Epoxy resin composition

Abstract

To provide an epoxy resin composition excellent in storage stability and cured physical properties in spite of being curable at a low temperature in a short time.SOLUTION: (A) a non-silicone-modified epoxy resin having two or more epoxy groups in one molecule, (B) an aromatic amine-based curing agent having two or more amino groups in one molecule, (C) a silicone-modified epoxy resin in an amount of 1 to 200 parts by mass with respect to 100 parts by mass of the component (A), (D) an aluminum chelate compound, and (E) a compound having one or more phenyl groups in one molecule, and one or more selected from an alkoxysilane having one or more alkoxy groups in one molecule and a partially hydrolyzed condensate of the alkoxysilane in an amount of 0.5 parts by mass or more and less than 3.0 parts by mass with respect to 100 parts by mass of the total of the components (A), (B), and (C), and (F) an inorganic filler in an amount of 10 parts by mass or more and 1,000 parts by mass or less with respect to 100 parts by mass of the total of the components (A), (B), and (C).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an epoxy resin composition, and preferably to an epoxy resin composition that is liquid at 25°C. [Background technology]

[0002] Epoxy resins are used in a wide range of applications, including electronic components, adhesives, and paints. Their properties and curing conditions vary depending on the type of curing agent, so they are used in combination with a variety of curing agents depending on the application. The main curing agents include amines, acid anhydrides, and phenols. Among these, aromatic amine curing agents are characterized by their ability to produce well-balanced cured products with adhesive properties and heat resistance, but have the disadvantage of requiring high-temperature curing.

[0003] In recent years, product development in line with the SDGs has been attracting attention, and there is a demand for epoxy resins with shorter curing times or low-temperature curing properties to save energy. To improve curing properties, it is common to add a curing accelerator to the epoxy resin composition.

[0004] As a curing accelerator for epoxy resins, for example, composite catalysts of metal complexes and silane compounds have been proposed. These composite catalysts do not remain as ionic impurities after acting to cure the epoxy resin, and therefore can accelerate the curing rate while preventing migration of the cured product (Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2008-255178 [Patent Document 2] Japanese Patent Application Laid-Open No. 2012-117033 Summary of the Invention [Problem to be solved by the invention]

[0006] However, adding a curing accelerator to an epoxy resin composition makes the reaction proceed easily even at room temperature, causing an increase in viscosity. This increase in viscosity shortens the pot life of the epoxy resin. Therefore, there is a trade-off between improved reactivity and increased viscosity, and it is difficult to create an epoxy resin composition that has both properties.

[0007] Therefore, an object of the present invention is to provide an epoxy resin composition that can be cured at low temperature in a short time, yet has excellent storage stability and cured physical properties. [Means for solving the problem]

[0008] In view of the above circumstances, the present inventors have conducted extensive research and found that the above problems can be solved by adding an aluminum chelate compound and a silane compound having a phenyl group to an epoxy resin composition containing an epoxy resin and an aromatic amine curing agent, thereby completing the present invention.

[0009] That is, the present invention provides the following epoxy resin composition [1]. [1] (A) a non-silicone-modified epoxy resin having two or more epoxy groups in one molecule; (B) an aromatic amine-based curing agent having two or more amino groups in one molecule, in an amount effective to cure the epoxy resin; (C) silicone-modified epoxy resin, 1 to 200 parts by mass per 100 parts by mass of component (A), (D) Aluminum chelate compound: 0.05 parts by mass or more and less than 3.0 parts by mass per 100 parts by mass of the total of the components (A), (B), and (C), (E) one or more selected from alkoxysilanes having one or more phenyl groups per molecule and one or more alkoxy groups per molecule, and partial hydrolysis condensates of such alkoxysilanes: 0.5 parts by mass or more but less than 3.0 parts by mass per 100 parts by mass of the total of the components (A), (B), and (C), and (F) inorganic filler: 10 parts by mass or more and 1,000 parts by mass or less per 100 parts by mass of the total of the (A) component, the (B) component, and the (C) component; 1. An epoxy resin composition comprising:

[0010] Furthermore, the present invention relates to an epoxy resin composition shown in any one of the following items [2] to

[11] . [2] The epoxy resin composition according to [1], wherein the amount of component (B) is such that the molar equivalent ratio of amino groups in component (B) per 1 molar equivalent of the total epoxy groups in components (A) and (C) is 0.8 or more and 1.2 or less. [3] The epoxy resin composition according to [1] or [2], wherein the component (C) is a hydrosilylation reaction product of an alkenyl group-containing epoxy resin having a weight-average molecular weight of 500 or more and an organohydrogen(poly)siloxane containing one or more hydrosilyl groups per molecule. [4] The epoxy resin composition according to any one of [1] to [3], wherein the organohydrogenpolysiloxane is represented by any one of the following formulas (1) to (3): [ka] (In formula (1), the siloxane units shown in each parentheses may be bonded randomly or may form block units, R is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and R 1 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R 2 is a group represented by the following formula (1'), and n 1 is an integer between 5 and 200, and n 2 is an integer between 0 and 2, and n 3 is an integer between 0 and 10, and n 4 is 0 or 1, and the R 1 at least one of the groups is a hydrogen atom [ka] (In formula (1'), R and R 1 is as above, and n 5 is an integer between 1 and 10) [ka] (In formula (2), the siloxane units shown in each parentheses may be bonded randomly or may form block units, R is as defined above, and n 6 is an integer between 1 and 10, and n 7 is 1 or 2, and n 6 +n 7 is 3 to 12) [ka] (In formula (3), R and R 1 is as defined above, r is an integer of 0 to 3, and R 3 is a hydrogen atom, or one or more groups selected from an alkyl group having 1 to 10 carbon atoms and an alkoxyalkyl group having 2 to 10 carbon atoms, and 1 or R 3 at least one of the groups is a hydrogen atom [5] The epoxy resin composition according to any one of [1] to [4], wherein the component (D) is a compound represented by the following formula (7): [ka] (In the above formula (7), R 3 are each independently an alkoxy group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms. [6] The epoxy resin composition according to any one of [1] to [5], wherein the component (D) is at least one selected from the group consisting of aluminum monoacetylacetonate bis(ethylacetoacetate) and aluminum tris(acetylacetonate). [7] The epoxy resin composition according to any one of [1] to [6], wherein the component (E) is an alkoxysilane having one or more phenyl groups in one molecule and one or more alkoxy groups having 1 to 4 carbon atoms in one molecule. [8] The epoxy resin composition according to any one of [1] to [7], wherein the silane compound of the component (E) is a partial hydrolysis condensate that is an oligomer having a degree of polymerization of 5 or less and containing one or more silanol groups. [9] The component (E) is an alkoxysilane represented by the following formula (8): [ka] (In formula (8), R 4 is an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 3. and one or more oligomers selected from the above-mentioned partial hydrolysis condensates of alkoxysilanes, each having a degree of polymerization of 5 or less.

[10] The epoxy resin composition according to any one of [1] to [9], wherein the mass ratio of the component (D) to the component (E) satisfies (mass of component D) / (mass of component E) = 1 / 1 to 1 / 50.

[11] The epoxy resin composition according to any one of [1] to

[10] , wherein the component (F) is surface-treated with a silane coupling agent. Furthermore, the present invention relates to potting agents, underfill agents, and epoxy resin adhesives containing the epoxy resin compositions shown in

[12] to

[17] below, as well as modes of use thereof.

[12] A potting agent containing the epoxy resin composition according to any one of the above [1] to

[11] .

[13] A power module sealed with the potting agent according to

[12] above.

[14] An underfill agent containing the epoxy resin composition according to any one of [1] to

[11] above.

[15] A flip chip package sealed with the underfill agent according to

[14] above.

[16] An epoxy resin adhesive containing the epoxy resin composition according to any one of [1] to

[11] above.

[17] A semiconductor device having a layer made of the adhesive according to

[16] above. [Effects of the Invention]

[0011] The epoxy resin composition of the present invention has an excellent pot life, and therefore thickening during storage at room temperature is suppressed. It can be cured in a short time or at low temperatures, and provides a cured product with good mechanical properties. DETAILED DESCRIPTION OF THE INVENTION

[0012] The present invention will be described in detail below. [(A) Epoxy resin] In the present invention, component (A) is a non-silicone-modified epoxy resin having two or more epoxy groups per molecule, and is used as the base component of the epoxy resin composition of the present invention. The epoxy resin may have two or more, preferably three or more, epoxy groups per molecule, and be non-silicone-modified. It can be appropriately selected from conventionally known non-silicone-modified epoxy resins. The state of component (A) at 25°C may be solid or liquid, but a liquid state is preferred from the viewpoint of ease of handling. Component (A) may be used alone or in combination with two or more. When a solid epoxy resin is used, it is preferably used in combination with a liquid epoxy resin. In this case, the solid epoxy resin should be blended in an amount that provides 1 to 30% by mass, preferably 5 to 20% by mass, of the total mass of component (A). This not only improves handleability but also improves the heat resistance of the cured product.

[0013] Examples of epoxy resins that are liquid at 25° C. include liquid bisphenol A-type epoxy resins, liquid bisphenol F-type epoxy resins, liquid naphthalene-type epoxy resins, liquid aminophenol-type epoxy resins, liquid hydrogenated bisphenol-type epoxy resins, liquid alcohol ether-type epoxy resins, liquid fluorene-type epoxy resins, and liquid alicyclic epoxy resins. Of these, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, naphthalene-type epoxy resins, and aminophenol-type epoxy resins are preferred.

[0014] Examples of epoxy resins that are solid at 25°C include biphenol-type epoxy resins such as 3,3',5,5'-tetramethyl-4,4'-biphenol-type epoxy resins and 4,4'-biphenol-type epoxy resins, phenol novolac-type epoxy resins, cresol novolac-type epoxy resins, bisphenol A novolac-type epoxy resins, stilbene-type epoxy resins, triazine skeleton-containing epoxy resins, fluorene skeleton-containing epoxy resins, trisphenolalkane-type epoxy resins, biphenyl-type epoxy resins, xylylene-type epoxy resins, biphenylaralkyl-type epoxy resins, naphthalene-type epoxy resins, dicyclopentadiene-type epoxy resins, alicyclic epoxy resins, diglycidyl ether compounds of polyfunctional phenols and polycyclic aromatics such as anthracene, and phosphorus-containing epoxy resins obtained by introducing a phosphorus compound into any of these.

[0015] Component (A) preferably has a viscosity of 3,000 to 10,000 mPa·s at 25°C. The viscosity is measured using a B-type viscometer in accordance with JIS K 7117-1:1999. The epoxy equivalent of component (A) is not particularly limited, but is, for example, 80 to 120, and preferably 90 to 180.

[0016] The amount of component (A) is preferably 1 to 40 mass %, more preferably 5 to 30 mass %, and even more preferably 5 to 20 mass %, based on the total mass of the epoxy resin composition.

[0017] [(B) Aromatic amine curing agent] In the present invention, component (B) is an aromatic amine-based curing agent having two or more amino groups per molecule, and is used as a curing agent that reacts with component (A) of the epoxy resin composition of the present invention. Component (B) may be one or more types appropriately selected from conventionally known aromatic amine-based curing agents. The state of component (B) at 25°C may be solid or liquid, but a liquid state is preferred from the viewpoint of ease of handling. Component (B) may be used alone or in combination with two or more types. However, when a solid aromatic amine-based curing agent is used, it is preferable to use it in combination with a liquid aromatic amine-based curing agent. This improves workability and also improves the heat resistance of the cured product.

[0018] The amount of aromatic amine curing agent added may be any amount effective for curing components (A) and (C). Preferably, the amount is such that the molar equivalent ratio of amino groups in component (B) to the total molar equivalent of epoxy groups in components (A) and (C) is 0.8 to 1.2, and more preferably 0.9 to 1.1. If the molar ratio exceeds this preferred range, the cured physical properties may be impaired.

[0019] Examples of aromatic amine curing agents that are liquid at 25° C. include 3,3′-diethyl-4,4′-diaminodiphenylmethane, 2,4-diamino-3,5-diethyltoluene, 2,6-diamino-3,5-diethyltoluene, dimethylthiotoluenediamine, etc. Among these, 3,3′-diethyl-4,4′-diaminodiphenylmethane is preferred.

[0020] Examples of aromatic amine curing agents that are solid at 25°C include 4,4'-methylenebis(2-ethyl-6-methylaniline), 2,2'-diisopropyl-6,6'-dimethyl-4,4'-methylenedianiline, 2,2',6,6'-tetraisopropyl-4,4'-methylenedianiline, 4,4'-methylenebis(2,6-diethylaniline), 4,4'-methylenebis(3-chloro-2,6-diethylaniline), 1,3-phenylenediamine, 2,4-di Examples include aminotoluene, 2,6-diaminotoluene, 2,4,6-trimethyl-1,3-phenylenediamine, 3-aminobiphenyl, 3-amino-4-methoxybiphenyl, 2-aminofluorene, 2-amino-9-fluorenone, 2,7-diaminofluorene, 3-aminobenzophenone, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4-diaminobenzophenone, 3,3'-diaminobenzophenone, etc. Among these, 4,4'-methylenebis(2-ethyl-6-methylaniline) is preferred.

[0021] [(C) Silicone-modified epoxy resin] Component (C) is a silicone-modified epoxy resin. The inclusion of the silicone-modified epoxy resin improves the curability and moisture resistance reliability of the epoxy resin composition. Examples of such silicone-modified epoxy resins include copolymers obtained by subjecting an alkenyl group-containing epoxy resin to a hydrosilylation reaction with an organohydrogenpolysiloxane. It is more preferable that component (C) of the present invention does not contain 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane.

[0022] Examples of alkenyl group-containing epoxy resins include those represented by the following formulas (4) to (6). [ka] [ka] [ka]

[0023] In the above formulas (4) to (6), R 1 is a glycidyl group (2,3-epoxypropyl group), Xs are each independently a hydrogen atom or a bromine atom, n is a number of 0 or more, preferably a number of 0 to 50, more preferably a number of 1 to 20, and m is an integer of 0 or more, preferably a number of 1 to 5, more preferably 1.

[0024] The organohydrogenpolysiloxane is preferably an organohydrogenpolysiloxane containing one or more hydrosilyl groups per molecule, as represented by any one of the following formulas (1) to (3). Of these, an organohydrogenpolysiloxane represented by the following formula (1) is more preferred. [ka] (In formula (1), the siloxane units shown in each parentheses may be bonded randomly or may form block units, R is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and R 1 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R 2 is a group represented by the following formula (1'), and n 1 is an integer between 5 and 200, and n 2 is an integer between 0 and 2, and n 3 is an integer between 0 and 10, and n 4 is 0 or 1, and the R 1 at least one of the groups is a hydrogen atom [ka] (In formula (1'), R and R 1 is as above, and n 5 is an integer between 1 and 10) [ka] (In formula (2), the siloxane units shown in each parentheses may be bonded randomly or may form block units, R is as defined above, and n6 is an integer between 1 and 10, and n 7 is 1 or 2, and n 6 +n 7 is 3 to 12) [ka] (In formula (3), R and R 1 is as defined above, r is an integer of 0 to 3, and R 3 is a hydrogen atom, or one or more groups selected from an alkyl group having 1 to 10 carbon atoms and an alkoxyalkyl group having 2 to 10 carbon atoms, and 1 or R 3 at least one of the groups is a hydrogen atom

[0025] In the above formula (1), R is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms. Examples of the monovalent hydrocarbon group include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, octyl, and decyl, aryl groups such as phenyl and tolyl, and aralkyl groups such as benzyl and phenylethyl.

[0026] R 1 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, provided that R 1 At least one of the groups is a hydrogen atom. Examples of the monovalent hydrocarbon group include the examples described above for R.

[0027] R 2 is a group represented by the above formula (1'). 1 is an integer of 5 to 200, preferably 9 to 150. 2 is an integer of 0 to 2, preferably 0 to 1. 3 is an integer of 0 to 10, preferably 0 to 5. 4 is 0 or 1. In formula (1′), R and R 1 is as above, and n 5 is an integer of 1 to 10, preferably 1 to 4.

[0028] In the above formula (2), R is as defined above, and n 6 is an integer of 1 to 10, preferably 1 to 5. 7 is 1 or 2, where n 6 +n 7 is an integer of 3 to 12, preferably 3 to 7.

[0029] In the above formula (3), R and R 1 is the same as above, r is an integer from 0 to 3, and R 3 is a hydrogen atom, or one or more groups selected from an alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, and an alkoxyalkyl group having 2 to 10 carbon atoms, preferably 2 to 4 carbon atoms. 1 or R 3 At least one of the is a hydrogen atom.

[0030] The organohydrogenpolysiloxane may, for example, be a compound represented by the following formula: [ka] [ka] [ka] [ka]

[0031] The organohydrogenpolysiloxane preferably has a weight-average molecular weight of 100 to 100,000, more preferably 500 to 20,000. When the weight-average molecular weight of the organohydrogenpolysiloxane is within this range, either a uniform structure in which the organohydrogenpolysiloxane is uniformly dispersed in a matrix or a sea-island structure in which the organohydrogenpolysiloxane forms fine layer separations in the matrix will appear, depending on the structure or weight-average molecular weight of the alkenyl group-containing epoxy resin to be reacted with the organohydrogenpolysiloxane.

[0032] When the weight-average molecular weight of the organohydrogenpolysiloxane is relatively small, particularly in the range of 100 to 10,000, a uniform structure is formed. When the weight-average molecular weight of the organohydrogenpolysiloxane is relatively large, particularly in the range of 10,000 to 100,000, a sea-island structure is formed. Either a uniform structure or a sea-island structure can be selected depending on the application. When the weight-average molecular weight of the organohydrogenpolysiloxane is less than 100, the resulting cured product is undesirably rigid and brittle. When the weight-average molecular weight of the organohydrogenpolysiloxane is greater than 100,000, the sea-island structure becomes large, undesirably generating localized stress in the resulting cured product.

[0033] In the present invention, the weight average molecular weight is a weight average molecular weight measured by gel permeation chromatography (GPC) using polystyrene as a standard substance, and is a value measured under the following conditions. [GPC measurement conditions] Developing solvent: tetrahydrofuran Flow rate: 0.6mL / min Column: TSK Guardcolumn SuperH-L TSKgel SuperH4000(6.0mmI.D.×15cm×1) TSKgel SuperH3000(6.0mmI.D.×15cm×1) TSKgel SuperH2000(6.0mmI.D.×15cm×2) (Both manufactured by Tosoh Corporation) Column temperature: 40℃ Sample injection volume: 20 μL (sample concentration: 0.5% by mass in tetrahydrofuran solution) Detector: Differential refractometer (RI)

[0034] The reaction of the alkenyl group-containing epoxy resin with the organohydrogenpolysiloxane can be carried out by a known method, such as an addition reaction of the alkenyl group-containing epoxy resin with the organohydrogenpolysiloxane in the presence of a platinum catalyst. In this manner, a silicone-modified epoxy resin can be obtained. The organohydrogenpolysiloxane is preferably copolymerized in an amount such that the SiH groups of the organohydrogenpolysiloxane are 0.1 to 1 mole per mole of alkenyl groups in the alkenyl group-containing epoxy resin.

[0035] The amount of (C) silicone-modified epoxy resin is preferably 1 to 200 parts by mass, more preferably 5 to 150 parts by mass, and even more preferably 10 to 100 parts by mass, per 100 parts by mass of (A) epoxy resin.

[0036] [(D) Aluminum chelate compound] In the epoxy resin composition of the present invention, component (D) is an aluminum chelate compound, which is a catalyst component that promotes the curing of the epoxy resin. Since it acts on the epoxy as a composite catalyst together with component (E), which will be described later, if either component is missing, the curing reaction will not be sufficiently promoted.

[0037] Examples of the component (D) include compounds in which a diketonato ligand is coordinated to aluminum, as shown in the following formula (7). [ka] In equation (7), R 3 are each independently an alkoxy group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms. Examples of the alkoxy group include a methoxy group and an ethoxy group, and examples of the alkyl group include a methyl group and an ethyl group.

[0038] Examples of the aluminum chelate compound represented by formula (7) include aluminum tris(ethylacetoacetate), aluminum monoacetylacetonate bis(ethylacetoacetate), and aluminum tris(acetylacetonate). These may be used alone or in combination of two or more. Among these, aluminum tris(acetylacetonate) is more preferred because it does not easily increase in viscosity at room temperature after mixing.

[0039] The blending amount of component (D) is 0.05 parts by mass or more but less than 3.0 parts by mass, preferably 0.1 to 2.0 parts by mass, and more preferably 0.2 to 1 part by mass, per 100 parts by mass of components (A), (B), and (C) combined.

[0040] [(E) Silane Compound Having a Phenyl Group] The component (E) of the present invention is a silane compound having one or more phenyl groups in one molecule, and is a catalyst component that accelerates the curing of epoxy resins when used in combination with the component (D).

[0041] The component (E) is at least one selected from alkoxysilanes (E) having one or more phenyl groups per molecule and one or more alkoxy groups per molecule, and partial hydrolysis condensates of the alkoxysilanes, and may contain a partial hydrolysis condensate of an alkoxysilane compound. The partial hydrolysis condensate is an oligomer in which a portion of the alkoxysilane contained in the alkoxysilane is hydrolyzed and condensed with other alkoxysilanes. An oligomer that is a hydrolysis condensate with a degree of polymerization of 5 or less is preferred.

[0042] The component (E) is preferably at least one selected from alkoxysilanes having an alkoxy group and a phenyl group, and oligomers having a degree of polymerization of 5 or less, which are partial hydrolysis condensates of the alkoxysilanes, as shown in the following formula (8): [ka]

[0043] In formula (8), R 4 is an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, or an isopropyl group. Of these, a methyl group is preferred. n is an integer of 1 to 3. From the viewpoint of improving reactivity and pot life, n is preferably 2 or 3, and more preferably n=2.

[0044] Examples of the component (E) include diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiisopropoxysilane, and methoxytriphenylsilane. These may be used alone or in combination of two or more. Among these, diphenyldimethoxysilane is more preferred. The component (E) may also be a partial hydrolysis condensate of these alkoxysilane compounds. The partial hydrolysis condensate is preferably an oligomer with a degree of polymerization of 5 or less.

[0045] The blending amount of component (E) is 0.5 parts by mass or more but less than 3.0 parts by mass, preferably 0.8 to 2.5 parts by mass, and more preferably 1.0 to 2.0 parts by mass, per 100 parts by mass of the combined total of components (A), (B), and (C).

[0046] The mechanism of action of the composite catalyst of the present invention will be described below. In the present invention, by adding two components, the (D) aluminum chelate compound and the (E) silane compound having a phenyl group, to an epoxy resin composition, these act as a composite catalyst to promote curing of the epoxy resin. Because the (E) silane compound has a bulky substituent, such as a phenyl group, its interaction with the (D) aluminum chelate compound is suppressed at room temperature. However, heating during use activates the thermal motion of each component, facilitating the interaction of the (D) aluminum chelate compound and the (E) silane compound. The composite formed by the interaction of the two components exhibits improved catalytic activity as a Bronsted acid due to the electron delocalization of the phenyl group. The above-described mechanism of action of the two components allows the epoxy resin composition of the present invention to be endowed with both pot life and curability.

[0047] The mass ratio of component (D) to component (E) in the epoxy resin composition of the present invention is preferably (D) / (E)=1 / 1 to 1 / 50, more preferably 1 / 1 to 1 / 20, and even more preferably 1 / 2 to 1 / 10. Within this range, both pot life and curability can be achieved.

[0048] [(F) Inorganic filler] Component (F) is an inorganic filler that is added to reduce the thermal expansion coefficient of the composition and improve the reliability of moisture and heat resistance.

[0049] Examples of inorganic fillers include silicas such as fused silica, crystalline silica, and cristobalite, alumina, silicon nitride, aluminum nitride, boron nitride, titanium oxide, glass fiber, and magnesium oxide. These may be used alone or in combination of two or more. The average particle size and shape of these inorganic fillers can be selected depending on the application. Among these, spherical alumina, spherical fused silica, and glass fiber are preferred. For example, the average particle size of the inorganic filler is preferably 1 to 100 μm, more preferably 5 to 90 μm, and even more preferably 10 to 80 μm. Here, the average particle size is the 50% cumulative distribution diameter on a volume basis measured by dynamic light scattering using a laser beam.

[0050] The inorganic filler is preferably surface-treated with a silane coupling agent. Examples of silane coupling agents for treating the inorganic filler include aminosilane coupling agents, epoxysilane coupling agents, vinylsilane coupling agents, methacrylsilane coupling agents, acrylicsilane coupling agents, mercaptosilane coupling agents, triazine-functional silane coupling agents, isocyanate-functional silane coupling agents, isocyanuric acid-functional silane coupling agents, benzotriazole-functional silane coupling agents, acid anhydride-functional silane coupling agents, azasilacyclopentane-functional silane coupling agents, imidazole-functional silane coupling agents, and unsaturated group-containing silane coupling agents. Component (F) of the present invention is surface-treated with one or more selected from these.

[0051] Examples of aminosilane coupling agents include N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, and N-phenyl-3-aminopropyltrimethoxysilane.

[0052] Examples of epoxy silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 8-glycidoxyoctyltrimethoxysilane.

[0053] Examples of the vinyl silane coupling agent include vinyl trimethoxy silane and vinyl triethoxy silane.

[0054] Examples of methacrylsilane coupling agents include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 8-methacryloxyoctyltrimethoxysilane.

[0055] Examples of the acrylic silane coupling agent include 3-acryloxypropyltrimethoxysilane.

[0056] Examples of the mercaptosilane coupling agent include 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane.

[0057] The amount of silane coupling agent to be blended relative to the inorganic filler is not particularly limited. The surface treatment of the inorganic filler with the silane coupling agent may be performed according to a conventional method. In the present invention, the silane coupling agent is used for surface treatment of the inorganic filler. The epoxy resin composition of the present invention contains an inorganic filler that has been surface-treated in advance with the silane coupling agent, and the silane coupling agent is not blended as a component of the epoxy resin composition. Therefore, the most preferred embodiment of the epoxy resin composition of the present invention does not contain the silane coupling agent. More preferably, the epoxy resin composition of the present invention does not contain an aminosilane coupling agent, an epoxysilane coupling agent, or a vinylsilane coupling agent such as vinyltrimethoxysilane.

[0058] The blending amount of component (F) is 10 parts by mass or more and 1,000 parts by mass or less, preferably 100 to 750 parts by mass, and more preferably 200 to 500 parts by mass, per 100 parts by mass of the combined total of components (A), (B), and (C).

[0059] [Other additives] In addition to the above components (A) to (F), other additives may be added to the epoxy resin composition of the present invention as needed, provided that the objects and effects of the present invention are not impaired. Examples of additives include colorants, flame retardants, antioxidants, adhesion promoters, stress reducers, and antifoaming agents. The amount of other additives added varies depending on the intended use of the epoxy resin composition of the present invention. It may be adjusted appropriately within a range that does not impair the effects of the present invention. For example, the total amount of other additives may be 5% by mass or less of the total epoxy resin composition.

[0060] When the epoxy resin composition of the present invention is stored at room temperature, it may be stored as a two-component composition. In this case, it is preferable that the main component be components (A), (C), and (F), and the curing agent be components (B) and (F). Components (D) and (E) may be added to either the main component or the curing agent. That is, the present invention preferably provides a two-component kit for obtaining an epoxy resin composition, which comprises a first part (resin component) containing a portion of components (A), (C), and (F), and a second part (curing agent component) containing the remainder of components (B) and (F), and in which components (D) and (E) and optional other components are contained in either or both of the first and second parts. The blending ratio of the first part (resin component) to the second part (curing agent component) may be such that the blending amounts of components (A) to (F) in the overall composition satisfy the above-mentioned ranges.

[0061] The epoxy resin composition of the present invention is preferably liquid at 25° C. The epoxy resin composition has a viscosity at 25° C. of 10 to 500 Pa s, preferably 20 to 400 Pa s, and more preferably 30 to 300 Pa s. The viscosity is measured at 25° C. using a rotational viscometer in accordance with JIS Z 8803:2011.

[0062] Method for producing epoxy resin composition The method for producing the epoxy resin composition of the present invention is not particularly limited. For example, the composition can be obtained by mixing, stirring, dissolving, and / or dispersing components (A) to (F) simultaneously or separately, while optionally subjecting them to heat treatment. The apparatus used for mixing, stirring, and dispersing in the production method is not particularly limited. For example, a mortar and pestle mill, a two-roll mill, a three-roll mill, a ball mill, a planetary mixer, or a mass colloider equipped with a stirring and heating device can be used, and these apparatuses may also be used in appropriate combination.

[0063] The curing conditions for the epoxy resin composition of the present invention are not particularly limited, but may be, for example, heating at a temperature of 60 to 200°C, preferably 80 to 180°C, for 30 minutes to 10 hours, preferably 1 to 5 hours. The epoxy resin composition of the present invention can be cured well at low temperatures in a short time. Therefore, it can be cured well even at a temperature of 100 to 120°C for 1 to 2 hours.

[0064] The present invention further provides a potting agent containing the above-mentioned epoxy resin composition. The blending ratio of the epoxy resin composition contained in the potting agent may be in accordance with that of conventionally known potting agents. The present invention also provides a power module sealed with the potting agent. The method for sealing the power module with the potting agent is not particularly limited.

[0065] The present invention further provides an underfill agent containing the above-described epoxy resin composition. The blending ratio of the epoxy resin composition in the underfill agent may be in accordance with that of conventionally known underfill agents. The present invention also provides a flip chip package sealed with the above-described underfill agent. The method for sealing the chip with the underfill agent is not particularly limited.

[0066] The present invention further provides an epoxy resin adhesive containing the above-described epoxy resin composition. The blending ratio of the epoxy resin composition in the adhesive may be in accordance with that of conventionally known epoxy resin adhesives. The present invention also provides a semiconductor device having a layer made of the above-described adhesive. The method for producing the semiconductor device is not particularly limited. [Example]

[0067] EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0068] [Examples 1 to 5 and Comparative Examples 1 to 8] The components shown below were mixed at 25°C in the compositions shown in Tables 1 and 2 to obtain epoxy resin compositions.

[0069] (A) Epoxy resin Epoxy resin that is liquid at 25°C (A1): Bisphenol A epoxy resin (YD-8125: manufactured by Nippon Steel Chemical & Material Co., Ltd.) Epoxy resin (A2) that is liquid at 25°C: Aminophenol-type trifunctional epoxy resin (jER630: manufactured by Mitsubishi Chemical Corporation)

[0070] (B) Aromatic amine curing agent Aromatic amine curing agent that is liquid at 25°C: 3,3'-diethyl-4,4'-diaminodiphenylmethane (Kayahard AA: manufactured by Nippon Kayaku Co., Ltd.)

[0071] (C) Silicone-modified epoxy resin A 1-liter four-neck flask equipped with a reflux condenser, a thermometer, a stirrer, and a dropping funnel was charged with the following formula (15): [ka] 200 g of a phenol novolak resin (phenol equivalent 125, allyl equivalent 1,100) modified with an allyl glycidyl ether represented by the formula (II), 800 g of chloromethyloxirane, and 0.6 g of cetyltrimethylammonium bromide were each placed in the flask and heated, followed by stirring and mixing at a temperature of 110°C for 3 hours. The mixture was cooled to 70°C and the pressure was reduced to 160 mmHg, after which 128 g of a 50% aqueous solution of sodium hydroxide was added dropwise over 3 hours while azeotropically dehydrating. The resulting mixture was distilled off under reduced pressure to remove the solvent, and then dissolved in a mixed solvent of 300 g of methyl isobutyl ketone and 300 g of acetone. The mixture was washed with water, and the solvent was distilled off under reduced pressure to obtain a mixture of the formula (16) below. [ka] An allyl group-containing epoxy resin (allyl equivalent 1590, epoxy equivalent 190) represented by the following formula (12) was obtained. This epoxy resin was added to 170 g of methyl isobutyl ketone, 330 g of toluene, and 0.07 g of a 2-ethylhexanol-modified chloroplatinic acid solution with a platinum concentration of 2% by mass, and azeotropic dehydration was carried out for 1 hour. [ka] 133 g of an organopolysiloxane (weight-average molecular weight: 8,000) represented by the formula was added dropwise over a 30-minute period. The mixture was stirred at the same temperature for four hours to allow the reaction to proceed. The resulting contents were then washed with water, and the solvent was distilled off under reduced pressure, yielding a yellow-white, opaque solid copolymer. The epoxy equivalent was 280, and the ICI melt viscosity at 150°C, measured using a cone-plate viscometer according to ASTM D4287, was 800 mPa·s. The silicon content was 31% by mass.

[0072] (D) Aluminum chelate compounds (D1) Aluminum tris(acetylacetonate) (Aluminum chelate A: manufactured by Kawaken Fine Chemicals Co., Ltd.) (D2) Aluminum monoacetylacetonate bis(ethylacetoacetate) (Aluminum chelate D: manufactured by Kawaken Fine Chemicals Co., Ltd.)

[0073] (E) Diphenyldimethoxysilane (KBM-202SS: manufactured by Shin-Etsu Chemical Co., Ltd.)

[0074] (F) Spherical silica with a volume average particle size of 15 μm, surface-treated with N-phenyl-3-aminopropyltrimethoxysilane

[0075] Comparative curing accelerator: Triphenylphosphine triphenylborane (TPP-S: manufactured by Hokko Chemical Co., Ltd.)

[0076] Comparative siloxane compound: 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane

[0077] Silane compound for comparison: vinyltrimethoxysilane (KBM-1003: manufactured by Shin-Etsu Chemical Co., Ltd.)

[0078] Silane coupling agent for comparison: 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine (KBE-9103P: manufactured by Shin-Etsu Chemical Co., Ltd.)

[0079] [evaluation] Tests were carried out using the evaluation methods shown below for each of the epoxy resin compositions of Examples 1 to 5 and Comparative Examples 1 to 8. The results are shown in Table 2. (1) Curability After preparing the epoxy resin compositions, they were molded at 120°C for 60 minutes. Those for which a cured product could be produced were marked with an ◯, and those for which the cured product was damaged when demolded due to insufficient curing and could not be produced were marked with an ×. The results are shown in Table 2.

[0080] (2) Bending strength The flexural strength of the cured product prepared under the above curing conditions was measured in accordance with JIS K 6911:2006. The results are shown in Table 2.

[0081] (3) Flexural modulus The flexural modulus of the cured product prepared under the above curing conditions was measured in accordance with JIS K 6911:2006. The results are shown in Table 2.

[0082] (4) Peak heat generation temperature The exothermic peak temperature due to the curing reaction of the epoxy resin composition was measured using a differential scanning calorimeter (DSC). 10 mg of the above epoxy resin composition was placed in a 40 μl aluminum sample pan and heated from 25°C to 300°C at a rate of 10°C / min. The exothermic peak temperature was calculated from the peak temperature on the resulting graph. The results are shown in Table 2.

[0083] (5) Viscosity increase The viscosity of the epoxy resin composition at 25°C was measured using a rotational viscometer in accordance with JIS Z 8803:2011. After storing the composition in an environment at 25°C for 12 hours, the viscosity of the epoxy resin composition was measured in the same manner, and the rate of increase in viscosity after storage relative to the viscosity before storage (viscosity after storage / viscosity before storage) was calculated. The results are shown in Table 2.

[0084] [Table 1]

[0085] [Table 2]

[0086] In Comparative Examples 1 and 2, in which either the (D) or (E) component of the present invention was added, viscosity increase at 25°C was suppressed, but a cured product could not be produced after 60 minutes at 120°C. In Comparative Example 3, triphenylphosphine triphenylborane was used as a curing accelerator instead of the (D) and (E) components of the present invention, but curing proceeded immediately after blending, making it impossible to measure the evaluation items. In Comparative Example 4, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine was used as a comparative silane coupling agent instead of the inorganic filler surface-treated with a silane coupling agent, but the DSC exothermic peak temperature was high and reactivity was poor. In Comparative Example 5, vinyltrimethoxysilane was used as a comparative silane compound, and in Comparative Example 6, 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane was used as a comparative siloxane compound, but both had poor flexural strength. In Comparative Example 7, in which the component (E) of the present invention was added in an amount exceeding the upper limit, the degree of increase in viscosity was high and the flexural strength was poor. In Comparative Example 8, in which no silicone-modified epoxy resin was added, the flexural modulus was high.

[0087] In contrast, the epoxy resin composition of the present invention is inhibited from thickening during storage at room temperature, has an excellent pot life, and is cured well in a short time or at a low temperature to give a cured product having excellent mechanical properties such as flexural modulus and flexural strength.

Claims

1. (A) a non-silicone-modified epoxy resin having two or more epoxy groups in one molecule; (B) an aromatic amine-based curing agent having two or more amino groups in one molecule, in an amount effective to cure the epoxy resin; (C) silicone-modified epoxy resin, 1 to 200 parts by mass per 100 parts by mass of component (A), (D) Aluminum chelate compound: 0.05 parts by mass or more and less than 3.0 parts by mass per 100 parts by mass of the total of the components (A), (B), and (C), (E) one or more selected from alkoxysilanes having one or more phenyl groups per molecule and one or more alkoxy groups per molecule, and partial hydrolysis condensates of such alkoxysilanes: 0.5 parts by mass or more but less than 3.0 parts by mass per 100 parts by mass of the total of the components (A), (B), and (C); and (F) inorganic filler: 10 parts by mass or more and 1,000 parts by mass or less per 100 parts by mass of the total of the (A) component, the (B) component, and the (C) component; 1. An epoxy resin composition comprising:

2. 2. The epoxy resin composition according to claim 1, wherein the amount of component (B) is such that the molar equivalent ratio of amino groups in component (B) per 1 molar equivalent of the total epoxy groups in components (A) and (C) is 0.8 or more and 1.2 or less.

3. 2. The epoxy resin composition according to claim 1, wherein component (C) is a hydrosilylation reaction product of an alkenyl group-containing epoxy resin having a weight average molecular weight of 500 or more and an organohydrogen(poly)siloxane containing one or more hydrosilyl groups per molecule.

4. 4. The epoxy resin composition according to claim 3, wherein the organohydrogenpolysiloxane is represented by any one of the following formulas (1) to (3): 【Chemistry 1】 (In formula (1), the siloxane units shown in each parentheses may be bonded randomly or may form block units, R is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R １ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ２ is a group represented by the following formula (1'), and n １ is an integer from 5 to 200, and n ２ is an integer from 0 to 2, and n ３ is an integer from 0 to 10, and n ４ is 0 or 1, and the R １ one or more of the following is a hydrogen atom: 【Chemistry 2】 (In formula (1′), R and R １ is as above, and n ５ is an integer from 1 to 10) 【Transformation 3】 (In formula (2), the siloxane units shown in each parentheses may be bonded randomly or may form block units, R is as defined above, and n ６ is an integer from 1 to 10, and n ７ is 1 or 2, and n ６ +n ７ is 3 to 12) 【Chemistry 4】 (In formula (3), R and R １ is as defined above, r is an integer from 0 to 3, and R ３ is a hydrogen atom or one or more groups selected from an alkyl group having 1 to 10 carbon atoms and an alkoxyalkyl group having 2 to 10 carbon atoms, １ or R ３ one or more of the following is a hydrogen atom:

5. 2. The epoxy resin composition according to claim 1, wherein the component (D) is a compound represented by the following formula (7): 【Transformation 5】 (In the above formula (7), R ３ are each independently an alkoxy group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms.

6. 5. The epoxy resin composition according to claim 4, wherein the component (D) is at least one selected from the group consisting of aluminum monoacetylacetonate bis(ethylacetoacetate) and aluminum tris(acetylacetonate).

7. 2. The epoxy resin composition according to claim 1, wherein the component (E) is an alkoxysilane having one or more phenyl groups per molecule and one or more alkoxy groups having 1 to 4 carbon atoms per molecule.

8. 2. The epoxy resin composition according to claim 1, wherein the silane compound of component (E) is a partial hydrolysis condensate that is an oligomer having a degree of polymerization of 5 or less and containing one or more silanol groups.

9. The component (E) is an alkoxysilane represented by the following formula (8): 【Transformation 6】 (In formula (8), R ４ is an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 3. and an oligomer having a degree of polymerization of 5 or less which is a partial hydrolysis condensation product of the alkoxysilane.

10. 2. The epoxy resin composition according to claim 1, wherein a mass ratio of the component (D) to the component (E) satisfies (mass of component D) / (mass of component E) = 1 / 1 to 1 / 50.

11. 2. The epoxy resin composition according to claim 1, wherein the component (F) is an inorganic filler that has been surface-treated with a silane coupling agent.

12. A potting agent comprising the epoxy resin composition according to any one of claims 1 to 11.

13. A power module encapsulated with the potting agent according to claim 12.

14. An underfill agent containing the epoxy resin composition according to any one of claims 1 to 11.

15. A flip chip package encapsulated with the underfill agent of claim 14.

16. An epoxy resin adhesive comprising the epoxy resin composition according to any one of claims 1 to 11.

17. A semiconductor device having a layer of the adhesive of claim 16.

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