Resin composition, cured product, sealing material, adhesive, semiconductor package, and method for producing same

Abstract

To provide a resin composition having excellent permeability even with low organic solvent content, good balance of curability and storage stability, and no void formation upon curing, and also to provide a cured product, a sealing material, an adhesive, a semiconductor package, and a method for producing the same.SOLUTION: The resin composition of the present invention comprises an epoxy resin (A), a polyimide resin (B), a curing agent (C), and an inorganic filler (D), the content of an organic solvent in the resin composition being 1 mass% or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin composition, a cured product, an encapsulant, an adhesive, a semiconductor package, and a method for producing the same. [Background technology]

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

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

[0004] Patent Document 2 describes an epoxy resin composition comprising (A) an epoxy resin, (B) an aromatic amine-based curing agent, (C) a curing accelerator, and (D) a stabilizer, wherein the ratio of the equivalents 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) is an aryl phosphine.

[0005] Patent Document 3 describes a resin composition containing (A) a solvent-soluble polyimide resin, (B) an epoxy resin having an anthracene skeleton, (C) a curing catalyst, and (D) an inorganic filler, and these components are dissolved or dispersed in an organic solvent. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2015-199804 [Patent Document 2] Japanese Patent Application Publication No. 2019-172738 [Patent Document 3] Japanese Patent Application Publication No. 2018-90664 Summary of the Invention [Problem to be solved by the invention]

[0007] Currently, commonly used epoxy resin compositions include so-called two-component epoxy resin compositions in which an epoxy resin and a curing agent are mixed at the time of use.

[0008] Although two-component epoxy resin compositions can be cured at room temperature, the epoxy resin and curing agent must be stored separately and then measured and mixed as needed before use. This makes storage and handling cumbersome. Furthermore, since the usable time is limited, it is not possible to premix a large amount of the components, which increases the mixing frequency and inevitably reduces efficiency.

[0009] To solve these problems associated with two-component epoxy resin compositions, several one-component epoxy resin compositions have been proposed, including, for example, epoxy resin compositions in which an epoxy resin curing agent is blended with an epoxy resin.

[0010] Recently, there are a wide variety of demands for electronic devices. Such demands include, for example, miniaturization, high functionality, light weight, high functionality, and multi-functionality. More specifically, for example, in semiconductor chip mounting technology, there is a demand for finer electrode pads and finer pad pitches to achieve even greater miniaturization, miniaturization, and higher density.

[0011] In addition, underfill is used as an adhesive placed in the gap between the chip and the substrate to protect the bump connections and the circuit surface of the chip, etc. In order to meet the demand for advanced fine pitch, there is a demand for underfill that can penetrate into narrower gaps.

[0012] Furthermore, in recent years, there has been a growing demand for not only finer pitches but also larger semiconductor chips, which may increase the penetration time of underfill. Therefore, underfills are also required to have minimal change in viscosity during high-temperature environments during penetration and storage.

[0013] As described above, the latent curing agent constituting the one-component epoxy resin composition is required to have both good curability after mixing with the epoxy resin and good storage stability, as well as good permeability into minute regions such as between densely packed fibers such as carbon fibers and glass fibers, and narrow gaps in electronic components.

[0014] In Patent Document 1, the curing agent used is solid, and there is room for improvement in terms of penetration into narrow gaps.

[0015] Patent Document 2 requires a step of adding an additive to improve the storage stability and adhesiveness of the curing agent, and there is room for improvement in terms of storage and handling.

[0016] Patent Document 3 describes a resin composition containing a polyimide resin, but it must be dissolved or dispersed in an organic solvent. Therefore, when used as an underfill, the solvent evaporates during curing, causing voids. Furthermore, when applied to a substrate to form a film, the fluidity is impaired, making it unusable as an underfill.

[0017] The problem to be solved by the present invention is to provide a resin composition, a cured product, an encapsulant, an adhesive, a semiconductor package, and a method for manufacturing the same, which have excellent permeability, can achieve both curability and storage stability, and do not generate voids during curing despite having a low content of organic solvent. [Means for solving the problem]

[0018] In view of the above-mentioned problems of the conventional art, the present inventors have conducted extensive research and have found that the above-mentioned problems of the conventional art can be solved by 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 mass % or less, and have thus completed the present invention.

[0019] The present invention includes the following aspects. [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 mass% or less.

[0020] [2] The resin composition according to [1], which has a viscosity at 25°C of 100 Pa·s or less.

[0021] [3] The resin composition according to [1] or [2], which satisfies the following formula (I) when the viscosity at 110°C is V1 at a rotation speed of 10 / sec and the viscosity at a rotation speed of 100 / sec is V2: 0.8≦V1 / V2≦1.2 (I)

[0022] [4] The resin composition according to any one of [1] to [3], wherein the polyimide resin (B) contains a condensate of a tetracarboxylic dianhydride and a diamine, and the blending ratio of the condensate (the tetracarboxylic dianhydride:the diamine) is 1.00:1.20 to 1.00:2.00 in terms of molar ratio.

[0023] [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) which 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) in which one molecule of the reactive compound is added to one molecule of the aromatic amine compound (C-1).

[0024] [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):

[0025] [ka]

[0026] (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.)

[0027] [ka]

[0028] (In formula (2), each R3 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.)

[0029] [7] The resin composition according to [5] or [6], wherein the reactive compound is an epoxy compound having one glycidyl group in the molecule.

[0030] [8] The resin composition according to any one of [1] to [7], further comprising a curing accelerator (E).

[0031] [9] The resin composition according to [8], which has a viscosity of 0.01 Pa·s to 4.50 Pa·s after being left at 110°C for 60 minutes.

[0032]

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

[0033]

[11] An encapsulant comprising the cured product according to

[10] .

[0034]

[12] The encapsulant according to

[11] , which is an encapsulant for semiconductors.

[0035]

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

[0036]

[14] A semiconductor package comprising the cured product according to

[10] .

[0037]

[15] A method for producing a semiconductor package, comprising the step of producing a semiconductor package using the resin composition according to any one of [1] to [9]. [Effects of the Invention]

[0038] According to the present invention, it is possible to provide a resin composition, a cured product, an encapsulant, an adhesive, a semiconductor package, and a method for manufacturing the same, which have excellent permeability, can achieve both curability and storage stability, and do not generate voids during curing despite having a low organic solvent content. DETAILED DESCRIPTION OF THE INVENTION

[0039] Hereinafter, an embodiment of the present invention (hereinafter simply referred to as "the present embodiment") will be described in detail.

[0040] The following embodiments are merely examples for explaining the present invention, and are not intended to limit the present invention to the following content. The present invention can be implemented by appropriately modifying it within the scope of the gist thereof. In this specification, when "~" is used to express a numerical value or a physical property value, the values ​​before and after the "~" are included.

[0041] In the present specification, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range. In addition, in the present specification, the upper or lower limit of a numerical range may be replaced with a value shown in the examples.

[0042] In the description of groups (atomic groups) in this specification, when a notation does not specify whether the group is substituted or unsubstituted, it encompasses both unsubstituted and substituted groups. For example, the term "alkyl group" encompasses not only alkyl groups without a substituent (unsubstituted alkyl groups) but also alkyl groups with a substituent (substituted alkyl groups).

[0043] ≪Resin composition≫ The resin composition of this embodiment (hereinafter also referred to as "epoxy resin composition") contains an epoxy resin (A), a polyimide (B), a curing agent (C), and an inorganic filler (D), and the content of an organic solvent in the resin composition is 1 mass% or less.

[0044] <Epoxy resin (A)> The resin composition contains an epoxy resin (A). As the epoxy resin, any commonly used epoxy resin can be used without any particular limitation. For example, an epoxy resin having two or more epoxy groups in one molecule is preferred.

[0045] The epoxy resin may be solid or liquid at room temperature, but is preferably liquid at room temperature from the viewpoint of filling properties. The epoxy resin may particularly be an epoxy resin that is liquid at room temperature (hereinafter also referred to as "liquid epoxy resin"), and a commonly used liquid epoxy resin may be used. The liquid epoxy resin preferably has a viscosity of, for example, 0.0001 to 10 Pa·s as measured with an E-type viscometer at room temperature.

[0046] Examples of epoxy resins include diglycidyl ether epoxy resins such as bisphenol-type epoxy resins (e.g., bisphenol A, bisphenol F, bisphenol AD, bisphenol S, and hydrogenated bisphenol A); naphthalene-type epoxy resins; epoxy resins obtained by epoxidizing novolac resins obtained from phenols and aldehydes, such as orthocresol novolac-type epoxy resins; glycidyl ester-type epoxy resins obtained by reacting polybasic acids (e.g., phthalic acid, dimer acid) with epichlorohydrin; glycidylamine-type epoxy resins obtained by reacting amine compounds (e.g., p-aminophenol, diaminodiphenylmethane, and isocyanuric acid) with epichlorohydrin; and linear aliphatic epoxy resins and alicyclic epoxy resins obtained by oxidizing olefin bonds with peracids (e.g., peracetic acid). These epoxy resins may be used singly or in combination.

[0047] Among these, for example, bisphenol-type epoxy resins are preferred from the viewpoint of fluidity, and for example, glycidylamine-type epoxy resins are preferred from the viewpoints of heat resistance, adhesiveness, and fluidity.

[0048] The epoxy resin is preferably at least one selected from the group consisting of bisphenol-type epoxy resins and glycidylamine-type epoxy resins. From the viewpoint of fluidity, 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).

[0049] 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, but from the viewpoints of heat resistance, adhesiveness, and fluidity, it is preferably, for example, 5:95 to 50:50, more preferably 10:90 to 40:60, and even more preferably 20:80 to 40:60.

[0050] From the viewpoint of fluidity, it is preferable that both the bisphenol type epoxy resin and the glycidylamine type epoxy resin are liquid at room temperature.

[0051] The total content of the bisphenol-type epoxy resin and the glycidylamine-type epoxy resin is not particularly limited, but from the viewpoints of heat resistance, adhesiveness, and fluidity, it is preferably, for example, 20% by mass or more, more preferably 30% by mass or more, even more preferably 50% by mass or more, and particularly preferably 80% by mass or more, based on the total amount of epoxy resin. There is no particular upper limit to the total content, and it can be determined within a range that achieves desired properties and characteristics from the viewpoints of viscosity, glass transition temperature, heat resistance, etc., and may be 100% by mass.

[0052] When a bisphenol-type epoxy resin and a glycidylamine-type epoxy are used in combination, the mass ratio (bisphenol-type epoxy resin:glycidylamine-type epoxy) is not particularly limited, but from the viewpoints of heat resistance, adhesiveness, and fluidity, it is preferably, for example, 20:80 to 95:5, more preferably 40:60 to 90:10, and even more preferably 60:40 to 80:20.

[0053] In this embodiment, an epoxy resin that is solid at room temperature can also be used.

[0054] 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.

[0055] There are no particular restrictions on the epoxy equivalent of the epoxy resin, but from the viewpoint of heat resistance, it is preferably 60 to 400 g / mol, more preferably 70 to 300 g / mol, and even more preferably 80 to 250 g / mol.

[0056] Here, the epoxy equivalent is the mass of resin per epoxy group (g / eq) and can be measured according to the method specified in JIS K 7236. Specifically, using a Mitsubishi Chemical Analytech Corporation automatic titrator "GT-200 Model," 2 g of epoxy resin is weighed into a 200 mL beaker, 90 mL of methyl ethyl ketone is added dropwise, and the resin is dissolved in an ultrasonic cleaner. Then, 10 mL of glacial acetic acid and 1.5 g of cetyltrimethylammonium bromide are added, and the resin is titrated with a 0.1 mol / L perchloric acid / acetic acid solution to determine the epoxy equivalent.

[0057] The epoxy resin preferably has a high purity. In particular, the amount of hydrolyzable chlorine is preferably small because it is involved in corrosion of aluminum wiring on elements such as ICs (Integrated Circuits). From the viewpoint of excellent moisture resistance, the amount of hydrolyzable chlorine is preferably, for example, 1500 ppm or less. Here, the amount of hydrolyzable chlorine is measured by dissolving 1 g of a sample epoxy resin in 30 mL of dioxane, adding 5 mL of 1N-KOH (potassium hydroxide) methanol solution, refluxing for 30 minutes, and then measuring the value obtained by potentiometric titration.

[0058] The content of the epoxy resin (A) is not particularly limited, but from the viewpoints of heat resistance, adhesiveness, and flowability, it is preferably, for example, 10 to 50 mass%, more preferably 15 to 45 mass%, and even more preferably 20 to 40 mass%, of the total amount (100 mass%) of the resin composition.

[0059] <Polyimide resin (B)> The resin composition contains a polyimide resin (B). Examples of the polyimide resin (B) include a condensate of a tetracarboxylic dianhydride and a diamine. The polyimide resin (B) is not particularly limited, but can be obtained, for example, by subjecting a tetracarboxylic dianhydride and a diamine to a condensation reaction using a known method. Specifically, the tetracarboxylic dianhydride and the diamine are subjected to an addition reaction in an organic solvent under a flow of an inert gas such as nitrogen at a reaction temperature of 80°C or less, preferably 0 to 60°C. The addition reaction time is typically about 1 minute to 24 hours. As the reaction proceeds, the viscosity of the reaction solution gradually increases, producing a polyamic acid, which is a polyimide precursor. A polyimide resin can be obtained by subjecting this polyamic acid to dehydration ring closure. Dehydration ring closure can be performed by a thermal ring closure method using heat treatment or a chemical ring closure method using a dehydrating agent. The heating temperature in the thermal ring closure method is typically 160 to 200°C, and the heating time is typically about 1 minute to 24 hours.

[0060] In the condensation reaction, the blending ratio of the tetracarboxylic dianhydride to the diamine (tetracarboxylic dianhydride:diamine) is usually 1.00:1.00 to 1.00:2.00 in terms of molar ratio. The blending ratio of the tetracarboxylic dianhydride to the diamine is preferably 1.00:1.00 to 1.00:2.00, more preferably 1.00:1.20 to 1.00:2.00, and even more preferably 1.00:1.50 to 1.00:2.00, from the viewpoints of further increasing the compatibility between the polyimide resin (B) and the epoxy resin when forming the composition and further improving the flowability of the composition. The ratio of diamine to tetracarboxylic dianhydride can be 2.00 or more, but since tetracarboxylic dianhydride can only react with a maximum of two diamines, the upper limit of the ratio is usually 2.00.

[0061] The condensation reaction may be carried out using an amine catalyst, such as triethylamine.

[0062] The tetracarboxylic dianhydride used as a raw material for 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-furanyl)-3-methyl-cyclohexene-1,2 dicarboxylic anhydride, pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, and 2,2',3,3'-benzophenonetetracarboxylic dianhydride. Nontetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride (hereinafter also referred to simply as "BPDA"), 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, methylene-4,4-diphthalic dianhydride, 1,1-ethylidene-4,4'-diphthalic dianhydride, 2,2-propylidene-4,4'-diphthalic dianhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethyl ethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene-4,4'-diphthalic dianhydride, 4,4'-oxydiphthalic dianhydride (hereinafter also referred to as "ODPA"), p-phenylenebis(trimellitate 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,-dicarboxyphenyl)benzene dianhydride, 1,3-bis(3,4-dicarboxyphenoxy) )benzene dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,3-bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzene dianhydride, 1,4-bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzene dianhydride, bis[3-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, bis[4-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, 2,2-bis[3-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, bis(3,4-dicarboxyphenoxy)dimethylsilane dianhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride, 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-phenanthracenetetracarboxylic dianhydride Nanthrenetetracarboxylic 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 acid dianhydride, cyclopentanone bisspironorbornane tetracarboxylic acid dianhydride, 3,3',4,4'-bicyclohexyl tetracarboxylic acid dianhydride, carbonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4'-bis(cyclohexane-12-dicarboxylic acid) dianhydride, 1,2-ethylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-ethylidene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 2,2-propylidene -4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, oxy-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, sulfonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, REL-[1S,5R,6R]-3-oxabicyclo[3,2]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride, and ethylene glycol-bis-3,4-dicarboxylic acid anhydride (phenyl) ether. The tetracarboxylic acid dianhydrides may be used alone or in combination of two or more.

[0063] The diamine used as a raw material for the polyimide resin is not particularly limited, and examples thereof include 4-aminophenyl-4'-aminobenzoate (hereinafter also simply 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 simply as "34ODA"), 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone (hereinafter also referred to simply as "44DAS"), 3,3'-diaminodiphenyl sulfone (hereinafter also referred to simply 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 simply 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-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 (hereinafter also referred to as simply "BAPP"), 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, m-tolidine (hereinafter also referred to as simply "m-TB"), 9,9-bis(4-aminophenyl)fluorene (hereinafter also referred to as simply "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'-di Aminodiphenyldifluoromethane, 3,4'-diaminodiphenyldifluoromethane, 4,4'-diaminodiphenyldifluoromethane, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl ketone, 3,4'-diaminodiphenyl ketone, 4,4'-diaminodiphenyl ketone, 2,2-bis(3-aminophenyl)propane, 2,2'-(3,4'-diaminodiphenyl)propane, 2,2-bis (3-aminophenyl)hexafluoropropane, 2,2-(3,4'-diaminodiphenyl)hexafluoropropane, 1,4-bis(3-aminophenoxy)benzene, 3,3'-(1,4-phenylenebis(1-methylethylidene))bisaniline, 3,4'-(1,4-phenylenebis(1-methylethylidene))bisaniline, 4,4'-(1,4-phenylenebis(1-methylethylidene))bisaniline, 2,2-bis(4-(3-aminophenoxy)phenyl)propane, 2,2-bis(4-(3-aminophenoxy)phenyl)hexafluoropropane Fluoropropane, 2,2-bis(4-(4-aminophenoxy)phenyl)hexafluoropropane, bis(4-(3-aminoenoxy)phenyl)sulfide, bis(4-(4-aminoenoxy)phenyl)sulfide, bis(4-(3-aminoenoxy)phenyl)sulfone, bis(4-(4-aminoenoxy)phenyl)sulfone, 3,5-diaminobenzoic acid, 1,3-bis(aminomethyl)cyclohexane, 2,2-bis(4-aminophenoxyphenyl)propane, diethyltoluenediamine (2,4-diamino-3,5-diethyltoluene), 2,6-diamino-3,5-diethyltoluene, and dimethylthiotoluenediamine. The polyimide resin may be used alone or in combination of two or more.

[0064] Commercially available products may also be used as raw materials for the polyimide resin, such as Ethacure (registered trademark) 100 Plus (+) (trade name, curing agent containing diethyltoluenediamine, manufactured by Mitsui Fine Chemicals, Inc.) and Ethacure (registered trademark) 300 (trade name, curing agent containing diethylthiotoluenediamine, manufactured by Mitsui Fine Chemicals, Inc.).

[0065] <Organic solvents> The organic solvent used when synthesizing a polyimide resin using the compound by the above-mentioned method is not particularly limited, but is preferably one that can dissolve or disperse the polyimide resin (B). Examples of such organic solvents include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and t-butyl alcohol; halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, and o-dichlorobenzene; halogenated phenols such as p-chlorophenol, pentachlorophenol, and pentafluorophenol; ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, and diethylene glycol dimethyl ether; ketones such as acetone, cyclohexanone, and methyl ethyl ketone; ethyl acetate, and γ-butyrolactone. Examples of suitable organic solvents include esters of ethylene carbonate, propylene carbonate, and other 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-butylphosphate. These organic solvents may be used singly or in combination of two or more.

[0066] The resin composition of this embodiment may contain the organic solvent used in the synthesis of the polyimide resin described above. The content of the organic solvent in the resin composition is preferably 1% by mass or less, from the viewpoint of more suitably suppressing the generation of voids when the resin composition is cured. The content of the organic solvent in the resin composition is preferably 0.7% by mass or less, more preferably 0.5% by mass or less. The lower limit of the organic solvent content is not particularly limited, and may be below the detection limit, which is 1 ppm or more. Furthermore, from the viewpoint of further improving the compatibility between the epoxy resin, the curing agent, and the polyimide and further improving the flowability of the composition, the content of the organic solvent is preferably 0.01% by mass or more. The organic solvent may contain an organic solvent other than the organic solvent used in the synthesis of the polyimide resin, as long as it is within the above content range.

[0067] The content of organic solvent in the resin composition can be controlled, for example, by appropriately setting the drying conditions when drying the polyimide resin powder obtained by reprecipitation. For drying, it is preferable to heat the polyimide resin powder in a vacuum oven under reduced pressure for 1 to 12 hours at a temperature of 50 to 100°C. Alternatively, the content can be controlled by adding the organic solvent when mixing the polyimide resin powder with the epoxy resin and curing agent. For specific control methods, see the examples.

[0068] The content of the polyimide resin (B) is not particularly limited, but from the viewpoint of reliability improvement effect and permeability, it is preferably, for example, 1 to 20 mass %, more preferably 1 to 15 mass %, and even more preferably 2 to 15 mass %, of the total amount (100 mass %) of the resin composition.

[0069] <Curing agent (C)> The resin composition contains a curing agent (C). 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. One type of curing agent may be used alone, or two or more types may be used in combination.

[0070] Examples of acid anhydride curing agents include, but are not limited to, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride.

[0071] Examples of phenolic curing agents include, but are not limited to, phenol novolac resin, cresol novolac resin, phenol aralkyl resin, cresol aralkyl resin, naphthol aralkyl resin, biphenyl-modified phenol resin, biphenyl-modified phenol aralkyl resin, dicyclopentadiene-modified phenol resin, aminotriazine-modified phenol resin, naphthol novolac resin, naphthol-phenol co-condensed novolac resin, naphthol-cresol co-condensed novolac resin, and allyl acrylic phenol resin.

[0072] Examples of thiol-based curing agents include, but are not limited to, thiol compounds obtained by an esterification reaction between a polyol, such as trimethylolpropane tris(thioglycolate), pentaerythritol tetrakis(thioglycolate), ethylene glycol dithioglycolate, trimethylolpropane tris(β-thiopropionate), pentaerythritol tetrakis(β-thiopropionate), or dipentaerythritol poly(β-thiopropionate), and a thiol organic acid; alkyl polythiol compounds, such as 1,4-butanedithiol, 1,6-hexanedithiol, or 1,10-decanedithiol; terminal thiol group-containing polyethers; terminal thiol group-containing polythioethers; thiol compounds obtained by the reaction of an epoxy compound with hydrogen sulfide; and thiol compounds having terminal thiol groups obtained by the reaction of a polythiol with an epoxy compound.

[0073] The curing agent of the present embodiment comprises an aromatic amine compound (C-1), and an aromatic amine adduct (C-2) which 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 it is preferable that the aromatic amine adduct (C-2) comprises an aromatic amine adduct (C-2-1) in which one molecule of the reactive compound is added to one molecule of the aromatic amine compound (C-1).

[0074] By including the above-described components, the curing agent of the present embodiment can have excellent permeability after being mixed with an epoxy resin, and can achieve both curability and storage stability.

[0075] When the curing agent of the present embodiment contains an aromatic amine adduct (C-2), it may contain an aromatic amine adduct (C-2-1) in which one molecule of a reactive compound is added to one molecule of an aromatic amine compound (C-1), and an aromatic amine adduct (C-2-2X) in which two or more molecules of a reactive compound are added to one molecule of an aromatic amine compound (C-1).

[0076] Here, as the aromatic amine compound, an amine compound having electron-withdrawing properties and an amine compound having multiple functional groups in the side chain are inferior in reactivity as an amine but superior in stability when formed into an amine adduct. Therefore, the ratio of aromatic amine (C-1) to aromatic amine adduct (C-2-1) (C-1 / C-2-1) may be large. In other words, the aromatic amine adduct (C-2) contains an aromatic amine adduct (C-2-1) in which one molecule of a reactive compound is added to one molecule of the aromatic amine compound (C-1). Examples of the aromatic amine compound include 4,4'-diaminodiphenyl sulfone (hereinafter also referred to simply as "44DAS"), diethyltoluenediamine (2,4-diamino-3,5-diethyltoluene, 2,6-diamino-3,5-diethyltoluene), dimethylthiotoluenediamine, etc. The aromatic amine compounds may be used alone or in combination of two or more.

[0077] Commercially available products may also be used as the electron-withdrawing amine compound and the amine compound having multiple functional groups in the side chain. Examples of such commercially available products include Ethacure (registered trademark) 100 Plus (+) (trade name, curing agent containing diethyltoluenediamine, manufactured by Mitsui Fine Chemicals, Inc.), Ethacure (registered trademark) 300 (trade name, curing agent containing diethylthiotoluenediamine, manufactured by Mitsui Fine Chemicals, Inc.), and Kayahard (registered trademark) AA (curing agent containing 3,3'-diethyl-4,4'-jaminodiphenylmethane, manufactured by Nippon Kayaku Co., Ltd.).

[0078] On the other hand, aromatic amine compounds that do not have electron-withdrawing properties and amine compounds that do not have functional groups in their side chains are highly reactive as amines and have excellent curing properties when formed into amine adducts, so the ratio of aromatic amine (C-1) to aromatic amine adduct (C-2-1) may be small. In other words, the aromatic amine adduct (C-2) contains an aromatic amine adduct (C-2-1) in which one molecule of a reactive compound is added to one molecule of the aromatic amine compound (C-1). As the aromatic amine compound, aromatic amines having a -O-, -O-CH-O-, -CH-, -CO-, -C(=O)O-, or -C(=O)NH- bond are preferred, and among these, aromatic amines having a -C(=O)O- bond are preferred. Examples of the aromatic amine compound include 4-aminophenyl-4-aminobenzoate (hereinafter simply referred to as "APAB"), 3,4'-diaminodiphenyl ether (hereinafter simply referred to as "34ODA"), and 1,3-bis(3-aminophenoxy)benzene (hereinafter simply referred to as "TPE-M"). Among these, 4-aminophenyl-4-aminobenzoate (APAB) is preferred. The aromatic amine compounds may be used alone or in combination of two or more.

[0079] From the viewpoints of curability and storage stability, in 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 from the analysis of the components in the epoxy resin curing agent described below, the ratio (C-1 / C-2-1) of the peak area of ​​the aromatic amine compound (C-1) to the peak area of ​​the aromatic amine adduct (C-2-1) is preferably 0.1 to 3.0, more preferably 0.2 to 2.5, and more preferably 0.3 to 2.0.

[0080] [Analysis of components in epoxy resin curing agents] The analytical methods for each component in the epoxy resin curing agent are as follows. 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 chromatogram-mass spectrometry) measurement. The detailed conditions for the LC-MS measurement are as follows.

[0081] LC: Apparatus: Ultra-high performance liquid chromatography (UPLC, manufactured by Waters) Column: ACQUITY UPLC BEH C8 1.7 μm (2.1 mm ID x 50 mm, Waters) Detection: Absorbance detector (PDA, 200-400 nm) Flow rate: 0.3mL / min Mobile phase: A = water (containing 0.1% formic acid) B = acetonitrile (containing 0.1% formic acid) Injection volume: 0.2μL

[0082] [Table 1]

[0083] MS: Equipment: Mass spectrometer (Synapt G2, manufactured by Waters) Ionization: Electron Spray Ionization (ESI+) Measurement range: m / z 50-2000

[0084] The peak areas of the PDA chromatogram at 300 nm obtained by the LC-MS measurement are determined, and the peak areas of the aromatic amine compound (C-1), aromatic amine adduct (C-2-1), and aromatic amine adduct (C-2-2X) are calculated from the peak area ratio according to the following calculation formula (1). The ratio of each peak area is calculated from the sum of all the peak areas obtained using the following calculation formula (1). Ratio of aromatic amine compounds (%) = [(peak area of ​​aromatic amine compounds) / {(peak area of ​​aromatic amine compounds) + (peak area of ​​aromatic amine adduct (C-2-1)) + (peak area of ​​aromatic amine adduct (C-2-2X))}] × 100 (1)

[0085] <Aromatic amine compounds (C-1)> The curing agent of the present 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.

[0086] 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).

[0087] [ka]

[0088] 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.

[0089] 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 even more preferably a monovalent organic group having 1 to 3 carbon atoms. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. a and b each independently represent an integer of preferably 0 to 2, and more preferably 0 or 1. 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.

[0090] Examples of aromatic amines 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, 3 ... Aminodiphenyl 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)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, m-tolidine, 2,2'-bis(trifluoromethyl)benzidine, 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,Examples of the aromatic amine represented by formula (1) include 5'-tetraethyldiphenylmethane. The aromatic amine represented by formula (1) may be used alone or in combination of two or more kinds, and it is preferable to use one or more kinds selected from these.

[0091] Among these, from the viewpoint of achieving both curability and stability when formed into a composition with an epoxy resin, aromatic amines having a -O-, -O-C6H4-O-, -CH2-, -CO-, -C(=O)O-, -SO2-, or -C(=O)NH- bond are preferred as X, and among these, aromatic amines having a -C(=O)O- bond are more preferred.

[0092] 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), or 3,3'-diethyl-4,4'-diaminodiphenylmethane, and more preferably at least one selected from the group consisting of 4-aminophenyl-4-aminobenzoate (APAB).

[0093] Alternatively, an aromatic amine compound having a methanediyl group (-CH2-), which has high amine reactivity, can also be used.

[0094] For the purpose of suppressing the reactivity as an amine and improving storage stability, it is preferable to use a compound other than an aromatic amine compound having a methanediyl group.

[0095] Examples of aromatic amine compounds having a methanediyl group include 3,3'-diethyl-4,4'-diaminodiphenylmethane (for example, Kayahard (registered trademark) AA (trade name) manufactured by Nippon Kayaku Co., Ltd.), 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, etc. The aromatic amine compounds having a methanediyl group may be used alone or in combination of two or more.

[0096] [ka]

[0097] In formula (2), R3's each independently represent a monovalent organic group having 1 to 20 carbon atoms or a halogen atom; c represents an integer of 1 to 4. 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 even more preferably a monovalent organic group having 1 to 3 carbon atoms. c is preferably an integer of 1 to 3, and more preferably 1 or 2.

[0098] Examples of aromatic amines represented by formula (2) include diethyltoluenediamine (2,4-diamino-3,5-diethyltoluene, 2,6-diamino-3,5-diethyltoluene), dimethylthiotoluenediamine, etc. The aromatic amines represented by formula (2) may be used singly or in combination of two or more, and it is preferable to use one or more selected from these. Among these, from the viewpoint of achieving both curability and stability when formed into 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.

[0099] <Aromatic amine adduct (C-2)> 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) may be used singly or in combination of two or more.

[0100] (reactive compounds) The reactive compound has a functional group capable of reacting with the aromatic amine compound (C-1). One type of reactive compound may be used alone, or two or more types may be used in combination. Examples of the functional group include a -C(=O)OC(=O)- group, a carboxyl group, a sulfo group, an isocyanato group, a carbonyl group, an epoxy group, a fluoro group, a chloro group, a bromo group, an iodo group, etc. Among these, the epoxy group is preferred as the functional group.

[0101] 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.

[0102] Examples of the carboxylic acid compound include succinic acid, adipic acid, sebacic acid, phthalic acid, and dimer acid.

[0103] Examples of the acid anhydride include succinic anhydride, adipic anhydride, sebacic anhydride, and phthalic anhydride.

[0104] Examples of the acid dianhydride include the tetracarboxylic acid dianhydrides exemplified above as raw materials for the polyimide resin.

[0105] Examples of sulfonic acid compounds include ethanesulfonic acid and p-toluenesulfonic acid.

[0106] Examples of the isocyanate compound include aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, aliphatic triisocyanates, and polyisocyanates.

[0107] Examples of aliphatic diisocyanates include ethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate.

[0108] 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.

[0109] Examples of aromatic diisocyanates include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylene diisocyanate, and 1,5-naphthalene diisocyanate.

[0110] Examples of the aliphatic triisocyanate include 1,3,6-triisocyanatomethylhexane and 2,6-diisocyanatohexanoate-2-isocyanatoethyl.

[0111] Examples of polyisocyanates include polymethylene polyphenyl polyisocyanate and polyisocyanates derived from the above diisocyanate compounds.

[0112] Examples of polyisocyanates derived from the above diisocyanates include isocyanurate-type polyisocyanates, biuret-type polyisocyanates, urethane-type polyisocyanates, allophanate-type polyisocyanates, and carbodiimide-type polyisocyanates.

[0113] Examples of the urea compound include urea, methyl urea, dimethyl urea, ethyl urea, and t-butyl urea.

[0114] As the epoxy compound, for example, a monoepoxy compound, a polyepoxy compound, or a mixture thereof can be used.

[0115] Examples of 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, para-tert-butylphenyl glycidyl ether, ethylene oxide, propylene oxide, paraxylyl glycidyl ether, glycidyl acetate, glycidyl butyrate, glycidyl hexoate, and glycidyl benzoate.

[0116] Examples of polyepoxy compounds include bisphenol-type epoxy compounds obtained by glycidylating 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 glycidylating dihydric phenols such as biphenol, dihydroxynaphthalene, and 9,9-bis(4-hydroxyphenyl)fluorene; epoxy compounds obtained by glycidylating trisphenols such as 1,1,1-tris(4-hydroxyphenyl)methane and 4,4-(1-(4-(1-(4-hydroxyphenyl)-1-methylethyl)phenyl)ethylidene)bisphenol; and epoxy compounds obtained by glycidylating tetrakisphenols such as 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane. compounds; novolac-type epoxy compounds obtained by glycidylating novolacs such as phenol novolac, cresol novolac, bisphenol A novolac, brominated phenol novolac, and brominated bisphenol A novolac; aliphatic ether-type epoxy compounds obtained by glycidylating polyhydric alcohols such as glycerin and polyethylene glycol; ether ester-type epoxy compounds obtained by glycidylating hydroxycarboxylic acids such as p-oxybenzoic acid and β-oxynaphthoic 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; and alicyclic epoxy compounds such as 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate.

[0117] Among the above, from the viewpoint of excellent curability and storage stability, the reactive compound is preferably an epoxy compound, and more preferably an epoxy compound having one glycidyl group in the molecule (i.e., a monoepoxy compound).

[0118] 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).

[0119] The aromatic amine adduct (C-2) is a reaction product between 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) used in the present embodiment can be obtained, for example, by reacting 1.0 to 5.0 moles of an aromatic amine compound (C-1) with a reactive compound (e.g., an epoxy compound) in a molar ratio of 0.2 to 5.0, optionally in the presence of a solvent, at a temperature of 50 to 250°C for 0.1 to 10 hours, and optionally removing unreacted aromatic amine compound (C-1) and the solvent.

[0120] The solvent used here is not particularly limited, but examples thereof 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, and these solvents may be used in combination.

[0121] The content of the curing agent (C) is not particularly limited, but from the viewpoint of curability and stability, it is preferably, for example, 1 to 50 mass %, more preferably 3 to 40 mass %, and even more preferably 5 to 30 mass %, of the total amount (100 mass %) of the resin composition.

[0122] <Inorganic filler (D)> The resin composition contains an inorganic filler (D). The inorganic filler (D) may be used alone or in combination of two or more.

[0123] The inorganic filler is not particularly limited, and examples thereof include powders such as silica such as fused silica and crystalline silica, calcium carbonate, clay, alumina such as alumina oxide, silicon nitride, silicon carbide, boron nitride, calcium silicate, potassium titanate, aluminum nitride, beryllia, zirconia, zircon, forsterite, steatite, spinel, mullite, and titania, as well as beads obtained by spheronizing these, and glass fiber.

[0124] The inorganic filler may be a flame-retardant inorganic filler, such as aluminum hydroxide, magnesium hydroxide, zinc borate, or zinc molybdate.

[0125] Among these, from the viewpoints of availability, chemical stability, and material cost, for example, silica is preferred, and fused silica is more preferred. The particle shape of the inorganic filler is not particularly limited, and may be amorphous or spherical, but from the viewpoints of flowability and permeability into fine gaps in the epoxy resin composition, spherical silica is preferred, and spherical fused silica is more preferred.

[0126] The inorganic filler may be surface-treated. Specifically, the inorganic filler may be surface-treated with a silane coupling agent. Examples of silane coupling agents 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, hydrosilane coupling agents, silazane coupling agents, alkoxysilane coupling agents, chlorosilane coupling agents, (meth)acrylic silane coupling agents, aminosilane coupling agents, isocyanurate silane coupling agents, ureidosilane coupling agents, mercaptosilane coupling agents, sulfide silane coupling agents, and isocyanate silane coupling agents. One type of silane coupling agent may be used alone, or two or more types may be used in combination.

[0127] 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 making the volume-average particle size of the inorganic filler 0.1 μm or more, dispersibility in the epoxy resin is improved, the epoxy resin composition is less likely to be imparted with thixotropy, and the flow properties of the epoxy resin composition tend to be improved. On the other hand, by making the size 10.0 μm or less, sedimentation of the inorganic filler in the epoxy resin composition tends to be easily suppressed, and the permeability and flow properties of the epoxy resin composition into fine gaps tend to be improved, thereby suppressing the occurrence of voids and unfilled portions. The volume-average particle size is the particle size at the point corresponding to 50% volume when a cumulative frequency distribution curve is calculated based on particle size, with the total volume of the particles being 100%, and can be measured using a particle size distribution measuring device using a laser diffraction scattering method.

[0128] The content of the inorganic filler (D) is not particularly limited, but is preferably 30 to 85 mass % relative to the total amount (100 mass %) of the resin composition, more preferably 40 to 80 mass %, and even more preferably 45 to 70 mass %. By setting the content of the inorganic filler to 30% by mass or more, it is likely that the effect of reducing the thermal expansion coefficient and the effect of improving temperature cycle resistance will be easily obtained. By setting the content of the inorganic filler to 85% by mass or less, it is likely that the increase in viscosity of the epoxy resin composition will be suppressed and the flowability, penetration property, and dispensability will be improved. In particular, from the viewpoint of the effect of improving temperature cycle resistance, it is preferable that the lower limit of the content of the inorganic filler is as high as possible.

[0129] In this embodiment, even if the content of the inorganic filler is increased as described above, it is possible to maintain the viscosity of the resin composition at a low level.

[0130] <Curing accelerator (E)> The 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.

[0131] The curing accelerator is preferably at least one selected from the group consisting of the compound (E-1) and the imidazole-based compound (E-2).

[0132] (Compound (E-1)) The compound (E-1) is at least one selected from the group consisting of compounds represented by the following formula (4), compounds represented by the following formula (5), and compounds represented by the following formula (6).

[0133] [ka]

[0134] [ka]

[0135] [ka]

[0136] In formulas (4) to (6), each R1 independently represents a hydrogen atom or an n-valent organic group having 1 to 15 carbon atoms which may have a hydroxy group, a carbonyl group, an ester bond, or an ether bond; R2 and R3 independently represent an unsubstituted or substituted alkyl group, aryl group, or aralkyl group having 1 to 12 carbon atoms, or combine to form a heterocycle having 7 or less carbon atoms; each R4 independently represents a hydrogen atom or an n-valent organic group having 1 to 30 carbon atoms which may have an oxygen atom; and n is an integer of 1 to 3. R5 represents a negatively charged nitrogen atom, and R6 represents a positively charged nitrogen atom.

[0137] In the compounds represented by formula (4), formula (5), and formula (6), R1 is presumed to contribute to lowering the energy of the cleavage of the N-N bond. R2 and R3 are presumed to contribute to lowering the energy of the cleavage reaction by destabilizing it through steric hindrance. R4 is presumed to contribute to liquefying the compound and suppressing a decrease in the glass transition temperature of the resulting cured product. Each group will be described in detail below.

[0138] In formulas (4), (5), and (6), each R1 independently represents a hydrogen atom or an n-valent organic group having 1 to 15 carbon atoms, which may have a hydroxy group, a carbonyl group, an ester bond, or an ether bond.

[0139] In R1, the organic group is not particularly limited, and examples thereof include a hydrocarbon group, a group in which hydrogen atoms bonded to carbon atoms in a hydrocarbon group are substituted with hydroxy groups or carbonyl groups, and a group in which some of the carbon atoms in a hydrocarbon group are substituted with ester bonds or ether bonds.

[0140] 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, hexadecinyl, and octadecynyl; aryl groups such as phenyl; and aralkyl groups containing a combination of an alkyl group and a phenyl group, 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.

[0141] In R1, the organic group may have other substituents, which are not particularly limited, but include, for example, halogen atoms, alkoxy groups, carbonyl groups, cyano groups, azo groups, azido groups, thiol groups, sulfo groups, nitro groups, hydroxy groups, acyl groups, and aldehyde groups.

[0142] In R1, the number of carbon atoms in the organic group is 1 to 15, preferably 1 to 12, and more preferably 1 to 7. When the number of carbon atoms in the organic group is within the above range, a liquid compound having an appropriate viscosity is easily obtained, and the curing performance of the compound tends to be further improved. Furthermore, when the number of carbon atoms in the organic group is within the above range, the availability of raw materials is further improved.

[0143] R2 and R3 each independently represent an unsubstituted or substituted alkyl group, aryl group or aralkyl group having 1 to 12 carbon atoms, or combine to form a heterocycle having 7 or less carbon atoms.

[0144] In R2 and R3, the alkyl group having 1 to 12 carbon atoms is not particularly limited, and examples thereof include linear alkyl groups such as methyl, ethyl, propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, and n-dodecyl groups; branched alkyl groups such as isopropyl, isobutyl, t-butyl, neopentyl, 2-hexyl, 2-octyl, 2-decyl, and 2-dodecyl groups; and cyclic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclodecyl, and cyclododecyl groups. The alkyl group may be a linear alkyl group or an alkyl group containing a combination of a branched alkyl group and a cyclic alkyl group. Furthermore, the alkyl group may contain an unsaturated bond group. Among these, R2 and R3 are preferably cyclic alkyl groups, and the cyclic alkyl group is more preferably a cyclohexyl group.

[0145] In R2 and R3, the alkyl groups each independently have 1 to 12 carbon atoms, preferably 2 to 10 carbon atoms, and more preferably 5 to 10 carbon atoms. Asymmetric dialkylhydrazine compounds with a small number of carbon atoms in the alkyl group (such as dimethylhydrazine) may pose risks such as explosion and may be toxic to humans. By ensuring that the alkyl groups in R2 and R3 have two or more carbon atoms, the use of raw materials with the above-mentioned toxicity risks can be avoided. Furthermore, by making the number of carbon atoms in the alkyl groups in R2 and R3 5 or more, a liquid compound having an appropriate viscosity is more likely to be obtained, and the curing performance of the compound tends to be further improved.

[0146] In R2 and R3, the aryl group is not particularly limited, but examples thereof include a phenyl group and a naphthyl group.

[0147] In R2 and R3, the aralkyl group is not particularly limited, but examples thereof include a methylphenyl group, an ethylphenyl group, a methylnaphthyl group, and a dimethylnaphthyl group.

[0148] Among these, R2 and R3 are preferably aralkyl groups, and more preferably methylphenyl groups (benzyl groups).

[0149] In R2 and R3, the substituent of the alkyl group, aryl group, or aralkyl group is not particularly limited, and examples thereof include a halogen atom, an alkoxy group, a carbonyl group, a cyano group, an azo group, an azido group, a thiol group, a sulfo group, a nitro group, a hydroxy group, an acyl group, and an aldehyde group.

[0150] R2 and R3 may be linked together to form a heterocycle having up to 7 carbon atoms together with R6 (a nitrogen atom having a positive charge). The heterocycle is not particularly limited, but examples thereof include four-membered rings such as an azetidine ring; five-membered rings such as a pyrrolidine ring, a pyrrole ring, a morpholine ring, and a thiazine ring; six-membered rings such as a piperidine ring; and seven-membered rings such as a hexamethyleneimine ring and an azepine ring. Among these, the heterocycle is preferably a pyrrole ring, a morpholine ring, a thiazine ring, a piperidine ring, a hexamethyleneimine ring, or an azepine ring, and more preferably a 6-membered ring or a 7-membered ring. By having such a group, a liquid compound is easily obtained, and the curing performance of the compound tends to be further improved. Among these, a hexamethyleneimine ring in which R2, R3, and R6 are linked is preferred.

[0151] The substituent is not particularly limited, but examples thereof include an alkyl group, an aryl group, or the substituents in R2 and R3 described above. Furthermore, when the heterocycle has an alkyl group as a substituent, an example thereof is a methyl group bonded to the carbon atom adjacent to R6.

[0152] In the formulae (4), (5) and (6), each R4 independently represents a hydrogen atom or an n-valent organic group having 1 to 30 carbon atoms and optionally containing an oxygen atom. In R4, the organic group is not particularly limited, and examples thereof include a hydrocarbon group, a group in which a hydrogen atom bonded to a carbon atom in a hydrocarbon group is substituted with a hydroxy group, a carbonyl group, or a group containing a silicon atom, and a group in which a part of the carbon atoms in a hydrocarbon group is substituted with an ester bond, an ether bond, or a silicon atom.

[0153] In R4, examples of the hydrocarbon group include linear, branched, or cyclic alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and ethylhexyl groups; alkenyl groups such as vinyl, propynyl, butynyl, pentynyl, hexynyl, octynyl, decynyl, dodecynyl, hexadecynyl, and octadecynyl groups; aryl groups such as phenyl; and aralkyl groups including a combination of an alkyl group and a phenyl group, such as methylphenyl, ethylphenyl, and propylphenyl groups.

[0154] In R4, the hydrocarbon group may contain 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. The organic group containing a bisphenol skeleton is not particularly limited, but examples thereof include groups in which a polyoxyalkylene group is added to the hydroxy group of each bisphenol skeleton.

[0155] In R4, the hydrocarbon group may have a polyoxyalkylene skeleton, for example, a polyoxyethylene skeleton.

[0156] Among these, the organic group represented by R4 in formula (4) or formula (5) is preferably an alkyl group, an alkenyl group, or an aralkyl group, more preferably an alkyl group or an alkenyl group, even more preferably an alkyl group, and even more preferably a branched alkyl group. These preferred groups may have a substituent. By having such a group, it is easier to obtain a liquid compound with an appropriate viscosity, and the curing performance of the compound tends to be further improved. In addition, the Tg of the cured product obtained using the compound tends to be further improved.

[0157] In R4, the number of carbon atoms in the organic group is preferably 1 to 50, more preferably 1 to 40, and even more preferably 1 to 30. When the number of carbon atoms in the organic group in R4 is within the above range, a liquid compound having an appropriate viscosity is easily obtained, and the curing performance of the compound tends to be further improved. In addition, the Tg of the cured product obtained using this compound is further improved, and further, when the number of carbon atoms in the organic group in R4 is within the above range, the availability of raw materials is further improved.

[0158] Among the above, R4 in formula (4) or formula (5) is preferably a linear or branched alkyl group having 3 to 12 carbon atoms. By containing such a group, a liquid compound having an appropriate viscosity is easily obtained, and the curing performance of the compound tends to be further improved.

[0159] In formulas (5) and (6), n is preferably 2 or 3. This improves the crosslink density during curing, making it possible to prepare a tough cured product with improved adhesiveness and reliability.

[0160] From the viewpoint of controlling the curing temperature or viscosity, the compound (E-1) preferably contains a plurality of compounds represented by formula (4), formula (5), or formula (6). Note that the compound (E-1) may contain a plurality of compounds represented by the same formula but with different structures.

[0161] Particularly from the viewpoint of viscosity control, it is preferable that compound (E-1) contains both the compound represented by formula (4) and the compound represented by formula (6). In this case, the content of the compound represented by formula (4) is preferably 0.1 to 99.5 mass% based on 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 mass% based on the total amount of the compound represented by formula (4) and the compound represented by formula (6).

[0162] When a plurality of compounds represented by formula (4), (5), or (6) are contained, the content of the compound represented by formula (4) is preferably 0.1 to 99.8 mass% based on the total amount of the compound represented by formula (4), the compound represented by formula (5), and the compound represented by formula (6). The content of the compound represented by formula (5) is preferably 0.1 to 99.8 mass% based on the total amount of the compound represented by formula (4), the compound represented by formula (5), and the compound represented by formula (6). The content of the compound represented by formula (6) is preferably 0.1 to 99.8 mass% based on the total amount of the compound represented by formula (4), the compound represented by formula (5), and the compound represented by formula (6). This allows for easy viscosity control.

[0163] A mixture containing a plurality of compounds represented by formula (4), (5), or (6) can be obtained by mixing a plurality of compounds, or by simultaneously producing a plurality of compounds in a compound production method described below.

[0164] The compound (E-1) preferably includes at least one selected from the group consisting of a compound represented by the following (E-1A) (hereinafter simply referred to as "compound (E-1A)"), a compound represented by the following (E-1B) (hereinafter simply referred to as "compound (E-1B)"), and a compound represented by the following (E-1C) (hereinafter simply referred to as "compound (E-1C)"). The use of these compounds makes it easier to control the viscosity.

[0165] [ka]

[0166] [ka]

[0167] It is also preferable that the compound (E-1) contains both the compound (E-1A) and the compound (E-1B).

[0168] The content of compound (E-1) is not particularly limited, but because it tends to make it easier to control the viscosity, it is preferably 0.1 to 10 mass%, more preferably 0.5 to 5 mass%, and even more preferably 1 to 5 mass%, of the total amount (100 mass%) of the resin composition.

[0169] The compound represented by formula (4), the compound represented by formula (5), or the compound represented by formula (6) can be produced, for example, but not limited to, by reacting an ester compound, a hydrazine compound, and a glycidyl ether compound.

[0170] The ester compound is not particularly limited, but examples thereof include monocarboxylic acid ester compounds, dicarboxylic acid ester compounds, etc. The ester compounds may be used alone or in combination of two or more.

[0171] Specific examples of monocarboxylic acid ester compounds 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 isocrotonate, methyl benzoylformate, 2-methoxybenzoylmethyl, 3-methoxybenzoylmethyl, 4-methoxybenzoylmethyl, 2-ethoxybenzoylmethyl, and 4-t-butoxybenzoylmethyl. Alternatively, ethyl esters, propyl esters, etc. may be used.

[0172] Specific examples of dicarboxylic acid ester compounds include dimethyl oxalate, dimethyl malonate, dimethyl succinate, dimethyl tartrate, dimethyl glutarate, dimethyl adipate, dimethyl pimelate, dimethyl suberate, dimethyl azelaate, dimethyl sebacate, dimethyl maleate, dimethyl fumarate, dimethyl itaconate, dimethyl phthalate, dimethyl isophthalate, dimethyl terephthalate, dimethyl 1,3-acetonedicarboxylate, and diethyl 1,3-acetonedicarboxylate. Alternatively, cyclic esters may be used. Specific examples of cyclic esters include α-acetolactone, β-propionolactone, γ-butyrolactone, δ-valerolactone, γ-valerolactone, ε-caprolactone, etc. Alternatively, diethyl esters, dipropyl esters, etc. may be used.

[0173] Among these, from the viewpoint of curability and liquefaction, the ester compound is preferably 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 isocrotonate, methyl benzoylformate, dimethyl oxalate, dimethyl malonate, dimethyl succinate, dimethyl tartrate, dimethyl glutarate, dimethyl adipate, dimethyl pimelate, dimethyl suberate, dimethyl azelaate, dimethyl maleate, dimethyl fumarate, dimethyl phthalate, dimethyl isophthalate, dimethyl terephthalate, dimethyl 1,3-acetonedicarboxylate, diethyl 1,3-acetonedicarboxylate, γ-butyrolactone, δ-valerolactone, or γ-valerolactone.

[0174] The hydrazine compound is not particularly limited, but 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.

[0175] Among these, from the viewpoints of curability and liquefaction, dimethylhydrazine, dibenzylhydrazine, 1-aminopiperidine, 1-aminopyrrolidine, and 1-aminomorpholine are preferred as the hydrazine compound. Furthermore, among these, from the viewpoints of availability and safety, dibenzylhydrazine and 1-aminopiperidine are more preferred. The hydrazine compounds may be used alone or in combination of two or more.

[0176] The glycidyl ether compound is not particularly limited, and examples thereof include monofunctional monoglycidyl ether compounds, bifunctional or higher functional polyglycidyl ether compounds, etc. The glycidyl ether compounds may be used alone or in combination of two or more.

[0177] Specific examples of the monoglycidyl ether compound include methyl glycidyl ether, ethyl glycidyl ether, n-butyl glycidyl ether, t-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, dodecyl glycidyl ether, higher alcohol glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, orthophenylphenol glycidyl ether, benzyl glycidyl ether, biphenylyl glycidyl ether, 4-t-butylphenyl glycidyl ether, t-butyldimethylsilyl glycidyl ether, and 3-[diethoxy(methyl)silyl]propyl glycidyl ether.

[0178] Specific examples of polyglycidyl ether compounds 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, and glycerin polyglycidyl ether. Examples of suitable polyglycidyl ethers include aliphatic polyglycidyl ethers such as glycidyl ether, diglycerin polyglycidyl ether, polyglycerin 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-added bisphenol A diglycidyl ether, propylene oxide-added bisphenol A diglycidyl ether, and hydrogenated condensates thereof; and aromatic polyglycidyl ether compounds such as resorcinol diglycidyl ether.

[0179] Among these, from the viewpoint of curability and liquefaction, preferred glycidyl ether compounds are methyl glycidyl ether, ethyl glycidyl ether, n-butyl glycidyl ether, t-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, t-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.

[0180] Furthermore, from the viewpoint of adhesiveness, epoxy resins having an ether structure are preferred, specifically 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.

[0181] The amounts of the ester compound, hydrazine compound, and glycidyl ether compound added to the reaction system can be determined based on the molar ratio of the functional groups.

[0182] 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, relative to 1 mol of the primary amine of the hydrazine compound.

[0183] The amount of the glycidyl group of 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 of the hydrazine compound.

[0184] By controlling the amount of the glycidyl group of the glycidyl ether compound added relative to 1 mole 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 simultaneously produced. 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.

[0185] In the above-mentioned methods for producing the compounds and mixtures, a solvent may be used in order to ensure that the reaction proceeds uniformly.

[0186] The solvent is not particularly limited, but examples thereof include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, butanol, and t-butyl alcohol; and ethers such as tetrahydrofuran and diethyl ether.

[0187] The reaction temperature is preferably 10°C or higher and 100°C or lower, more preferably 40°C or higher and 95°C or lower. When the reaction temperature is 10°C or higher, the reaction proceeds quickly, and the purity of the obtained compound tends to be further improved. Furthermore, when the reaction temperature is 95°C or lower, the polymerization reaction between glycidyl ether compounds can be efficiently suppressed, and the purity of the compound tends to be further improved.

[0188] 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.

[0189] After the reaction is completed, the resulting reaction product can be purified by known purification methods such as washing, extraction, recrystallization, column chromatography, etc. For example, the reaction solution dissolved in an organic solvent is washed with water, and then the organic layer is heated under normal or reduced pressure to remove unreacted raw materials and the organic solvent from the reaction solution, thereby recovering the target compound. The target compound can also be recovered by purification using column chromatography. The solvent used for the above-mentioned washing is not particularly limited as long as it can dissolve the raw material residues, but 1-hexane, 1-pentane, and cyclohexane are preferred from the viewpoints of yield, purity, and ease of removal.

[0190] The organic solvent used in the extraction is not particularly limited as long as it can dissolve the target compound. From the viewpoints of yield, purity, and ease of removal, however, 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.

[0191] The packing material used in column chromatography may be a known one such as alumina, silica gel, etc. The developing solvent may be a known one such as ethyl acetate, dichloromethane, chloroform, carbon tetrachloride, tetrahydrofuran, diethyl ether, acetone, methyl isobutyl ketone, acetonitrile, methanol, ethanol, isopropanol, etc., which may be used alone or in combination.

[0192] (Imidazole Compounds (E-2)) The imidazole compound (E-2) can be used without any particular limitation. The imidazole compound (E-2) may be used alone or in combination of two or more.

[0193] 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, imidazolyl succinic acid, 2-methylimidazole succinic acid, 2-ethylimidazole succinic acid, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, and 1-cyanoethyl-2-phenylimidazole.

[0194] As the imidazole compound (E-2), 2-phenyl-4-methyl-5-hydroxymethylimidazole is preferred because it tends to be easier to control the viscosity.

[0195] The content of the imidazole compound (E-2) is not particularly limited, but since this tends to make it easier to control the viscosity, it is preferably, for example, 1 to 10 mass % of the total amount (100 mass %) of the resin composition, more preferably 1 to 5 mass %, and even more preferably 1.5 to 5 mass %.

[0196] The content of the curing accelerator (E) is not particularly limited, but because it tends to be easier to control the viscosity, it is preferably 0.1 to 10 mass %, more preferably 0.5 to 5 mass %, and even more preferably 1 to 5 mass %, of the total amount (100 mass %) of the resin composition.

[0197] <Viscosity of Resin Composition> From the viewpoint of permeability, the epoxy resin composition of the present embodiment has a viscosity at 25°C of preferably 100 Pa·s or less, more preferably 97 Pa·s or less, and even more preferably 95 Pa·s or less. From the viewpoint of curability, the resin composition of this embodiment preferably has a viscosity at 25° C. of 0.1 Pa·s or more, more preferably 1.0 Pa·s or more, and even more preferably 2.0 Pa·s or more.

[0198] The viscosity (Pa s) of the resin composition at 25°C can be measured by dropping the epoxy resin composition into a measuring cup and measuring it with an E-type viscometer (for example, "TV-20" (trade name) manufactured by Toki Sangyo Co., Ltd.) 5 minutes after the sample temperature reaches 25°C (measurement conditions: cone No. 5, 3°, R=12 mm). For specific measurement methods, see the Examples.

[0199] The resin composition of the present embodiment preferably has a viscosity of 0.01 Pa·s to 4.50 Pa·s after being left at 110°C for 60 minutes, more preferably 0.01 Pa·s to 4.00 Pa·s, and even more preferably 0.01 Pa·s to 3.50 Pa·s. 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). For specific measurement methods, see the examples.

[0200] The resin composition of the present embodiment preferably has a viscosity increase rate after being left at 110°C for 60 minutes of 1.0 times or more and 50.0 times or less, more preferably 1.0 times or more and 47.0 times or less, and even more preferably 1.0 times or more and 45.0 times or less.

[0201] The viscosity increase rate after leaving at 110°C for 60 minutes is measured using a rheometer (HAAKE MARS, manufactured by Thermo Scientific) 5 minutes and 60 minutes after the sample temperature reaches 110°C, by dropping the epoxy resin composition onto a measurement plate (measurement conditions: aluminum cone plate, R=20 mm, shear rate 20 ( / sec)). 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 the viscosity increase rate. For specific measurement methods, see the Examples.

[0202] The resin composition of this embodiment preferably satisfies the following formula (I), where V1 is the viscosity at 110°C when the rotation speed is 10 / sec and V2 is the viscosity at 100 / sec. 0.8≦V1 / V2≦1.2 (I)

[0203] The viscosity (Pa s) of the epoxy resin composition at 110°C can be measured by dropping the resin composition onto a measurement plate, and once the sample temperature reaches 110°C, using a rheometer (for example, HAAKE (registered trademark) MARS (trade name), manufactured by Thermo Scientific) while varying the shear rate in the range of 10 ( / sec) to 100 ( / sec) (measurement conditions: aluminum cone plate R = 20 mm). For specific measurement methods, see the examples.

[0204] This tends to improve the flow characteristics of the resin composition of this embodiment. 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 the value tends to increase as the molecular weight increases.

[0205] <Cure rate of resin composition> The resin composition of this embodiment preferably has a cure rate of 70% or more and 100% or less when cured at 165°C, more preferably 80% or more and 100% or less, and even more preferably 90% or more and 100% or less.

[0206] The cure rate when the resin composition of this embodiment is cured at 165°C can be determined, for example, by using EXSTER6000 (trade name, Hitachi High-Tech Science Corporation) to raise the temperature from 25°C to 300°C at a rate of 5°C / min and calculating the total amount of heat generated in the temperature range from 100°C to 250°C. Furthermore, measurements may be taken in the same manner after placing the sample in a small high-temperature chamber (manufactured by Espec Corporation) at 180°C for two hours, and the change in calorific value within the same temperature range may be calculated as a percentage. Measurements may also be taken in the same manner after placing the sample in a small high-temperature chamber (manufactured by Espec Corporation) at 165°C for two hours, and the change in calorific value within the same temperature range may be calculated as a percentage. The calculation formula is as follows. For specific measurement methods, see the Examples. Initial heat release A: DSC peak heat release of the epoxy resin composition Post-cure heat release B: DSC peak heat release of the epoxy resin composition after heating Cure rate (%) = 100 x (initial heat generation amount A - heat generation amount after curing B) ÷ initial heat generation amount A

[0207] <Method of manufacturing resin composition> The resin composition of this embodiment can be produced, for example, by dry blending the components contained in the resin composition of this embodiment, or by preparing the composition using an apparatus typically used for mixing polymeric substances. Examples of the mixing apparatus include kneading apparatuses such as a Banbury mixer, a Labo Plastomill, a single-screw extruder, and a twin-screw extruder. The resin composition is preferably obtained, for example, by stirring and mixing the components contained in the resin composition of the present embodiment in a planetary centrifugal mixer (for example, "ARE-310" (trade name) manufactured by Thinky Corporation) and then kneading with a three-roll mill. The resin composition is preferably prepared by first dissolving and dispersing a powder of the polyimide resin (B) in the epoxy resin (A) and the curing agent (C) to prepare a solution, dispersing the inorganic filler (D) in the solution to prepare a dispersion, stirring and mixing the dispersion in a planetary centrifugal mixer, and then kneading the mixture with a three-roll mill.

[0208] <Application> The resin composition and cured product of this embodiment are useful as adhesives, encapsulants, filler materials, insulating materials, conductive materials, anisotropic conductive materials, sealing materials, prepregs, etc. As adhesives, they are useful as liquid adhesives, film adhesives, die bonding materials, etc. As encapsulants, they are useful as solid encapsulants, liquid encapsulants, film encapsulants, etc., and as liquid encapsulants, they are useful as underfill materials, potting materials, dam 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.; and as anisotropic conductive materials, they are useful as anisotropic conductive films, anisotropic conductive pastes, etc.

[0209] <Adhesive> The adhesive of this embodiment contains the epoxy resin composition of this embodiment. The epoxy resin composition of the present embodiment can be suitably used as an adhesive.

[0210] ≪Cured product≫ The cured product of the present embodiment includes the epoxy resin composition of the present embodiment. The cured product is obtained by curing the epoxy resin composition.

[0211] <Sealing material> The encapsulant of this embodiment includes the cured product of this embodiment. The cured product of this embodiment can be suitably used as an encapsulant. The encapsulant is preferably an encapsulant for semiconductors.

[0212] <Semiconductor Package> The semiconductor package of this embodiment includes the cured product of this embodiment. The cured product of this embodiment can be suitably used as a semiconductor package. The method for producing a semiconductor package of this embodiment includes a step of producing a semiconductor package using the epoxy resin composition of this embodiment. The step of manufacturing a semiconductor package using the epoxy resin composition of the present embodiment may include a step of preparing the epoxy resin composition of the present embodiment. The process for producing a semiconductor package using the epoxy resin composition of the present embodiment may be a process for producing a semiconductor package by appropriately molding a prepared epoxy resin composition and curing it by heating at a predetermined temperature for a predetermined time. [Example]

[0213] 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. In other words, a person skilled in the art can practice the present invention by making various modifications to the examples shown below. In the following, unless otherwise specified, "parts" are based on mass.

[0214] [Analysis of components in epoxy resin curing agents] Analysis was carried out by the method described in the above section [Analysis of Components in Epoxy Resin Curing Agent], and 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.

[0215] [Method for measuring viscosity of epoxy resin composition at 25°C] The viscosity (Pa s) of the epoxy resin composition at 25°C was measured by dropping 0.3 mL of the resin composition obtained in each of the Examples and Comparative Examples into a measuring cup, and measuring the viscosity using an E-type viscometer (TV-20 (trade name) manufactured by Toki Sangyo Co., Ltd.) 5 minutes after the sample temperature reached 25°C (measurement conditions: cone No. 5, 3°, R=12 mm). The viscosity was evaluated according to the following criteria. [Evaluation criteria] A: The viscosity at 25°C was 20 Pa·s or less. B: Viscosity at 25°C was greater than 20 Pa·s and less than 50 Pa·s. C: Viscosity at 25°C was greater than 50 Pa·s and less than 100 Pa·s. D: Viscosity at 25°C exceeds 100 Pa·s.

[0216] [Method for measuring viscosity of epoxy resin composition at 110°C] The viscosity (Pa s) of the epoxy resin composition at 110°C was measured by dropping 0.2 mL of the resin composition obtained in each of the Examples and Comparative Examples onto a measurement plate, and once the sample temperature reached 110°C, using a rheometer (HAAKE (registered trademark) MARS (product name), manufactured by Thermo Scientific) at a shear rate varying from 10 ( / s) to 100 ( / s) (measurement conditions: aluminum cone plate R = 20 mm). 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," and the value was calculated as V1 / V2. The obtained values ​​were evaluated according to the following evaluation criteria. [Evaluation criteria] A: V1 / V2 was greater than or equal to 0.8 and less than or equal to 1.2. B: V1 / V2 was less than 0.8 and greater than 1.2.

[0217] [Method for evaluating viscosity stability at 110°C (high temperature)] The viscosity stability of the epoxy resin composition at 110°C was evaluated by dropping 0.2 mL of the resin composition obtained in each of the Examples and Comparative Examples onto a measurement plate, and measuring the viscosity at 5 minutes and 60 minutes after the sample temperature reached 110°C using a rheometer (HAAKE (registered trademark) MARS (trade name), manufactured by Thermo Scientific) at a constant measurement temperature (110°C) in oscillation mode (f = 1 Hz) (measurement conditions: aluminum cone plate R = 20 mm, shear rate 20 ( / s)). The viscosity after 5 minutes was defined as "η1" and the viscosity after 60 minutes as "η2," and the value calculated as η2 / η1 was determined as the viscosity increase rate. The obtained viscosity increase rate was evaluated according to the following evaluation criteria. "η2" is the viscosity after standing at 110°C for 60 minutes. The lower the viscosity increase rate, the better the storage stability. [Evaluation criteria] A: The viscosity increase rate was less than 5.0 times. B: The viscosity increase rate was 5.0 times or more and less than 10.0 times. C: The viscosity increase rate was 10.0 times or more and less than 50.0 times. D: The viscosity increase rate was 50.0 times or more.

[0218] [Flow evaluation] A test piece was prepared by fixing a glass plate instead of a semiconductor element on a glass substrate (26 mm wide x 75 mm long) with a 25 μm gap. Next, this test piece was placed on a hot plate set at 110°C, and the resin compositions obtained in the Examples and Comparative Examples were applied to one end of the glass plate, and the time (seconds) required for the resin to pass through the gap and reach a point 20 mm away was measured. The obtained time was evaluated according to the following evaluation criteria. The better the flowability, the better the penetration. [Evaluation criteria] A: The arrival time was less than 80 seconds. B: The arrival time was between 80 seconds and 120 seconds. C: The arrival time was between 120 seconds and 200 seconds. D: The arrival time was more than 200 seconds.

[0219] [Curing rate when cured at 165℃] The cure rate when the epoxy resin composition was cured at 165°C was measured using the following method. The resin compositions obtained in the Examples and Comparative Examples were placed in an EXSTER6000 (trade name, Hitachi High-Tech Science Corporation), and the temperature was raised from 25°C to 300°C at 5°C / min. The total amount of heat generated in the temperature range from 100°C to 250°C was calculated. The same measurement was also performed after placing the composition in a small high-temperature chamber (manufactured by Espec Corporation) at 165°C for 2 hours, and the change in heat generated in the same temperature range was calculated as a percentage. The calculation formula is as follows: Initial heat release A: DSC peak heat release of the epoxy resin composition Post-cure heat release B: DSC peak heat release of the epoxy resin composition after heating Cure rate (%) = 100 x (initial heat generation amount A - heat generation amount after curing B) ÷ initial heat generation amount A The obtained cure rates were evaluated according to the following evaluation criteria. [Evaluation criteria] A: The cure rate was 99% or more. B: The cure rate was less than 99% and 95% or more. C: The cure rate was less than 95% and more than 90%. D: The cure rate was less than 90%.

[0220] [Solvent content] The resin compositions obtained in the examples and comparative examples were used as samples and subjected to GC-MS measurement 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 and measured under the same measurement conditions as the sample, and a calibration curve was created to quantify the solvent content (the content of organic solvent in the resin composition). (Measurement conditions) Apparatus: Agilent 7890 / MSD5975C (trade name, gas chromatograph-mass spectrometer, manufactured by Agilent Technologies) Column: DB1 (trade name, 30 m x 0.25 mm i.d., manufactured by Agilent Technologies, liquid phase thickness 0.25 μm) Column temperature: 40°C / 5 min to 20°C / min, heating temperature: 320°C (held for 11 min) Column flow rate: 1 ml / min, constant flow Inlet temperature: 300℃ Injection method: Split method (split ratio 200:1) Interface temperature: 300℃ Ionization method: EI (electron ionization) method (temperature 230°C) Measurement method: Scan method Pyrolysis device: Frontier-lab PY-3030D (product name, manufactured by Frontier lab) Heating temperature (time): Sample (400°C (1 hour)), Standard sample (400°C (3 min.)) Sample amount: 0.2 to 5 mg [Evaluation criteria] A: The solvent content in the epoxy resin composition was 1% by mass or less. B: The solvent content in the epoxy resin composition exceeded 1% by mass.

[0221] [Void] The resin compositions obtained in the examples and comparative examples were poured into a Teflon (registered trademark) mold, air bubbles in the resin compositions were removed in a vacuum oven, and cured products were produced by heating at 165°C for 2 hours. The cured products obtained were evaluated according to the following evaluation criteria. [Evaluation criteria] A: No voids were observed visually. B: The occurrence of voids was visually observed.

[0222] The abbreviations of the components in the examples have the following meanings: (epoxy resin) EXA-850CRP (bisphenol A liquid epoxy resin, EPICLON® EXA-850CRP (product name), 185 g / eq, manufactured by DIC Corporation) EXA-830CRP (bisphenol F liquid epoxy resin, EPICLON® EXA-830CRP (product name), 162 g / eq, manufactured by DIC Corporation) jER (registered trademark)-630LSD (product name, aminophenol-type epoxy resin, 95 g / eq, hydrolyzable chlorine content: 1200 ppm, manufactured by Mitsubishi Chemical Corporation) HP4032D (naphthalene-type epoxy resin, EPICLON® HP4032D (trade name), 141 g / eq, hydrolyzable chlorine content: 100 ppm, manufactured by DIC Corporation)

[0223] (Tetracarboxylic acid dianhydride) BPDA: 4,4'-biphenyltetracarboxylic dianhydride ODPA: 4,4'-oxydiphthalic anhydride TAHQ: p-phenylenebis(trimellitate anhydride) BPAF: 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride

[0224] (diamine) APAB: 4-aminophenyl-4'-aminobenzoate 44DAS: 4,4'-diaminodiphenyl sulfone 33DAS: 3,3'-diaminodiphenyl sulfone TPE-M: 1,3-bis(3-aminophenoxy)benzene 34ODA: 3,4'-diaminodiphenyl ether m-TB: m-Tolidine BAPP: 2,2-bis[4-(4-aminophenoxy)phenyl]propane BAFL: 9,9-bis(4-aminophenyl)fluorene Ethacure® 100 Plus (+): A curing agent containing diethyltoluenediamine (manufactured by Mitsui Fine Chemicals, Inc.) Ethacure (registered trademark) 300: a curing agent containing diethylthiotoluenediamine (manufactured by Mitsui Fine Chemicals, Inc.)

[0225] (Aromatic amine compound (C-1)) APAB: 4-aminophenyl-4'-aminobenzoate 44DAS: 4,4'-diaminodiphenyl sulfone 34ODA: 3,4'-diaminodiphenyl ether TPE-M: 1,3-bis(3-aminophenoxy)benzene Ethacure (registered trademark) 300: a curing agent containing diethylthiotoluenediamine (manufactured by Mitsui Fine Chemicals, Inc.) Ethacure® 100 Plus (+): A curing agent containing diethyltoluenediamine (manufactured by Mitsui Fine Chemicals, Inc.) Kayahard (registered trademark) AA: a hardener containing 3,3'-diethyl-4,4'-diaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd.)

[0226] (reactive compounds) 2-EH: 2-ethylhexyl glycidyl ether BGE: butyl glycidyl ether ph-GE: phenyl glycidyl ether

[0227] (curing accelerator) 2P4MHZ-PW (Curezol (registered trademark) 2P4MHZ-PW, 2-phenyl-4-methyl-5-hydroxymethylimidazole, manufactured by Shikoku Chemicals Corporation)

[0228] (inorganic filler) SE203G-SEJ (spherical fused silica, volume average particle size 0.5 μm, manufactured by Admatechs Co., Ltd.)

[0229] <Preparation of polyimide (PI) resin> (Synthesis Example 1-1) A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen. 21 g of N-methyl-2-pyrrolidone (NMP) and 14.62 g (50 mmol) of 1,3-bis(3-aminophenoxy)benzene (TPE-M) were added and stirred until homogenous. 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 then added. The mixture was stirred at room temperature under a nitrogen flow for 1 hour to carry out the addition reaction. The temperature was then raised to 180 °C, and polymerization was carried out for 4 hours. One hour after reaching 180 °C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to 80 °C, and NMP was added to obtain a 20% by mass solution of PI in NMP. The NMP solution was dropped into ethanol to reprecipitate the PI, and the resin powder was collected by suction filtration. The collected powder was washed with water and then vacuum-dried in an oven at 80°C for 4 hours to obtain PI1 powder.

[0230] (Synthesis Example 1-2) A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen. 30 g of N-methyl-2-pyrrolidone (NMP) and 20.53 g (50 mmol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) were added and stirred until homogenous. 7.36 g (25 mmol) of biphenyltetracarboxylic dianhydride (BPDA), 22 g of NMP, 23.3 g of 1-butanol, and 174 μL of triethylamine were then added. The mixture was stirred at room temperature for 1 hour under a nitrogen flow to carry out an addition reaction. The mixture was then heated to 180°C, and after reaching 180°C, dehydration ring closure was carried out for 4 hours. One hour after reaching 180°C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to 80°C, and NMP was added to obtain a 20% by mass solution of PI in NMP. The NMP solution was dropped into ethanol to reprecipitate the PI, and the resin powder was collected by suction filtration. The collected powder was washed with water and then vacuum-dried in an oven at 80°C for 4 hours to obtain PI2 powder.

[0231] (Synthesis Example 1-3) A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen. 26 g of N-methyl-2-pyrrolidone (NMP) and 17.43 g (50 mmol) of 9,9-bis(4-aminophenyl)fluorene (BAFL) were added and stirred until homogenous. 7.36 g (25 mmol) of biphenyltetracarboxylic dianhydride (BPDA), 20 g of NMP, 22.6 g of 1-butanol, and 174 μL of triethylamine were then added. The mixture was stirred at room temperature for 1 hour under a nitrogen flow to carry out the addition reaction. The mixture was then heated to 180 °C, and after reaching 180 °C, dehydration ring closure was carried out for 4 hours. One hour after reaching 180 °C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to 80 °C, and NMP was added to obtain a 20% by mass solution of PI in NMP. The NMP solution was dropped into ethanol to reprecipitate the PI, and the resin powder was collected by suction filtration. The collected powder was washed with water and then vacuum-dried in an oven at 80°C for 4 hours to obtain PI3 powder.

[0232] (Synthesis Example 1-4) A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen, and then 15 g of N-methyl-2-pyrrolidone (NMP) and 8.91 g (50 mmol) of Ethacure® 100 Plus were added and stirred until homogenous. Next, 7.36 g (25 mmol) of biphenyltetracarboxylic dianhydride (BPDA), 15 g of NMP, 19.9 g of 1-butanol, and 174 μL of triethylamine were added. The mixture was stirred at room temperature for 1 hour under a nitrogen flow to carry out an addition reaction. The mixture was then heated to 180°C, and after reaching 180°C, dehydration ring closure was carried out for 4 hours. One hour after reaching 180°C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to an internal temperature of 80°C, and NMP was added to obtain a 20% by mass solution of PI in NMP. The NMP solution was dropped into ethanol to reprecipitate the PI, and the resin powder was collected by suction filtration. The collected powder was washed with water and then vacuum-dried in an oven at 80°C for 4 hours or 1 hour to obtain PI4 powder.

[0233] (Synthesis Example 1-5) A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen, and then 20 g of N-methyl-2-pyrrolidone (NMP) and 10.72 g (50 mmol) of Ethacure® 300 were added and stirred until homogenous. Subsequently, 7.36 g (25 mmol) of biphenyltetracarboxylic dianhydride (BPDA), 14 g of NMP, 20.5 g of 1-butanol, and 174 μL of triethylamine were added. The mixture was stirred at room temperature for 1 hour under a nitrogen flow to carry out an addition reaction. The mixture was then heated to 180°C, and after reaching 180°C, dehydration ring closure was carried out for 4 hours. One hour after reaching 180°C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to an internal temperature of 80°C, and NMP was added to obtain a 20% by mass solution of PI in NMP. The NMP solution was dropped into ethanol to reprecipitate the PI, and the resin powder was collected by suction filtration. The collected powder was washed with water and then vacuum-dried in an oven at 80°C for 4 hours to obtain PI5 powder.

[0234] (Synthesis Example 1-6) A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen. Then, 22 g of N-methyl-2-pyrrolidone (NMP) and 14.62 g (50 mmol) of 1,3-bis(3-aminophenoxy)benzene (TPE-M) were added and stirred until homogenous. Then, 7.76 g (25 mmol) of 4,4'-oxydiphthalic anhydride (ODPA), 20 g of NMP, 22 g of 1-butanol, and 174 μL of triethylamine were added. The mixture was stirred at room temperature for 1 hour under a nitrogen flow to carry out an addition reaction. The mixture was then heated to 180 °C, and after reaching 180 °C, dehydration ring closure was carried out for 4 hours. One hour after reaching 180 °C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to 80 °C, and NMP was added to obtain a 20% by mass solution of PI in NMP. The NMP solution was dropped into ethanol to reprecipitate the PI, and the resin powder was collected by suction filtration. The collected powder was washed with water and then vacuum-dried in an oven at 80°C for 4 hours to obtain PI6 powder.

[0235] (Synthesis Example 1-7) A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen. 30 g of N-methyl-2-pyrrolidone (NMP) and 20.53 g (50 mmol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) were added and stirred until homogenous. 7.76 g (25 mmol) of 4,4'-oxydiphthalic anhydride (ODPA), 23 g of NMP, 23.6 g of 1-butanol, and 174 μL of triethylamine were then added. The mixture was stirred at room temperature for 1 hour under a nitrogen flow to carry out the addition reaction. The mixture was then heated to 180 °C, and after reaching 180 °C, dehydration ring closure was carried out for 4 hours. One hour after reaching 180 °C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to an internal temperature of 80°C, and NMP was added to obtain a 20% by mass solution of PI in NMP. This 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 PI7 powder.

[0236] (Synthesis Example 1-8) A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen. 27 g of N-methyl-2-pyrrolidone (NMP) and 17.43 g (50 mmol) of 9,9-bis(4-aminophenyl)fluorene (BAFL) were added and stirred until homogenous. 7.76 g (25 mmol) of 4,4'-oxydiphthalic anhydride (ODPA), 20 g of NMP, 22.9 g of 1-butanol, and 174 μL of triethylamine were then added. The mixture was stirred at room temperature for 1 hour under a nitrogen flow to carry out an addition reaction. The mixture was then heated to 180 °C, and after reaching 180 °C, dehydration ring closure was carried out for 4 hours. One hour after reaching 180 °C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to 80 °C, and NMP was added to obtain a 20% by mass solution of PI in NMP. The NMP solution was dropped into ethanol to reprecipitate the PI, and the resin powder was collected by suction filtration. The collected powder was washed with water and then vacuum-dried in an oven at 80°C for 4 hours to obtain PI8 powder.

[0237] (Synthesis Example 1-9) A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen, and then 15 g of N-methyl-2-pyrrolidone (NMP) and 8.91 g (50 mmol) of Ethacure® 100 Plus were added and stirred until homogenous. Next, 7.76 g (25 mmol) of 4,4'-oxydiphthalic anhydride (ODPA), 15 g of NMP, 20 g of 1-butanol, and 174 μL of triethylamine were added. The mixture was stirred at room temperature for 1 hour under a nitrogen flow to carry out an addition reaction. The mixture was then heated to 180°C, and after reaching 180°C, dehydration ring closure was carried out for 4 hours. One hour after reaching 180°C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to an internal temperature of 80°C, and NMP was added to obtain a 20% by mass solution of PI in NMP. The NMP solution was dropped into ethanol to reprecipitate the PI, and the resin powder was collected by suction filtration. The collected powder was washed with water and then vacuum-dried in an oven at 80°C for 4 hours to obtain PI9 powder.

[0238] (Synthesis Example 1-10) A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen, and then 20 g of N-methyl-2-pyrrolidone (NMP) and 10.72 g (50 mmol) of Ethacure® 300 were added and stirred until homogenous. Subsequently, 7.76 g (25 mmol) of 4,4'-oxydiphthalic anhydride (ODPA), 14 g of NMP, 20.6 g of 1-butanol, and 174 μL of triethylamine were added. The mixture was stirred at room temperature for 1 hour under a nitrogen flow to carry out an addition reaction. The mixture was then heated to 180°C, and after reaching 180°C, dehydration ring closure was carried out for 4 hours. One hour after reaching 180°C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to an internal temperature of 80°C, and NMP was added to obtain a 20% by mass solution of PI in NMP. The NMP solution was dropped into ethanol to reprecipitate the PI, and the resin powder was collected by suction filtration. The collected powder was washed with water and then vacuum-dried in an oven at 80°C for 4 hours to obtain PI10 powder.

[0239] (Synthesis Example 1-11) A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen. Then, 28 g of N-methyl-2-pyrrolidone (NMP) and 14.62 g (50 mmol) of 1,3-bis(3-aminophenoxy)benzene (TPE-M) were added and stirred until homogenous. Next, 11.46 g (25 mmol) of p-phenylenebis(trimellitate anhydride) (TAHQ), 20 g of NMP, 22.8 g of 1-butanol, and 174 μL of triethylamine were added. The mixture was stirred at room temperature for 1 hour under a nitrogen flow to carry out the addition reaction. The mixture was then heated to 180 °C, and after reaching 180 °C, dehydration ring closure was carried out for 4 hours. One hour after reaching 180 °C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to an internal temperature of 80°C, and NMP was added to obtain a 20% by mass solution of PI in NMP. This 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.

[0240] (Synthesis Example 1-12) A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen. 30 g of N-methyl-2-pyrrolidone (NMP) and 20.53 g (50 mmol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) were added and stirred until homogenous. 11.46 g (25 mmol) of p-phenylenebis(trimellitate anhydride) (TAHQ), 29 g of NMP, 25 g of 1-butanol, and 174 μL of triethylamine were then added. The mixture was stirred at room temperature for 1 hour under a nitrogen flow to carry out the addition reaction. The mixture was then heated to 180 °C, and after reaching 180 °C, dehydration ring closure was carried out for 4 hours. One hour after reaching 180 °C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to an internal temperature of 80°C, and NMP was added to obtain a 20% by mass solution of PI in NMP. This 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.

[0241] (Synthesis Example 1-13) A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen. Then, 34 g of N-methyl-2-pyrrolidone (NMP) and 17.43 g (50 mmol) of 9,9-bis(4-aminophenyl)fluorene (BAFL) were added and stirred until homogenous. Next, 11.46 g (25 mmol) of p-phenylenebis(trimellitate anhydride) (TAHQ), 20 g of NMP, 23.6 g of 1-butanol, and 174 μL of triethylamine were added. The mixture was stirred at room temperature for 1 hour under a nitrogen flow to carry out an addition reaction. The mixture was then heated to 180 °C, and after reaching 180 °C, dehydration ring closure was carried out for 4 hours. One hour after reaching 180 °C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to 80 °C, and NMP was added to obtain a 20% by mass solution of PI in NMP. The NMP solution was dropped into ethanol to reprecipitate the PI, and the resin powder was collected by suction filtration. The collected powder was washed with water and then vacuum-dried in an oven at 80°C for 4 hours to obtain PI13 powder.

[0242] (Synthesis Example 1-14) A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen, and then 20 g of N-methyl-2-pyrrolidone (NMP) and 8.91 g (50 mmol) of Ethacure® 100 Plus were added and stirred until homogenous. Next, 11.46 g (25 mmol) of p-phenylenebis(trimellitate anhydride) (TAHQ), 18 g of NMP, 21.2 g of 1-butanol, and 174 μL of triethylamine were added. The mixture was stirred at room temperature for 1 hour under a nitrogen flow to carry out an addition reaction. The mixture was then heated to 180°C, and after reaching 180°C, dehydration ring closure was carried out for 4 hours. One hour after reaching 180°C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to an internal temperature of 80°C, and NMP was added to obtain a 20% by mass NMP solution of PI. The NMP solution was dropped into ethanol to reprecipitate the PI, and the resin powder was collected by suction filtration. The collected powder was washed with water and then vacuum-dried in an oven at 80°C for 4 hours to obtain PI14 powder.

[0243] (Synthesis Example 1-15) A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen, and then 21 g of N-methyl-2-pyrrolidone (NMP) and 10.72 g (50 mmol) of Ethacure® 300 were added and stirred until homogenous. Subsequently, 11.46 g (25 mmol) of p-phenylenebis(trimellitate anhydride) (TAHQ), 20 g of NMP, 21.8 g of 1-butanol, and 174 μL of triethylamine were added. The mixture was stirred at room temperature for 1 hour under a nitrogen flow to carry out an addition reaction. The mixture was then heated to 180°C, and after reaching 180°C, dehydration ring closure was carried out for 4 hours. One hour after reaching 180°C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to an internal temperature of 80°C, and NMP was added to obtain a 20% by mass solution of PI in NMP. The NMP solution was dropped into ethanol to reprecipitate the PI, and the resin powder was collected by suction filtration. The collected powder was washed with water and then vacuum-dried in an oven at 80°C for 4 hours to obtain PI15 powder.

[0244] (Synthesis Example 1-16) A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen. Then, 22 g of N-methyl-2-pyrrolidone (NMP) and 11.41 g (50 mmol) of 4-aminophenyl-4'-aminobenzoate (APAB) were added and stirred until homogenous. Next, 11.46 g (25 mmol) of 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BPAF), 20 g of NMP, 22.1 g of 1-butanol, and 174 μL of triethylamine were added. The mixture was stirred at room temperature for 1 hour under a nitrogen flow to carry out the addition reaction. The mixture was then heated to 180 °C, and after reaching 180 °C, dehydration ring closure was carried out for 4 hours. One hour after reaching 180 °C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to an internal temperature of 80°C, and NMP was added to obtain a 20% by mass solution of PI in NMP. This 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 PI16 powder.

[0245] (Synthesis Example 1-17) A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen. Then, 24 g of N-methyl-2-pyrrolidone (NMP) and 12.42 g (50 mmol) of 4,4'-diaminodiphenyl sulfone (44DAS) were added and stirred until homogenous. Next, 11.46 g (25 mmol) of 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BPAF), 20 g of NMP, 22.2 g of 1-butanol, and 174 μL of triethylamine were added. The mixture was stirred at room temperature for 1 hour under a nitrogen flow to carry out the addition reaction. The mixture was then heated to 180 °C, and after reaching 180 °C, dehydration ring closure was carried out for 4 hours. One hour after reaching 180 °C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to an internal temperature of 80°C, and NMP was added to obtain a 20% by mass solution of PI in NMP. This 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 PI17 powder.

[0246] (Synthesis Example 1-18) A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen. Then, 24 g of N-methyl-2-pyrrolidone (NMP) and 12.42 g (50 mmol) of 3,3'-diaminodiphenyl sulfone (33DAS) were added and stirred until homogenous. Next, 11.46 g (25 mmol) of 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BPAF), 20 g of NMP, 22.2 g of 1-butanol, and 174 μL of triethylamine were added. The mixture was stirred at room temperature for 1 hour under a nitrogen flow to carry out the addition reaction. The mixture was then heated to 180 °C, and after reaching 180 °C, dehydration ring closure was carried out for 4 hours. One hour after reaching 180 °C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to an internal temperature of 80°C, and NMP was added to obtain a 20% by mass solution of PI in NMP. This 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 PI18 powder.

[0247] (Synthesis Example 1-19) A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen. Then, 28 g of N-methyl-2-pyrrolidone (NMP) and 14.62 g (50 mmol) of 1,3-bis(3-aminophenoxy)benzene (TPE-M) were added and stirred until homogenous. Then, 11.46 g (25 mmol) of 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BPAF), 20 g of NMP, 22.8 g of 1-butanol, and 174 μL of triethylamine were added. The mixture was stirred at room temperature for 1 hour under a nitrogen flow to carry out the addition reaction. The mixture was then heated to 180 °C, and after reaching 180 °C, dehydration ring closure was carried out for 4 hours. One hour after reaching 180 °C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to an internal temperature of 80°C, and NMP was added to obtain a 20% by mass solution of PI in NMP. This 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 PI19 powder.

[0248] (Synthesis Example 1-20) A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen. Then, 20 g of N-methyl-2-pyrrolidone (NMP) and 10.01 g (50 mmol) of 3,4'-diaminodiphenyl ether (34ODA) were added and stirred until homogenous. Next, 11.46 g (25 mmol) of 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BPAF), 20 g of NMP, 21.5 g of 1-butanol, and 174 μL of triethylamine were added. The mixture was stirred at room temperature for 1 hour under a nitrogen flow to carry out the addition reaction. The mixture was then heated to 180 °C, and after reaching 180 °C, dehydration ring closure was carried out for 4 hours. One hour after reaching 180 °C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to an internal temperature of 80°C, and NMP was added to obtain a 20% by mass solution of PI in NMP. This 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 PI20 powder.

[0249] (Synthesis Example 1-21) A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen. Then, 21 g of N-methyl-2-pyrrolidone (NMP) and 10.62 g (50 mmol) of m-tolidine (m-TB) were added and stirred until homogenous. Next, 11.46 g (25 mmol) of 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BPAF), 20 g of NMP, 21.7 g of 1-butanol, and 174 μL of triethylamine were added. The mixture was stirred at room temperature for 1 hour under a nitrogen flow to carry out an addition reaction. The mixture was then heated to 180 °C, and after reaching 180 °C, dehydration ring closure was carried out for 4 hours. One hour after reaching 180 °C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to 80 °C, and NMP was added to obtain a 20% by mass solution of PI in NMP. The NMP solution was dropped into ethanol to reprecipitate the PI, and the resin powder was collected by suction filtration. The collected powder was washed with water and then vacuum-dried in an oven at 80°C for 4 hours to obtain PI21 powder.

[0250] (Synthesis Example 1-22) A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen. Then, 30 g of N-methyl-2-pyrrolidone (NMP) and 20.53 g (50 mmol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) were added and stirred until homogenous. Next, 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 1 hour under a nitrogen flow to carry out the addition reaction. The mixture was then heated to 180 °C, and after reaching 180 °C, dehydration ring closure was carried out for 4 hours. One hour after reaching 180 °C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to 80°C, and NMP was added to obtain a 20% by mass solution of PI in NMP. This 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 PI22 powder.

[0251] (Synthesis Example 1-23) A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen. Then, 34 g of N-methyl-2-pyrrolidone (NMP) and 17.43 g (50 mmol) of 9,9-bis(4-aminophenyl)fluorene (BAFL) were added and stirred until homogenous. Next, 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 1 hour under a nitrogen flow to carry out the addition reaction. The mixture was then heated to 180 °C, and after reaching 180 °C, dehydration ring closure was carried out for 4 hours. One hour after reaching 180 °C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to an internal temperature of 80°C, and NMP was added to obtain a 20% by mass solution of PI in NMP. This 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 PI23 powder.

[0252] (Synthesis Example 1-24) A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen, and then 20 g of N-methyl-2-pyrrolidone (NMP) and 8.91 g (50 mmol) of Ethacure® 100 Plus were added and stirred until homogenous. Next, 11.46 g (25 mmol) of 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BPAF), 18 g of NMP, 21.2 g of 1-butanol, and 174 μL of triethylamine were added. The mixture was stirred at room temperature for 1 hour under a nitrogen flow to carry out an addition reaction. The mixture was then heated to 180°C, and after reaching 180°C, dehydration ring closure was carried out for 4 hours. One hour after reaching 180°C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to an internal temperature of 80°C, and NMP was added to obtain a 20% by mass solution of PI in NMP. The NMP solution was dropped into ethanol to reprecipitate the PI, and the resin powder was collected by suction filtration. The collected powder was washed with water and then vacuum-dried in an oven at 80°C for 4 hours to obtain PI24 powder.

[0253] (Synthesis Example 1-25) A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen, and then 21 g of N-methyl-2-pyrrolidone (NMP) and 10.72 g (50 mmol) of Ethacure® 300 were added and stirred until homogenous. Next, 11.46 g (25 mmol) of 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BPAF), 20 g of NMP, 21.8 g of 1-butanol, and 174 μL of triethylamine were added. The mixture was stirred at room temperature for 1 hour under a nitrogen flow to carry out an addition reaction. The mixture was then heated to 180°C, and after reaching 180°C, dehydration ring closure was carried out for 4 hours. One hour after reaching 180°C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to an internal temperature of 80°C, and NMP was added to obtain a 20% by mass solution of PI in NMP. The NMP solution was dropped into ethanol to reprecipitate the PI, and the resin powder was collected by suction filtration. The collected powder was washed with water and then vacuum-dried in an oven at 80°C for 4 hours to obtain PI25 powder.

[0254] (Synthesis Example 1-26) A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen, and then 15 g of N-methyl-2-pyrrolidone (NMP) and 6.42 g (36 mmol) of Ethacure® 100 Plus were added and stirred until homogenous. Next, 8.83 g (30 mmol) of biphenyltetracarboxylic dianhydride (BPDA), 13 g of NMP, 19.5 g of 1-butanol, and 209 μL of triethylamine were added. The mixture was stirred at room temperature for 1 hour under a nitrogen flow to carry out an addition reaction. The mixture was then heated to 180°C, and after reaching 180°C, dehydration ring closure was carried out for 4 hours. One hour after reaching 180°C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to an internal temperature of 80°C, and NMP was added to obtain a 20% by mass solution of PI in NMP. The NMP solution was dropped into ethanol to reprecipitate the PI, and the resin powder was collected by suction filtration. The collected powder was washed with water and then vacuum-dried in an oven at 80°C for 4 hours to obtain PI26 powder.

[0255] (Synthesis Example 1-27) A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen, and then 15 g of N-methyl-2-pyrrolidone (NMP) and 8.02 g (45 mmol) of Ethacure® 100 Plus were added and stirred until homogenous. Next, 8.83 g (30 mmol) of biphenyltetracarboxylic dianhydride (BPDA), 16 g of NMP, 20.0 g of 1-butanol, and 209 μL of triethylamine were added. The mixture was stirred at room temperature for 1 hour under a nitrogen flow to carry out an addition reaction. The mixture was then heated to 180°C, and after reaching 180°C, dehydration ring closure was carried out for 4 hours. One hour after reaching 180°C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to an internal temperature of 80°C, and NMP was added to obtain a 20% by mass solution of PI in NMP. The NMP solution was dropped into ethanol to reprecipitate the PI, and the resin powder was collected by suction filtration. The collected powder was washed with water and then vacuum-dried in an oven at 80°C for 4 hours to obtain PI27 powder.

[0256] (Synthesis Example 1-28) A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen, and then 15 g of N-methyl-2-pyrrolidone (NMP) and 6.42 g (36 mmol) of Ethacure® 100 Plus were added and stirred until homogenous. Next, 9.31 g (30 mmol) of 4,4'-oxydiphthalic anhydride (ODPA), 14 g of NMP, 19.9 g of 1-butanol, and 209 μL of triethylamine were added. The mixture was stirred at room temperature for 1 hour under a nitrogen flow to carry out an addition reaction. The mixture was then heated to 180°C, and after reaching 180°C, dehydration ring closure was carried out for 4 hours. One hour after reaching 180°C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to an internal temperature of 80°C, and NMP was added to obtain a 20% by mass solution of PI in NMP. The NMP solution was dropped into ethanol to reprecipitate the PI, and the resin powder was collected by suction filtration. The collected powder was washed with water and then vacuum-dried in an oven at 80°C for 4 hours to obtain PI28 powder.

[0257] (Synthesis Example 1-29) A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen, and then 15 g of N-methyl-2-pyrrolidone (NMP) and 8.02 g (45 mmol) of Ethacure® 100 Plus were added and stirred until homogenous. Next, 9.31 g (30 mmol) of 4,4'-oxydiphthalic anhydride (ODPA), 17 g of NMP, 20.3 g of 1-butanol, and 209 μL of triethylamine were added. The mixture was stirred at room temperature for 1 hour under a nitrogen flow to carry out an addition reaction. The mixture was then heated to 180°C, and after reaching 180°C, dehydration ring closure was carried out for 4 hours. One hour after reaching 180°C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to an internal temperature of 80°C, and NMP was added to obtain a 20% by mass solution of PI in NMP. The NMP solution was dropped into ethanol to reprecipitate the PI, and the resin powder was collected by suction filtration. The collected powder was washed with water and then vacuum-dried in an oven at 80°C for 4 hours to obtain PI29 powder.

[0258] (Synthesis Example 1-30) A 500 mL four-neck flask equipped with a reflux condenser and a Dean-Stark tube was purged with nitrogen, and then 15 g of N-methyl-2-pyrrolidone (NMP) and 6.15 g (34.5 mmol) of Ethacure® 100 Plus were added and stirred until homogenous. Next, 8.83 g (30 mmol) of biphenyltetracarboxylic dianhydride (BPDA), 12 g of NMP, 19.5 g of 1-butanol, and 209 μL of triethylamine were added. The mixture was stirred at room temperature for 1 hour under a nitrogen flow to carry out an addition reaction. The mixture was then heated to 180°C, and after reaching 180°C, dehydration ring closure was carried out for 4 hours. One hour after reaching 180°C, the water and 1-butanol mixture was removed from the Dean-Stark tube. After 4 hours, the mixture was cooled to an internal temperature of 80°C, and NMP was added to obtain a 20% by mass solution of PI in NMP. The NMP solution was dropped into ethanol to reprecipitate the PI, and the resin powder was collected by suction filtration. The collected powder was washed with water and then vacuum-dried in an oven at 80°C for 4 hours to obtain PI30 powder.

[0259] Table 2 shows the components used in Synthesis Examples 1-1 to 1-30.

[0260] [Table 2]

[0261] <Preparation of epoxy resin curing agent> (Synthesis Example 2-1) A 500 mL four-neck flask equipped with a reflux condenser and a stirring blade was purged with nitrogen, and then 20 g of 1-butanol and 0.05 mol of 4,4'-diaminodiphenyl sulfone (44DAS) were added and heated to an internal temperature of 120°C. Then, using a dropping funnel, 0.03 mol of 2-ethylhexyl glycidyl ether (2-EH) was added dropwise over 30 minutes. After the dropwise addition was complete, the reaction solution was heated at 120°C for 6 hours while stirring to complete the reaction. The resulting solution was distilled off 1-butanol over 2 hours using an evaporator, maintaining the temperature at 80°C and the pressure at 15 mmHg or less, to obtain epoxy resin curing agent (A-1). The obtained epoxy resin curing agent (A-1) contains an amine adduct compound in which one molecule of the reactive compound 2-ethylhexyl glycidyl ether (2-EH) is added to one molecule of the aromatic amine compound 4,4'-diaminodiphenyl sulfone (44DAS).

[0262] (Synthesis Example 2-2) Synthesis and purification were carried out under the same conditions as in Synthesis Example 2-1, except that 0.03 mol of 2-ethylhexyl glycidyl ether (2-EH) was changed to 0.035 mol of butyl glycidyl ether (BGE), to obtain an epoxy resin curing agent (A-2). The obtained epoxy resin curing agent (A-2) contains an amine adduct compound in which one molecule of the reactive compound butyl glycidyl ether (BGE) is added to one molecule of the aromatic amine compound 4,4'-diaminodiphenyl sulfone (44DAS).

[0263] (Synthesis Example 2-3) Synthesis and purification were carried out under the same conditions as in Synthesis Example 2-1, except that 4,4'-diaminodiphenyl sulfone (44DAS) was changed to 1,3-bis(3-aminophenoxy)benzene (TPE-M), to obtain an amine adduct (B). The obtained amine adduct (B) contains an amine adduct compound in which one molecule of the reactive compound 2-ethylhexyl glycidyl ether (2-EH) is added to one molecule of the aromatic amine compound 1,3-bis(3-aminophenoxy)benzene (TPE-M).

[0264] (Synthesis Example 2-4) Synthesis and purification were carried out under the same conditions as in Synthesis Example 2-1, except that 4,4'-diaminodiphenyl sulfone (44DAS) was changed to 4-aminophenyl-4'-aminobenzoate (APAB) and the amount of 2-ethylhexyl glycidyl ether (2-EH) was changed from 0.03 mol to 0.05 mol, to obtain an amine adduct (C-1). The obtained amine adduct (C-1) contains an amine adduct compound in which one molecule of the aromatic amine compound 4-aminophenyl-4'-aminobenzoate (APAB) is added to one molecule of the reactive compound 2-ethylhexyl glycidyl ether (2-EH).

[0265] (Synthesis Example 2-5) Amine adduct (C-2) was obtained by synthesis and purification under the same conditions as in Synthesis Example 2-4, except that 2-ethylhexyl glycidyl ether was replaced with butyl glycidyl ether. The obtained amine adduct (C-2) contains an amine adduct compound in which one molecule of the reactive compound butyl glycidyl ether (BGE) is added to one molecule of the aromatic amine compound 4-aminophenyl-4'-aminobenzoate (APAB).

[0266] (Synthesis Example 2-6) Amine adduct (D-1) was obtained by synthesis and purification under the same conditions as in Synthesis Example 2-1, except that 4,4'-diaminodiphenyl sulfone (44DAS) was changed to 3,4'-oxydianiline (34ODA) and the amount of 2-ethylhexyl glycidyl ether (2-EH) was changed from 0.03 mol to 0.05 mol. The obtained amine adduct (D-1) contains an amine adduct compound in which one molecule of the aromatic amine compound 3,4'-oxydianiline (34ODA) is added to one molecule of the reactive compound 2-ethylhexyl glycidyl ether (2-EH).

[0267] (Synthesis Example 2-7) Amine adduct (D-2) was obtained by synthesis and purification under the same conditions as in Synthesis Example 2-6, except that 2-ethylhexyl glycidyl ether was replaced with butyl glycidyl ether. The obtained amine adduct (D-2) contains an amine adduct compound in which one molecule of the reactive compound butyl glycidyl ether (BGE) is added to one molecule of the aromatic amine compound 3,4'-oxydianiline (34ODA).

[0268] (Synthesis Example 2-8) Synthesis and purification were carried out under the same conditions as in Synthesis Example 2-1, except that 4,4'-diaminodiphenyl sulfone (44DAS) was changed to Kayahard (registered trademark) AA and that the amount of 2-ethylhexyl glycidyl ether (2-EH) was changed from 0.03 mol to 0.04 mol, to obtain an amine adduct (E-1). The obtained amine adduct (E-1) contains an amine adduct compound in which one molecule of the aromatic amine compound, Kayahard (registered trademark) AA, is added to one molecule of the reactive compound, 2-ethylhexyl glycidyl ether (2-EH).

[0269] (Synthesis Example 2-9) Amine adduct (E-2) was obtained by synthesis and purification under the same conditions as in Synthesis Example 2-8, except that 2-ethylhexyl glycidyl ether (2-EH) was replaced with phenyl glycidyl ether (ph-GE). The obtained amine adduct (E-2) contains an amine adduct compound in which one molecule of the aromatic amine compound, Kayahard (registered trademark) AA, is added to one molecule of the reactive compound, phenyl glycidyl ether (ph-GE).

[0270] (Synthesis Example 2-10) Synthesis and purification were carried out under the same conditions as in Synthesis Example 2-1, except that 4,4'-diaminodiphenyl sulfone (44DAS) was changed to Ethacure (registered trademark) 100 Plus and 2-ethylhexyl glycidyl ether (2-EH) was changed from 0.03 mol to 0.025 mol, to obtain an amine adduct (F-1). The obtained amine adduct (F-1) contains an amine adduct compound in which one molecule of the aromatic amine compound, Ethacure (registered trademark) 100 Plus, is added to one molecule of the reactive compound, 2-ethylhexyl glycidyl ether (2-EH).

[0271] (Synthesis Example 2-11) Amine adduct (F-2) was obtained by synthesis and purification under the same conditions as in Synthesis Example 2-10, except that 0.025 mol of 2-ethylhexyl glycidyl ether (2-EH) was changed to 0.03 mol of butyl glycidyl ether (BGE). The obtained amine adduct (F-2) contains an amine adduct compound in which one molecule of the aromatic amine compound Ethacure (registered trademark) 100 Plus is added to one molecule of the reactive compound butyl glycidyl ether (BGE).

[0272] (Synthesis Example 2-12) Amine adduct (F-3) was obtained by synthesis and purification under the same conditions as in Synthesis Example 2-10, 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) contains an amine adduct compound in which one molecule of the aromatic amine compound Ethacure (registered trademark) 100 Plus is added to one molecule of the reactive compound phenyl glycidyl ether (ph-GE).

[0273] (Synthesis Example 2-13) Synthesis and purification were carried out under the same conditions as in Synthesis Example 2-1, except that 4,4'-diaminodiphenyl sulfone (44DAS) was replaced with Ethacure (registered trademark) 300, to obtain an amine adduct (G). The obtained amine adduct (G) contains an amine adduct compound in which one molecule of the aromatic amine compound, Ethacure (registered trademark) 300, is added with one molecule of the reactive compound, 2-ethylhexyl glycidyl ether (2-EH).

[0274] Table 3 shows the components used in Synthesis Examples 2-1 to 2-13, the reaction ratios, and the LC-MS peak area ratios of each component.

[0275] [Table 3]

[0276] (Synthesis of Compound (Mixture Containing E-1A and E-1B)) 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 ChemTech Corporation), and 1.67 g (0.0105 mol) of EXA-830CRP were weighed into a recovery flask, and the flask was heated in an oil bath to 90 ° C. Next, 6.00 g (0.06 mol) of 1-aminopiperidine was added dropwise over 15 minutes. After the completion of the addition, the mixture was stirred for 4 hours while maintaining the temperature at 90 ° C., and the reaction was completed. The resulting reaction solution was concentrated under reduced pressure at 80 ° C. to remove the by-product alcohol and unreacted raw materials, and a liquid product, Compound A [a mixture containing Compound (E-1A) and Compound (E-1B)], was obtained. The structures of compound (E-1A) and compound (E-1B) are shown below.

[0277] [ka]

[0278] (Synthesis of compound (E-1C)) 3.93 g (0.038 mol) of ethyl propionate and 5.00 g (0.038 mol) of n-butyl glycidyl ether were weighed into a recovery flask, and the flask was heated in an oil bath to 90 ° C. Next, 3.85 g (0.038 mol) of 1-aminopiperidine was added dropwise over 15 minutes. After the completion of the addition, the mixture was stirred for 4 hours while maintaining the temperature at 90 ° C., and the reaction was completed. The resulting reaction solution was concentrated under reduced pressure at 80 ° C. to remove the by-product alcohol and unreacted raw materials, and a liquid product, Compound (E-1C), was obtained. The structure of compound (E-1C) is shown below.

[0279] [ka]

[0280] (Synthesis of compound (E-1D)) 1.94 g (0.019 mol) of ethyl propionate and 5.00 g (0.009 mol) of polyethylene glycol diglycidyl ether were weighed into a recovery flask, and the flask was heated in an oil bath to 90 °C. Next, 1.62 g (0.016 mol) of 1-aminopiperidine was added dropwise over 15 minutes. After the completion of the addition, the mixture was stirred for 4 hours while maintaining the temperature at 90 °C, and the reaction was completed. The resulting reaction solution was concentrated under reduced pressure at 80 °C to remove the by-product alcohol and unreacted raw materials, and a liquid product, compound (E-1D) represented by the following formula (E-1D), was obtained. The structure of compound (E-1D) is as follows: The structure of compound (E-1D) is the same as the structure of compound (E-1A).

[0281] [ka]

[0282] (Examples 1 to 54, and Comparative Example 1) The components shown in Tables 4 to 8 were placed in a plastic stirring vessel in the amounts shown in Tables 4 to 8, and the mixture was stirred and mixed using a planetary centrifugal mixer ("ARE-310" (trade name) manufactured by Thinky Corporation), followed by kneading using a three-roll mill to prepare an epoxy resin composition. In Examples 1 to 54 and Comparative Example 1, polyimide resin powder (PI1 to PI30) was dissolved and dispersed in epoxy resin and curing agent, and then an inorganic filler was dispersed in the resulting solution. The resulting dispersion was then placed in a plastic stirring vessel. In Examples 1 to 48 and 50 to 54, polyimide resins dried for 4 hours were used as PI1 to PI30, and in Example 49, a polyimide resin dried for 1 hour was used as PI4. In Comparative Example 1, a polyimide resin dried for 4 hours was used as PI4. When dissolving and dispersing PI4 in epoxy resin and curing agent, a predetermined amount of organic solvent (N-methyl-2-pyrrolidone (NMP)) was added, and then an inorganic filler was dispersed in the solution to prepare a dispersion.

[0283] Each of the obtained epoxy resin compositions was poured into a Teflon (registered trademark) mold and heated at 165°C for 2 hours to prepare a cured product. Tables 4 to 8 show the evaluation results of the resin compositions and cured products obtained in Examples 1 to 54 and Comparative Example 1.

[0284] [Table 4]

[0285] [Table 5]

[0286] [Table 6]

[0287] [Table 7]

[0288] [Table 8]

[0289] As shown in Tables 4 to 8, all of the resin compositions of the examples contained a polyimide resin, but exhibited fluidity due to their low viscosity at room temperature. By heating it to a high temperature (110°C), the viscosity was further reduced, resulting in improved fluidity and excellent flow and penetration. Furthermore, in Examples 1 to 54, cured products were obtained and had excellent viscosity stability. Therefore, the resin compositions of the Examples contained polyimide resins, but were able to achieve both permeability, curability, and storage stability. In particular, the resin compositions and cured products obtained in Examples 1 to 48 and 50 to 54 contained 0.5 mass% or less of organic solvent, and had even better curability.

[0290] In contrast, the comparative example contained more than 1% by mass of organic solvent, and therefore, like the examples, it showed high fluidity and excellent permeability, but the organic solvent volatilized during the curing reaction, causing numerous voids. When such a material is used as an encapsulant, cracks and other problems are likely to occur starting from the voids that have formed, leading to reduced reliability.

[0291] The resin compositions of the examples can be suitably used as sealing materials, particularly as underfill materials used for sealing semiconductor chips and the like. [Industrial Applicability]

[0292] The resin composition and cured product of the present invention are useful as adhesives, sealing materials, filling materials, insulating materials, conductive materials, anisotropic conductive materials, sealing materials, prepregs, etc.

Claims

1. an epoxy resin (A); A polyimide resin (B), a curing agent (C); An inorganic filler (D), A resin composition, wherein the content of an organic solvent in the resin composition is 1 mass% or less.

2. 2. The resin composition according to claim 1, having a viscosity at 25°C of 100 Pa·s or less.

3. 2. The resin composition according to claim 1, wherein the following formula (I) is satisfied when the viscosity at a rotation speed of 10 / sec at 110°C is V1 and the viscosity at a rotation speed of 100 / sec is V2: 0.8≦V1 / V2≦1.2...(I)

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

5. The curing agent (C) an aromatic amine compound (C-1); an aromatic amine adduct (C-2) which 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); Including, The resin composition according to claim 1, wherein the aromatic amine adduct (C-2) comprises an aromatic amine adduct (C-2-1) in which one molecule of the reactive compound is added to one molecule of the aromatic amine compound (C-1).

6. 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): 【Chemical 1】 (In formula (1), R 1 and R 2 each independently represents a monovalent organic group having 1 to 20 carbon atoms or a halogen atom, a and b each independently represents an integer of 0 to 4, and X represents a divalent organic group or a single bond. 【Chemistry 2】 (In formula (2), R 3 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.

8. The resin composition according to claim 1 , further comprising a curing accelerator (E).

9. The resin composition according to claim 8, having a viscosity of 0.01 Pa·s to 4.50 Pa·s after being left at 110°C for 60 minutes.

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

11. A sealing material comprising the cured product according to claim 10.

12. The encapsulant according to claim 11, which is an encapsulant for semiconductors.

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

14. A semiconductor package comprising the cured product according to claim 10.

15. A method for producing a semiconductor package, comprising a step of producing a semiconductor package using the resin composition according to any one of claims 1 to 9.

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