Resin composition, cured product, structure, curing agent, sealing material, adhesive, semiconductor package, and method for producing semiconductor package

Abstract

This resin composition contains an epoxy resin (A), an amine compound (B), and an inorganic filler (D), wherein the amine compound (B) contains a compound represented by formula (1). (In formula (1), R1 represents a monovalent organic group having 1-20 carbon atoms or a halogen atom, a represents an integer of 0-3, and b represents an integer of 1-3.)

Description

Resin composition, cured product, structure, curing agent, sealing material, adhesive, semiconductor package, and method for manufacturing semiconductor package

[0001] The present invention relates to a resin composition, a cured product, a structure, a curing agent, an encapsulant, an adhesive, a semiconductor package, and a method for manufacturing the semiconductor package.

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

[0003] For example, Patent Document 1 discloses an epoxy resin composition that combines multiple types of epoxy resins having different numbers of glycidyl groups with multiple types of aromatic polyamines having different structures.

[0004] Furthermore, Patent Document 2 discloses an underfill resin composition containing (A) an epoxy resin, (B) an aromatic amine compound, (C) an inorganic filler, and (D) an organic phosphorus compound, in which the (A) epoxy resin contains a bisphenol-type epoxy resin and a glycidylamine-type epoxy resin in a mass ratio of bisphenol-type epoxy resin:glycidylamine-type epoxy resin = 60:40 to 95:5, and the organic phosphorus compound is at least one selected from the group consisting of phosphine oxide compounds, phosphonate esters, phosphites, phosphorane compounds, phosphalkene compounds, and phosphaalkyne compounds.

[0005] Furthermore, Patent Document 3 discloses a curing agent in which a plurality of aromatic amine compounds having different structures are combined, and a cured product using the curing agent.

[0006] JP 2022-137823 A JP 2021-014588 A Japanese Patent No. 7242628

[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] Since the two-component epoxy resin composition can be cured at room temperature, the epoxy resin and the curing agent are stored separately and are used after being measured and mixed as needed. This makes storage and handling cumbersome. Furthermore, since the usable time is limited, it is not possible to mix a large amount in advance, which increases the mixing frequency and inevitably reduces efficiency.

[0009] To solve the problems associated with two-component epoxy resin compositions as described above, various one-component epoxy resin compositions have been proposed, including, for example, one-component epoxy resin compositions in which a predetermined epoxy resin curing agent is blended with an epoxy resin.

[0010] Meanwhile, in recent years, there have been a wide variety of demands for electronic devices, such as miniaturization, high functionality, light weight, high functionality, multi-functionality, etc. More specifically, in semiconductor chip mounting technology, there is a demand for further miniaturization, miniaturization, and high density by making electrode pads and pad pitches finer.

[0011] Additionally, 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, but in order to meet the demand for even finer pitches, there is a demand for underfill that can penetrate narrower gaps.

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

[0013] As described above, a one-component epoxy resin composition obtained by mixing an epoxy resin and an epoxy resin curing agent is required to have both good curability and storage stability, and also good permeability into fine regions such as between densely packed fibers such as carbon fibers and glass fibers, and narrow gaps in electronic components.

[0014] However, the epoxy resin compositions and cured products disclosed in Patent Documents 1 and 3 do not contain an inorganic filler, and therefore have a problem that the linear expansion coefficient is not yet sufficient for practical use and there is room for improvement. In addition, the cured product disclosed in Patent Document 3 has a problem that there is room for improvement in the curing rate because a curing agent with low reactivity is used.

[0015] Furthermore, the resin composition disclosed in Patent Document 2 has a problem in that the proportion of aromatic rings in the bisphenol-type epoxy resin is high, and therefore the crack resistance and toughness values ​​are not yet sufficient for practical use, and there is room for improvement.

[0016] Therefore, the first object of the present invention is to provide a resin composition, a cured product, an encapsulant, an adhesive, a semiconductor package, and a method for manufacturing a semiconductor package that can achieve both curability and storage stability and have a low high-temperature modulus of elasticity and a low coefficient of linear expansion (CTE).The second object of the present invention is to provide a resin composition, a cured product, a structure including the cured product, an encapsulant, an adhesive, a semiconductor package, and a method for manufacturing a semiconductor package, that can produce a cured product that can achieve both high toughness and a low coefficient of linear expansion (CTE).Furthermore, the third object of the present invention is to provide a resin composition, a curing agent that can produce a cured product, and a resin composition, a cured product, an encapsulant, an adhesive, a semiconductor package, and a method for manufacturing a semiconductor package that use the curing agent, that can achieve both curability and storage stability.

[0017] The present inventors have conducted extensive research in light of the above-mentioned problems of the conventional art, and have found that the above-mentioned problems of the conventional art can be solved by first specifying a resin composition containing an epoxy resin, an amine compound, and an inorganic filler to contain a predetermined compound as the amine compound, thereby completing the present invention. Furthermore, the present inventors have conducted extensive research in light of the above-mentioned first problem, and have found that the above-mentioned first problem can be solved by specifying a resin composition containing an epoxy resin, an amine compound, and an inorganic filler to contain an epoxy resin having a predetermined structure, thereby completing the present invention. Furthermore, the present inventors have conducted extensive research in light of the above-mentioned second problem, and have found that the above-mentioned second problem can be solved by specifying a resin composition containing an epoxy resin, an inorganic filler, and an amine compound based on the maximum peak intensity ratio in a predetermined region in the infrared absorption spectrum of a cured product of the resin composition, thereby completing the present invention. Furthermore, the present inventors have conducted extensive research in light of the third problem described above and have found that the third problem can be solved by using a curing agent containing a primary amine compound having an ionization potential within a predetermined numerical range and a secondary amine compound having a predetermined structure, thereby completing the present invention.

[0018] [1] A resin composition comprising an epoxy resin (A), an amine compound (B), and an inorganic filler (D), wherein the amine compound (B) contains a compound represented by the following formula (1):

[0019]

[0020] In formula (1), R １ represents a monovalent organic group having 1 to 20 carbon atoms or a halogen atom; a is an integer of 0 to 3; and b is an integer of 1 to 3.

[0021] [2] The epoxy resin (A) is a glycidylamine type epoxy resin (A １ -1) and bisphenol-type epoxy resin (A １-2), and the bisphenol-type epoxy resin (A １ The resin composition according to the above [1], wherein the amine compound (B-2) satisfies the following formula (I): 0.05≦(molecular weight of aromatic rings in one molecule / molecular weight of one molecule)≦0.4 (I) [3] ... １ -1), and an amine compound (B) in which the value Ip* calculated from the following formula (II) is 9.7<Ip*≦11.0: １ The resin composition according to [1] or [2] above, further comprising:

[0022]

[0023] In formula (II), Ip is the value of the ionization potential before correction, and Ip* is the value of the ionization potential after correction using the substituent constant. a is the number of substituents bonded to the o-position relative to the amino group. b is the number of substituents bonded to the m-position relative to the amino group. c is the number of substituents bonded to the p-position relative to the amino group. Es(AMD) is a steric parameter evaluated from the acid hydrolysis reaction rate of ortho-substituted benzamide. σm is the substituent constant when bonded to the m-position among Hammett's substituent constants. σp is the substituent constant when bonded to the p-position among Hammett's substituent constants.

[0024] [4] The amine compound (B １ The resin composition according to [3] above, wherein the compound represented by formula (1) is a compound represented by formula (2) or formula (3):

[0025]

[0026] In formula (2), R ２ and R ３ each independently represents a monovalent organic group having 1 to 20 carbon atoms or a halogen atom; c and d each independently represent an integer of 0 to 4; and X represents a divalent organic group or a single bond.

[0027]

[0028] In formula (3), R ４ represents a monovalent organic group having 1 to 20 carbon atoms or a halogen atom, and e is an integer of 1 to 4.

[0029] [5] The amine compound (B １ -1) and the amine compound (B １ amine adduct (C １ [6] The resin composition according to [3] or [4] above, containing the glycidyl amine type epoxy resin (A-1). １ -1) and the bisphenol type epoxy resin (A １ The mass ratio of (A −2) is １ -1): (A １ [7] The resin composition according to any one of [2] to [5], wherein the amine compound (B −2) is 50:50 to 95:5. １ -1) and the amine compound (B １ The mass ratio of (B −2) is １ -1): (B １ [8] The resin composition according to any one of [3] to [6] above, wherein the ratio of the hydroxyl group to the hydroxyl group is 10:90 to 90:10. [9] A cured product of the resin composition according to any one of [2] to [7] above.

[10] The cured product of the resin composition according to any one of [2] to [7] above.

[11] The cured product of the resin composition has an infrared (IR) absorption spectrum of 1,420 to 1,440 cm －１ The maximum peak intensity Ia present in the region of 1,450 to 1,550 cm －１and a maximum peak intensity Ib existing in the region of Ia / Ib, satisfying the following formula (i): 0.24≦Ia / Ib≦0.4 (i)

[10] A cured product of the resin composition according to any one of [1] to [8] above.

[11] A structure comprising a first layer, a second layer, and a plurality of copper pillars connecting the first layer and the second layer, wherein the first layer and the second layer each contain at least one type selected from the group consisting of resin, silicon, ceramics, compound semiconductor, and glass, and the distance between adjacent copper pillars of the plurality of copper pillars is 150 μm or less, and a third layer is provided between the first layer and the second layer in contact with each of the first layer and the second layer, wherein the third layer is the cured product according to

[10] above.

[12] A structure comprising a primary amine compound (A) having a value Ip* calculated from the following formula (II) of 6.0≦Ip*≦9.7. ３ -1) and a secondary amine compound (B ３ ), and the primary amine compound (A ３ -1) is a compound represented by the following formula (4) or the following formula (5), and the secondary amine compound (B ３ ) is a compound represented by the following formula (6) or the following formula (7):

[0030]

[0031] In formula (4), R ２ and R ３ each independently represents a monovalent organic group having 1 to 20 carbon atoms or a halogen atom; c and d each independently represent an integer of 0 to 4; and X represents a divalent organic group or a single bond.

[0032]

[0033] In formula (5), R ４ represents a monovalent organic group having 1 to 20 carbon atoms or a halogen atom, and e is an integer of 1 to 4.

[0034]

[0035] In formula (6), R ８ and R ９each independently represents a monovalent organic group having 1 to 20 carbon atoms or a halogen atom; f and g each independently represent an integer of 0 to 4; X represents a divalent organic group or a single bond; R ６ and R ７ each independently represents a monovalent alkyl group, aryl group, or aralkyl group having 2 to 10 carbon atoms.

[0036]

[0037] In formula (7), R １２ represents a monovalent organic group having 1 to 20 carbon atoms or a halogen atom, h is an integer of 1 to 4, and R １０ and R １１ each independently represents a monovalent alkyl group, aryl group, or aralkyl group having 2 to 10 carbon atoms.

[0038]

[0039] In formula (II), Ip is the value of the ionization potential before correction, and Ip* is the value of the ionization potential after correction using the substituent constant. a is the number of substituents bonded to the o-position relative to the amino group. b is the number of substituents bonded to the m-position relative to the amino group. c is the number of substituents bonded to the p-position relative to the amino group. Es(AMD) is a steric parameter evaluated from the acid hydrolysis reaction rate of ortho-substituted benzamide. σm is the substituent constant when bonded to the m-position among Hammett's substituent constants. σp is the substituent constant when bonded to the p-position among Hammett's substituent constants.

[0040]

[13] The primary amine compound (A ３ -1) and the secondary amine compound (B ３

[14] The curing agent according to

[12] , wherein the primary amine compound (A) is a combination of the compound represented by formula (4) and the compound represented by formula (7), or a combination of the compound represented by formula (5) and the compound represented by formula (6). ３ -1) and the secondary amine compound (B ３ ) mass ratio is (A ３ -1): (B ３

[15] The curing agent according to

[12] or

[13] above, wherein the primary amine compound (A) is 75:25 to 5:95. ３ Amine adduct (A-1) is a reaction product of a reactive compound having a functional group capable of reacting with ３

[16] The curing agent according to any one of

[12] to

[14] above, further comprising a nitrogen-containing compound (D-1-1) represented by any one of the following formulas (8) to (10): ３ The curing agent according to any one of

[12] to

[15] above, further comprising:

[0041]

[0042]

[0043]

[0044] In formulas (8) to (10), R １３ each 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; R １４ and R １５ each independently represents an unsubstituted or substituted alkyl group, aryl group, or aralkyl group having 1 to 12 carbon atoms, or combines to form a heterocycle having 7 or less carbon atoms; R １６ R each independently represents a hydrogen atom or an n-valent organic group having 1 to 30 carbon atoms which may contain an oxygen atom; n represents an integer of 1 to 3. １７ represents a negatively charged nitrogen atom, and R １３ indicates a positively charged nitrogen atom.

[0045]

[17] A resin composition comprising the curing agent according to any one of

[12] to

[16] above, and an epoxy resin, wherein the mass ratio of the curing agent to the epoxy resin is curing agent:epoxy resin = 10:90 to 65:35.

[18] A cured product of the resin composition according to

[17] above.

[19] An encapsulant comprising the cured product according to any one of [8],

[10] , and

[18] above.

[20] The encapsulant according to

[19] above, which is an encapsulant for semiconductors.

[21] An adhesive comprising the resin composition according to any one of [1] to [7], [9], and

[17] above.

[22] A semiconductor package comprising the cured product according to any one of [8],

[10] , and

[18] above.

[23] A method for manufacturing a semiconductor package, comprising a step of manufacturing a semiconductor package using the resin composition according to any one of [1] to [7], [9], and

[17] above.

[0046] The present invention provides a resin composition, a cured product, an encapsulant, an adhesive, a semiconductor package, and a method for manufacturing a semiconductor package that can achieve both curability and storage stability and have a low high-temperature modulus of elasticity and a low coefficient of linear expansion (CTE).The present invention also provides a resin composition, a cured product, a structure including the cured product, an encapsulant, a semiconductor package, and a method for manufacturing a semiconductor package that can achieve both high toughness and a low coefficient of linear expansion (CTE).The present invention also provides a resin composition, a curing agent that can achieve both curability and storage stability and a cured product, a resin composition, a cured product, an encapsulant, an adhesive, a semiconductor package, and a method for manufacturing the same that use the curing agent.

[0047] Hereinafter, a detailed description will be given of an embodiment of the present invention (hereinafter simply referred to as "the present embodiment"). The following embodiment is an example for explaining the present invention and is not intended to limit the present invention to the following content. The present invention can be implemented by appropriate modifications within the scope of the gist thereof. In this specification, when a numerical value or physical property value is enclosed before and after "~", the preceding and following values ​​are included. In the numerical ranges described in this specification in stages, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described in stages. Furthermore, in the numerical ranges described in this specification, the upper or lower limit of that numerical range may be replaced with a value shown in the Examples. In the description of groups (atomic groups) in this specification, a notation that does not specify whether they are substituted or unsubstituted includes both unsubstituted and substituted groups. For example, the term "alkyl group" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups).

[0048] [Resin Composition] The resin composition of the present embodiment contains an epoxy resin (A), an amine compound (B), and an inorganic filler (D), wherein the amine compound (B) contains a compound represented by the following formula (1):

[0049]

[0050] In formula (1), R １ represents a monovalent organic group having 1 to 20 carbon atoms or a halogen atom; a is an integer of 0 to 3; and b is an integer of 1 to 3.

[0051] By having the above-described structure, it is possible to provide a resin composition that can achieve both curability and storage stability, and that can give a cured product that has a low high-temperature modulus of elasticity and a low coefficient of linear expansion (CTE), and that can achieve both high toughness and a low coefficient of linear expansion (CTE).

[0052] [First embodiment] [Resin composition] A resin composition of a first embodiment (hereinafter, sometimes referred to as an "epoxy resin composition") contains an epoxy resin (A), an amine compound (B), and an inorganic filler (D). The epoxy resin (A) is a glycidylamine-type epoxy resin (A １ -1) and bisphenol-type epoxy resin (A １ -2), and the bisphenol-type epoxy resin (A １ -2) satisfies the following formula (I): 0.05≦(molecular weight of aromatic rings in one molecule / molecular weight of one molecule)≦0.4 (I)

[0053] By having the above-mentioned constitution, it is possible to obtain a resin composition which can achieve both curability and storage stability and has a low high-temperature elastic modulus and linear expansion coefficient. Note that the curability, storage stability, high-temperature elastic modulus, and linear expansion coefficient can be measured and evaluated by the methods described in the examples below. The constituent components of the resin composition will be described below.

[0054] (Epoxy resin (A １ The resin composition of the first embodiment contains an epoxy resin (A) (in the first embodiment, １ ) is sometimes written as ). １ ) is a glycidylamine type epoxy resin (A １ -1), and bisphenol-type epoxy resin (A １ Contains bisphenol type epoxy resin (A-2). １ -2) satisfies the following formula (I): 0.05≦(molecular weight of aromatic rings in one molecule / molecular weight of one molecule)≦0.4 (I)

[0055] The epoxy resin (A) used in the resin composition of the first embodiment １) may be solid or liquid at room temperature, but from the viewpoint of the filling property of the resin composition of the first embodiment, an epoxy resin that is liquid at room temperature (hereinafter also referred to as "liquid epoxy resin") is preferred. As the liquid epoxy resin, a commonly used liquid epoxy resin can 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.

[0056] <Glycidylamine type epoxy resin (A １ -1) Glycidylamine type epoxy resin (A １ Examples of -1) include, but are not limited to, epoxy resins obtained by reacting an amine compound such as p-aminophenol, diaminodiphenylmethane, or isocyanuric acid with epichlorohydrin.

[0057] <Bisphenol type epoxy resin (A １ -2) Bisphenol type epoxy resin (A １ Examples of -2) include, but are not limited to, diglycidyl ether epoxy resins such as bisphenol A, bisphenol F, bisphenol AD, bisphenol S, and hydrogenated bisphenol A.

[0058] <Other Epoxy Resins> The resin composition of the first embodiment may contain a glycidylamine type epoxy resin (A １ -1), bisphenol type epoxy resin (A １ -2) may contain other epoxy resins. Examples of other epoxy resins include, but are not limited to, naphthalene-type epoxy resins; epoxy resins obtained by epoxidizing novolak resins obtained from phenols and aldehydes, such as orthocresol novolak-type epoxy resins; glycidyl ester-type epoxy resins obtained by reacting epichlorohydrin with polybasic acids, such as phthalic acid and dimer acid; fluorene-type epoxy resins obtained from fluorene derivatives having a cardo structure in which fluorene is bonded to an aromatic ring; and linear aliphatic epoxy resins and alicyclic epoxy resins obtained by oxidizing olefin bonds with peracids, such as peracetic acid.

[0059] The resin composition of the first embodiment is a glycidylamine type epoxy resin (A １ From the viewpoint of crack resistance, the epoxy resin (A-1) having a bisphenol skeleton is １ -2).

[0060] In addition, as shown in the formula (I), bisphenol type epoxy resin (A １ The ratio of the aromatic rings in the bisphenol epoxy resin molecule to the molecular weight of one molecule is 0.05 or more and 0.4 or less. By setting the ratio of the aromatic rings in the bisphenol epoxy resin molecule to the molecular weight of one molecule in the above-mentioned range, a stress relaxation effect is achieved, and from the viewpoint of the crack resistance and heat resistance of the resin composition and the cured product of the first embodiment, the ratio is preferably 0.07 or more, more preferably 0.1 or more. Furthermore, the ratio is preferably 0.35 or less, more preferably 0.3 or less.

[0061] The epoxy resin (A １ The (molecular weight of the aromatic rings in one molecule / molecular weight of one molecule) in -2) can be controlled within the above numerical range by adjusting the amount of dialcohol added to the bisphenol structure when synthesizing the epoxy resin.

[0062] When the resin composition of the first embodiment contains a naphthalene-type epoxy resin as the other epoxy resin, the epoxy resin (A １ -1) and (A １ Mass ratio of naphthalene type epoxy resin to the total of glycidylamine type epoxy resin (A-2) = (mass ratio of naphthalene type epoxy resin to glycidylamine type epoxy resin (A-2) １ -1) and bisphenol type epoxy resin (A １ The sum of (-2)) is not particularly limited, but from the viewpoint of the heat resistance, adhesiveness, and flowability of the resin composition of the present embodiment, it is preferably 5:95 to 50:50, more preferably 10:90 to 40:60, and even more preferably 15:80 to 40:60.

[0063] Glycidylamine type epoxy resin (A １ -1) and bisphenol-type epoxy resin (A １In view of the fluidity of the resin composition of the first embodiment, it is preferable that the resin composition-2) is liquid at room temperature.

[0064] The glycidylamine type epoxy resin (A １ -1) and bisphenol-type epoxy resin (A １ The total content of -2) is not particularly limited, but from the viewpoints of the heat resistance, adhesiveness, and fluidity of the resin composition of the first embodiment, it is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 50% by mass or more, and even more preferably 80% by mass or more, relative to the total amount of epoxy resin (A). The upper limit of the total content is not particularly limited, but can be determined within a range in which desired properties and characteristics are obtained from the viewpoints of the viscosity, glass transition temperature, heat resistance, and the like of the resin composition of the first embodiment, and may be 100% by mass.

[0065] The glycidylamine type epoxy resin (A １ -1) and bisphenol type epoxy resin (A １ -2) = (glycidylamine type epoxy resin (A １ -1): Bisphenol type epoxy resin (A １ -2)) is not particularly limited, but from the viewpoint of the heat resistance, adhesiveness, and fluidity of the resin composition of the first embodiment, it is preferably 50:50 to 95:5, more preferably 60:40 to 90:10, and even more preferably 70:30 to 90:10.

[0066] In the resin composition of the first embodiment, the epoxy resin (A １ The content of the epoxy resin that is solid at room temperature is determined from the viewpoint of the fluidity of the resin composition of the first embodiment, by adjusting the content of the epoxy resin (A １ ) It is preferably 0 to 30% by mass, more preferably 0 to 25% by mass, and even more preferably 0 to 20% by mass, based on the total amount.

[0067] Epoxy resin (A １The epoxy equivalent of the epoxy resin (A) is not particularly limited, but from the viewpoint of the heat resistance of the resin composition of the first embodiment, it is preferably 60 to 1000 g / mol, more preferably 70 to 900 g / mol, and even more preferably 80 to 800 g / mol. Here, the epoxy equivalent is the mass of resin per epoxy group (g / eq) and can be measured according to the method specified in JIS K 7236. Specifically, using an automatic titrator "GT-200" manufactured by Mitsubishi Chemical Analytech Co., Ltd., 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. After that, 10 mL of glacial acetic acid and 1.5 g of cetyltrimethylammonium bromide are added, and the epoxy equivalent is determined by titration with a 0.1 mol / L perchloric acid / acetic acid solution.

[0068] The epoxy resin (A) used in the resin composition of the first embodiment １ ) is preferably of high purity. In particular, the amount of hydrolyzable chlorine is preferably small because it affects the corrosion of aluminum wiring on elements such as ICs (integrated circuits), and from the viewpoint of the moisture resistance of the resin composition of this embodiment, it is preferably 1500 ppm or less, for example. 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 a 1N KOH (potassium hydroxide) methanol solution, refluxing for 30 minutes, and then measuring the value determined by potentiometric titration.

[0069] The epoxy resin (A １ The content of the hydroxybenzoate is not particularly limited, but from the viewpoint of the heat resistance, adhesiveness, and flowability of the resin composition of the first embodiment, it is preferably 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.

[0070] (Amine Compound (B １ The resin composition of the first embodiment contains an amine compound (B) (in the first embodiment, the amine compound (B １ ) is sometimes written as ). １Examples of the amine compound (B) include aromatic amines, aliphatic amines, and alicyclic amines, but aromatic amines are preferred from the viewpoint of heat resistance. １ ) is an amine compound (B) described later from the viewpoint of storage stability and curability of the resin composition of the present embodiment. １ -1) and an amine compound (B １ It is preferable that the two types of the above-mentioned compounds are contained.

[0071] The amine compound (B １ The amine compound (B-1) is an amine compound in which the value Ip* calculated from the following formula (II) satisfies the following condition: 6.0≦Ip*≦9.7. １ -2) is an amine compound in which the value Ip* calculated from the following formula (II) is 9.7<Ip*≦11.0.

[0072]

[0073] In formula (II), Ip is the value of the ionization potential before correction, and Ip* is the value of the ionization potential after correction using the substituent constant. a is the number of substituents bonded to the o-position relative to the amino group. b is the number of substituents bonded to the m-position relative to the amino group. c is the number of substituents bonded to the p-position relative to the amino group. Es(AMD) is a steric parameter evaluated from the acid hydrolysis reaction rate of ortho-substituted benzamide. σm is the substituent constant when bonded to the m-position among Hammett's substituent constants. σp is the substituent constant when bonded to the p-position among Hammett's substituent constants.

[0074] The amine compound (B １ -1) is preferably an aromatic amine compound represented by the following formula (2) or an aromatic amine compound represented by the following formula (3):

[0075]

[0076] In formula (2), R ２ and R ３each independently represents a monovalent organic group having 1 to 20 carbon atoms or a halogen atom; c and d each independently represent an integer of 0 to 4; and X represents a divalent organic group or a single bond.

[0077] R ２ and R ３ In the above formula, 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 a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. a and b are each independently preferably an integer of 0 to 2, and more preferably 0 or 1. In X, the number of carbon atoms in the divalent organic group is preferably 1 to 10, more preferably 1 to 8, and even more preferably 1 to 6.

[0078] Examples of the amine compound represented by formula (2) include, but are not limited to, 4,4'-diaminodiphenyl sulfone, 4-aminophenyl-4'-aminobenzoate, 1,3-bis(3-aminophenoxy)benzene, Kayahard (registered trademark) AA (a curing agent containing 3,3'-diethyl-4,4'-diaminodiphenylmethane, manufactured by Nippon Kayaku Co., Ltd.), Ethacure (registered trademark) 100 Plus (+) (a trade name, a curing agent containing diethyltoluenediamine, manufactured by Mitsui Chemicals Fine Co., Ltd.), etc. The amine compound represented by formula (2) may be used alone or in combination of two or more, and it is preferable to use one or more selected from these.

[0079] Among these, the amine compound represented by the formula (2) is preferably selected from the group consisting of -O-, -O-CH-O-, -CH-, -CO-, -C(=O)O-, -SO, and the like, from the viewpoint of achieving both curability and stability when mixed with the epoxy resin (A) to form a resin composition. ２ Aromatic amine compounds having a — or —C(═O)NH— bond are preferred, and aromatic amine compounds having a —C(═O)O— bond are particularly preferred.

[0080] Furthermore, as the aromatic amine compound represented by formula (2), an aromatic amine compound having a methanediyl group (-CH2-), which has high reactivity as an amine, can also be used. Note that, from the viewpoint of suppressing the reactivity as an amine and improving the storage stability of the resin composition of this embodiment, it is preferable to use a compound other than an aromatic amine compound having a methanediyl group as the aromatic amine compound represented by formula (2).

[0081] Examples of aromatic amine compounds having a methanediyl group include, but are not limited to, 3,3'-diethyl-4,4'-diaminodiphenylmethane (for example, Kayahard (registered trademark) AA (trade name) manufactured by Nippon Kayaku Co., Ltd.), 4,4'-diaminodiphenylmethane, and 3,3'-diaminodiphenylmethane. The aromatic amine compounds having a methanediyl group may be used alone or in combination of two or more.

[0082]

[0083] In formula (3), R ４ represents a monovalent organic group having 1 to 20 carbon atoms or a halogen atom, and e is an integer of 1 to 4. ４ In the formula (I), 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. e is preferably an integer of 1 to 3, and more preferably 2 or 3.

[0084] Examples of aromatic amines represented by formula (3) include, but are not limited to, diethyltoluenediamine (2,4-diamino-3,5-diethyltoluene, 2,6-diamino-3,5-diethyltoluene). The aromatic amines represented by formula (3) 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, 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 from the viewpoint of achieving both curability and stability when mixed with epoxy resin (A) to form a resin composition.

[0085] Amine compound (B １ As the compound-2), an aromatic amine compound represented by the following formula (1) is preferred.

[0086]

[0087] In formula (1), R １ R each independently represents a monovalent organic group having 1 to 20 carbon atoms or a halogen atom, a is an integer of 0 to 3, and b is an integer of 1 to 3. １ In the formula (I), 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. a is an integer of 0 to 3, preferably 1 or 2. b is an integer of 1 to 3, preferably 2 or 3.

[0088] Examples of the aromatic amine represented by formula (1) include, but are not limited to, Ethacure (registered trademark) 300 (trade name, curing agent containing diethylthiotoluenediamine, manufactured by Mitsui Fine Chemicals, Inc.), 2,4,6-tris(methylthio)-1,3-benzenediamine, and 2-methyl-4,5,6-tris(methylthio)-1,3-benzenediamine.

[0089] <Ionization Potential> The ionization potential (Ip) of an amine compound is known to be correlated with its electron donating ability. Since the higher the electron donating ability of an amine compound, the higher the reactivity of the compound; therefore, the smaller the ionization potential (Ip), the higher the reactivity of the amine compound. Furthermore, when an amino group is bonded to an aromatic ring, other substituents affect the reactivity due to electron donating ability, steric hindrance, etc. Therefore, taking into account the influence of the substituent, correction using a substituent constant is necessary. The value obtained by correcting the ionization potential (Ip) for the substituent is defined as Ip*; the smaller this value, the higher the reactivity, and the larger this value, the lower the reactivity. Ip* is calculated using the following formula (II):

[0090]

[0091] E ｓ (AMD): Steric parameter σ evaluated from the acid hydrolysis reaction rate of ortho-substituted benzamide ｍ : Hammett's substituent constant when bonded to m-position σ ｐ : Hammett's substituent constant when bonded to the p-position a: Number of substituents bonded to the o-position from the amino group b: Number of substituents bonded to the m-position from the amino group c: Number of substituents bonded to the p-position from the amino group

[0092] The amine compound (B １ From the viewpoint of the cure rate of the resin composition of the first embodiment, the amine compound (B-1) preferably has an Ip* value of 6.0 or more and 9.7 or less, more preferably 6.5 or more and 9.7 or less, even more preferably 7.0 or more and 9.7 or less, and even more preferably 7.4 or more and 9.7 or less. １ As for -2), from the viewpoint of the storage stability of the resin composition of the first embodiment, the value of Ip* is preferably greater than 9.7 and equal to or less than 11.0, more preferably greater than 9.7 and equal to or less than 12.0, and even more preferably greater than 9.7 and equal to or less than 11.0. As described above, Ip* is a value that can be calculated from the molecular structure of the amine compound, and tends to increase by, for example, introducing an electron-withdrawing substituent, and tends to decrease by introducing an electron-donating substituent.

[0093] In the resin composition of the present embodiment, the amine compound (B １ -1) and the amine compound (B １ The mass ratio of (B-2) is determined from the viewpoint of curability. １ -1): (B １ -2) is preferably 10:90 to 90:10, more preferably 20:80 to 90:10, and even more preferably 30:70 to 90:10.

[0094] The amine compound (B １ From the viewpoint of curability, the content of the copolymer (C1) is preferably 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.

[0095] (Curing agent (C １ The resin composition of the first embodiment contains a curing agent (C １ ) may be contained. １ ) may be, for example, the above-mentioned amine compound (B １ -1), (B １ Examples of the curing agent include aromatic amine compounds other than those of the curing agent (C-2), aromatic amine adducts, acid anhydride-based curing agents, phenol-based curing agents, and thiol-based curing agents. １ ) may be used alone or in combination of two or more.

[0096] 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.

[0097] Examples of phenol-based curing agents include, but are not limited to, phenol novolac resin, cresol novolac resin, phenol aralkyl resin, cresol aralkyl resin, naphthol aralkyl resin, biphenyl-modified phenol resin, biphenyl-modified phenol aralkyl resin, dicyclopentadiene-modified phenol resin, aminotriazine-modified phenol resin, naphthol novolac resin, naphthol-phenol co-condensed novolac resin, naphthol-cresol co-condensed novolac resin, and allyl acrylic phenol resin.

[0098] Examples of thiol-based curing agents include, but are not limited to, thiol compounds obtained by an esterification reaction between a polyol and a thiol organic acid, such as trimethylolpropane tris(thioglycolate), pentaerythritol tetrakis(thioglycolate), ethylene glycol dithioglycolate, trimethylolpropane tris(β-thiopropionate), pentaerythritol tetrakis(β-thiopropionate), and dipentaerythritol poly(β-thiopropionate); alkyl polythiol compounds such as 1,4-butanedithiol, 1,6-hexaneedithiol, and 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.

[0099] Hardener (C １ ) is an amine compound (B １ -1) and an amine compound (B １ amine adduct (C １ -1), and an amine adduct (C １ -1) is an amine compound (B １ An amine adduct (C １ It is preferable that the curing agent (C-1-1) is contained. １When the curing agent (C) has the above-described structure, it tends to have excellent permeability after being mixed with the epoxy resin (A), and to be able to achieve both curability and storage stability. １ ) is the amine adduct (C １ When the amine adduct (C-1) is contained, １ -1) is an amine compound (B- １ 1) to one molecule of a reactive compound, to give an amine adduct (C １ -1-1), and an amine compound (B １ An aromatic amine adduct (C １ -1-2X).

[0100] From the viewpoint of the curability and storage stability of the resin composition of the first embodiment, the amine compound (B １ -1), amine adduct (C １ -1), and amine adducts (C １ In each peak area of ​​the amine compound (B １ -1) and the peak area of ​​the amine adduct (C １ -1) and the peak area ratio (B １ -1 / C １ −1) is preferably 0.1 to 3.0, more preferably 0.2 to 2.5, and even more preferably 0.3 to 2.0.

[0101] <Analysis of Components in Epoxy Resin Curing Agent> The method for analyzing each component in the epoxy resin curing agent is as follows. After adjusting the concentration of the curing agent to 10% by mass with THF (tetrahydrofuran), 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:

[0102] LC: Apparatus: Ultra high performance liquid chromatography (UPLC, manufactured by Waters) Column: ACQUITY UPLC BEH C8 1.7 μm (2.1 mm I.D. × 50 mm, manufactured by Waters) Detection: Absorbance detector (PDA, 200-400 nm) Flow rate: 0.3 mL / min Mobile phase: A = water (containing 0.1% formic acid) B = acetonitrile (containing 0.1% formic acid) Injection volume: 0.2 μL

[0103] Table 1 shows the change in mobile phase composition over time.

[0104]

[0105] MS: Apparatus: Mass spectrometer (Synapt G2, manufactured by Waters) Ionization: Electron spray method (ESI+) Measurement range: m / z 50 to 2000

[0106] The peak areas of the PDA chromatogram at 300 nm obtained by the LC-MS measurement were determined, and the ratio of the peak areas was calculated from the following calculation formula (1-1) to determine the ratio of the amine compound (B １ -1), amine adduct (C １ -1) and amine adduct (C １ The ratio of each peak area is calculated from the sum of all the peak areas obtained using the following calculation formula (1-1): Ratio of amine compound (%) = [(amine compound (B １ Peak area of ​​amine compound (B −1)) / {(peak area of ​​amine compound (B −1)) １ −1) + (peak area of ​​amine adduct (C １ −1) + (peak area of ​​amine adduct (C １ −1−2X) peak area) × 100 (1-1)

[0107] <Amine adduct (C １ -1) As described above, the amine adduct (C １ -1) is an amine compound (B １ -1) and the amine compound (B １The amine adduct (C-1) is a reaction product of a reactive compound having a functional group capable of reacting with the amine adduct (C-1) and a reactive compound having a functional group capable of reacting with the amine adduct (C-1). １ -1) may be used alone or in combination of two or more.

[0108] <Reactive Compound> The reactive compound is an amine compound (B １ The reactive compound has a functional group capable of reacting with -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, but are not limited to, 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, and an iodo group. Among these, an epoxy group is preferred as the functional group.

[0109] 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.

[0110] Examples of carboxylic acid compounds include, but are not limited to, succinic acid, adipic acid, sebacic acid, phthalic acid, dimer acid, etc. Examples of acid anhydrides include, but are not limited to, succinic anhydride, adipic anhydride, sebacic anhydride, phthalic anhydride, etc. Examples of acid dianhydrides include, but are not limited to, tetracarboxylic acid dianhydride, etc. Examples of sulfonic acid compounds include, but are not limited to, ethanesulfonic acid, p-toluenesulfonic acid, etc.

[0111] Examples of isocyanate compounds include, but are not limited to, aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, aliphatic triisocyanates, polyisocyanates, etc. Examples of aliphatic diisocyanates include, but are not limited to, ethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, etc. Examples of alicyclic diisocyanates include, but are not limited to, isophorone diisocyanate, 4-4'-dicyclohexylmethane diisocyanate, norbornane diisocyanate, 1,4-isocyanatocyclohexane, 1,3-bis(isocyanatomethyl)-cyclohexane, 1,3-bis(2-isocyanatopropyl-2-yl)-cyclohexane, etc. Examples of aromatic diisocyanates include, but are not limited to, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylene diisocyanate, and 1,5-naphthalene diisocyanate. Examples of aliphatic triisocyanates include, but are not limited to, 1,3,6-triisocyanatomethylhexane and 2,6-diisocyanatohexanoate-2-isocyanatoethyl. Examples of polyisocyanates include, but are not limited to, polymethylene polyphenyl polyisocyanate and polyisocyanates derived from the diisocyanate compounds. Examples of polyisocyanates derived from the diisocyanates include, but are not limited to, isocyanurate polyisocyanates, biuret polyisocyanates, urethane polyisocyanates, allophanate polyisocyanates, and carbodiimide polyisocyanates.

[0112] Examples of the urea compound include, but are not limited to, urea, methyl urea, dimethyl urea, ethyl urea, and t-butyl urea.

[0113] Examples of epoxy compounds include, but are not limited to, monoepoxy compounds, polyepoxy compounds, and mixtures thereof. Examples of monoepoxy compounds include, but are not limited to, 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.Examples of polyepoxy compounds include, but are not limited to, 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. 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.

[0114] Among the above, from the viewpoint of achieving excellent curability and storage stability of the resin composition of the first embodiment, 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). Examples of the monoepoxy compound include, but are not limited to, butyl glycidyl ether (BGE), phenyl glycidyl ether (ph-GE), and 2-ethylhexyl glycidyl ether (2-EH).

[0115] As mentioned above, the amine adduct (C １ -1) is an amine compound (B １ -1) and the amine compound (B １ Amine adducts (C-1) are reaction products of reactive compounds having functional groups capable of reacting with the amine adducts (C-1). １ -1) is, for example, 1.0 to 5.0 moles of an amine compound (B １ -1) is reacted with a reactive compound (e.g., an epoxy compound) in a molar ratio of 0.2 to 5.0, for example, at a temperature of 50 to 250°C for 0.1 to 10 hours, in the presence of a solvent as required, and if necessary, an unreacted amine compound (B １ -1) and the solvent can be removed.

[0116] The solvent used here is not limited to the following, but examples include hydrocarbons such as benzene, toluene, xylene, cyclohexane, mineral spirits, naphtha, etc.; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.; esters such as ethyl acetate, n-butyl acetate, propylene glycol monomethyl ether acetate, etc.; alcohols such as methanol, isopropanol, 1-butanol, butyl cellosolve, butyl carbitol, etc.; water, etc. These solvents may be used alone or in combination of two or more.

[0117] The curing agent (C １Although not limited to the following, from the viewpoint of the curability and storage stability of the resin composition of the present embodiment, the content of the hydroxybenzoate is preferably 0 to 50 mass %, more preferably 0 to 40 mass %, and even more preferably 0 to 30 mass % of the total amount (100 mass %) of the resin composition.

[0118] (Inorganic filler (D １ The resin composition of the first embodiment contains an inorganic filler (D) (in the first embodiment, the inorganic filler (D １ ) is sometimes written as ). １ ) may be used alone or in combination of two or more.

[0119] Inorganic filler (D １ Examples of the inorganic filler (D) include, but are not limited to, silica such as fused silica and crystalline silica, calcium carbonate, clay, alumina such as alumina oxide, silicon nitride, silicon carbide, boron nitride, calcium silicate, potassium titanate, aluminum nitride, beryllia, zirconia, zircon, forsterite, steatite, spinel, mullite, titania, and other powders, as well as beads obtained by spheronizing these, glass fiber, and the like. １ As the inorganic filler (D), an inorganic filler having a flame retardant effect may be used. Examples of the inorganic filler having a flame retardant effect include, but are not limited to, aluminum hydroxide, magnesium hydroxide, zinc borate, zinc molybdate, etc. Among these, from the viewpoints of availability, chemical stability, and material cost, for example, silica is preferred, and fused silica is more preferred. １ The particle shape of the silica particles is not limited to the following, but may be amorphous or spherical. From the viewpoint of the fluidity and permeability of the resin composition of the first embodiment into fine gaps, spherical silica is preferred, and spherical fused silica is more preferred.

[0120] Inorganic filler (D １ The inorganic filler (D) may be surface-treated. １) may be surface-treated using a silane coupling agent. Examples of the silane coupling agent include, but are not limited to, aminosilane coupling agents, epoxysilane coupling agents, phenylsilane coupling agents, alkylsilane coupling agents, alkenylsilane coupling agents, alkynylsilane coupling agents, haloalkylsilane coupling agents, siloxane coupling agents, hydrosilane coupling agents, silazane coupling agents, alkoxysilane coupling agents, chlorosilane coupling agents, (meth)acrylicsilane coupling agents, aminosilane coupling agents, isocyanuratesilane coupling agents, ureidosilane coupling agents, mercaptosilane coupling agents, sulfidesilane coupling agents, and isocyanatesilane coupling agents.

[0121] Inorganic filler (D １ The volume average particle size of the inorganic filler (D) is not limited to the following, 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. １ By making the volume average particle diameter of the epoxy resin (A) 0.1 μm or more, １ ) is more easily dispersible in the resin composition of the first embodiment, making it difficult for the resin composition of the first embodiment to be thixotropic, and the flow characteristics of the resin composition tend to be improved. On the other hand, by making the particle size 10.0 μm or less, the inorganic filler (D １ Furthermore, the permeability and fluidity of the resin composition of the first embodiment into fine gaps are improved, which tends to suppress the occurrence of voids and unfilled portions. Note that the volume average particle size is the particle size at a point corresponding to 50% volume when a cumulative frequency distribution curve of particle size is calculated assuming the total volume of particles to be 100%, and can be measured using a particle size distribution measuring device using a laser diffraction scattering method, etc.

[0122] The inorganic filler (D １The content of the inorganic filler (D) is preferably 30 to 85% by mass, more preferably 40 to 80% by mass, and even more preferably 45 to 70% by mass, relative to the total amount (100% by mass) of the resin composition of the first embodiment. １ By making the content of the inorganic filler (D) 30% by mass or more, the effect of reducing the thermal expansion coefficient and the effect of improving the temperature cycle resistance tend to be easily obtained in the resin composition of the first embodiment. １ By setting the content of the inorganic filler (D) to 85% by mass or less, an increase in viscosity of the resin composition is suppressed, and the flowability, penetration property, and dispensability tend to be improved. In particular, from the viewpoint of the effect of improving the temperature cycle resistance, １ In the first embodiment, the lower limit of the content of the inorganic filler (D １ Even if the content of ) is increased as described above, it is possible to maintain the viscosity of the resin composition at a low level.

[0123] (Curing accelerator (E １ The resin composition of the first embodiment contains a curing accelerator (E １ It is preferable that the curing agent further contains a curing accelerator (E １ ) may be used alone or in combination of two or more.

[0124] Curing accelerator (E １ ) includes the following compound (E １ -1) is preferably at least one selected from the group consisting of:

[0125] <Compound (E １ -1)> Compound (E １ -1) is at least one selected from the group consisting of compounds represented by the following formula (12), compounds represented by the following formula (13), and compounds represented by the following formula (14).

[0126]

[0127]

[0128]

[0129] In the formulas (12) to (14), R１ each 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; R ２ and R ３ each independently represents an unsubstituted or substituted alkyl group, aryl group, or aralkyl group having 1 to 12 carbon atoms, or combines to form a heterocycle having 7 or less carbon atoms; R ４ R each independently represents a hydrogen atom or an n-valent organic group having 1 to 30 carbon atoms which may contain an oxygen atom; n represents an integer of 1 to 3. ５ represents a negatively charged nitrogen atom, and R ６ indicates a positively charged nitrogen atom.

[0130] In the compound represented by the formula (12), the compound represented by the formula (13), and the compound represented by the formula (14), R １ is presumed to contribute to lowering the energy of the N-N bond cleavage. ２ and R ３ It is speculated that this contributes to the lowering of the energy of the cleavage reaction due to instability caused by steric hindrance. ４ is presumed to contribute to liquefying the compound and suppressing a decrease in the glass transition temperature of the cured product obtained from the resin composition of the present embodiment. Each group will be described in detail below.

[0131] In the formulas (12), (13), and (14), R １ each 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.

[0132] R １ Among these, examples of the organic group include, but are not limited to, hydrocarbon groups, groups in which hydrogen atoms bonded to carbon atoms in a hydrocarbon group are substituted with hydroxy groups or carbonyl groups, and groups in which some of the carbon atoms in a hydrocarbon group are substituted with ester bonds or ether bonds.

[0133] R １Among these, 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 groups; and aralkyl groups containing a combination of an alkyl group and a phenyl group, such as methylphenyl, ethylphenyl, and propylphenyl groups. Among these, R １ As the alkyl group, a linear, branched, or cyclic alkyl group is preferable, a linear alkyl group is more preferable, and a methyl group, an ethyl group, or a propyl group is even more preferable.

[0134] R １ The organic group may have other substituents, including, but not limited to, 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.

[0135] R １ Among them, 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 (E １ -1) is easily obtained, and the compound (E １ In addition, by having the number of carbon atoms in the organic group within the above range, the availability of raw materials is improved.

[0136] In the formulas (12), (13), and (14), R ２ and R ３ each independently represents an unsubstituted or substituted alkyl group, aryl group, or aralkyl group having 1 to 12 carbon atoms, or combines to form a heterocycle having 7 or less carbon atoms.

[0137] R ２ and R ３Among these, examples of the alkyl group having 1 to 12 carbon atoms include, but are not limited to, linear alkyl groups such as methyl, ethyl, propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, and n-dodecyl; branched alkyl groups such as isopropyl, isobutyl, t-butyl, neopentyl, 2-hexyl, 2-octyl, 2-decyl, and 2-dodecyl; and cyclic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclodecyl, and cyclododecyl. 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, R ２ and R ３ The cyclic alkyl group is preferably a cyclic alkyl group, and a cyclohexyl group is more preferred as the cyclic alkyl group.

[0138] R ２ and R ３ The number of carbon atoms in the alkyl groups is, independently, 1 to 12, preferably 2 to 10, and more preferably 5 to 10. Asymmetric dialkylhydrazine compounds with a small number of carbon atoms in the alkyl groups (such as dimethylhydrazine) may be explosive and may be toxic to the human body. ２ and R ３ By making the number of carbon atoms of the alkyl group in R 2 or more, it is possible to avoid using raw materials that pose the risk of toxicity, etc. ２ and R ３ By making the number of carbon atoms in the alkyl group in the alkyl group 5 or more, a liquid compound (E １ -1) is easily obtained, and the compound (E １ -1) The curing performance tends to be further improved.

[0139] R ２ and R ３ Among them, the aryl group is not limited to the following, but examples thereof include a phenyl group and a naphthyl group. ２ and R ３Among these, examples of the aralkyl group include, but are not limited to, a methylphenyl group, an ethylphenyl group, a methylnaphthyl group, and a dimethylnaphthyl group. ２ and R ３ As the alkyl group, an aralkyl group is preferable, and a methylphenyl group (benzyl group) is more preferable.

[0140] R ２ and R ３ Among these, examples of the substituent of the alkyl group, aryl group, or aralkyl group include, but are not limited to, 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.

[0141] R ２ and R ３ are concatenated to form R ６ (a nitrogen atom having a positive charge) together to form a heterocycle having 7 or less carbon atoms. Examples of the heterocycle include, but are not limited to, a 4-membered ring such as an azetidine ring; a 5-membered ring such as a pyrrolidine ring, a pyrrole ring, a morpholine ring, or a thiazine ring; a 6-membered ring such as a piperidine ring; and a 7-membered ring such as a hexamethyleneimine ring or 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, with a 6-membered ring and a 7-membered ring being more preferred. By having such a group, it is possible to obtain a liquid compound (E １ -1) is easily obtained, and the compound (E １ -1) tends to further improve the curing performance. ２ And, R ３ And, R ６ and are preferably linked hexamethyleneimine rings.

[0142] Also, R ２ and R ３ The substituent that may be possessed by R is not particularly limited, but may be, for example, an alkyl group, an aryl group, or the above-mentioned R ２ and R ３ Furthermore, when the heterocycle has an alkyl group as a substituent, R６ and a methyl group bonded to a carbon atom adjacent to the carbon atom.

[0143] In the formulas (12), (13) and (14), R ４ R each independently represents a hydrogen atom or an n-valent organic group having 1 to 30 carbon atoms which may contain an oxygen atom. ４ Among these, examples of the organic group include, but are not limited to, hydrocarbon groups, groups in which hydrogen atoms bonded to carbon atoms in a hydrocarbon group are substituted with hydroxy groups, carbonyl groups, or groups containing silicon atoms, and groups in which some of the carbon atoms in a hydrocarbon group are substituted with ester bonds, ether bonds, or silicon atoms.

[0144] R ４ Among these, 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, hexadecinyl, 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.

[0145] R ４ Among these, 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. Examples of organic groups containing a bisphenol skeleton include, but are not limited to, groups in which a polyoxyalkylene group is added to the hydroxy group of each bisphenol skeleton.

[0146] R ４ The hydrocarbon group may have a polyoxyalkylene skeleton, such as a polyoxyethylene skeleton.

[0147] Among these, R in formula (12) or formula (13)４ The organic group represented by the formula (I) 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 easy to obtain a liquid compound having 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.

[0148] R ４ 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. ４ Since the number of carbon atoms of the organic group in the compound (E) is within the above range, a liquid compound (E) having an appropriate viscosity can be obtained. １ -1) is easily obtained, and the compound (E １ In addition, the curing performance of the compound (E-1) tends to be further improved. １ -1) further improves the Tg of the cured product obtained by using R ４ When the number of carbon atoms of the organic group in the olefin falls within the above range, the availability of raw materials is further improved.

[0149] Among the above, R in formula (12) or formula (13) ４ is preferably a linear or branched alkyl group having 3 to 12 carbon atoms. By having such a group, a liquid compound (E １ -1) is easily obtained, and the compound (E １ -1) The curing performance tends to be further improved.

[0150] In formula (13) and formula (14), 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.

[0151] From the viewpoint of controlling the curing temperature or viscosity of the resin composition of the first embodiment, the compound (E １-1) preferably contains a plurality of compounds represented by the formula (12), the formula (13), or the formula (14). It is also possible to contain a plurality of compounds having different structures but represented by the same formula.

[0152] In particular, from the viewpoint of viscosity control of the resin composition of this embodiment, the compound (E １ -1) preferably contains both the compound represented by formula (12) and the compound represented by formula (14). In this case, the content of the compound represented by formula (12) is preferably 0.1 to 99.5% by mass based on the total amount of the compound represented by formula (12) and the compound represented by formula (14). The content of the compound represented by formula (14) is preferably 0.5 to 99.9% by mass based on the total amount of the compound represented by formula (12) and the compound represented by formula (14).

[0153] When a plurality of compounds represented by the formula (12), the formula (13), or the formula (14) are contained, the content ratio of the compound represented by the formula (12) is preferably 0.1 to 99.8% by mass relative to the total amount of the compound represented by the formula (12), the compound represented by the formula (13), and the compound represented by the formula (14). The content of the compound represented by the formula (13) is preferably 0.1 to 99.8% by mass relative to the total amount of the compound represented by the formula (12), the compound represented by the formula (13), and the compound represented by the formula (14). The content of the compound represented by the formula (14) is preferably 0.1 to 99.8% by mass relative to the total amount of the compound represented by the formula (12), the compound represented by the formula (13), and the compound represented by the formula (14). This makes it possible to easily control the viscosity of the resin composition of this embodiment.

[0154] The mixture containing a plurality of compounds represented by the formula (12), (13), or (14) can be obtained by mixing a plurality of compounds, or by simultaneously producing a plurality of compounds in a compound production method described later.

[0155] Compound (E １The compound represented by formula (E-1) preferably includes at least one selected from the group consisting of a compound represented by formula (E-1A) below (hereinafter also simply referred to as "compound (E-1A)"), a compound represented by formula (E-1B) below (hereinafter also simply referred to as "compound (E-1B)"), and a compound represented by formula (E-1C) below (hereinafter also simply referred to as "compound (E-1C)"). By using these compounds, the viscosity of the resin composition of the present embodiment can be more easily controlled.

[0156]

[0157]

[0158] Compound (E １ -1) preferably contains both the compound (E-1A) and the compound (E-1B).

[0159] Compound (E １ The content of -1) is not particularly limited, but because it tends to make it easier to control the viscosity of the resin composition, 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 of the present embodiment.

[0160] The compound represented by the formula (12), the compound represented by the formula (13), or the compound represented by the formula (14) can be produced, for example, by reacting an ester compound, a hydrazine compound, and a glycidyl ether compound, although this is not limited thereto.

[0161] Examples of the ester compound include, but are not limited to, monocarboxylic acid ester compounds, dicarboxylic acid ester compounds, etc. The ester compounds may be used alone or in combination of two or more.

[0162] Examples of monocarboxylic acid ester compounds include, but are not limited to, 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, 4-t-butoxybenzoylmethyl, etc. Alternatively, ethyl esters, propyl esters, etc. may be used.

[0163] Examples of dicarboxylic acid ester compounds include, but are not limited to, 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. Examples of cyclic esters include, but are not limited to, α-acetolactone, β-propionolactone, γ-butyrolactone, δ-valerolactone, γ-valerolactone, and ε-caprolactone. Alternatively, diethyl esters, dipropyl esters, and the like may be used.

[0164] 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.

[0165] Examples of the hydrazine compound include, but are not limited to, 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.

[0166] Among these, the compound (E １From the viewpoint of curability and liquefaction of the above-1), preferred hydrazine compounds are dimethylhydrazine, dibenzylhydrazine, 1-aminopiperidine, 1-aminopyrrolidine, and 1-aminomorpholine. Furthermore, among these, dibenzylhydrazine and 1-aminopiperidine are more preferred from the viewpoint of availability and safety. One type of hydrazine compound may be used alone, or two or more types may be used in combination.

[0167] 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.

[0168] Examples of monoglycidyl ether compounds include, but are not limited to, 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.

[0169] Examples of polyglycidyl ether compounds include, but are not limited to, 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, ... Examples of the polyglycidyl ether include aliphatic polyglycidyl ethers such as serine polyglycidyl 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.

[0170] Among these, the compound (E １-1) From the viewpoint of curability and liquefaction, the glycidyl ether compound is preferably 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 adduct bisphenol A diglycidyl ether, propylene oxide adduct bisphenol A diglycidyl ether, polyethylene glycol diglycidyl ether, and 1-phenoxy-1,4- (oxiranylmethoxy) -3,6,9,12-tetraoxatetradecane.

[0171] Furthermore, from the viewpoint of the adhesiveness of the resin composition of this embodiment, the glycidyl ether compound is preferably an epoxy compound having an ether structure, such as 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.

[0172] The amounts of the ester compound, hydrazine compound, and glycidyl ether compound added to the reaction system can be set based on the molar ratio of the functional groups. 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. 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.

[0173] 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 (12) and the compound represented by formula (14) can be simultaneously produced. Specifically, the amount of the glycidyl group of the glycidyl ether compound added relative to 1 mole of the primary amine of the hydrazine compound is preferably 0.1 mol to 3.0 mol, more preferably 0.3 mol to 2.0 mol, and even more preferably 0.5 mol to 1.0 mol.

[0174] In the above-described methods for producing the compound or mixture, a solvent may be used to ensure uniform reaction. Examples of the solvent include, but are not limited to, alcohols such as methanol, ethanol, 1-propanol, 2-propanol, butanol, and t-butyl alcohol; and ethers such as tetrahydrofuran and diethyl ether.

[0175] 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 resulting compound (E １ In addition, by controlling the reaction temperature to 95° C. or less, the polymerization reaction between the glycidyl ether compounds can be efficiently suppressed, and therefore the purity of the compound (E １ 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.

[0176] After completion of the reaction, the obtained 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 pressure 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 residual raw materials, but 1-hexane, 1-pentane, and cyclohexane are preferred from the viewpoints of yield, purity, and ease of removal.

[0177] 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.

[0178] 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.

[0179] The curing accelerator (E １ The content of the hydroxybenzoate is not particularly limited, but 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, because this tends to make it easier to control the viscosity.

[0180] [Physical Properties of Resin Composition] (Viscosity) The resin composition of the first embodiment preferably has a viscosity of 0.01 Pa·s to 4.50 Pa·s after being left at 100°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 being left at 100°C for 60 minutes can be measured using a rheometer (for example, HAAKE (registered trademark) MARS (trade name), manufactured by Thermo Scientific). A specific measurement method will be described in the examples below.

[0181] (Viscosity increase rate) The resin composition of the first embodiment has a viscosity increase rate after being left at 100 ° C. for 60 minutes of 1.0 times or more and 50.0 times or less, more preferably 1.0 times or more and 40.0 times or less, even more preferably 1.0 times or more and 30.0 times or less, even more preferably 1.0 times or more and 20.0 times or less, and even more preferably 1.0 times or more and 10.0 times or less. The viscosity increase rate after being left at 100 ° C. for 60 minutes is measured by dropping the resin composition of this embodiment onto a measurement plate, and measuring it using a rheometer (HAAKE MARS, manufactured by Thermo Scientific) 5 minutes and 60 minutes after the sample temperature reaches 100 ° C. (Measurement conditions: aluminum cone plate, R = 20 mm, shear rate 20 ( / sec)). The viscosity after 5 minutes is "η1", the viscosity after 60 minutes is "η2", and the value calculated by η2 / η1 is the viscosity increase rate. A specific measurement method will be described in the Examples below.

[0182] (Cure Rate) The cure rate of the resin composition of the first embodiment when cured at 165°C is preferably 70% or more and 100% or less, more preferably 80% or more and 100% or less, and even more preferably 90% or more and 100% or less. The cure rate when the resin composition of the first embodiment is cured at 165°C can be calculated, for example, by using an 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. The calculation formula is as follows. A specific measurement method will be described in the Examples below. Initial heat generation amount A: DSC peak heat generation amount of the epoxy resin composition Post-curing heat generation amount B: DSC peak heat generation amount of the epoxy resin composition after heating Cure rate (%) = 100 × (initial heat generation amount A - post-curing heat generation amount B) ÷ initial heat generation amount A

[0183] [Method for producing resin composition] The resin composition of the first embodiment can be produced, for example, by a method of dry blending the constituent components, or a method of preparing the resin composition using an apparatus typically used for mixing polymeric substances. Examples of the apparatus for mixing the components include, but are not limited to, kneading apparatuses such as a Banbury mixer, a Labo Plastomill, a single-screw extruder, and a twin-screw extruder. The resin composition of the first embodiment is preferably produced, for example, by stirring and mixing the components using a planetary mixer (for example, "ARE-310" (trade name) manufactured by Thinky Corporation) and then kneading using a triple roll mill. In addition, the epoxy resin (A １ ) are mixed and stirred in advance, and then the inorganic filler (D １ ) to prepare a dispersion, and then an amine compound (B １ -1), amine compounds (B １ It is preferable to add the curing accelerator (E-2) and mix them by stirring with a rotation / revolution mixer, and then knead them with a three-roll mill. １ When an amine compound (B １ -1), amine compounds (B １ -2) was added, and then the curing accelerator (E １) is added, and then the mixture is stirred and mixed in a planetary centrifugal mixer, and then kneaded using a three-roll mill.

[0184] [Cured Product] The cured product of the first embodiment includes the resin composition of the first embodiment. The cured product is obtained by curing the resin composition.

[0185] [Uses of Resin Composition and Cured Product] The resin composition and cured product of the first embodiment are useful as adhesives, encapsulants, filling materials, insulating 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.

[0186] (Adhesive) The adhesive of the first embodiment includes the resin composition of the first embodiment. The resin composition of the first embodiment can be suitably used as an adhesive.

[0187] (Sealant) The sealant of the first embodiment includes the cured product of the first embodiment. The cured product of the first embodiment can be suitably used as a sealant. The sealant is preferably a sealant for semiconductors.

[0188] (Semiconductor Package) The semiconductor package of the first embodiment includes the cured product of the first embodiment. The cured product of the first embodiment can be suitably used as a semiconductor package. The method for manufacturing the semiconductor package of the first embodiment includes a step of manufacturing a semiconductor package using the resin composition of the first embodiment. The step of manufacturing a semiconductor package using the resin composition of the first embodiment may include a step of preparing the resin composition of the first embodiment. The step of manufacturing a semiconductor package using the resin composition of the first embodiment may be a step of manufacturing a semiconductor package by appropriately molding the resin composition and heating it at a predetermined temperature and time to cure it.

[0189] [Second embodiment] [Resin composition] The resin composition of the second embodiment contains the above-described epoxy resin (A), amine compound (B), and inorganic filler (D), and the amine compound contains a compound represented by formula (1), and a cured product of the resin composition has a wavelength of 1,420 to 1,440 cm in an infrared (IR) absorption spectrum. －１ The maximum peak intensity Ia present in the region of 1,450 to 1,550 cm －１ and the maximum peak intensity Ib present in the region satisfies the following formula (i): 0.24≦Ia / Ib≦0.4 (i)

[0190] [Cured Product] The cured product of the second embodiment is a cured product of the resin composition of the second embodiment described above, and has an infrared (IR) absorption spectrum of 1,420 to 1,440 cm －１ The maximum peak intensity Ia present in the region of 1,450 to 1,550 cm －１ and the maximum peak intensity Ib present in the region satisfies the following formula (i): 0.24≦Ia / Ib≦0.4 (i)

[0191] The composition described above allows for a cured product that has both high toughness and a low CTE (coefficient of linear expansion). The toughness and CTE of the cured product can be measured and evaluated by the methods described in the Examples below.

[0192] In the following, the cured product of the second embodiment will be described first, and the resin composition constituting the cured product of the second embodiment will be described later. When Ia / Ib satisfies the above (i), the concentration of the specific functional group relative to the aromatic ring in the constituent components of the cured product falls within a preferred range, and the molecular free volume and the curing rate of the cured product increase, making it possible to obtain a cured product that satisfies high toughness and low CTE.

[0193] From the viewpoint of increasing the toughness of the cured product of the second embodiment, the ratio Ia / Ib is 0.24 or more, preferably 0.25 or more, and more preferably 0.26 or more. From the viewpoint of the curability of the cured product of the second embodiment, the ratio Ia / Ib is 0.4 or less, preferably 0.39 or less, and more preferably 0.38 or less.

[0194] 1,420 to 1,440 cm in the infrared absorption spectrum －１ The peak in the region is the S-CH of the methylthio group of the curing agent in the resin composition. ３ Preferably, the carbon nanotube is derived from －１ The peak in the region of 1,420 to 1,440 cm in the infrared (IR) absorption spectrum is preferably due to C═C in the aromatic ring. －１ The maximum peak intensity Ia present in the region of 1,450 to 1,550 cm －１ When the maximum peak intensity Ia / Ib in the region of 0.24 satisfies the formula (i), the concentration of specific functional groups relative to aromatic rings in the components of the cured product falls within a preferred range. When 0.24≦Ia / Ib is satisfied, the free volume of the molecules increases, resulting in high toughness, and when Ia / Ib≦0.4 is satisfied, the cure rate increases, resulting in a low CTE.

[0195] Assuming that the resin composition used for the cured product of the second embodiment contains a curing agent having a methylthio group, the Ia / Ib ratio in formula (i) can be controlled within the above numerical range by adjusting the content of the curing agent having a methylthio group. Alternatively, the ratio can be controlled within the above numerical range by adjusting the content of an epoxy resin having a methylthio group, additives, etc. Furthermore, the Ia / Ib ratio can also be controlled within the above numerical range by adjusting the content of aromatic rings in the epoxy resin and curing agent in the resin composition used for the cured product of the second embodiment. The resin composition will be described later.

[0196] [Structure] The structure of the second embodiment has a first layer, a second layer, and a plurality of copper pillars connecting the first layer and the second layer. The first layer and the second layer each contain at least one material selected from the group consisting of resin, silicon, ceramics, compound semiconductors, and glass. The distance between adjacent copper pillars among the plurality of copper pillars is 150 μm or less. A third layer is provided between the first layer and the second layer, contacting both the first layer and the second layer, and the third layer is the cured product of the second embodiment described above.

[0197] According to the above configuration, a structure that can achieve both high toughness and low CTE can be obtained. The components of the structure of the second embodiment will be described below.

[0198] (First Layer and Second Layer) The first layer and the second layer contain at least one material selected from the group consisting of resin, silicon, ceramics, compound semiconductor, and glass. The first layer and the second layer may be made of different materials from these materials, may be made of the same material, or may be made of a combination of these materials.

[0199] Examples of resins include, but are not limited to, polyacetal, polyamide (PA), polycarbonate (PC), modified polyphenylene ether, polybutylene terephthalate, glass fiber (GF) reinforced polyethylene terephthalate, ultra-high molecular weight polyethylene, syndiotactic polystyrene, epoxy, glass epoxy (FR-4), phenol, silicon, amorphous polyarylate, polysulfone, polyethersulfone, polyphenylene sulfide, polyetheretherketone, polyimide (PI), polyetherimide, fluororesin, and LCP (Liquid Crystal Polymer).

[0200] The ceramics include, but are not limited to, alumina (Al ２ O ３ Examples of the compound semiconductor include, but are not limited to, gallium nitride, indium phosphide, gallium arsenide, and gallium phosphide.

[0201] The area of ​​the first layer is not limited to the following, but is preferably 100 to 22,500 mm from the viewpoint of increasing the capacity of the electronic device. ２The thickness is, but is not limited to, for example, 500 to 1,000 μm from the viewpoint of packaging density. The area of ​​the second layer is, but is not limited to, for example, 100 to 250,000 mm from the viewpoint of increasing the capacity of electronic devices. ２ The thickness is not limited to the following, but may be, for example, 500 to 10,000 μm from the viewpoint of packaging density.

[0202] (Copper Pillars) The structure of the second embodiment has a plurality of copper pillars connecting the first layer and the second layer. The copper pillars serve as metal wiring for electrical connection. The copper pillars may be connected between the first layer and the second layer by solder. The metal wiring referred to here refers to a metal region for electrical connection, and the shape of the metal region when viewed vertically from the horizontal surface of the mounting substrate may be, for example, dot-like, round, rectangular, or linear, or may be a combination of two or more of these.

[0203] The distance between adjacent copper pillars among the plurality of pillars is set to 150 μm or less from the viewpoint of good electrical connection and large capacity of the electronic device. It is preferably set to 140 μm or less, and more preferably set to 130 μm or less. In the structure of this embodiment, the distances between adjacent copper pillars among the plurality of copper pillars may all be the same or may be in different combinations. In the structure of this embodiment, the number of copper pillars is set to 1 mm or less from the viewpoint of high density. ２ The number of copper pillars per layer is preferably 10 to 50, more preferably 15 to 50, and even more preferably 20 to 50. The distance between the first layer and the second layer connected by the copper pillar corresponds to the length of the copper pillar in the vertical direction and the thickness of the third layer described below, and is preferably 1 μm to 100 μm, more preferably 5 μm to 100 μm, and even more preferably 10 μm to 100 μm.

[0204] (Third Layer, Cured Product) The structure of the second embodiment has a third layer between the first layer and the second layer, the third layer being in contact with each of the first layer and the second layer. The third layer is made of the cured product of the second embodiment, and is a cured product of the resin composition of the second embodiment described below.

[0205] [Resin Composition of Second Embodiment] As described above, the resin composition of the second embodiment contains an epoxy resin, an amine compound, and an inorganic filler. In the resin composition of the second embodiment, the amine compound is a curing agent, and a curing agent other than the amine compound may be used as the curing agent. The curing agent will be described later. A cured product of the resin composition of the second embodiment has a peak at 1,420 to 1,440 cm in an infrared (IR) absorption spectrum. －１ The maximum peak intensity Ia present in the region of 1,450 to 1,550 cm －１ and the maximum peak intensity Ib present in the region Ib, the following formula (i) is satisfied: 0.24≦Ia / Ib≦0.4 (i)

[0206] (Epoxy Resin) The epoxy resin may be any commonly used epoxy resin and is not particularly limited. The epoxy resin used in the resin composition of the second embodiment is preferably, for example, an epoxy resin having two or more epoxy groups per molecule. The epoxy resin may be solid or liquid at room temperature. However, from the viewpoint of the filling property of the resin composition of the second embodiment, an epoxy resin that is liquid at room temperature (hereinafter also referred to as "liquid epoxy resin") is preferred, and commonly used liquid epoxy resins can 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.

[0207] Examples of epoxy resins include, but are not limited to, diglycidyl ether epoxy resins such as bisphenol-type epoxy resins such as bisphenol A, bisphenol F, bisphenol AD, bisphenol S, and hydrogenated bisphenol A; epoxy resins obtained by epoxidizing novolac resins obtained from phenols and aldehydes, such as orthocresol novolac epoxy resins; glycidyl ester epoxy resins obtained by reacting epichlorohydrin with polybasic acids such as phthalic acid and dimer acid; glycidylamine epoxy resins obtained by reacting epichlorohydrin with amine compounds such as p-aminophenol, diaminodiphenylmethane, and isocyanuric acid; fluorene epoxy resins obtained from fluorene derivatives having a cardo structure in which fluorene is bonded to an aromatic ring; and linear aliphatic epoxy resins and alicyclic epoxy resins obtained by oxidizing olefin bonds with peracids such as peracetic acid. These epoxy resins may be used alone or in combination of two or more.

[0208] Among these, bisphenol-type epoxy resins are preferred from the viewpoint of the fluidity of the resin composition, and from the viewpoint of the crack resistance of the cured product, it is preferred to include a bisphenol-type epoxy resin having a bisphenol skeleton and a ratio of aromatic rings in the molecule to the molecular weight of the molecule of 0.05 to 0.4. Furthermore, from the viewpoints of the heat resistance and adhesiveness of the resin composition and the cured product, and the fluidity of the resin composition, glycidylamine-type epoxy resins are preferred.

[0209] When a naphthalene-type epoxy resin is used in addition to a glycidylamine-type epoxy resin and a bisphenol-type epoxy resin as the epoxy resin, the mass ratio (naphthalene-type epoxy resin:total of glycidylamine-type epoxy resin and bisphenol-type epoxy resin) is preferably 5:95 to 50:50, more preferably 10:90 to 40:60, and even more preferably 15:80 to 40:60, from the viewpoints of the heat resistance and adhesiveness of the resin composition and the cured product of the second embodiment, and the fluidity of the resin composition.

[0210] From the viewpoint of fluidity, it is preferable that both the glycidylamine type epoxy resin and the bisphenol type epoxy resin are liquid at room temperature.

[0211] When a glycidylamine-type epoxy resin and a bisphenol-type epoxy resin are used as the epoxy resin, the total content of the glycidylamine-type epoxy resin and the bisphenol-type epoxy resin is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 50% by mass or more, and even more preferably 80% by mass or more, based on the total amount of epoxy resin, from the viewpoints of the heat resistance, adhesiveness, and fluidity of the cured product and resin composition of the second embodiment. There is no particular upper limit to the total content, and a range can be selected in which the desired properties and characteristics are obtained, from the viewpoints of the viscosity of the resin composition of the second embodiment, the glass transition temperature and heat resistance of the cured product of the second embodiment, and the like, and it may even be 100% by mass.

[0212] When a glycidylamine type epoxy resin and a bisphenol type epoxy resin are used as the epoxy resin, the mass ratio of the glycidylamine type epoxy resin to the bisphenol type epoxy resin (glycidylamine type epoxy:bisphenol type epoxy resin) is preferably 50:50 to 95:5, more preferably 60:40 to 90:10, and even more preferably 70:30 to 90:10, from the viewpoints of the heat resistance, adhesiveness, and fluidity of the cured product and resin composition of the second embodiment.

[0213] Furthermore, as the epoxy resin constituting the resin composition of the second embodiment, an epoxy resin that is solid at room temperature can also be used.

[0214] From the viewpoint of the fluidity of the resin composition of the second embodiment, the content of the epoxy resin that is solid at room temperature is preferably 0 to 30 mass %, more preferably 0 to 25 mass %, and even more preferably 0 to 20 mass %, relative to the total amount of the epoxy resin.

[0215] The epoxy equivalent of the epoxy resin is not particularly limited, but from the viewpoint of the heat resistance of the cured product of the second embodiment, it is preferably 60 to 1000 g / mol, more preferably 70 to 900 g / mol, and even more preferably 80 to 800 g / mol.

[0216] Here, the epoxy equivalent is the mass (g / eq) of the resin per epoxy group, and can be measured according to the method specified in JIS K 7236. Specifically, using an automatic titrator "GT-200 Model" manufactured by Mitsubishi Chemical Analytech Co., Ltd., 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. After that, 10 mL of glacial acetic acid and 1.5 g of cetyltrimethylammonium bromide are added, and the epoxy equivalent is determined by titration with a 0.1 mol / L perchloric acid / acetic acid solution.

[0217] It is preferable that the purity of the epoxy resin is high. 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, for example, a value of 1500 ppm or less is preferable. 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.

[0218] The content of the epoxy resin in the resin composition used for the cured product of the second embodiment is not particularly limited, but from the viewpoints of the heat resistance, adhesiveness, and flowability of the cured product and resin composition of the second embodiment, it is preferably 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.

[0219] (Curing Agent) The epoxy resin composition used for the cured product of the second embodiment contains a curing agent. The curing agent may be the above-mentioned amine compound (B) ((B) in the first embodiment). １ )) That is, it contains an amine compound represented by the following formula (1).

[0220]

[0221] In formula (1), R １ represents a monovalent organic group having 1 to 20 carbon atoms or a halogen atom; a is an integer of 0 to 3; and b is an integer of 1 to 3.

[0222] From the viewpoint of toughness of the cured product of the second embodiment, the compound represented by formula (1) has a methylthio group.

[0223] In addition to the compound represented by formula (1), curing agents used to obtain the cured product of the second embodiment include, but are not limited to, aromatic amine curing agents, aromatic amine adduct curing agents, acid anhydride curing agents, phenolic curing agents, and thiol curing agents.

[0224] Examples of aromatic amine curing agents include, but are not limited to, 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'-diaminodiphenylmethane, manufactured by Nippon Kayaku Co., Ltd.), MDEA (trade name, 4,4'-methylenebis(2,6-diethylaniline), manufactured by Kumiai Chemical Industry Co., Ltd.), Curehard MED (trade name, 4,4'-methylenebis(2-ethyl-6-methylaniline), manufactured by Kumiai Chemical Industry Co., Ltd.), MBDA (trade name, 4,4'-methylenebis[N-(sec-butyl)aniline], manufactured by Kumiai Chemical Industry Co., Ltd.), and the like.

[0225] Examples of aromatic amine adduct curing agents include, but are not limited to, compounds obtained by reacting a compound having one or more reactive groups with an aromatic amine compound. Examples of compounds having one or more reactive groups include, but are not limited to, epoxy resins, epoxy-based reactive diluents, alcohol compounds, alkyl halide compounds, isocyanate compounds, and ester compounds.

[0226] 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.

[0227] Examples of phenol-based curing agents include, but are not limited to, phenol novolac resin, cresol novolac resin, phenol aralkyl resin, cresol aralkyl resin, naphthol aralkyl resin, biphenyl-modified phenol resin, biphenyl-modified phenol aralkyl resin, dicyclopentadiene-modified phenol resin, aminotriazine-modified phenol resin, naphthol novolac resin, naphthol-phenol co-condensed novolac resin, naphthol-cresol co-condensed novolac resin, and allyl acrylic phenol resin.

[0228] Examples of thiol-based curing agents include, but are not limited to, thiol compounds obtained by an esterification reaction between a polyol and a thiol organic acid, such as trimethylolpropane tris(thioglycolate), pentaerythritol tetrakis(thioglycolate), ethylene glycol dithioglycolate, trimethylolpropane tris(β-thiopropionate), pentaerythritol tetrakis(β-thiopropionate), and dipentaerythritol poly(β-thiopropionate); alkyl polythiol compounds such as 1,4-butanedithiol, 1,6-hexaneedithiol, and 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.

[0229] The resin composition of the second embodiment contains an amine-based curing agent (A ２ -1) and an amine-based curing agent (A ２ -1) and an amine-based curing agent (A ２and an aromatic amine adduct which is a reaction product of the amine-based curing agent (A-1) and a reactive compound having a functional group capable of reacting with the amine-based curing agent (A-2). ２ An aromatic amine adduct (A-1) in which one molecule of a reactive compound is added to one molecule of the aromatic amine adduct (A-1) ２ -1-1), and an amine-based curing agent (A ２ An aromatic amine adduct (A-1) in which two or more molecules of a reactive compound are added to one molecule of the aromatic amine adduct (A-1) ２ -1-2X).

[0230] Here, with regard to the aromatic amine compounds used in the aromatic amine adduct curing agent, amine compounds having electron-withdrawing properties and amine compounds having multiple functional groups in the side chain are inferior in reactivity as amines but are excellent in stability when made into amine adducts. Suitable examples of such aromatic amine compounds include, but are not limited to, 4,4'-diaminodiphenyl sulfone, diethyltoluenediamine (2,4-diamino-3,5-diethyltoluene, 2,6-diamino-3,5-diethyltoluene), dimethylthiotoluenediamine, etc.

[0231] On the other hand, with regard to the aromatic amine compounds used in the aromatic amine adduct curing agents, amine compounds that do not have electron-withdrawing properties and amine compounds that do not have functional groups in their side chains are highly reactive as amines and exhibit excellent curing properties when formed into amine adducts. As such aromatic amine compounds, aromatic amine compounds having a -CO-, -C(=O)O-, -, or -C(=O)NH- bond are preferred, and among these, aromatic amine compounds having a -C(=O)O- bond are particularly preferred. Examples of the aromatic amine compound include, but are not limited to, 4-aminophenyl-4-aminobenzoate (APAB), 3,4'-diaminodiphenyl ether (34ODA), and 1,3-bis(3-aminophenoxy)benzene (TPE-M), with 4-aminophenyl-4-aminobenzoate (APAB) being more preferred.

[0232] As described above, the resin composition used for the cured product of the second embodiment contains an epoxy resin and a curing agent containing an amine compound, and the mass ratio of the curing agent to the epoxy resin (curing agent:epoxy resin) is preferably 1:99 to 50:50, more preferably 5:95 to 50:50, and even more preferably 10:90 to 50:50, from the viewpoint of the heat resistance and adhesiveness of the cured product and resin composition of the second embodiment.

[0233] (Inorganic Filler) The cured product of the second embodiment and the resin composition of the second embodiment contain an inorganic filler. One type of inorganic filler may be used alone, or two or more types may be used in combination.

[0234] Examples of inorganic fillers include, but are not limited to, silica such as fused silica and crystalline silica, calcium carbonate, clay, alumina such as alumina oxide, silicon nitride, silicon carbide, boron nitride, calcium silicate, potassium titanate, aluminum nitride, beryllia, zirconia, zircon, forsterite, steatite, spinel, mullite, titania, and other powders, as well as beads obtained by spheronizing these, and glass fiber.

[0235] The inorganic filler may be an inorganic filler having a flame retardant effect, and examples of the inorganic filler having a flame retardant effect include, but are not limited to, aluminum hydroxide, magnesium hydroxide, zinc borate, and zinc molybdate.

[0236] 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 the flowability and permeability of the resin composition of the second embodiment into fine gaps, spherical silica is preferred, and spherical fused silica is more preferred.

[0237] In addition, the inorganic filler may be surface-treated. Specifically, the inorganic filler may be surface-treated using a silane coupling agent. Examples of the silane coupling agent include, but are not limited to, aminosilane coupling agents, epoxysilane coupling agents, phenylsilane coupling agents, alkylsilane coupling agents, alkenylsilane coupling agents, alkynylsilane coupling agents, haloalkylsilane coupling agents, siloxane coupling agents, hydrosilane coupling agents, silazane coupling agents, alkoxysilane coupling agents, chlorosilane coupling agents, (meth)acrylicsilane coupling agents, aminosilane coupling agents, isocyanurate silane coupling agents, ureidosilane coupling agents, mercaptosilane coupling agents, sulfide silane coupling agents, and isocyanate silane coupling agents.

[0238] The volume average particle size of the inorganic filler is not limited to the following, 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. When the volume average particle size of the inorganic filler is 0.1 μm or more, the dispersibility in the epoxy resin is improved, the resin composition of the second embodiment is less likely to be imparted with thixotropy, and the flow characteristics of the resin composition of the second embodiment tend to be improved. On the other hand, when the volume average particle size of the inorganic filler is 10.0 μm or less, the settling of the inorganic filler in the resin composition of the second embodiment tends to be easily suppressed, and the permeability and flowability of the resin composition into fine gaps tend to be improved, which tends to suppress the occurrence of voids and unfilled portions in the cured product of the second embodiment. The volume average particle size refers to the particle size at the point corresponding to 50% volume when a cumulative frequency distribution curve of particle size is calculated, assuming the total volume of the particles to be 100%, and can be measured using a particle size distribution measuring device using a laser diffraction scattering method, for example.

[0239] The content of the inorganic filler in the cured product and resin composition of the second embodiment is not limited to the following, but is preferably 30 to 85% by mass, more preferably 40 to 80% by mass, and even more preferably 45 to 70% by mass, relative to the total amount (100% by mass) of the resin composition or cured product. When the content of the inorganic filler is 30% by mass or more, the effect of reducing the thermal expansion coefficient and the effect of improving temperature cycle resistance tend to be easily obtained. When the content of the inorganic filler is 85% by mass or less, the increase in viscosity of the resin composition of the second embodiment tends to be suppressed, and the fluidity, penetration, and dispensability tend to be improved. In particular, from the viewpoint of the effect of improving temperature cycle resistance, it is preferable to increase the lower limit of the content of the inorganic filler.

[0240] [Method for Producing Resin Composition] The resin composition of the second embodiment can be produced by, for example, dry-blending the components or by preparing the composition using an apparatus typically used for mixing polymeric substances. Examples of mixing apparatuses for the components include, but are not limited to, kneading apparatuses such as a Banbury mixer, a Labo Plastomill, a single-screw extruder, and a twin-screw extruder. The resin composition of the second embodiment is preferably produced, for example, by stirring and mixing the components in a planetary centrifugal mixer (e.g., "ARE-310" (trade name) manufactured by Thinky Corporation) and then kneading with a three-roll mill. Alternatively, the epoxy resin is preferably mixed and stirred in advance, an inorganic filler is dispersed therein to prepare a dispersion, and then a curing agent is added and stirred and mixed with a planetary centrifugal mixer, followed by three-roll mill kneading. When a curing accelerator is added to the resin composition of the second embodiment, it is preferable to add the curing accelerator after the curing agent, then stir and mix with a planetary centrifugal mixer, and then knead with a three-roll mill.

[0241] [Method for producing a cured product] The cured product of the second embodiment can be obtained by curing the resin composition of the second embodiment. Examples of the curing method include a thermal curing method. When performing thermal curing, a method of heating at 80 to 180°C for 1 to 10 hours can be used. Examples of the heating method include a method using a heating oven, a clean oven, a pressure oven, or the like.

[0242] [Method for Manufacturing Structure] The structure of the second embodiment can be manufactured by injecting the resin composition of the second embodiment described above between the first layer and the second layer constituting the structure described above, molding the resin composition, and then heat-curing the resin composition. Specifically, the first layer and the second layer connected by the copper pillars can be obtained by using a method such as aligning the semiconductor chip and the substrate using a connecting device such as a flip-chip bonder, and then pressing the semiconductor chip and the substrate together while heating them at a temperature equal to or higher than the melting point of the solder bumps to connect the semiconductor chip and the substrate, or by aligning the semiconductor chip and the substrate, pressing the semiconductor chip and the substrate together at a temperature lower than the melting point of the solder bumps to temporarily fix them, and then performing a heat treatment in a reflow furnace to melt the solder bumps and connect the semiconductor chip and the substrate. Thereafter, a resin composition is injected between the first and second layers using a casting machine, a transfer molding machine, a compression molding machine, an injection molding machine, a jet dispenser, or the like, and molded appropriately, followed by heating at 80°C to 180°C for 1 to 10 hours, thereby producing a structure having a first layer, a second layer, and a third layer between the first and second layers. Examples of heating methods include methods using a heating oven, a clean oven, a pressurized oven, or the like.

[0243] [Uses] The cured product and resin composition of the second embodiment are useful, for example, as adhesives, encapsulants, filling materials, insulating materials, and sealing materials. Examples of adhesives include liquid adhesives, film adhesives, and die bonding materials. Examples of encapsulants include solid encapsulants, liquid encapsulants, and film encapsulants, and examples of liquid encapsulants include underfill materials, potting materials, and dam materials. Examples of insulating materials include insulating adhesive films, insulating adhesive pastes, and solder resists.

[0244] (Sealant) The sealant of the second embodiment includes the cured product of the second embodiment. The cured product of the second embodiment can be suitably used as a sealant. The sealant is preferably a sealant for semiconductors.

[0245] (Semiconductor Package) The semiconductor package of the second embodiment includes the cured product of the second embodiment. The cured product of the second embodiment can be suitably used as a semiconductor package. The semiconductor package of the second embodiment preferably includes the structure of the second embodiment described above and the encapsulant of this embodiment. The method for manufacturing the semiconductor package of the second embodiment includes a step of manufacturing a semiconductor package using the resin composition of the second embodiment. The step of manufacturing a semiconductor package using the resin composition of the second embodiment may include a step of preparing the resin composition of the second embodiment. The step of manufacturing a semiconductor package using the resin composition of the second embodiment may be a step of manufacturing a semiconductor package by appropriately molding the prepared resin composition and heating it at a predetermined temperature and time to cure it.

[0246] [Third embodiment] [Cured product] The curing agent of the third embodiment is a primary amine compound (A) having a value Ip* calculated from the following formula (II) of 6.0≦Ip*≦9.7: ３ -1) and a secondary amine compound (B ３ ), and the primary amine compound (A ３ -1) is a compound represented by the following formula (4) or the following formula (5), and the secondary amine compound (B ３ ) is a compound represented by the following formula (6) or the following formula (7):

[0247]

[0248] In formula (4), R ２ and R ３ each independently represents a monovalent organic group having 1 to 20 carbon atoms or a halogen atom; c and d each independently represent an integer of 0 to 4; and X represents a divalent organic group or a single bond.

[0249]

[0250] In formula (5), R ４ represents a monovalent organic group having 1 to 20 carbon atoms or a halogen atom, and e is an integer of 1 to 4.

[0251]

[0252] In formula (6), R ８ and R ９ each independently represents a monovalent organic group having 1 to 20 carbon atoms or a halogen atom; f and g each independently represent an integer of 0 to 4; X represents a divalent organic group or a single bond; R ６ and R ７ each independently represents a monovalent alkyl group, aryl group, or aralkyl group having 2 to 10 carbon atoms.

[0253]

[0254] In formula (7), R １２ represents a monovalent organic group having 1 to 20 carbon atoms or a halogen atom, h is an integer of 1 to 4, and R １０ and R １１ each independently represents a monovalent alkyl group, aryl group, or aralkyl group having 2 to 10 carbon atoms.

[0255]

[0256] In formula (II), Ip is the value of the ionization potential before correction, and Ip* is the value of the ionization potential after correction using the substituent constant. a is the number of substituents bonded to the o-position relative to the amino group. b is the number of substituents bonded to the m-position relative to the amino group. c is the number of substituents bonded to the p-position relative to the amino group. Es(AMD) is a steric parameter evaluated from the acid hydrolysis reaction rate of ortho-substituted benzamide. σm is the substituent constant when bonded to the m-position among Hammett's substituent constants. σp is the substituent constant when bonded to the p-position among Hammett's substituent constants.

[0257] By having the above-mentioned configuration, it is possible to obtain a resin composition and a curing agent that can obtain a cured product that can achieve both curability and storage stability. The curability and storage stability can be measured and evaluated by the methods described in the examples below. The components of the curing agent of the third embodiment will be described below.

[0258] (Primary amine compound (A ３-1)) Primary amine compound (A) used in the curing agent of the third embodiment ３ -1) is an aromatic amine compound represented by the following formula (4) or (5):

[0259]

[0260] In formula (4), R ２ and R ３ each independently represents a monovalent organic group having 1 to 20 carbon atoms or a halogen atom; c and d each independently represent an integer of 0 to 4; and X represents a divalent organic group or a single bond.

[0261] R ２ and R ３ In the above formula, 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 a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. c and d are each independently preferably an integer of 0 to 2, more preferably 0 or 1. In X, the number of carbon atoms in the divalent organic group is preferably 1 to 10, more preferably 1 to 8, and even more preferably 1 to 6.

[0262] Examples of the aromatic amine compound represented by formula (4) include, but are not limited to, 4,4'-diaminodiphenyl sulfone, 4-aminophenyl-4'-aminobenzoate, 1,3-bis(3-aminophenoxy)benzene, Kayahard (registered trademark) AA (a curing agent containing 3,3'-diethyl-4,4'-diaminodiphenylmethane, manufactured by Nippon Kayaku Co., Ltd.), Ethacure (registered trademark) 100 Plus (+) (a trade name, a curing agent containing diethyltoluenediamine, manufactured by Mitsui Chemicals Fine Co., Ltd.), etc. The aromatic amine compound represented by formula (4) may be used alone or in combination of two or more.

[0263] The above-mentioned primary amine compound (A ３Among the above-1), from the viewpoint of achieving both curability and storage stability when combined with an epoxy resin to form a resin composition, X is preferably —O—, —O—C6H4—O—, —CH2—, —CO—, —C(═O)O—, —SO ２ Aromatic amines having a — or —C(═O)NH— bond are preferred, and aromatic amines having a —C(═O)O— bond are particularly preferred.

[0264] In addition, the primary amine compound (A ３ As the aromatic amine compound-1), an aromatic amine compound having a methanediyl group (—CH—), which has high reactivity as an amine, can also be used. From the viewpoint of suppressing 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. Examples of aromatic amine compounds having a methanediyl group include, but are not limited to, 3,3′-diethyl-4,4′-diaminodiphenylmethane (e.g., Kayahard (registered trademark) AA (trade name) manufactured by Nippon Kayaku Co., Ltd.), 4,4′-diaminodiphenylmethane, and 3,3′-diaminodiphenylmethane. The aromatic amine compounds having a methanediyl group may be used alone or in combination of two or more.

[0265]

[0266] In the formula (5), R ４ R each independently represents a monovalent organic group having 1 to 20 carbon atoms or a halogen atom, and e is an integer of 1 to 4. ４ In the formula (I), 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. e is preferably an integer of 1 to 3, and more preferably 1 or 2.

[0267] Examples of aromatic amines represented by formula (5) include, but are not limited to, diethyltoluenediamine (2,4-diamino-3,5-diethyltoluene, 2,6-diamino-3,5-diethyltoluene). The aromatic amines represented by formula (5) 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, 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 from the viewpoint of achieving both curability and storage stability when combined with an epoxy resin to form a resin composition.

[0268] (Primary amine compound (A ３ The curing agent of the third embodiment is the primary amine compound (A ３ -2), and the primary amine compound (A ３ As the compound-2), an aromatic amine compound represented by the following formula (16) is preferred.

[0269]

[0270] In the formula (16), R ４ each independently represents a monovalent organic group having 1 to 20 carbon atoms; d is an integer of 0 to 3; and e is an integer of 1 to 3.

[0271] The primary amine compound (A ３ -1) and the primary amine compound (A ３ -2) may have secondary or higher amines in its structure as long as it has a primary amine.

[0272] Examples of the aromatic amine represented by formula (16) include, but are not limited to, Ethacure (registered trademark) 300 (trade name, curing agent containing diethylthiotoluenediamine, manufactured by Mitsui Fine Chemicals, Inc.), 2,4,6-tris(methylthio)-1,3-benzenediamine, and 2-methyl-4,5,6-tris(methylthio)-1,3-benzenediamine.

[0273] (Secondary amine compound (B ３The curing agent of the third embodiment is the secondary amine compound (B ３ The secondary amine compound (B ３ ) is a compound represented by the following formula (6) or (7):

[0274]

[0275] In formula (6), R ８ and R ９ each independently represents a monovalent organic group having 1 to 20 carbon atoms or a halogen atom; f and g each independently represent an integer of 0 to 4; X represents a divalent organic group or a single bond; R ６ and R ７ each independently represents a monovalent alkyl group, aryl group, or aralkyl group having 2 to 10 carbon atoms.

[0276]

[0277] In formula (7), R １２ represents a monovalent organic group having 1 to 20 carbon atoms or a halogen atom, h is an integer of 1 to 4, and R １０ and R １１ each independently represents a monovalent alkyl group, aryl group, or aralkyl group having 2 to 10 carbon atoms.

[0278] Examples of the aromatic amine represented by the formula (6) include, but are not limited to, MBDA (trade name, 4,4'-methylenebis[N-(sec-butyl)aniline] (manufactured by Kumiai Chemical Industry Co., Ltd.) and the like.

[0279] The aromatic amine represented by the formula (7) is not limited to the following, but examples thereof include N,N'-di-sec-butyl-1,4-phenylenediamine.

[0280] Secondary amine compound (B ３ ) may have a tertiary amine in its structure, but does not include a primary amine in its structure.

[0281] (Ionization Potential) The ionization potential (Ip) of an amine compound is known to be correlated with electron donating ability. Since the higher the electron donating ability of an amine compound, the higher the reactivity, the smaller the ionization potential (Ip) of the amine compound. Furthermore, when an amino group is bonded to an aromatic ring, other substituents affect the reactivity due to electron donating ability, steric hindrance, etc. Therefore, taking into account the influence of the substituent, correction with a substituent constant is necessary. The value obtained by correcting the ionization potential (Ip) for the substituent is defined as Ip*, and the smaller this value, the higher the reactivity, and the larger this value, the lower the reactivity. Ip* is calculated using the following formula (II):

[0282]

[0283] E ｓ (AMD): Steric parameter σ evaluated from the acid hydrolysis reaction rate of ortho-substituted benzamide ｍ : Hammett's substituent constant when bonded to m-position σ ｐ : Hammett's substituent constant when bonded to the p-position a: Number of substituents bonded to the o-position from the amino group b: Number of substituents bonded to the m-position from the amino group c: Number of substituents bonded to the p-position from the amino group

[0284] The primary amine compound (A ３ From the viewpoint of the curing rate of the resin composition using the curing agent of the third embodiment, the primary amine compound (A-1) has an Ip* value of 6.0 or more and 9.7 or less, preferably 6.5 or more and 9.7 or less, more preferably 7.0 or more and 9.7 or less, and even more preferably 7.4 or more and 9.7 or less. ３From the viewpoint of the storage stability of a resin composition and a cured product using the curing agent of the third embodiment, the Ip* value is set to be greater than 9.7 and not greater than 13.0, more preferably greater than 9.7 and not greater than 12.0, and even more preferably greater than 9.7 and not greater than 11.0. As described above, Ip* is a value that can be calculated from the molecular structure of the amine compound, and tends to increase by introducing, for example, an electron-withdrawing substituent, and tends to decrease by introducing an electron-donating substituent.

[0285] The primary amine compound (A ３ -1) and the secondary amine compound (B ３ ) is preferably a combination of the compound represented by formula (4) and the compound represented by formula (7), or a combination of the compound represented by formula (5) and the compound represented by formula (6). This has the effect of further suppressing precipitation when a resin composition containing these compounds is stored in a frozen state.

[0286] (Nitrogen-containing compounds (D ３ The curing agent of the present embodiment is a nitrogen-containing compound (D) represented by the following formulas (8) to (10): ３ Nitrogen-containing compounds (D ３ ) may be used alone or in combination of two or more.

[0287]

[0288]

[0289]

[0290] In the formulas (8) to (10), R １３ each 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; R １４ and R １５ each independently represents an unsubstituted or substituted alkyl group, aryl group, or aralkyl group having 1 to 12 carbon atoms, or combines to form a heterocycle having 7 or less carbon atoms; R １６R each independently represents a hydrogen atom or an n-valent organic group having 1 to 30 carbon atoms which may contain an oxygen atom; n represents an integer of 1 to 3. １７ represents a negatively charged nitrogen atom, and R １８ indicates a positively charged nitrogen atom.

[0291] In the compound represented by the formula (8), the compound represented by the formula (9), and the compound represented by the formula (10), R １３ is presumed to contribute to lowering the energy of the N-N bond cleavage. １４ and R １５ It is speculated that this contributes to the lowering of the energy of the cleavage reaction due to instability caused by steric hindrance. １６ It is presumed that these groups contribute to liquefying the compound and preventing a decrease in the glass transition temperature of the resulting cured product. Each group will be described in detail below.

[0292] In the formulas (8) to (10), R １３ each independently represents a hydrogen atom or a monovalent organic group having 1 to 15 carbon atoms which may have a hydroxy group, a carbonyl group, an ester bond or an ether bond.

[0293] R １３ Among these, the organic group is not particularly limited, but 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 or a carbonyl group, and a group in which a part of the carbon atoms in a hydrocarbon group is substituted with an ester bond or an ether bond.

[0294] R １３ Among these, 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 containing a combination of an alkyl group and a phenyl group, such as methylphenyl, ethylphenyl, and propylphenyl groups.８ As the alkyl group, a linear, branched, or cyclic alkyl group is preferred, a linear alkyl group is more preferred, and a methyl group, an ethyl group, or a propyl group is even more preferred.

[0295] R １３ The organic group may have other substituents, including, but not limited to, 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.

[0296] R １３ Among these, 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.

[0297] R １４ and R １５ each independently represents an unsubstituted or substituted alkyl group, aryl group, or aralkyl group having 1 to 12 carbon atoms, or combines to form a heterocycle having 7 or less carbon atoms.

[0298] R １４ and R １５ Among these, examples of the alkyl group having 1 to 12 carbon atoms include, but are not limited to, linear alkyl groups such as methyl, ethyl, propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, and n-dodecyl; branched alkyl groups such as isopropyl, isobutyl, t-butyl, neopentyl, 2-hexyl, 2-octyl, 2-decyl, and 2-dodecyl; and cyclic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclodecyl, and cyclododecyl. 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, R１４ and R １５ The cyclic alkyl group is preferably a cyclic alkyl group, and a cyclohexyl group is more preferred as the cyclic alkyl group.

[0299] R １４ and R １５ The number of carbon atoms in the alkyl groups is, independently, 1 to 12, preferably 2 to 10, and more preferably 5 to 10. Asymmetric dialkylhydrazine compounds with a small number of carbon atoms in the alkyl groups (such as dimethylhydrazine) may be explosive and may be toxic to the human body. ９ and R １０ By making the number of carbon atoms of the alkyl group in R 2 or more, it is possible to avoid using raw materials that pose the risk of toxicity, etc. １４ and R １５ By making the number of carbon atoms in the alkyl group 5 or more, a liquid compound having an appropriate viscosity is easily obtained, and the curing performance of the compound tends to be further improved.

[0300] R １４ and R １５ Among them, the aryl group is not limited to the following, but examples thereof include a phenyl group and a naphthyl group. １４ and R １５ Among these, examples of the aralkyl group include, but are not limited to, a methylphenyl group, an ethylphenyl group, a methylnaphthyl group, and a dimethylnaphthyl group.

[0301] Among these, R １４ and R １５ As the alkyl group, an aralkyl group is preferable, and a methylphenyl group (benzyl group) is more preferable.

[0302] R １４ and R １５ Among these, examples of the substituent of the alkyl group, aryl group, or aralkyl group include, but are not limited to, 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.

[0303] R １４ and R１５ are concatenated to form R １８ (a nitrogen atom having a positive charge) together to form a heterocycle having 7 or less carbon atoms. The heterocycle is not particularly limited, but examples thereof include 4-membered rings such as an azetidine ring; 5-membered rings such as a pyrrolidine ring, a pyrrole ring, a morpholine ring, and a thiazine ring; 6-membered rings such as a piperidine ring; and 7-membered rings such as a hexamethyleneimine ring and an azepine ring. Among these, as the heterocycle, a pyrrole ring, a morpholine ring, a thiazine ring, a piperidine ring, a hexamethyleneimine ring, and an azepine ring are preferred, and 6-membered rings and 7-membered rings are more preferred. By having such a group, a liquid compound is easily obtained, and the curing performance of the compound tends to be further improved. Among them, R １４ And, R １５ And, R １８ is preferably a hexamethyleneimine ring in which

[0304] Also, R １４ And, R １５ And, R １８ The heterocycle to which R is linked may have a substituent. The substituent may be, but is not limited to, an alkyl group, an aryl group, or the above-mentioned R １４ and R １５ Furthermore, when the heterocycle has an alkyl group as a substituent, R １８ and a methyl group bonded to a carbon atom adjacent to the carbon atom.

[0305] In the formulas (8), (9) and (10), R １６ R each independently represents a hydrogen atom or an n-valent organic group having 1 to 30 carbon atoms which may contain an oxygen atom. １６ Among these, 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.

[0306] R １６Among these, examples of hydrocarbon groups include, but are not limited to, 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.

[0307] R １６ Among these, 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. Examples of organic groups containing a bisphenol skeleton include, but are not limited to, groups in which a polyoxyalkylene group is added to the hydroxy group of each bisphenol skeleton.

[0308] R １６ The hydrocarbon group may have a polyoxyalkylene skeleton, such as a polyoxyethylene skeleton.

[0309] Among these, R in the formulas (8) to (10) １６ The organic group represented by the formula (I) 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 easy to obtain a liquid compound having 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.

[0310] R １６ 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. １６When 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. In addition, the Tg of the cured product obtained using this compound is further improved, and further, １６ When the number of carbon atoms of the organic group in the olefin falls within the above range, the availability of raw materials is further improved.

[0311] Among the above, R in the formulas (8) to (10) １６ 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.

[0312] In the formulas (9) and (10), n is preferably 2 or 3. This improves the crosslink density during curing, making it possible to prepare a tough cured product, and improving the adhesiveness and reliability of the cured product.

[0313] From the viewpoint of controlling the curing temperature or viscosity, the compound (D ３ Preferably, the compound represented by formula (8), the compound represented by formula (9), or the compound represented by formula (10) contains a plurality of compounds. The compound represented by formula (8), the compound represented by formula (9), or the compound represented by formula (10) may contain a plurality of compounds having different structures and represented by the same formula.

[0314] In particular, from the viewpoint of viscosity control of the resin composition using the curing agent of the third embodiment, the nitrogen-containing compound (D ３ ) preferably contains both the compound represented by formula (8) and the compound represented by formula (10). In this case, the content of the compound represented by formula (8) is preferably 0.1 to 99.5 mass% based on the total amount of the compound represented by formula (8) and the compound represented by formula (10). The content of the compound represented by formula (10) is preferably 0.5 to 99.9 mass% based on the total amount of the compound represented by formula (8) and the compound represented by formula (10).

[0315] When a plurality of compounds represented by the formula (8), the formula (9), or the formula (10) are contained, the content ratio of the compound represented by the formula (8) is preferably 0.1 to 99.8% by mass relative to the total amount of the compound represented by the formula (8), the compound represented by the formula (9), and the compound represented by the formula (10). The content of the compound represented by the formula (8) is preferably 0.1 to 99.8% by mass relative to the total amount of the compound represented by the formula (8), the compound represented by the formula (9), and the compound represented by the formula (10). The content of the compound represented by the formula (10) is preferably 0.1 to 99.8% by mass relative to the total amount of the compound represented by the formula (8), the compound represented by the formula (9), and the compound represented by the formula (10). This makes it possible to easily control the viscosity of the resin composition.

[0316] The mixture containing a plurality of compounds represented by the formula (8), (9), or (10) can be obtained by mixing a plurality of compounds, or by simultaneously producing a plurality of compounds in a compound production method described later.

[0317] Nitrogen-containing compounds (D ３ The compound (D-A) preferably contains at least one selected from the group consisting of a compound represented by the following (D-A) (hereinafter also simply referred to as "compound (D-A)"), a compound represented by the following (D-B) (hereinafter also simply referred to as "compound (D-B)"), and a compound represented by the following (D-C) (hereinafter also simply referred to as "compound (D-C)"). By using these compounds, the viscosity of the resin composition can be more easily controlled.

[0318]

[0319] In the formulas (D-A) to (D-C), R represents an alkyl group having 1 to 5 carbon atoms, l and m represent integers of 2 to 3, and X and Z each independently represent an aromatic ring, which may or may not have a substituent. Y represents a divalent organic group or a direct bond. From the viewpoint of controlling the cure rate and viscosity of the resin composition and cured product of this embodiment, R preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 2 to 4 carbon atoms. l and m are preferably 2 to 3. X and Z are preferably unsubstituted aromatic rings or aromatic rings having two methyl groups. Y is preferably a methylene group, a dimethylmethylene group, or a direct bond.

[0320] The nitrogen-containing compound (D ３ ) preferably includes both the compound (DA) and the compound (DB).

[0321] Compound (D ３ The content of the curing agent of the third embodiment is not particularly limited, but 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 using the curing agent of the third embodiment, since this tends to make it easier to control the viscosity of the resin composition. Also, from the viewpoint of the cure rate of the resin composition using the curing agent of the third embodiment, the content of the curing agent of the present embodiment is preferably 1 to 30 mass%, more preferably 2 to 27 mass%, and even more preferably 3 to 25 mass%, of the total amount (100 mass%) of the curing agent of the present embodiment.

[0322] The compound represented by the formula (8), the compound represented by the formula (9), or the compound represented by the formula (10) can be produced, for example, by reacting an ester compound, a hydrazine compound, and a glycidyl ether compound, although this is not limited thereto.

[0323] The ester compounds used to produce the compounds of formulas (8) to (10) include, but are not limited to, monocarboxylic acid ester compounds, dicarboxylic acid ester compounds, etc. The ester compounds may be used alone or in combination of two or more.

[0324] Examples of the monocarboxylic acid ester compound include, but are not limited to, 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, 4-t-butoxybenzoylmethyl, etc. Alternatively, ethyl esters, propyl esters, etc. may be used.

[0325] Examples of the dicarboxylic acid ester compound include, but are not limited to, 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. Examples of the cyclic ester include, but are not limited to, α-acetolactone, β-propionolactone, γ-butyrolactone, δ-valerolactone, γ-valerolactone, and ε-caprolactone. Alternatively, diethyl esters, dipropyl esters, and the like may be used.

[0326] Among these, the curability of the resin composition and the compound (D ３From the viewpoint of liquefaction of the above-mentioned ester compounds, preferred ester compounds are 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, and γ-valerolactone.

[0327] The hydrazine compound used to produce the compounds of formulas (8) to (10) includes, but is not limited to, 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, 1-aminomorpholine, and the like.

[0328] 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.

[0329] The glycidyl ether compounds used to produce the compounds of formulas (8) to (10) include, but are not limited to, monofunctional monoglycidyl ether compounds, difunctional or higher functional polyglycidyl ether compounds, etc. One type of glycidyl ether compound may be used alone, or two or more types may be used in combination.

[0330] Examples of monoglycidyl ether compounds include, but are not limited to, 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.

[0331] Examples of polyglycidyl ether compounds include, but are not limited to, 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, ... Examples of the polyglycidyl ether include aliphatic polyglycidyl ethers such as serine polyglycidyl 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.

[0332] Among these, the curability of the resin composition and the compound (D ３From the viewpoint of liquefaction of the above-mentioned glycidyl ether compounds, preferred glycidyl ether compounds include 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.

[0333] Furthermore, in terms of adhesiveness of the resin composition and the cured product using the curing agent of the present embodiment, the compound (D ３ The glycidyl ether compound used to produce the epoxy resin (A) is preferably an epoxy resin having an ether structure, 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.

[0334] The amounts of the ester compound, hydrazine compound, and glycidyl ether compound added to the reaction system for producing the compounds of the formulae (8) to (10) can be determined based on the molar ratio of the functional groups.

[0335] The amount of the ester group of the ester compound is preferably 0.8 to 3.0 moles, more preferably 0.9 to 2.8 moles, and even more preferably 0.95 to 2.5 moles, per mole of the primary amine of the hydrazine compound.

[0336] The amount of the glycidyl group in the glycidyl ether compound is preferably 0.80 mol to 2.00 mol, more preferably 0.90 mol to 1.50 mol, and even more preferably 0.95 mol to 1.40 mol, per mol of the primary amine in the hydrazine compound.

[0337] 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 compounds represented by the formulas (8) to (10) can be simultaneously produced. Specifically, the amount of the glycidyl group of the glycidyl ether compound added relative to 1 mole of the primary amine of the hydrazine compound is preferably 0.1 mol to 3.0 mol, more preferably 0.3 mol to 2.0 mol, and even more preferably 0.5 mol to 1.0 mol.

[0338] In the above-described methods for producing the compound or mixture, a solvent may be used to ensure uniform reaction. Examples of the solvent include, but are not limited to, alcohols such as methanol, ethanol, 1-propanol, 2-propanol, butanol, and t-butyl alcohol; and ethers such as tetrahydrofuran and diethyl ether.

[0339] 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 more 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. The reaction time is preferably 1 hour or higher and 168 hours or lower, more preferably 1 hour or higher and 96 hours or higher, and even more preferably 1 hour or higher and 48 hours or lower.

[0340] After the reaction is complete, the resulting reaction product can be purified by known purification methods such as washing, extraction, recrystallization, and column chromatography. For example, the reaction solution dissolved in an organic solvent can be washed with water, and then the organic layer can be 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. However, from the viewpoints of yield, purity, and ease of removal, 1-hexane, 1-pentane, and cyclohexane are preferred. The organic solvent used for the above-mentioned extraction is not particularly limited as long as it can dissolve the target compound. However, from the viewpoints of yield, purity, and ease of removal, ethyl acetate, dichloromethane, chloroform, carbon tetrachloride, toluene, diethyl ether, and methyl isobutyl ketone are preferred, and ethyl acetate, chloroform, toluene, and methyl isobutyl ketone are more preferred. Known packing materials such as alumina and silica gel can be used for column chromatography. The developing solvent may be any known solvent such as ethyl acetate, dichloromethane, chloroform, carbon tetrachloride, tetrahydrofuran, diethyl ether, acetone, methyl isobutyl ketone, acetonitrile, methanol, ethanol, or isopropanol, and may be used alone or in combination.

[0341] (Content of components in curing agent) <Primary amine compound (A ３ In the curing agent of the third embodiment, the content of the primary amine compound (A-1) ３ The preferred content of the primary amine compound (A-1) is ３ -1), primary amine compounds (A ３ -2), secondary amine compounds (B ３ ) and nitrogen-containing compounds (D ３ ) is 1 to 90% by mass, more preferably 3 to 80% by mass, and even more preferably 4 to 70% by mass of the total amount of the polymers.

[0342] <Primary amine compound (A ３ The content of the primary amine compound (A-2) in the curing agent of the third embodiment is ３When the primary amine compound (A-2) is contained, ３ The preferred content of the primary amine compound (A-2) is ３ -1), primary amine compounds (A ３ -2), secondary amine compounds (B ３ ) and nitrogen-containing compounds (D ３ ) in the total amount of the primary amine compound (A), the curing agent of the third embodiment is preferably 1 to 90 mass %, more preferably 5 to 80 mass %, and even more preferably 9 to 75 mass %. ３ When the primary amine compound (A-2) is contained, ３ -1) and a primary amine compound (A ３ The mass ratio of (A-2) is determined from the viewpoint of curability and storage stability. ３ -1): (A ３ -2) is preferably 90:10 to 20:80, more preferably 80:20 to 30:70, and even more preferably 70:30 to 30:70.

[0343] <Secondary amine compound (B ３ ) content in the curing agent of the third embodiment> ３ The content of the primary amine compound (A ３ -1), primary amine compounds (A ３ -2), secondary amine compounds (B ３ ) and nitrogen-containing compounds (D ３ ) in the total amount of the secondary amine compound (B ) is preferably 5 to 90 mass %, more preferably 10 to 90 mass %, and even more preferably 20 to 90 mass %. ３ Regarding the content of the primary amine compound (A ３ -1) and a secondary amine compound (B ３ The mass ratio of (A ３ -1): (B ３ ) is preferably 75:25 to 5:95, more preferably 80:20 to 10:90, and even more preferably 80:20 to 20:80.

[0344] <Nitrogen-containing compounds (D ３The content of the nitrogen-containing compound (D) in the curing agent of the third embodiment ３ ), the nitrogen-containing compound (D ３ The preferred content of the primary amine compound (A ３ -1), primary amine compounds (A ３ -2), secondary amine compounds (B ３ ) and nitrogen-containing compounds (D ３ ), the content is 1 to 30% by mass, more preferably 3 to 25% by mass, and even more preferably 5 to 25% by mass of the total amount of the primary amine compound (A). ３ -1) and a nitrogen-containing compound (D ３ The mass ratio of (A ３ The ratio of (-1):(D) is preferably 95:5 to 60:40, more preferably 90:10 to 65:35, and even more preferably 90:10 to 70:30.

[0345] <Nitrogen-containing compounds (D ３ In the curing agent of the third embodiment, the ratio of the primary amine compound (A ３ -1) and the primary amine compound (A ３ -2) nitrogen-containing compound (D ３ ) and the mass ratio ((A ３ -1) + (A ３ -2)): (D ３ From the viewpoint of the storage stability and curing rate of the resin composition and the cured product using the curing agent of the third embodiment, the ratio of the primary amine compound (A) to the cured product is preferably 99:1 to 60:40, more preferably 99:1 to 70:30, and even more preferably 99:1 to 80:20. ３ -1) and a secondary amine compound (B ３ ) nitrogen-containing compounds (D ３ ) and the mass ratio ((A ３ -1) + (B ３ )): (D ３ ) is preferably 99:1 to 60:40, more preferably 99:1 to 70:30, and even more preferably 99:1 to 80:20, from the viewpoint of the storage stability and cure rate of the resin composition and cured product using the curing agent of the third embodiment.

[0346] <Content of Curing Agent in Epoxy Resin> The curing agent (primary amine compound (A)) of the third embodiment ３ -1), primary amine compounds (A ３ -2), secondary amine compounds (B ３ ) and nitrogen-containing compounds (D ３ )) to the epoxy resin described below is preferably curing agent:epoxy resin=10:90 to 65:35, more preferably 15:85 to 60:40, and even more preferably 15:85 to 50:50.

[0347] <Content of Curing Agent in Resin Composition> The curing agent (primary amine compound (A)) of the third embodiment ３ -1), primary amine compounds (A ３ -2), secondary amine compounds (B ３ ) and nitrogen-containing compounds (D ３ ) is not particularly limited, but from the viewpoint of curability and stability, it is preferably 1 to 50 mass %, more preferably 1 to 40 mass %, and even more preferably 1 to 30 mass %, of the total amount (100 mass %) of the resin composition described below.

[0348] [Resin Composition] The curing agent of the third embodiment described above is preferably for an epoxy resin. A resin composition containing the curing agent of the third embodiment contains at least an epoxy resin.

[0349] (Epoxy Resin) As the epoxy resin, a commonly used epoxy resin can be used. For example, an epoxy resin having two or more epoxy groups per molecule is preferred. The epoxy resin may be solid or liquid at room temperature, but from the viewpoint of the filling property of the resin composition of this embodiment, an epoxy resin that is liquid at room temperature (hereinafter also referred to as "liquid epoxy resin") is preferred, and a commonly used liquid epoxy resin can 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.

[0350] Examples of epoxy resins used in the resin composition of the third embodiment include, but are not limited to, diglycidyl ether epoxy resins such as bisphenol-type epoxy resins such as bisphenol A, bisphenol F, bisphenol AD, bisphenol S, and hydrogenated bisphenol A; naphthalene-type epoxy resins; epoxy resins obtained by epoxidizing novolak resins obtained from phenols and aldehydes, such as orthocresol novolak-type epoxy resins; glycidyl ester-type epoxy resins obtained by reacting polybasic acids such as phthalic acid and dimer acid with epichlorohydrin; glycidylamine-type epoxy resins obtained by reacting amine compounds such as p-aminophenol, diaminodiphenylmethane, and isocyanuric acid with epichlorohydrin; fluorene-type epoxy resins obtained from fluorene derivatives having a cardo structure in which fluorene and an aromatic ring are bonded; and linear aliphatic epoxy resins and alicyclic epoxy resins obtained by oxidizing olefin bonds with peracids such as peracetic acid. Among these, from the viewpoint of the heat resistance, adhesiveness, and fluidity of the resin composition of the third embodiment, it is preferable to contain a glycidylamine type epoxy resin, and from the viewpoint of the crack resistance of the cured product of the resin composition of the present embodiment, it is preferable to contain a bisphenol type epoxy resin which has a bisphenol skeleton and in which the ratio of aromatic rings in the molecule to the molecular weight of one molecule is 0.05 or more and 0.4 or less.

[0351] When a naphthalene-type epoxy resin is also included as an epoxy resin, the mass ratio thereof (naphthalene-type epoxy resin:total of glycidylamine-type epoxy resin and bisphenol-type epoxy resin) is preferably 5:95 to 50:50, more preferably 10:90 to 40:60, and even more preferably 15:80 to 40:60, from the viewpoints of the heat resistance, adhesiveness, and fluidity of the resin composition of the third embodiment.

[0352] From the viewpoint of the fluidity of the resin composition of the third embodiment, it is preferable that both the glycidylamine type epoxy resin and the bisphenol type epoxy resin are liquid at room temperature.

[0353] From the viewpoints of heat resistance, adhesiveness, and flowability of the resin composition of the third embodiment, the total content of the glycidylamine-type epoxy resin and the bisphenol-type epoxy resin is, for example, preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 50% by mass or more, and even more preferably 80% by mass or more, relative to the total amount of epoxy resin. There is no particular restriction on the upper limit of the total content, and it can be determined within a range in which desired properties and characteristics are obtained from the viewpoints of viscosity, glass transition temperature, heat resistance, etc., and may be 100% by mass.

[0354] From the viewpoint of the heat resistance, adhesiveness, and fluidity of the resin composition of the third embodiment, the mass ratio of the glycidylamine type epoxy to the bisphenol type epoxy resin (glycidylamine type epoxy:bisphenol type epoxy resin) is, for example, preferably 50:50 to 95:5, more preferably 60:40 to 90:10, and even more preferably 70:30 to 90:10.

[0355] In addition, in the third embodiment, an epoxy resin that is solid at room temperature can also be used. From the viewpoint of fluidity, the content of the epoxy resin that is solid at room temperature is, for example, preferably 0 to 30 mass %, more preferably 0 to 25 mass %, and even more preferably 0 to 20 mass %, relative to the total amount of the epoxy resin.

[0356] There are no particular restrictions on the epoxy equivalent of the epoxy resin used in the resin composition of the third embodiment, but from the viewpoint of the heat resistance of the resin composition of the third embodiment, it is preferably 60 to 1000 g / mol, more preferably 70 to 900 g / mol, and even more preferably 80 to 800 g / mol.

[0357] Here, the epoxy equivalent is the mass (g / eq) of the resin per epoxy group, and can be measured according to the method specified in JIS K 7236. Specifically, using an automatic titrator "GT-200 Model" manufactured by Mitsubishi Chemical Analytech Co., Ltd., 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. After that, 10 mL of glacial acetic acid and 1.5 g of cetyltrimethylammonium bromide are added, and the epoxy equivalent is determined by titration with a 0.1 mol / L perchloric acid / acetic acid solution.

[0358] The epoxy resin used in the resin composition of the third embodiment preferably has a high purity. In particular, the amount of hydrolyzable chlorine is preferably low, as this is related to corrosion of aluminum wiring on elements such as integrated circuits (ICs). From the viewpoint of excellent moisture resistance, for example, a value of 1,500 ppm or less is preferred. 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 a 1N KOH (potassium hydroxide) methanol solution, refluxing for 30 minutes, and then measuring the value obtained by potentiometric titration.

[0359] The resin composition of the third embodiment contains a curing agent and an epoxy resin. From the viewpoints of heat resistance and adhesiveness, the mass ratio of the curing agent to the epoxy resin (curing agent:epoxy resin) is preferably 10:90 to 65:35, more preferably 15:85 to 60:40, and even more preferably 15:85 to 50:50.

[0360] (Inorganic filler (E ３ The resin composition of the present embodiment contains an inorganic filler (E ３ ) may be contained. ３ ) may be used alone or in combination of two or more.

[0361] Examples of inorganic fillers include, but are not limited to, silica such as fused silica and crystalline silica, calcium carbonate, clay, alumina such as alumina oxide, silicon nitride, silicon carbide, boron nitride, calcium silicate, potassium titanate, aluminum nitride, beryllia, zirconia, zircon, forsterite, steatite, spinel, mullite, and titania powders, as well as beads and glass fibers obtained by sphering these materials. Flame-retardant inorganic fillers may also be used. Flame-retardant inorganic fillers include, for example, aluminum hydroxide, magnesium hydroxide, zinc borate, and zinc molybdate. Among these, silica is preferred, and fused silica is more preferred, from the viewpoints of availability, chemical stability, and material cost. The particle shape of the inorganic filler is not particularly limited and may be amorphous or spherical. However, from the viewpoints of the flowability and permeability of the resin composition of the third embodiment into fine gaps, spherical silica is preferred, and spherical fused silica is more preferred.

[0362] In addition, the inorganic filler may be surface-treated. Specifically, the inorganic filler may be surface-treated using a silane coupling agent. Examples of the silane coupling agent include, but are not limited to, aminosilane coupling agents, epoxysilane coupling agents, phenylsilane coupling agents, alkylsilane coupling agents, alkenylsilane coupling agents, alkynylsilane coupling agents, haloalkylsilane coupling agents, siloxane coupling agents, hydrosilane coupling agents, silazane coupling agents, alkoxysilane coupling agents, chlorosilane coupling agents, (meth)acrylicsilane coupling agents, aminosilane coupling agents, isocyanurate silane coupling agents, ureidosilane coupling agents, mercaptosilane coupling agents, sulfide silane coupling agents, and isocyanate silane coupling agents.

[0363] The volume average particle size of the inorganic filler is not limited to the following, but is preferably 0.1 to 10.0 μm, more preferably 0.2 to 5.0 μm, and even more preferably 0.3 to 3.0 μm. By setting the volume average particle size of the inorganic filler to 0.1 μm or more, dispersibility in the epoxy resin is improved, thixotropy is less likely to be imparted to the resin composition of the third embodiment, and the flow characteristics of the resin composition tend to be improved. On the other hand, by setting the volume average particle size to 10.0 μm or less, sedimentation of the inorganic filler in the resin composition of the third embodiment tends to be easily suppressed, and the permeability and flowability of the resin composition into fine gaps tend to be improved, which tends to suppress the occurrence of voids and unfilled portions. The volume average particle size refers to the particle size at the point corresponding to 50% volume when a cumulative frequency distribution curve based on particle size is calculated, assuming the total volume of the particles to be 100%, and can be measured using a particle size distribution measuring device using a laser diffraction scattering method.

[0364] Inorganic filler (E ３ The content of the inorganic filler is preferably 30 to 85% by mass, more preferably 40 to 80% by mass, and even more preferably 45 to 70% by mass, relative to the total amount (100% by mass) of the resin composition of the third embodiment. By making the content of the inorganic filler 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 are easily obtained. By making the content of the inorganic filler 85% by mass or less, it is likely that an increase in viscosity of the resin composition of the third embodiment is suppressed, and the flowability, penetration, and dispensability are improved. In particular, from the viewpoint of the effect of improving temperature cycle resistance, the higher the lower limit of the content of the inorganic filler, the more preferable. In the resin composition of the third embodiment, even if the content of the inorganic filler is increased as described above, the nitrogen-containing compound (D ３ ), it is possible to maintain the viscosity of the resin composition at a low level.

[0365] The resin composition of the third embodiment contains the above-mentioned primary amine compound (A ３ -1), primary amine compounds (A ３ -2), secondary amine compounds (B ３ ), nitrogen-containing compounds (D ３) may contain other curing accelerators.

[0366] (Other Curing Agents) The resin composition of the third embodiment contains the above-mentioned primary amine compound (A ３ -1), primary amine compounds (A ３ -2), secondary amine compounds (B ３ The curing agent may contain a curing agent other than the primary amine compound (A) (hereinafter, sometimes referred to as "other curing agent"). ３ -1), primary amine compounds (A ３ -2), and secondary amine compounds (B ３ Examples of suitable curing agents include aromatic amine compounds other than those listed above, amine adducts, acid anhydride curing agents, phenolic curing agents, and thiol curing agents.

[0367] <Amine Adduct> The curing agent of the third embodiment preferably contains an amine adduct, which is a reaction product of an amine compound and a reactive compound having a functional group reactive with the amine compound. In particular, the amine adduct preferably contains an amine adduct in which one molecule of the reactive compound is added to one molecule of the amine compound. When the curing agent of the third embodiment contains an amine adduct, it may contain an amine adduct in which one molecule of the reactive compound is added to one molecule of the amine compound, or an amine adduct in which two or more molecules of the reactive compound are added to one molecule of the amine compound.

[0368] From the viewpoint of the curability and storage stability of the resin composition and cured product of the third embodiment, among the peak areas of the amine compound, the amine adduct, and the amine adduct obtained from the analysis of the components in the curing agent of the third embodiment, the ratio of the peak area of ​​the amine compound to the peak area of ​​the amine adduct 1 adduct (peak area of ​​the amine compound / peak area of ​​the amine adduct 1 adduct) is preferably 0.1 to 3.0, more preferably 0.2 to 2.5, and even more preferably 0.3 to 2.0.

[0369] The amine adduct is a reaction product of an amine compound and a reactive compound having a functional group capable of reacting with the amine compound. The amine adduct may be used alone or in combination of two or more. In the curing agent of this embodiment, the primary amine compound (A ３ Amine adduct (A-1) is a reaction product of a reactive compound having a functional group capable of reacting with ３ It is preferable that the primary amine compound (A-1-1) is contained. ３ Amine adduct (A-2) is a reaction product of a reactive compound having a functional group capable of reacting with ３ -2-1) is preferably included.

[0370] <Reactive Compound> The reactive compound has a functional group capable of reacting with an amine compound. 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, but are not limited to, 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, and an iodo group. Among these, an epoxy group is preferred as the functional group.

[0371] 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.

[0372] Examples of carboxylic acid compounds include, but are not limited to, succinic acid, adipic acid, sebacic acid, phthalic acid, dimer acid, etc. Examples of acid anhydrides include, but are not limited to, succinic anhydride, adipic anhydride, sebacic anhydride, phthalic anhydride, etc. Examples of acid dianhydrides include, but are not limited to, tetracarboxylic acid dianhydride, etc. Examples of sulfonic acid compounds include, but are not limited to, ethanesulfonic acid, p-toluenesulfonic acid, etc.

[0373] Examples of isocyanate compounds include, but are not limited to, aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, aliphatic triisocyanates, polyisocyanates, etc. Examples of aliphatic diisocyanates include, but are not limited to, ethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, etc. Examples of alicyclic diisocyanates include, but are not limited to, isophorone diisocyanate, 4-4'-dicyclohexylmethane diisocyanate, norbornane diisocyanate, 1,4-isocyanatocyclohexane, 1,3-bis(isocyanatomethyl)-cyclohexane, 1,3-bis(2-isocyanatopropyl-2-yl)-cyclohexane, etc. Examples of aromatic diisocyanates include, but are not limited to, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylene diisocyanate, and 1,5-naphthalene diisocyanate. Examples of aliphatic triisocyanates include, but are not limited to, 1,3,6-triisocyanatomethylhexane and 2,6-diisocyanatohexanoate-2-isocyanatoethyl. Examples of polyisocyanates include, but are not limited to, polymethylene polyphenyl polyisocyanate and polyisocyanates derived from the diisocyanate compounds. Examples of polyisocyanates derived from the diisocyanates include, but are not limited to, isocyanurate polyisocyanates, biuret polyisocyanates, urethane polyisocyanates, allophanate polyisocyanates, and carbodiimide polyisocyanates.

[0374] Examples of the urea compound include, but are not limited to, urea, methyl urea, dimethyl urea, ethyl urea, and t-butyl urea.

[0375] Examples of epoxy compounds include, but are not limited to, monoepoxy compounds, polyepoxy compounds, and mixtures thereof. Examples of monoepoxy compounds include, but are not limited to, 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.Examples of polyepoxy compounds include, but are not limited to, 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. 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.

[0376] Among the above, from the viewpoint of achieving excellent curability and storage stability of the resin composition of the third embodiment, 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). Examples of the monoepoxy compound include, but are not limited to, ethyl glycidyl ether, butyl glycidyl ether (BGE), phenyl glycidyl ether (ph-GE), and 2-ethylhexyl glycidyl ether (2-EH).

[0377] The amine adduct can be obtained, for example, by reacting 1.0 to 5.0 moles of an amine compound with a reactive compound in a molar ratio of 0.2 to 5.0, if necessary in the presence of a solvent, at a temperature of 50 to 250°C for 0.1 to 10 hours, and, if necessary, removing the unreacted amine compound and the solvent.

[0378] The solvent used here is not limited to the following, but examples include hydrocarbons such as benzene, toluene, xylene, cyclohexane, mineral spirits, naphtha, etc.; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.; esters such as ethyl acetate, n-butyl acetate, propylene glycol monomethyl ether acetate, etc.; alcohols such as methanol, isopropanol, 1-butanol, butyl cellosolve, butyl carbitol, etc.; and water. These solvents may be used alone or in combination of two or more. The amine compound used to produce the amine adduct is preferably an aromatic amine.

[0379] <Acid Anhydride Curing Agent> 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.

[0380] <Phenol-Based Curing Agent> Examples of the phenol-based curing agent 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.

[0381] <Thiol-Based Curing Agent> Examples of thiol-based curing agents include, but are not limited to, thiol compounds obtained by an esterification reaction between a polyol and a thiol organic acid, such as trimethylolpropane tris(thioglycolate), pentaerythritol tetrakis(thioglycolate), ethylene glycol dithioglycolate, trimethylolpropane tris(β-thiopropionate), pentaerythritol tetrakis(β-thiopropionate), and dipentaerythritol poly(β-thiopropionate); alkyl polythiol compounds such as 1,4-butanedithiol, 1,6-hexanedithiol, and 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 a terminal thiol group obtained by the reaction of a polythiol with an epoxy compound.

[0382] [Method for Producing Resin Composition] The resin composition of the third embodiment can be produced, for example, by a method of dry-blending the constituent components, or by a method of preparing the resin composition using an apparatus typically used for mixing polymeric substances. Examples of the apparatus for mixing the components include, but are not limited to, kneading apparatuses such as a Banbury mixer, a Labo Plastomill, a single-screw extruder, and a twin-screw extruder. The resin composition of the present embodiment is preferably produced, for example, by stirring and mixing the components using a planetary mixer (for example, "ARE-310" (trade name) manufactured by Thinky Corporation), followed by kneading using a triple roll mill. Alternatively, the epoxy resin may be mixed and stirred in advance, and an inorganic filler may be dispersed therein to prepare a dispersion, and then a primary amine compound (A ３ -1) and a primary amine compound (A ３ -2), secondary amine compounds (B ３ ), and nitrogen-containing compounds (D ３ ), and the mixture is stirred and mixed in a planetary mixer, and then kneaded using a triple roll mill. ３ -1) and a primary amine compound (A ３ -2) or secondary amine compound (B ３ ) is added, followed by adding a curing accelerator, followed by stirring and mixing in a planetary mixer, and then kneading with a triple roll mill.

[0383] [Physical Properties of Resin Composition] (Viscosity) The resin composition of the third embodiment preferably has a viscosity of 0.01 Pa·s to 4.50 Pa·s after being left at 100°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 being left at 100°C for 60 minutes can be measured using a rheometer (for example, HAAKE (registered trademark) MARS (trade name), manufactured by Thermo Scientific). A specific measurement method will be described in the examples below.

[0384] (Thickening rate) The resin composition of the third embodiment has a viscosity increase rate after being left at 100 ° C. for 60 minutes of 1.0 times or more and 50.0 times or less, more preferably 1.0 times or more and 40.0 times or less, even more preferably 1.0 times or more and 30.0 times or less, even more preferably 1.0 times or more and 20.0 times or less, and even more preferably 1.0 times or more and 10.0 times or less. The viscosity increase rate after being left at 100 ° C. for 60 minutes is measured by dropping the resin composition of the third embodiment onto a measurement plate, and measuring it using a rheometer (HAAKE MARS, manufactured by Thermo Scientific) 5 minutes and 60 minutes after the sample temperature reaches 100 ° C. (Measurement conditions: aluminum cone plate, R = 20 mm, shear rate 20 ( / sec)). The viscosity after 5 minutes is "η1", the viscosity after 60 minutes is "η2", and the value calculated by η2 / η1 is the viscosity increase rate. A specific measurement method will be described in the Examples below.

[0385] (Cure Rate) The cure rate of the resin composition of the third embodiment when cured at 165°C is preferably 70% or more and 100% or less, more preferably 80% or more and 100% or less, and even more preferably 90% or more and 100% or less. The cure rate when the resin composition of the third embodiment is cured at 165°C can be calculated, for example, by using an 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 observed in the temperature range from 100°C to 250°C. The calculation formula is as follows. A specific measurement method will be described in the Examples below. Initial heat generation amount A: DSC peak heat generation amount of the epoxy resin composition Post-curing heat generation amount B: DSC peak heat generation amount of the epoxy resin composition after heating Cure rate (%) = 100 × (initial heat generation amount A - post-curing heat generation amount B) ÷ initial heat generation amount A

[0386] [Cured Product] The cured product of the third embodiment includes the resin composition of the third embodiment. The cured product of the third embodiment is a cured product of the resin composition of the third embodiment, and is obtained by curing the resin composition of the third embodiment.

[0387] [Uses of Resin Composition and Cured Product] The resin composition and cured product containing the curing agent of the third embodiment are useful as adhesives, encapsulants, filling materials, insulating 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.

[0388] (Adhesive) The adhesive of the third embodiment includes the curing agent of the third embodiment. The adhesive of the third embodiment also includes the resin composition of the third embodiment. The resin composition of the third embodiment can be suitably used as an adhesive.

[0389] (Sealant) The sealant of the third embodiment includes the cured product of the third embodiment. The cured product of the third embodiment can be suitably used as a sealant. The sealant is preferably a sealant for semiconductors.

[0390] (Semiconductor Package) The semiconductor package of the third embodiment includes the cured product of this embodiment. The cured product of the third embodiment can be suitably used as a semiconductor package. The method for manufacturing the semiconductor package of the third embodiment includes a step of manufacturing a semiconductor package using the curing agent of the third embodiment and the resin composition of the third embodiment. The step of manufacturing a semiconductor package using the resin composition of the third embodiment may include a step of manufacturing the resin composition of this embodiment. The step of manufacturing a semiconductor package using the resin composition of the third embodiment may be a step of manufacturing a semiconductor package by appropriately molding the manufactured resin composition and heating it at a predetermined temperature and time to cure it.

[0391] Hereinafter, the present embodiment will be described with reference to specific examples and comparative examples, but the present invention is not limited to the following examples and comparative examples. That is, 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.

[0392] [First Example] [Methods for measuring and evaluating physical properties and characteristics of epoxy resin compositions] The physical properties and characteristics of the epoxy resin compositions prepared in the examples and comparative examples described below were measured as follows.

[0393] (High-Temperature Elastic Modulus) The epoxy resin compositions of the Examples and Comparative Examples described below were cured at 165°C, and the resulting cured products were cut into test pieces measuring 35 x 10 x 2 mm. Using the test pieces and a dynamic mechanical analysis (DMA) device (trade name: RSA-G2, manufactured by TA Instruments), measurements were performed in a three-point bending mode from 0 to 270°C at a rate of 5°C / min and a frequency of 1 Hz. The storage modulus at 260°C was defined as the high-temperature modulus, and the evaluation was based on the following criteria. <Evaluation Criteria> A: The storage modulus at 260°C was less than 0.05 GPa. B: The storage modulus at 260°C was 0.05 GPa or more but less than 0.2 GPa. C: The storage modulus at 260°C was 0.2 GPa or more.

[0394] (Method for Evaluating Viscosity Stability at 100°C (High Temperature)) The viscosity stability of the epoxy resin composition at 100°C was evaluated as follows. Each of the resin compositions (0.5 mL) of the examples and comparative examples described below was dropped onto a measurement plate. Five minutes and 60 minutes after the sample temperature reached 100°C, the viscosity was measured using a rheometer (HAAKE (registered trademark) MARS (trade name), manufactured by Thermo Scientific) at a constant measurement temperature (100°C) in oscillation mode (f = 1 Hz) (measurement conditions: aluminum cone plate R = 35 mm, shear rate 20 ( / sec)). The viscosity after 5 minutes was designated "η1" and the viscosity after 60 minutes was designated "η2," and the value calculated by η2 / η1 was determined as the viscosity increase ratio. The viscosity increase ratio was used to evaluate the viscosity stability according to the following evaluation criteria. Note that "η2" is the viscosity after standing at 100°C for 60 minutes. The lower the viscosity increase rate, the more excellent the viscosity stability was evaluated. <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.

[0395] (Cure rate when cured at 165°C) The cure rate when the resin composition was cured at 165°C was measured by 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 a rate of 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 cure rate was calculated based on the change in heat generated in the same temperature range. The calculation formula is as follows: Initial heat generation amount A: DSC peak heat generation amount of the epoxy resin composition Post-curing heat generation amount B: DSC peak heat generation amount of the epoxy resin composition after heating Cure rate (%) = 100 × (initial heat generation amount A - post-curing heat generation amount B) ÷ initial heat generation amount A The obtained cure rate was evaluated according to the following evaluation criteria. <Evaluation criteria> A: The cure rate was 99% or more. B: The cure rate was 95% or more but less than 99%. C: The cure rate was less than 95%.

[0396] (Measurement and Evaluation of Coefficient of Linear Expansion (CTE)) A test specimen was prepared by cutting a 5 mm x 5 mm piece from a cured epoxy resin composition cured at 165°C for 2 hours. Using the test specimen and a thermomechanical analyzer (trade name: TMA450, manufactured by TA Instruments) in compression mode, the temperature was raised from -30 to 250°C at 5°C / min, then cooled to -30°C, and again raised to 250°C at 5°C / min. The CTE was measured by the slope of the tangent line from 0 to 30°C of the second measurement result, which was taken as the CTE and evaluated according to the following criteria. <Evaluation Criteria> A: The CTE was 25 ppm / K or less. B: The CTE was greater than 25 ppm / K and less than 35 ppm / K. C: The CTE was greater than 35 ppm / K and less than 40 ppm / K. D: CTE was greater than 40 ppm / K.

[0397] [Preparation of Epoxy Resin Compositions] Epoxy resin compositions were prepared in Examples 1-1 to 1-35 and Comparative Examples 1-1 to 1-4 described below. The materials used in preparing the epoxy resin compositions are listed below. The abbreviations for the components used in the examples and comparative examples have the following meanings:

[0398] (Epoxy resin (A １ -1) jER (registered trademark) 630LSD: (trade name, aminoglycidyl type epoxy resin, 95 g / eq, manufactured by Mitsubishi Chemical Corporation)

[0399] (Epoxy resin (A １ -2)) EXA-4850-150: (bisphenol-type liquid epoxy resin, EPICLON (registered trademark) EXA-4850-150 (trade name), 450 g / eq, manufactured by DIC Corporation) Epoxy of Production Example 1: (epoxy resin described in Production Example 1 of Japanese Patent No. 6125775, 371 g / eq) Epoxy of Production Example 2: (epoxy resin described in Production Example 2 of Japanese Patent No. 6125775, 252 g / eq) Epoxy of Production Example 3: (epoxy resin described in Production Example 3 of Japanese Patent No. 6125775, 447 g / eq) BEO-60E: (trade name, bisphenol A bis(triethylene glycol glycidyl ether) ether, 366 g / eq, manufactured by New Japan Chemical Co., Ltd.)

[0400] The epoxy resin (A １ The following formula (I) was calculated for each of the aromatic rings in each molecule / molecular weight of each molecule, and the calculation results are shown in Table 2 below. 0.05≦(molecular weight of aromatic rings in each molecule / molecular weight of each molecule)≦0.4 (I)

[0401]

[0402] (Other epoxy resins (A １ -3)) EXA-850CRP: (bisphenol A type liquid epoxy resin, EPICLON (registered trademark) EXA-850CRP (trade name), 185 g / eq, manufactured by DIC Corporation) HP4032D: (naphthalene type epoxy resin, EPICLON (registered trademark) HP4032D (trade name), 141 g / eq, manufactured by DIC Corporation) jER (registered trademark) 604: (trade name, diaminodiphenylmethane type epoxy resin, 117 g / eq, manufactured by Mitsubishi Chemical Corporation) YX4000H: (trade name, tetramethylbiphenol type solid epoxy resin, 186 g / eq, manufactured by Mitsubishi Chemical Corporation) PG-100: (trade name, fluorene type epoxy resin, 250 g / eq, manufactured by Osaka Gas Chemicals Co., Ltd.) EG-200: (Product name: fluorene-type epoxy resin, 288 g / eq, manufactured by Osaka Gas Chemicals Co., Ltd.)

[0403] (Amine Compound B １ -1) 4DAS: 4,4'-diaminodiphenyl sulfone APAB: 4-aminophenyl-4'-aminobenzoate TPE-M: 1,3-bis(3-aminophenoxy)benzene Kayahard (registered trademark) AA: curing agent containing 3,3'-diethyl-4,4'-diaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd.) DETDA (Ethacure (registered trademark) 100 Plus (+)): curing agent containing diethyltoluenediamine (manufactured by Mitsui Fine Chemicals, Inc.) MDEA: 4,4'-methylenebis(2,6-diethylaniline) (manufactured by Kumiai Chemical Industry Co., Ltd.) MED-J: 4,4'-methylenebis(2-ethyl-6-methylaniline) (manufactured by Kumiai Chemical Industry Co., Ltd.) TEBDA: 2,4,6-triethyl-1,3-benzenediamine

[0404] (Amine Compound B１ -2) DMTDA (Ethacure (registered trademark) 300): a curing agent containing diethylthiotoluenediamine (manufactured by Mitsui Fine Chemicals, Inc.) TTBDA: 2,4,6-tris(methylthio)-1,3-benzenediamine MTBDA: 2-methyl-4,5,6-tris(methylthio)-1,3-benzenediamine

[0405] The amine compound (B １ -1)), (amine compound (B １ For each of the amine compounds described in Item 1-2), Ip* was calculated using the following formula (II).

[0406]

[0407] In formula (II), Ip is the value of the ionization potential before correction, and Ip* is the value of the ionization potential after correction using the substituent constant. a is the number of substituents bonded to the o-position relative to the amino group. b is the number of substituents bonded to the m-position relative to the amino group. c is the number of substituents bonded to the p-position relative to the amino group. Es(AMD) is a steric parameter evaluated from the acid hydrolysis reaction rate of ortho-substituted benzamide. σm is the substituent constant when bonded to the m-position among Hammett's substituent constants. σp is the substituent constant when bonded to the p-position among Hammett's substituent constants.

[0408] <Calculation of Ip*> Amine compound (B １ -1) and amine compound (B １ The Ip* of the amine compound (B-2) was calculated using density functional theory (DFT) calculations according to the following procedure. [Calculation of ionization potential] １ -1) and amine compound (B １For each compound of (B-2), the ionization potential was calculated under the following conditions. Initial structure creation Functional / basis function: B3LYP / 6-31G(d) Structure optimization, vibrational analysis, ΔSCF calculation (ionization potential) Software: Gaussian16 Functional / basis function: ωB97XD / 6-31G(d) Charge analysis: Mulliken, ESP, NPA ΔSCF: Calculated under the condition of charge +1 using the structure after structure optimization [Calculation of Ip*] Amine compound (B １ -1) and amine compound (B １ The ionization potential value of each amine compound obtained by the above calculation was corrected using the substituent constant of the substituent possessed by each compound of formula (2) above to obtain Ip*.

[0409] Table 3 below shows the substituent constants Es, σm, and σp used for the correction.

[0410]

[0411] The amine compound (B １ -1)), (amine compound (B １ For each of the amine compounds described in Item 1-2), the uncorrected Ip in formula (II), the correction coefficient shown as an absolute value in formula (II), and the corrected Ip* are shown in Table 4 below.

[0412]

[0413] (Inorganic filler (D １ ) SE203G-SEJ (spherical fused silica, volume average particle size 0.5 μm, manufactured by Admatechs Co., Ltd.)

[0414] (Curing agent (C １ )) The curing agent (C １) is described below. <Synthesis Example 1-1> After replacing the air in a 500 mL four-neck flask equipped with a reflux condenser and a stirring blade with nitrogen, 20 g of 1-butanol and 0.05 mol of 4,4'-diaminodiphenyl sulfone (4DAS) were added and the flask was heated until the internal temperature reached 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 completed, the reaction solution was stirred while being heated at 120°C for 6 hours to complete the reaction. Using an evaporator, the temperature was kept at 80°C and the pressure was kept at 15 mmHg or less, and 1-butanol was distilled off from the resulting solution over 2 hours, leaving a curing agent for epoxy resins (C １ The epoxy resin curing agent (C-(1)) was obtained. １ -(1)) includes an amine adduct in which one molecule of 2-ethylhexyl glycidyl ether (2-EH), a reactive compound, is added to one molecule of 4,4'-diaminodiphenyl sulfone (4DAS), an aromatic amine compound, and an amine adduct in which two molecules of the reactive compound are added.

[0415] Synthesis Example 1-2 Synthesis and purification were carried out under the same conditions as in Synthesis Example 1-1, except that 0.03 mol of 2-ethylhexyl glycidyl ether (2-EH) was changed to 0.035 mol of butyl glycidyl ether (BGE), to obtain a curing agent for epoxy resin (C １ Here, the obtained epoxy resin curing agent (C １ -(2)) includes an amine adduct 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 (4DAS), and an amine adduct in which two molecules of the reactive compound are added.

[0416] Synthesis Example 1-3 Synthesis and purification were carried out under the same conditions as in Synthesis Example 1-1, except that 4,4'-diaminodiphenyl sulfone (4DAS) 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 １The resulting amine adduct (C １ -(3)) includes an amine adduct 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-aminophenyl-4'-aminobenzoate (APAB), and an amine adduct in which two molecules of the reactive compound are added.

[0417] Synthesis Example 1-4 Synthesis and purification were carried out under the same conditions as in Synthesis Example 1-3, except that 2-ethylhexyl glycidyl ether was changed to butyl glycidyl ether, to obtain an amine adduct (C １ The resulting amine adduct (C １ -(4)) includes an amine adduct 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), and an amine adduct in which two molecules of the reactive compound are added.

[0418] Synthesis Example 1-5 Synthesis and purification were carried out under the same conditions as in Synthesis Example 1-1, except that 4,4'-diaminodiphenyl sulfone (4DAS) was changed to 1,3-bis(3-aminophenoxy)benzene (TPE-M), to obtain an amine adduct (C １ The resulting amine adduct (C １ -(5)) includes an amine adduct 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), and an amine adduct in which two molecules of the reactive compound are added to one molecule of the aromatic amine compound 1,3-bis(3-aminophenoxy)benzene (TPE-M).

[0419] Synthesis Example 1-6 Synthesis and purification were carried out under the same conditions as in Synthesis Example 1-1, except that 4,4'-diaminodiphenyl sulfone (4DAS) was changed to Kayahard (registered trademark) AA and 2-ethylhexyl glycidyl ether (2-EH) was changed from 0.03 mol to 0.04 mol, to obtain an amine adduct (C １ The resulting amine adduct (C１ -(6)) includes an amine adduct in which one molecule of 2-ethylhexyl glycidyl ether (2-EH), a reactive compound, is added to one molecule of Kayahard (registered trademark) AA, an aromatic amine compound, and an amine adduct in which two molecules of the reactive compound are added to one molecule of Kayahard (registered trademark) AA.

[0420] Synthesis Example 1-7 Synthesis and purification were carried out under the same conditions as in Synthesis Example 1-6, except that 2-ethylhexyl glycidyl ether (2-EH) was changed to phenyl glycidyl ether (ph-GE), to obtain an amine adduct (C １ The resulting amine adduct (C １ -(7)) includes an amine adduct in which one molecule of phenyl glycidyl ether (ph-GE), a reactive compound, is added to one molecule of Kayahard (registered trademark) AA, an aromatic amine compound, and an amine adduct in which two molecules of the reactive compound are added.

[0421] Synthesis Example 1-8 Synthesis and purification were carried out under the same conditions as in Synthesis Example 1-1, except that 4,4'-diaminodiphenyl sulfone (4DAS) 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 (C １ The resulting amine adduct (C １ -(8)) includes an amine adduct in which one molecule of 2-ethylhexyl glycidyl ether (2-EH), a reactive compound, is added to one molecule of Ethacure (registered trademark) 100 Plus, an aromatic amine compound, and an amine adduct in which two molecules of the reactive compound are added.

[0422] Synthesis Example 1-9 Synthesis and purification were carried out under the same conditions as in Synthesis Example 1-8, except that 0.025 mol of 2-ethylhexyl glycidyl ether (2-EH) was changed to 0.03 mol of butyl glycidyl ether (BGE), to obtain an amine adduct (C １ The resulting amine adduct (C １-(9)) includes an amine adduct in which one molecule of butyl glycidyl ether (BGE), a reactive compound, is added to one molecule of Ethacure (registered trademark) 100 Plus, an aromatic amine compound, and an amine adduct in which two molecules of the reactive compound are added.

[0423] Synthesis Example 1-10 Synthesis and purification were carried out under the same conditions as in Synthesis Example 1-8, except that 0.025 mol of 2-ethylhexyl glycidyl ether (2-EH) was changed to 0.035 mol of phenyl glycidyl ether (ph-GE), to obtain an amine adduct (C １ The resulting amine adduct (C １ -(10)) includes an amine adduct in which one molecule of phenyl glycidyl ether (ph-GE), a reactive compound, is added to one molecule of Ethacure (registered trademark) 100 Plus, an aromatic amine compound, and an amine adduct in which two molecules of the reactive compound are added.

[0424] The components and reaction ratios used in Synthesis Examples 1-1 to 1-10 are shown in Table 5. In Table 5, the structures of the aromatic amines are shown in the following formulas (2) and (3).

[0425]

[0426] (In formula (2), R ２ and R ３ each independently represents a monovalent organic group having 1 to 20 carbon atoms or a halogen atom, c and d each independently represents an integer of 0 to 4, and X represents a divalent organic group or a single bond.

[0427]

[0428] (In formula (3), R ４ represents a monovalent organic group having 1 to 20 carbon atoms or a halogen atom, and e is an integer of 1 to 4.

[0429]

[0430] (Curing accelerator (E １)) <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, and after completion of the dropwise 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 distill off the by-produced 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 the compounds (E-1A) and (E-1B) are as follows:

[0431]

[0432] <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 completion of the addition, the mixture was stirred for 4 hours while maintaining the temperature at 90°C, and the reaction was completed. The resulting reaction solution was concentrated under reduced pressure at 80°C to remove the by-product alcohol and unreacted raw materials, yielding Compound (E-1C) as a liquid product. The structure of Compound (E-1C) is shown below.

[0433]

[0434] <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 completion of the addition, the mixture was stirred for 4 hours while maintaining the temperature at 90°C, and the reaction was completed. The resulting reaction solution was concentrated under reduced pressure at 80°C to remove the by-product alcohol and unreacted raw materials, yielding a liquid product, compound (E-1D), represented by formula (E-1D) below. The structure of compound (E-1D) is shown below. The structure of compound (E-1D) is the same as that of compound (E-1A).

[0435]

[0436] [Examples 1-1 to 1-35], [Comparative Examples 1-1 to 1-4] The components shown in Tables 6 to 11 were placed in a plastic stirring vessel in the amounts shown in the tables, and the mixture was stirred and mixed using a planetary centrifugal mixer ("ARE-310" (trade name) manufactured by Thinky Corporation) and then kneaded using a three-roll mill to prepare epoxy resin compositions. In Examples 1-1 to 1-35 and Comparative Examples 1-1 to 1-4, the epoxy resin (A １ The amine compound (B) was mixed and stirred in advance and then charged into a plastic stirring vessel. The solid resin was heated and dissolved, then stirred, and then charged into a plastic stirring vessel. １ -1), (B １ -2) and a hardener (C １ ) were heated, dissolved, and stirred in advance, and then charged into a plastic stirring vessel. Each of the obtained epoxy resin compositions was poured into a Teflon mold and heated at 165°C for 2 hours to produce a cured product. The evaluation results of the epoxy resin compositions and cured products obtained in Examples 1-1 to 1-35 and Comparative Examples 1-1 to 1-4 are shown in Tables 6 to 11.

[0437]

[0438]

[0439]

[0440]

[0441]

[0442]

[0443] As shown in Tables 6 to 11, all of the epoxy resin compositions of the Examples achieved both stability at high temperatures (100°C) and high cure rates. In contrast, Comparative Example 1, which contained only one curing agent, demonstrated stability at high temperatures (100°C), but had a low cure rate and failed to produce a cured product. Materials with poor curability like this cannot be used as encapsulants. Furthermore, Comparative Examples 1-2, which contained an epoxy resin with a high proportion of aromatic rings, demonstrated a high cure rate and produced a cured product, but exhibited poor stability at high temperatures (100°C) and a high high-temperature modulus. When such materials are used as encapsulants, maintaining them at high temperatures for long periods during filling not only deteriorates dischargeability, but also increases the likelihood of cracking and other problems occurring when the semiconductor retains heat after encapsulation, leading to reduced reliability. The resin compositions of the Examples are suitable for use as encapsulants, particularly underfill materials used to encapsulate semiconductor chips.

[0444] [Second Example] [Methods for measuring and evaluating physical properties and characteristics of epoxy resin compositions] The physical properties and characteristics of the cured products of the epoxy resin compositions prepared in the examples and comparative examples described below were measured as follows.

[0445] (Measurement and Evaluation of Intensity Ratio of IR Spectrum) The epoxy resin composition was cured at 165°C for 2 hours, and the intensity ratio (Ia / Ib) of the IR spectrum of the cured product was measured by the following method. Apparatus: LUMOS microscopic FT-IR apparatus (manufactured by Bruker Japan Co., Ltd.) Conditions: Attenuated Total Reflection (Ge) Incident angle: 30° Aperture size: 124 x 124 µm Resolution: 4 cm －１ Accumulation count: 64 times Contact pressure: High Measurement range: 600 to 5000 cm －１ Spectral vertical axis: absorbance <Procedure> 1. 2000-2500 cm－１ Draw a baseline based on this. 2. 1,450-1,550 cm －１ Normalize with the maximum peak present in the range of 3.1,420 to 1,440 cm －１ 4. Read the maximum peak intensity in the range of 1,420 to 1,440 cm of the IR spectrum. －１ The maximum peak intensity present in the range of Ia, 1,450 to 1,550 cm －１ The peak intensity ratio was calculated from the following formula, where Ib was the maximum peak intensity present in the range. Peak intensity ratio=Ia / Ib <Evaluation criteria> The peak intensity ratios calculated as described above were evaluated according to the following criteria. A: Ia / Ib was 0.24 or more and 0.4 or less. B: Ia / Ib was less than 0.24 and more than 0.4.

[0446] (Three-point bending evaluation (toughness)) The epoxy resin composition was cured at 165°C for 2 hours, and the cured product was cut into a size of 35 x 5 x 2 mm. Testing was carried out at a support distance of 20 mm and a movement speed of 1 mm / min. A graph was drawn with bending stress on the vertical axis and strain on the horizontal axis, and the area up to the strain value at which the sample broke was taken as toughness. Ten samples were measured, and the average toughness was adopted. <Evaluation criteria> A: The toughness value was 500 or more. B: The toughness value was 300 or more but less than 500. C: The toughness value was less than 300.

[0447] (Measurement and Evaluation of Coefficient of Linear Expansion (CTE)) An epoxy resin composition was cured at 165°C for 2 hours, and the cured product was cut into a size of 5 mm x 5 mm to prepare a test specimen. Using the test specimen and a thermomechanical analyzer (trade name: TMA450, manufactured by TA Instruments) in compression mode, the temperature was raised from -30 to 250°C at 5°C / min, then cooled to -30°C, and again raised to 250°C at 5°C / min to measure. The slope of the tangent line from 10 to 30°C of the second measurement result was taken as the CTE, and the result was evaluated according to the following criteria. <Evaluation Criteria> A: The CTE was less than 30 ppm / K. B: The CTE was 30 ppm / K or more but less than 35 ppm / K. C: The CTE was 35 ppm / K or more.

[0448] [Preparation of Epoxy Resin Compositions] Epoxy resin compositions were prepared in Examples 2-1 to 2-35 and Comparative Examples 2-1 and 2-2 described below. The materials used in preparing the epoxy resin compositions are listed below. The abbreviations for the components used in the examples and comparative examples have the following meanings:

[0449] (Epoxy Resins) EXA-850CRP: (Bisphenol A type liquid epoxy resin, EPICLON (registered trademark) EXA-850CRP (trade name), 185 g / eq, manufactured by DIC Corporation) EXA-830CRP: (Bisphenol F type liquid epoxy resin, EPICLON (registered trademark) EXA-830CRP (trade name), 162 g / eq, manufactured by DIC Corporation) jER (registered trademark) 630LSD: (trade name, aminophenol type epoxy resin, 95 g / eq, manufactured by Mitsubishi Chemical Corporation) HP4032D: (naphthalene type epoxy resin, EPICLON (registered trademark) HP4032D (trade name), 141 g / eq, manufactured by DIC Corporation) Epoxy of Production Example 1: (Epoxy resin described in Production Example 1 of Japanese Patent No. 6125775, 371 g / eq) Epoxy of Production Example 2: (epoxy resin described in Production Example 2 of Japanese Patent No. 6125775, 252 g / eq) Epoxy of Production Example 3: (epoxy resin described in Production Example 3 of Japanese Patent No. 6125775, 447 g / eq) jER (registered trademark) 604: (trade name, diaminodiphenylmethane type epoxy resin, 117 g / eq, manufactured by Mitsubishi Chemical Corporation) YX4000H: (trade name, tetramethylbiphenol type solid epoxy resin, 186 g / eq, manufactured by Mitsubishi Chemical Corporation) BEO-60E: (trade name, bisphenol A bis(triethylene glycol glycidyl ether) ether, 366 g / eq, manufactured by New Japan Chemical Co., Ltd.) PG-100: (trade name, fluorene type epoxy resin, 250 g / eq, manufactured by Osaka Gas Chemicals Co., Ltd.) EG-200: (Product name: fluorene-type epoxy resin, 288 g / eq, manufactured by Osaka Gas Chemicals Co., Ltd.)

[0450] (Amine-based curing agent A ２-1) 4DAS: 4,4'-diaminodiphenyl sulfone APAB: 4-aminophenyl-4'-aminobenzoate TPE-M: 1,3-bis(3-aminophenoxy)benzene Kayahard (registered trademark) AA: curing agent containing 3,3'-diethyl-4,4'-diaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd.) DETDA: Ethacure (registered trademark) 100 Plus (+): curing agent containing diethyltoluenediamine (manufactured by Mitsui Chemicals Fine Co., Ltd.) MDEA: 4,4'-methylenebis(2,6-diethylaniline) (manufactured by Kumiai Chemical Industry Co., Ltd.) MED-J: 4,4'-methylenebis(2-ethyl-6-methylaniline) (manufactured by Kumiai Chemical Industry Co., Ltd.) TEBDA: 2,4,6-triethyl-1,3-benzenediamine

[0451] (Amine-based curing agent A ２ -2) DMTDA: Ethacure (registered trademark) 300: a curing agent containing diethylthiotoluenediamine (manufactured by Mitsui Fine Chemicals, Inc.) TTBDA: 2,4,6-tris(methylthio)-1,3-benzenediamine MTBDA: 2-methyl-4,5,6-tris(methylthio)-1,3-benzenediamine

[0452] (Inorganic filler (C ２ ) SE203G-SEJ (spherical fused silica, volume average particle size 0.5 μm, manufactured by Admatechs Co., Ltd.)

[0453] (Epoxy resin curing agent (B ２ )) The curing agent (B ２ Synthesis Example 2-1: After replacing the air in a 500 mL four-neck flask equipped with a reflux condenser and a stirring blade with nitrogen, 20 g of 1-butanol and an amine-based curing agent (A ２0.05 mol of 4,4'-diaminodiphenyl sulfone (4DAS), a compound used in the reaction of 4,4'-diaminodiphenyl sulfone (4DAS), was added and the mixture was heated until the internal temperature reached 120°C. Then, using a dropping funnel, 0.03 mol of 2-ethylhexyl glycidyl ether (2-EH), a reactive compound, was added dropwise over 30 minutes. After the dropwise addition was completed, the reaction solution was heated at 120°C for 6 hours while stirring, to complete the reaction. Using an evaporator, the temperature was kept at 80°C and the pressure at 15 mmHg or less, and 1-butanol was distilled off from the resulting solution over 2 hours, leaving a curing agent for epoxy resin (B ２ Here, the obtained epoxy resin curing agent (B ２ -1-1) is an aromatic amine compound (A ２ An amine adduct compound (A-1) in which one molecule of 4,4'-diaminodiphenyl sulfone (4DAS) is added with one molecule of 2-ethylhexyl glycidyl ether (2-EH), a reactive compound, is obtained. ２ -1-1), and aromatic amine compounds (A ２ An aromatic amine adduct (A-1) in which two or more molecules of a reactive compound are added to one molecule of the aromatic amine adduct (A-1) ２ -1-2X).

[0454] 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 the reactive compound 2-ethylhexyl glycidyl ether (2-EH) was changed to 0.035 mol of the reactive compound butyl glycidyl ether (BGE), to obtain an epoxy resin curing agent (B ２ The epoxy resin curing agent (B-1-2) was obtained. ２ -1-2) is an aromatic amine compound (A ２ An amine adduct compound (A-1) in which one molecule of 4,4'-diaminodiphenyl sulfone (4DAS) is added with one molecule of butyl glycidyl ether (BGE), a reactive compound, is obtained. ２ -1-1), and aromatic amine compounds (A ２ An aromatic amine adduct (A-1) in which two or more molecules of a reactive compound are added to one molecule of the aromatic amine adduct (A-1) ２ -1-2X).

[0455] Synthesis Example 2-3 Aromatic amine compound (A ２ Synthesis and purification were carried out under the same conditions as in Synthesis Example 2-1, except that 4,4'-diaminodiphenyl sulfone (4DAS) in Example 2-1 was changed to 4-aminophenyl-4'-aminobenzoate (APAB), and the reactive compound 2-ethylhexyl glycidyl ether (2-EH) was changed from 0.03 mol to 0.05 mol, to obtain an amine adduct (B ２ The resulting amine adduct (B ２ -2-1) is an aromatic amine compound (A ２ An amine adduct compound (A-1) in which one molecule of 4-aminophenyl-4'-aminobenzoate (APAB) is added with one molecule of 2-ethylhexyl glycidyl ether (2-EH), a reactive compound, is obtained. ２ -1-1), and aromatic amine compounds (A ２ An aromatic amine adduct (A-1) in which two or more molecules of a reactive compound are added to one molecule of the aromatic amine adduct (A-1) ２ -1-2X).

[0456] Synthesis Example 2-4 Synthesis and purification were carried out under the same conditions as in Synthesis Example 3, except that the reactive compound 2-ethylhexyl glycidyl ether was changed to the reactive compound butyl glycidyl ether, to obtain an amine adduct (B ２ The resulting amine adduct (B-2-2) was obtained. ２ -2-2) is an aromatic amine compound (A ２ An amine adduct compound (A-1) is obtained by adding one molecule of butyl glycidyl ether (BGE), a reactive compound, to one molecule of 4-aminophenyl-4'-aminobenzoate (APAB). ２ -1-1) and an aromatic amine compound (A ２ An aromatic amine adduct (A-1) in which two or more molecules of a reactive compound are added to one molecule of the aromatic amine adduct (A-1) ２ -1-2X).

[0457] Synthesis Example 2-5: Aromatic amine compound (A ２Synthesis and purification were carried out under the same conditions as in Synthesis Example 2-1, except that 4,4'-diaminodiphenyl sulfone (4DAS) in Example 2-1 was replaced with 1,3-bis(3-aminophenoxy)benzene (TPE-M), to obtain an amine adduct (B ２ The resulting amine adduct (B-3) was ２ -3) is an aromatic amine compound (A ２ An amine adduct compound (A-1) in which one molecule of 1,3-bis(3-aminophenoxy)benzene (TPE-M) is added with one molecule of 2-ethylhexyl glycidyl ether (2-EH), a reactive compound, is obtained. ２ -1-1), and aromatic amine compounds (A ２ An aromatic amine adduct (A-1) in which two or more molecules of a reactive compound are added to one molecule of the aromatic amine adduct (A-1) ２ -1-2X).

[0458] Synthesis Example 2-6: Aromatic amine compound (A ２ Synthesis and purification were carried out under the same conditions as in Synthesis Example 2-1, except that 4,4'-diaminodiphenyl sulfone (4DAS) used as the amine adduct (B-1) was changed to Kayahard (registered trademark) AA, and the reactive compound 2-ethylhexyl glycidyl ether (2-EH) was changed from 0.03 mol to 0.04 mol. ２ The resulting amine adduct (B ２ -4-1) is an aromatic amine compound (A ２ An amine adduct compound (A-1) in which one molecule of Kayahard (registered trademark) AA is added with one molecule of 2-ethylhexyl glycidyl ether (2-EH), a reactive compound, is obtained. ２ -1-1), and aromatic amine compounds (A ２ An aromatic amine adduct (A-1) in which two or more molecules of a reactive compound are added to one molecule of the aromatic amine adduct (A-1) ２ -1-2X).

[0459] Synthesis Example 2-7 Synthesis and purification were carried out under the same conditions as in Synthesis Example 2-6, except that the reactive compound 2-ethylhexyl glycidyl ether (2-EH) was changed to the reactive compound phenyl glycidyl ether (ph-GE), to obtain an amine adduct (B２ The resulting amine adduct (B ２ -4-2) is an aromatic amine compound (A ２ An amine adduct compound (A-1) in which one molecule of Kayahard (registered trademark) AA is added with one molecule of phenyl glycidyl ether (ph-GE), which is a reactive compound. ２ -1-1), and aromatic amine compounds (A ２ An aromatic amine adduct (A-1) in which two or more molecules of a reactive compound are added to one molecule of the aromatic amine adduct (A-1) ２ -1-2X).

[0460] Synthesis Example 2-8 Aromatic amine compound (A ２ Synthesis and purification were carried out under the same conditions as in Synthesis Example 2-1, except that 4,4'-diaminodiphenyl sulfone (4DAS) used as the amine adduct (B-1) was replaced with Ethacure (registered trademark) 100 Plus, and the reactive compound 2-ethylhexyl glycidyl ether (2-EH) was replaced with 0.025 mol instead of 0.03 mol. ２ The resulting amine adduct (B ２ -5-1) is an aromatic amine compound (A ２ An amine adduct compound (A-1) in which one molecule of Ethacure (registered trademark) 100 Plus is added with one molecule of 2-ethylhexyl glycidyl ether (2-EH), a reactive compound, is obtained. ２ -1-1), and aromatic amine compounds (A ２ An aromatic amine adduct (A-1) in which two or more molecules of a reactive compound are added to one molecule of the aromatic amine adduct (A-1) ２ -1-2X).

[0461] Synthesis Example 2-9 Synthesis and purification were carried out under the same conditions as in Synthesis Example 2-8, except that 0.025 mol of the reactive compound 2-ethylhexyl glycidyl ether (2-EH) was changed to 0.03 mol of the reactive compound butyl glycidyl ether (BGE). ２ The resulting amine adduct (B ２ -5-2) is an aromatic amine compound (A ２An amine adduct compound (A-1) in which one molecule of Ethacure (registered trademark) 100 Plus is added with one molecule of butyl glycidyl ether (BGE), a reactive compound. ２ -1-1), and aromatic amine compounds (A ２ An aromatic amine adduct (A-1) in which two or more molecules of a reactive compound are added to one molecule of the aromatic amine adduct (A-1) ２ -1-2X).

[0462] Synthesis Example 2-10 Synthesis and purification were carried out under the same conditions as in Synthesis Example 2-8, except that 0.025 mol of the reactive compound 2-ethylhexyl glycidyl ether (2-EH) was changed to 0.035 mol of the reactive compound phenyl glycidyl ether (ph-GE), to obtain an amine adduct (B ２ The resulting amine adduct (B ２ -5-3) is an aromatic amine compound (A ２ An amine adduct compound (A-1) in which one molecule of Ethacure (registered trademark) 100 Plus is added with one molecule of phenyl glycidyl ether (ph-GE), which is a reactive compound. ２ -1-1), and aromatic amine compounds (A ２ An aromatic amine adduct (A-1) in which two or more molecules of a reactive compound are added to one molecule of the aromatic amine adduct (A-1) ２ -1-2X).

[0463] The components, reaction ratios, and LC-MS peak area ratios of each component used in the above-mentioned Synthesis Examples 2-1 to 2-10 are shown in Table 13. The amine-based curing agent (A ２ -1), aromatic amine adduct (A ２ -1-1), and aromatic amine adducts (A ２ The LC-MS peak area ratios of the compounds (-1-2X) ​​were analyzed as follows.

[0464] [Analysis of Components in Epoxy Resin Curing Agent] The method for analyzing each component in the epoxy resin curing agent is as follows. The curing agent prepared 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.

[0465] LC: Apparatus: Ultra high performance liquid chromatography (UPLC, manufactured by Waters) Column: ACQUITY UPLC BEH C8 1.7 μm (2.1 mm I.D. × 50 mm, manufactured by Waters) Detection: Absorbance detector (PDA, 200-400 nm) Flow rate: 0.3 mL / min Mobile phase: A = water (containing 0.1% formic acid) B = acetonitrile (containing 0.1% formic acid) Injection volume: 0.2 μL

[0466]

[0467] MS: Apparatus: Mass spectrometer (Synapt G2, manufactured by Waters) Ionization: Electron spray method (ESI+) Measurement range: m / z 50 to 2000

[0468] The peak areas of the PDA chromatogram at 300 nm obtained by the LC-MS measurement were determined, and the amine-based curing agent (A) was calculated from the peak area ratio according to the following calculation formula (2-1). ２ -1), aromatic amine adduct (A ２ -1-1) and aromatic amine adduct (A ２ The peak area of ​​each of the aromatic amine compounds (A-1-2X) ​​was calculated. The ratio of each peak area was calculated from the sum of all the obtained peak areas using the following calculation formula (2-1): Ratio of aromatic amine compounds (%) = [(peak area of ​​amine curing agent) / {(peak area of ​​amine curing agent) + (aromatic amine adduct (A ２ -1-1)) + (peak area of ​​aromatic amine adduct (A ２ −1−2X) peak area) × 100...calculation formula (2-1)

[0469]

[0470] (Curing accelerator (D ２ )) <Synthesis of Compound (Mixture Containing D-A and D-B)> 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, and after completion of the dropwise addition, the reaction was carried out with stirring 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 distill off the by-product alcohol and unreacted raw materials, and a liquid product compound [mixture containing compound (D-A) and compound (D-B)] was obtained. The structures of the compound (DA) and the compound (DB) are as follows:

[0471]

[0472] <Synthesis of Compound (D-C)> 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 completion of the addition, the mixture was stirred for 4 hours while maintaining the temperature at 90°C, and the reaction was completed. The resulting reaction solution was concentrated under reduced pressure at 80°C to remove the by-product alcohol and unreacted raw materials, yielding Compound (D-C) as a liquid product. The structure of Compound (D-C) is shown below.

[0473]

[0474] <Synthesis of Compound (D-D)> 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 completion of the addition, the reaction was continued for 4 hours while stirring 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 distill off the by-product alcohol and unreacted raw materials, yielding a liquid product, compound (D-D), represented by formula (D-D) below. The structure of compound (D-D) is as follows. The structure of compound (D-D) is the same as that of compound (D-A).

[0475]

[0476] Examples 2-1 to 2-35 and Comparative Examples 2-1 to 2-2 The components shown in Tables 14 to 18 were placed in a plastic stirring vessel in the amounts shown in the tables, and the mixture was stirred and mixed using a planetary centrifugal mixer ("ARE-310" (trade name) manufactured by Thinky Corporation) and then kneaded using a three-roll mill to prepare resin compositions. In Examples 2-1 to 2-35 and Comparative Examples 2-1 and 2-2, the epoxy resins were mixed and stirred in advance and then charged into the plastic stirring vessel. In addition, solid resins were heated and dissolved, stirred, and then charged into the plastic stirring vessel. The amine-based curing agent (A ２ -1), amine-based curing agent (A ２ -2), hardener (B ２ ) were heated, dissolved, and stirred in advance and then charged into a plastic stirring vessel. A resin composition was prepared in this manner, and a cured product was prepared using the resin composition. The evaluation results of Examples 2-1 to 2-35 and Comparative Examples 2-1 to 2-2 are shown in Tables 14 to 18 below.

[0477]

[0478]

[0479]

[0480]

[0481]

[0482] As shown in Tables 14 to 18, all of the cured products of the Examples had IR peak intensities of 0.24 or higher and exhibited high toughness values. Such materials can be expected to have high reliability. In contrast, Comparative Example 1, which had an IR peak intensity of less than 0.24, exhibited a low toughness value. When such materials are used, cracks and other problems tend to occur due to stress, resulting in reduced reliability. Comparative Example 2-2, which did not contain an inorganic filler, exhibited a high toughness value despite having an IR peak intensity of less than 0.24, but because it did not contain an inorganic filler, it exhibited a high CTE value. When such materials are used, the CTE mismatch during thermal expansion and contraction increases the applied stress, resulting in reduced reliability. The cured products of the Examples can be suitably used as encapsulants, particularly underfill materials used to encapsulate semiconductor chips, etc.

[0483] [Third Example] [Methods for measuring and evaluating physical properties and characteristics of epoxy resin compositions] The physical properties and characteristics of the epoxy resin compositions prepared in the examples and comparative examples described below were measured as follows.

[0484] (Method for Evaluating Viscosity Stability at 100°C (High Temperature)) The viscosity stability of the epoxy resin composition at 100°C was evaluated by dropping 0.5 mL of the epoxy resin composition obtained in each of the Examples and Comparative Examples onto a measurement plate. Five minutes and 60 minutes after the sample temperature reached 100°C, the viscosity was measured using a rheometer (HAAKE (registered trademark) MARS (trade name), manufactured by Thermo Scientific) at a constant measurement temperature (100°C) in oscillation mode (f = 1 Hz) (measurement conditions: aluminum cone plate R = 35 mm, shear rate 20 ( / sec)). The viscosity after 5 minutes was designated "η1" and the viscosity after 60 minutes was designated "η2", and the value calculated by η2 / η1 was determined as the viscosity increase ratio. The obtained viscosity increase ratio was evaluated according to the following evaluation criteria. "η2" is the viscosity after standing at 100°C for 60 minutes. The lower the viscosity increase ratio, 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.

[0485] (Cure rate when cured at 165°C) The cure rate when the epoxy resin composition was cured at 165°C was measured by the following method. The epoxy 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 a rate of 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 cure rate was calculated based on the change in heat generated in the same temperature range. The calculation formula is as follows: Initial heat generation amount A: DSC peak heat generation amount of the epoxy resin composition Post-curing heat generation amount B: DSC peak heat generation amount of the epoxy resin composition after heating Cure rate (%) = 100 × (initial heat generation amount A - post-curing heat generation amount B) ÷ initial heat generation amount A The obtained cure rate was evaluated according to the following evaluation criteria. <Evaluation criteria> A: The cure rate was 99% or more. B: The cure rate was 95% or more but less than 99%. C: The cure rate was less than 95%.

[0486] [Preparation of Epoxy Resin Compositions] Epoxy resin compositions were prepared in Reference Examples 3-1 to 3-13, Examples 3-14 to 3-15, Reference Examples 3-16 to 3-32, Example 3-33, Reference Examples 3-34 to 3-38, Example 3-39, Reference Example 3-40, Examples 3-41 to 3-44, and Comparative Examples 3-1 to 3-3, which will be described later. The materials used in preparing the epoxy resin compositions are listed below. The abbreviations for the components used in the examples and comparative examples have the following meanings.

[0487] (Epoxy Resins) EXA-850CRP: (Bisphenol A type liquid epoxy resin, EPICLON (registered trademark) EXA-850CRP (trade name), 185 g / eq, manufactured by DIC Corporation) EXA-830CRP: (Bisphenol F type liquid epoxy resin, EPICLON (registered trademark) EXA-830CRP (trade name), 162 g / eq, manufactured by DIC Corporation) jER (registered trademark) 630LSD: (trade name, aminophenol type epoxy resin, 95 g / eq, manufactured by Mitsubishi Chemical Corporation) HP4032D: (naphthalene type epoxy resin, EPICLON (registered trademark) HP4032D (trade name), 141 g / eq, manufactured by DIC Corporation) Epoxy of Production Example 1: (Epoxy resin described in Production Example 1 of Japanese Patent No. 6125775, 371 g / eq) Epoxy of Production Example 2: (epoxy resin described in Production Example 2 of Japanese Patent No. 6125775, 252 g / eq) Epoxy of Production Example 3: (epoxy resin described in Production Example 3 of Japanese Patent No. 6125775, 447 g / eq) jER (registered trademark) 604: (trade name, diaminodiphenylmethane type epoxy resin, 117 g / eq, manufactured by Mitsubishi Chemical Corporation) YX4000H: (trade name, tetramethylbiphenol type solid epoxy resin, 186 g / eq, manufactured by Mitsubishi Chemical Corporation) BEO-60E: (trade name, bisphenol A bis(triethylene glycol glycidyl ether) ether, 366 g / eq, manufactured by New Japan Chemical Co., Ltd.) PG-100: (trade name, fluorene type epoxy resin, 250 g / eq, manufactured by Osaka Gas Chemicals Co., Ltd.) EG-200: (Product name: fluorene-type epoxy resin, 288 g / eq, manufactured by Osaka Gas Chemicals Co., Ltd.)

[0488] (Amine-based curing agent A ３ -1: primary amine compound) 4DAS: 4,4'-diaminodiphenyl sulfone APAB: 4-aminophenyl-4'-aminobenzoate TPE-M: 1,3-bis(3-aminophenoxy)benzene Kayahard (registered trademark) AA: curing agent containing 3,3'-diethyl-4,4'-diaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd.) DETDA: Ethacure (registered trademark) 100 Plus (+): curing agent containing diethyltoluenediamine (manufactured by Mitsui Fine Chemicals, Inc.) MDEA: 4,4'-methylenebis(2,6-diethylaniline) (manufactured by Kumiai Chemical Industry Co., Ltd.) MED-J: 4,4'-methylenebis(2-ethyl-6-methylaniline) (manufactured by Kumiai Chemical Industry Co., Ltd.) TEBDA: 2,4,6-triethyl-1,3-benzenediamine

[0489] (Amine-based curing agent A ３ -2: Primary amine compound) DMTDA: Ethacure (registered trademark) 300: Curing agent containing diethylthiotoluenediamine (manufactured by Mitsui Fine Chemicals, Inc.) TTBDA: 2,4,6-tris(methylthio)-1,3-benzenediamine MTBDA: 2-methyl-4,5,6-tris(methylthio)-1,3-benzenediamine

[0490] The amine-based curing agent (A ３ -1)), (amine-based curing agent (A ３ For each of the amine compounds described in Item 1-2), Ip* was calculated using the following formula (II).

[0491]

[0492] In formula (II), Ip is the value of the ionization potential before correction, and Ip* is the value of the ionization potential after correction using the substituent constant. a is the number of substituents bonded to the o-position relative to the amino group. b is the number of substituents bonded to the m-position relative to the amino group. c is the number of substituents bonded to the p-position relative to the amino group. Es(AMD) is a steric parameter evaluated from the acid hydrolysis reaction rate of ortho-substituted benzamide. σm is the Hammett's substituent constant for the substituent bonded to the m-position. σp is the Hammett's substituent constant for the substituent bonded to the p-position.

[0493] <Calculation of Ip*> Amine-based curing agent (A ３ -1) and an amine-based curing agent (A ３ The Ip* of the amine-based curing agent (A-2) was calculated using density functional theory (DFT) calculations according to the following procedure. ３ -1) and an amine-based curing agent (A ３ For each compound in (A-2), the ionization potential was calculated under the following conditions. Initial structure creation Functional / basis function: B3LYP / 6-31G(d) Structure optimization, vibration analysis, ΔSCF calculation (ionization potential) Software: Gaussian16 Functional / basis function: ωB97XD / 6-31G(d) Charge analysis: Mulliken, ESP, NPA ΔSCF: Calculated under the condition of charge +1 using the structure after structure optimization [Calculation of Ip*] Amine-based curing agent (A ３ -1) and an amine-based curing agent (A ３ The ionization potential value of each amine-based curing agent obtained by the above calculation was corrected by the above formula (II) using the substituent constant of the substituent possessed by each compound of (2) to obtain Ip*.

[0494] Table 19 below shows the substituent constants Es, σm, and σp used for the correction.

[0495]

[0496] The amine-based curing agent (A ３ -1)), (amine-based curing agent (A ３For each of the amine compounds described in Item 1-2), the uncorrected Ip in formula (II), the correction coefficient shown as an absolute value in formula (II), and the corrected Ip* are shown in Table 2 below.

[0497]

[0498] (Amine-based hardener B ３ : secondary amine compound) MBDA: 4,4'-methylenebis[N-(sec-butyl)aniline] (manufactured by Kumiai Chemical Industry Co., Ltd.) DBPDA: N,N'-di-sec-butyl-1,4-phenylenediamine

[0499] (Inorganic filler (E ３ ) SE203G-SEJ (spherical fused silica, volume average particle size 0.5 μm, manufactured by Admatechs Co., Ltd.)

[0500] (Curing agent (C ３ Preparation of the curing agent (C) in the table ３ ) is described below. <Synthesis Example 3-1> After replacing the air in a 500 mL four-neck flask equipped with a reflux condenser and a stirring blade with nitrogen, 20 g of 1-butanol and 0.05 mol of 4,4'-diaminodiphenyl sulfone (4DAS) were added and the flask was heated until the internal temperature reached 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 completed, the reaction solution was stirred while being heated at 120°C for 6 hours to complete the reaction. Using an evaporator, the temperature was kept at 80°C and the pressure was kept at 15 mmHg or less, and 1-butanol was distilled off from the resulting solution over 2 hours, leaving a curing agent for epoxy resins (C ３ Here, the obtained epoxy resin curing agent (C-1) was ３ -1) is an amine adduct (C) in which one molecule of the aromatic amine compound 4,4'-diaminodiphenyl sulfone (4DAS) is added with one molecule of the reactive compound 2-ethylhexyl glycidyl ether (2-EH). ３ -2-1), and an amine adduct (C ３ -2-2X).

[0501] Synthesis Example 3-2 Synthesis and purification were carried out under the same conditions as in Synthesis Example 3-1, except that 0.03 mol of 2-ethylhexyl glycidyl ether (2-EH) was changed to 0.035 mol of butyl glycidyl ether (BGE), to obtain a curing agent for epoxy resin (C ３ Here, the obtained epoxy resin curing agent (C-2) was ３ -2) is an amine adduct (C) in which one molecule of the aromatic amine compound 4,4'-diaminodiphenyl sulfone (4DAS) is added with one molecule of the reactive compound butyl glycidyl ether (BGE). ３ -2-1), and an amine adduct (C ３ -2-2X).

[0502] Synthesis Example 3-3 Synthesis and purification were carried out under the same conditions as in Synthesis Example 3-1, except that 4,4'-diaminodiphenyl sulfone (4DAS) 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 ３ The resulting amine adduct (C-3) was ３ -3) is an amine adduct (C) in which one molecule of the aromatic amine compound 4-aminophenyl-4'-aminobenzoate (APAB) is added with one molecule of the reactive compound 2-ethylhexyl glycidyl ether (2-EH). ３ -2-1), and an amine adduct (C ３ -2-2X).

[0503] Synthesis Example 3-4 Synthesis and purification were carried out under the same conditions as in Synthesis Example 3-3, except that 2-ethylhexyl glycidyl ether was changed to butyl glycidyl ether, to obtain an amine adduct (C ３ The resulting amine adduct (C-4) was obtained. ３ -4) is an amine adduct (C) in which one molecule of the aromatic amine compound 4-aminophenyl-4'-aminobenzoate (APAB) is added with one molecule of the reactive compound butyl glycidyl ether (BGE).３ -2-1), and an amine adduct (C ３ -2-2X).

[0504] Synthesis Example 3-5 Synthesis and purification were carried out under the same conditions as in Synthesis Example 3-1, except that 4,4'-diaminodiphenyl sulfone (4DAS) was changed to 1,3-bis(3-aminophenoxy)benzene (TPE-M), to obtain an amine adduct (C ３ The resulting amine adduct (C-5) was ３ -5) is an amine adduct (C) in which one molecule of the aromatic amine compound 1,3-bis(3-aminophenoxy)benzene (TPE-M) is added with one molecule of the reactive compound 2-ethylhexyl glycidyl ether (2-EH). ３ -2-1), and an amine adduct (C ３ -2-2X).

[0505] Synthesis Example 3-6 Synthesis and purification were carried out under the same conditions as in Synthesis Example 3-1, except that 4,4'-diaminodiphenyl sulfone (4DAS) was changed to Kayahard (registered trademark) AA and 2-ethylhexyl glycidyl ether (2-EH) was changed from 0.03 mol to 0.04 mol, to obtain an amine adduct (C ３ The resulting amine adduct (C-6) was ３ -6) is an amine adduct (C) in which one molecule of the aromatic amine compound Kayahard (registered trademark) AA is added with one molecule of the reactive compound 2-ethylhexyl glycidyl ether (2-EH). ３ -2-1), and an amine adduct (C ３ -2-2X).

[0506] Synthesis Example 3-7 Synthesis and purification were carried out under the same conditions as in Synthesis Example 3-6, except that 2-ethylhexyl glycidyl ether (2-EH) was changed to phenyl glycidyl ether (ph-GE), to obtain an amine adduct (C ３ The resulting amine adduct (C-7) was ３-7) is an amine adduct (C) in which one molecule of the aromatic amine compound Kayahard (registered trademark) AA is added with one molecule of the reactive compound phenyl glycidyl ether (ph-GE). ３ -2-1), and an amine adduct (C ３ -2-2X).

[0507] Synthesis Example 3-8 Synthesis and purification were carried out under the same conditions as in Synthesis Example 3-1, except that 4,4'-diaminodiphenyl sulfone (4DAS) 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 (C ３ The resulting amine adduct (C-8) was ３ -8) is an amine adduct (C) in which one molecule of the aromatic amine compound Ethacure (registered trademark) 100 Plus is added with one molecule of the reactive compound 2-ethylhexyl glycidyl ether (2-EH). ３ -2-1), and an amine adduct (C ３ -2-2X).

[0508] Synthesis Example 3-9 Synthesis and purification were carried out under the same conditions as in Synthesis Example 3-8, except that 0.025 mol of 2-ethylhexyl glycidyl ether (2-EH) was changed to 0.03 mol of butyl glycidyl ether (BGE), to obtain an amine adduct (C ３ The resulting amine adduct (C-9) was ３ -9) is an amine adduct (C) in which one molecule of the aromatic amine compound Ethacure (registered trademark) 100 Plus is added with one molecule of the reactive compound butyl glycidyl ether (BGE). ３ -2-1), and an amine adduct (C ３ -2-2X).

[0509] Synthesis Example 3-10 Synthesis and purification were carried out under the same conditions as in Synthesis Example 3-8, except that 0.025 mol of 2-ethylhexyl glycidyl ether (2-EH) was changed to 0.035 mol of phenyl glycidyl ether (ph-GE), to obtain an amine adduct (C ３ The resulting amine adduct (C-10) was ３ -10) is an amine adduct (C) in which one molecule of the aromatic amine compound Ethacure (registered trademark) 100 Plus is added with one molecule of the reactive compound phenyl glycidyl ether (ph-GE). ３ -2-1), and an amine adduct (C ３ -2-2X).

[0510] The components used in Synthesis Examples 1 to 10, the reaction ratios, and the LC-MS peak area ratios of each component are shown in Table 22. In Table 22, formulas (4) and (5) are shown below.

[0511]

[0512] In formula (4), R ２ and R ３ each independently represents a monovalent organic group having 1 to 20 carbon atoms or a halogen atom; c and d each independently represent an integer of 0 to 4; and X represents a divalent organic group or a single bond.

[0513]

[0514] In formula (5), R ４ represents a monovalent organic group having 1 to 20 carbon atoms or a halogen atom, and e is an integer of 1 to 4.

[0515] In the column of LC-MS peak area ratio, "aromatic amine" indicates the ratio of aromatic amine calculated by the following calculation formula (3-1), and "aromatic amine adduct (C-2-1)" indicates the ratio of aromatic amine adduct (C-2-1) calculated by the calculation formula (3-1). ３ -2-1), and "aromatic amine adduct (C ３ -2-2X) is the aromatic amine adduct (C ３ -2-2X).

[0516] [Analysis of Components in Curing Agent] The method for analyzing each component in the curing agent is as follows. The amine adduct synthesized in the synthesis example was adjusted to a concentration of 10 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.

[0517] LC: Apparatus: Ultra high performance liquid chromatography (UPLC, manufactured by Waters) Column: ACQUITY UPLC BEH C8 1.7 μm (2.1 mm I.D. × 50 mm, manufactured by Waters) Detection: Absorbance detector (PDA, 200-400 nm) Flow rate: 0.3 mL / min Mobile phase: A = water (containing 0.1% formic acid) B = acetonitrile (containing 0.1% formic acid) Injection volume: 0.2 μL

[0518]

[0519] MS: Apparatus: Mass spectrometer (Synapt G2, manufactured by Waters) Ionization: Electron spray method (ESI+) Measurement range: m / z 50 to 2000

[0520] The peak areas of the PDA chromatogram at 300 nm obtained by the LC-MS measurement were determined, and the ratio of the peak areas was calculated according to the following formula (3-1). ３ -2-1) and aromatic amine adduct (C ３ The peak area of ​​each of the aromatic amines (C-2-2X) was calculated. The ratio of each peak area was calculated from the sum of all the peak areas obtained using the following calculation formula (3-1): Ratio of aromatic amine (%) = [(Aromatic amine peak area) / {(Aromatic amine peak area) + (Aromatic amine adduct (C ３ -2-1)) + (peak area of ​​aromatic amine adduct (C ３ −2−2X) peak area) × 100 (3-1)

[0521]

[0522] (Curing accelerator (D ３)) <Synthesis of Compound (Mixture Containing D-A and D-B)> 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, and after completion of the dropwise addition, the reaction was carried out with stirring 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 distill off the by-product alcohol and unreacted raw materials, and a liquid product compound [mixture containing compound (D-A) and compound (D-B)] was obtained. The structures of the compound (DA) and the compound (DB) are as follows:

[0523]

[0524] <Synthesis of Compound (D-C)> 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 completion of the addition, the mixture was stirred for 4 hours while maintaining the temperature at 90°C, and the reaction was completed. The resulting reaction solution was concentrated under reduced pressure at 80°C to remove the by-product alcohol and unreacted raw materials, yielding Compound (D-C) as a liquid product. The structure of Compound (D-C) is shown below.

[0525]

[0526] <Synthesis of Compound (D-D)> 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 completion of the addition, the reaction was continued for 4 hours while stirring 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 distill off the by-product alcohol and unreacted raw materials, yielding a liquid product, compound (D-D), represented by formula (D-D) below. The structure of compound (D-D) is as follows. The structure of compound (D-D) is the same as that of compound (D-A).

[0527]

[0528] [Reference Examples 3-1 to 3-13, Examples 3-14 to 3-15, Reference Examples 3-16 to 3-32, Example 3-33, Reference Examples 3-34 to 3-38, Example 3-39, Reference Example 3-40, Example 3-41 to 3-44, and Comparative Examples 3-1 to 3-3] Each of the components shown in Tables 23 to 28 was placed in a plastic stirring vessel in the amounts shown in the tables, and the mixture was stirred and mixed using a planetary centrifugal mixer ("ARE-310" (trade name) manufactured by Thinky Corporation) and then kneaded using a three-roll mill to prepare an epoxy resin composition. In the Examples, Reference Examples, and Comparative Examples, the epoxy resins were mixed and stirred in advance before being charged into the plastic stirring vessel. Furthermore, solid resins were heated and dissolved, stirred, and then charged into the plastic stirring vessel. The amine-based curing agent (A ３ -1), amine-based curing agent (A ３ -2), amine-based curing agent (B ３ ) were heated, dissolved, and stirred in advance and then charged into a plastic stirring vessel. The evaluation results of the resin compositions obtained in the Examples, Reference Examples, and Comparative Examples are shown in Tables 23 to 28.

[0529]

[0530]

[0531]

[0532]

[0533]

[0534]

[0535] As shown in the table, all of the resin compositions of the examples were able to achieve both stability at high temperatures (100°C) and a high curing rate. ３ Comparative Example 1, which contained only (A-1), showed stability at high temperatures (100°C), but the curing rate was low. Materials with poor curing properties like this cannot be used as encapsulants. ３ -2), (B ３ ), (D ３ Comparative Example 2, which did not contain any of the above, showed a high cure rate, but had poor stability at high temperatures (100°C). When such a material is used as an encapsulant, if it is kept at high temperatures for a long time during filling, the dischargeability deteriorates. The resin compositions of the examples can be suitably used as encapsulants, particularly as underfill materials used for encapsulating semiconductor chips, etc.

[0536] This application is based on Japanese patent applications (Patent Application Nos. 2024-115118, 2024-115122, and 2024-115111) filed with the Japan Patent Office on July 18, 2024, the contents of which are incorporated herein by reference.

[0537] The cured product of the present invention has industrial applicability as an encapsulant or constituent material for semiconductor chips and semiconductor packages.

Claims

1. A resin composition comprising an epoxy resin (A), an amine compound (B), and an inorganic filler (D), wherein the amine compound (B) comprises a compound represented by the following formula (1): (In formula (1), R １ represents a monovalent organic group having 1 to 20 carbon atoms or a halogen atom, a is an integer of 0 to 3, and b is an integer of 1 to 3.

2. The epoxy resin (A) is a glycidylamine type epoxy resin (A １ -1) and bisphenol-type epoxy resin (A １ -2), and the bisphenol-type epoxy resin (A １ The resin composition according to claim 1, wherein the molecular weight of the aromatic ring per molecule / the molecular weight of the molecule satisfies the following formula (I): 0.05≦(molecular weight of the aromatic ring per molecule / molecular weight of the molecule)≦0.4 (I) 3. The amine compound (B) is an amine compound (B) in which the value Ip* calculated from the following formula (II) is 6.0≦Ip*≦9.

7. １ -1), and an amine compound (B) in which the value Ip* calculated from the following formula (II) is 9.7<Ip*≦11.0: １ The resin composition according to claim 2, further comprising: (In formula (II), Ip is the value of the ionization potential before correction, and Ip* is the value of the ionization potential after correction using the substituent constant. a is the number of substituents bonded to the o-position relative to the amino group. b is the number of substituents bonded to the m-position relative to the amino group. c is the number of substituents bonded to the p-position relative to the amino group. Es(AMD) is a steric parameter evaluated from the acid hydrolysis reaction rate of ortho-substituted benzamide. σm is the Hammett's substituent constant for the substituent bonded to the m-position. σp is the Hammett's substituent constant for the substituent bonded to the p-position.) 4. The amine compound (B １ The resin composition according to claim 3, wherein -1) is a compound represented by the following formula (2) or (3): (In formula (2), R ２ and R ３ each independently represents a monovalent organic group having 1 to 20 carbon atoms or a halogen atom, c and d each independently represents an integer of 0 to 4, and X represents a divalent organic group or a single bond. (In formula (3), R ４ represents a monovalent organic group having 1 to 20 carbon atoms or a halogen atom, and e is an integer of 1 to 4.

5. The amine compound (B １ -1) and the amine compound (B １ amine adduct (C １ The resin composition according to claim 3, further comprising:

6. The glycidylamine type epoxy resin (A １ -1) and the bisphenol type epoxy resin (A １ The mass ratio of (A −2) is １ -1): (A １ The resin composition according to claim 2, wherein the ratio of the hydroxybenzoate to the hydroxybenzoate is 50:50 to 95:

5.

7. The amine compound (B １ -1) and the amine compound (B １ The mass ratio of (B −2) is １ -1): (B １ The resin composition according to claim 3, wherein the ratio of the hydroxyl group to the total weight of the resin composition is 10:90 to 90:

10.

8. A cured product of the resin composition according to claim 2.

9. The cured product of the resin composition has an infrared (IR) absorption spectrum of 1,420 to 1,440 cm －１ The maximum peak intensity Ia present in the region of 1,450 to 1,550 cm －１ The resin composition according to claim 1, wherein the following formula (i) is satisfied in relation to the maximum peak intensity Ia / Ib present in the region of 0.24≦Ia / Ib≦0.4 (i).

10. A cured product of the resin composition according to claim 9.

11. A structure comprising a first layer, a second layer, and a plurality of copper pillars connecting the first layer and the second layer, wherein the first layer and the second layer each comprise at least one material selected from the group consisting of resin, silicon, ceramics, compound semiconductor, and glass, wherein the distance between adjacent copper pillars among the plurality of copper pillars is 150 μm or less, and wherein a third layer is provided between the first layer and the second layer and in contact with each of the first layer and the second layer, and wherein the third layer is the cured product described in claim 10.

12. A primary amine compound (A) having a value Ip* calculated from the following formula (II) of 6.0≦Ip*≦9.7: ３ -1) and a secondary amine compound (B ３ ), and the primary amine compound (A ３ -1) is a compound represented by the following formula (4) or the following formula (5), and the secondary amine compound (B ３ ) is a compound represented by the following formula (6) or the following formula (7): (In formula (4), R ２ and R ３ each independently represents a monovalent organic group having 1 to 20 carbon atoms or a halogen atom, c and d each independently represents an integer of 0 to 4, and X represents a divalent organic group or a single bond. (In formula (5), R ４ represents a monovalent organic group having 1 to 20 carbon atoms or a halogen atom, and e is an integer of 1 to 4. (In formula (6), R ８ and R ９ each independently represents a monovalent organic group having 1 to 20 carbon atoms or a halogen atom; f and g each independently represent an integer of 0 to 4; X represents a divalent organic group or a single bond; R ６ and R ７ each independently represents a monovalent alkyl group, aryl group, or aralkyl group having 2 to 10 carbon atoms. (In formula (7), R １２ represents a monovalent organic group having 1 to 20 carbon atoms or a halogen atom, h is an integer of 1 to 4, and R １０ and R １１ each independently represents a monovalent alkyl group, aryl group, or aralkyl group having 2 to 10 carbon atoms. (In formula (II), Ip is the value of the ionization potential before correction, and Ip* is the value of the ionization potential after correction using the substituent constant. a is the number of substituents bonded to the o-position relative to the amino group. b is the number of substituents bonded to the m-position relative to the amino group. c is the number of substituents bonded to the p-position relative to the amino group. Es(AMD) is a steric parameter evaluated from the acid hydrolysis reaction rate of ortho-substituted benzamide. σm is the Hammett's substituent constant for the substituent bonded to the m-position. σp is the Hammett's substituent constant for the substituent bonded to the p-position.) 13. The primary amine compound (A ３ -1) and the secondary amine compound (B ３ 13. The curing agent according to claim 12, wherein the curing agent is a combination of the compound represented by formula (4) and the compound represented by formula (7), or a combination of the compound represented by formula (5) and the compound represented by formula (6).

14. The primary amine compound (A ３ -1) and the secondary amine compound (B ３ ) mass ratio is (A ３ -1): (B ３ 13. The curing agent according to claim 12, wherein the ratio of the hydroxybenzoates to the hydroxybenzoates is 75:25 to 5:

95.

15. The primary amine compound (A ３ Amine adduct (A-1) is a reaction product of a reactive compound having a functional group capable of reacting with ３ The curing agent according to claim 12, further comprising:

16. A nitrogen-containing compound (D) represented by any one of the following formulas (8) to (10): ３ The curing agent of claim 12 further comprising: (In formulas (8) to (10), R １３ each 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; R １４ and R １５ each independently represents an unsubstituted or substituted alkyl group, aryl group, or aralkyl group having 1 to 12 carbon atoms, or combines to form a heterocycle having 7 or less carbon atoms; R １６ R each independently represents a hydrogen atom or an n-valent organic group having 1 to 30 carbon atoms which may contain an oxygen atom; n represents an integer of 1 to 3. １７ represents a negatively charged nitrogen atom, and R １３ indicates a positively charged nitrogen atom.) 17. A resin composition comprising the curing agent according to claim 12 and an epoxy resin, wherein the mass ratio of the curing agent to the epoxy resin is curing agent:epoxy resin = 10:90 to 65:

35.

18. A cured product of the resin composition according to claim 17.

19. A sealing material comprising the cured product according to any one of claims 8, 10 and 18.

20. The encapsulant according to claim 19, which is an encapsulant for semiconductors.

21. An adhesive containing the resin composition according to any one of claims 1 to 7, 9, and 17.

22. A semiconductor package comprising the cured product according to any one of claims 8, 10 and 18.

23. A method for manufacturing a semiconductor package, comprising the step of manufacturing a semiconductor package using the resin composition according to any one of claims 1 to 7, 9, and 17.

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