtained by adding one molecule of butyl glycidyl ether (BGE) as a reactive compound to one molecule of 4-aminophenyl-4'-aminobenzoate (APAB) as an aromatic amine compound.

[0621] (Synthesis Example A2-6)

[0622] Amine adduct (D-1) was synthesized and purified under the same conditions as in Synthesis Example A2-1, except that 4,4'-diaminodiphenylsulfone (44DAS) was replaced with 3,4'-oxydiphenylamine (34ODA) and 0.05 mol of 2-ethylhexyl glycidyl ether (2-EH) was used instead of 0.03 mol. Here, the obtained amine adduct (D-1) contained an amine adduct compound obtained by adding one molecule of 2-ethylhexyl glycidyl ether (2-EH) as a reactive compound to one molecule of 3,4'-oxydiphenylamine (34ODA) as an aromatic amine compound.

[0623] (Synthesis Example A2-7)

[0624] Amine adduct (D-2) was obtained by synthesis and purification under the same conditions as in Synthesis Example A2-6, except that butyl glycidyl ether was used instead of 2-ethylhexyl glycidyl ether. The obtained amine adduct (D-2) comprised an amine adduct compound obtained by adding one molecule of butyl glycidyl ether (BGE) as a reactive compound to one molecule of 3,4'-oxydiphenylamine (34ODA) as an aromatic amine compound.

[0625] (Synthesis Example A2-8)

[0626] Amine adduct (E-1) was obtained by synthesis and purification under the same conditions as in Synthesis Example A2-1, except that 4,4'-diaminodiphenyl sulfone (44DAS) was replaced with KAYAHARD (registered trademark) AA and 0.04 mol of 2-ethylhexyl glycidyl ether (2-EH) was replaced with 0.03 mol. Here, the obtained amine adduct (E-1) contained an amine adduct compound obtained by adding one molecule of 2-ethylhexyl glycidyl ether (2-EH) as a reactive compound to one molecule of KAYAHARD (registered trademark) AA as an aromatic amine compound.

[0627] (Synthesis Example A2-9)

[0628] Amine adduct (E-2) was obtained by synthesis and purification under the same conditions as in Synthesis Example A2-8, except that phenyl glycidyl ether (ph-GE) was used instead of 2-ethylhexyl glycidyl ether (2-EH). Here, the obtained amine adduct (E-2) included an amine adduct compound obtained by adding one molecule of phenyl glycidyl ether (ph-GE) as a reactive compound to one molecule of KAYAHARD (registered trademark) AA as an aromatic amine compound.

[0629] (Synthesis Example A2-10)

[0630] Amine adduct (F-1) was synthesized and purified under the same conditions as in Synthesis Example A2-1, except that 4,4'-diaminodiphenyl sulfone (44DAS) was replaced with ETHACURE (registered trademark) 100 Plus and 0.03 mol of 2-ethylhexyl glycidyl ether (2-EH) was replaced with 0.025 mol. Here, the obtained amine adduct (F-1) contained an amine adduct compound obtained by adding one molecule of 2-ethylhexyl glycidyl ether (2-EH) as a reactive compound to one molecule of ETHACURE (registered trademark) 100 Plus as an aromatic amine compound.

[0631] (Synthesis Example A2-11)

[0632] Amine adduct (F-2) was obtained by synthesis and purification under the same conditions as in Synthesis Example A2-10, except that 0.025 mol of 2-ethylhexyl glycidyl ether (2-EH) was replaced with 0.03 mol of butyl glycidyl ether (BGE). The obtained amine adduct (F-2) consisted of an amine adduct compound obtained by adding one molecule of butyl glycidyl ether (BGE) as a reactive compound to one molecule of ETHACURE (registered trademark) 100 Plus as an aromatic amine compound.

[0633] (Synthesis Example A2-12)

[0634] Amine adduct (F-3) was obtained by synthesis and purification under the same conditions as in Synthesis Example A2-10, except that 0.025 mol of 2-ethylhexyl glycidyl ether (2-EH) was replaced with 0.035 mol of phenyl glycidyl ether (ph-GE). The obtained amine adduct (F-3) consisted of an amine adduct compound obtained by adding one molecule of phenyl glycidyl ether (ph-GE) as a reactive compound to one molecule of ETHACURE (registered trademark) 100 Plus as an aromatic amine compound.

[0635] (Synthesis Example A2-13)

[0636] Amine adduct (G) was obtained by synthesis and purification under the same conditions as in Synthesis Example A2-1, except that 4,4'-diaminodiphenylsulfone (44DAS) was replaced with ETHACURE (registered trademark) 300. The obtained amine adduct (G) comprised an amine adduct compound obtained by adding one molecule of 2-ethylhexyl glycidyl ether (2-EH) as a reactive compound to one molecule of ETHACURE (registered trademark) 300 as an aromatic amine compound.

[0637] Table 3 shows the components used in Synthesis Examples A2-1 to A2-13, the reaction ratios, and the LC-MS peak area ratios of the components.

[0638] [Table 3]

[0639]

[0640] (Synthesis of Compound (Mixture Containing E-1A and E-1B))

[0641] Into an eggplant-shaped flask were weighed 7.20 g (0.07 mol) of ethyl propionate, 13.17 g (0.0245 mol) of DENACOL (registered trademark) EX-830 (polyethylene glycol diglycidyl ether, Nagase ChemteX), and 1.67 g (0.0105 mol) of EXA-830CRP. 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 addition was complete, the reaction was allowed to proceed while stirring for 4 hours while maintaining the temperature at 90°C, thereby completing the reaction. The resulting reaction solution was concentrated under reduced pressure at 80°C to distill off the by-produced alcohol and unreacted raw materials, yielding Compound A (a mixture containing Compound (E-1A) and Compound (E-1B)) as a liquid product.

[0642] In addition, the structures of compound (E-1A) and compound (E-1B) are shown below.

[0643]

[0644] (Synthesis of Compound (E-1C))

[0645] 3.93 g (0.038 mol) of ethyl propionate and 5.00 g (0.038 mol) of n-butyl glycidyl ether were weighed into an eggplant-shaped flask and 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 addition was complete, the mixture was stirred for 4 hours while maintaining the temperature at 90°C to complete the reaction. The resulting reaction solution was concentrated under reduced pressure at 80°C to distill off the by-produced alcohol and unreacted starting materials, yielding Compound (E-1C) as a liquid product.

[0646] In addition, the structure of compound (E-1C) is shown below.

[0647]

[0648] (Synthesis of Compound (E-1D))

[0649] 1.94 g (0.019 mol) of ethyl propionate and 5.00 g (0.009 mol) of polyethylene glycol diglycidyl ether were weighed into an eggplant-shaped flask and 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 addition was complete, the mixture was stirred for 4 hours while maintaining the temperature at 90°C to complete the reaction. The resulting reaction solution was concentrated under reduced pressure at 80°C to distill off the by-produced alcohol and unreacted starting materials, yielding the compound (E-1D) represented by the following formula (E-1D) as a liquid product.

[0650] The structure of compound (E-1D) is shown below: The structure of compound (E-1D) is the same as that of compound (E-1A).

[0651]

[0652] (Examples A1 to A54, and Comparative Example A1)

[0653] The components listed in Tables 4 to 8 were placed in the amounts listed in Tables 4 to 8 in a plastic stirring container, stirred and mixed using a rotation / revolution stirrer ("ARE-310" (trade name) manufactured by THINKY Corporation), and then kneaded using a three-roll mill to prepare epoxy resin compositions.

[0654] It should be noted that in Examples A1 to A54 and Comparative Example A1, the powder of the polyimide resin (PI1 to P30) is dissolved and dispersed in the epoxy resin and the curing agent, respectively, and then the inorganic filler is dispersed in the solution, and the dispersion is added to a plastic stirring container. In Examples A1 to A48 and A50 to A54, polyimide resins dried for 4 hours are used as PI1 to 30, and in Example A49, polyimide resins dried for 1 hour are used as PI4. Regarding Comparative Example A1, a polyimide resin dried for 4 hours is used as PI4, but when dissolving and dispersing the PI4 in the epoxy resin and the curing agent, a specified amount of organic solvent (N-methyl-2-pyrrolidone (NMP)) is added, and then the inorganic filler is dispersed in the solution to prepare a dispersion.

[0655] The obtained epoxy resin composition was poured into a Teflon (registered trademark) mold, and heated at 165° C. for 2 hours to produce a cured product.

[0656] The evaluation results of the resin compositions and cured products obtained in Examples A1 to A54 and Comparative Example 1 are shown in Tables 4 to 8.

[0657] [Table 4]

[0658]

[0659] [Table 5]

[0660]

[0661] [Table 6]

[0662]

[0663] [Table 7]

[0664]

[0665] [Table 8]

[0666]

[0667] As shown in Tables 4 to 8, all the resin compositions in Examples contained a polyimide resin, but had low room temperature viscosities and thus exhibited fluidity.

[0668] Heating to a high temperature (110°C) further reduces the viscosity, thereby improving the fluidity, resulting in excellent flowability and permeability.

[0669] Furthermore, Examples A1 to A54 produced cured products with excellent viscosity stability. Thus, despite containing a polyimide resin, the resin compositions of the Examples were able to achieve a balance between permeability, curability, and storage stability. In particular, the resin compositions and cured products obtained in Examples A1 to A48 and A50 to A54 contained an organic solvent content of 0.5% by mass or less, resulting in even better curability.

[0670] In contrast, the comparative examples contain more than 1% by mass of organic solvent, and thus exhibit high fluidity and excellent permeability, similar to the examples. However, during the curing reaction, the organic solvent evaporates, creating numerous voids. When used as a packaging material, these materials are prone to cracking, starting from the voids, resulting in reduced reliability.

[0671] The resin composition of the Examples can be suitably used as a packaging material, particularly an underfill material used when sealing a semiconductor chip or the like.

[0672] [Examples and Comparative Examples of Structure, Second Epoxy Resin Composition, Second Cured Product, etc.]

[0673] [Measurement and evaluation methods of physical properties and characteristics of cured products of epoxy resin compositions]

[0674] Using the epoxy resin compositions prepared in the Examples and Comparative Examples described below, cured products were prepared as follows, and the physical properties of the cured products were measured as follows.

[0675] (Production of Cured Material)

[0676] A TEG (Test Element Group) was constructed using Cu pillar bumps, a 10 mm x 10 mm silicon chip, and a 30 mm x 30 mm organic resin substrate. The epoxy resin compositions prepared in the examples and comparative examples were injected into the TEGs and heated and cured at 165°C for 2 hours to obtain a cured product.

[0677] (Measurement and Evaluation of Intensity Ratio of IR Spectra)

[0678] The intensity ratio (Ia / Ib) of the IR spectrum of the cured product was measured by the following method.

[0679] Apparatus: Microscopic FT-IR apparatus LUMOS (manufactured by Bruker Japan)

[0680] Condition: Attenuated Total Reflection (Ge)

[0681] Angle of incidence: 30°

[0682] Aperture size: 124×124μm

[0683] Resolution: 4cm -1

[0684] Cumulative number of times: 32 times

[0685] Contact pressure: High

[0686] Measuring range: 600-5000cm -1

[0687] Spectral vertical axis: absorbance

[0688] Optical path length: 1cm

[0689] <Steps>

[0690] 1. 2000~2500cm -1 Draw a baseline as a benchmark.

[0691] 2. Utilize the presence of 1,450-1,550cm -1 Normalize to the largest peak within the range.

[0692] 3. Read the presence of 1,700 to 1,800 cm -1 The maximum peak intensity in the range.

[0693] 4. Calculate the IR spectrum in the range of 1,700 to 1,800 cm according to the following formula: -1 The maximum peak intensity in the range of 1,450 to 1,550 cm -1 The peak intensity ratio when the maximum peak intensity within the range is set to Ib.

[0694] Peak intensity ratio = Ia / Ib

[0695] <Evaluation Criteria>

[0696] The peak intensity ratio calculated as described above was evaluated according to the following criteria.

[0697] A: Ia / Ib is 0.1 or more and 0.5 or less.

[0698] B: Ia / Ib is a value less than 0.1 or greater than 0.5.

[0699] (Evaluation of pores)

[0700] An image observed from a direction perpendicular to the surface of the cured product was acquired using the following measuring device, and the area ratio of the void portion was calculated and evaluated according to the following criteria.

[0701] It should be noted that the pores Figure 1 As shown in the figure, it is the observed white part.

[0702] in addition, Figure 2 It shows an image when there are no pores (0%).

[0703] Measuring device: Fine SAT FS300II (manufactured by Hitachi Construction Machinery Finetech Co., Ltd.)

[0704] Probe frequency: 200MHz

[0705] <Evaluation Criteria>

[0706] ○: The area occupied by the holes is less than 1% of the chip area

[0707] ×: The area occupied by the holes is greater than 1% of the chip area

[0708] (Measurement and evaluation of coefficient of linear expansion (CTE))

[0709] A cured product of the epoxy resin composition obtained by curing at 165° C. for 2 hours was cut into a size of 5 mm×5 mm to prepare a test piece.

[0710] Using a test piece and a thermomechanical analyzer (trade name: TMA450, manufactured by TA Instruments), the temperature was raised from -30°C to 250°C at 5°C / min in compression mode, then cooled to -30°C, and then raised to 250°C at 5°C / min for measurement.

[0711] The tangent slope at 10 to 30° C. of the second measurement result was defined as CTE, and evaluation was performed based on the following criteria.

[0712] <Evaluation Criteria>

[0713] A: CTE is less than 30ppm / K.

[0714] B: CTE is 30 ppm / K or more and less than 35 ppm / K.

[0715] C: CTE is 35 ppm / K or higher.

[0716] [Preparation of epoxy resin composition]

[0717] In Examples and Comparative Examples, epoxy resin compositions were prepared using (A) epoxy resin, (B) polyimide resin, (C) curing agent, (D) inorganic filler, (E) curing accelerator, and (F) solvent.

[0718] The abbreviations of the components in this example may refer to the above-mentioned [Examples and Comparative Examples of the First Epoxy Resin Composition and the First Cured Material, etc.].

[0719] ((B) Polyimide resin)

[0720] <Preparation of Polyimide Resin (PI)>

[0721] [Synthesis Example B1-1: PI-1]

[0722] After nitrogen substitution in a 500 mL four-necked flask equipped with a reflux tube and a Dean-Stark tube, 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 uniform. Subsequently, 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 temperature was raised to 180°C under a nitrogen flow, and after reaching 180°C, a polymerization reaction was carried out for 4 hours. One hour after reaching 180°C, the mixture of water and 1-butanol was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled until the internal temperature reached 80°C, and NMP was added to obtain an NMP solution of a polyimide resin (PI) with a concentration of 20% by mass. The NMP solution was added dropwise to ethanol to reprecipitate the polyimide resin (PI), and the resin powder was recovered by suction filtration. The recovered powder was washed with water and vacuum-dried in an oven at 80° C. to obtain a powder of the polyimide resin (PI-1).

[0723] [Synthesis Example B1-2: PI-2]

[0724] After nitrogen purge, a 500 mL four-necked flask equipped with a reflux tube and a Dean-Stark tube was charged with 30 g of N-methyl-2-pyrrolidone (NMP) and 20.53 g (50 mmol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) and stirred until homogeneous. Subsequently, 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 added. The temperature was raised to 180°C under a nitrogen flow, and a polymerization reaction was carried out for 4 hours after reaching 180°C. One hour after reaching 180°C, the mixture of water and 1-butanol was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled until the internal temperature reached 80°C, and NMP was added to obtain an NMP solution of polyimide resin (PI) with a concentration of 20% by mass. The NMP solution was added dropwise to ethanol to reprecipitate the polyimide resin (PI), and the resin powder was recovered by suction filtration. The recovered powder was washed with water and vacuum-dried in an oven at 80° C. to obtain a powder of the polyimide resin (PI-2).

[0725] [Synthesis Example B1-3: PI-3]

[0726] After nitrogen substitution in a 500mL four-necked flask equipped with a reflux tube and a Dean Stark tube, 26g of N-methyl-2-pyrrolidone (NMP) and 17.43g (50mmol) of 9,9-bis(4-aminophenyl)fluorene (BAFL) were added and stirred until uniform. Subsequently, 7.36g (25mmol) of biphenyltetracarboxylic dianhydride (BPDA), 20g of NMP, 22.6g of 1-butanol, and 174μL of triethylamine were added, and the temperature was raised to 180°C under nitrogen flow. After reaching 180°C, a polymerization reaction was carried out for 4 hours. One hour after reaching 180°C, a mixture of water and 1-butanol was removed from the Dean Stark tube. After 4 hours, the mixture was cooled until the internal temperature reached 80°C, and NMP was added to obtain an NMP solution of a polyimide resin (PI) with a concentration of 20% by mass. The NMP solution was added dropwise to ethanol to reprecipitate the polyimide resin (PI), and the resin powder was recovered by suction filtration. The recovered powder was washed with water and vacuum-dried in an oven at 80° C. to obtain a powder of the polyimide resin (PI-3).

[0727] [Synthesis Example B1-4: PI-4]

[0728] After nitrogen substitution in a 500mL four-necked flask equipped with a reflux tube and a Dean Stark tube, 15g of N-methyl-2-pyrrolidone (NMP) and 8.91g (50mmol) of ETHACURE100 Plus were added and stirred until uniform. Subsequently, 7.36g (25mmol) of biphenyltetracarboxylic dianhydride (BPDA), 15g of NMP, 19.9g of 1-butanol, and 174μL of triethylamine were added, and the temperature was raised to 180°C under nitrogen flow. After reaching 180°C, a polymerization reaction was carried out for 4 hours. One hour after reaching 180°C, a mixture of water and 1-butanol was removed from the Dean Stark tube. After 4 hours, the mixture was cooled until the internal temperature reached 80°C, and NMP was added to obtain an NMP solution of a polyimide resin (PI) having a concentration of 20% by mass. The NMP solution was added dropwise to ethanol to reprecipitate the polyimide resin (PI), and the resin powder was recovered by suction filtration. The recovered powder was washed with water and vacuum-dried in an oven at 80° C. to obtain a powder of the polyimide resin (PI-4).

[0729] [Synthesis Example B1-5: PI-5]

[0730] After nitrogen substitution in a 500mL four-necked flask equipped with a reflux tube and a Dean Stark tube, 20g of N-methyl-2-pyrrolidone (NMP) and 10.72g (50mmol) of ETHACURE300 were added and stirred until uniform. Subsequently, 7.36g (25mmol) of biphenyltetracarboxylic dianhydride (BPDA), 14g of NMP, 20.5g of 1-butanol, and 174μL of triethylamine were added, and the temperature was raised to 180°C under nitrogen flow. After reaching 180°C, a polymerization reaction was carried out for 4 hours. One hour after reaching 180°C, a mixture of water and 1-butanol was taken out from the Dean Stark tube. After 4 hours, the mixture was cooled until the internal temperature reached 80°C, and NMP was added to obtain an NMP solution of a polyimide resin (PI) having a concentration of 20% by mass. The NMP solution was added dropwise to ethanol to reprecipitate the polyimide resin (PI), and the resin powder was recovered by suction filtration. The recovered powder was washed with water and vacuum-dried in an oven at 80° C. to obtain a powder of the polyimide resin (PI-5).

[0731] [Synthesis Example B1-6: PI-6]

[0732] After nitrogen substitution in a 500mL four-necked flask equipped with a reflux tube and a Dean Stark tube, 22g of N-methyl-2-pyrrolidone (NMP) and 14.62g (50mmol) of 1,3-bis(3-aminophenoxy)benzene (TPE-M) were added and stirred until uniform. Subsequently, 7.76g (25mmol) of 4,4'-oxydiphthalic anhydride (ODPA), 20g of NMP, 22g of 1-butanol, and 174μL of triethylamine were added, and the temperature was raised to 180°C under nitrogen flow. After reaching 180°C, a polymerization reaction was carried out for 4 hours. One hour after reaching 180°C, a mixture of water and 1-butanol was taken out from the Dean Stark tube. After 4 hours, the mixture was cooled until the internal temperature reached 80°C, and NMP was added to obtain an NMP solution of a polyimide resin (PI) with a concentration of 20% by mass. The NMP solution was added dropwise to ethanol to reprecipitate the polyimide resin (PI), and the resin powder was recovered by suction filtration. The recovered powder was washed with water and vacuum-dried in an oven at 80° C. to obtain a powder of the polyimide resin (PI-6).

[0733] [Synthesis Example B1-7: PI-7]

[0734] After nitrogen purge, a 500 mL four-necked flask equipped with a reflux tube and a Dean-Stark tube was charged with 30 g of N-methyl-2-pyrrolidone (NMP) and 20.53 g (50 mmol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) and stirred until homogeneous. Subsequently, 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 added. The temperature was raised to 180°C under a nitrogen flow, and after reaching 180°C, a polymerization reaction was carried out for 4 hours. One hour after reaching 180°C, the mixture of water and 1-butanol was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled until the internal temperature reached 80°C, and NMP was added to obtain an NMP solution of polyimide resin (PI) with a concentration of 20% by mass. The NMP solution was added dropwise to ethanol to reprecipitate the polyimide resin (PI), and the resin powder was recovered by suction filtration. The recovered powder was washed with water and vacuum-dried in an oven at 80° C. to obtain a powder of the polyimide resin (PI-7).

[0735] [Synthesis Example B1-8: PI-8]

[0736] After nitrogen substitution in a 500mL four-necked flask equipped with a reflux tube and a Dean Stark tube, 27g of N-methyl-2-pyrrolidone (NMP) and 17.43g (50mmol) of 9,9-bis(4-aminophenyl)fluorene (BAFL) were added and stirred until uniform. Subsequently, 7.76g (25mmol) of 4,4'-oxydiphthalic anhydride (ODPA), 20g of NMP, 22.9g of 1-butanol, and 174μL of triethylamine were added, and the temperature was raised to 180°C under nitrogen flow. After reaching 180°C, a polymerization reaction was carried out for 4 hours. One hour after reaching 180°C, a mixture of water and 1-butanol was taken out from the Dean Stark tube. After 4 hours, the mixture was cooled until the internal temperature reached 80°C, and NMP was added to obtain an NMP solution of a polyimide resin (PI) with a concentration of 20% by mass. The NMP solution was added dropwise to ethanol to reprecipitate the polyimide resin (PI), and the resin powder was recovered by suction filtration. The recovered powder was washed with water and vacuum-dried in an oven at 80° C. to obtain a powder of the polyimide resin (PI-8).

[0737] [Synthesis Example B1-9: PI-9]

[0738] After nitrogen substitution in a 500mL four-necked flask equipped with a reflux tube and a Dean Stark tube, 15g of N-methyl-2-pyrrolidone (NMP) and 8.91g (50mmol) of ETHACURE100 Plus were added and stirred until uniform. Subsequently, 7.76g (25mmol) of 4,4'-oxydiphthalic anhydride (ODPA), 15g of NMP, 20g of 1-butanol, and 174μL of triethylamine were added, and the temperature was raised to 180°C under nitrogen flow. After reaching 180°C, a polymerization reaction was carried out for 4 hours. One hour after reaching 180°C, a mixture of water and 1-butanol was removed from the Dean Stark tube. After 4 hours, the mixture was cooled until the internal temperature reached 80°C, and NMP was added to obtain an NMP solution of a polyimide resin (PI) with a concentration of 20% by mass. The NMP solution was added dropwise to ethanol to reprecipitate the polyimide resin (PI), and the resin powder was recovered by suction filtration. The recovered powder was washed with water and vacuum-dried in an oven at 80° C. to obtain a powder of the polyimide resin (PI-9).

[0739] [Synthesis Example B1-10: PI-10]

[0740] After nitrogen substitution in a 500mL four-necked flask equipped with a reflux tube and a Dean Stark tube, 20g of N-methyl-2-pyrrolidone (NMP) and 10.72g (50mmol) of ETHACURE300 were added and stirred until uniform. Subsequently, 7.76g (25mmol) of 4,4'-oxydiphthalic anhydride (ODPA), 14g of NMP, 20.6g of 1-butanol, and 174μL of triethylamine were added, and the temperature was raised to 180°C under nitrogen flow. After reaching 180°C, a polymerization reaction was carried out for 4 hours. One hour after reaching 180°C, a mixture of water and 1-butanol was removed from the Dean Stark tube. After 4 hours, the mixture was cooled until the internal temperature reached 80°C, and NMP was added to obtain an NMP solution of a polyimide resin (PI) with a concentration of 20% by mass. The NMP solution was added dropwise to ethanol to reprecipitate the polyimide resin (PI), and the resin powder was recovered by suction filtration. The recovered powder was washed with water and vacuum-dried in an oven at 80° C. to obtain a powder of the polyimide resin (PI-10).

[0741] [Synthesis Example B1-11: PI-11]

[0742] After nitrogen purge, a 500 mL four-necked flask equipped with a reflux tube and a Dean-Stark tube was added with 28 g of N-methyl-2-pyrrolidone (NMP) and 14.62 g (50 mmol) of 1,3-bis(3-aminophenoxy)benzene (TPE-M), and stirred until homogeneous. Subsequently, 11.46 g (25 mmol) of p-phenylene bis(trimellitic anhydride) (TAHQ), 20 g of NMP, 22.8 g of 1-butanol, and 174 μL of triethylamine were added. The temperature was raised to 180°C under a nitrogen flow, and after reaching 180°C, a polymerization reaction was carried out for 4 hours. One hour after reaching 180°C, the mixture of water and 1-butanol was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled until the internal temperature reached 80°C, and NMP was added to obtain an NMP solution of polyimide resin (PI) with a concentration of 20% by mass. The NMP solution was added dropwise to ethanol to reprecipitate the polyimide resin (PI), and the resin powder was recovered by suction filtration. The recovered powder was washed with water and vacuum-dried in an oven at 80° C. to obtain a powder of the polyimide resin (PI-11).

[0743] [Synthesis Example B1-12: PI-12]

[0744] After nitrogen purge, a 500 mL four-necked flask equipped with a reflux tube and a Dean-Stark tube was charged with 30 g of N-methyl-2-pyrrolidone (NMP) and 20.53 g (50 mmol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) and stirred until homogeneous. Subsequently, 11.46 g (25 mmol) of p-phenylene bis(trimellitic anhydride) (TAHQ), 29 g of NMP, 25 g of 1-butanol, and 174 μL of triethylamine were added. The temperature was raised to 180°C under a nitrogen flow, and a polymerization reaction was carried out for 4 hours after reaching 180°C. One hour after reaching 180°C, the mixture of water and 1-butanol was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled until the internal temperature reached 80°C, and NMP was added to obtain an NMP solution of polyimide resin (PI) with a concentration of 20% by mass. The NMP solution was added dropwise to ethanol to reprecipitate the polyimide resin (PI), and the resin powder was recovered by suction filtration. The recovered powder was washed with water and vacuum-dried in an oven at 80° C. to obtain a powder of the polyimide resin (PI-12).

[0745] [Synthesis Example B1-13: PI-13]

[0746] After nitrogen substitution in a 500 mL four-necked flask equipped with a reflux tube and a Dean-Stark tube, 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 uniform. Subsequently, 11.46 g (25 mmol) of p-phenylene bis(trimellitic anhydride) (TAHQ), 20 g of NMP, 23.6 g of 1-butanol, and 174 μL of triethylamine were added. The temperature was raised to 180°C under a nitrogen flow, and after reaching 180°C, a polymerization reaction was carried out for 4 hours. One hour after reaching 180°C, the mixture of water and 1-butanol was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled until the internal temperature reached 80°C, and NMP was added to obtain an NMP solution of a polyimide resin (PI) with a concentration of 20% by mass. The NMP solution was added dropwise to ethanol to reprecipitate the polyimide resin (PI), and the resin powder was recovered by suction filtration. The recovered powder was washed with water and vacuum-dried in an oven at 80° C. to obtain a powder of the polyimide resin (PI-13).

[0747] [Synthesis Example B1-14: PI-14]

[0748] After nitrogen purge, a 500 mL four-necked flask equipped with a reflux tube and a Dean-Stark tube was charged with 20 g of N-methyl-2-pyrrolidone (NMP) and 8.91 g (50 mmol) of ETHACURE 100 Plus and stirred until homogeneous. Subsequently, 11.46 g (25 mmol) of p-phenylene bis(trimellitic anhydride) (TAHQ), 18 g of NMP, 21.2 g of 1-butanol, and 174 μL of triethylamine were added. The temperature was raised to 180°C under a nitrogen flow, and a polymerization reaction was carried out for 4 hours after reaching 180°C. One hour after reaching 180°C, the mixture of water and 1-butanol was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled until the internal temperature reached 80°C, and NMP was added to obtain an NMP solution of a polyimide resin (PI) with a concentration of 20% by mass. The NMP solution was added dropwise to ethanol to reprecipitate the polyimide resin (PI), and the resin powder was recovered by suction filtration. The recovered powder was washed with water and vacuum-dried in an oven at 80° C. to obtain a powder of the polyimide resin (PI-14).

[0749] [Synthesis Example B1-15: PI-15]

[0750] After nitrogen purge, a 500 mL four-necked flask equipped with a reflux tube and a Dean-Stark tube was charged with 21 g of N-methyl-2-pyrrolidone (NMP) and 10.72 g (50 mmol) of ETHACURE 300, and stirred until homogeneous. Subsequently, 11.46 g (25 mmol) of p-phenylene bis(trimellitic anhydride) (TAHQ), 20 g of NMP, 21.8 g of 1-butanol, and 174 μL of triethylamine were added. The temperature was raised to 180°C under a nitrogen flow, and a polymerization reaction was carried out for 4 hours after reaching 180°C. One hour after reaching 180°C, the mixture of water and 1-butanol was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled until the internal temperature reached 80°C, and NMP was added to obtain an NMP solution of a polyimide resin (PI) with a concentration of 20% by mass. The NMP solution was added dropwise to ethanol to reprecipitate the polyimide resin (PI), and the resin powder was recovered by suction filtration. The recovered powder was washed with water and vacuum-dried in an oven at 80° C. to obtain a powder of the polyimide resin (PI-15).

[0751] [Synthesis Example B1-16: PI-16]

[0752] After nitrogen purge, a 500mL four-necked flask equipped with a reflux tube and a Dean-Stark tube was charged with 22g of N-methyl-2-pyrrolidone (NMP) and 11.41g (50mmol) of 4-aminophenyl-4'-aminobenzoate (APAB), and stirred until homogeneous. Subsequently, 11.46g (25mmol) of 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride (BPAF), 20g of NMP, 22.1g of 1-butanol, and 174μL of triethylamine were added. The temperature was raised to 180°C under a nitrogen flow, and a polymerization reaction was carried out for 4 hours after reaching 180°C. One hour after reaching 180°C, the mixture of water and 1-butanol was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled until the internal temperature reached 80°C, and NMP was added to obtain an NMP solution of polyimide resin (PI) with a concentration of 20% by mass. The NMP solution was added dropwise to ethanol to reprecipitate the polyimide resin (PI), and the resin powder was recovered by suction filtration. The recovered powder was washed with water and vacuum-dried in an oven at 80° C. to obtain a powder of the polyimide resin (PI-16).

[0753] [Synthesis Example B1-17: PI-17]

[0754] After nitrogen purge, a 500 mL four-necked flask equipped with a reflux tube and a Dean-Stark tube was charged with 24 g of N-methyl-2-pyrrolidone (NMP) and 12.42 g (50 mmol) of 4,4'-diaminodiphenylsulfone (44DAS) and stirred until homogeneous. Subsequently, 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 temperature was raised to 180°C under a nitrogen flow, and a polymerization reaction was carried out for 4 hours after reaching 180°C. One hour after reaching 180°C, the mixture of water and 1-butanol was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled until the internal temperature reached 80°C, and NMP was added to obtain a 20% by mass solution of polyimide resin (PI) in NMP. The NMP solution was added dropwise to ethanol to reprecipitate the polyimide resin (PI), and the resin powder was recovered by suction filtration. The recovered powder was washed with water and vacuum-dried in an oven at 80° C. to obtain a powder of the polyimide resin (PI-17).

[0755] [Synthesis Example B1-18: PI-18]

[0756] After nitrogen purge, a 500 mL four-necked flask equipped with a reflux tube and a Dean-Stark tube was charged with 24 g of N-methyl-2-pyrrolidone (NMP) and 12.42 g (50 mmol) of 3,3'-diaminodiphenylsulfone (33DAS) and stirred until homogeneous. Subsequently, 11.46 g (25 mmol) of 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride (BPAF), 20 g of NMP, 22.2 g of 1-butanol, and 174 μL of triethylamine were added. The temperature was raised to 180°C under a nitrogen flow, and a polymerization reaction was carried out for 4 hours after reaching 180°C. One hour after reaching 180°C, the mixture of water and 1-butanol was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled until the internal temperature reached 80°C, and NMP was added to obtain a 20% by mass solution of polyimide resin (PI) in NMP. The NMP solution was added dropwise to ethanol to reprecipitate the polyimide resin (PI), and the resin powder was recovered by suction filtration. The recovered powder was washed with water and vacuum-dried in an oven at 80° C. to obtain a powder of the polyimide resin (PI-18).

[0757] [Synthesis Example B1-19: PI-19]

[0758] After nitrogen purge, a 500 mL four-necked flask equipped with a reflux tube and a Dean-Stark tube was charged with 28 g of N-methyl-2-pyrrolidone (NMP) and 14.62 g (50 mmol) of 1,3-bis(3-aminophenoxy)benzene (TPE-M) and stirred until homogeneous. Subsequently, 11.46 g (25 mmol) of 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride (BPAF), 20 g of NMP, 22.8 g of 1-butanol, and 174 μL of triethylamine were added. The temperature was raised to 180°C under a nitrogen flow, and a polymerization reaction was carried out for 4 hours after reaching 180°C. One hour after reaching 180°C, the mixture of water and 1-butanol was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled until the internal temperature reached 80°C, and NMP was added to obtain an NMP solution of polyimide resin (PI) with a concentration of 20% by mass. The NMP solution was added dropwise to ethanol to reprecipitate the polyimide resin (PI), and the resin powder was recovered by suction filtration. The recovered powder was washed with water and vacuum-dried in an oven at 80° C. to obtain a powder of the polyimide resin (PI-19).

[0759] [Synthesis Example B1-20: PI-20]

[0760] After nitrogen purge, a 500 mL four-necked flask equipped with a reflux tube and a Dean-Stark tube was added with 20 g of N-methyl-2-pyrrolidone (NMP) and 10.01 g (50 mmol) of 3,4'-diaminodiphenyl ether (34ODA) and stirred until homogeneous. Subsequently, 11.46 g (25 mmol) of 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride (BPAF), 20 g of NMP, 21.5 g of 1-butanol, and 174 μL of triethylamine were added. The temperature was raised to 180°C under a nitrogen flow, and after reaching 180°C, a polymerization reaction was carried out for 4 hours. One hour after reaching 180°C, the mixture of water and 1-butanol was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled until the internal temperature reached 80°C, and NMP was added to obtain an NMP solution of polyimide resin (PI) with a concentration of 20% by mass. The NMP solution was added dropwise to ethanol to reprecipitate the polyimide resin (PI), and the resin powder was recovered by suction filtration. The recovered powder was washed with water and vacuum-dried in an oven at 80° C. to obtain a powder of the polyimide resin (PI-20).

[0761] [Synthesis Example B1-21: PI-21]

[0762] After nitrogen purge, a 500mL four-necked flask equipped with a reflux tube and a Dean-Stark tube was added with 21g of N-methyl-2-pyrrolidone (NMP) and 10.62g (50mmol) of m-tolidine (m-TB), and stirred until uniform. Subsequently, 11.46g (25mmol) of 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride (BPAF), 20g of NMP, 21.7g of 1-butanol, and 174μL of triethylamine were added. The temperature was raised to 180°C under a nitrogen flow, and after reaching 180°C, a polymerization reaction was carried out for 4 hours. One hour after reaching 180°C, the mixture of water and 1-butanol was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled until the internal temperature reached 80°C, and NMP was added to obtain an NMP solution of a polyimide resin (PI) with a concentration of 20% by mass. The NMP solution was added dropwise to ethanol to reprecipitate the polyimide resin (PI), and the resin powder was recovered by suction filtration. The recovered powder was washed with water and vacuum-dried in an oven at 80° C. to obtain a powder of the polyimide resin (PI-21).

[0763] [Synthesis Example B1-22: PI-22]

[0764] After nitrogen purge, a 500 mL four-necked flask equipped with a reflux tube and a Dean-Stark tube was charged with 30 g of N-methyl-2-pyrrolidone (NMP) and 20.53 g (50 mmol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) and stirred until homogeneous. Subsequently, 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 temperature was raised to 180°C under a nitrogen flow, and a polymerization reaction was carried out for 4 hours after reaching 180°C. One hour after reaching 180°C, the mixture of water and 1-butanol was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled until the internal temperature reached 80°C, and NMP was added to obtain a 20% by mass solution of polyimide resin (PI) in NMP. The NMP solution was added dropwise to ethanol to reprecipitate the polyimide resin (PI), and the resin powder was recovered by suction filtration. The recovered powder was washed with water and vacuum-dried in an oven at 80° C. to obtain a powder of the polyimide resin (PI-22).

[0765] [Synthesis Example B1-23: PI-23]

[0766] After nitrogen purge, a 500 mL four-necked flask equipped with a reflux tube and a Dean-Stark tube was added with 34 g of N-methyl-2-pyrrolidone (NMP) and 17.43 g (50 mmol) of 9,9-bis(4-aminophenyl)fluorene (BAFL) and stirred until homogeneous. Subsequently, 11.46 g (25 mmol) of 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride (BPAF), 20 g of NMP, 23.6 g of 1-butanol, and 174 μL of triethylamine were added. The temperature was raised to 180°C under a nitrogen flow, and after reaching 180°C, a polymerization reaction was carried out for 4 hours. One hour after reaching 180°C, the mixture of water and 1-butanol was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled until the internal temperature reached 80°C, and NMP was added to obtain an NMP solution of polyimide resin (PI) with a concentration of 20% by mass. The NMP solution was added dropwise to ethanol to reprecipitate the polyimide resin (PI), and the resin powder was recovered by suction filtration. The recovered powder was washed with water and vacuum-dried in an oven at 80° C. to obtain a powder of the polyimide resin (PI-23).

[0767] [Synthesis Example B1-24: PI-24]

[0768] After nitrogen purge, a 500mL four-necked flask equipped with a reflux tube and a Dean-Stark tube was charged with 20g of N-methyl-2-pyrrolidone (NMP) and 8.91g (50mmol) of ETHACURE100 Plus and stirred until homogeneous. Subsequently, 11.46g (25mmol) of 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride (BPAF), 18g of NMP, 21.2g of 1-butanol, and 174μL of triethylamine were added. The temperature was raised to 180°C under a nitrogen flow, and a polymerization reaction was carried out for 4 hours after reaching 180°C. One hour after reaching 180°C, the mixture of water and 1-butanol was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled until the internal temperature reached 80°C, and NMP was added to obtain a 20% by mass solution of polyimide resin (PI) in NMP. The NMP solution was added dropwise to ethanol to reprecipitate the polyimide resin (PI), and the resin powder was recovered by suction filtration. The recovered powder was washed with water and vacuum-dried in an oven at 80° C. to obtain a powder of the polyimide resin (PI-24).

[0769] [Synthesis Example B1-25: PI-25]

[0770] After nitrogen purge, a 500mL four-necked flask equipped with a reflux tube and a Dean-Stark tube was charged with 21g of N-methyl-2-pyrrolidone (NMP) and 10.72g (50mmol) of ETHACURE300 and stirred until homogeneous. Subsequently, 11.46g (25mmol) of 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride (BPAF), 20g of NMP, 21.8g of 1-butanol, and 174μL of triethylamine were added. The temperature was raised to 180°C under a nitrogen flow, and a polymerization reaction was carried out for 4 hours after reaching 180°C. One hour after reaching 180°C, the mixture of water and 1-butanol was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled until the internal temperature reached 80°C, and NMP was added to obtain an NMP solution of polyimide resin (PI) with a concentration of 20% by mass. The NMP solution was added dropwise to ethanol to reprecipitate the polyimide resin (PI), and the resin powder was recovered by suction filtration. The recovered powder was washed with water and vacuum-dried in an oven at 80° C. to obtain a powder of the polyimide resin (PI-25).

[0771] [Synthesis Example B1-26: PI-26]

[0772] After nitrogen replacement of a 500mL four-necked flask with a reflux tube and a Dean Stark tube, N-methyl-2-pyrrolidone (NMP) 15g, ETHACURE (registered trademark) 100Plus 6.42g (36mmol) were added and stirred until uniform. Thereafter, biphenyltetracarboxylic dianhydride (BPDA) 8.83g (30mmol), NMP 13g, 1-butanol 19.5g, and triethylamine 209 μL were added and stirred at room temperature for 1 hour under nitrogen flow for addition reaction. Thereafter, the temperature was raised to 180°C, and after reaching 180°C, a dehydration ring closure was performed for 4 hours. After 1 hour after reaching 180°C, a mixture of water and 1-butanol was taken out 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 an NMP solution of a polyimide resin (PI) having a concentration of 20% by mass. The NMP solution was added dropwise to ethanol to reprecipitate the polyimide resin (PI), and the resin powder was recovered by suction filtration. The recovered powder was washed with water and then vacuum-dried in an oven at 80°C for 4 hours to obtain a powder of the polyimide resin (PI-26).

[0773] [Synthesis Example B1-27: PI-27]

[0774] After nitrogen replacement of a 500mL four-necked flask with a reflux tube and a Dean Stark tube, N-methyl-2-pyrrolidone (NMP) 15g, ETHACURE (registered trademark) 100Plus 8.02g (45mmol) were added and stirred until uniform. Thereafter, biphenyltetracarboxylic dianhydride (BPDA) 8.83g (30mmol), NMP 16g, 1-butanol 20.0g, triethylamine 209μL were added and stirred at room temperature for 1 hour under nitrogen flow for addition reaction. Thereafter, the temperature was raised to 180°C, and after reaching 180°C, a dehydration ring closure was performed for 4 hours. After 1 hour after reaching 180°C, a mixture of water and 1-butanol was taken out 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 an NMP solution of a polyimide resin (PI) having a concentration of 20% by mass. The NMP solution was added dropwise to ethanol to reprecipitate the polyimide resin (PI), and the resin powder was recovered by suction filtration. The recovered powder was washed with water and then vacuum-dried in an oven at 80°C for 4 hours to obtain a powder of the polyimide resin (PI-27).

[0775] [Synthesis Example B1-28: PI-28]

[0776] After nitrogen substitution in a 500mL four-necked flask equipped with a reflux tube and a Dean Stark tube, 15g of N-methyl-2-pyrrolidone (NMP) and 6.42g (36mmol) of ETHACURE (registered trademark) 100Plus were added and stirred until uniform. Subsequently, 9.31g (30mmol) of 4,4'-oxydiphthalic anhydride (ODPA), 14g of NMP, 19.9g of 1-butanol, and 209μL of triethylamine were added and stirred at room temperature for 1 hour under nitrogen flow to carry out an addition reaction. Thereafter, the temperature was raised to 180°C, and after reaching 180°C, a dehydration ring closure was performed for 4 hours. One hour after reaching 180°C, a mixture of water and 1-butanol was taken out from the Dean Stark tube. After 4 hours, the mixture was cooled until the internal temperature reached 80°C, and NMP was added to obtain an NMP solution of a polyimide resin (PI) having a concentration of 20% by mass. The NMP solution was added dropwise to ethanol to reprecipitate the polyimide resin (PI), and the resin powder was recovered by suction filtration. The recovered powder was washed with water and then vacuum-dried in an oven at 80°C for 4 hours to obtain a powder of the polyimide resin (PI-28).

[0777] [Synthesis Example B1-29: PI-29]

[0778] After nitrogen substitution in a 500mL four-necked flask equipped with a reflux tube and a Dean Stark tube, 15g of N-methyl-2-pyrrolidone (NMP) and 8.02g (45mmol) of ETHACURE (registered trademark) 100Plus were added and stirred until uniform. Subsequently, 9.31g (30mmol) of 4,4'-oxydiphthalic anhydride (ODPA), 17g of NMP, 20.3g of 1-butanol, and 209μL of triethylamine were added and stirred at room temperature for 1 hour under nitrogen flow to carry out an addition reaction. Thereafter, the temperature was raised to 180°C, and after reaching 180°C, a dehydration ring closure was performed for 4 hours. One hour after reaching 180°C, a mixture of water and 1-butanol was taken out from the Dean Stark tube. After 4 hours, the mixture was cooled until the internal temperature reached 80°C, and NMP was added to obtain an NMP solution of a polyimide resin (PI) having a concentration of 20% by mass. The NMP solution was added dropwise to ethanol to reprecipitate the polyimide resin (PI), and the resin powder was recovered by suction filtration. The recovered powder was washed with water and then vacuum-dried in an oven at 80°C for 4 hours to obtain a powder of the polyimide resin (PI-29).

[0779] (Synthesis example B1-30)

[0780] After nitrogen replacement of a 500mL four-necked flask with a reflux tube and a Dean Stark tube, N-methyl-2-pyrrolidone (NMP) 15g, ETHACURE (registered trademark) 100Plus 6.15g (34.5mmol) were added and stirred until uniform. Thereafter, biphenyltetracarboxylic dianhydride (BPDA) 8.83g (30mmol), NMP 12g, 1-butanol 19.5g, triethylamine 209μL were added and stirred at room temperature for 1 hour under nitrogen flow for addition reaction. Thereafter, the temperature was raised to 180°C, and after reaching 180°C, a dehydration ring closure was performed for 4 hours. After 1 hour after reaching 180°C, a mixture of water and 1-butanol was taken out 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 an NMP solution of a polyimide resin (PI) having a concentration of 20% by mass. The NMP solution was added dropwise to ethanol to reprecipitate the polyimide resin (PI), and the resin powder was recovered by suction filtration. The recovered powder was washed with water and then vacuum-dried in an oven at 80°C for 4 hours to obtain a powder of the polyimide resin (PI-30).

[0781] Table 9 below also shows polyimides PI-1 to PI-30 of Synthesis Examples B1-1 to B1-30, the acid dianhydride and diamine used, and the molar ratio of diamine to acid dianhydride.

[0782] [Table 9]

[0783]

[0784] ((C) Curing agent)

[0785] <Preparation of Curing Agent>

[0786] [Synthesis Example B2-1: Curing Agent (A-1)]

[0787] After nitrogen purge, a 500ml four-necked flask equipped with a reflux tube and a stirring blade was added with 20g of 1-butanol and 0.05mol of 4,4'-diaminodiphenylsulfone (44DAS), and heated until the internal temperature reached 120°C. Subsequently, 0.03mol of 2-ethylhexyl glycidyl ether (2-EH) was added dropwise using a dropping funnel over 30 minutes. After the addition was complete, the reaction solution was heated at 120°C for 6 hours while stirring to complete the reaction. Using a rotary evaporator, 1-butanol was distilled off from the resulting solution over 2 hours while maintaining the temperature at 80°C and the pressure below 15 mmHg to obtain epoxy resin curing agent (A-1).

[0788] [Synthesis Example B2-2: Curing Agent (A-2)]

[0789] Except that 0.03 mol of 2-ethylhexyl glycidyl ether (2-EH) was changed to 0.035 mol of butyl glycidyl ether (BGE), synthesis / purification were carried out under the same conditions as above (Synthesis Example B2-1) to obtain a curing agent (A-2) for epoxy resin.

[0790] [Synthesis Example B2-3: Amine Adduct (B)]

[0791] Amine adduct (B) was obtained by synthesis and purification under the same conditions as those in the above (Synthesis Example B2-1), except that 4,4′-diaminodiphenylsulfone (44DAS) was replaced with 1,3-bis(3-aminophenoxy)benzene (TPE-M).

[0792] [Synthesis Example B2-4: Amine Adduct (C-1)]

[0793] Except that 4,4'-diaminodiphenyl sulfone (44DAS) was changed to 4-aminophenyl-4'-aminobenzoate (APAB) and 0.03 mol of 2-ethylhexyl glycidyl ether (2-EH) was changed to 0.05 mol, synthesis / purification was carried out under the same conditions as described above (Synthesis Example B2-1) to obtain an amine adduct (C-1).

[0794] [Synthesis Example B2-5: Amine Adduct (C-2)]

[0795] Amine adduct (C-2) was obtained by synthesis and purification under the same conditions as those in the above (Synthesis Example B2-4) except that butyl glycidyl ether (BGE) was used instead of 2-ethylhexyl glycidyl ether (2-EH).

[0796] [Synthesis Example B2-6: Amine Adduct (D-1)]

[0797] Amine adduct (D-1) was obtained by synthesis / purification under the same conditions as above (Synthesis Example B2-1), except that 4,4'-diaminodiphenyl sulfone (44DAS) was changed to 3,4'-oxydiphenylamine (34ODA) and 0.03 mol of 2-ethylhexyl glycidyl ether (2-EH) was changed to 0.05 mol.

[0798] [Synthesis Example B2-7: Amine Adduct (D-2)]

[0799] Amine adduct (D-2) was obtained by synthesis and purification under the same conditions as those in the above (Synthesis Example B2-6), except that 2-ethylhexyl glycidyl ether (2-EH) was replaced with butyl glycidyl ether (BGE).

[0800] [Synthesis Example B2-8: Amine Adduct (E-1)]

[0801] Amine adduct (E-1) was obtained by synthesis and purification under the same conditions as above (Synthesis Example B2-1), except that 4,4′-diaminodiphenyl sulfone (44DAS) was changed to KAYAHARD AA and 0.04 mol of 2-ethylhexyl glycidyl ether (2-EH) was changed from 0.03 mol to 0.04 mol.

[0802] [Synthesis Example B2-9: Amine Adduct (E-2)]

[0803] Amine adduct (E-2) was obtained by synthesis and purification under the same conditions as those in the above (Synthesis Example B2-8), except that 2-ethylhexyl glycidyl ether (2-EH) was replaced with phenyl glycidyl ether (ph-GE).

[0804] [Synthesis Example B2-10: Amine Adduct (F-1)]

[0805] Amine adduct (F-1) was obtained by synthesis and purification under the same conditions as those in Synthesis Example B2-1, except that 4,4′-diaminodiphenyl sulfone (44DAS) was replaced with ETHACURE 100 Plus and 0.03 mol of 2-ethylhexyl glycidyl ether (2-EH) was replaced with 0.025 mol.

[0806] [Synthesis Example B2-11: Amine Adduct (F-2)]

[0807] Amine adduct (F-2) was obtained by synthesis and purification under the same conditions as above (Synthesis Example B2-10), except that 0.025 mol of 2-ethylhexyl glycidyl ether (2-EH) was changed to 0.03 mol of butyl glycidyl ether (BGE).

[0808] [Synthesis Example B2-12: Amine Adduct (F-3)]

[0809] Amine adduct (F-3) was obtained by synthesis and purification under the same conditions as above (Synthesis Example B2-10), except that 0.025 mol of 2-ethylhexyl glycidyl ether (2-EH) was changed to 0.035 mol of phenyl glycidyl ether (ph-GE).

[0810] [Synthesis Example B2-13: Amine Adduct (G)]

[0811] Amine adduct (G) was obtained by synthesis and purification under the same conditions as those in the above (Synthesis Example B2-1), except that 4,4′-diaminodiphenylsulfone (44DAS) was replaced with ETHACURE300.

[0812] Table 10 below shows the curing agents of Synthesis Examples B2-1 to B2-13, as well as the aromatic amines and reactive compounds used.

[0813] [Table 10]

[0814]

[0815] ((E) Curing accelerator)

[0816] <Preparation of Curing Accelerator>

[0817] [Compound: Preparation of a mixture containing compound (E-1A) and compound (E-1B)]

[0818] 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 an eggplant-shaped flask and 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 addition, the mixture was stirred for 4 hours while maintaining the temperature at 90°C to complete the reaction. The resulting reaction solution was concentrated under reduced pressure at 80°C to distill off the by-produced alcohol and unreacted raw materials, yielding a liquid product: a mixture of Compound (E-1A) and Compound (E-1B).

[0819] In the following tables, the mixture is represented as compound E-1A / E-1B.

[0820] In addition, the structures of compound (E-1A) and compound (E-1B) are shown below.

[0821]

[0822] [Preparation of Compound (E-1C)]

[0823] 3.93 g (0.038 mol) of ethyl propionate and 5.00 g (0.038 mol) of butyl glycidyl ether were weighed into an eggplant-shaped flask and 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 addition was complete, the mixture was stirred for 4 hours while maintaining the temperature at 90°C to complete the reaction. The resulting reaction solution was concentrated under reduced pressure at 80°C to distill off the by-produced alcohol and unreacted starting materials, yielding Compound (E-1C) as a liquid product.

[0824] In addition, the structure of compound (E-1C) is shown below.

[0825]

[0826] [Preparation of Compound (E-1D)]

[0827] 1.94 g (0.019 mol) of ethyl propionate and 5.00 g (0.009 mol) of polyethylene glycol diglycidyl ether were weighed into an eggplant-shaped flask and 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 addition was complete, the mixture was stirred for 4 hours while maintaining the temperature at 90°C to complete the reaction. The resulting reaction solution was concentrated under reduced pressure at 80°C to distill off the by-produced alcohol and unreacted starting materials, yielding Compound (E-1D) as a liquid product.

[0828] In addition, the structure of compound (E-1D) is shown below.

[0829]

[0830] [Example B1 to Example B56], [Comparative Example B1]

[0831] The components listed in Tables 11 to 16 below were placed in the amounts listed in the tables in a plastic stirring container, stirred and mixed using a rotary / revolving stirrer ("ARE-310" manufactured by THINKY), and then kneaded using a three-roll mill to prepare epoxy resin compositions.

[0832] In addition, as for the PI powder, one that has been dispersed or dissolved in advance in an epoxy resin or a curing agent can be used.

[0833] [Table 11]

[0834]

[0835] [Table 12]

[0836]

[0837] [Table 13]

[0838]

[0839] [Table 14]

[0840]

[0841] [Table 15]

[0842]

[0843] [Table 16]

[0844]

[0845] As shown in Tables 11 to 16, the embodiments are all cured products comprising polyimide resins having excellent thermal properties, and therefore, exhibit low coefficient of linear expansion (CTE) values. Furthermore, in the embodiments, since the content of the organic solvent in the epoxy resin composition is less than 1% by mass, no voids are generated due to the curing reaction. In addition, regarding the peak intensity of the IR spectrum, since it is correlated with the ratio of the polyimide, if it falls within the preferred range, a low CTE effect is exhibited. Therefore, it can be seen that the cured products of the embodiments do not produce voids that become the starting point of cracks, etc., and low CTE is achieved, so the reliability is excellent.

[0846] Comparative Example 1 contains a high amount of organic solvent, which evaporates during the curing reaction, creating numerous voids with an area ratio exceeding 1%. Furthermore, even when mixed with a polyimide resin, the residual organic solvent can increase the CTE. When using this material, cracks are likely to form starting from the resulting voids, reducing reliability. Furthermore, a high CTE increases the stress caused by thermal expansion and contraction due to CTE mismatch, reducing reliability.

[0847] Industrial applicability

[0848] The resin composition and cured product of the present invention are useful as adhesives, encapsulating materials, filling materials, insulating materials, conductive materials, anisotropic conductive materials, sealing materials, prepregs, and the like.

[0849] The epoxy resin composition and cured product of the present invention are useful as structures, adhesives, encapsulating materials, filling materials, insulating materials, conductive materials, anisotropic conductive materials, sealing materials, prepregs, and the like.

[0850] The structure of the present invention has industrial applicability as a semiconductor chip.

Claims

1. A resin composition comprising an epoxy resin (A), a polyimide resin (B), a curing agent (C) and an inorganic filler (D), The content of the organic solvent in the resin composition is 1% by mass or less. 2 . The resin composition according to claim 1 , which has a viscosity at 25° C. of 100 Pa·s or less.

3. The resin composition according to claim 1, wherein At 110°C, when the viscosity at a shear rate of 10 / sec is defined as V1 and the viscosity at a shear rate of 100 / sec is defined as V2, the following formula (I) is satisfied: 0.8≤V1 / V2≤1.2…(I).

4. The resin composition according to claim 1, wherein The polyimide resin (B) comprises a condensate of tetracarboxylic dianhydride and diamine, The mixing ratio of the condensate, that is, the tetracarboxylic dianhydride: the diamine, is 1.00:1.20 to 1.00:2.00 in terms of molar ratio.

5. The resin composition according to claim 1, wherein The curing agent (C) comprises an aromatic amine compound (C-1) and an aromatic amine adduct (C-2), wherein the aromatic amine adduct (C-2) is a reaction product of the aromatic amine compound (C-1) and a reactive compound having a functional group capable of reacting with the aromatic amine compound (C-1). The aromatic amine adduct (C-2) includes an aromatic amine adduct (C-2-1) obtained by adding one molecule of the reactive compound to one molecule of the aromatic amine compound (C-1). The resin composition according to claim 5, wherein The aromatic amine compound (C-1) is an aromatic amine compound represented by the following formula (1) or an aromatic amine compound represented by the following formula (2), In formula (1), R1 and R2 each independently represent a monovalent organic group having 1 to 20 carbon atoms or a halogen atom, a and b each independently represent an integer of 0 to 4, X represents a divalent organic group or a single bond, In formula (2), R3 each independently represents a monovalent organic group having 1 to 20 carbon atoms or a halogen atom, and c is an integer of 1 to 4.

7. The resin composition according to claim 5, wherein The reactive compound is an epoxy compound having one glycidyl group in the molecule. The resin composition according to claim 1 , further comprising a curing accelerator (E). 9 . The resin composition according to claim 8 , which has a viscosity of 0.01 to 4.50 Pa·s after being allowed to stand at 110° C. for 60 minutes. 10 . A cured product comprising the resin composition according to claim 1 .

11. A structure comprising 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 include at least one selected from the group consisting of resin, silicon, ceramics, compound semiconductors, and glass. Among the plurality of copper pillars, the distance between adjacent pillars is less than 150 μm. A third layer is provided between the first layer and the second layer and is in contact with the first layer and the second layer respectively. The third layer is the cured product according to claim 10, The ratio of the area of ​​the pores in the third layer to the surface area of ​​the third layer is 1% or less.

12. The structure according to claim 11, wherein The infrared (IR) absorption spectrum of the third layer is present in the range of 1,700 to 1,800 cm -1 The maximum peak intensity Ia in the range of 1,450-1,550 cm -1 The maximum peak intensity Ib within the range satisfies the following formula (i), 0.1≤Ia / Ib≤0.5…(i).

13. A cured product for forming a third layer between a first layer and a second layer connected by a plurality of copper pillars having a distance between adjacent copper pillars of 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 ratio of the area of ​​the pores in the third layer to the surface area of ​​the third layer is 1% or less.

14. A structure comprising 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 include at least one selected from the group consisting of resin, silicon, ceramics, compound semiconductors, and glass. Among the plurality of copper pillars, the distance between adjacent pillars is less than 150 μm. A third layer is provided between the first layer and the second layer and is in contact with the first layer and the second layer respectively. The third layer is the cured product according to claim 13, The ratio of the area of ​​the pores in the third layer to the surface area of ​​the third layer is 1% or less.

15. The cured product according to claim 13, wherein The epoxy resin composition contains an organic solvent in an amount of 1% by mass or less.

16. The cured product according to claim 13, wherein In the infrared (IR) absorption spectrum, there is a -1 The maximum peak intensity Ia in the range of 1,450-1,550 cm -1 The maximum peak intensity Ib within the range satisfies the following formula (i), 0.1≤Ia / Ib≤0.5…(i).

17. A packaging material comprising the cured product according to claim 10 or 13. The packaging material according to claim 17 , which is a packaging material for a semiconductor.

19. An adhesive comprising the resin composition according to any one of claims 1 to 9.

20. A semiconductor package comprising the cured product according to claim 10 or 13.

21. A method for manufacturing a semiconductor package, comprising: A process for producing a semiconductor package using the resin composition according to any one of claims 1 to 9.

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