Curing agent for epoxy resin, epoxy resin composition, sealing material, conductive material, thermally conductive material, insulating material, adhesive for camera module, adhesive for structure, matrix resin for fiber-reinforced plastic, impregnated fixing material, film-type solder resist, cured product of epoxy resin composition, semiconductor device, printed wiring board, semiconductor chip package, and electronic device

Abstract

Disclosed is a curing agent for an epoxy resin, the curing agent containing a reaction product of an epoxy compound and (C) a basic nitrogen-containing compound. The epoxy compound contains at least one compound that is selected from the group consisting of (A) an aliphatic epoxy compound and (B) an epoxy compound which has, as a partial structure, at least one structure that is selected from the group consisting of a tert-butylphenyl structure, a biphenyl structure, and an N,N-diglycidylaniline structure.

Description

Curing agents for epoxy resins, epoxy resin compositions, sealing materials, conductive materials, thermally conductive materials, insulating materials, adhesives for camera modules, structural adhesives, matrix resins for fiber-reinforced plastics, impregnating adhesives, film-type solder resists, cured products of epoxy resin compositions, semiconductor devices, printed wiring boards, semiconductor chip packages, and electronic devices

[0001] The present invention relates to a curing agent for epoxy resins, an epoxy resin composition, an encapsulating material, an electrically conductive material, a thermally conductive material, an insulating material, an adhesive for camera modules, a structural adhesive, a matrix resin for fiber-reinforced plastics, an impregnating fixing material, a film-type solder resist, a cured product of an epoxy resin composition, a semiconductor device, a printed wiring board, a semiconductor chip package, and an electronic device.

[0002] Epoxy resins have traditionally been used in a wide range of applications, such as insulating materials for electric and electronic components, sealing materials, adhesives, conductive materials, matrix resins for fiber-reinforced plastics, and impregnating adhesives for motor coils.

[0003] In particular, the demands for electronic devices are diverse, including miniaturization, high performance, light weight, and multi-functionality, and in semiconductor chip mounting technology, the electrode pads are being made finer, resulting in further miniaturization, miniaturization, and higher density. Accordingly, there is a demand for further improvements in the heat resistance and adhesive strength of peripheral components.

[0004] In order to improve the connection reliability of circuits, to use materials with low heat resistance in order to reduce the weight of mobile devices, and also for the purpose of significantly improving productivity, there is a demand for higher potential for one-component epoxy resin compositions used as connecting materials.

[0005] For example, Patent Documents 1 and 2 report epoxy resin curing agents that are amine adducts obtained by reacting bisphenol-type epoxy resins with various amine compounds, including imidazole, but do not describe their curability or cured product properties. Furthermore, the development of the latent potential of these amine adducts requires a microencapsulation process, which poses productivity challenges. Meanwhile, bisphenol-type epoxy resins are particularly prone to contain compounds with a 1,2-diol structure at one end and a glycidyl group at the other end, generated during the manufacturing process. These compounds and their amine adducts differ in reactivity and the properties of the cured product developed upon curing from bisphenol-type epoxy resins and their amine adducts, which have glycidyl groups at both ends. Therefore, it is preferable to exclude these compounds from the composition, as this makes it difficult to control the properties of the cured product. However, due to their molecular weight and chemical structure, it is difficult to remove these compounds and their amine adducts alone, even using various purification methods such as distillation. However, it is difficult to produce curing agents that exhibit high curing steepness and cured product properties, such as adhesion and heat resistance, without using raw materials containing a bisphenol structure. Furthermore, Patent Document 3 reports an amine adduct obtained by reacting phenylphenol glycidyl ether with imidazole, but does not describe the physical properties of the cured product or the steepness of the curing.

[0006] Patent No. 4583373 Patent No. 5534615 Patent No. 7316009

[0007] An object of the present invention is to provide an epoxy resin curing agent that can give an epoxy resin composition that has excellent curing steepness and provides a cured product with excellent heat resistance and adhesive strength, and an epoxy resin composition containing the same.

[0008] As a result of extensive research, the present inventors have found that the above object can be achieved by the following technical means, and have thus completed the present invention.

[0009] That is, the present invention includes the following embodiments: <1> An epoxy resin curing agent containing a reaction product of an epoxy compound and (C) a basic nitrogen-containing compound, wherein the epoxy compound contains at least one selected from the group consisting of: (A) an aliphatic epoxy compound, and (B) an epoxy compound having, as a partial structure, at least one selected from the group consisting of a tert-butylphenyl structure, a biphenyl structure, and an N,N-diglycidylaniline structure. <2> An epoxy resin curing agent comprising a reaction product of an epoxy compound and (C) a basic nitrogen-containing compound, wherein: (1) in the reaction product, bonds between carbon atoms and oxygen atoms of all epoxy groups in the epoxy compound are cleaved, the carbon atoms are directly bonded to nitrogen atoms of the (C) basic nitrogen-containing compound, and the oxygen atoms form hydroxyl groups, the structure of which has a solubility parameter defined by Fedor's equation of 11.0 to 15.0; (2) the softening point of the epoxy resin curing agent is 90 to 140°C; and (3) the epoxy resin curing agent does not contain a compound having a bisphenol structure. <3> The epoxy resin curing agent according to <1>, wherein (1) the solubility parameter defined by Fedor's equation for a structure in which bonds between carbon atoms and oxygen atoms of all epoxy groups in the epoxy compound in the reactant are cleaved, the carbon atoms are directly bonded to nitrogen atoms of the (C) basic nitrogen-containing compound, and the oxygen atoms form hydroxyl groups, is 11.0 to 15.0; (2) the softening point of the epoxy resin curing agent is 90 to 140°C; and (3) the curing agent does not contain a compound containing a bisphenol structure. <4> The epoxy resin curing agent according to any one of <1> to <3>, wherein the epoxy compound contains an epoxy compound having a melting point of 0°C or less. <5> The epoxy resin curing agent according to any one of <1> to <4>, wherein the epoxy compound contains 2 to 10 epoxy compounds selected from the group consisting of (A) and (B). <6> The epoxy resin curing agent according to any one of <1> to <5>, wherein the epoxy compound contains at least an epoxy compound having a hydrogenated bisphenol structure. <7> The epoxy resin curing agent according to any one of <1> to <6>, wherein the (C) basic nitrogen-containing compound includes an imidazole compound.<8> The epoxy resin curing agent according to any one of <1> to <7>, wherein the epoxy compound comprises at least an epoxy compound having an N,N-diglycidylaniline structure. <9> The epoxy resin curing agent according to any one of <1> to <8>, wherein the epoxy compound comprises (A) and (B). <10> The epoxy resin curing agent according to any one of <1> to <9>, wherein the epoxy compound comprises an epoxy compound having a hydrogenated bisphenol structure and an epoxy compound having an N,N-diglycidylaniline structure, and the (C) basic nitrogen-containing compound comprises an imidazole compound. <11> The epoxy resin curing agent according to any one of <1> to <10>, wherein the curing agent is a microcapsule-type curing agent the surface of which is coated with a shell. <12> An epoxy resin composition comprising the epoxy resin curing agent according to any one of <1> to <11>. <13> The epoxy resin composition according to <12>, further comprising epoxy compound (I). <14> The epoxy resin composition according to <13>, wherein the epoxy compound (I) does not contain a bisphenol-type epoxy resin. <15> The epoxy resin composition according to either <13> or <14>, wherein the epoxy compound (I) has a viscosity of 0.1 to 10 Pa s at 25°C. <16> The epoxy resin composition according to any one of <13> to <15>, wherein the epoxy compound (I) contains at least one component selected from the group consisting of: (A): an aliphatic epoxy compound, and (B): an epoxy compound having, as a partial structure, at least one component selected from the group consisting of a tert-butylphenyl structure, a biphenyl structure, and an N,N-diglycidylaniline structure. <17> The epoxy resin composition according to <16>, wherein the epoxy compound (I) contains at least one component selected from the group consisting of (A) and (B) in an amount of 60 mass% or more, based on the total mass of the epoxy compound (I). <18> The epoxy resin composition according to <16> or <17>, wherein the epoxy compound (I) comprises an epoxy resin having a hydrogenated bisphenol structure and / or an epoxy resin having a biphenyl structure. <19> An encapsulating material comprising the epoxy resin composition according to any one of <12> to <18>.<20> A conductive material containing the epoxy resin composition according to any one of <12> to <18>. <21> A thermally conductive material containing the epoxy resin composition according to any one of <12> to <18>. <22> An insulating material containing the epoxy resin composition according to any one of <12> to <18>. <23> An adhesive for camera modules containing the epoxy resin composition according to any one of <12> to <18>. <24> A structural adhesive containing the epoxy resin composition according to any one of <12> to <18>. <25> A matrix resin for fiber-reinforced plastics containing the epoxy resin composition according to any one of <12> to <18>. <26> An impregnated fixing material containing the epoxy resin composition according to any one of <12> to <18>. <27> A film-type solder resist containing the epoxy resin composition according to any one of <12> to <18>. <28> A cured product of the epoxy resin composition according to any one of <12> to <18>. <29> A semiconductor device comprising the epoxy resin composition according to any one of <12> to <18> or a cured product thereof. <30> A printed wiring board comprising the epoxy resin composition according to any one of <12> to <18> or a cured product thereof. <31> A semiconductor chip package comprising the epoxy resin composition according to any one of <12> to <18> or a cured product thereof. <32> An electronic device comprising the printed wiring board according to <30>. <33> An electronic device comprising the semiconductor chip package according to <31>.

[0010] According to the present invention, it is possible to provide an epoxy resin curing agent which can give an epoxy resin composition having excellent curing steepness and excellent heat resistance and adhesive strength of the cured product, and an epoxy resin composition containing the same.

[0011] Hereinafter, a mode for carrying out the present invention (hereinafter also simply referred to as "embodiment") will be described in detail. The embodiment is an example for explaining the present invention, and the present invention is not limited to only the embodiment. In other words, the present invention can be modified in various ways without departing from the gist of the present invention. In this specification, when an expression is expressed using "~" with a numerical value or physical property value before and after it, it is used to include the values ​​before and after it.

[0012] In one aspect, the epoxy resin curing agent of this embodiment contains a reaction product of an epoxy compound and a basic nitrogen-containing compound (hereinafter also referred to as a "basic component"). In the epoxy resin curing agent of this embodiment, the epoxy compound contains at least one selected from the group consisting of: (A) an aliphatic epoxy compound; and (B) an epoxy compound having, as a partial structure, at least one selected from the group consisting of a tert-butylphenyl structure, a biphenyl structure, and an N,N-diglycidylaniline structure. According to this embodiment, an epoxy resin curing agent or the like can be obtained that can produce an epoxy resin composition that exhibits excellent curing steepness and provides a cured product with excellent heat resistance and adhesive strength.

[0013] In one aspect, the epoxy resin curing agent of this embodiment includes a reaction product of an epoxy compound and a basic nitrogen-containing compound, and has the following characteristics: (1) The solubility parameter defined by the Fedor equation (hereinafter also referred to as the "solubility parameter of the basic component") for a structure in which the bonds between the carbon atoms and oxygen atoms of all epoxy groups in the epoxy compound in the reaction product are cleaved, the carbon atoms are directly bonded to the nitrogen atoms of the (C) basic nitrogen-containing compound, and the oxygen atoms form hydroxyl groups is 11.0 to 15.0; (2) The softening point of the epoxy resin curing agent is 90 to 140°C; and (3) The epoxy resin curing agent does not contain a compound containing a bisphenol structure. According to this embodiment, an epoxy resin curing agent or the like can be obtained that can produce an epoxy resin composition that exhibits excellent curing steepness and excellent heat resistance and adhesive strength of the cured product.

[0014] In this embodiment, the solubility parameter (SP value) of the basic component is preferably 11.0 or more, more preferably 11.5 or more, and even more preferably 12.0 or more. The upper limit of the solubility parameter (SP value) of the basic component is preferably 15.0 or less, more preferably 14.5 or less, and even more preferably 14.0 or less. The solubility parameter is defined by the Fedor equation. Here, the solubility parameter is a value for a structure (basic component structure) in which the bond between the carbon atom and oxygen atom of the epoxy group in the epoxy compound in the reactant is cleaved, the carbon atom is directly bonded to the nitrogen atom of the basic nitrogen-containing compound (C), and the oxygen atom forms a hydroxyl group. By setting the solubility parameter (SP value) of the basic component within this range, excellent solubility with various epoxy resins can be achieved, and curing steepness and adhesion can be improved.

[0015] The SP value can be calculated as the sum (ΔH) of the molar heat of vaporization (Δe1) and the sum (V) of the molar volume (Δv1) of the atomic groups described in Robert F. Fedors, "POLYMER ENGINEERING AND SCIENCE," 1974, Vol. 14, No. 2, pp. 151-153.

[0016] When two or more types of epoxy compounds are contained, the solubility parameter is calculated for each structure of the basic component, and it is sufficient that at least one type of basic component falls within the above-mentioned range of SP values, but it is preferable that all of the basic components fall within the above-mentioned range of SP values.

[0017] The reaction product of the above-mentioned epoxy compound and basic nitrogen-containing compound may contain a reaction product other than that having a solubility parameter defined by the Fedor equation of 11.0 to 15.0 with respect to a structure in which bonds between carbon atoms and oxygen atoms of all epoxy groups in the epoxy compound are cleaved, the carbon atoms are directly bonded to nitrogen atoms of the basic nitrogen-containing compound (C), and the oxygen atoms form hydroxyl groups.

[0018] The softening point of the epoxy resin curing agent is preferably 90°C or higher, more preferably 95°C or higher, and even more preferably 100°C or higher. The upper limit of the softening point of the epoxy resin curing agent is preferably 140°C or lower, more preferably 135°C or lower, and even more preferably 130°C or lower. By controlling the softening point of the epoxy resin curing agent to fall within this range, it is possible to obtain an epoxy resin composition that not only improves raw material processability but also has an excellent balance between heat resistance and adhesive strength. The softening point is measured in accordance with JIS K-7234:1986 (ring and ball method). For example, the softening point tends to increase when a rigid skeleton or a molecular structure that facilitates stacking of molecules is introduced, and tends to decrease when a flexible skeleton such as an aliphatic linear chain is introduced.

[0019] In this embodiment, from the viewpoint of reactivity and control of the physical properties of the cured product, it is preferable not to contain a compound containing a bisphenol structure. Raw materials containing a bisphenol structure have a high melting point, which poses problems in manufacturability, and the presence of a compound having a 1,2-diol structure at one end and a glycidyl group at the other end reduces the cure steepness and adhesive strength. The bisphenol structure is the following partial structure.

[0020]

[0021] In formula (1), X is any tetravalent substituent, and R １ ~R ４ is an arbitrary monovalent substituent, and * is a bonding site. Since the epoxy compound (I) described below does not contain a bisphenol-type epoxy resin, it does not substantially contain a compound having a 1,2-diol structure at one end and a glycidyl group at the other end, which is contained in a bisphenol-type epoxy resin, and therefore tends to have excellent curing steepness.

[0022] In the epoxy resin curing agent of this embodiment, the epoxy compound preferably contains at least one selected from the group consisting of: (A) an aliphatic epoxy compound; and (B) an epoxy compound having, as a partial structure, at least one selected from the group consisting of a tert-butylphenyl structure, a biphenyl structure, and an N,N-diglycidylaniline structure.

[0023] In this embodiment, the basic component, which is the reaction product of an epoxy compound and a basic nitrogen-containing compound, may be an amine adduct having an amine structure. The term "amine adduct" refers to a product obtained by the addition of a basic nitrogen-containing compound having an amino group containing active hydrogen to an epoxy compound. For example, an amine adduct having residual active hydrogen can be obtained by reacting an epoxy resin with an amine-based active hydrogen compound to consume the epoxy group. Amine adducts typically have a relatively high molecular weight, which offers the advantages of having less odor due to low-volatility components, allowing for a larger amount to be incorporated into the resin, and reducing weighing errors.

[0024] In this embodiment, the molecular weight distribution of the amine adduct is preferably 1.01 or more and 10 or less, more preferably 1.03 or more and 9.0 or less, and even more preferably 1.05 or more and 7.0 or less. By using an amine adduct (A) having the above molecular weight distribution, an epoxy resin composition with high curability can be obtained. Here, the molecular weight distribution is defined as the ratio of the weight average molecular weight to the number average molecular weight, and is calculated from the molecular weight determined in polystyrene equivalent terms using gel permeation chromatography (hereinafter referred to as GPC).

[0025] From the viewpoint of manufacturability, it is desirable that the epoxy resin curing agent does not contain a compound containing a dihydroxybenzene structure. The dihydroxybenzene structure is the following partial structure.

[0026]

[0027] In formula (3), R １ ~R ４ is any monovalent substituent, and * is a binding site

[0028] Examples of the form of the solid basic component include lumps, granules, powder, etc. Among these, granules or powder are preferred, and powder is more preferred.

[0029] The average particle size of the solid basic component (D ５０ ) is preferably 0.3 μm or more and 12 μm or less, more preferably 1.0 μm or more and 10 μm or less, and even more preferably 1.5 μm or more and 5.0 μm or less.

[0030] Here, the average particle diameter (D ５０ The average particle size is the Stokes diameter measured by a laser diffraction / light scattering method, and refers to the median diameter measured by this method. When the average particle size is 12 μm or less, a homogeneous cured product tends to be obtained, and when the particle size exceeds 0.3 μm, aggregation between particles tends to be suppressed.

[0031] D ９９ / D ５０ is preferably 0.5 or more and 6.0 or less, more preferably 1.0 or more and 5.5 or less, and even more preferably 1.5 or more and 5.0 or less. ９９ / D ５０ When the D is within this range, the number of coarse particles in the powder particles is small, the formation of aggregates is suppressed, and the mechanical properties of the cured product are improved, while the production cost can be kept low. ９９ is the Stokes diameter measured by a laser diffraction / light scattering method, and means the Stokes diameter at which the volume frequency measured by this method is 99%.

[0032] The circularity of the basic component may be improved by surface treatment. The circularity of the basic component is preferably 0.93 or more, more preferably 0.95 or more, and even more preferably 0.97 or more. The closer the circularity is to 1, the closer it is to a perfect sphere. The closer the circularity of the basic component is to 1, the lower the viscosity of the blend and the more workability is improved.

[0033] The circularity can be measured by a flow particle image analysis method. More specifically, a sample is flowed in a liquid, the particles are photographed, the particle diameter is determined from the particle projected area, and the circularity can be determined from the ratio of the perimeter of the particle projected image to the circumference of a circle equivalent to the particle diameter. The basic component can be formed, for example, by subjecting irregular particles to hot air treatment, and the circularity can be controlled to the above-mentioned numerical range by adjusting the treatment conditions.

[0034] A method for obtaining a basic component with a high degree of circularity includes spraying irregular particles into hot air sprayed from a hot air spray nozzle, and melting the surface of the particles by contact with the hot air.

[0035] The temperature of the hot air during the hot air treatment is preferably 100°C or higher and 400°C or lower. When the temperature of the hot air is 100°C or higher, the surface of the basic component can be sufficiently heated and the desired circularity can be controlled. When the temperature of the hot air is 400°C or lower, thermal decomposition of the basic component can be suppressed. From the above viewpoints, the hot air temperature is more preferably 150°C or higher and 300°C or lower, and even more preferably 180°C or higher and 250°C or lower.

[0036] The epoxy resin curing agent of the present embodiment has, in the basic component, a skeleton derived from at least one selected from the group consisting of (A) an aliphatic epoxy compound and (B) an epoxy compound having a specific partial structure. This makes it possible to weaken intermolecular interactions, improve diffusibility and curability at or above the softening point, and improve curing steepness.

[0037] Generally, a curing agent with excellent curing steepness tends to easily result in a non-uniform composition of the cured product, and the physical properties of the cured product, such as heat resistance and adhesive strength, tend to decrease. However, the basic component of the present embodiment also has excellent diffusibility, making it possible to achieve both rapid curing and good physical properties of the cured product.

[0038] (Component (A): Aliphatic Epoxy Compound) The epoxy resin curing agent of this embodiment may use (A) an aliphatic epoxy compound (hereinafter also referred to as "component (A)") as a raw material. Aliphatics generally have weak intermolecular interactions, so the resulting basic component exhibits high diffusibility. When (A) an aliphatic epoxy compound is used, the solid of the basic component exhibits high diffusibility in a temperature environment above its softening point. The aliphatic epoxy compound preferably has epoxy groups such as glycidyl groups at both ends.

[0039] (A) Aliphatic epoxy compounds include, but are not limited to, hydrogenated bisphenol A type epoxy resins, hydrogenated bisphenol F type epoxy resins, hydrogenated bisphenol AD ​​type epoxy resins, (poly)ethylene glycol diglycidyl ether, (poly)propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,3-cyclohexanedimethanol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, polytetramethylene ether glycol diglycidyl ether, glycerin diglycidyl ether, and neopentyl glycol Examples of epoxy resins include polyfunctional epoxy resins such as diglycidyl ether, (3,4-epoxycyclohexyl)methyl-3,4-epoxycyclohexylcarboxylate, cyclohexane diglycidyl ether, dicyclopentadiene diglycidyl ether, vinylcyclohexene dioxide, and 1,2-cyclohexanedicarboxylate diglycidyl; and monofunctional epoxy resins such as n-butyl glycidyl ether, t-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, α-pinene oxide, allyl glycidyl ether, 1-vinyl-3,4-epoxycyclohexane, 1,2-epoxy-4-(2-methyloxiranyl)-1-methylcyclohexane, 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane, and neodecanoic acid glycidyl ester.

[0040] In this embodiment, the epoxy compound that is the raw material of the basic component is preferably a hydrogenated bisphenol epoxy resin, more preferably a hydrogenated bisphenol A epoxy resin, from the viewpoint of further improving the curing steepness.

[0041] (Component (B): Epoxy Compound Having a Specific Partial Structure) The epoxy resin curing agent of this embodiment may use, as a raw material, (B) an epoxy compound having at least one partial structure selected from the group consisting of a tert-butylphenyl structure, a biphenyl structure, and an N,N-diglycidylaniline structure (hereinafter also referred to as an "epoxy compound having a specific partial structure" or "component (B)"). The partial structure described above has sufficient steric bulk to improve diffusibility by weakening intermolecular interactions, and at the same time, has excellent compatibility with bisphenol-type liquid epoxy resins, which are commonly used epoxy resins. The epoxy compound having a specific partial structure preferably has epoxy groups such as glycidyl groups at both ends.

[0042] Specific examples of epoxy compounds having a tert-butylphenyl structure include, but are not limited to, tert-butylphenyl glycidyl ether, catechol-type epoxy, etc. Specific examples of epoxy compounds having a biphenyl structure include, but are not limited to, tetramethylbiphenol-type epoxy resins, biphenyl novolac-type epoxy resins, phenylphenol glycidyl ether, etc. Specific examples of epoxy compounds having an N,N-diglycidylaniline structure include, but are not limited to, N,N-bis(2,3-epoxypropyl)-4-(2,3-epoxypropoxy)aniline, 4,4'-methylenebis(N,N-diglycidylaniline), N-[2-methyl-4-(oxiranylmethoxy)phenyl]-N-(oxiranylmethyl)oxiranemethanamine, etc.

[0043] In the present embodiment, the epoxy compound that is a raw material for the basic component preferably contains a biphenyl structure or an N,N-diglycidylaniline structure, and more preferably contains an N,N-diglycidylaniline structure, from the viewpoint of improving heat resistance and adhesive strength.

[0044] The epoxy compound according to this embodiment may use one type alone from component (A) and component (B), or two or more types may be used in combination. The epoxy compound according to this embodiment preferably contains 2 to 10 types selected from the group consisting of component (A) and component (B). By using multiple types in combination, it becomes possible to weaken the cohesiveness of the basic component and increase its diffusibility. This improves diffusibility and curing properties, and improves curing steepness. Furthermore, from the viewpoint of maintaining uniformity of the cured product, the number of types is preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less.

[0045] When two or more types of component (A) and component (B) are used in combination, the larger the SP value difference and the greater the steric bulkiness of the combination, from the viewpoint of improving diffusibility. Specifically, when two or more types of component (A) are selected, two or more types of alicyclic aliphatic epoxy compounds are preferred, and a combination of diglycidyl 1,2-cyclohexanedicarboxylate and hydrogenated bisphenol A epoxy resin is more preferred.

[0046] When two or more components are selected from component (B), N,N-bis(2,3-epoxypropyl)-4-(2,3-epoxypropoxy)aniline and phenylphenol glycidyl ether are preferred.

[0047] When one or more types of component (A) and one or more types of component (B) are mixed and used, a combination of hydrogenated bisphenol A epoxy and N,N-bis(2,3-epoxypropyl)-4-(2,3-epoxypropoxy)aniline is preferred. From the viewpoint of reducing the amount of each component, the blending mass ratio (component (A) / component (B)) is preferably 25 / 75 to 75 / 25, more preferably 40 / 60 to 60 / 40, and even more preferably 30 / 70 to 70 / 30. In this embodiment, the difference in component proportions between component (A) and component (B) is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less.

[0048] The total chlorine content in component (A) and component (B) is preferably 2500 ppm or less, more preferably 2000 ppm or less, even more preferably 1500 ppm or less, and even more preferably 900 ppm or less, from the viewpoint of obtaining a cured epoxy resin material having excellent electrical properties and an excellent balance between curability and storage stability. The lower limit of the total chlorine content is not particularly limited, but from the viewpoint of the balance between the obtained effect and economic efficiency, it is preferably 0.01 ppm or more, more preferably 0.02 ppm or more, even more preferably 0.05 ppm or more, even more preferably 0.1 ppm or more, still more preferably 0.2 ppm or more, and particularly preferably 0.5 ppm or more.

[0049] Here, the total chlorine content in components (A) and (B) refers to the total amount of organic chlorine and inorganic chlorine contained in components (A) and (B), and is a value based on the mass of components (A) and (B). The total chlorine content in components (A) and (B) is measured by the following method. Components (A) and (B) are washed with xylene, and washing and filtration are repeated until no epoxy resin remains in the xylene washing solution. The filtrate is then distilled under reduced pressure at 100°C or less to obtain the epoxy resin. A 1-10 g sample of the obtained epoxy resin is precisely weighed to a titer of 3-7 mL, dissolved in 25 mL of ethylene glycol monobutyl ether, and 25 mL of 1 N KOH propylene glycol solution is added to the sample, followed by boiling for 20 minutes. The total chlorine content can be calculated from the titer obtained by titration with an aqueous silver nitrate solution.

[0050] Here, of the total chlorine, the chlorine contained in 1,2-chlorohydrin groups is generally referred to as hydrolyzable chlorine. The amount of hydrolyzable chlorine in component (A) and component (B) is preferably 100 ppm or less, more preferably 50 ppm or less, even more preferably 0.01 ppm or more and 20 ppm or less, and even more preferably 0.05 ppm or more and 10 ppm or less. A hydrolyzable chlorine amount of 100 ppm or less is advantageous from the viewpoint of achieving both high curability and storage stability in the epoxy resin composition of this embodiment, and a cured product of the epoxy resin composition of this embodiment tends to exhibit excellent electrical properties.

[0051] The hydrolyzable chlorine in components (A) and (B) can be measured by the following method: 3 g of a sample is dissolved in 50 mL of toluene, 20 mL of a 0.1 N KOH methanol solution is added to the solution, and the mixture is boiled for 15 minutes. The amount of hydrolyzable chlorine can be calculated from the amount of titration obtained by titration with an aqueous silver nitrate solution.

[0052] In the present embodiment, the epoxy compound serving as a raw material for the basic component preferably contains an epoxy compound having a melting point of 0° C. or lower, from the viewpoint of ease of handling as a raw material. When the melting point is 0° C. or lower, a step such as crystal dissolution is not required during production, and productivity is excellent.

[0053] Examples of epoxy compounds having a melting point of 0°C or less include hydrogenated bisphenol A type epoxy resins, hydrogenated bisphenol F type epoxy resins, hydrogenated bisphenol AD ​​type epoxy resins, (poly)ethylene glycol diglycidyl ether, (poly)propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,3-cyclohexanedimethanol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, polytetramethylene ether glycol diglycidyl ether, glycerin diglycidyl ether, neopentyl glycol diglycidyl ether, (3,4-epoxycyclohexyl)methyl-3,4-epoxycyclohexylcarboxylate, cyclohexane type diglycidyl ether, dicyclopentadiene type diglycidyl ether, vinylcyclohexyl polyfunctional epoxy resins such as ethylene oxide and 1,2-cyclohexanedicarboxylate diglycidyl; n-butyl glycidyl ether, t-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, α-pinene oxide, allyl glycidyl ether, 1-vinyl-3,4-epoxycyclohexane, 1,2-epoxy-4-(2-methyloxiranyl)-1-methylcyclohexane, 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane, glycidyl neodecanoate Examples of suitable epoxy resins include monofunctional epoxy resins such as diphenyl ether, tert-butylcatechol type epoxy, tetramethylbiphenol type epoxy resin, biphenyl novolac type epoxy resin, phenylphenol glycidyl ether, N,N-bis(2,3-epoxypropyl)-4-(2,3-epoxypropoxy)aniline, 4,4′-methylenebis(N,N-diglycidylaniline), N-[2-methyl-4-(oxiranylmethoxy)phenyl]-N-(oxiranylmethyl)oxiranemethanamine, and the like.

[0054] In the present embodiment, the amount of the epoxy compound having a melting point of 0°C or less is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, and even more preferably 90 to 100% by mass, based on the total amount of the epoxy compounds.

[0055] (Component (C): Basic Nitrogen-Containing Compound) The resin composition of the present embodiment contains (C) a basic nitrogen-containing compound (hereinafter, may be referred to as component (C)). (C) The basic nitrogen-containing compound preferably has active hydrogen.

[0056] Examples of component (C) include compounds having at least one primary amino group and / or secondary amino group but no tertiary amino group; and compounds having at least one tertiary amino group and at least one active hydrogen group.

[0057] Examples of compounds having at least one primary amino group and / or secondary amino group but no tertiary amino group include the following:

[0058] Examples of primary amines having no tertiary amino group include, but are not limited to, methylamine, ethylamine, propylamine, butylamine, ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, ethanolamine, propanolamine, cyclohexylamine, isophoronediamine, aniline, toluidine, diaminodiphenylmethane, and diaminodiphenylsulfone.

[0059] Examples of secondary amines having no tertiary amino group include, but are not limited to, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, dimethanolamine, diethanolamine, dipropanolamine, dicyclohexylamine, piperidine, piperidone, diphenylamine, phenylmethylamine, and phenylethylamine.

[0060] In the compound having at least one tertiary amino group and at least one active hydrogen group, examples of the active hydrogen group include a primary amino group, a secondary amino group, a hydroxyl group, a thiol group, a carboxylic acid, and a hydrazide group.

[0061] Examples of the compound having at least one tertiary amino group and at least one active hydrogen group include, but are not limited to, amino alcohols such as 2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol, methyldiethanolamine, triethanolamine, and N-β-hydroxyethylmorpholine; 2-(dimethylaminomethyl)phenol, 2,4,6-trimethyl-2-dimethylaminoethanol, ... aminophenols such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-aminoethyl-2-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-ethyl-4-methylimidazole, 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazole, 1-( imidazoles such as 1-(2-hydroxy-3-butoxypropyl)-2-ethyl-4-methylimidazole; 1-(2-hydroxy-3-phenoxypropyl)-2-phenylimidazoline, 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazoline, 2-methylimidazoline, 2,4-dimethylimidazoline, 2-ethylimidazoline, 2-ethyl-4-methylimidazoline, 2-benzylimidazoline, 2-phenylimidazoline, 2-(o-tolyl)-imidazoline, tetramethylene-bis-imidazoline, 1 , 1,3-trimethyl-1,4-tetramethylene-bis-imidazoline, 1,3,3-trimethyl-1,4-tetramethylene-bis-imidazoline, 1,1,3-trimethyl-1,4-tetramethylene-bis-4-methylimidazoline, 1,3,3-trimethyl-1,4-tetramethylene-bis-4-methylimidazoline, 1,2-phenylene-bis-imidazoline, 1,3-phenylene-bis-imidazoline, 1,4-phenylene-bis-imidazoline, 1,4-phenylene-bis-4-methylimidazoline and other imidazolines;Tertiary aminoamines such as dimethylaminopropylamine, diethylaminopropylamine, dipropylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, dipropylaminoethylamine, dibutylaminoethylamine, N-methylpiperazine, N-aminoethylpiperazine, and diethylaminoethylpiperazine; aminomercaptans such as 2-dimethylaminoethanethiol, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptopyridine, and 4-mercaptopyridine; aminocarboxylic acids such as N,N-dimethylaminobenzoic acid, N,N-dimethylglycine, nicotinic acid, isonicotinic acid, and picolinic acid; and aminohydrazides such as N,N-dimethylglycine hydrazide, nicotinic acid hydrazide, and isonicotinic acid hydrazide. As the amine compound, compounds having at least one tertiary amino group and at least one active hydrogen group are preferred, and imidazoles are more preferred, due to their excellent curing steepness. ;

[0062] In producing the basic component, when component (A) and / or component (B) are reacted with component (C), the reaction is carried out, for example, at a temperature of 50 to 250°C for 0.1 to 20 hours, in the presence of a solvent as needed, so that the active hydrogen groups in the amine compound are preferably in the range of 0.3 to 5 equivalents per equivalent of epoxy groups in the epoxy resin. Regarding the ratio of epoxy resin to amine compound, in order to control the molecular weight distribution, the active hydrogen equivalent of the amine in component (C) is preferably 0.3 or more, more preferably 0.4 or more, and even more preferably 0.5 or more per equivalent of epoxy groups in component (A) and / or component (B). Furthermore, from the viewpoint of economic efficiency in recovering the remaining unreacted amine compound, the ratio is preferably 5 or less, more preferably 4 or less, even more preferably 3 or less, and even more preferably 2 or less.

[0063] The solvent used as needed in producing the basic component is not particularly limited, 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, n-butanol, butyl cellosolve, butyl carbitol, etc., water, etc., and these solvents may be used in combination. The solvent used is preferably removed by distillation or the like.

[0064] (Microencapsulation) From the viewpoint of further improving solvent resistance and thermal stability, the surface of the basic component may be microencapsulated with a shell.

[0065] The microcapsule-type curing agent preferably has a structure in which the surface of a core is covered with a shell containing at least one kind selected from the group consisting of resins and inorganic oxides.

[0066] Among these, from the viewpoints of the stability of the film constituting the shell, the ease of destruction when heated, and the uniformity of the cured product, it is preferable that the shell constituting the microcapsule-type curing agent contains a resin.

[0067] Resins contained in the shell include, but are not limited to, epoxy resins, phenol resins, polyester resins, polyethylene resins, nylon resins, polystyrene resins, urethane resins, etc. Among these, epoxy resins, phenol resins, and urethane resins are preferred.

[0068] Examples of epoxy resins used for the shell include, but are not limited to, epoxy resins having two or more epoxy groups, resins produced by reacting an epoxy resin having two or more epoxy groups with a compound having two or more active hydrogens, and reaction products of a compound having two or more epoxy groups with a compound having one active hydrogen and a carbon-carbon double bond.

[0069] Among these, from the viewpoint of stability, a resin produced by the reaction of a compound having two or more epoxy groups with a compound having two or more active hydrogens, in particular a reaction product of an amine-based curing agent with an epoxy resin having two or more epoxy groups, is preferred.

[0070] Examples of phenolic resins used for the shell include, but are not limited to, phenol-formaldehyde polycondensates, cresol-formaldehyde polycondensates, resorcinol-formaldehyde polycondensates, bisphenol A-formaldehyde polycondensates, and polyethylene polyamine-modified phenol-formaldehyde polycondensates.

[0071] Examples of polyester resins used for the shell include, but are not limited to, ethylene glycol-terephthalic acid-polypropylene glycol polycondensates, ethylene glycol-butylene glycol-terephthalic acid polycondensates, and terephthalic acid-ethylene glycol-polyethylene glycol polycondensates.

[0072] The polyethylene resin used for the shell is not limited to the following, but examples thereof include ethylene-propylene-vinyl alcohol copolymer, ethylene-vinyl acetate copolymer, and ethylene-vinyl acetate-acrylic acid copolymer.

[0073] The nylon resin used for the shell is not limited to the following, but examples thereof include adipic acid-hexamethylenediamine polycondensate, sebacic acid-hexamethylenediamine polycondensate, and p-phenylenediamine-terephthalic acid polycondensate.

[0074] Examples of polystyrene resins used for the shell include, but are not limited to, styrene-butadiene copolymers, styrene-butadiene-acrylonitrile copolymers, acrylonitrile-styrene-divinylbenzene copolymers, and styrene-propenyl alcohol copolymers.

[0075] Examples of urethane resins used for the shell include, but are not limited to, isocyanate monomers such as butyl isocyanate, cyclohexyl isocyanate, octadecyl isocyanate, phenyl isocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tolidine diisocyanate, naphthalene diisocyanate, and triphenylmethane triisocyanate, condensates thereof, and polycondensates of isocyanate monomers with monoalcohols or polyhydric alcohols. Among these, urethane resins that are addition products of monoalcohols or polyhydric alcohols and monoisocyanates or polyhydric isocyanates are preferred.

[0076] The inorganic oxide used for the shell is not limited to the following, but examples thereof include boron compounds such as boron oxide, silicon dioxide, calcium oxide, etc. Among these, boron oxide is preferred from the viewpoints of film stability and ease of destruction when heated.

[0077] Furthermore, the shell constituting the microcapsule-type curing agent preferably contains a reaction product of any two or more selected from the group consisting of an isocyanate compound, an active hydrogen compound, a curing agent for an epoxy resin, an epoxy resin, and an amine compound.

[0078] The isocyanate compound used in the reaction product may be one contained in the core of the microcapsule-type curing agent.

[0079] The active hydrogen compound used in the reaction product is not limited to the following, but examples thereof include water, a compound having at least one primary amino group and / or a secondary amino group, a compound having at least one hydroxyl group, etc. The active hydrogen compounds may be used alone or in combination of two or more.

[0080] Examples of the compound having at least one primary amino group and / or secondary amino group include aliphatic amines, alicyclic amines, and aromatic amines.

[0081] Examples of aliphatic amines include, but are not limited to, alkylamines such as methylamine, ethylamine, propylamine, butylamine, and dibutylamine; alkylenediamines such as ethylenediamine, propylenediamine, butylenediamine, and hexamethylenediamine; polyalkylenepolyamines such as diethylenetriamine, triethylenetetramine, and tetraethylenepentamine; and polyoxyalkylenepolyamines such as polyoxypropylenediamine and polyoxyethylenediamine.

[0082] Examples of alicyclic amines include, but are not limited to, cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, and isophoronediamine.

[0083] Examples of aromatic amines include, but are not limited to, aniline, toluidine, benzylamine, naphthylamine, diaminodiphenylmethane, and diaminodiphenylsulfone.

[0084] Examples of the compound having at least one hydroxyl group include alcohol compounds and phenol compounds.

[0085] Examples of alcohol compounds include, but are not limited to, methyl alcohol, propyl alcohol, butyl alcohol, amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, dodecyl alcohol, stearyl alcohol, eicosyl alcohol, allyl alcohol, crotyl alcohol, propargyl alcohol, cyclopentanol, cyclohexanol, benzyl alcohol, cinnamyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diglyceryl alcohol, methyl glycerin ... Examples of the polyhydric alcohols include monoalcohols such as ethylene glycol monobutyl; polyhydric alcohols such as ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-butanediol, 1,4-butanediol, hydrogenated bisphenol A, neopentyl glycol, glycerin, trimethylolpropane, and pentaerythritol; and polyhydric alcohols such as compounds having two or more secondary hydroxyl groups per molecule, which are obtained by reacting a compound having at least one epoxy group with a compound having at least one hydroxyl group, carboxyl group, primary amino group, secondary amino group, or thiol group.

[0086] These alcohol compounds may be primary alcohols, secondary alcohols, or tertiary alcohols.

[0087] Examples of phenol compounds include, but are not limited to, monophenols such as carbolic acid, cresol, xylenol, carvacrol, motil, and naphthol, and polyphenols such as catechol, resorcinol, hydroquinone, bisphenol A, bisphenol F, pyrogallol, phloroglucin, 2-(dimethylaminomethyl)phenol, and 2,4,6-tris(dimethylaminomethyl)phenol.

[0088] From the viewpoint of latency and solvent resistance, these compounds having at least one hydroxyl group are preferably polyhydric alcohols or polyhydric phenols, more preferably polyhydric alcohols.

[0089] The reaction conditions for producing two or more reactants selected from the group consisting of an isocyanate compound, an active hydrogen compound, a curing agent for an epoxy resin, an epoxy resin, and an amine compound, which are contained in the shell constituting the microcapsule-type curing agent as described above, are not particularly limited, but are usually a temperature range of −10° C. to 150° C. and a reaction time of 10 minutes to 12 hours.

[0090] When an isocyanate compound and an active hydrogen compound are used, the compounding ratio (isocyanate group in the isocyanate compound):(active hydrogen in the active hydrogen compound) (equivalent ratio) is preferably in the range of 1:0.1 to 1:1000.

[0091] The reaction can be carried out in a predetermined dispersion medium, if necessary, such as a solvent, a plasticizer, or a resin.

[0092] Examples of the solvent include, but are not limited to, hydrocarbons such as benzene, toluene, xylene, cyclohexane, mineral spirits, and naphtha; ketones such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK); esters such as ethyl acetate, n-butyl acetate, and propylene glycol monomethyl ethyl ether acetate; alcohols such as methanol, isopropanol, n-butanol, butyl cellosolve, and butyl carbitol; and water.

[0093] Examples of plasticizers include, but are not limited to, phthalate diester plasticizers such as dibutyl phthalate and di(2-ethylhexyl) phthalate; aliphatic dibasic acid ester plasticizers such as di(2-ethylhexyl) adipate; phosphate triester plasticizers such as tricresyl phosphate; glycol ester plasticizers such as polyethylene glycol ester; etc. Examples of resins include, but are not limited to, silicone resins, epoxy resins, phenolic resins, etc.

[0094] The proportion of the reaction product as described above in the shell is usually 1% by mass or more, preferably 50% by mass or more, and may be 100% by mass.

[0095] In the microcapsule-type curing agent, methods for forming a shell that covers the surface of the core include, for example, the following methods (1) to (3): (1) A method in which the shell components and curing agent particles are dissolved and dispersed in a solvent that is a dispersion medium, and then the solubility of the shell components in the dispersion medium is reduced to precipitate the shell on the surface of the epoxy resin curing agent particles; (2) A method in which curing agent particles are dispersed in a dispersion medium, and a material that forms the shell is added to the dispersion medium to precipitate it on the epoxy resin curing agent particles; and (3) A method in which raw material components that form the shell are added to the dispersion medium, and the surface of the curing agent particles is used as a reaction site to generate the shell-forming material there.

[0096] Here, the above methods (2) and (3) are preferred because they allow reaction and coating to be carried out simultaneously.

[0097] Examples of the dispersion medium include a solvent, a plasticizer, a resin, etc. As the solvent, the plasticizer, and the resin, those exemplified as solvents, plasticizers, and resins that can be used when obtaining a reaction product of two or more of the above-mentioned isocyanate compound, active hydrogen compound, curing agent for epoxy resin, epoxy resin, and amine compound can be used.

[0098] After forming the shell by the above methods (2) and (3), the method for separating the microcapsule-type curing agent from the dispersion medium is not particularly limited, but it is preferable to separate and remove the unreacted raw materials after the shell is formed together with the dispersion medium. Such a method includes a method of removing the dispersion medium and the unreacted shell-forming materials by filtration.

[0099] After removing the dispersion medium, it is preferable to wash the microcapsule-type curing agent, which can remove unreacted shell-forming materials adhering to the surface of the microcapsule-type curing agent.

[0100] The washing method is not particularly limited, but the residue after filtration can be washed using a solvent that does not dissolve the dispersion medium or the microencapsulated curing agent. By drying the microencapsulated curing agent after filtration or washing, the microencapsulated curing agent can be obtained in powder form. The drying method is not particularly limited, but drying at a temperature below the melting point or softening point of the curing agent is preferred, and examples include vacuum drying. By converting the microencapsulated curing agent into a powder, it can be easily blended with an epoxy resin. Furthermore, using an epoxy resin as a dispersion medium is preferable because a masterbatch of the microencapsulated curing agent integrated with the epoxy resin can be obtained simultaneously with shell formation.

[0101] The shell formation reaction is usually carried out at a temperature ranging from -10°C to 150°C, preferably from 0°C to 100°C, for a reaction time of 10 minutes to 72 hours, preferably 30 minutes to 24 hours.

[0102] Furthermore, the thickness of the shell constituting the microcapsule-type curing agent is preferably 5 nm to 1000 nm, more preferably 10 nm to 100 nm. By making the shell thickness 5 nm or more, the storage stability of the epoxy resin curing agent obtained by the production method of this embodiment can be further improved. Furthermore, by making the shell thickness 1000 nm or less, the curability can be further improved. Note that the thickness referred to here is the average layer thickness, and can be measured using a transmission electron microscope.

[0103] In the case of an epoxy resin curing agent (II), the following method can be used to evaluate whether the core surface is covered with a shell. The epoxy resin curing agent (II) is electron-stained by coexisting it with ruthenium tetroxide in a sealed, light-shielded container at room temperature and atmospheric pressure for 10 minutes, and then mixed with a predetermined epoxy resin composition and cured at 40°C for 42 hours to obtain a cured product in which the epoxy resin curing agent is embedded. 80 nm slices are then prepared using an ultramicrotome, and the slices are coexisted with osmium tetroxide in a sealed, light-shielded container at room temperature and atmospheric pressure for 2 hours to obtain observation samples electron-stained with osmium tetroxide vapor. The observation samples are irradiated with an electron beam using a TEM, adjusted so that the focus is on the sample, and observed at an accelerating voltage of 120 kV and a magnification of 30,000 times to obtain images of the core (A) and shell (B), allowing evaluation.

[0104] [Epoxy Resin Composition] The epoxy resin curing agent of the present embodiment can be an epoxy resin composition containing the epoxy compound (I). The above-described epoxy resin composition can also be used as a masterbatch-type epoxy resin curing agent composition. That is, the present embodiment also includes a masterbatch-type epoxy resin curing agent composition containing the epoxy resin curing agent of the present embodiment.

[0105] The method for mixing the epoxy resin curing agent of the present embodiment with the epoxy compound (I) to obtain a masterbatch type curing agent for a one-component epoxy resin composition is not particularly limited, but examples thereof include a method of mixing using a general three-roll mill, a non-bubbling kneader, a planetary mixer, or the like.

[0106] From the viewpoint of ease of handling during work, the epoxy resin composition of this embodiment preferably has a low viscosity at room temperature (25°C). The viscosity of the epoxy resin composition of this embodiment is preferably 300 Pa s, more preferably 100 Pa s or less, and even more preferably 50 Pa s or less. On the other hand, if the viscosity is too low, splashing during work is likely to occur, so the viscosity of the epoxy resin composition of this embodiment is preferably 0.1 Pa s or more, more preferably 0.5 Pa s or more, and even more preferably 1.0 Pa s or more.

[0107] The content of the epoxy compound (I) in the epoxy resin composition of the present embodiment is preferably 10% by mass or more and 99% by mass or less, more preferably 20% by mass or more and 90% by mass or less, and even more preferably 30% by mass or more and 80% by mass or less, based on the total amount of the epoxy resin composition.

[0108] The content of the epoxy resin curing agent in the epoxy resin composition of the present embodiment is preferably 1% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 45% by mass or less, and even more preferably 10% by mass or more and 40% by mass or less, relative to the total amount of the epoxy resin composition.

[0109] The epoxy resin composition of the present embodiment preferably does not contain a bisphenol-type epoxy resin. By not containing a bisphenol-type epoxy resin, the composition does not substantially contain a compound having a 1,2-diol structure at one end and a glycidyl group at the other end, which is contained in bisphenol-type epoxy resins, and tends to have excellent cure steepness.

[0110] The epoxy resin composition of the present embodiment preferably contains, as the epoxy compound (I), at least one component selected from the group consisting of: (A) an aliphatic epoxy compound; and (B) an epoxy compound having, as a partial structure, at least one selected from the group consisting of a tert-butylphenyl structure, a biphenyl structure, and an N,N-diglycidylaniline structure (hereinafter, this may be referred to as component (B) or an epoxy resin (B) having a specific partial structure).

[0111] Aliphatic epoxy compounds (A) generally have low polarity and thus exhibit weak interactions with the highly polar capsule membrane components described above. In the epoxy resin composition of this embodiment, when an aliphatic epoxy compound (A) is used as the epoxy compound (I), swelling and destruction of the capsule membrane can be minimized, and the stability at high temperatures is improved, which tends to improve the cure steepness.

[0112] From the viewpoint of heat resistance of the cured product, the epoxy compound (I) is preferably an epoxy resin having a hydrogenated bisphenol structure, and more preferably an epoxy resin having a hydrogenated bisphenol A structure. By incorporating the above-mentioned hydrogenated bisphenol structure as a partial structure, the steric bulkiness is increased and the permeability into the voids of the capsule membrane described below is reduced, which tends to minimize the elution of the epoxy resin curing agent (II). From the viewpoint of heat resistance, the epoxy resin composition of this embodiment preferably uses an epoxy resin containing a biphenyl structure as the epoxy compound (I).

[0113] The epoxy compound (I) used in the epoxy resin composition of this embodiment may be one of the above-mentioned (A) and (B), or a combination of two or more thereof. From the viewpoint of suppressing crystallization during storage of the epoxy resin composition of this embodiment, it is preferable to use a combination of (A) and (B), and it is more preferable to include an epoxy resin having a hydrogenated bisphenol structure and an epoxy resin having a biphenyl structure. When two or more epoxy compounds from (A) and (B) are used in combination, the mass ratio of (A) to (B) is preferably (A):(B) = 1:9 to 9:1.

[0114] From the viewpoint of obtaining a cured epoxy resin material having excellent electrical properties and an excellent balance between curability and storage stability, the total chlorine content contained in (A) and (B) is preferably 2500 ppm or less, more preferably 2000 ppm or less, even more preferably 1500 ppm or less, and still more preferably 900 ppm or less. The lower limit of the total chlorine content contained in (A) and (B) is not particularly limited, but from the viewpoint of the balance between the obtained effect and economic efficiency, it is preferably 0.01 ppm or more, more preferably 0.02 ppm or more, even more preferably 0.05 ppm or more, still more preferably 0.1 ppm or more, still more preferably 0.2 ppm or more, and still more preferably 0.5 ppm or more.

[0115] From the viewpoint of improving the curing steepness and the mechanical strength of the cured product, the epoxy compound (I) preferably contains at least one kind of component selected from the group consisting of (A) and (B) in an amount of preferably 60 mass% or more, more preferably 65 mass% or more, even more preferably 70 mass% or more, and still more preferably 100 mass% based on the total amount of the epoxy compound (I).

[0116] The epoxy compound (I) preferably has a low viscosity from the viewpoint of improving the curing steepness and mechanical properties due to improved diffusibility of the curing agent. From the above viewpoints, the viscosity of the epoxy compound (I) is preferably 0.1 to 10 Pa s, more preferably 0.2 to 8 Pa s, and even more preferably 0.3 to 6 Pa s. The viscosity of the epoxy compound (I) can be controlled within the above numerical range by adjusting the molecular weight or by adjusting the compounding ratio of a high-viscosity resin and a low-viscosity resin.

[0117] The epoxy resin composition of the present embodiment may contain, as necessary, at least one additive selected from the group consisting of organic fillers, inorganic fillers, colorants, antifoaming agents, flow control agents, thickeners, release agents, wetting agents, flame retardants, surfactants, and resins.

[0118] The organic filler functions as a shock absorber, capable of mitigating stress generated by impact.

[0119] Examples of organic fillers include, but are not limited to, acrylic resin, silicone resin, butadiene rubber, polyester, polyurethane, polyvinyl butyral, polyarylate, polymethyl methacrylate, acrylic rubber, polystyrene, NBR (acrylonitrile-butadiene rubber), SBR (styrene-butadiene rubber), silicone-modified resin, and organic fine particles of copolymers containing these as components.

[0120] From the viewpoint of improving adhesiveness, preferred organic fine particles include, for example, alkyl (meth)acrylate-butadiene-styrene copolymer, alkyl (meth)acrylate-silicone copolymer, silicone-(meth)acrylic copolymer, a complex of silicone and (meth)acrylic acid, a complex of alkyl (meth)acrylate-butadiene-styrene and silicone, and a complex of alkyl (meth)acrylate and silicone.

[0121] Furthermore, organic fine particles having a core-shell structure, in which the core layer and the shell layer have different compositions, can also be used as the organic filler. Examples of core-shell organic fine particles include particles having a silicone-acrylic rubber core to which an acrylic resin is grafted, and particles having an acrylic copolymer to which an acrylic resin is grafted. These organic fillers may be used alone or in combination of two or more.

[0122] The inorganic filler can improve the physical strength of the epoxy resin composition of the present embodiment, and therefore the printed wiring board has excellent long-term reliability.

[0123] Examples of inorganic fillers include, but are not limited to, silicates such as talc, calcined clay, uncalcined clay, mica, and glass; oxides such as silica oxides such as titanium oxide, zinc oxide, zirconium oxide, antimony oxide, aluminum oxide (alumina), fused silica (fused spherical silica, fused crushed silica), synthetic silica, and crystalline silica; carbonates such as calcium carbonate, magnesium carbonate, and hydrotalcite; hydroxides such as aluminum hydroxide, magnesium hydroxide, and calcium hydroxide; sulfates such as barium sulfate, zinc sulfide, and calcium sulfate; sulfites such as calcium sulfite; titanates such as potassium titanate and lead titanate; borates such as zinc borate, barium metaborate, aluminum borate, calcium borate, and sodium borate; and nitrides such as aluminum nitride, boron nitride, and silicon nitride.

[0124] Among these, for example, titanium oxide is preferred as an inorganic filler contained in a resin composition applied to a light-emitting diode mounting substrate from the viewpoint of white appearance and reflectance.

[0125] The shape of the inorganic filler is not particularly limited, and may be, for example, amorphous, spherical, or scaly, and there is no particular limit to whether or not the inorganic filler is surface-treated. These inorganic fillers may be used alone or in combination of two or more.

[0126] Examples of colorants include, but are not limited to, phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, leuco crystal violet, carbon black, naphthalene black, solvent blue, etc. These colorants may be used alone or in combination of two or more.

[0127] Examples of the antifoaming agent include silicone-based antifoaming agents and non-silicone-based antifoaming agents. Examples of the silicone-based antifoaming agent include KS-66 (manufactured by Shin-Etsu Chemical Co., Ltd.). Examples of the non-silicone-based antifoaming agent include FOAMKILLER NSI-0.00 (manufactured by Aoki Oil & Fat Industries Co., Ltd.). These colorants may be used alone or in combination of two or more.

[0128] Examples of flow control agents include, but are not limited to, organic silane compounds such as silane coupling agents; organic titanium compounds such as titanium tetraisopropoxide and titanium diisopropoxybis(acetylacetonate); and organic zirconium compounds such as zirconium tetra-normal-butoxide and zirconium tetraacetylacetonate.

[0129] Examples of thickeners include, but are not limited to, animal-based thickeners such as gelatin; plant-based thickeners such as polysaccharides and cellulose; and chemically synthesized thickeners such as polyacrylic thickeners, modified polyacrylic thickeners, polyether thickeners, urethane-modified polyether thickeners, and carboxymethyl cellulose.

[0130] Examples of the release agent include, but are not limited to, fluorine-based release agents, silicone-based release agents, and acrylic release agents made of a copolymer of glycidyl (meth)acrylate and a linear alkyl (meth)acrylate having 16 to 22 carbon atoms.

[0131] Examples of wetting agents include, but are not limited to, unsaturated polyester copolymer wetting agents having acidic groups, such as acrylic polyphosphate esters.

[0132] Examples of flame retardants include, but are not limited to, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, halogen-based flame retardants such as chlorine compounds and bromine compounds, phosphorus-based flame retardants such as condensed phosphate esters, antimony-based flame retardants such as antimony trioxide and antimony pentoxide, and inorganic oxides such as silica fillers.

[0133] Examples of surfactants include, but are not limited to, anionic surfactants such as alkylbenzene sulfonates and alkyl polyoxyethylene sulfates, cationic surfactants such as alkyl dimethyl ammonium salts, amphoteric surfactants such as alkyl dimethyl amine oxides and alkyl carboxy betaines, and nonionic surfactants such as linear alcohols and fatty acid esters having 25 or more carbon atoms.

[0134] Examples of resins include, but are not limited to, polyester resin, polyurethane resin, acrylic resin, polyether resin, melamine resin, and modified epoxy resins such as urethane-modified epoxy resin, rubber-modified epoxy resin, and alkyd-modified epoxy resin.

[0135] In addition, for the purpose of imparting desired physical properties within a range that does not deviate from the effects of the present invention, antioxidants, thermal polymerization inhibitors, ultraviolet absorbers, antistatic agents, antiaging agents, antibacterial and antifungal agents, leveling agents, thixotropy-imparting agents, photoinitiator assistants, sensitizers, radical polymerization inhibitors, curing accelerators, surface treatment agents, dispersants, dispersion assistants, surface modifiers, stabilizers, fluorescent materials, and the like may be added.

[0136] The epoxy resin composition of the present embodiment can be suitably used as a paste-like composition, a film-like composition, an adhesive, a bonding paste, a bonding film, a conductive material, an anisotropically conductive material, an anisotropically conductive film, an insulating material, a sealing material, a coating material, a paint composition, a prepreg, a thermally conductive material, or a fuel cell separator material.

[0137] [Specific Aspects of Epoxy Resin Composition] The epoxy resin composition of the present embodiment is suitable for, but not limited to, sealing materials for electric and electronic components such as underfill materials and relay sealing materials, conductive materials such as conductive pastes, thermally conductive materials, insulating materials, adhesives for camera modules, structural adhesives, matrix resins for fiber-reinforced plastics, impregnation and fixing materials for motor coils, and the like.

[0138] In addition to the above, the epoxy resin composition of the present embodiment is suitable for, but not limited to, interlayer insulating films, film-type solder resists, sealing sheets, conductive films, anisotropically conductive films, thermally conductive films, and the like.

[0139] For each of the above-mentioned applications, one epoxy resin composition of the present embodiment may serve multiple applications. Examples of such applications include, but are not limited to, when the epoxy resin composition of the present embodiment contains silver particles as a filler, the electrically conductive material obtainable from the epoxy resin composition can also serve as a thermally conductive material.

[0140] As described above, the epoxy resin composition of this embodiment can be preferably used as a sealing material, an electrically conductive material, a thermally conductive material, an insulating material, an adhesive for a camera module, a structural adhesive, a matrix resin for fiber-reinforced plastics, an impregnating adhesive, a film-type solder resist, an encapsulating sheet, a conductive film, an anisotropic conductive film, and / or a thermally conductive film. In other words, the sealing material, the electrically conductive material, the thermally conductive material, the insulating material, the adhesive for a camera module, a structural adhesive, a matrix resin for fiber-reinforced plastics, an impregnating adhesive, a film-type solder resist, an encapsulating sheet, a conductive film, an anisotropic conductive film, and a thermally conductive film of this embodiment all contain the epoxy resin composition of this embodiment (the epoxy resin curing agent of this embodiment). The insulating material may be in any form, but is preferably an interlayer insulating film.

[0141] For example, when the epoxy resin composition of the present embodiment is used as an underfill material, it is required to have heat stability for rapid penetration between the semiconductor chip and the substrate, and excellent curing properties at 120°C to 150°C. The epoxy resin composition of the present embodiment contains an epoxy resin curing agent, and therefore can have all of these properties.

[0142] The conductive material may contain metal particles such as solder particles, nickel particles, nano-sized metal crystals, particles in which the surface of a metal is coated with another metal, and copper and silver gradient particles, as well as solvents. However, the epoxy resin curing agent of this embodiment has a strong layer (B) and is therefore resistant to metal particles and also to solvents. Therefore, an epoxy resin composition containing the epoxy resin curing agent of this embodiment can provide a conductive material with excellent stability.

[0143] Thermally conductive materials are made up of a curing agent and a metal with high thermal conductivity, such as silver, a metal oxide such as zinc oxide, a ceramic such as boron nitride, aluminum nitride, or alumina, or an inorganic filler such as silica. Thermoelectrically conductive materials require stability during storage, but it is difficult to achieve this stability unless the curing agent is isolated from the liquid component. Even if a coating layer is present to isolate the curing agent component from the liquid component, if the coating layer's strength is insufficient, it will be destroyed upon impact with the filler. The epoxy resin composition containing the epoxy resin curing agent of this embodiment has excellent properties in these respects, making it possible to provide a stable thermally conductive material.

[0144] Structural adhesives, such as those typically used for automobile structures, are often placed in high-temperature, high-humidity environments after application, and require excellent stability against both heat and moisture. The epoxy resin composition containing the epoxy resin curing agent of the present embodiment can provide a structural adhesive that has excellent stability against both heat and moisture.

[0145] In camera module adhesives, for example, dual-curing adhesives that are cured by both light and heat are used when performing active alignment between a lens holder and an electronic component equipped with an image sensor such as a CMOS sensor, and dual-curing adhesives contain both an epoxy resin and an acrylic resin. The epoxy resin composition containing the epoxy resin curing agent of this embodiment can provide a camera module adhesive that has both sufficient stability and reactivity even when containing both.

[0146] Matrix resins for fiber-reinforced plastics and impregnating and fixing materials for motor coils are required to have performance throughout the process from impregnation to curing, i.e., the ability to penetrate into gaps in fine fibers or coils, stability during penetration, and curing ability. The epoxy resin composition containing the epoxy resin curing agent of this embodiment is suitable because it can combine all of these properties.

[0147] [Film Comprising Epoxy Resin Composition of the Present Embodiment] This embodiment also includes a film having a resin composition layer comprising the epoxy resin curing agent and / or epoxy resin composition of the present embodiment.

[0148] In this case, the epoxy resin composition can also function as an epoxy resin curing agent or curing accelerator. The epoxy resin composition of the present embodiment has excellent solvent resistance and is suitable for films.

[0149] The film of the present embodiment has, for example, a predetermined support and a resin composition layer formed on the support from an epoxy resin composition preparation liquid described below, and may have a protective layer on the surface of the resin composition layer opposite to the support, as necessary.

[0150] The support is preferably a material that can withstand the temperature during drying of the organic solvent. Examples of such a support include, but are not limited to, polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, cellulose derivative film, etc. These films can also be stretched as needed.

[0151] The protective layer is preferably made of a material capable of sufficiently maintaining the surface smoothness of the resin composition layer, and examples of such a protective layer include, but are not limited to, polyethylene film, polypropylene film, polyethylene terephthalate film treated for easy peeling, and oriented polypropylene film.

[0152] [Method for Preparing Epoxy Resin Composition Preparation for Film] Examples of a method for preparing an epoxy resin composition preparation for forming a resin composition layer of a film include a method of mixing the epoxy resin curing agent and / or the epoxy resin composition of the present embodiment with other additives, a film-forming polymer, etc., further adding an organic solvent, and mixing the mixture using a planetary mixer or the like.

[0153] As the film-forming polymer, any polymer can be used that has the effect of suppressing cracking, cissing, and excessive flow when the epoxy resin composition preparation liquid is coated and then the organic solvent is dried to form a film, and that has the effect of maintaining the film shape. Examples of such film-forming polymers include, but are not limited to, phenoxy resin, polyvinyl butyral resin, polyvinyl acetal resin, polyacrylic resin, polyimide resin, and elastomers having functional groups such as carboxyl groups, hydroxyl groups, vinyl groups, and amino groups. Film-forming polymers are also sometimes called binder polymers.

[0154] The organic solvent is not particularly limited, and known organic solvents can be used, including, but not limited to, hydrocarbons such as toluene, xylene, cyclohexane, mineral spirits, and solvent naphtha; ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), and cyclohexanone; esters such as ethyl acetate, n-butyl acetate, and propylene glycol monomethyl ethyl ether acetate; alcohols such as methanol, isopropanol, n-butanol, butyl cellosolve, and butyl carbitol; and amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone.

[0155] [Film Manufacturing Method] The film of the present embodiment can be manufactured by sequentially laminating a support, a resin composition layer, and, if necessary, a protective layer.

[0156] As a method for laminating the support, the resin composition layer, and the protective layer, a known method can be adopted.

[0157] For example, a preparation containing the epoxy resin composition of this embodiment and an organic solvent is prepared, and the preparation is first applied to a support using a known method such as an applicator or bar coater, followed by drying to form a resin composition layer on the support. The drying method is not particularly limited, but examples include oven drying and hot air blowing. The drying temperature and time are also not particularly limited. However, from the viewpoint of thoroughly removing the solvent while suppressing deformation of the support due to excessive heating and excessive reaction of the resin composition layer during drying, drying at a temperature range of 50°C to 160°C for a drying time of 1 minute to 30 minutes is preferred, and drying at 80°C to 150°C for 3 minutes to 25 minutes is more preferred. The drying temperature may be constant or may be varied with a temperature gradient. Next, if necessary, a protective layer may be laminated on the formed resin composition layer to produce a film.

[0158] [Specific Embodiments of Film Comprising Epoxy Resin Composition of the Present Embodiment] The film comprising the epoxy resin composition of the present embodiment can be used as, for example, an interlayer insulating film, a film-type solder resist, a sealing sheet, a conductive film, an anisotropic conductive film, a thermally conductive film, and the like, but is not limited thereto.

[0159] The epoxy resin composition of the present embodiment has excellent solvent resistance and storage stability, and therefore, it is possible to extend the coatable period of an epoxy resin composition preparation for film containing the composition, and also to extend the storage period of the obtained film.

[0160] Furthermore, since the epoxy resin composition of the present embodiment has excellent curability at 150° C. or less, the film of the present embodiment also has excellent curability.

[0161] The above-mentioned properties are commonly required for interlayer insulating films, film-type solder resists, sealing sheets, conductive films, anisotropic conductive films, and thermally conductive films, and therefore the film of this embodiment is suitable for these applications.

[0162] [Cured Product] The cured product of the present embodiment is obtained by curing the above-described epoxy resin composition.

[0163] [Printed Wiring Board] The printed wiring board of this embodiment includes the epoxy resin composition of this embodiment or a cured product thereof, and preferably has a cured product layer made of the cured product of the epoxy resin composition of this embodiment. When manufacturing a printed wiring board using the film-type adhesive of this embodiment described above, the film-type adhesive manufactured by the above method is attached to a patterned inner layer circuit board, and laminated while applying pressure and heat from the support side. The inner layer circuit surface may be pre-roughened. Lamination is performed under normal or reduced pressure, either batchwise or continuously with a roll, but lamination on both sides simultaneously is preferred. The lamination conditions are preferably a pressure bonding temperature of 70°C to 150°C and a pressure bonding pressure of 0.1 to 1 MPa. Furthermore, to prevent the generation of voids, lamination is preferably performed under reduced pressure of 2 KPa or less. After lamination, the board is cooled to room temperature, the support film is peeled off, and the adhesive film laminated on the inner layer circuit board is heat-cured to form a cured product layer. As for the curing conditions, the curing temperature is preferably in the range of 130 to 200° C., and the curing time is preferably in the range of 30 to 120 minutes.

[0164] Next, via holes are drilled using a laser such as a carbon dioxide laser, and then roughening treatment is performed using an oxidizing agent such as permanganate, dichromate, or ozone to remove smears and improve adhesion with the plating. Subsequently, conductor circuits are selectively formed on the cured product layer using electroless plating or electrolytic plating, and simultaneously, conductors are formed on the inner walls of the via holes to form outer layer circuits. Annealing is then performed at 150 to 200°C for 30 to 60 minutes to improve adhesion between the conductor layer and the resin layer. By repeating the above manufacturing process using a film-type adhesive on the conductor circuit layer thus obtained, multiple build-up layers can be formed to produce a printed wiring board.

[0165] As described above, the cured product of the epoxy resin composition of the present embodiment has little warpage, high heat resistance, and high strength, and therefore can be widely used for printed wiring boards such as rigid substrates, flexible substrates, single-area laminate substrates, and thin substrates, and can be particularly suitably used as a build-up layer for multilayer printed wiring boards.

[0166] [Semiconductor Device] The semiconductor device of this embodiment includes a semiconductor element sealed or bonded using the above-described resin paste, or a semiconductor element sealed or bonded using the above-described resin film. Accordingly, the semiconductor device of this embodiment includes the epoxy resin composition of this embodiment or a cured product thereof, and preferably has a cured layer made of the cured product of the epoxy resin composition of this embodiment. By using the epoxy resin composition of this embodiment, uniform sealing or bonding is achieved, and the cured layer exhibits a high glass transition temperature and suppresses a decrease in elastic modulus in the high-temperature range, which is preferable because it allows the production of a semiconductor device with excellent reliability that can withstand heat generation and long-term use.

[0167] The semiconductor device is not particularly limited as long as it is a device that functions by incorporating semiconductor components, and examples thereof include various semiconductor devices used in electrical appliances such as personal computers, smartphones, game consoles, digital cameras, and televisions, vehicles such as motorcycles, automobiles, trains, ships, and aircraft, and high-speed communication antennas, servers, etc.

[0168] The semiconductor device of this embodiment is not particularly limited, but can be manufactured by, for example, mounting various semiconductor chips at the locations of a wiring board where circuit connections are made, thereby establishing electrical continuity.

[0169] The method for mounting a semiconductor chip when manufacturing a semiconductor device is not particularly limited, but specific examples include a wire bonding mounting method, a flip chip mounting method, a mounting method using a bumpless build-up layer (BBUL), a mounting method using an anisotropic conductive film, and a mounting method using a non-conductive film. In mounting, the epoxy resin composition of the present embodiment, and a resin paste or resin film using the same can be used to seal, bond, etc. the semiconductor chip.

[0170] [Electronic Device] The electronic device of this embodiment includes the printed wiring board and / or semiconductor chip package of this embodiment described above. The printed wiring board and semiconductor chip package of this embodiment have a cured material layer with low warpage, high heat resistance, and high strength. Therefore, even when mounted on an electronic device that is miniaturized, downsized, and highly dense, they can prevent poor connection and cracks due to warpage and can withstand heat generated by the increasing volume of electronic information handled. Therefore, the resulting electronic device has excellent long-term reliability, which is preferable.

[0171] The electronic device is not particularly limited as long as it is a device that functions by incorporating electronic components, and examples include electrical appliances such as personal computers, smartphones, game consoles, digital cameras and televisions, vehicles such as motorcycles, automobiles, trains, ships and aircraft, and various electronic devices used in high-speed communication antennas, servers, etc.

[0172] The electronic device of this embodiment can be manufactured by mounting various semiconductor chips at circuit connection locations on a printed wiring board to ensure electrical continuity. A configuration in which a semiconductor chip and wiring are coated with an insulating resin is called a semiconductor chip package, and this is widely used in electronic materials to protect them from the external environment and improve connection reliability to printed wiring boards, etc. The semiconductor chip package of this embodiment contains the epoxy resin composition of this embodiment or a cured product thereof, and preferably has a cured product layer made of the cured product of the epoxy resin composition of this embodiment.

[0173] The method for mounting a semiconductor chip when manufacturing the electronic device of this embodiment is not particularly limited, but specific examples include a wire bonding mounting method, a flip chip mounting method, a mounting method using a bumpless build-up layer (BBUL), a mounting method using an anisotropic conductive film, a mounting method using a non-conductive film, etc. Furthermore, in mounting, the epoxy resin composition of this embodiment, and a resin paste or film-type adhesive using the same can be used to seal, bond, etc. the semiconductor chip.

[0174] Hereinafter, the present embodiment will be described in more detail with reference to examples, but these are merely illustrative and the present embodiment is not limited thereto. That is, a person skilled in the art can practice the present embodiment by making various modifications to the examples shown below. In the following, "parts" and "%" are based on mass unless otherwise specified.

[0175] [Measurement Method] (SP Value) In the reaction product, the bond between the terminal carbon atom and the oxygen atom in all epoxy groups in the structure of the epoxy compound is cleaved, the terminal carbon atom is directly bonded to the nitrogen atom of the basic nitrogen-containing compound, and the oxygen atom forms a hydroxyl group. The SP value was determined by substituting the structure into the following formula (1) (unit: (cal / cm ３ ) １／２ ) (where Δe1 is the molar heat of vaporization of the atomic group and v1 is the molar volume.)

[0176] (Softening Point) The softening point of the reaction product was measured in accordance with JIS K-7234:1986 (ring and ball method).

[0177] (Melting Point) The melting point of the epoxy compound was measured in accordance with JIS K-0064:1992.

[0178] (Viscosity) The viscosity of the epoxy compound and the epoxy resin composition was measured at room temperature (25° C.) using an E-type viscometer (TVE-35H, manufactured by Toki Sangyo Co., Ltd.).

[0179] [Component Description] Components (A) to (C) used in the examples and comparative examples are shown in Table 1 below.

[0180] (Component (A): Aliphatic Epoxy Compound) EP1 (manufactured by Mitsubishi Chemical Corporation, hydrogenated bisphenol A epoxy resin, epoxy equivalent: 197 g / eq, melting point: 0°C or less) EP2 (manufactured by Tokyo Chemical Industry Co., Ltd., 1,2-cyclohexanedicarboxylate diglycidyl, epoxy equivalent: 142 g / eq, melting point: 0°C or less)

[0181] (Component (B): Epoxy compound having a specific partial structure) EP3 (manufactured by Mitsubishi Chemical Corporation, N,N-bis(2,3-epoxypropyl)-4-(2,3-epoxypropoxy)aniline, epoxy equivalent: 100 g / eq, melting point: 0°C or less) EP4 (manufactured by Sakamoto Yakuhin Co., Ltd., o-phenylphenol glycidyl ether, epoxy equivalent: 231 g / eq, melting point: 0°C or less) EP5 (manufactured by Tokyo Chemical Industry Co., Ltd., 4-tert-butylphenyl glycidyl ether, epoxy equivalent: 206 g / eq, melting point: 0°C or less) EP6 (manufactured by Nippon Kayaku Co., Ltd., biphenyl novolac epoxy, epoxy equivalent: 275 g / eq, melting point: 0°C or less)

[0182] (Other Epoxy Compounds) EP7 (manufactured by Tokyo Chemical Industry Co., Ltd., 2,2-bis(4-glycidyloxyphenyl)propane, epoxy equivalent: 170 g / eq, melting point: 43°C) EP8 (manufactured by Tokyo Chemical Industry Co., Ltd., glycidyl phenyl ether, epoxy equivalent: 150 g / eq, melting point: 4°C) EP9 (manufactured by Mitsubishi Chemical Corporation, anthracene-type epoxy resin, epoxy equivalent: 169 g / eq, melting point: 109°C) EP10 (manufactured by Nagase ChemteX Corporation, resorcinol-type epoxy resin, epoxy equivalent: 117 g / eq, melting point: 32°C) EP11 (manufactured by DIC Corporation, 1,6-bis(2,3-epoxypropoxy)naphthalene, epoxy equivalent: 140 g / eq, melting point: 80°C)

[0183] (Component (C): Basic nitrogen-containing compound) HA1 (2-ethyl-4-methylimidazole, manufactured by Tokyo Chemical Industry Co., Ltd.) HA2 (diethylenetriamine, manufactured by Tokyo Chemical Industry Co., Ltd.) HA3 (2-undecymylimidazole, manufactured by Shikoku Chemical Industry Co., Ltd.) HA4 (imidazole, manufactured by Tokyo Chemical Industry Co., Ltd.)

[0184] (Production Example of Epoxy Resin Curing Agent) Example 1-1 EP1 and HA1 were mixed so that the active hydrogen equivalent of the amine was 0.7 per equivalent of epoxy group, and the mixture was reacted in a 1:1 mixed solvent of n-butanol and toluene at 80°C for 10 hours to obtain an amine adduct as a reaction product. Thereafter, excess amine was distilled off together with the solvent under reduced pressure, and a solid mass of amine adduct was obtained at 25°C. Next, the mass of amine adduct was pulverized in a jet mill, and then, using a Kryptron Orb manufactured by EarthTechnica Corporation, the mixture was pulverized in an environment of a temperature of 10°C, a humidity of 30%, a rotation speed of 13,500 rpm, a feed rate of 10 kg / hr, and an air volume of 3 m ３ / min, shape correction treatment was performed, and a cyclone type collector and a bag filter were attached to adjust the specific surface area value, and the circularity was 0.97 and the average particle size D ５０ is 2.3 μm, D ９９ / D ５０ A powdered epoxy resin curing agent having a viscosity of 2.7 was prepared by classification using a classifier.

[0185] Example 1-2 A mixed resin of EP1 and EP2 in a 1:1 mass ratio and HA1 were mixed so that the active hydrogen equivalent of the amine was 0.7 per equivalent of epoxy group, and the mixture was reacted in a 1:1 mixed solvent of n-butanol and toluene at 80°C for 10 hours to obtain an amine adduct as a reaction product. The excess amine was then distilled off together with the solvent under reduced pressure, and a solid mass of the amine adduct was obtained at 25°C. The mass of the amine adduct was then pulverized in a jet mill, and then crushed using a Kryptron Orb manufactured by EarthTechnica Corporation, in an environment of 10°C temperature and 30% humidity, at a rotation speed of 13,500 rpm, a feed rate of 10 kg / hr, and an air volume of 3 m. ３ / min, shape correction treatment was performed, and a cyclone type collector and a bag filter were attached to adjust the specific surface area value, and the circularity was 0.97 and the average particle size D ５０ is 2.3 μm, D ９９ / D ５０ A powdered epoxy resin curing agent having a viscosity of 2.7 was prepared by classification using a classifier.

[0186] Example 1-3 A mixed resin of EP3 and EP4 in a 1:1 mass ratio and HA1 were mixed so that the active hydrogen equivalent of the amine was 0.7 per equivalent of epoxy group, and the mixture was reacted in a 1:1 mixed solvent of n-butanol and toluene at 80°C for 10 hours to obtain an amine adduct as a reaction product. The excess amine was then distilled off together with the solvent under reduced pressure, and a solid mass of the amine adduct was obtained at 25°C. The mass of the amine adduct was then pulverized in a jet mill, and then crushed using a Kryptron Orb manufactured by EarthTechnica Corporation, in an environment of 10°C temperature and 30% humidity, at a rotation speed of 13,500 rpm, a feed rate of 10 kg / hr, and an air volume of 3 m. ３ / min, shape correction treatment was performed, and a cyclone type collector and a bag filter were attached to adjust the specific surface area value, and the circularity was 0.97 and the average particle size D ５０ is 2.3 μm, D ９９ / D ５０ A powdered epoxy resin curing agent having a viscosity of 2.7 was prepared by classification using a classifier.

[0187] Example 1-4 A mixed resin of EP1 and EP3 in a mass ratio of 1:1 was mixed with HA1 so that the active hydrogen equivalent of the amine was 0.7 per equivalent of epoxy group, and the mixture was reacted in a 1:1 mixed solvent of n-butanol and toluene at 80°C for 10 hours to obtain an amine adduct as a reaction product. The excess amine was then distilled off together with the solvent under reduced pressure, and a solid mass of the amine adduct was obtained at 25°C. The mass of the amine adduct was then pulverized in a jet mill, and then crushed using a Kryptron Orb manufactured by EarthTechnica Corporation, in an environment of 10°C temperature and 30% humidity, at a rotation speed of 13,500 rpm, a feed rate of 10 kg / hr, and an air volume of 3 m. ３ / min, shape correction treatment was performed, and a cyclone type collector and a bag filter were attached to adjust the specific surface area value, and the circularity was 0.97 and the average particle size D ５０ is 2.3 μm, D ９９ / D ５０ A powdered epoxy resin curing agent having a viscosity of 2.7 was prepared by classification using a classifier.

[0188] Example 1-5 A mixed resin of EP2 and EP3 in a 1:1 mass ratio and HA1 were mixed so that the active hydrogen equivalent of the amine was 0.7 per equivalent of epoxy group, and the mixture was reacted in a 1:1 mixed solvent of n-butanol and toluene at 80°C for 10 hours to obtain an amine adduct as a reaction product. The excess amine was then distilled off together with the solvent under reduced pressure, and a solid mass of the amine adduct was obtained at 25°C. The mass of the amine adduct was then pulverized in a jet mill, and then crushed using a Kryptron Orb manufactured by EarthTechnica Corporation, in an environment of 10°C temperature and 30% humidity, at a rotation speed of 13,500 rpm, a feed rate of 10 kg / hr, and an air volume of 3 m. ３ / min, shape correction treatment was performed, and a cyclone type collector and a bag filter were attached to adjust the specific surface area value, and the circularity was 0.97 and the average particle size D ５０ is 2.3 μm, D ９９ / D ５０ A powdered epoxy resin curing agent having a viscosity of 2.7 was prepared by classification using a classifier.

[0189] Example 1-6 A mixed resin of EP1 and EP3 in a 1:1 mass ratio and HA2 were mixed so that the active hydrogen equivalent of the amine was 0.7 per equivalent of epoxy group, and the mixture was reacted in a 1:1 mixed solvent of n-butanol and toluene at 80°C for 10 hours to obtain an amine adduct as a reaction product. The excess amine was then distilled off together with the solvent under reduced pressure, and a solid mass of the amine adduct was obtained at 25°C. The mass of the amine adduct was then pulverized in a jet mill, and then crushed using a Kryptron Orb manufactured by EarthTechnica Corporation, in an environment of 10°C temperature and 30% humidity, at a rotation speed of 13,500 rpm, a feed rate of 10 kg / hr, and an air volume of 3 m. ３ / min, shape correction treatment was performed, and a cyclone type collector and a bag filter were attached to adjust the specific surface area value, and the circularity was 0.97 and the average particle size D ５０ is 2.3 μm, D ９９ / D ５０ A powdered epoxy resin curing agent having a viscosity of 2.7 was prepared by classification using a classifier.

[0190] Example 1-7 A mixed resin of EP1 and EP4 in a mass ratio of 1:1 and HA1 were mixed so that the active hydrogen equivalent of the amine was 0.7 per equivalent of epoxy group, and the mixture was reacted in a 1:1 mixed solvent of n-butanol and toluene at 80°C for 10 hours to obtain an amine adduct as a reaction product. The excess amine was then distilled off together with the solvent under reduced pressure, and a solid mass of the amine adduct was obtained at 25°C. The mass of the amine adduct was then pulverized in a jet mill, and then crushed using a Kryptron Orb manufactured by EarthTechnica Corporation, in an environment of 10°C temperature and 30% humidity, at a rotation speed of 13,500 rpm, a feed rate of 10 kg / hr, and an air volume of 3 m. ３ / min, shape correction treatment was performed, and a cyclone type collector and a bag filter were attached to adjust the specific surface area value, and the circularity was 0.97 and the average particle size D ５０ is 2.3 μm, D ９９ / D ５０ A powdered epoxy resin curing agent having a viscosity of 2.7 was prepared by classification using a classifier.

[0191] Example 1-8 A 1:1 mass ratio mixed resin of EP1 and EP5 and HA1 were mixed so that the active hydrogen equivalent of the amine was 0.7 per equivalent of epoxy group, and the mixture was reacted in a 1:1 mixed solvent of n-butanol and toluene at 80°C for 10 hours to obtain an amine adduct as a reaction product. The excess amine was then distilled off together with the solvent under reduced pressure, and a solid mass of the amine adduct was obtained at 25°C. The mass of the amine adduct was then pulverized in a jet mill, and then crushed using a Kryptron Orb manufactured by EarthTechnica Corporation, in an environment of 10°C temperature and 30% humidity, at a rotation speed of 13,500 rpm, a feed rate of 10 kg / hr, and an air volume of 3 m. ３ / min, shape correction treatment was performed, and a cyclone type collector and a bag filter were attached to adjust the specific surface area value, and the circularity was 0.97 and the average particle size D ５０ is 2.3 μm, D ９９ / D ５０ A powdered epoxy resin curing agent having a viscosity of 2.7 was prepared by classification using a classifier.

[0192] Comparative Example 1-1 EP7 and HA1 were mixed so that the active hydrogen equivalent of the amine was 0.7 per equivalent of epoxy group, and the mixture was reacted in a 1:1 mixed solvent of n-butanol and toluene at 80°C for 10 hours to obtain an amine adduct as a reaction product. The excess amine was then distilled off together with the solvent under reduced pressure, and a solid mass of the amine adduct was obtained at 25°C. The mass of the amine adduct was then pulverized in a jet mill, and then crushed using a Kryptron Orb manufactured by EarthTechnica Corporation, in an environment of 10°C temperature and 30% humidity, at a rotation speed of 13,500 rpm, a feed rate of 10 kg / hr, and an air volume of 3 m. ３ / min, shape correction treatment was performed, and a cyclone type collector and a bag filter were attached to adjust the specific surface area value, and the circularity was 0.97 and the average particle size D ５０ is 2.3 μm, D ９９ / D ５０ A powdered epoxy resin curing agent having a viscosity of 2.7 was prepared by classification using a classifier.

[0193] Comparative Example 1-2 EP8 and HA1 were mixed so that the active hydrogen equivalent of the amine was 0.7 per equivalent of epoxy group, and the mixture was reacted in a 1:1 mixed solvent of n-butanol and toluene at 80°C for 10 hours to obtain an amine adduct as a reaction product. The excess amine was then distilled off together with the solvent under reduced pressure, and a solid mass of the amine adduct was obtained at 25°C. The mass of the amine adduct was then pulverized in a jet mill, and then crushed using a Kryptron Orb manufactured by EarthTechnica Corporation, in an environment of 10°C temperature and 30% humidity, at a rotation speed of 13,500 rpm, a feed rate of 10 kg / hr, and an air volume of 3 m. ３ / min, shape correction treatment was performed, and a cyclone type collector and a bag filter were attached to adjust the specific surface area value, and the circularity was 0.97 and the average particle size D ５０ is 2.3 μm, D ９９ / D ５０ A powdered epoxy resin curing agent having a viscosity of 2.7 was prepared by classification using a classifier.

[0194] Comparative Example 1-3 EP8 and HA2 were mixed so that the active hydrogen equivalent of the amine was 0.7 per equivalent of epoxy group, and the mixture was reacted in a 1:1 mixed solvent of n-butanol and toluene at 80°C for 10 hours to obtain an amine adduct as a reaction product. The excess amine was then distilled off together with the solvent under reduced pressure, and a solid mass of the amine adduct was obtained at 25°C. The mass of the amine adduct was then pulverized in a jet mill, and then crushed using a Kryptron Orb manufactured by EarthTechnica Corporation, in an environment of 10°C temperature and 30% humidity, at a rotation speed of 13,500 rpm, a feed rate of 10 kg / hr, and an air volume of 3 m. ３ / min, shape correction treatment was performed, and a cyclone type collector and a bag filter were attached to adjust the specific surface area value, and the circularity was 0.97 and the average particle size D ５０ is 2.3 μm, D ９９ / D ５０ A powdered epoxy resin curing agent having a viscosity of 2.7 was prepared by classification using a classifier.

[0195] Comparative Example 1-4 EP9 and HA3 were mixed so that the active hydrogen equivalent of the amine was 0.7 per equivalent of epoxy group, and the mixture was reacted in a 1:1 mixed solvent of n-butanol and toluene at 80°C for 10 hours to obtain an amine adduct as a reaction product. The excess amine was then distilled off together with the solvent under reduced pressure, and a solid mass of the amine adduct was obtained at 25°C. The mass of the amine adduct was then pulverized in a jet mill, and then crushed using a Kryptron Orb manufactured by EarthTechnica Corporation, in an environment of 10°C temperature and 30% humidity, at a rotation speed of 13,500 rpm, a feed rate of 10 kg / hr, and an air volume of 3 m. ３ / min, shape correction treatment was performed, and a cyclone type collector and a bag filter were attached to adjust the specific surface area value, and the circularity was 0.97 and the average particle size D ５０ is 2.3 μm, D ９９ / D ５０ A powdered epoxy resin curing agent having a viscosity of 2.7 was prepared by classification using a classifier.

[0196] Comparative Example 1-5 EP10 and HA4 were mixed so that the active hydrogen equivalent of the amine was 0.7 per equivalent of epoxy group, and the mixture was reacted in a 1:1 mixed solvent of n-butanol and toluene at 80°C for 10 hours to obtain an amine adduct as a reaction product. The excess amine was then distilled off together with the solvent under reduced pressure, and a solid mass of the amine adduct was obtained at 25°C. The mass of the amine adduct was then pulverized in a jet mill, and then crushed using a Kryptron Orb manufactured by EarthTechnica Corporation, in an environment of 10°C temperature and 30% humidity, at a rotation speed of 13,500 rpm, a feed rate of 10 kg / hr, and an air volume of 3 m. ３ / min, shape correction treatment was performed, and a cyclone type collector and a bag filter were attached to adjust the specific surface area value, and the circularity was 0.97 and the average particle size D ５０ is 2.3 μm, D ９９ / D ５０ A powdered epoxy resin curing agent having a viscosity of 2.7 was prepared by classification using a classifier.

[0197] [Preparation of Epoxy Resin Composition] 10 parts by mass of an epoxy resin curing agent and 100 parts by mass of bisphenol A type epoxy resin were stirred in a planetary mixer at 25° C. for 30 minutes to obtain an epoxy resin composition.

[0198] [Evaluation Method] (Cure Steepness (1)) The cure steepness of the epoxy resin composition was evaluated as follows. Using a differential scanning calorimeter (DSC7020, manufactured by Hitachi High-Tech Science Corporation), a 10 mg sample was heated from 30°C to 250°C at a heating rate of 10°C / min, and the temperature difference between the exothermic start temperature and the peak top temperature was evaluated according to the following criteria. <Evaluation Criteria> Temperature difference < 30°C ... A 30°C ≦ Temperature difference < 40°C ... B 40°C ≦ Temperature difference < 50°C ... C 50°C ≦ Temperature difference ... D

[0199] (Heat resistance of cured product) The epoxy resin composition was cured at 150°C for 2 hours to produce a cured product. The glass transition temperature (Tg) of the cured product was measured using a dynamic viscoelasticity measuring apparatus (DMA) according to the following procedures (I) to (III). (I) The cured product was cut into a piece approximately 8 mm wide x 30-50 mm long x approximately 2 mm thick, and the exact dimensions were measured and recorded to prepare a sample. (II) The sample was placed in the dynamic viscoelasticity measuring apparatus (DMA) and measured under the following conditions. - Apparatus: TA Instruments, "RSA-G2" - Measurement mode: 3-point bending - Frequency f = 1 Hz - Normal force: FN = -0.2 N - Temperature: 25 to 250°C (heating: 4°C / min) (III) From the storage modulus (G') and loss modulus (G'') obtained by the above measurement, the loss tangent (tan δ) = G'' / G' was calculated, and the peak top temperature of tan δ was determined as the glass transition temperature (Tg) of the cured product, which was evaluated according to the following criteria. <Evaluation criteria> Tg > 150°C .... A 150°C ≥ Tg > 140°C .... B 140°C ≥ Tg > 130°C .... C 120°C ≥ Tg .... D

[0200] (Adhesion: Shear Bond Strength) Test specimens were prepared from the epoxy resin composition in accordance with JIS K6850. Furthermore, as the adherend, a 12.5 mm wide x 100 mm long x 1.6 mm thick adherend (cold-rolled steel plate) conforming to JIS C3141 was used. After thermal curing at 100°C for 1 hour and then at 150°C for 1 hour, the maximum load at which the adhesive surface of the test specimen broke and the test specimen separated was measured, and this was taken as the shear bond strength, which was evaluated according to the following criteria. <Evaluation Criteria> Shear bond strength > 13 MPa ... A 13 MPa ≥ shear bond strength > 12 MPa ... B 12 MPa ≥ shear bond strength > 11 MPa ... C 11 MPa ≥ shear bond strength ... D

[0201] The evaluation results of Examples 1-1 to 1-8 and Comparative Examples 1-1 to 1-5 are shown in Table 1 below.

[0202]

[0203] As shown in Table 1, epoxy resin curing agents having SP values ​​and softening points within specific ranges and not containing a compound having a bisphenol structure are superior in various performance characteristics compared to those shown in the comparative examples. Furthermore, Examples 1-2 to 1-4, which used two or more types selected from the group consisting of components (A) and (B), showed improved cure steepness compared to Example 1-1, which used a single type. Furthermore, Example 1-4, which used a hydrogenated bisphenol-type epoxy as component (A), showed improved cure steepness compared to Example 1-5. Example 1-4, which used an imidazole compound as component (C), showed increased cure steepness compared to Example 1-6. Example 1-4, which used N,N-diglycidylaniline as component (B), showed improved heat resistance and adhesive strength of the cured product compared to Examples 1-7 and 1-8.

[0204] Example 2-1 (Epoxy Resin Curing Agent) EP1 and HA1 were mixed so that the active hydrogen equivalent of the amine was 0.7 per equivalent of epoxy group, and the mixture was reacted in a 1:1 mixed solvent of n-butanol and toluene at 80°C for 10 hours to obtain an amine adduct as a reaction product. The excess amine was then distilled off together with the solvent under reduced pressure, and a solid mass of the amine adduct was obtained at 25°C. The mass of the amine adduct was then pulverized in a jet mill, and then, using a Kryptron Orb manufactured by EarthTechnica Corporation, the mixture was pulverized in an environment of 10°C temperature and 30% humidity at a rotation speed of 13,500 rpm, a feed rate of 10 kg / hr, and an air volume of 3 m ３ / min, shape correction treatment was performed, and a cyclone type collector and a bag filter were attached to adjust the specific surface area value, and the circularity was 0.97 and the average particle size D ５０ is 2.3 μm, D ９９ / D ５０ A powdered epoxy resin curing agent with a viscosity of 2.7 was prepared by classification using a classifier. (Epoxy Resin Composition) 100 parts by mass of EP1, 100 parts by mass of EP4, 100 parts by mass of the curing agent, and 5 parts by mass of an encapsulating agent (Tosoh Corporation, Coronate T100) were then added and thoroughly dispersed and mixed, followed by reaction at 45°C for 10 hours to obtain a masterbatch-type curing agent. The TEM observation described above confirmed that the curing agent particles were microencapsulated.

[0205] Example 2-2 (Epoxy Resin Curing Agent) A mixed resin of EP1 and EP2 in a mass ratio of 1:1 was mixed with HA1 so that the active hydrogen equivalent of the amine was 0.7 per equivalent of epoxy group, and the mixture was reacted in a 1:1 mixed solvent of n-butanol and toluene at 80°C for 10 hours to obtain an amine adduct as a reaction product. The excess amine was then distilled off together with the solvent under reduced pressure, and a solid mass of the amine adduct was obtained at 25°C. The mass of the amine adduct was then pulverized in a jet mill, and then, using a Kryptron Orb manufactured by EarthTechnica Corporation, the mixture was pulverized in an environment of 10°C temperature and 30% humidity at a rotation speed of 13,500 rpm, a feed rate of 10 kg / hr, and an air volume of 3 m. ３ / min, shape correction treatment was performed, and a cyclone type collector and a bag filter were attached to adjust the specific surface area value, and the circularity was 0.97 and the average particle size D ５０ is 2.3 μm, D ９９ / D ５０ A powdered epoxy resin curing agent with a viscosity of 2.7 was prepared by classification using a classifier. (Epoxy Resin Composition) 100 parts by mass of EP1, 100 parts by mass of EP4, 100 parts by mass of the curing agent, and 5 parts by mass of an encapsulating agent (Tosoh Corporation, Coronate T100) were then added and thoroughly dispersed and mixed, followed by reaction at 45°C for 10 hours to obtain a masterbatch-type curing agent. The TEM observation described above confirmed that the curing agent particles were microencapsulated.

[0206] Example 2-3 (Epoxy Resin Curing Agent) A 1:1 mass ratio mixed resin of EP3 and EP4 was mixed with HA1 so that the active hydrogen equivalent of the amine was 0.7 per equivalent of epoxy group, and the mixture was reacted in a 1:1 mixed solvent of n-butanol and toluene at 80°C for 10 hours to obtain an amine adduct as a reaction product. The excess amine was then distilled off together with the solvent under reduced pressure, and a solid mass of the amine adduct was obtained at 25°C. The mass of the amine adduct was then pulverized in a jet mill, and then, using a Kryptron Orb manufactured by EarthTechnica Corporation, the mixture was pulverized in an environment of 10°C temperature and 30% humidity at a rotation speed of 13,500 rpm, a feed rate of 10 kg / hr, and an air volume of 3 m. ３ / min, shape correction treatment was performed, and a cyclone type collector and a bag filter were attached to adjust the specific surface area value, and the circularity was 0.97 and the average particle size D ５０ is 2.3 μm, D ９９ / D ５０ A powdered epoxy resin curing agent with a viscosity of 2.7 was prepared by classification using a classifier. (Epoxy Resin Composition) 100 parts by mass of EP1, 100 parts by mass of EP4, 100 parts by mass of the curing agent, and 5 parts by mass of an encapsulating agent (Tosoh Corporation, Coronate T100) were then added and thoroughly dispersed and mixed, followed by reaction at 45°C for 10 hours to obtain a masterbatch-type curing agent. The TEM observation described above confirmed that the curing agent particles were microencapsulated.

[0207] Example 2-4 (Epoxy Resin Curing Agent) A mixed resin of EP1 and EP3 in a mass ratio of 1:1 was mixed with HA1 so that the active hydrogen equivalent of the amine was 0.7 per equivalent of epoxy group, and the mixture was reacted in a 1:1 mixed solvent of n-butanol and toluene at 80°C for 10 hours to obtain an amine adduct as a reaction product. The excess amine was then distilled off together with the solvent under reduced pressure, and a solid mass of the amine adduct was obtained at 25°C. The mass of the amine adduct was then pulverized in a jet mill, and then, using a Kryptron Orb manufactured by EarthTechnica Corporation, the mixture was pulverized in an environment of 10°C temperature and 30% humidity at a rotation speed of 13,500 rpm, a feed rate of 10 kg / hr, and an air volume of 3 m. ３ / min, shape correction treatment was performed, and a cyclone type collector and a bag filter were attached to adjust the specific surface area value, and the circularity was 0.97 and the average particle size D ５０ is 2.3 μm, D ９９ / D ５０ A powdered epoxy resin curing agent with a viscosity of 2.7 was prepared by classification using a classifier. (Epoxy Resin Composition) 100 parts by mass of EP1, 100 parts by mass of EP4, 100 parts by mass of the curing agent, and 5 parts by mass of an encapsulating agent (Tosoh Corporation, Coronate T100) were then added and thoroughly dispersed and mixed, followed by reaction at 45°C for 10 hours to obtain a masterbatch-type curing agent. The TEM observation described above confirmed that the curing agent particles were microencapsulated.

[0208] Example 2-5 (Epoxy Resin Curing Agent) A mixed resin of EP1 and EP3 in a mass ratio of 1:1 was mixed with HA1 so that the active hydrogen equivalent of the amine was 0.7 per equivalent of epoxy group, and the mixture was reacted in a 1:1 mixed solvent of n-butanol and toluene at 80°C for 10 hours to obtain an amine adduct as a reaction product. The excess amine was then distilled off together with the solvent under reduced pressure, and a solid mass of the amine adduct was obtained at 25°C. The mass of the amine adduct was then pulverized in a jet mill, and then, using a Kryptron Orb manufactured by EarthTechnica Corporation, the mixture was pulverized in an environment of 10°C temperature and 30% humidity at a rotation speed of 13,500 rpm, a feed rate of 10 kg / hr, and an air volume of 3 m. ３ / min, shape correction treatment was performed, and a cyclone type collector and a bag filter were attached to adjust the specific surface area value, and the circularity was 0.97 and the average particle size D ５０ is 2.3 μm, D ９９ / D ５０ A powdered epoxy resin curing agent with a viscosity of 2.7 was prepared by classification using a classifier. (Epoxy Resin Composition) 100 parts by mass of EP1, 100 parts by mass of EP6, 100 parts by mass of the curing agent, and 5 parts by mass of an encapsulating agent (Tosoh Corporation, Coronate T100) were then added and thoroughly dispersed and mixed, followed by reaction at 45°C for 10 hours to obtain a masterbatch-type curing agent. The TEM observation described above confirmed that the curing agent particles were microencapsulated.

[0209] Example 2-6 (Epoxy Resin Curing Agent) A mixed resin of EP1 and EP3 in a mass ratio of 1:1 was mixed with HA1 so that the active hydrogen equivalent of the amine was 0.7 per equivalent of epoxy group, and the mixture was reacted in a 1:1 mixed solvent of n-butanol and toluene at 80°C for 10 hours to obtain an amine adduct as a reaction product. The excess amine was then distilled off together with the solvent under reduced pressure, and a solid mass of the amine adduct was obtained at 25°C. The mass of the amine adduct was then pulverized in a jet mill, and then, using a Kryptron Orb manufactured by EarthTechnica Corporation, the mixture was pulverized in an environment of 10°C temperature and 30% humidity at a rotation speed of 13,500 rpm, a feed rate of 10 kg / hr, and an air volume of 3 m. ３ / min, shape correction treatment was performed, and a cyclone type collector and a bag filter were attached to adjust the specific surface area value, and the circularity was 0.97 and the average particle size D ５０ is 2.3 μm, D ９９ / D ５０ A powdered epoxy resin curing agent with a σ of 2.7 was prepared by classification using a classifier. (Epoxy Resin Composition) 150 parts by mass of EP1, 50 parts by mass of E11, 100 parts by mass of the curing agent, and 5 parts by mass of an encapsulating agent (Tosoh Corporation, Coronate T100) were then added, thoroughly dispersed and mixed, and reacted at 45°C for 10 hours to obtain a masterbatch-type curing agent. The TEM observation described above confirmed that the curing agent particles were microencapsulated.

[0210] Example 2-7 (Epoxy Resin Curing Agent) A mixed resin of EP1 and EP3 in a mass ratio of 1:1 was mixed with HA1 so that the active hydrogen equivalent of the amine was 0.7 per equivalent of epoxy group, and the mixture was reacted in a 1:1 mixed solvent of n-butanol and toluene at 80°C for 10 hours to obtain an amine adduct as a reaction product. The excess amine was then distilled off together with the solvent under reduced pressure, and a solid mass of the amine adduct was obtained at 25°C. The mass of the amine adduct was then pulverized in a jet mill, and then, using a Kryptron Orb manufactured by EarthTechnica Corporation, the mixture was pulverized in an environment of 10°C temperature, 30% humidity, at a rotation speed of 13,500 rpm, a feed rate of 10 kg / hr, and an air volume of 3 m. ３ / min, shape correction treatment was performed, and a cyclone type collector and a bag filter were attached to adjust the specific surface area value, and the circularity was 0.97 and the average particle size D ５０ is 2.3 μm, D ９９ / D ５０ A powdered epoxy resin curing agent with a viscosity of 2.7 was prepared by classification using a classifier. (Epoxy Resin Composition) 50 parts by mass of EP1, 150 parts by mass of EP11, 100 parts by mass of the curing agent, and 5 parts by mass of an encapsulating agent (Tosoh Corporation, Coronate T100) were then added and thoroughly dispersed and mixed, followed by reaction at 45°C for 10 hours to obtain a masterbatch-type curing agent. The TEM observation described above confirmed that the curing agent particles were microencapsulated.

[0211] Example 2-8 (Epoxy Resin Curing Agent) A mixed resin of EP1 and EP3 in a mass ratio of 1:1 was mixed with HA1 so that the active hydrogen equivalent of the amine was 0.7 per equivalent of epoxy group, and the mixture was reacted in a 1:1 mixed solvent of n-butanol and toluene at 80°C for 10 hours to obtain an amine adduct as a reaction product. The excess amine was then distilled off together with the solvent under reduced pressure, and a solid mass of the amine adduct was obtained at 25°C. The mass of the amine adduct was then pulverized in a jet mill, and then, using a Kryptron Orb manufactured by EarthTechnica Corporation, the mixture was pulverized in an environment of 10°C temperature and 30% humidity at a rotation speed of 13,500 rpm, a feed rate of 10 kg / hr, and an air volume of 3 m. ３ / min, shape correction treatment was performed, and a cyclone type collector and a bag filter were attached to adjust the specific surface area value, and the circularity was 0.97 and the average particle size D ５０ is 2.3 μm, D ９９ / D ５０ A powdered epoxy resin curing agent with a σ of 2.7 was prepared by classification using a classifier. (Epoxy Resin Composition) 200 parts by mass of EP11, 100 parts by mass of the curing agent, and 5 parts by mass of an encapsulating agent (Tosoh Corporation, Coronate T100) were then added, thoroughly dispersed and mixed, and reacted at 45°C for 10 hours to obtain a masterbatch-type curing agent. The TEM observation described above confirmed that the curing agent particles were microencapsulated.

[0212] Example 2-9 (Epoxy Resin Curing Agent) A mixed resin of EP1 and EP3 in a mass ratio of 1:1 was mixed with HA1 so that the active hydrogen equivalent of the amine was 0.7 per equivalent of epoxy group, and the mixture was reacted in a 1:1 mixed solvent of n-butanol and toluene at 80°C for 10 hours to obtain an amine adduct as a reaction product. The excess amine was then distilled off together with the solvent under reduced pressure, and a solid mass of the amine adduct was obtained at 25°C. The mass of the amine adduct was then pulverized in a jet mill, and then, using a Kryptron Orb manufactured by EarthTechnica Corporation, the mixture was pulverized in an environment of 10°C temperature and 30% humidity at a rotation speed of 13,500 rpm, a feed rate of 10 kg / hr, and an air volume of 3 m. ３ / min, shape correction treatment was performed, and a cyclone type collector and a bag filter were attached to adjust the specific surface area value, and the circularity was 0.97 and the average particle size D５０ is 2.3 μm, D ９９ / D ５０ A powdered epoxy resin curing agent with a viscosity of 2.7 was prepared by classification using a classifier. (Epoxy Resin Composition) 50 parts by mass of EP1, 150 parts by mass of EP6, 100 parts by mass of the curing agent, and 5 parts by mass of an encapsulating agent (Tosoh Corporation, Coronate T100) were then added and thoroughly dispersed and mixed, followed by reaction at 45°C for 10 hours to obtain a masterbatch-type curing agent. The TEM observation described above confirmed that the curing agent particles were microencapsulated.

[0213] Example 2-10 (Epoxy Resin Curing Agent) A 1:1 mixed resin of EP1 and EP3 was mixed with HA1 so that the active hydrogen equivalent of the amine was 0.7 per equivalent of epoxy group, and the mixture was reacted in a 1:1 mixed solvent of n-butanol and toluene at 80°C for 10 hours to obtain an amine adduct as a reaction product. Thereafter, excess amine was distilled off together with the solvent under reduced pressure, and a solid block-shaped amine adduct was obtained at 25°C. The block-shaped amine adduct was then jet milled to obtain an average particle size D ５０ is 2.3 μm, D ９９ / D ５０ The epoxy resin curing agent prepared as described above was subjected to a pulverization treatment using a Kryptron Orb manufactured by EarthTechnica Corporation under an environment of a temperature of 10°C, a humidity of 30%, a rotation speed of 13,500 rpm, a supply rate of 10 kg / hr, and an air volume of 3 m ３ / min, shape correction was performed, and a surface-modified product (B'-1) was produced. A cyclone collector and a bag filter were attached to adjust the specific surface area, and a classifier was used to produce an epoxy resin curing agent with a circularity of 0.97 and an average particle size of 2.6 μm. (Epoxy Resin Composition) 200 parts by mass of EP4, 100 parts by mass of the curing agent, and 5 parts by mass of an encapsulating agent (Tosoh Corporation, Coronate T100) were then added, thoroughly dispersed and mixed, and reacted at 45°C for 10 hours to produce a masterbatch-type curing agent. The TEM observation described above confirmed that the curing agent particles were microencapsulated.

[0214] Example 2-11 (Epoxy Resin Curing Agent) A 1:1 mixed resin of EP2 and EP3 was mixed with HA1 so that the active hydrogen equivalent of the amine was 0.7 per equivalent of epoxy group, and the mixture was reacted in a 1:1 mixed solvent of n-butanol and toluene at 80°C for 10 hours to obtain an amine adduct as a reaction product. The excess amine was then distilled off together with the solvent under reduced pressure, and a solid block-shaped amine adduct was obtained at 25°C. The block-shaped amine adduct was then jet milled to obtain an average particle size D ５０ is 2.3 μm, D ９９ / D ５０ The epoxy resin curing agent prepared as described above was subjected to a pulverization treatment using a Kryptron Orb manufactured by EarthTechnica Corporation under an environment of a temperature of 10°C, a humidity of 30%, a rotation speed of 13,500 rpm, a supply rate of 10 kg / hr, and an air volume of 3 m ３ / min, shape correction was performed, and a surface-modified product (B'-1) was produced. A cyclone collector and a bag filter were attached to adjust the specific surface area, and a classifier was used to produce an epoxy resin curing agent with a circularity of 0.97 and an average particle size of 2.6 μm. (Epoxy Resin Composition) 100 parts by mass of EP1, 100 parts by mass of EP4, 100 parts by mass of the curing agent, and 5 parts by mass of an encapsulating agent (Tosoh Corporation, Coronate T100) were then added, thoroughly dispersed and mixed, and reacted at 45°C for 10 hours to produce a masterbatch-type curing agent. The TEM observation described above confirmed that the curing agent particles were microencapsulated.

[0215] Example 2-12 (Epoxy Resin Curing Agent) A 1:1 mixed resin of EP1 and EP3 was mixed with HA2 so that the active hydrogen equivalent of the amine was 0.7 per equivalent of epoxy group, and the mixture was reacted in a 1:1 mixed solvent of n-butanol and toluene at 80°C for 10 hours to obtain an amine adduct as a reaction product. The excess amine was then distilled off together with the solvent under reduced pressure, and a solid block-shaped amine adduct was obtained at 25°C. The block-shaped amine adduct was then jet milled to obtain an average particle size D ５０ is 2.3 μm, D ９９ / D ５０The epoxy resin curing agent prepared as described above was subjected to a pulverization treatment using a Kryptron Orb manufactured by EarthTechnica Corporation under an environment of a temperature of 10°C, a humidity of 30%, a rotation speed of 13,500 rpm, a supply rate of 10 kg / hr, and an air volume of 3 m ３ / min, shape correction was performed, and a surface-modified product (B'-1) was produced. A cyclone collector and a bag filter were attached to adjust the specific surface area, and a classifier was used to produce an epoxy resin curing agent with a circularity of 0.97 and an average particle size of 2.6 μm. (Epoxy Resin Composition) 100 parts by mass of EP1, 100 parts by mass of EP4, 100 parts by mass of the curing agent, and 5 parts by mass of an encapsulating agent (Tosoh Corporation, Coronate T100) were then added, thoroughly dispersed and mixed, and reacted at 45°C for 10 hours to produce a masterbatch-type curing agent. The TEM observation described above confirmed that the curing agent particles were microencapsulated.

[0216] Example 2-13 (Epoxy Resin Curing Agent) A 1:1 mixed resin of EP1 and EP4 was mixed with HA1 so that the active hydrogen equivalent of the amine was 0.7 per equivalent of epoxy group, and the mixture was reacted in a 1:1 mixed solvent of n-butanol and toluene at 80°C for 10 hours to obtain an amine adduct as a reaction product. Thereafter, excess amine was distilled off together with the solvent under reduced pressure, and a solid block-shaped amine adduct was obtained at 25°C. The block-shaped amine adduct was then jet milled to obtain an average particle size D ５０ is 2.3 μm, D ９９ / D ５０ The epoxy resin curing agent prepared as described above was subjected to a pulverization treatment using a Kryptron Orb manufactured by EarthTechnica Corporation under an environment of a temperature of 10°C, a humidity of 30%, a rotation speed of 13,500 rpm, a supply rate of 10 kg / hr, and an air volume of 3 m ３ / min, shape correction was performed, and a surface-modified product (B'-1) was produced. A cyclone collector and a bag filter were attached to adjust the specific surface area, and a classifier was used to produce an epoxy resin curing agent with a circularity of 0.97 and an average particle size of 2.6 μm. (Epoxy Resin Composition) 100 parts by mass of EP1, 100 parts by mass of EP4, 100 parts by mass of the curing agent, and 5 parts by mass of an encapsulating agent (Tosoh Corporation, Coronate T100) were then added, thoroughly dispersed and mixed, and reacted at 45°C for 10 hours to produce a masterbatch-type curing agent. The TEM observation described above confirmed that the curing agent particles were microencapsulated.

[0217] Example 2-14 (Epoxy Resin Curing Agent) A 1:1 mixed resin of EP1 and EP5 was mixed with HA1 so that the active hydrogen equivalent of the amine was 0.7 per equivalent of epoxy group, and the mixture was reacted in a 1:1 mixed solvent of n-butanol and toluene at 80°C for 10 hours to obtain an amine adduct as a reaction product. Thereafter, excess amine was distilled off together with the solvent under reduced pressure, and a solid block-shaped amine adduct was obtained at 25°C. The block-shaped amine adduct was then jet milled to obtain an average particle size D ５０ is 2.3 μm, D ９９ / D ５０ The epoxy resin curing agent prepared as described above was subjected to a pulverization treatment using a Kryptron Orb manufactured by EarthTechnica Corporation under an environment of a temperature of 10°C, a humidity of 30%, a rotation speed of 13,500 rpm, a supply rate of 10 kg / hr, and an air volume of 3 m ３ / min, shape correction was performed, and a surface-modified product (B'-1) was produced. A cyclone collector and a bag filter were attached to adjust the specific surface area, and a classifier was used to produce an epoxy resin curing agent with a circularity of 0.97 and an average particle size of 2.6 μm. (Epoxy Resin Composition) 100 parts by mass of EP1, 100 parts by mass of EP4, 100 parts by mass of the curing agent, and 5 parts by mass of an encapsulating agent (Tosoh Corporation, Coronate T100) were then added, thoroughly dispersed and mixed, and reacted at 45°C for 10 hours to produce a masterbatch-type curing agent. The TEM observation described above confirmed that the curing agent particles were microencapsulated.

[0218] [Evaluation Method] (Cure Steepness (2)) The cure steepness of the epoxy resin composition was evaluated as follows. Using a differential scanning calorimeter (DSC7020, manufactured by Hitachi High-Tech Science Corporation), a 10 mg sample was heated from 30°C to 250°C at a heating rate of 10°C / min, and the temperature difference between the exothermic start temperature and the peak top temperature was evaluated according to the following criteria. <Evaluation Criteria> Temperature difference < 20°C ... A 20°C ≦ Temperature difference < 30°C ... B 30°C ≦ Temperature difference < 40°C ... C 40°C ≦ Temperature difference ... D

[0219] (Heat resistance of cured product) The epoxy resin composition was cured at 150°C for 2 hours to produce a cured product. The glass transition temperature (Tg) of the cured product was measured using a dynamic viscoelasticity measuring device (DMA) according to the following procedures (I) to (III). (I): The cured product was cut into a piece approximately 8 mm wide x 30-50 mm long x approximately 2 mm thick, and the exact dimensions were measured and recorded to prepare a sample. (II): The sample was set in the dynamic viscoelasticity measuring device (DMA) and measured under the following conditions. - Apparatus: TA Instruments, "RSA-G2" - Measurement mode: 3-point bending - Frequency f = 1 Hz - Normal force: FN = -0.2 N - Temperature: 25 to 250°C (heating: 4°C / min) (III): From the storage modulus (G') and loss modulus (G'') obtained by the above measurement, the loss tangent (tan δ) = G'' / G' was calculated, and the peak top temperature of tan δ was determined as the glass transition temperature (Tg) of the cured product, which was evaluated according to the following criteria. <Evaluation criteria> Tg > 150°C .... A 150°C ≥ Tg > 140°C .... B 140°C ≥ Tg > 130°C .... C 120°C ≥ Tg .... D

[0220] (Adhesion: Shear Bond Strength) Test specimens were prepared from the epoxy resin composition in accordance with JIS K6850. Furthermore, as the adherend, a 12.5 mm wide x 100 mm long x 1.6 mm thick adherend (cold-rolled steel plate) conforming to JIS C3141 was used. After thermal curing at 100°C for 1 hour and then at 150°C for 1 hour, the maximum load at which the adhesive surface of the test specimen broke and the test specimen separated was measured, and this was taken as the shear bond strength, which was evaluated according to the following criteria. <Evaluation Criteria> Shear bond strength > 13 MPa ... A 13 MPa ≥ shear bond strength > 12 MPa ... B 12 MPa ≥ shear bond strength > 11 MPa ... C 11 MPa ≥ shear bond strength ... D

[0221] The evaluation results of Examples 2-1 to 2-14 are shown in Table 2 below.

[0222]

[0223] As shown in Table 2, Example 2-7, which used an epoxy compound with a viscosity of 0.1 to 10 Pa s at 25°C, showed improved cure steepness and adhesive strength compared to Examples 2-9 and 2-10, which had a viscosity outside the range of 0.1 to 10 Pa s. Example 2-7, in which the proportion of component (A) or component (B) as the epoxy resin was less than 60 mass%, showed deterioration in various physical properties compared to Example 2-6, in which the proportion was 60 mass% or more.

[0224] Example A [Preparation of Encapsulant and Film] 100 parts by weight of hydrogenated bisphenol A epoxy resin (YX8000D, manufactured by Mitsubishi Chemical Corporation), 40 parts by weight of HN-2200 (manufactured by Hitachi Chemical Co., Ltd.), a curing agent primarily composed of phthalic anhydride, and 80 parts by weight of spherical fused silica with an average particle size of 16 μm, were uniformly dispersed and blended. Five parts by weight of the epoxy resin curing agent obtained in Example 1 were added to obtain an epoxy resin composition. The resulting epoxy resin composition was applied to a 1 cm square area on a printed wiring board to a thickness of 60 μm and semi-cured by heating in an oven at 110°C for 10 minutes. A 370 μm thick, 1 cm square silicon chip was then placed on the semi-cured epoxy resin composition, and a load was applied to maintain contact between the bumps and the chip electrodes while the chip was fully cured at 220°C for 1 hour. The resulting encapsulant made from the epoxy resin composition was useful, with no problems in appearance or chip conductivity. 100 parts by mass of bisphenol F epoxy resin (manufactured by Mitsubishi Chemical Corporation: jER YL983U), 40 parts by mass of HN-2200 (manufactured by Hitachi Chemical Co., Ltd.) curing agent, which is primarily composed of phthalic anhydride, and 80 parts by mass of spherical fused silica with an average particle size of 16 μm, were dissolved in 20 parts by mass of a 1:1 (mass ratio) mixed solvent of methyl ethyl ketone and butyl cellosolve acetate to obtain a solution. To this solution, 30 parts by mass of the epoxy resin curing agent obtained in Example 1 was added, and the mixture was further mixed uniformly. The mixture was cast onto a 40 μm thick polypropylene film and dried and semi-cured at 80°C for 60 minutes to obtain a 35 μm thick sealing film. The resulting sealing film made from the epoxy resin composition was useful and had no problems with appearance or chip conductivity.

[0225] Example B [Preparation of Conductive Material and Film] 100 parts by weight of hydrogenated bisphenol A epoxy resin (YX8000D, manufactured by Mitsubishi Chemical Corporation), 10 parts by weight of the epoxy resin curing agent obtained in Example 1, 150 g of flaky silver powder (manufactured by Tokuriki Chemical Laboratory Co., Ltd.) with an average particle size of 14 μm and an aspect ratio of 11, and 60 g of flaky nickel powder (manufactured by Kojundo Chemical Co., Ltd., product name "NI110104") with an average particle size of 10 μm and an aspect ratio of 9 were added, stirred until homogeneous, and then dispersed uniformly using a three-roll mill to prepare a conductive paste. The resulting conductive paste was screen-printed on a 1.4 mm thick polyimide film substrate and then heat-cured at 200°C for 1 hour. The conductivity of the resulting wiring board was measured, and it was found to be useful as a conductive paste. 15 parts by mass of hydrogenated bisphenol A epoxy resin (manufactured by Mitsubishi Chemical Corporation: YX8000D), 6 parts by mass of phenol novolac resin (manufactured by Showa Polymer Co., Ltd., product name "BRG-558"), and 4 parts by mass of synthetic rubber (manufactured by Nippon Zeon Corporation, product name "Nipol 1072", weight average molecular weight 300,000) were dissolved in 20 parts by mass of a 1:1 (mass ratio) mixed solvent of methyl ethyl ketone and butyl cellosolve acetate to obtain a solution. 74 parts by mass of silver powder was mixed with this solution and further kneaded using a three-roll mill. 30 parts by mass of the epoxy resin curing agent obtained in Example 1 was then added to this mixture and further mixed uniformly to obtain a conductive adhesive. The obtained conductive adhesive was cast onto a 40 μm thick polypropylene film and dried and semi-cured at 80°C for 60 minutes to obtain a conductive film with a 35 μm thick conductive adhesive layer. Using this conductive film, a conductive adhesive layer was transferred to the backside of a silicon wafer on a heat block at 80°C. Furthermore, the silicon wafer was fully diced, and a semiconductor chip with conductive adhesive was attached to a lead frame on a heat block and cured at 200°C for 2 minutes, revealing that there were no problems with the chip's conductivity.

[0226] Example C [Preparation of Thermally Conductive Material and Film] 100 parts by weight of hydrogenated bisphenol A epoxy resin (YX8000D, manufactured by Mitsubishi Chemical Corporation), 40 parts by weight of a 50% methyl ethyl ketone solution of phenol novolac resin (Tamanol 759, manufactured by Arakawa Chemical Industries, Ltd.) as an epoxy resin curing agent, and 15 parts by weight of flake graphite powder (HOPG, manufactured by Union Carbide Corporation) were stirred until homogeneous and then dispersed uniformly using a three-roll mill. 15 parts by weight of the epoxy resin curing agent obtained in Example 1 was added and thoroughly stirred to prepare a thermally conductive material. A semiconductor chip (1.5 mm square, 0.8 mm thick) was mounted on a Cu lead frame using the resulting thermally conductive material and heat-cured at 150°C for 30 minutes to obtain an evaluation sample. The thermal conductivity of the resulting sample was measured using a laser flash method. That is, the thermal conductivity K was calculated from the measured thermal diffusivity α, specific heat Cp, and density σ using the following formula, K = α × Cp × σ, and it was found that K was 5 × 10 －３ The thermal conductivity was greater than or equal to cal / cm·sec·°C, making it a useful thermally conductive material. 100 parts by mass of hydrogenated bisphenol A epoxy resin (YX8000D, manufactured by Mitsubishi Chemical Corporation), 30 parts by mass of phenoxy resin (YP-50, manufactured by Tohto Kasei Co., Ltd.), 40 parts by mass of a 50% methyl ethyl ketone solution of phenol novolac resin (Tamanol 759, manufactured by Arakawa Chemical Industries, Ltd.) as an epoxy resin curing agent, and 15 parts by mass of flake graphite powder (HOPG, manufactured by Union Carbide Corporation) were stirred until homogeneous, and then uniformly dispersed using a three-roll mill. To this mixture, 15 parts by mass of the epoxy resin curing agent obtained in Example 1 was added, and the mixture was thoroughly stirred and mixed to form a thermally conductive film. Using the resulting thermally conductive film, a semiconductor chip (1.5 mm square, 0.8 mm thick) was mounted on a Cu lead frame and heat-cured at 150°C for 30 minutes to obtain an evaluation sample. The thermal conductivity of the obtained sample was measured by a laser flash method. That is, the thermal conductivity K was calculated from the measured thermal diffusivity α, specific heat Cp, and density σ using the following formula, K = α × Cp × σ. K was found to be 5 × 10 －３ cal / cm·sec·°C or more, and was useful as a thermally conductive film.

[0227] Example D [Preparation of Insulating Material and Film] 100 parts by mass of hydrogenated bisphenol A epoxy resin (manufactured by Mitsubishi Chemical Corporation: YX8000D), 4 parts by mass of dicyandiamide, 100 parts by mass of silica powder, 10 parts by mass of phenyl glycidyl ether as a diluent, and 1 part by mass of an organic phosphate ester (manufactured by Nippon Kayaku Co., Ltd., trade name "PM-2") were thoroughly mixed and then further kneaded with a three-roll mill. 30 parts by mass of the epoxy resin curing agent obtained in Example 1 were added thereto, and the mixture was further mixed uniformly. The mixture was then subjected to vacuum degassing and centrifugal degassing treatments to produce an insulating paste. The resulting insulating paste was used to bond a semiconductor chip to a resin substrate by heating and curing at 200°C for 1 hour, and the paste was found to be useful as an insulating paste. 100 parts by mass of hydrogenated bisphenol A epoxy resin (YX8000D manufactured by Mitsubishi Chemical Corporation), 100 parts by mass of phenoxy resin (YP50 manufactured by Nippon Steel Chemical & Material Co., Ltd.), phenolic resin curing agent (LA7054 manufactured by DIC Corporation), 20 parts by mass of activated ester resin (HPC8000 manufactured by DIC Corporation), and 200 parts by mass of filler (SO-C2 manufactured by Admatechs Co., Ltd.) were uniformly dispersed and blended. Five parts by mass of the epoxy resin curing agent obtained in Example 1 were added to this mixture to obtain an epoxy resin composition. A mold made of 100 mm x 100 mm Teflon plates was sandwiched between two Teflon plates, and the epoxy resin composition was poured into the mold and thermally cured at 180°C for 60 minutes to obtain a cured product. The cured product was cut into test pieces measuring 2 mm wide and 80 mm long, and the dielectric constant (ε) and dielectric loss tangent (tanδ) were measured at a measurement frequency of 1.0 GHz by the cavity resonance method using a cavity resonator perturbation dielectric constant measuring device manufactured by Kanto Applied Electronics Development Co., Ltd. and a network analyzer E8362B manufactured by Agilent Technologies, Inc. The epoxy resin composition of this embodiment had a value of √ε × tanδ of 0.01, and was therefore useful as an interlayer insulating film.

[0228] (Example E) [Preparation of Camera Module Adhesive] 100 parts by mass of hydrogenated bisphenol A epoxy resin (manufactured by Mitsubishi Chemical Corporation: YX8000D), 65 parts by mass of thiol curing agent (manufactured by SC Organic Chemical Co., Ltd.: PEMP), and 30 parts by mass of the epoxy resin curing agent obtained in Example 1 were added and mixed uniformly, and subjected to reduced pressure degassing and centrifugal degassing treatment to produce a camera module adhesive. Using the obtained camera module adhesive, a camera holder and a Si-based semiconductor chip were bonded by heat curing at 80 ° C. for 5 minutes. The test piece obtained was then heated and cured at 80 ° C. for 5 minutes. Using an AGX-5kNX manufactured by Shimadzu Corporation, the maximum load at which the adhesive surface of the test piece broke and the test piece separated was measured at a speed of 5 kN and 5 mm / min. The value obtained by dividing the maximum load at which the test piece separated by the adhesive area was 20 MPa, making it useful as an adhesive for camera modules.

[0229] Example F Preparation of a structural adhesive 100 parts by mass of hydrogenated bisphenol A epoxy resin (YX8000D manufactured by Mitsubishi Chemical Corporation) and 4 parts by mass of dicyandiamide were thoroughly mixed and then further kneaded using a triple roll mill. 30 parts by mass of the epoxy resin curing agent obtained in Example 1 was then added thereto, and the mixture was further mixed uniformly. The mixture was then subjected to vacuum degassing and centrifugal degassing treatments to produce a structural adhesive.

[0230] Example G: Prepreg Preparation (Example of Use as a Matrix Resin for Fiber-Reinforced Plastics) The prepreg of this embodiment uses an epoxy resin composition containing the epoxy resin curing agent of this embodiment described above. The prepreg of this embodiment can be produced by impregnating a reinforcing substrate with the epoxy resin composition of this embodiment and heating it, as described, for example, in JP-A-9-71633 and WO 98 / 44017. Examples of solvents for the varnish used for impregnation include methyl ethyl ketone, acetone, ethyl cellosolve, methanol, ethanol, isopropyl alcohol, etc., and it is preferable that these solvents do not remain in the prepreg. The type of reinforcing substrate is not particularly limited, but examples include paper, glass cloth, glass nonwoven fabric, aramid cloth, and liquid crystal polymer. The ratio of the epoxy resin composition to the reinforcing substrate is also not particularly limited, but it is generally preferable to adjust the resin content in the prepreg to 20 to 80% by mass. The prepreg of this embodiment produces a cured product with excellent heat resistance and breaking elongation.

[0231] Example H Preparation of Impregnating Fixing Material 100 parts by mass of hydrogenated bisphenol A epoxy resin (YX8000D manufactured by Mitsubishi Chemical Corporation) and 40 parts by mass of HN-2200 (manufactured by Hitachi Chemical Co., Ltd.), a curing agent primarily composed of phthalic anhydride, were uniformly dispersed and blended. Five parts by mass of the epoxy resin curing agent obtained in Example 1 were added to obtain an epoxy resin composition. The glass transition temperature of the cured product of the obtained epoxy resin composition was measured using a thermomechanical analyzer, TMA / SS6000 manufactured by Seiko Instruments Inc., at a heating rate of 10°C / min, at temperatures of 30°C to 250°C, and in an air atmosphere. The epoxy resin composition of this embodiment had excellent heat resistance and was useful as an impregnating fixing material.

[0232] Example J [Preparation of Film-Type Solder Resist] 18 parts by mass of hydrogenated bisphenol A epoxy resin (YX8000D, manufactured by Mitsubishi Chemical Corporation), 18 parts by mass of phenoxy resin (YP50, manufactured by Nippon Steel Chemical & Material Co., Ltd.), 90 parts by mass of alkali-soluble resin (8KQ-2001, manufactured by Taisei Fine Chemical Co., Ltd.), 6 parts by mass of photopolymerization initiator (HCPK, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 15 parts by mass of photosensitive monomer (DPHA, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were uniformly dispersed and blended. One part by mass of the epoxy resin curing agent obtained in Example 1 was added to the mixture to obtain an epoxy resin composition. A film using the epoxy resin composition of this embodiment exhibited excellent adhesion and was useful as a film-type solder resist.

[0233] The curing agent for epoxy resins of the present invention is used in various paste materials such as insulating adhesive paste, conductive paste, anisotropic conductive paste, and thermally conductive paste, various coating materials, paints, etc., and has industrial applicability.

Claims

1. An epoxy resin curing agent comprising a reaction product of an epoxy compound and (C) a basic nitrogen-containing compound, wherein the epoxy compound comprises at least one selected from the group consisting of: (A) an aliphatic epoxy compound, and (B) an epoxy compound having at least one partial structure selected from the group consisting of a tert-butylphenyl structure, a biphenyl structure, and an N,N-diglycidylaniline structure.

2. An epoxy resin curing agent comprising a reaction product of an epoxy compound and (C) a basic nitrogen-containing compound, wherein: (1) the bond between the carbon atom and the oxygen atom of all epoxy groups in the epoxy compound in the reaction product is cleaved, the carbon atom is directly bonded to the nitrogen atom of the (C) basic nitrogen-containing compound, and the oxygen atom forms a hydroxyl group, and the solubility parameter defined by Fedor's equation is 11.0 to 15.0; (2) the softening point of the epoxy resin curing agent is 90 to 140°C; and (3) the epoxy resin curing agent does not contain a compound with a bisphenol structure.

3. The epoxy resin curing agent according to claim 1, wherein: (1) the solubility parameter defined by Fedor's equation for a structure in which the bonds between the carbon atoms and oxygen atoms of all epoxy groups in the epoxy compound in the reactant are cleaved, the carbon atoms are directly bonded to the nitrogen atoms of the (C) basic nitrogen-containing compound, and the oxygen atoms form hydroxyl groups, is 11.0 to 15.0; (2) the softening point of the epoxy resin curing agent is 90 to 140°C; and (3) the curing agent does not contain a compound containing a bisphenol structure.

4. The epoxy resin curing agent according to claim 1, wherein the epoxy compound comprises an epoxy compound having a melting point of 0°C or less.

5. The epoxy resin curing agent according to claim 2, wherein the epoxy compound comprises an epoxy compound having a melting point of 0°C or less.

6. The epoxy resin curing agent according to claim 1, wherein the epoxy compound comprises 2 to 10 species selected from the group consisting of (A) and (B).

7. The epoxy resin curing agent according to claim 1, wherein the epoxy compound comprises at least an epoxy compound having a hydrogenated bisphenol structure.

8. The epoxy resin curing agent according to claim 1, wherein the (C) basic nitrogen-containing compound comprises an imidazole compound.

9. The epoxy resin curing agent according to claim 1, wherein the epoxy compound contains at least an epoxy compound having an N,N-diglycidylaniline structure.

10. The epoxy resin curing agent according to claim 1, wherein the epoxy compound comprises (A) and (B).

11. The epoxy resin curing agent according to claim 1, wherein the epoxy compound comprises an epoxy compound having a hydrogenated bisphenol structure and an epoxy compound having an N,N-diglycidylaniline structure, and the (C) basic nitrogen-containing compound comprises an imidazole compound.

12. The epoxy resin curing agent according to claim 1, which is a microcapsule-type curing agent whose surface is coated with a shell.

13. An epoxy resin composition containing the epoxy resin curing agent according to any one of claims 1 to 12.

14. The epoxy resin composition according to claim 13, further comprising an epoxy compound (I).

15. The epoxy resin composition according to claim 14, wherein the epoxy compound (I) does not contain a bisphenol-type epoxy resin.

16. The epoxy resin composition according to claim 14, wherein the epoxy compound (I) contains at least one component selected from the group consisting of: (A): an aliphatic epoxy compound, and (B): an epoxy compound having at least one partial structure selected from the group consisting of a tert-butylphenyl structure, a biphenyl structure, and an N,N-diglycidylaniline structure.

17. The epoxy resin composition according to claim 15, wherein the epoxy compound (I) has a viscosity of 0.1 to 10 Pa·s at 25°C.

18. The epoxy resin composition according to claim 16, wherein the epoxy compound (I) contains at least one component selected from the group consisting of (A) and (B) in an amount of 60 mass% or more based on the total amount of the epoxy compound (I).

19. The epoxy resin composition according to claim 15, wherein the epoxy compound (I) comprises an epoxy resin having a hydrogenated bisphenol structure and / or an epoxy resin having a biphenyl structure.

20. An encapsulating material containing the epoxy resin composition according to claim 13.

21. A conductive material containing the epoxy resin composition according to claim 13.

22. A thermally conductive material containing the epoxy resin composition according to claim 13.

23. An insulating material containing the epoxy resin composition according to claim 13.

24. An adhesive for camera modules, comprising the epoxy resin composition according to claim 13.

25. A structural adhesive containing the epoxy resin composition of claim 13.

26. A matrix resin for fiber-reinforced plastics, comprising the epoxy resin composition according to claim 13.

27. An impregnating adhesive containing the epoxy resin composition of claim 13.

28. A film-type solder resist containing the epoxy resin composition according to claim 13.

29. A cured product of the epoxy resin composition according to claim 13.

30. A semiconductor device comprising the epoxy resin composition according to claim 13 or a cured product thereof.

31. A printed wiring board comprising the epoxy resin composition of claim 13 or a cured product thereof.

32. A semiconductor chip package comprising the epoxy resin composition of claim 13 or a cured product thereof.

33. An electronic device comprising the printed wiring board of claim 31.

34. An electronic device comprising the semiconductor chip package of claim 32.

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