Two-pack liquid resin composition and electronic device

Abstract

To provide a two-pack liquid resin composition improved in performance balance between storage stability and low-temperature curability.SOLUTION: The two-pack liquid resin composition comprises a first liquid and a second liquid. The first liquid contains an epoxy resin. The second liquid contains one or more amine-based curing agents selected from the group consisting of alicyclic amine-based curing agents and aromatic amine-based curing agents.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a two-component liquid resin composition and an electronic device. [Background technology]

[0002] Epoxy resin is used as a sealing material for sealing a substrate and a semiconductor element. As a technology relating to a sealing material, for example, the technology described in Patent Document 1 can be mentioned.

[0003] Patent Document 1 describes a filler for semiconductor encapsulation, which is blended into an encapsulation material to reduce the linear expansion coefficient of the encapsulation material and maintain the encapsulation material at a low viscosity to improve penetration, and a semiconductor encapsulation composition using the filler. The filler is characterized by comprising an inorganic substance and an organic layer chemically bonded to the surface of the inorganic substance and having functional groups capable of reacting with an epoxy resin, and also describes a semiconductor encapsulation material containing the filler and an epoxy resin. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2009-67890 Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention provides a two-component liquid resin composition having an improved balance of storage stability and low-temperature curing properties. [Means for solving the problem]

[0006] The present inventors have conducted extensive research to achieve the above object, and as a result have found that the performance balance between storage stability and low-temperature curing property of a two-component liquid resin composition can be improved by including a specific amine-based curing agent as a curing agent for the two-component liquid resin composition, thereby completing the present invention.

[0007] According to the present invention, there is provided the following two-component liquid resin composition.

[0008] [1] a two-component liquid resin composition consisting of a first liquid and a second liquid, The first liquid contains an epoxy resin, The second liquid is a two-component liquid resin composition containing one or more amine-based curing agents selected from the group consisting of alicyclic amine-based curing agents and aromatic amine-based curing agents. [2] The two-component liquid resin composition according to [1] above, wherein the amine-based curing agent comprises a structure represented by the following general formula (1): [ka] (In the above general formula (1), R1 represents a linear or branched alkylene group having 1 to 5 carbon atoms.) [3] The two-component liquid resin composition according to [1] or [2] above, wherein the amine-based curing agent comprises one or more selected from the group consisting of 1,3-bisaminomethylcyclohexane and metaxylenediamine. [4] The two-component liquid resin composition according to any one of [1] to [3] above, wherein the content of the amine-based curing agent is 50% by mass or more and 100% by mass or less, when the entire second liquid is taken as 100% by mass. [5] The two-component liquid resin composition according to any one of [1] to [4] above, wherein the content of the second liquid is 1 part by mass or more and 50 parts by mass or less when the total content of the first liquid is 100 parts by mass. [6] The two-component liquid resin composition according to any one of the above [1] to [5], wherein the epoxy resin comprises a bisphenol-type epoxy resin. [7] The two-component liquid resin composition according to [6] above, wherein the bisphenol epoxy resin comprises one or more selected from the group consisting of bisphenol A epoxy resins and bisphenol F epoxy resins. [8] The two-component liquid resin composition according to any one of [1] to [7] above, wherein the content of the epoxy resin is 10% by mass or more and 50% by mass or less, when the total amount of the first liquid is 100% by mass. [9] The two-component liquid resin composition according to any one of the above [1] to [8], wherein the first component further contains an inorganic filler.

[10] The two-component liquid resin composition according to [9] above, wherein the inorganic filler comprises one or more selected from the group consisting of silica, alumina, aluminum hydroxide, and calcium carbonate.

[11] The average particle diameter D of the inorganic filler when the cumulative value is 50% in the volume frequency particle size distribution measured by the laser diffraction scattering method 50 The two-component liquid resin composition according to [9] or

[10] above, wherein the particle size is 1 μm or more and 200 μm or less.

[12] The two-component liquid resin composition according to any one of [9] to

[11] above, wherein the content of the inorganic filler is 50% by mass or more and 90% by mass or less, when the total amount of the first liquid is 100% by mass.

[13] The two-component liquid resin composition according to any one of the above [1] to

[12] , wherein the first component further contains an anti-settling agent.

[14] The two-component liquid resin composition according to

[13] above, wherein the content of the anti-settling agent is 0.01% by mass or more and 2.0% by mass or less, when the total amount of the first liquid is 100% by mass.

[15] The two-component liquid resin composition according to any one of [1] to

[14] above, wherein the content of the curing accelerator is 1.0 mass % or less when the total amount of the two-component liquid resin composition is taken as 100 mass %.

[16] The two-component liquid resin composition according to any one of [1] to

[15] above, which has a glass transition temperature 1 (Tg1) of 50°C or higher and 100°C or lower, as determined by the following (Method 1): (Method 1) The second liquid is mixed with 50 g of the first liquid at 25°C so that the equivalent ratio of the active hydrogen equivalent of the amine-based curing agent to the epoxy equivalent of the epoxy resin in the first liquid is 1, to obtain a mixture. The mixture is poured into an aluminum cup and cured at 40°C for 8 hours. After slowly cooling to 25°C, a test piece is cut out to dimensions of 10 mm x 5 mm x 5 mm. The test piece is measured using a thermomechanical analyzer under conditions of a measurement temperature range of 0°C to 230°C and a heating rate of 10°C / min, and the glass transition temperature (°C) is calculated from the measurement results.

[17] The two-component liquid resin composition according to

[16] above, which has a glass transition temperature 2 (Tg2) of 80°C or higher and 200°C or lower, as determined by the following (Method 2): (Method 2) The second liquid is mixed with 50 g of the first liquid at 25°C so that the equivalent ratio of the active hydrogen equivalent of the amine-based curing agent to the epoxy equivalent of the epoxy resin in the first liquid is 1, to obtain a mixture. The mixture is poured into an aluminum cup and cured at 40°C for 8 hours, and then at 80°C for 1 hour. After slowly cooling to 25°C, a test piece measuring 10 mm x 5 mm x 5 mm is cut out. The test piece is measured using a thermomechanical analyzer under conditions of a measurement temperature range of 0°C to 230°C and a heating rate of 10°C / min, and the glass transition temperature (°C) is calculated from the measurement results.

[18] The two-component liquid resin composition according to

[17] above, wherein the ratio of Tg2 to Tg1 (Tg2 / Tg1) is 1.0 or more and 2.0 or less.

[19] The two-component liquid resin composition according to any one of [1] to

[18] above, having a Rockwell hardness 1 of 50 or more and 130 or less, measured by the following (Method 3): (Method 3) The second liquid is mixed with 50 g of the first liquid at 25°C so that the equivalent ratio of the active hydrogen equivalent of the amine-based curing agent to the epoxy equivalent of the epoxy resin in the first liquid is 1, to obtain a mixture. The mixture is poured into an aluminum cup and cured at 40°C for 8 hours. After slowly cooling to 25°C, a test piece measuring 10 mm x 10 mm x 10 mm is cut out. The test piece is used to measure Rockwell hardness 1 at 25°C using the M hardness scale in accordance with JIS K7202:2001.

[20] The two-component liquid resin composition according to

[19] above, having a Rockwell hardness 2 measured by the following (Method 4) of 50 or more and 130 or less. (Method 4) The second liquid is mixed with 50 g of the first liquid at 25°C so that the equivalent ratio of the active hydrogen equivalent of the amine-based curing agent to the epoxy equivalent of the epoxy resin in the first liquid is 1 to obtain a mixture. The mixture is poured into an aluminum cup and cured at 40°C for 8 hours, and then at 80°C for 1 hour. After slowly cooling to 25°C, a test piece measuring 10 mm x 10 mm x 10 mm is cut out. The test piece is used to measure Rockwell hardness 2 at 25°C using the M hardness scale in accordance with JIS K7202:2001. [twenty one] The two-component liquid resin composition according to

[20] above, wherein the ratio of the Rockwell hardness 2 to the Rockwell hardness 1 is 0.5 or more and 1.5 or less. [twenty two] The two-component liquid resin composition according to any one of [1] to

[21] above, which has a flexural strength 1 measured by the following (Method 5) of 50 MPa or more and 150 MPa or less. (Method 5) The second liquid is mixed with 50 g of the first liquid at 25°C so that the equivalent ratio of the active hydrogen equivalent of the amine-based curing agent to the epoxy equivalent of the epoxy resin in the first liquid is 1 to obtain a mixture. The mixture is poured into an aluminum cup and cured at 40°C for 8 hours. After slowly cooling to 25°C, a test piece measuring 100 mm x 10 mm x 4 mm is cut out. The flexural strength 1 of the test piece is measured at 25°C in accordance with JIS K 6911:2006. [twenty three] The two-component liquid resin composition according to

[22] above, having a flexural strength 2 measured by the following (Method 6) of 70 MPa or more and 250 MPa or less. (Method 6) The second liquid is mixed with 50 g of the first liquid at 25°C so that the equivalent ratio of the active hydrogen equivalent of the amine-based curing agent to the epoxy equivalent of the epoxy resin in the first liquid is 1 to obtain a mixture. The mixture is poured into an aluminum cup and cured at 40°C for 8 hours, and then at 80°C for 1 hour. After slowly cooling to 25°C, a test piece measuring 100 mm x 10 mm x 4 mm is cut out. The flexural strength 2 of the test piece is measured at 25°C in accordance with JIS K 6911:2006. [twenty four] The two-component liquid resin composition according to

[23] above, wherein the ratio of the flexural strength 2 to the flexural strength 1 is 0.5 or more and 1.5 or less. [twenty five] The two-component liquid resin composition according to any one of [1] to

[24] above, which can be used to encapsulate a structure comprising a substrate including a circuit layer and an electronic component on the circuit layer of the substrate.

[26] a substrate including a circuit layer; an electronic component on the circuit layer of the substrate; a sealing material for sealing the substrate and the electronic component; Equipped with An electronic device, wherein the sealing material comprises a cured product of the two-component liquid resin composition according to any one of [1] to

[25] above. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a two-component liquid resin composition having an improved balance of storage stability and low-temperature curing properties. DETAILED DESCRIPTION OF THE INVENTION

[0010] Hereinafter, an embodiment of the present invention will be described. In this specification, numerical ranges indicated with "to" indicate ranges that include the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In the numerical ranges described in stages in this specification, the upper or lower limit of a certain numerical range can be arbitrarily combined with the upper or lower limit of another numerical range. In the numerical ranges described in this specification, the upper or lower limit of the numerical range may be replaced with a value shown in the examples. "A or B" may include either A or B, or may include both. Unless otherwise specified, the materials exemplified in this specification can be used alone or in combination of two or more. In this specification, when multiple substances corresponding to each component are present in the composition, the content of each component in the composition refers to the total amount of the multiple substances present in the composition, unless otherwise specified. In this specification, the expression "when the entire two-component liquid resin composition (or the first and second components) is taken as 100% by mass" means that components such as solvents that volatilize when the two-component liquid resin composition is cured are excluded.

[0011] <Two-component liquid resin composition> The two-component liquid resin composition of the present embodiment is a two-component liquid resin composition consisting of a first liquid and a second liquid, wherein the first liquid contains an epoxy resin, and the second liquid contains one or more amine-based curing agents selected from the group consisting of alicyclic amine-based curing agents and aromatic amine-based curing agents.

[0012] The two-component liquid resin composition of this embodiment can improve the balance of storage stability and low-temperature curing properties. Although the reason for this is not clear, it is thought that the amine-based curing agent has a structure such as an aromatic ring structure or an alicyclic structure, which provides sufficient curing properties even in a low-temperature reaction and suppresses curing due to changes over time.

[0013] The components used in the two-component liquid resin composition of this embodiment will be described in detail below.

[0014] [Epoxy resin] The two-part liquid resin composition of this embodiment includes an epoxy resin in the first part. From the viewpoint of further improving the performance balance of the mechanical properties, thermal expansion coefficient, thermal conductivity, heat dissipation, and electrical properties of a cured product of the two-part liquid resin composition, the epoxy resin of this embodiment preferably includes one or more resins selected from the group consisting of alicyclic epoxy resins, bisphenol-type epoxy resins, novolac-type epoxy resins, aromatic glycidylamine-type epoxy resins, aminophenol-type epoxy resins, biphenyl-type epoxy resins, aryl alkylene-type epoxy resins, naphthalene-type epoxy resins, anthracene-type epoxy resins, phenoxy-type epoxy resins, dicyclopentadiene-type epoxy resins, norbornene-type epoxy resins, glycidyl ether-type epoxy resins, glycidylamine-type epoxy resins, adamantane-type epoxy resins, and fluorene-type epoxy resins. From the viewpoint of further improving the performance balance of the storage stability and low-temperature curing properties of the two-part liquid resin composition and the mechanical properties of a cured product of the two-part liquid resin composition, the epoxy resin of this embodiment more preferably includes a bisphenol-type epoxy resin.

[0015] The alicyclic epoxy resin of this embodiment is preferably an epoxy-[epoxy-oxaspiro C] such as vinylcyclopentadiene dioxide, vinylcyclohexene monodioxide, vinylcyclohexene dioxide, dicyclopentadiene oxide, or 3,4-epoxy-1-[8,9-epoxy-2,4-dioxaspiro[5.5]undecan-3-yl]-cyclohexane. 8-15 Alkyl]-cycloC 5-12Alkanes; Epoxy C such as 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 4,5-epoxycyclooctylmethyl-4',5'-epoxycyclooctanecarboxylate 5-12 Cycloalkyl C 1-3 Alkyl-Epoxy C 5-12 Cycloalkane carboxylates; bis(C) such as bis(2-methyl-3,4-epoxycyclohexylmethyl) adipate 1-3 Alkyl Epoxy C 5-12 Cycloalkyl C 1-3 The compound may contain one or more selected from the group consisting of alkyl)dicarboxylates.

[0016] The bisphenol type epoxy resin of the present embodiment preferably comprises one or more types selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, bisphenol M type epoxy resin (4,4'-(1,3-phenylenediisopridiene)bisphenol type epoxy resin), bisphenol P type epoxy resin (4,4'-(1,4-phenylenediisopridiene)bisphenol type epoxy resin), and bisphenol Z type epoxy resin (4,4'-cyclohexidiene bisphenol type epoxy resin), and more preferably comprises one or more types selected from the group consisting of bisphenol A type epoxy resin and bisphenol F type epoxy resin, from the viewpoint of further improving the performance balance of the storage stability and low-temperature curing ability of the two-part liquid resin composition, and the mechanical properties of the cured product of the two-part liquid resin composition.

[0017] The novolac epoxy resin of the present embodiment preferably includes one or more resins selected from the group consisting of phenol novolac epoxy resins, cresol novolac epoxy resins, trisphenol methane novolac epoxy resins, tetraphenol ethane novolac epoxy resins, and novolac epoxy resins having a condensed ring aromatic hydrocarbon structure.

[0018] The aromatic glycidylamine-type epoxy resin of the present embodiment preferably contains one or more compounds selected from the group consisting of N,N-diglycidylaniline, N,N-diglycidyltoluidine, diaminodiphenylmethane-type glycidylamine, and aminophenol-type glycidylamine.

[0019] The epoxy resin of the present embodiment may contain an epoxy resin diluent from the viewpoint of further improving the performance balance of the storage stability, low-temperature curing property, and handleability of the two-component liquid resin composition. The epoxy resin diluent of this embodiment preferably contains one or more compounds selected from the group consisting of bisphenol compounds such as bisphenol A, bisphenol F, and biphenol, or derivatives thereof; diols having an alicyclic structure such as hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated biphenol, cyclohexanediol, cyclohexanedimethanol, and cyclohexanediethanol, or derivatives thereof; bifunctional epoxidized aliphatic diols such as propanediol, butanediol, hexanediol, octanediol, nonanediol, and decanediol, or derivatives thereof; trifunctional compounds having a trihydroxyphenylmethane skeleton or an aminophenol skeleton; and polyfunctional epoxidized compounds such as phenol novolac resins, cresol novolac resins, phenol aralkyl resins, biphenyl aralkyl resins, and naphthol aralkyl resins.

[0020] When the epoxy resin of the present embodiment contains an epoxy resin diluent, the content of the epoxy resin diluent is preferably 0.1% by mass or more and 50% by mass or less, more preferably 0.1% by mass or more and 40% by mass or less, and even more preferably 0.1% by mass or more and 30% by mass or less, when the total epoxy resin is taken as 100% by mass, from the viewpoint of further improving the performance balance of the storage stability, low-temperature curing property, and handleability of the two-component liquid resin composition.

[0021] From the viewpoint of further improving the performance balance among the storage stability and low-temperature curing ability of the two-component liquid resin composition and the mechanical properties of a cured product of the two-component liquid resin composition, the epoxy equivalent of the epoxy resin of the present embodiment is preferably from 50 g / eq to 1,000 g / eq, more preferably from 55 g / eq to 950 g / eq, even more preferably from 60 g / eq to 900 g / eq, even more preferably from 65 g / eq to 850 g / eq, even more preferably from 70 g / eq to 800 g / eq, even more preferably from 80 g / eq to 750 g / eq, even more preferably from 90 g / eq to 700 g / eq, even more preferably from 100 g / eq to 600 g / eq, even more preferably from 110 g / eq to 500 g / eq, even more preferably from 120 g / eq to 400 g / eq, even more preferably from 130 g / eq to 300 g / eq, and even more preferably from 140 g / eq to 200 g / eq.

[0022] From the viewpoint of further improving the performance balance of the storage stability and low-temperature curing ability of the two-component liquid resin composition and the mechanical properties of a cured product of the two-component liquid resin composition, the content of the epoxy resin in the two-component liquid resin composition of this embodiment is preferably 10% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 45% by mass or less, even more preferably 10% by mass or more and 40% by mass or less, even more preferably 10% by mass or more and 35% by mass or less, and even more preferably 10% by mass or more and 30% by mass or less, when the entire two-component liquid resin composition is taken as 100% by mass.

[0023] From the viewpoint of further improving the performance balance of the storage stability and low-temperature curing properties of the two-component liquid resin composition and the mechanical properties of the cured product of the two-component liquid resin composition, the content of the epoxy resin in the first liquid of this embodiment is preferably 10% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 45% by mass or less, even more preferably 10% by mass or more and 40% by mass or less, and even more preferably 10% by mass or more and 35% by mass or less, when the entire first liquid is taken as 100% by mass.

[0024] [Amine-based curing agent] The two-component liquid resin composition of this embodiment contains one or more amine-based curing agents selected from the group consisting of alicyclic amine-based curing agents and aromatic amine-based curing agents in the second component, thereby improving the balance of storage stability and low-temperature curing properties.

[0025] From the viewpoint of further improving the performance balance of the storage stability and low-temperature curing property of the two-component liquid resin composition and the mechanical properties of the cured product of the two-component liquid resin composition, the amine-based curing agent of the present embodiment preferably contains a structure represented by the following general formula (1), and more preferably contains two structures represented by the following general formula (1) in one molecule.

[0026] [ka]

[0027] In the above general formula (1), R1 represents a linear or branched alkylene group having 1 to 5 carbon atoms.

[0028] In the above general formula (1), from the viewpoint of further improving the performance balance between the low-temperature curing property of the two-component liquid resin composition and the mechanical properties of the cured product of the two-component liquid resin composition, R1 is preferably a linear or branched alkylene group having 1 to 5 carbon atoms, more preferably a linear or branched alkylene group having 1 to 4 carbon atoms, even more preferably a linear or branched alkylene group having 1 to 3 carbon atoms, even more preferably an alkylene group having 1 to 2 carbon atoms, and even more preferably a methylene group.

[0029] The alicyclic amine curing agent of the present embodiment preferably includes one or more selected from the group consisting of 1,3-bisaminomethylcyclohexane, 1,3-diaminocyclohexane, isophoronediamine, 4,4'-methylenedicyclohexanediamine (hydrogenated methylenedianiline), and bis(4-amino-3-methyldicyclohexyl)methane. The aromatic amine curing agent of the present embodiment preferably contains one or more selected from the group consisting of metaxylenediamine, paraxylenediamine, metaphenylenediamine, paraphenylenediamine, diethyltoluenediamine, diaminodiphenylmethane, 4,4'-methylenebis(2-ethyl-6-methylaniline), 1,3-bis[2-(4-aminophenyl)-2-propyl)]benzene, and 1,4-bis[2-(4-aminophenyl)-2-propyl)]benzene. Among these, the amine-based curing agent of the present embodiment more preferably includes one or more selected from the group consisting of 1,3-bisaminomethylcyclohexane and metaxylenediamine, from the viewpoint of further improving the performance balance of the storage stability and low-temperature curing property of the two-component liquid resin composition and the mechanical properties of the cured product of the two-component liquid resin composition.

[0030] From the viewpoint of further improving the performance balance of the storage stability and low-temperature curing ability of the two-component liquid resin composition and the mechanical properties of the cured product of the two-component liquid resin composition, the active hydrogen equivalent of the amine-based curing agent of the present embodiment is preferably from 10 g / eq to 500 g / eq, more preferably from 15 g / eq to 400 g / eq, even more preferably from 20 g / eq to 300 g / eq, even more preferably from 25 g / eq to 200 g / eq, even more preferably from 30 g / eq to 100 g / eq, and even more preferably from 30 g / eq to 50 g / eq.

[0031] In the two-component liquid resin composition of this embodiment, the equivalent ratio of the active hydrogen equivalent of the amine curing agent in the second component to the epoxy equivalent of the epoxy resin in the first component ([amine curing agent content] / [active hydrogen equivalent of amine curing agent]:[epoxy resin content] / [epoxy equivalent of epoxy resin]) is preferably 10:1 or more and 1:10 or less, more preferably 5:1 or more and 1:5 or less, even more preferably 3:1 or more and 1:3 or less, even more preferably 2:1 or more and 1:2 or less, even more preferably 1.5:1 or more and 1:1.5 or less, and even more preferably 1.1:1 or more and 1:1.1 or less, from the viewpoint of further improving the performance balance between the low-temperature curing property of the two-component liquid resin composition and the mechanical properties of the cured product of the two-component liquid resin composition.

[0032] From the viewpoint of further improving the performance balance of the storage stability and low-temperature curing ability of the two-component liquid resin composition and the mechanical properties of a cured product of the two-component liquid resin composition, the content of the amine-based curing agent in the two-component liquid resin composition of this embodiment is preferably 1% by mass or more and 20% by mass or less, more preferably 1% by mass or more and 18% by mass or less, even more preferably 2% by mass or more and 15% by mass or less, even more preferably 3% by mass or more and 13% by mass or less, and even more preferably 4% by mass or more and 10% by mass or less, when the entire two-component liquid resin composition is taken as 100% by mass.

[0033] From the viewpoint of further improving the performance balance of the storage stability and low-temperature curing ability of the two-component liquid resin composition and the mechanical properties of a cured product of the two-component liquid resin composition, the content of the amine-based curing agent in the second liquid of this embodiment is preferably from 50% by mass to 100% by mass, more preferably from 60% by mass to 100% by mass, even more preferably from 70% by mass to 100% by mass, even more preferably from 80% by mass to 100% by mass, even more preferably from 90% by mass to 100% by mass, even more preferably from 95% by mass to 100% by mass, and even more preferably from 98% by mass to 100% by mass, when the entire second liquid is taken as 100% by mass.

[0034] [Other ingredients] The two-component liquid resin composition of the present embodiment may contain inorganic fillers, anti-settling agents, coupling agents, colorants, anti-foaming agents, curing accelerators, and the like, as needed.

[0035] (Inorganic filler) The two-component liquid resin composition of the present embodiment preferably further contains an inorganic filler. The inorganic filler of the present embodiment may be contained in either the first or second liquid, but from the viewpoint of improving the performance balance between the storage stability of the two-component liquid resin composition and the mechanical properties of a cured product of the two-component liquid resin composition, the inorganic filler of the present embodiment is preferably further contained in the first liquid.

[0036] In order to further improve the storage stability of the two-component liquid resin composition and the mechanical properties of the cured product of the two-component liquid resin composition, the inorganic filler of this embodiment preferably includes one or more inorganic fillers selected from the group consisting of silica, alumina, zircon, iron oxide, zinc oxide, titanium oxide, silicon nitride, boron nitride, aluminum nitride, silicon carbide, glass fiber, glass flake, alumina fiber, carbon fiber, graphite, carbon black, ferrite, graphite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, manganese carbonate, magnesium carbonate, barium sulfate, potassium titanate, calcium silicate, inorganic balloons, and silver powder. In order to further improve the mechanical properties of the cured product of the two-component liquid resin composition, the inorganic filler more preferably includes one or more inorganic fillers selected from the group consisting of silica, alumina, aluminum hydroxide, and calcium carbonate. The inorganic filler may also be surface-treated. Examples of surface treatments include, but are not limited to, alkylation, trimethylsilylation, silicone treatment, and treatment with a silane coupling agent.

[0037] The shape of the inorganic filler of the present embodiment is preferably fibrous, amorphous or spherical, and more preferably spherical, from the viewpoint of further improving the performance balance of the storage stability of the two-component liquid resin composition and the mechanical properties of the cured product of the two-component liquid resin composition. Here, the spherical shape may be a perfect sphere, an ellipse, or a substantially spherical shape including an oval shape, etc. The inorganic filler of this embodiment preferably has an aspect ratio (ratio of major axis to minor axis) of 1.3 or less, more preferably 1.2 or less, and even more preferably 1.1 or less.

[0038] The average particle diameter D of the inorganic filler of this embodiment when the cumulative value is 50% in the volume frequency particle size distribution measured by a laser diffraction scattering method 50 From the viewpoint of further improving the storage stability of the two-component liquid resin composition and the performance balance of the mechanical properties of a cured product of the two-component liquid resin composition, the thickness is preferably 1 μm or more and 200 μm or less, more preferably 2 μm or more and 150 μm or less, even more preferably 3 μm or more and 100 μm or less, even more preferably 5 μm or more and 75 μm or less, even more preferably 8 μm or more and 50 μm or less, even more preferably 10 μm or more and 45 μm or less, even more preferably 13 μm or more and 40 μm or less, even more preferably 15 μm or more and 35 μm or less, even more preferably 18 μm or more and 30 μm or less, and even more preferably 20 μm or more and 25 μm or less. The inorganic filler of this embodiment has the above average particle diameter D 50 Within the range of two or more different average particle diameters D 50 The composition may include an inorganic filler having the formula:

[0039] The average particle diameter D of the inorganic filler of this embodiment 50 can be measured, for example, by a laser diffraction scattering measurement method using a laser diffraction particle size distribution analyzer (for example, SALD-7000, manufactured by Shimadzu Corporation).

[0040] From the viewpoint of further improving the storage stability of the two-component liquid resin composition and the performance balance of the mechanical properties of a cured product of the two-component liquid resin composition, the content of the inorganic filler in the two-component liquid resin composition of this embodiment is preferably 45% by mass or more and 90% by mass or less, more preferably 50% by mass or more and 90% by mass or less, even more preferably 55% by mass or more and 90% by mass or less, and even more preferably 60% by mass or more and 90% by mass or less, when the entire two-component liquid resin composition is taken as 100% by mass.

[0041] From the viewpoint of further improving the performance balance between the storage stability of the first liquid and the mechanical properties of the cured product of the two-component liquid resin composition, the content of the inorganic filler in the first liquid of this embodiment is preferably 50% by mass or more and 90% by mass or less, more preferably 53% by mass or more and 90% by mass or less, even more preferably 55% by mass or more and 90% by mass or less, even more preferably 58% by mass or more and 90% by mass or less, even more preferably 60% by mass or more and 90% by mass or less, even more preferably 63% by mass or more and 90% by mass or less, and even more preferably 65% ​​by mass or more and 90% by mass or less, when the entire first liquid is taken as 100% by mass.

[0042] In order to further improve the storage stability of the second liquid, the content of the inorganic filler in the second liquid of this embodiment is preferably 5% by mass or less, more preferably 4% by mass or less, even more preferably 3% by mass or less, even more preferably 2% by mass or less, even more preferably 1% by mass or less, even more preferably 0.5% by mass or less, and even more preferably less than 0.1% by mass, when the entire second liquid is taken as 100% by mass.

[0043] (Anti-settling agent) The two-component liquid resin composition of the present embodiment preferably further contains an anti-settling agent. The anti-settling agent of the present embodiment may be contained in either the first or second component, but from the viewpoint of improving the performance balance between the storage stability of the two-component liquid resin composition and the mechanical properties of a cured product of the two-component liquid resin composition, the first component preferably further contains the anti-settling agent of the present embodiment.

[0044] From the viewpoint of further improving the storage stability of the two-component liquid resin composition and the performance balance of the mechanical properties of a cured product of the two-component liquid resin composition, the anti-settling agent of the present embodiment preferably contains one or more selected from the group consisting of inorganic thickeners (excluding the inorganic fillers described above) and dispersants, and more preferably contains an inorganic thickener.

[0045] Inorganic thickeners The inorganic thickener of the present embodiment preferably contains a layered inorganic mineral, from the viewpoint of further improving the performance balance between the storage stability of the two-component liquid resin composition and the mechanical properties of a cured product of the two-component liquid resin composition.

[0046] The layered inorganic mineral of the present embodiment preferably contains one or more selected from the group consisting of clay and talc, and more preferably contains an organo-clay, from the viewpoint of further improving the storage stability of the two-component liquid resin composition and the performance balance of the mechanical properties of a cured product of the two-component liquid resin composition.

[0047] The clay of the present embodiment preferably contains one or more clays selected from the group consisting of kaolin, smectite, illite, bentonite (montmorillonite), hectorite, pyrophyllite, attapulgite, sepiolite, and laponite, and more preferably contains bentonite, from the viewpoint of further improving the storage stability of the two-component liquid resin composition and the performance balance of the mechanical properties of a cured product of the two-component liquid resin composition. Furthermore, from the viewpoint of further improving the storage stability of the two-component liquid resin composition and the performance balance of the mechanical properties of a cured product of the two-component liquid resin composition, the organized clay of the present embodiment preferably contains one or more clays selected from the group consisting of organized kaolin, organized smectite, organized illite, organized bentonite (organized montmorillonite), organized hectorite, organized pyrophyllite, organized attapulgite, organized sepiolite, and organized laponite, and more preferably contains organized bentonite. Here, organoclay is a layered silicate (clay) in which an organic compound is intercalated between the layers of the layered silicate planes. Interlayer cations, such as sodium ions or calcium ions, exist between the layered silicate planes, maintaining the layered crystal structure. By ion-exchanging the interlayer cations with organic cations, the organic compound is chemically bonded to the surface of the silicate planes and inserted between the layers.

[0048] In the organized clay, the organic compound ion-exchanged with the intermediate layer cation preferably contains a quaternary ammonium salt, more preferably a quaternary alkylammonium salt, and even more preferably one or more selected from the group consisting of trimethylstearylammonium salt, dimethylstearylbenzylammonium salt, dimethyloctadecylammonium salt, oleylbis(2-hydroxyethyl)methylammonium salt, dimethylstearylammonium salt, benzyldimethylstearylammonium salt, and dimethyldistearylammonium salt.

[0049] Examples of commercially available organic bentonite for use in this embodiment include Benton 34, Benton SD-1, Benton SD-2, Benton SD-3, Benton 57, and Benton 52 manufactured by ELEMENTIS Co., Ltd.; Esben NX, Esben N400, Esben WX, Esben NZ, Esben, Esben W, Esben C, Esben E, Esben NZ70, Esben NTO, Esben NX80, Esben NO12S, Esben NEZ, Esben NO12, and Esben NE manufactured by Hojun Co., Ltd.; and Kunibis 110, Kunibis 120, and Kunibis 127 manufactured by Kunimine Kogyo Co., Ltd.

[0050] Dispersant From the viewpoint of further improving the storage stability of the two-component liquid resin composition and the performance balance of the mechanical properties of a cured product of the two-component liquid resin composition, the dispersant of the present embodiment preferably contains an ester compound containing a long-chain hydrocarbon group, and more preferably contains one or more compounds selected from the group consisting of carboxylic acid ester compounds containing a long-chain hydrocarbon group, phosphate ester compounds containing a long-chain hydrocarbon group, sulfate ester compounds containing a long-chain hydrocarbon group, nitrate ester compounds containing a long-chain hydrocarbon group, and carbonate ester compounds containing a long-chain hydrocarbon group.

[0051] The long-chain hydrocarbon group in the ester compound containing a long-chain hydrocarbon group of this embodiment preferably contains one or more groups selected from the group consisting of alkylene groups, alkyl groups, alkenyl groups, aralkyl groups, aryl groups, and aryl groups in which one, two, or three hydrogen atoms of the hydrocarbon are substituted with substituents, from the viewpoint of further improving the storage stability of the two-component liquid resin composition and the performance balance of the mechanical properties of a cured product of the two-component liquid resin composition. The long-chain hydrocarbon group may be linear or branched. Some of the hydrogen atoms in the long-chain hydrocarbon group may be substituted with a substituent such as a hydroxy group, an aldehyde group, a carbonyl group, a carboxy group, an amino group, a nitro group, a sulfo group, or a halogeno group. The long-chain hydrocarbon group may contain an oxygen-containing bond such as an ether bond or an ester bond in the long chain.

[0052] The ester group in the ester compound containing a long-chain hydrocarbon group of the present embodiment preferably contains one or more groups selected from the group consisting of a carboxylic acid ester group, a phosphate ester group, a sulfate ester group, a nitrate ester group, and a carbonate ester group, from the viewpoint of further improving the storage stability of the two-component liquid resin composition and the performance balance of the mechanical properties of a cured product of the two-component liquid resin composition.

[0053] The number of carbon atoms in the long-chain hydrocarbon group in the ester compound containing a long-chain hydrocarbon group of the present embodiment is preferably 4 or more and 1,000 or less, more preferably 4 or more and 800 or less, even more preferably 6 or more and 600 or less, even more preferably 8 or more and 400 or less, and even more preferably 10 or more and 200 or less, from the viewpoint of further improving the storage stability of the two-component liquid resin composition and the performance balance of the mechanical properties of a cured product of the two-component liquid resin composition.

[0054] The mass average molecular weight of the ester compound containing a long-chain hydrocarbon group of this embodiment is preferably 300 or more and 50,000 or less, more preferably 400 or more and 50,000 or less, even more preferably 500 or more and 30,000 or less, even more preferably 600 or more and 30,000 or less, even more preferably 700 or more and 15,000 or less, and even more preferably 800 or more and 10,000 or less, from the viewpoint of further improving the storage stability of the two-component liquid resin composition and the performance balance of the mechanical properties of a cured product of the two-component liquid resin composition.

[0055] The ester compound containing a long-chain hydrocarbon group of the present embodiment preferably contains one or more compounds selected from the group consisting of polyhydroxycarboxylic acid esters, acidic phosphoric acid esters, and carboxyl group-containing modified polymers, from the viewpoint of further improving the storage stability of the two-component liquid resin composition and the performance balance of the mechanical properties of a cured product of the two-component liquid resin composition.

[0056] An example of a commercially available polyhydroxycarboxylic acid ester of this embodiment is BYK-R606 manufactured by BYK Japan.

[0057] An example of a commercially available acidic phosphate ester of this embodiment is BYK-W9010 manufactured by BYK Japan.

[0058] Commercially available products of the carboxyl group-containing modified polymer of this embodiment include, for example, FLOWLEN G-700, FLOWLEN G-900, FLOWLEN G-1500, and NC-500 manufactured by Kyoeisha Chemical Co., Ltd.

[0059] The content of the anti-settling agent in the two-component liquid resin composition of this embodiment, when the total amount of the two-component liquid resin composition is taken as 100% by mass, is preferably from 0.01 to 2.00% by mass, more preferably from 0.03 to 1.50% by mass, even more preferably from 0.05 to 1.00% by mass, even more preferably from 0.08 to 0.80% by mass, even more preferably from 0.10 to 0.50% by mass, even more preferably from 0.13 to 0.30% by mass, even more preferably from 0.15 to 0.25% by mass, and even more preferably from 0.18 to 0.20% by mass, from the viewpoint of further improving the performance balance of the storage stability and low-temperature curing ability of the two-component liquid resin composition and the mechanical properties of a cured product of the two-component liquid resin composition.

[0060] From the viewpoint of further improving the performance balance between the storage stability of the first liquid and the mechanical properties of the cured product of the two-component liquid resin composition, the content of the anti-settling agent in the first liquid in this embodiment is preferably 0.01% by mass or more and 2.00% by mass or less, more preferably 0.03% by mass or more and 1.50% by mass or less, even more preferably 0.05% by mass or more and 1.00% by mass or less, even more preferably 0.08% by mass or more and 0.80% by mass or less, even more preferably 0.10% by mass or more and 0.50% by mass or less, even more preferably 0.13% by mass or more and 0.30% by mass or less, and even more preferably 0.15% by mass or more and 0.25% by mass or less, when the entire first liquid is taken as 100% by mass.

[0061] In order to further improve the storage stability of the second liquid, the content of the anti-settling agent in the second liquid of this embodiment is preferably 5% by mass or less, more preferably 4% by mass or less, even more preferably 3% by mass or less, even more preferably 2% by mass or less, even more preferably 1% by mass or less, even more preferably 0.5% by mass or less, and even more preferably less than 0.1% by mass, when the entire second liquid is taken as 100% by mass.

[0062] (coupling agent) The two-component liquid resin composition of the present embodiment may contain a coupling agent from the viewpoint of improving the interfacial strength between the epoxy resin and the inorganic filler. The coupling agent of the present embodiment may be contained in either the first liquid or the second liquid, but is preferably contained in the first liquid from the viewpoint of improving the interfacial strength between the epoxy resin and the inorganic filler. From the viewpoint of being able to improve the interfacial strength between the epoxy resin and the inorganic filler, the coupling agent of the present embodiment preferably contains one or more selected from the group consisting of an epoxy silane coupling agent, an amino silane coupling agent, a ureido silane coupling agent, and a mercapto silane coupling agent, and more preferably contains an epoxy silane coupling agent.

[0063] The epoxy silane coupling agent preferably includes one or more selected from the group consisting of γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and more preferably includes γ-glycidoxypropyltrimethoxysilane. The aminosilane coupling agent preferably includes one or more selected from the group consisting of γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropyltriethoxysilane, N-(6-aminohexyl)3-aminopropyltrimethoxysilane, and N-(3-(trimethoxysilylpropyl)-1,3-benzenedimethanane. The ureidosilane coupling agent includes, for example, one or more selected from the group consisting of γ-ureidopropyltriethoxysilane and hexamethyldisilazane.

[0064] From the viewpoint of improving the interfacial strength between the epoxy resin and the inorganic filler, the content of the coupling agent in the two-component liquid resin composition of this embodiment is preferably 0.01% by mass or more and 3.00% by mass or less, more preferably 0.02% by mass or more and 2.00% by mass or less, even more preferably 0.03% by mass or more and 1.00% by mass or less, even more preferably 0.04% by mass or more and 0.50% by mass or less, and even more preferably 0.05% by mass or more and 0.30% by mass or less, when the entire two-component liquid resin composition is taken as 100% by mass.

[0065] (coloring agent) The two-component liquid resin composition of the present embodiment may further contain a colorant. The colorant of the present embodiment may be contained in either the first or second liquid, but from the viewpoint of improving the balance of storage stability and low-temperature curing properties, it is preferable that the first liquid further contains the colorant of the present embodiment. The colorant of the present embodiment preferably contains one or more selected from the group consisting of carbon black, titanium oxide, barium sulfate, iron black, red iron oxide, aniline black, and alizanin, and more preferably contains carbon black.

[0066] From the viewpoint of improving the performance balance between storage stability and low-temperature curing property, the content of the colorant in the two-component liquid resin composition of this embodiment is preferably 0.01% by mass or more and 1.00% by mass or less, more preferably 0.02% by mass or more and 0.90% by mass or less, even more preferably 0.03% by mass or more and 0.80% by mass or less, even more preferably 0.04% by mass or more and 0.65% by mass or less, and even more preferably 0.05% by mass or more and 0.50% by mass or less, when the entire two-component liquid resin composition is taken as 100% by mass.

[0067] (Antifoaming agent) The two-component liquid resin composition of the present embodiment may further contain an antifoaming agent. The antifoaming agent of the present embodiment may be contained in either the first or second component, but from the viewpoint of improving the performance balance of storage stability, low-temperature curing ability, and mechanical strength of the cured product of the two-component liquid resin composition, it is preferable that the first component further contains the antifoaming agent of the present embodiment. The defoaming agent of the present embodiment preferably includes one or more selected from the group consisting of a silicone-based defoaming agent, a fluorine-based defoaming agent, and a polymer-based defoaming agent, and more preferably includes a silicone-based defoaming agent.

[0068] From the viewpoint of improving the performance balance among storage stability, low-temperature curing ability, and mechanical strength of a cured product of the two-component liquid resin composition, the content of the antifoaming agent in the two-component liquid resin composition of the present embodiment is preferably 0.01% by mass or more and 1.00% by mass or less, more preferably 0.02% by mass or more and 0.90% by mass or less, even more preferably 0.03% by mass or more and 0.80% by mass or less, even more preferably 0.04% by mass or more and 0.65% by mass or less, and even more preferably 0.05% by mass or more and 0.50% by mass or less, when the entire two-component liquid resin composition is taken as 100% by mass.

[0069] (curing accelerator) The two-component liquid resin composition of the present embodiment may contain a curing accelerator. The curing accelerator of the present embodiment may be contained in either the first or second liquid. Examples of the curing accelerator of the present embodiment include tertiary amines, quaternary ammonium salts, imidazoles, organic phosphines, and Lewis acid catalysts.

[0070] Examples of the tertiary amine include trimethylamine, triethylamine, tripropylamine, tributylamine, and benzyldimethylamine.

[0071] Examples of quaternary ammonium salts include organic acid salts of diazabicycloundecene, such as octylate salt of DBU [1,8-diazabicyclo[5.4.0]undecene-7] (manufactured by San-Apro Ltd., trade name: SA102), DBN [1,5-diazabicyclo[4.3.0]-5-nonene], quaternary ammonium salts which are salts of tertiary amines and carboxylic acids (manufactured by San-Apro Ltd., trade name: U-CAT2313), octadecyltrimethylammonium chloride (manufactured by NOF Corporation, trade name: Nissan Cation), and tetraalkyl ammonium salts (each alkyl group having 1 to 18 carbon atoms) (e.g., tetraethylammonium bromide, tetrabutylammonium bromide, tetraalkylammonium carboxylates (carboxylic acid having 1 to 12 carbon atoms)).

[0072] Examples of imidazoles include 1-benzyl-2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1,2-dimethylimidazole, and 1-benzyl-2-phenylimidazole.

[0073] Examples of organic phosphines include triphenylphosphine, triphenylphosphine-triphenylborate, tris(p-methoxyphenyl)phosphine, and tetraphenylphosphonium tetraphenylborate.

[0074] Examples of the Lewis acid catalyst include boron trifluoride amine complex, boron trichloride amine complex, and boron trifluoride ethylamine complex.

[0075] From the viewpoint of improving the performance balance between storage stability and low-temperature curing ability, the content of the curing accelerator in the two-component liquid resin composition of this embodiment is preferably 1.0 mass % or less, more preferably 0.8 mass % or less, even more preferably 0.5 mass % or less, even more preferably 0.3 mass % or less, even more preferably 0.1 mass % or less, even more preferably 0.05 mass % or less, and even more preferably 0.01 mass % or less, when the entire two-component liquid resin composition is taken as 100 mass %.

[0076] [Physical Properties] The glass transition temperature 1 (Tg1) of the two-component liquid resin composition of this embodiment, as determined by the following (Method 1), is preferably 50°C or higher and 100°C or lower, more preferably 53°C or higher and 90°C or lower, even more preferably 56°C or higher and 85°C or lower, and even more preferably 60°C or higher and 80°C or lower, from the viewpoint of improving the performance balance among storage stability, low-temperature curing ability, and mechanical strength of the cured product of the two-component liquid resin composition.

[0077] (Method 1) The second liquid is mixed with 50 g of the first liquid at 25°C so that the equivalent ratio of the active hydrogen equivalent of the amine-based curing agent to the epoxy equivalent of the epoxy resin in the first liquid is 1, to obtain a mixture. The mixture is poured into an aluminum cup and cured at 40°C for 8 hours. After slowly cooling to 25°C, a test piece is cut out to dimensions of 10 mm x 5 mm x 5 mm. The test piece is measured using a thermomechanical analyzer under conditions of a measurement temperature range of 0°C to 230°C and a heating rate of 10°C / min, and the glass transition temperature (°C) is calculated from the measurement results.

[0078] The glass transition temperature 2 (Tg2) of the two-component liquid resin composition of this embodiment, according to (Method 2), is preferably 80°C or higher and 200°C or lower, more preferably 83°C or higher and 180°C or lower, even more preferably 85°C or higher and 160°C or lower, even more preferably 88°C or higher and 140°C or lower, and even more preferably 90°C or higher and 135°C or lower, from the viewpoint of improving the performance balance among storage stability, low-temperature curing ability, and mechanical strength of the cured product of the two-component liquid resin composition.

[0079] (Method 2) The second liquid is mixed with 50 g of the first liquid at 25°C so that the equivalent ratio of the active hydrogen equivalent of the amine-based curing agent to the epoxy equivalent of the epoxy resin in the first liquid is 1, to obtain a mixture. The mixture is poured into an aluminum cup and cured at 40°C for 8 hours, and then at 80°C for 1 hour. After slowly cooling to 25°C, a test piece measuring 10 mm x 5 mm x 5 mm is cut out. The test piece is measured using a thermomechanical analyzer under conditions of a measurement temperature range of 0°C to 230°C and a heating rate of 10°C / min, and the glass transition temperature (°C) is calculated from the measurement results.

[0080] The ratio of Tg2 to Tg1 (Tg2 / Tg1) of the two-component liquid resin composition of this embodiment is preferably 1.0 or more and 2.0 or less, more preferably 1.1 or more and 2.0 or less, even more preferably 1.2 or more and 1.9 or less, even more preferably 1.3 or more and 1.8 or less, and even more preferably 1.4 or more and 1.7 or less, from the viewpoint of improving the performance balance of storage stability, low-temperature curing ability, and mechanical strength of the cured product of the two-component liquid resin composition.

[0081] The glass transition temperatures (Tg1 and Tg2) of the two-component liquid resin composition of this embodiment can be measured using, for example, a commercially available thermomechanical analyzer (for example, TMA7100 manufactured by Hitachi High-Tech Science Corporation).

[0082] The Rockwell hardness 1 of the two-component liquid resin composition of this embodiment, measured by the following (Method 3), is preferably 50 or more and 130 or less, more preferably 50 or more and 125 or less, even more preferably 55 or more and 120 or less, even more preferably 55 or more and 115 or less, even more preferably 60 or more and 110 or less, even more preferably 65 or more and 100 or less, and even more preferably 70 or more and 90 or less, from the viewpoint of improving the performance balance of storage stability, low-temperature curing ability, and mechanical strength of the cured product of the two-component liquid resin composition.

[0083] (Method 3) The second liquid is mixed with 50 g of the first liquid at 25°C so that the equivalent ratio of the active hydrogen equivalent of the amine-based curing agent to the epoxy equivalent of the epoxy resin in the first liquid is 1, to obtain a mixture. The mixture is poured into an aluminum cup and cured at 40°C for 8 hours. After slowly cooling to 25°C, a test piece measuring 10 mm x 10 mm x 10 mm is cut out. The test piece is used to measure Rockwell hardness 1 at 25°C using the M hardness scale in accordance with JIS K7202:2001.

[0084] The Rockwell hardness 2 of the two-component liquid resin composition of this embodiment, measured by the following (Method 4), is preferably 50 or more and 130 or less, more preferably 55 or more and 125 or less, even more preferably 60 or more and 120 or less, even more preferably 65 or more and 115 or less, even more preferably 75 or more and 110 or less, and even more preferably 80 or more and 100 or less, from the viewpoint of improving the performance balance of storage stability, low-temperature curing ability, and mechanical strength of the cured product of the two-component liquid resin composition.

[0085] (Method 4) The second liquid is mixed with 50 g of the first liquid at 25°C so that the equivalent ratio of the active hydrogen equivalent of the amine-based curing agent to the epoxy equivalent of the epoxy resin in the first liquid is 1 to obtain a mixture. The mixture is poured into an aluminum cup and cured at 40°C for 8 hours, and then at 80°C for 1 hour. After slowly cooling to 25°C, a test piece measuring 10 mm x 10 mm x 10 mm is cut out. The test piece is used to measure Rockwell hardness 2 at 25°C using the M hardness scale in accordance with JIS K7202:2001.

[0086] The ratio of Rockwell hardness 2 to Rockwell hardness 1 of the two-component liquid resin composition of this embodiment is preferably 0.5 or more and 1.5 or less, more preferably 0.7 or more and 1.4 or less, even more preferably 0.9 or more and 1.3 or less, and even more preferably 1.0 or more and 1.2 or less, from the viewpoint of improving the performance balance of storage stability, low-temperature curing ability, and mechanical strength of the cured product of the two-component liquid resin composition.

[0087] The bending strength 1 of the two-component liquid resin composition of this embodiment, measured by the following (Method 5), is preferably 50 MPa or more and 150 MPa or less, more preferably 50 MPa or more and 145 MPa or less, even more preferably 55 MPa or more and 140 MPa or less, even more preferably 60 MPa or more and 135 MPa or less, even more preferably 65 MPa or more and 130 MPa or less, and even more preferably 70 MPa or more and 120 MPa or less, from the viewpoint of improving the performance balance of storage stability, low-temperature curing ability, and mechanical strength of the cured product of the two-component liquid resin composition.

[0088] (Method 5) The second liquid is mixed with 50 g of the first liquid at 25°C so that the equivalent ratio of the active hydrogen equivalent of the amine-based curing agent to the epoxy equivalent of the epoxy resin in the first liquid is 1 to obtain a mixture. The mixture is poured into an aluminum cup and cured at 40°C for 8 hours. After slowly cooling to 25°C, a test piece measuring 100 mm x 10 mm x 4 mm is cut out. The flexural strength 1 of the test piece is measured at 25°C in accordance with JIS K 6911:2006.

[0089] The bending strength 2 of the two-component liquid resin composition of this embodiment, measured by the following (Method 6), is preferably 70 MPa or more and 250 MPa or less, more preferably 70 MPa or more and 225 MPa or less, even more preferably 75 MPa or more and 200 MPa or less, even more preferably 80 MPa or more and 175 MPa or less, even more preferably 85 MPa or more and 150 MPa or less, and even more preferably 90 MPa or more and 125 MPa or less, from the viewpoint of improving the performance balance of storage stability, low-temperature curing ability, and mechanical strength of the cured product of the two-component liquid resin composition.

[0090] (Method 6) The second liquid is mixed with 50 g of the first liquid at 25°C so that the equivalent ratio of the active hydrogen equivalent of the amine-based curing agent to the epoxy equivalent of the epoxy resin in the first liquid is 1 to obtain a mixture. The mixture is poured into an aluminum cup and cured at 40°C for 8 hours, and then at 80°C for 1 hour. After slowly cooling to 25°C, a test piece measuring 100 mm x 10 mm x 4 mm is cut out. The flexural strength 2 of the test piece is measured at 25°C in accordance with JIS K 6911:2006.

[0091] The ratio of the flexural strength 2 to the flexural strength 1 of the two-component liquid resin composition of this embodiment is preferably 0.5 or more and 1.5 or less, more preferably 0.7 or more and 1.5 or less, even more preferably 0.9 or more and 1.4 or less, and even more preferably 1.1 or more and 1.3 or less, from the viewpoint of improving the performance balance of storage stability, low-temperature curing ability, and the mechanical strength of the cured product of the two-component liquid resin composition.

[0092] <Method for producing two-component liquid resin composition> The method for producing the two-component liquid resin composition of this embodiment will be described in detail below. The two-component liquid resin composition of the present embodiment can be produced by thoroughly mixing and stirring the epoxy resin and other components as the first component and the curing agent and other components as the second component by a known method, among the above-mentioned components.

[0093] Methods for mixing and stirring the components to obtain the first or second liquid in the two-component liquid resin composition of this embodiment include methods using a mixer or other mixing machine, or a kneader or other kneading machine.

[0094] The two-component liquid resin composition of the present embodiment is used in the form of a mixed liquid obtained by mixing the first and second liquids. Examples of a method for mixing the first and second liquids include a method using a mixer or other mixer, or a kneader or other kneading machine.

[0095] In the two-component liquid resin composition of this embodiment, the content of the second liquid when mixing the first and second liquids is preferably 1 part by mass or more and 50 parts by mass or less, more preferably 1 part by mass or more and 40 parts by mass or less, even more preferably 1 part by mass or more and 30 parts by mass or less, even more preferably 1 part by mass or more and 20 parts by mass or less, and even more preferably 1 part by mass or more and 10 parts by mass or less, based on 100 parts by mass of the entire first liquid, from the viewpoint of further improving the performance balance between the low-temperature curing property of the two-component liquid resin composition and the mechanical properties of the cured product of the two-component liquid resin composition.

[0096] <Uses of two-component liquid resin compositions> The two-component liquid resin composition of the present embodiment can be cured by a known method to form a cured product. The cured product of the present embodiment can be used for any of the known uses of cured products.

[0097] The two-component liquid resin composition of this embodiment can be molded into a molded article by a known method. Examples of molding methods for obtaining the molded article of this embodiment include injection molding, transfer molding, and compression molding. Conditions such as molding temperature and molding time when molding the resin molding material of this embodiment can be appropriately adjusted by the molding method, molding device, or blending of the resin molding material.

[0098] (electronic equipment) The two-component liquid resin composition of the present embodiment can be preferably used to encapsulate a structure including a substrate including a circuit layer and an electronic component on the circuit layer of the substrate. More specifically, the two-component liquid resin composition of the present embodiment can be used in a method for manufacturing an electronic device, which includes a sealing step of sealing a structure including a substrate including a circuit layer and electronic components on the circuit layer of the substrate.

[0099] The electronic device of the present embodiment preferably comprises a substrate including a circuit layer, electronic components on the circuit layer of the substrate, and an encapsulant for encapsulating the substrate and the electronic components, wherein the encapsulant comprises a cured product of the two-component liquid resin composition of the present embodiment.

[0100] The electronic component of this embodiment preferably includes one or more elements selected from the group consisting of semiconductor elements such as integrated circuits, large-scale integrated circuits, MEMS, transistors, thyristors, diodes, solid-state imaging devices, and electrolytic capacitor elements; power semiconductor elements such as rectifier diodes, power transistors, MOS transistors, insulated gate bipolar transistors (IGBTs), thyristors, gate turn-off thyristors (GTOs), and triacs; chip resistors; microcomputers; terminals; bus bars; and connectors.

[0101] The electronic device of this embodiment can be obtained by the following method for manufacturing an electronic device. The method for manufacturing an electronic device of this embodiment preferably includes a sealing step of sealing a structure including a substrate including a circuit layer and electronic components on the circuit layer of the substrate with the two-component liquid resin composition of this embodiment, and the sealing step includes, in this order, a step of covering at least a portion of the structure with a mixture including the first liquid and the second liquid, a step of primarily curing the mixture at a temperature of 20°C or higher and lower than 60°C, and a step of secondary curing the obtained primary cured product at a temperature of 60°C or higher and 150°C or lower.

[0102] In the method for manufacturing an electronic device of this embodiment, the temperature for primary curing the mixture is 20°C or higher and lower than 60°C, preferably 25°C or higher and lower than 55°C, more preferably 30°C or higher and lower than 50°C, and even more preferably 35°C or higher and lower than 45°C.

[0103] In the method for manufacturing an electronic device of this embodiment, the time for primary curing the mixture is preferably 1 hour or more and 48 hours or less, more preferably 2 hours or more and 24 hours or less, even more preferably 4 hours or more and 12 hours or less, and even more preferably 6 hours or more and 9 hours or less.

[0104] In the method for manufacturing an electronic device of this embodiment, the temperature for secondary curing of the primary cured product is 60°C or higher and 150°C or lower, preferably 60°C or higher and 140°C or lower, more preferably 65°C or higher and 130°C or lower, even more preferably 70°C or higher and 120°C or lower, even more preferably 70°C or higher and 110°C or lower, even more preferably 75°C or higher and 100°C or lower, and even more preferably 75°C or higher and 90°C or lower.

[0105] In the method for manufacturing an electronic device of this embodiment, the time for secondary curing of the primary cured product is preferably 0.1 hours or more and 12 hours or less, more preferably 0.1 hours or more and 6 hours or less, even more preferably 0.2 hours or more and 3 hours or less, and even more preferably 0.3 hours or more and 2 hours or less.

[0106] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various other configurations may be adopted. Furthermore, the present invention is not limited to the above-described embodiments, and modifications and improvements within the scope of achieving the object of the present invention are included in the present invention. [Example]

[0107] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples in any way.

[0108] <Examples and Comparative Examples> The first liquid (main agent) was obtained by mixing the components shown in "First Liquid" in Table 1 in the amounts (parts by mass) shown in Table 1. Separately, the components shown in "Second Liquid" in Table 1 were mixed in the amounts (parts by mass) shown in Table 1 to obtain the second liquid (curing agent). Details of each component in Table 1 are as follows:

[0109] <Epoxy resin> Epoxy resin 1: Bisphenol A epoxy resin (Mitsubishi Chemical Corporation, jER828EL, epoxy equivalent: 187g / eq) Epoxy resin 2: Bisphenol F epoxy resin (Mitsubishi Chemical Corporation, jER807, epoxy equivalent: 169 g / eq) <Inorganic filler> Inorganic filler 1: spherical fused silica (manufactured by Denka Co., Ltd., FB-950, average particle diameter D 50 :23μm) Inorganic filler 2: Aluminum hydroxide (Sumitomo Chemical Co., Ltd., CW-325LV, average particle size D 50 :21μm) <Curing agent> Curing agent 1: Amidoamine (aliphatic amine curing agent, manufactured by Tsuno Group Co., Ltd., Vegichem Green (registered trademark) G747, active hydrogen equivalent: 108 g / eq) Curing agent 2: Metaxylenediamine (aromatic amine curing agent, Mitsubishi Gas Chemical Company, Inc., MXDA, active hydrogen equivalent: 34g / eq) Curing agent 3: 1,3-bisaminomethylcyclohexane (alicyclic amine curing agent, Mitsubishi Gas Chemical Company, Inc., 1,3-BAC, active hydrogen equivalent: 35.6 g / eq)

[0110] <Other ingredients> Colorant: Carbon black (Mitsubishi Chemical Corporation, Carbon #5) Coupling agent: Epoxy silane coupling agent (Momentive Performance Materials, A-187) Anti-settling agent: Organized bentonite (Hojun Co., Ltd., Esben N-400) Antifoaming agent: Silicone antifoaming agent (KS603, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0111] The average particle diameter D of the inorganic filler 50 The measured value at 50% of the integrated value of the volume-based particle size distribution was obtained by a laser diffraction scattering measurement method using a laser diffraction particle size distribution analyzer (SALD-7000, manufactured by Shimadzu Corporation).

[0112] <Physical property evaluation> The first and second liquids obtained in each of the examples and comparative examples were measured for the following physical properties.

[0113] (glass transition temperature (Tg)) For each Example and Comparative Example, 50 g of the first liquid was mixed by hand at 25°C for 10 seconds with the "blending ratio (first liquid / second liquid)" shown in Table 1, so that the equivalent ratio of the active hydrogen equivalent of the amine-based curing agent to the epoxy equivalent of the epoxy resin in the first liquid was 1. The mixture was poured into an aluminum cup and cured at 40°C for 8 hours. After slowly cooling to 25°C, the mixture was cut into 10 mm x 5 mm x 5 mm specimens. The specimens were measured using a thermomechanical analyzer (Hitachi High-Tech Science Corporation, model number: TMA7100) at a temperature range of 0°C to 230°C and a heating rate of 10°C / min. The glass transition temperature 1 (Tg1) (°C) was calculated from the measurement results. Next, the above mixture was obtained in the same manner, and then poured into an aluminum cup and cured at 40°C for 8 hours, followed by curing at 80°C for 1 hour. After slowly cooling to 25°C, a test piece measuring 10 mm x 5 mm x 5 mm was cut out. The test piece was measured using a thermomechanical analyzer under conditions of a measurement temperature range of 0°C to 230°C and a heating rate of 10°C / min, and the glass transition temperature 2 (Tg2) (°C) was calculated from the measurement results. The ratio of glass transition temperature 2 to glass transition temperature 1 (Tg2 / Tg1) was calculated from the measured values ​​of glass transition temperature 1 and glass transition temperature 2. The results are shown in Table 1.

[0114] (Rockwell hardness) For each Example and Comparative Example, 50 g of the first liquid was mixed by hand at 25°C for 10 seconds with the second liquid according to the "blending ratio (first liquid / second liquid)" shown in Table 1, so that the equivalent ratio of the active hydrogen equivalent of the amine-based curing agent to the epoxy equivalent of the epoxy resin in the first liquid was 1. The mixture was poured into an aluminum cup and cured at 40°C for 8 hours. After gradual cooling to 25°C, a test specimen measuring 10 mm x 10 mm x 10 mm was obtained. The test specimen was then measured for Rockwell hardness 1 at 25°C using the M hardness scale according to JIS K7202:2001. Next, the above mixture was obtained in the same manner, and then poured into an aluminum cup and cured at 40°C for 8 hours, followed by curing at 80°C for 1 hour. After slowly cooling to 25°C, a test piece measuring 10 mm x 10 mm x 10 mm was cut out. Using the test piece, the Rockwell hardness 2 at 25°C was measured using the M hardness scale in accordance with JIS K7202:2001. The ratio of Rockwell hardness 2 to Rockwell hardness 1 (Rockwell hardness 2 / Rockwell hardness 1) was calculated from the measured values ​​of Rockwell hardness 1 and Rockwell hardness 2. The results are shown in Table 1.

[0115] (bending strength) For each Example and Comparative Example, 50 g of the first liquid was mixed by hand at 25°C for 10 seconds with the "blending ratio (first liquid / second liquid)" shown in Table 1 so that the equivalent ratio of the active hydrogen equivalent of the amine-based curing agent to the epoxy equivalent of the epoxy resin in the first liquid was 1. The mixture was poured into an aluminum cup and cured at 40°C for 8 hours. After gradual cooling to 25°C, a test specimen measuring 100 mm x 10 mm x 4 mm was cut out. The flexural strength 1 of the test specimen was measured at 25°C in accordance with JIS K 6911:2006. Next, the above mixture was obtained in the same manner, and then poured into an aluminum cup and cured at 40°C for 8 hours, followed by curing at 80°C for 1 hour. After slowly cooling to 25°C, a test piece measuring 100 mm x 10 mm x 4 mm was cut out. The flexural strength 2 of the test piece was measured at 25°C in accordance with JIS K 6911:2006. The ratio of bending strength 2 to bending strength 1 (bending strength 2 / bending strength 1) was calculated from the measured values ​​of bending strength 1 and bending strength 2. The results are shown in Table 1.

[0116] (Storage stability) The viscosity of the first liquid in each example and comparative example was measured at a rotation speed of 10 rpm and a temperature of 25°C using an E-type viscometer and a 3°×R14 cone rotor (rotor No. 4), and the measured value was recorded as a viscosity η A At this time, the viscosity η AThe viscosity was measured one minute after the cone rotor set on the E-type viscometer started to rotate. Thereafter, the first liquid of each of the Examples and Comparative Examples was stored in a dark place at 25°C for 6 months. After storage, the viscosity of the first liquid of each example and comparative example was measured in the same manner as above, and the measured value was recorded as viscosity η B It was decided. Measured viscosity η A and viscosity η B The storage stability was evaluated according to the following criteria. A:η B / η A is between 0.8 and 1.2 B:η B / η A is less than 0.8 or more than 1.2

[0117] [Table 1]

[0118] In each of the Examples in which an alicyclic amine curing agent or an aromatic amine curing agent was used, the performance balance of storage stability and low-temperature curing property was improved compared to Comparative Example 1 in which an alicyclic amine curing agent or an aromatic amine curing agent was not used.

Claims

1. a two-component liquid resin composition consisting of a first liquid and a second liquid, the first liquid contains an epoxy resin, The second liquid is a two-component liquid resin composition, which contains one or more amine-based curing agents selected from the group consisting of alicyclic amine-based curing agents and aromatic amine-based curing agents.

2. 2. The two-component liquid resin composition according to claim 1, wherein the amine-based curing agent comprises a structure represented by the following general formula (1): 【Chemical 1】 (In the general formula (1), R １ represents a linear or branched alkylene group having 1 to 5 carbon atoms)

3. 3. The two-component liquid resin composition according to claim 1, wherein the amine-based curing agent comprises one or more selected from the group consisting of 1,3-bisaminomethylcyclohexane and metaxylenediamine.

4. 3. The two-component liquid resin composition according to claim 1, wherein the content of the amine-based curing agent is 50% by mass or more and 100% by mass or less, when the entire second liquid is taken as 100% by mass.

5. 3. The two-component liquid resin composition according to claim 1, wherein the content of the second liquid is 1 part by mass or more and 50 parts by mass or less when the total amount of the first liquid is 100 parts by mass.

6. 3. The two-component liquid resin composition according to claim 1, wherein the epoxy resin comprises a bisphenol-type epoxy resin.

7. 7. The two-component liquid resin composition according to claim 6, wherein the bisphenol type epoxy resin comprises one or more selected from the group consisting of bisphenol A type epoxy resins and bisphenol F type epoxy resins.

8. 3. The two-component liquid resin composition according to claim 1, wherein the content of the epoxy resin is 10% by mass or more and 50% by mass or less, when the total amount of the first liquid is 100% by mass.

9. The two-component liquid resin composition according to claim 1 or 2, wherein the first liquid further contains an inorganic filler.

10. 10. The two-component liquid resin composition according to claim 9, wherein the inorganic filler comprises one or more selected from the group consisting of silica, alumina, aluminum hydroxide, and calcium carbonate.

11. The average particle diameter D of the inorganic filler at which the cumulative value reaches 50% in the volume frequency particle size distribution measured by a laser diffraction scattering method ５０ The two-component liquid resin composition according to claim 9, wherein the average particle size is 1 μm or more and 200 μm or less.

12. 10. The two-component liquid resin composition according to claim 9, wherein the content of the inorganic filler is 50% by mass or more and 90% by mass or less, when the total mass of the first liquid is 100% by mass.

13. The two-component liquid resin composition according to claim 1 or 2, wherein the first component further comprises an anti-settling agent.

14. 14. The two-component liquid resin composition according to claim 13, wherein the content of the anti-settling agent is 0.01% by mass or more and 2.00% by mass or less, when the total amount of the first liquid is 100% by mass.

15. 3. The two-component liquid resin composition according to claim 1, wherein the content of the curing accelerator is 1.0% by mass or less when the total amount of the two-component liquid resin composition is taken as 100% by mass.

16. 3. The two-component liquid resin composition according to claim 1, wherein the glass transition temperature 1 (Tg1) measured by the following method 1 is 50°C or higher and 100°C or lower. (Method 1) The second liquid is mixed with 50 g of the first liquid at 25°C so that the equivalent ratio of the active hydrogen equivalent of the amine-based curing agent to the epoxy equivalent of the epoxy resin in the first liquid is 1, to obtain a mixture. The mixture is poured into an aluminum cup and cured at 40° C. for 8 hours. After slowly cooling to 25° C., a test piece measuring 10 mm×5 mm×5 mm is cut out. The test piece is measured using a thermomechanical analyzer under conditions of a measurement temperature range of 0° C. to 230° C. and a temperature rise rate of 10° C. / min, and the glass transition temperature 1 (° C.) is calculated from the measurement results.

17. The two-component liquid resin composition according to claim 16, wherein the glass transition temperature 2 (Tg2) measured by the following method 2 is 80°C or higher and 200°C or lower. (Method 2) The second liquid is mixed with 50 g of the first liquid at 25°C so that the equivalent ratio of the active hydrogen equivalent of the amine-based curing agent to the epoxy equivalent of the epoxy resin in the first liquid is 1, to obtain a mixture. The mixture is poured into an aluminum cup and cured at 40° C. for 8 hours, and then cured at 80° C. for 1 hour. After slowly cooling to 25° C., a test piece measuring 10 mm×5 mm×5 mm is cut out. The test piece is measured using a thermomechanical analyzer under conditions of a measurement temperature range of 0°C to 230°C and a temperature rise rate of 10°C / min, and the glass transition temperature 2 (°C) is calculated from the measurement results.

18. 18. The two-component liquid resin composition according to claim 17, wherein the ratio of Tg2 to Tg1 (Tg2 / Tg1) is 1.0 or more and 2.0 or less.

19. 3. The two-component liquid resin composition according to claim 1, wherein the composition has a Rockwell hardness 1 of 50 or more and 130 or less, as measured by the following method (Method 3). (Method 3) The second liquid is mixed with 50 g of the first liquid at 25°C so that the equivalent ratio of the active hydrogen equivalent of the amine-based curing agent to the epoxy equivalent of the epoxy resin in the first liquid is 1, to obtain a mixture. The mixture is poured into an aluminum cup and cured at 40° C. for 8 hours. After slowly cooling to 25° C., a test piece measuring 10 mm×10 mm×10 mm is cut out. Using the test piece, Rockwell hardness 1 is measured at 25° C. on the M hardness scale in accordance with JIS K7202:2001.

20. 20. The two-component liquid resin composition according to claim 19, having a Rockwell hardness 2 measured by the following method (Method 4) of 50 or more and 130 or less. (Method 4) The second liquid is mixed with 50 g of the first liquid at 25°C so that the equivalent ratio of the active hydrogen equivalent of the amine-based curing agent to the epoxy equivalent of the epoxy resin in the first liquid is 1, to obtain a mixture. The mixture is poured into an aluminum cup and cured at 40° C. for 8 hours, and then cured at 80° C. for 1 hour. After slowly cooling to 25° C., a test piece measuring 10 mm×10 mm×10 mm is cut out. Using the test piece, Rockwell hardness 2 is measured at 25° C. on the M hardness scale in accordance with JIS K7202:2001.

21. 21. The two-component liquid resin composition according to claim 20, wherein the ratio of the Rockwell hardness 2 to the Rockwell hardness 1 is 0.5 or more and 1.5 or less.

22. 3. The two-component liquid resin composition according to claim 1, wherein the bending strength 1 measured by the following method 5 is 50 MPa or more and 150 MPa or less. (Method 5) The second liquid is mixed with 50 g of the first liquid at 25°C so that the equivalent ratio of the active hydrogen equivalent of the amine-based curing agent to the epoxy equivalent of the epoxy resin in the first liquid is 1, to obtain a mixture. The mixture is poured into an aluminum cup and cured at 40° C. for 8 hours. After slowly cooling to 25° C., a test piece having dimensions of 100 mm×10 mm×4 mm is cut out. The test piece is used to measure bending strength 1 at 25°C in accordance with JIS K 6911:2006.

23. The two-component liquid resin composition according to claim 22, wherein the bending strength 2 measured by the following method (Method 6) is 70 MPa or more and 250 MPa or less. (Method 6) The second liquid is mixed with 50 g of the first liquid at 25°C so that the equivalent ratio of the active hydrogen equivalent of the amine-based curing agent to the epoxy equivalent of the epoxy resin in the first liquid is 1, to obtain a mixture. The mixture is poured into an aluminum cup and cured at 40° C. for 8 hours, and then cured at 80° C. for 1 hour. After slowly cooling to 25° C., a test piece measuring 100 mm×10 mm×4 mm is cut out. The test piece is used to measure bending strength 2 at 25°C in accordance with JIS K 6911:2006.

24. 24. The two-component liquid resin composition according to claim 23, wherein the ratio of the flexural strength 2 to the flexural strength 1 is 0.5 or more and 1.5 or less.

25. 3. The two-component liquid resin composition according to claim 1, which can be used to encapsulate a structure comprising a substrate including a circuit layer and an electronic component on the circuit layer of the substrate.

26. a substrate including a circuit layer; an electronic component on the circuit layer of the substrate; a sealing material for sealing the substrate and the electronic component; Equipped with An electronic device, wherein the encapsulant comprises a cured product of the two-component liquid resin composition according to claim 1 or 2.

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