Two-component liquid resin composition and power module

Abstract

To provide a two-component liquid resin composition which achieves improved performance balance between storage stability and fluidity.SOLUTION: A two-component liquid resin composition comprises a first liquid and a second liquid, wherein the first liquid contains an epoxy resin (A), an inorganic filler (C), and a sedimentation inhibitor (D); the second liquid contains an acid anhydride (B), an inorganic filler (C), and a sedimentation inhibitor (D); the sedimentation inhibitor (D) includes a dispersant; and the viscosity η5A of the first liquid is from 1.0 Pa s to 50.0 Pa s as measured under conditions of 5 rpm and 25°C using an E-type viscometer and a 3°×R14 cone rotor.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a two-component liquid resin composition and a power module.

Background Art

[0002] Epoxy resins are used as encapsulants for encapsulating substrates and semiconductor elements in power modules. As a technique related to an encapsulant for a power module, for example, the technique described in Patent Document 1 can be mentioned.

[0003] Patent Document 1 aims to provide a filler for a semiconductor encapsulant that is blended into an encapsulant to reduce the linear expansion coefficient of the encapsulant and, at the same time, maintains the encapsulant at a low viscosity to improve invasiveness, and a semiconductor encapsulant composition using the same. A filler for a semiconductor encapsulant characterized by comprising an inorganic substance and an organic layer having a functional group capable of reacting with an epoxy resin chemically bonded to the surface of the inorganic substance, and a semiconductor encapsulant containing this filler and an epoxy resin are described.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] The present invention provides a two-component liquid resin composition with improved performance balance of storage stability and fluidity.

Means for Solving the Problems

[0006] The inventors of the present invention have intensively studied to achieve the above problems. As a result, by including a dispersant as an anti-settling agent and adjusting the viscosity of the liquid resin composition containing an epoxy resin in the two-component liquid resin composition to a specific range, it has been found that the performance balance of the storage stability and fluidity of the two-component liquid resin composition can be improved, and the present invention has been completed.

[0007] According to the present invention, the following two-component liquid resin composition and power module are provided.

[0008] [1] A two-component liquid resin composition comprising a first liquid and a second liquid, wherein the first liquid contains an epoxy resin (A), an inorganic filler (C), and an anti-settling agent (D), the second liquid contains an acid anhydride (B), an inorganic filler (C), and an anti-settling agent (D), the anti-settling agent (D) contains a dispersant, The viscosity η of the first liquid measured using an E-type viscometer and a 3°×R14 cone rotor under the conditions of a rotation speed of 5 rpm and a temperature of 25°C, 5A is a two-component liquid resin composition that is 1.0 Pa·s or more and 50.0 Pa·s or less. [2] The viscosity η of the first liquid measured using an E-type viscometer and a 3°×R14 cone rotor under the conditions of a rotation speed of 10 rpm and a temperature of 25°C, 10A is the two-component liquid resin composition according to [1] above that is 1.0 Pa·s or more and 50.0 Pa·s or less. [3] The above viscosity η 10A The viscosity ratio Ti of the above viscosity η 5A to the above viscosity η A (η 5A / η 10A ) is a two-component liquid resin composition according to [2] above that is 0.4 or more and 1.5 or less. [4] The viscosity η of the second liquid measured using an E-type viscometer and a 3°×R14 cone rotor under the conditions of a rotation speed of 5 rpm and a temperature of 25°C, 5BThe two-component liquid resin composition according to any one of the above [1] to [3], wherein the viscosity is 1.0 Pa·s or more and 70.0 Pa·s or less. [5] The viscosity η of the second liquid, measured using an E-type viscometer and a 3°×R14 cone rotor under the conditions of a rotation speed of 10 rpm and a temperature of 25°C. 10B The two-component liquid resin composition according to the above [4], wherein the viscosity is 1.0 Pa·s or more and 50.0 Pa·s or less. [6] The above viscosity η 10B The above viscosity η with respect to 5B The viscosity ratio Ti B (η 5B / η 10B ) is 0.5 or more and 4.0 or less. The two-component liquid resin composition according to the above [5]. [7] The viscosity η of the mixed liquid of the first liquid and the second liquid, measured using an E-type viscometer and a 3°×R14 cone rotor under the conditions of a rotation speed of 5 rpm and a temperature of 25°C. 5P The two-component liquid resin composition according to any one of the above [1] to [6], wherein the viscosity is 1.0 Pa·s or more and 50.0 Pa·s or less. [8] The viscosity η of the mixed liquid of the first liquid and the second liquid, measured using an E-type viscometer and a 3°×R14 cone rotor under the conditions of a rotation speed of 10 rpm and a temperature of 25°C. 10P The two-component liquid resin composition according to the above [7], wherein the viscosity is 10.0 Pa·s or more and 50.0 Pa·s or less. [9] The above viscosity η 10P The above viscosity η with respect to 5P The viscosity ratio Ti P (η 5P / η 10P ) is 0.5 or more and 2.0 or less. The two-component liquid resin composition according to the above [8].

[10] The two-component liquid resin composition according to any one of the above [1] to [9], wherein the dispersant contains an ester compound containing a long-chain hydrocarbon group.

[11] The two-component liquid resin composition according to the above

[10] , wherein the ester compound containing the long-chain hydrocarbon group contains one or more selected from the group consisting of polyhydroxycarboxylic acid esters, acidic phosphate esters, and carboxyl group-containing polymer modified products.

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

[11] , wherein the content of the anti-settling agent (D) is 0.01% by mass or more and 2.0% by mass or less when the total amount of the two-component liquid resin composition is 100% by mass.

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

[12] , wherein the epoxy resin (A) contains an alicyclic epoxy resin.

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

[13] , wherein the content of the alicyclic epoxy resin is 50 parts by mass or more and 100 parts by mass or less when the content of the epoxy resin (A) is 100 parts by mass.

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

[14] , wherein the content of the epoxy resin (A) is 5% by mass or more and 30% by mass or less when the total amount of the two-component liquid resin composition is 100% by mass.

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

[15] , wherein the acid anhydride (B) contains one or more selected from the group consisting of methyl-5-norbornene-2,3-dicarboxylic anhydride, methylcyclohexane-1,2-dicarboxylic anhydride, and methyltetrahydrophthalic anhydride.

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

[16] , wherein the content of the acid anhydride (B) is 5% by mass or more and 20% by mass or less when the total amount of the two-component liquid resin composition is 100% by mass.

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

[17] , wherein the inorganic filler (C) contains one or more selected from the group consisting of silica, alumina, aluminum hydroxide, and calcium carbonate.

[19] The average particle diameter D at which the cumulative value is 50% in the volume frequency particle size distribution of the inorganic filler (C) measured by the laser diffraction scattering method 50 is 0.5 μm or more and 100 μm or less, and the two-component liquid resin composition according to any one of the above [1] to

[18] .

[20] The content of the inorganic filler (C) is 65% by mass or more and 85% by mass or less when the total amount of the two-component liquid resin composition is 100% by mass, and the two-component liquid resin composition according to any one of the above [1] to

[19] .

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

[20] , further comprising a curing accelerator (E).

[22] The curing accelerator (E) contains one or more selected from the group consisting of tertiary amines, quaternary ammonium salts, imidazoles, organic phosphines, and Lewis acid catalysts, and the two-component liquid resin composition according to the above

[21] .

[23] The content of the curing accelerator (E) is 0.01% by mass or more and 1.00% by mass or less when the total amount of the two-component liquid resin composition is 100% by mass, and the two-component liquid resin composition according to the above

[21] or

[22] .

[24] A power module including a substrate for a power module including a circuit layer and a power semiconductor element on the circuit layer of the substrate for a power module, and which can be used for encapsulating by an injection molding method, and the two-component liquid resin composition according to any one of the above [1] to

[23] .

[25] A substrate for a power module including a circuit layer, a power semiconductor element on the circuit layer of the substrate for a power module, a sealing material for sealing the substrate for a power module and the power semiconductor element, and comprising a power module, wherein the sealing material contains a cured product of the two-component liquid resin composition according to any one of the above [1] to

[24] .

[26] The power module according to the above

[25] , wherein the power semiconductor element includes one or more selected from the group consisting of a MOS transistor and an insulated gate bipolar transistor (IGBT).

Advantages of the Invention

[0009] According to the present invention, it is possible to provide a two-component liquid resin composition with improved performance balance between storage stability and fluidity, and a power module using the two-component liquid resin composition.

Embodiments for Carrying Out the Invention

[0010] Hereinafter, embodiments of the present invention will be described. In this specification, a numerical range indicated by using "~" indicates a range including the numerical values described before and after "~" as the minimum value and the maximum value, respectively. In the numerical ranges described stepwise in this specification, the upper limit value or the lower limit value of a certain stepwise numerical range can be arbitrarily combined with the upper limit value or the lower limit value of another stepwise numerical range. In the numerical ranges described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples. "A or B" means that either A or B may be included, or both may be included. The materials exemplified in this specification can be used alone or in combination of two or more, unless otherwise specified. In this specification, the content of each component in the composition means the total amount of the plurality of substances corresponding to each component in the composition, unless otherwise specified, when there are a plurality of substances corresponding to each component in the composition. In this specification, the description "when the total of the two-component liquid resin composition (or the first liquid and the second liquid) is 100% by mass" means excluding components such as solvents that volatilize when the two-component liquid resin composition is cured.

[0011] [Two-Component Liquid Resin Composition] The two-component liquid resin composition of the present embodiment is a two-component liquid resin composition composed of a first liquid and a second liquid. The first liquid contains an epoxy resin (A), an inorganic filler (C), and an anti-settling agent (D). The second liquid contains an acid anhydride (B), an inorganic filler (C), and an anti-settling agent (D). The anti-settling agent (D) contains a dispersant. The viscosity η of the first liquid, measured using an E-type viscometer and a 3°×R14 cone rotor under the conditions of a rotation speed of 5 rpm and a temperature of 25°C 5A is 1.0 Pa·s or more and 50.0 Pa·s or less.

[0012] By satisfying the above configuration, the two-component liquid resin composition of the present embodiment can improve the performance balance between storage stability and fluidity. In the two-component liquid resin composition of the present embodiment, specific components in the first liquid and the second liquid of the two-component liquid resin composition are considered to contribute to maintaining a preferable dispersion state of the inorganic filler (C) in the first liquid and the second liquid. Further, when the viscosity η of the first liquid 5A is within the above numerical range, the fluidity of the first liquid at rest becomes preferable from the viewpoint of storage stability, and it is considered that sedimentation of the inorganic filler (C) in the first liquid can be physically suppressed. As a result, it is considered that the two-component liquid resin composition of the present embodiment can improve the performance balance of storage stability and fluidity suitable for the states of the first liquid and the second liquid and casting workability.

[0013] In the two-component liquid resin composition of the present embodiment, the viscosity η 5A is preferably 3.0 Pa·s or more, more preferably 5.0 Pa·s or more, still more preferably 8.0 Pa·s or more, still more preferably 10.0 Pa·s or more, still more preferably 15.0 Pa·s or more, still more preferably 20.0 Pa·s or more, and preferably 40.0 Pa·s or less, more preferably 30.0 Pa·s or less, still more preferably 25.0 Pa·s or less, from the viewpoint of further improving the performance balance between storage stability and fluidity of the two-component liquid resin composition. The viscosity η of the two-component liquid resin composition of the present embodiment 5A refers to the viscosity 1 minute after starting the rotation of the cone rotor set in the E-type viscometer.

[0014] In the two-component liquid resin composition of the present embodiment, the viscosity η of the first liquid measured under the conditions of a rotational speed of 10 rpm and a temperature of 25°C using an E-type viscometer and a 3°×R14 cone rotor 10A is preferably 1.0 Pa·s or more, more preferably 3.0 Pa·s or more, still more preferably 5.0 Pa·s or more, still more preferably 8.0 Pa·s or more, still more preferably 10.0 Pa·s or more, still more preferably 15.0 Pa·s or more, still more preferably 20.0 Pa·s or more, from the viewpoint of further improving the balance of storage stability and fluidity performance of the two-component liquid resin composition, and is preferably 50.0 Pa·s or less, more preferably 40.0 Pa·s or less, still more preferably 30.0 Pa·s or less. The viscosity η of the two-component liquid resin composition of the present embodiment 10A refers to the viscosity 1 minute after starting the rotation of the cone rotor set in the E-type viscometer.

[0015] In the two-component liquid resin composition of the present embodiment, the viscosity η 10A The viscosity ratio Ti of the above viscosity η 5A to the above viscosity η A (η 5A / η 10A ) is preferably 0.4 or more, more preferably 0.5 or more, still more preferably 0.6 or more, still more preferably 0.7 or more, still more preferably 0.8 or more, from the viewpoint of further improving the balance of storage stability and fluidity performance of the two-component liquid resin composition, and is preferably 1.5 or less, more preferably 1.3 or less, still more preferably 1.1 or less, still more preferably 0.9 or less.

[0016] In the two-component liquid resin composition of the present embodiment, the viscosity η of the second liquid measured under the conditions of a rotational speed of 5 rpm and a temperature of 25°C using an E-type viscometer and a 3°×R14 cone rotor 5BFrom the viewpoint of further improving the balance of the storage stability and fluidity performance of the two-component liquid resin composition, it is preferably 1.0 Pa·s or more, more preferably 5.0 Pa·s or more, still more preferably 10.0 Pa·s or more, still more preferably 15.0 Pa·s or more, still more preferably 20.0 Pa·s or more, and preferably 70.0 Pa·s or less, more preferably 65.0 Pa·s or less, still more preferably 60.0 Pa·s or less, still more preferably 55.0 Pa·s or less, still more preferably 50.0 Pa·s or less, still more preferably 45.0 Pa·s or less, still more preferably 40.0 Pa·s or less, still more preferably 35.0 Pa·s or less. The viscosity η of the two-component liquid resin composition of this embodiment 5B refers to the viscosity 1 minute after starting the rotation of the cone rotor set in the E-type viscometer.

[0017] In the two-component liquid resin composition of this embodiment, the viscosity η of the second liquid measured under the conditions of a rotation speed of 10 rpm and a temperature of 25 °C using an E-type viscometer and a 3°×R14 cone rotor 10B From the viewpoint of further improving the balance of the storage stability and fluidity performance of the two-component liquid resin composition, it is preferably 1.0 Pa·s or more, more preferably 3.0 Pa·s or more, still more preferably 5.0 Pa·s or more, still more preferably 10.0 Pa·s or more, still more preferably 15.0 Pa·s or more, and preferably 50.0 Pa·s or less, more preferably 45.0 Pa·s or less, still more preferably 40.0 Pa·s or less, still more preferably 35.0 Pa·s or less, still more preferably 30.0 Pa·s or less. The viscosity η of the two-component liquid resin composition of this embodiment 10B refers to the viscosity 1 minute after starting the rotation of the cone rotor set in the E-type viscometer.

[0018] In the two-component liquid resin composition of this embodiment, the viscosity η 10B The viscosity η with respect to 5B The viscosity ratio Ti of B (η 5B / η 10B) is preferably 0.5 or more, more preferably 0.8 or more, still more preferably 1.0 or more, and preferably 4.0 or less, more preferably 3.5 or less, still more preferably 3.0 or less, still more preferably 2.5 or less, still more preferably 2.0 or less, still more preferably 1.5 or less, from the viewpoint of further improving the performance balance between the storage stability and fluidity of the two-component liquid resin composition.

[0019] In the two-component liquid resin composition of the present embodiment, the viscosity η of the mixed liquid of the first liquid and the second liquid, measured under the conditions of a rotation speed of 5 rpm and a temperature of 25°C using an E-type viscometer and a 3°×R14 cone rotor 5P is preferably 1.0 Pa·s or more, more preferably 5.0 Pa·s or more, still more preferably 10.0 Pa·s or more, still more preferably 15.0 Pa·s or more, still more preferably 20.0 Pa·s or more, and preferably 50.0 Pa·s or less, more preferably 45.0 Pa·s or less, still more preferably 40.0 Pa·s or less, still more preferably 35.0 Pa·s or less, still more preferably 30.0 Pa·s or less, still more preferably 28.0 Pa·s or less, from the viewpoint of further improving the performance balance between the storage stability and fluidity of the two-component liquid resin composition. The viscosity η of the two-component liquid resin composition of the present embodiment 5P refers to the viscosity 1 minute after starting the rotation of the cone rotor set in the E-type viscometer.

[0020] In the two-component liquid resin composition of the present embodiment, the viscosity η of the mixed liquid of the first liquid and the second liquid, measured under the conditions of a rotation speed of 10 rpm and a temperature of 25°C using an E-type viscometer and a 3°×R14 cone rotor 10PFrom the perspective of further improving the performance balance between the storage stability and fluidity of the two-component liquid resin composition, it is preferably 10.0 Pa·s or more, more preferably 12.0 Pa·s or more, still more preferably 14.0 Pa·s or more, still more preferably 16.0 Pa·s or more, still more preferably 18.0 Pa·s or more, still more preferably 20.0 Pa·s or more, still more preferably 21.0 Pa·s or more, and preferably 50.0 Pa·s or less, more preferably 45.0 Pa·s or less, still more preferably 40.0 Pa·s or less, still more preferably 35.0 Pa·s or less, still more preferably 30.0 Pa·s or less, still more preferably 27.0 Pa·s or less. The viscosity η of the two-component liquid resin composition of this embodiment 10P refers to the viscosity 1 minute after starting the rotation of the cone rotor set in the E-type viscometer.

[0021] In the two-component liquid resin composition of this embodiment, the viscosity η 10P with respect to the viscosity η 5P viscosity ratio Ti P (η 5P / η 10P ) From the perspective of further improving the performance balance between the storage stability and fluidity of the two-component liquid resin composition, it is preferably 0.5 or more, more preferably 0.6 or more, still more preferably 0.7 or more, still more preferably 0.8 or more, still more preferably 0.9 or more, still more preferably 1.0 or more, and preferably 2.0 or less, more preferably 1.9 or less, still more preferably 1.8 or less, still more preferably 1.7 or less, still more preferably 1.6 or less, still more preferably 1.5 or less, still more preferably 1.4 or less, still more preferably 1.3 or less, still more preferably 1.2 or less.

[0022] Hereinafter, the components used in the resin composition of this embodiment will be described in detail.

[0023] (Epoxy resin (A)) The two-component liquid resin composition of this embodiment contains an epoxy resin (A). As the epoxy resin of this embodiment, from the viewpoint of further improving the performance balance of strength, hardness, elastic modulus, coefficient of thermal expansion, thermal conductivity, heat dissipation, and electrical properties of the cured product of the two-component liquid resin composition, preferably, an alicyclic epoxy resin; 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-phenylene diisoprene) bisphenol type epoxy resin), bisphenol P type epoxy resin (4,4'-(1,4-phenylene diisoprene) bisphenol type epoxy resin), bisphenol Z type epoxy resin (4,4'-cyclohexadiene bisphenol type epoxy resin), etc. of bisphenol type epoxy resins; phenol novolac type epoxy resin, cresol novolac type epoxy resin, tris-phenol group methane type novolac type epoxy resin, tetra-phenol group ethane type novolac type epoxy resin, novolac type epoxy resins having a condensed ring aromatic hydrocarbon structure, etc. of novolac type epoxy resins; aromatic glycidylamine type epoxy resins such as N,N-diglycidylaniline, N,N-diglycidyltoluidine, diaminodiphenylmethane type glycidylamine, aminophenol type glycidylamine; aminophenol type epoxy resins; biphenyl type epoxy resins; arylalkylene type epoxy resins such as xylylene type epoxy resins, biphenyl aralkyl type epoxy resins; naphthylene ether type epoxy resins, naphthol type epoxy resins, naphthalene diol type epoxy resins, bifunctional to tetrafunctional epoxy type naphthalene resins, binaphthyl type epoxy resins, naphthalene aralkyl type epoxy resins, etc. of naphthalene type epoxy resins; anthracene type epoxy resins; phenoxy type epoxy resins; dicyclopentadiene type epoxy resins; norbornene type epoxy resins; adamantane type epoxy resins; fluorene type epoxy resins, and contains one or more selected from the group consisting of them, and from the viewpoint of further improving the fluidity of the two-component liquid resin composition, more preferably contains an alicyclic epoxy resin.

[0024] The alicyclic epoxy resin of this embodiment preferably contains an alicyclic epoxy resin that is liquid at 25°C, more preferably vinylcyclopentadiene dioxide, vinylcyclohexene monodioxide, vinylcyclohexene dioxide, dicyclopentadiene oxide, 3,4-epoxy-1-[8,9-epoxy-2,4-dioxaspiro[5.5]undecane-3-yl]-cyclohexane, etc. epoxy-[epoxy-oxaspiro C 8-15 alkyl]-cyclo C 5-12 alkane; 3,4-epoxycyclohexylmethyl-3’,4’-epoxycyclohexanecarboxylate, 4,5-epoxycyclooctylmethyl-4’,5’-epoxycyclooctanecarboxylate, etc. epoxy C 5-12 cycloalkyl C 1-3 alkyl-epoxy C 5-12 cycloalkanecarboxylate; bis(2-methyl-3,4-epoxycyclohexylmethyl) adipate, etc. bis(C 1-3 alkylepoxy C 5-12 cycloalkyl C 1-3 alkyl) dicarboxylate selected from the group consisting of one or more of these, more preferably epoxy C 5-12 cycloalkyl C 1-3 alkyl-epoxy C 5-12 cycloalkanecarboxylate, and even more preferably contains 3,4-epoxycyclohexylmethyl-3’,4’-epoxycyclohexanecarboxylate. Commercially available products of 3,4-epoxycyclohexylmethyl-3’,4’-epoxycyclohexanecarboxylate include those manufactured by Daicel Corporation, trade name: Celoxide #2021P (epoxy equivalent: 128 - 140), and are preferably used.

[0025] When the epoxy resin (A) of the present embodiment contains an alicyclic epoxy resin, from the viewpoint of further improving the fluidity of the two-component liquid resin composition, when the content of the epoxy resin (A) is 100 parts by mass, it is preferably 50 parts by mass or more, more preferably 60 parts by mass or more, still more preferably 70 parts by mass or more, still more preferably 80 parts by mass or more, still more preferably 90 parts by mass or more, still more preferably 95 parts by mass or more, and the upper limit is not particularly limited, but for example, it may be 100 parts by mass or less.

[0026] From the viewpoint of further improving the performance balance of strength, hardness, elastic modulus, coefficient of thermal expansion, thermal conductivity, heat dissipation property, and electrical properties of the cured product of the two-component liquid resin composition, when the total amount of the two-component liquid resin composition is 100% by mass, the content of the epoxy resin (A) in the two-component liquid resin composition of the present embodiment is preferably 5% by mass or more, more preferably 6% by mass or more, still more preferably 7% by mass or more, still more preferably 8% by mass or more, still more preferably 9% by mass or more, still more preferably 10% by mass or more. And from the viewpoint of further improving the performance balance of the storage stability and fluidity of the two-component liquid resin composition, it is preferably 30% by mass or less, more preferably 28% by mass or less, still more preferably 25% by mass or less, still more preferably 23% by mass or less, still more preferably 20% by mass or less, still more preferably 18% by mass or less, still more preferably 15% by mass or less, still more preferably 13% by mass or less, still more preferably 11% by mass or less.

[0027] (Acid anhydride (B)) The two-component liquid resin composition of the present embodiment contains an acid anhydride (B). The acid anhydride (B) functions as a curing agent for the epoxy resin (A).

[0028] As the acid anhydride (B) of the present embodiment, from the viewpoint of improving the curability of the two-component liquid resin composition, preferably, dodecenyl succinic anhydride, polyadipic anhydride, polyazelaic anhydride, polysebacic anhydride, poly(ethyl octadecanedioic) anhydride, poly(phenylhexadecanedioic) anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hymic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexenedicarboxylic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, ethylene glycol bistrimellitate, het acid anhydride, tetrahydrophthalic anhydride, methyl nadic anhydride (methyl-5-norbornene-2,3-dicarboxylic anhydride), methyl hymic anhydride (methyl-3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride), methylcyclohexane-1,2-dicarboxylic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexane-1,2-dicarboxylic anhydride, including one or more selected from the group consisting of, from the viewpoint of further improving the performance balance of the storage stability and fluidity of the two-component liquid resin composition, more preferably including one or more selected from the group consisting of methyl-5-norbornene-2,3-dicarboxylic anhydride, methylcyclohexane-1,2-dicarboxylic anhydride and methyltetrahydrophthalic anhydride, and even more preferably including methyl-5-norbornene-2,3-dicarboxylic anhydride.

[0029] In the two-component liquid resin composition of the present embodiment, from the viewpoint of improving the curability of the two-component liquid resin composition, the content of the acid anhydride (B) is preferably 5% by mass or more, more preferably 7% by mass or more, still more preferably 9% by mass or more, still more preferably 11% by mass or more when the total amount of the two-component liquid resin composition is 100% by mass. And from the viewpoint of further improving the performance balance of the storage stability and fluidity of the two-component liquid resin composition, it is preferably 20% by mass or less, more preferably 18% by mass or less, still more preferably 16% by mass or less, still more preferably 14% by mass or less, still more preferably 13% by mass or less.

[0030] (Inorganic filler (C)) The two-component liquid resin composition of the present embodiment contains an inorganic filler (C). As the inorganic filler (C), from the viewpoint of further improving the performance balance of the strength, hardness, elastic modulus, thermal expansion coefficient, thermal conductivity, heat dissipation property and electrical properties of the cured product of the two-component liquid resin composition, preferably, it contains one or more 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 balloon and silver powder. From the viewpoint of further improving the performance balance of the storage stability and fluidity of the two-component liquid resin composition, more preferably, it contains one or more selected from the group consisting of silica, alumina, aluminum hydroxide and calcium carbonate. Further, the inorganic filler may be surface-treated. Examples of the surface treatment include alkylation treatment, trimethylsilylation treatment, silicone treatment, treatment with a silane coupling agent, etc., but it is not particularly limited.

[0031] From the viewpoint of further improving the performance balance of strength, hardness, elastic modulus, coefficient of thermal expansion, thermal conductivity, heat dissipation, and electrical properties of the cured product of the two-component liquid resin composition, the shape of the inorganic filler (C) in the present embodiment is preferably fibrous, amorphous, or spherical, and more preferably spherical from the viewpoint of further improving the performance balance of storage stability and fluidity of the two-component liquid resin composition. Here, the spherical shape may be a true sphere, an ellipse, or a substantially spherical shape including an oval shape. The aspect ratio (ratio of major axis to minor axis) of the inorganic filler (C) in the present embodiment is preferably 1.3 or less, more preferably 1.2 or less, and still more preferably 1.1 or less.

[0032] In the volume frequency particle size distribution of the inorganic filler (C) in the present embodiment measured by the laser diffraction scattering method, the average particle diameter D when the cumulative value is 50% 50 is, from the viewpoint of further improving the performance balance of storage stability and fluidity of the two-component liquid resin composition, preferably 0.5 μm or more, more preferably 1.0 μm or more, still more preferably 3.0 μm or more, still more preferably 5.0 μm or more, still more preferably 7.0 μm or more, still more preferably 10.0 μm or more, still more preferably 12.0 μm or more, still more preferably 15.0 μm or more, still more preferably 17.0 μm or more, still more preferably 20.0 μm or more, and preferably 100.0 μm or less, more preferably 90.0 μm or less, still more preferably 80.0 μm or less, still more preferably 70.0 μm or less, still more preferably 60.0 μm or less, still more preferably 50.0 μm or less, still more preferably 40.0 μm or less, still more preferably 30.0 μm or less. The inorganic filler (C) in the present embodiment has the above average particle diameter D 50 within the range, and may contain an inorganic filler having two or more different average particle diameters D 50 .

[0033] The average particle diameter D of the inorganic filler (C) in the present embodiment 50It can be measured, for example, by a laser diffraction scattering measurement method using a laser diffraction particle size distribution measuring apparatus (for example, SALD-7000 manufactured by Shimadzu Corporation).

[0034] From the viewpoint of further improving the performance balance between the storage stability and fluidity of the two-component liquid resin composition, the content of the inorganic filler (C) in the two-component liquid resin composition of the present embodiment is preferably 65% by mass or more, more preferably 67% by mass or more, still more preferably 69% by mass or more, still more preferably 71% by mass or more, still more preferably 73% by mass or more, still more preferably 75% by mass or more when the total amount of the two-component liquid resin composition is 100% by mass, and preferably 85% by mass or less, more preferably 83% by mass or less, still more preferably 81% by mass or less, still more preferably 79% by mass or less, still more preferably 77% by mass or less.

[0035] From the viewpoint of further improving the performance balance between the storage stability and fluidity of the first liquid, the content of the inorganic filler (C) in the first liquid of the present embodiment is preferably 65% by mass or more, more preferably 67% by mass or more, still more preferably 69% by mass or more, still more preferably 71% by mass or more, still more preferably 73% by mass or more, still more preferably 75% by mass or more, still more preferably 77% by mass or more when the total amount of the first liquid is 100% by mass, and preferably 85% by mass or less, more preferably 83% by mass or less, still more preferably 81% by mass or less, still more preferably 79% by mass or less.

[0036] From the viewpoint of further improving the performance balance between the storage stability and fluidity of the second liquid, the content of the inorganic filler (C) in the second liquid of the present embodiment is preferably 65% by mass or more, more preferably 67% by mass or more, still more preferably 69% by mass or more, still more preferably 71% by mass or more, still more preferably 73% by mass or more when the total amount of the second liquid is 100% by mass, and preferably 85% by mass or less, more preferably 83% by mass or less, still more preferably 81% by mass or less, still more preferably 79% by mass or less, still more preferably 77% by mass or less.

[0037] (Anti-settling agent (D)) The two-component liquid resin composition of this embodiment contains a dispersant as the anti-settling agent (D). By including a dispersant as the anti-settling agent (D), the sedimentation of the inorganic filler (C) in the two-component liquid resin composition can be suppressed. The dispersant of this embodiment preferably contains an ester compound containing a long-chain hydrocarbon group, more preferably one or more selected from the group consisting of a carboxylic acid ester compound containing a long-chain hydrocarbon group, a phosphate ester compound containing a long-chain hydrocarbon group, a sulfate ester compound containing a long-chain hydrocarbon group, a nitrate ester compound containing a long-chain hydrocarbon group, and a carbonate ester compound containing a long-chain hydrocarbon group, and even more preferably one or more selected from the group consisting of a carboxylic acid ester compound containing a long-chain hydrocarbon group and a phosphate ester compound containing a long-chain hydrocarbon group. Such an ester compound containing a long-chain hydrocarbon group can suppress the secondary aggregation of the inorganic filler (C) due to the steric hindrance of the long-chain hydrocarbon group, so it is considered that the performance balance of the storage stability and fluidity of the two-component liquid resin composition can be further improved.

[0038] From the viewpoint of further improving the performance balance of the storage stability and fluidity of the two-component liquid resin composition, the long-chain hydrocarbon group in the ester compound containing a long-chain hydrocarbon group of this embodiment preferably contains one or more selected from the group consisting of an alkylene group, an alkyl group, an alkenyl group, an aralkyl group, an aryl group, and an aryl group in which one, two, or three hydrogen atoms of the hydrocarbon are substituted by substituents, and more preferably contains one or more selected from the group consisting of an alkylene group, an alkyl group, and an alkenyl group. The long-chain hydrocarbon group may be linear or branched. In the long-chain hydrocarbon group, some of the hydrogens may be substituted by substituents such as a hydroxy group, an aldehyde group, a carbonyl group, a carboxy group, an amino group, a nitro group, a sulfo group, a halogeno group, etc. The long-chain hydrocarbon group may contain a bond group containing oxygen such as an ether bond or an ester bond in the long chain.

[0039] In the ester compound containing a long-chain hydrocarbon group of the present embodiment, from the viewpoint of further improving the balance of storage stability and fluidity performance of the two-component liquid resin composition, the ester group preferably contains one or more selected from the group consisting of a carboxylic acid ester group, a phosphoric acid ester group, a sulfuric acid ester group, a nitric acid ester group, and a carbonic acid ester group, and more preferably contains one or more selected from the group consisting of a carboxylic acid ester group and a phosphoric acid ester group.

[0040] In the ester compound containing a long-chain hydrocarbon group of the present embodiment, from the viewpoint of further improving the balance of storage stability and fluidity performance of the two-component liquid resin composition, the number of carbon atoms of the long-chain hydrocarbon group is preferably 4 or more, more preferably 6 or more, still more preferably 8 or more, still more preferably 10 or more, and preferably 1000 or less, more preferably 800 or less, still more preferably 600 or less, still more preferably 400 or less, still more preferably 200 or less.

[0041] In the ester compound containing a long-chain hydrocarbon group of the present embodiment, from the viewpoint of further improving the balance of storage stability and fluidity performance of the two-component liquid resin composition, the mass average molecular weight is preferably 300 or more, more preferably 400 or more, still more preferably 500 or more, still more preferably 600 or more, still more preferably 700 or more, still more preferably 800 or more, and preferably 50000 or less, more preferably 30000 or less, still more preferably 15000 or less, still more preferably 10000 or less.

[0042] In the ester compound containing a long-chain hydrocarbon group of the present embodiment, from the viewpoint of further improving the balance of storage stability and fluidity performance of the two-component liquid resin composition, it preferably contains one or more selected from the group consisting of polyhydroxycarboxylic acid esters, acidic phosphoric acid esters, and carboxyl group-containing polymer modified products.

[0043] From the perspective of further improving the performance balance between the storage stability and fluidity of the two-component liquid resin composition, the polyhydroxycarboxylic acid ester of the present embodiment preferably contains a compound represented by the following general formula (I).

[0044] [Chemical formula]

[0045] In the above general formula (I), v and y are each independently 1 or 2, w is an integer of 0 or more and 10 or less, and x is an integer of 14 or more and 40 or less. Note that -(CH=CH) w -(CH 2 ) x - may be a block-like structure in which w consecutive (CH=CH) are connected, followed by x consecutive (CH 2 ) being connected, or a random structure in which (CH=CH) and (CH 2 ) are randomly arranged.

[0046] In the above general formula (I), from the perspective of further improving the performance balance between the storage stability and fluidity of the two-component liquid resin composition, w is preferably an integer of 0 or more and 8 or less. Also, from the perspective of further improving the performance balance between the storage stability and fluidity of the two-component liquid resin composition, x is preferably an integer of 18 or more and 36 or less.

[0047] Examples of commercially available products of the polyhydroxycarboxylic acid ester of the present embodiment include BYK-R606 manufactured by BYK-Chemie Japan Co., Ltd.

[0048] From the perspective of further improving the performance balance between the storage stability and fluidity of the two-component liquid resin composition, the acidic phosphate ester of the present embodiment preferably contains a compound represented by the following general formula (II).

[0049] [Chemical formula]

[0050] In the general formula (II) above, R 1 is a saturated or unsaturated hydrocarbyl group having 4 to 20 carbon atoms, R 2 is a saturated hydrocarbylene group having 1 to 20 carbon atoms, R 3 is a saturated hydrocarbylene group having 2 or 3 carbon atoms, R 4 is a saturated or unsaturated hydrocarbylene group having 1 to 8 carbon atoms, k, l and m are each an integer of 0 or more and 20 or less, and n is 1 or 2. When there are a plurality of R 1 , the plurality of R 1 may be the same or different, and when there are a plurality of R 2 , the plurality of R 2 may be the same or different, and when there are a plurality of R 3 , the plurality of R 3 may be the same or different, and when there are a plurality of R 4 , the plurality of R 4 may be the same or different. The order formed by k -COR 2 O- groups, l -R 3 O- groups, and m -COR 4 COO- groups is arbitrary. When n = 2, the two R 1 O(COR 2 O) k (R 3 O) l (COR 4 COO) m groups may be the same or different.

[0051] In the general formula (II) above, R 1 is not particularly limited as long as it is a saturated or unsaturated hydrocarbyl group having 4 to 20 carbon atoms. R 1Preferably, it contains one or more selected from the group consisting of saturated hydrocarbon groups and unsaturated hydrocarbon groups. The saturated hydrocarbon group preferably contains one or more selected from the group consisting of an octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, hexadecyl group, and octadecyl group. The unsaturated hydrocarbon group preferably contains one or more selected from the group consisting of a phenyl group and a nonylphenyl group. R 1 The carbon number of is preferably 6 or more and 18 or less from the viewpoint of further improving the balance of storage stability and fluidity performance of the two-component liquid resin composition. When k = l = m = 0, the carbon number of R 1 is preferably 10 or more and 18 or less.

[0052] In the general formula (II) above, R 2 is a saturated hydrocarbylene group having 1 to 20 carbon atoms. The carbon number of R 2 is preferably 1 or more and 16 or less. R 2 Preferably contains one or more selected from the group consisting of a methylene group, an ethylene group, a pentylene group, a tetradecylene group, and a pentadecylene group from the viewpoint of further improving the balance of storage stability and fluidity performance of the two-component liquid resin composition.

[0053] In the general formula (II) above, R 3 is a saturated hydrocarbylene group having 2 or 3 carbon atoms. R 3 Preferably, it is a saturated hydrocarbylene group having 2 carbon atoms, more preferably an ethylene group, from the viewpoint of further improving the balance of storage stability and fluidity performance of the two-component liquid resin composition.

[0054] In the general formula (II) above, R 4 is a saturated or unsaturated hydrocarbylene group having 1 to 8 carbon atoms. The carbon number of R 4 is preferably 1 or more and 6 or less. R 4From the viewpoint of further improving the performance balance between the storage stability and fluidity of the two-component liquid resin composition, it preferably contains one or more selected from the group consisting of a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a phenyl group.

[0055] In the above general formula (II), k, l, and m are preferably integers from 0 to 10 from the viewpoint of further improving the performance balance between the storage stability and fluidity of the two-component liquid resin composition.

[0056] In the above general formula (II), the monomer units represented together with k, l, and m, that is, k -COR 2 O- groups, l -R 3 O- groups, and m -COR 4 COO- groups can be arranged in any order between the R 1 O- group and the phosphorus atom. These groups do not necessarily have to be arranged as in the general formula (II). Also, -(COR 2 O) k (R 3 O) l (COR 4 COO) m - groups may be block copolymers or random copolymers.

[0057] Examples of commercially available products of the acidic phosphate ester of this embodiment include BYK-W9010 manufactured by BYK-Chemie Japan Co., Ltd.

[0058] The carboxyl group-containing polymer modified product of this embodiment contains an ester compound of an α-olefins-maleic anhydride copolymer and a monohydric alcohol. In such an ester compound, the arrangement of a hydrophobic part such as a hydrocarbon group derived from α-olefins and a hydrophilic part such as a carboxyl group formed by ring-opening addition of a maleic anhydride group derived from maleic anhydrides is controlled.

[0059] The α-olefins that constitute the ester compound of the α-olefins-maleic anhydride copolymer and monohydric alcohols in this embodiment preferably contain linear or branched unsaturated hydrocarbons having 6 or more carbon atoms from the viewpoint of further improving the balance of storage stability and fluidity performance of the two-component liquid resin composition, and preferably contain unsaturated hydrocarbons having 6 or more and 30 or less carbon atoms. The unsaturated hydrocarbons having 6 or more and 30 or less carbon atoms preferably contain one or more selected from the group consisting of 1-dodecene and 1-tetradecene.

[0060] The monohydric alcohols that constitute the ester compound of the α-olefins-maleic anhydride copolymer and monohydric alcohols in this embodiment preferably contain one or more selected from the group consisting of aliphatic alcohols, aromatic alcohols, and polyalkylene glycol monoalkyl ethers from the viewpoint of further improving the balance of storage stability and fluidity performance of the two-component liquid resin composition.

[0061] The aliphatic alcohol in this embodiment preferably contains one or more selected from the group consisting of cetyl alcohol and stearyl alcohol.

[0062] The aromatic alcohol in this embodiment preferably contains one or more selected from the group consisting of 1-phenyl-1-propanol and α-phenoxy-2-propanol.

[0063] The polyalkylene glycol monoalkyl ether in this embodiment preferably contains a polyethylene glycol monoalkyl ether having a molecular weight of 400 to 700.

[0064] The acid value of the carboxyl group-containing polymer modified product in this embodiment is preferably 10 mgKOH / g or more and 100 mgKOH / g or less, more preferably 15 mgKOH / g or more and 60 mgKOH / g or less.

[0065] Examples of commercially available carboxyl group-containing polymer modified products of the present embodiment include Floren G-700, Floren G-900, Floren G-1500, NC-500, etc. manufactured by Kyoeisha Chemical Co., Ltd.

[0066] When the content of the anti-settling agent (D) in the two-component liquid resin composition of the present embodiment is based on 100% by mass of the entire two-component liquid resin composition, from the viewpoint of suppressing the sedimentation of the inorganic filler (C) in the two-component liquid resin composition, it is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, still more preferably 0.05% by mass or more, still more preferably 0.08% by mass or more, still more preferably 0.10% by mass or more, still more preferably 0.13% by mass or more, still more preferably 0.15% by mass or more. And from the viewpoint of further improving the performance balance of the storage stability and fluidity of the two-component liquid resin composition, it is preferably 2.00% by mass or less, more preferably 1.50% by mass or less, still more preferably 1.00% by mass or less, still more preferably 0.80% by mass or less, still more preferably 0.50% by mass or less, still more preferably 0.30% by mass or less, still more preferably 0.25% by mass or less, still more preferably 0.20% by mass or less.

[0067] When the content of the anti-settling agent (D) in the first liquid of the present embodiment is based on 100% by mass of the entire first liquid, from the viewpoint of suppressing the sedimentation of the inorganic filler (C) in the first liquid, it is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, still more preferably 0.05% by mass or more, still more preferably 0.08% by mass or more, still more preferably 0.10% by mass or more, still more preferably 0.13% by mass or more, still more preferably 0.15% by mass or more, still more preferably 0.18% by mass or more. And from the viewpoint of further improving the performance balance of the storage stability and fluidity of the first liquid, it is preferably 2.00% by mass or less, more preferably 1.50% by mass or less, still more preferably 1.00% by mass or less, still more preferably 0.80% by mass or less, still more preferably 0.50% by mass or less, still more preferably 0.30% by mass or less, still more preferably 0.25% by mass or less.

[0068] From the viewpoint of suppressing the sedimentation of the inorganic filler (C) in the second liquid, the content of the anti-sedimentation agent (D) in the second liquid of the present embodiment is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, still more preferably 0.05% by mass or more, still more preferably 0.08% by mass or more, when the total amount of the second liquid is 100% by mass. And from the viewpoint of further improving the performance balance of the storage stability and fluidity of the second liquid, it is preferably 2.00% by mass or less, more preferably 1.50% by mass or less, still more preferably 1.00% by mass or less, still more preferably 0.80% by mass or less, still more preferably 0.50% by mass or less, still more preferably 0.30% by mass or less, still more preferably 0.25% by mass or less, still more preferably 0.20% by mass or less, still more preferably 0.15% by mass or less.

[0069] (Curing accelerator (E)) The two-component liquid resin composition of the present embodiment preferably further contains a curing accelerator (E) from the viewpoint of promoting the reaction between the epoxy resin (A) and the acid anhydride (B) and improving the curability of the two-component liquid resin composition. The curing accelerator (E) of the present embodiment is preferably contained in the second liquid from the viewpoint of further improving the performance balance of the storage stability and fluidity of the two-component liquid resin composition.

[0070] The curing accelerator (E) of the present embodiment preferably contains one or more selected from the group consisting of tertiary amines, quaternary ammonium salts, imidazoles, organic phosphines, and Lewis acid catalysts, and more preferably contains a quaternary ammonium salt, from the viewpoint of improving the curability of the two-component liquid resin composition.

[0071] The tertiary amine preferably contains one or more selected from the group consisting of trimethylamine, triethylamine, tripropylamine, tributylamine, and benzyldimethylamine.

[0072] The quaternary ammonium salt preferably contains one or more selected from the group consisting of organic acid salts of diazabicycloundecene such as octylate of DBU [1,8-diazabicyclo[5.4.0]undecene-7] (manufactured by San-Apro Ltd., trade name: SA102), quaternary ammonium salts which are salts of DBN [1,5-diazabicyclo[4.3.0]-5-nonene], a tertiary amine and a carboxylic acid (manufactured by San-Apro Ltd., trade name: U-CAT2313), octadecyltrimethylammonium chloride (manufactured by NOF Corporation, trade name: Nissan Cation), and tetraalkyl (each alkyl group having 1 to 18 carbon atoms) ammonium salts (for example, tetraethylammonium bromide, tetrabutylammonium bromide, tetraalkylammonium carboxylates (the carboxylic acid having 1 to 12 carbon atoms)). From the viewpoint of improving the curability of the two-component liquid resin composition, the curing accelerator (E) of the present embodiment more preferably contains an organic acid salt of diazabicycloundecene.

[0073] The imidazoles preferably contain one or more selected from the group consisting of 1-benzyl-2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1,2-dimethylimidazole, and 1-benzyl-2-phenylimidazole.

[0074] The organic phosphine preferably contains one or more selected from the group consisting of triphenylphosphine, triphenylphosphine-triphenylborate, tris(p-methoxyphenyl)phosphine, and tetraphenylphosphonium·tetraphenylborate.

[0075] The Lewis acid catalyst preferably contains one or more selected from the group consisting of boron trifluoride amine complex, boron trichloride amine complex, and boron trifluoride ethylamine complex.

[0076] From the perspective of improving the curability of the two-component liquid resin composition of the present embodiment, when the total amount of the two-component liquid resin composition is 100% by mass, the content of the curing accelerator (E) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.10% by mass or more, still more preferably 0.15% by mass or more, still more preferably 0.20% by mass or more. And from the perspective of further improving the performance balance of the storage stability and fluidity of the two-component liquid resin composition, it is preferably 1.00% by mass or less, more preferably 0.80% by mass or less, still more preferably 0.50% by mass or less, still more preferably 0.30% by mass or less.

[0077] (Other components) The two-component liquid resin composition of the present embodiment may contain, if necessary, a coupling agent, a colorant such as carbon black, an antifoaming agent such as a silicone antifoaming agent, etc.

[0078] From the perspective of improving the interfacial strength between the epoxy resin (A) and the inorganic filler (C), the coupling agent of the present embodiment preferably contains one or more selected from the group consisting of epoxy silane coupling agents, amino silane coupling agents, ureido silane coupling agents, and mercapto silane coupling agents, and more preferably contains an epoxy silane coupling agent.

[0079] The epoxy silane coupling agent preferably contains one or more selected from the group consisting of γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and more preferably contains γ-glycidoxypropyltrimethoxysilane. The aminosilane coupling agent preferably contains 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-benzenedimethanamine. The ureidosilane coupling agent contains one or more selected from the group consisting of, for example, γ-ureidopropyltriethoxysilane and hexamethyldisilazane.

[0080] From the viewpoint of improving the interfacial strength between the epoxy resin (A) and the inorganic filler (C), the content of the coupling agent in the two-component liquid resin composition of the present embodiment is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, still more preferably 0.05% by mass or more, still more preferably 0.08% by mass or more, and preferably 1.00% by mass or less, more preferably 0.80% by mass or less, still more preferably 0.60% by mass or less, still more preferably 0.40% by mass or less, still more preferably 0.20% by mass or less when the total amount of the two-component liquid resin composition is 100% by mass.

[0081] 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, cadmium yellow, aniline black, and alizarin, and more preferably contains carbon black.

[0082] When the content of the colorant in the two-component liquid resin composition of the present embodiment is based on 100% by mass of the entire two-component liquid resin composition, it is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, still more preferably 0.03% by mass or more, still more preferably 0.04% by mass or more, still more preferably 0.05% by mass or more, and is preferably 0.50% by mass or less, more preferably 0.40% by mass or less, still more preferably 0.30% by mass or less, still more preferably 0.20% by mass or less, still more preferably 0.10% by mass or less.

[0083] The defoaming agent of the present embodiment preferably contains one or more selected from the group consisting of silicone-based defoaming agents, fluorine-based defoaming agents, and polymer-based defoaming agents, and more preferably contains a silicone-based defoaming agent.

[0084] When the content of the defoaming agent in the two-component liquid resin composition of the present embodiment is based on 100% by mass of the entire two-component liquid resin composition, it is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, still more preferably 0.05% by mass or more, still more preferably 0.08% by mass or more, and is preferably 1.00% by mass or less, more preferably 0.80% by mass or less, still more preferably 0.60% by mass or less, still more preferably 0.40% by mass or less, still more preferably 0.20% by mass or less.

[0085] (Manufacturing method of two-component liquid resin composition) The manufacturing method of the two-component liquid resin composition of the present embodiment will be described in detail. Among the above-described components, the two-component liquid resin composition of the present embodiment can be manufactured by sufficiently mixing and stirring, by a known method, an epoxy resin (A), an inorganic filler (C), an anti-settling agent (D), and other components as the first liquid, and an acid anhydride (B), an inorganic filler (C), an anti-settling agent (D), and other components as the second liquid. When the two-component liquid resin composition of the present embodiment contains a curing accelerator (E), preferably the second liquid contains the curing accelerator (E).

[0086] As a method for mixing and stirring each component to obtain the first liquid or the second liquid in the two-component liquid resin composition of the present embodiment, methods using a mixer such as a mixer, a kneader such as a roll and a kneader can be mentioned.

[0087] The two-component liquid resin composition of the present embodiment is used in a state of a mixed liquid obtained by mixing the above first liquid and second liquid. As a method for mixing the first liquid and the second liquid, methods using a mixer such as a mixer, a kneader such as a roll and a kneader can be mentioned.

[0088] In the two-component liquid resin composition of the present embodiment, when the second liquid is further mixed with the first liquid and the second liquid, the content of the second liquid is preferably 50 parts by mass or more, more preferably 70 parts by mass or more, still more preferably 90 parts by mass or more, and preferably 150 parts by mass or less, more preferably 130 parts by mass or less, still more preferably 110 parts by mass or less, from the viewpoint of further improving the performance balance of the fluidity, heat resistance at the time of curing, and mechanical properties of the two-component liquid resin composition, when the amount of the first liquid is 100 parts by mass.

[0089] (Use of the two-component liquid resin composition) The two-component liquid resin composition of the present embodiment can preferably be used for encapsulating a power module including a circuit layer and a power semiconductor element on the circuit layer of the power module substrate by an injection molding method.

[0090] [Power module] The power module of the present embodiment includes a power module substrate including a circuit layer, a power semiconductor element on the circuit layer of the power module substrate, and a sealing material for sealing the power module substrate and the power semiconductor element, and the sealing material includes a cured product of the two-component liquid resin composition of the present embodiment described above.

[0091] The power module of this embodiment may be a small to medium-sized power module for home appliances, computers, etc., or a large-sized power module for use in controlling automobiles, railway vehicles, and substations. The power module of this embodiment is preferably one or more selected from the group consisting of a rectifier, a frequency converter, a regulator, and an inverter.

[0092] The power semiconductor device in the power module of this embodiment preferably includes one or more selected from the group consisting of a rectifier diode, a power transistor, a MOS transistor, an insulated gate bipolar transistor (IGBT), a thyristor, a gate turn-off thyristor (GTO), and a triac, and more preferably includes one or more selected from the group consisting of a MOS transistor and an insulated gate bipolar transistor (IGBT).

[0093] The power module of this embodiment can be obtained by casting the above-described two-component liquid resin composition of this embodiment so as to cover these substrates and the power semiconductor device on a power module substrate on which a circuit layer is formed, and curing the two-component liquid resin composition by heating. During casting, and / or before and after casting, it is preferable to perform vacuum degassing on the two-component liquid resin composition. By performing vacuum degassing, air and the like contained in the two-component liquid resin composition can be removed, and a power module with few voids in the cured product of the two-component liquid resin composition can be obtained. The heating method for curing the two-component liquid resin composition of this embodiment is not particularly limited, and for example, conventionally known methods such as hot air circulation heating, infrared heating, and high-frequency heating can be adopted.

[0094] The heating temperature of the power module of the present embodiment is preferably 100°C or higher, more preferably 110°C or higher, still more preferably 120°C or higher, and even more preferably 130°C or higher from the viewpoint of the manufacturing efficiency of the power module, and preferably 220°C or lower, more preferably 210°C or lower, still more preferably 200°C or lower from the viewpoint of improving the performance balance between the reliability and mechanical strength of the power module.

[0095] The heating time of the power module of the present embodiment is preferably 30 seconds or longer, more preferably 60 seconds or longer, still more preferably 300 seconds or longer from the viewpoint of improving the performance balance between the reliability and mechanical strength of the power module, and preferably 10 hours or shorter, more preferably 5 hours or shorter, still more preferably 3 hours or shorter from the viewpoint of the manufacturing efficiency of the power module.

[0096] As described above, the embodiments of the present invention have been described, but these are examples of the present invention, and various configurations other than the above can be adopted. Further, the present invention is not limited to the above-described embodiments, and modifications, improvements, etc. within the scope that can achieve the object of the present invention are included in the present invention.

Examples

[0097] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereby.

[0098] <Examples, Comparative Examples> The components shown in the "First Liquid" in Table 1 were mixed in the amounts (parts by mass) shown in Table 1 to obtain a first liquid (main agent). Separately, the components shown in the "Second Liquid" in Table 1 were mixed in the amounts (parts by mass) shown in Table 1 to obtain a second liquid (curing agent). Then, the first liquid and the second liquid were mixed at the ratio shown in the "Mixing Ratio (First Liquid / Second Liquid)" in Table 1 to produce a mixed liquid (liquid resin composition). Details of each component in Table 1 are as follows.

[0099] <Epoxy Resin (A)> · Epoxy resin 1: 3,4-epoxycyclohexylmethyl-3’,4’-epoxycyclohexanecarboxylate (alicyclic epoxy resin, manufactured by Daicel Corporation, Celoxide 2021P) · Epoxy resin 2: Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, jER828EL) · Epoxy resin 3: Bisphenol F type epoxy resin (manufactured by Mitsubishi Chemical Corporation, jER807) · Epoxy resin 4: Aminophenol type epoxy resin (manufactured by Mitsubishi Chemical Corporation, JER630) <Acid anhydride (B)> · Acid anhydride 1: Methyl nadic anhydride (manufactured by Showa Denko Materials Co., Ltd., MHAC-P) <Curing accelerator (E)> · Curing accelerator 1: DBU-octylate (manufactured by San-Apro Ltd., U-CAT SA102) <Inorganic filler (C)> · Inorganic filler 1: Spherical fused silica (manufactured by Denka Co., Ltd., FB-950, average particle size D 50 : 23μm) <Anti-settling agent (D)> · Anti-settling agent 1: Polyhydroxycarboxylic acid ester (manufactured by BYK-Chemie Japan Co., Ltd., BYK-R606) · Anti-settling agent 2: Acidic phosphate ester (manufactured by BYK-Chemie Japan Co., Ltd., BYK-W9010) · Anti-settling agent 3: Carboxyl group-containing polymer modified product (manufactured by Kyoeisha Chemical Co., Ltd., Flowlen G700) · Anti-settling agent 4: Organophilic bentonite (manufactured by Hoejung Co., Ltd., Esben NTO)

[0100] <Other components> · Colorant: Carbon black (manufactured by Mitsubishi Chemical Corporation, Carbon #5) · Coupling agent: Epoxysilane coupling agent (manufactured by Momentive Performance Materials Inc., A-187) · Defoaming agent: Silicone-based defoaming agent (manufactured by Nisshio Sangyo Co., Ltd., TSA750)

[0101] The average particle size D of the above inorganic filler 50The measured value at 50% of the integrated value of the volume-based particle size distribution by the laser diffraction scattering measurement method using a laser diffraction type particle size distribution measuring device (manufactured by Shimadzu Corporation, SALD-7000) was used.

[0102] <Physical property evaluation> For the first liquid, second liquid, and mixed liquid obtained in each example and each comparative example, the following physical properties were measured.

[0103] (Viscosity and thixotropy at 25 °C) For the first liquid obtained in each example and each comparative example, the viscosity η at a rotation speed of 5 rpm and a temperature of 25 °C was measured using an E-type viscometer and a cone rotor of 3°×R14 (rotor No. 4). 5A At this time, for the measurement result of viscosity η 5A the viscosity 1 minute after starting the rotation of the cone rotor set in the E-type viscometer was used. Next, the viscosity η of the first liquid was measured in the same manner as above except that the rotation speed was changed to 10 rpm. 10A Furthermore, the thixotropy of the first liquid was calculated from the following formula using the above measurement results. (Thixotropy of the first liquid) = (viscosity η 5A ) / (viscosity η 10A ) Similarly, for the second liquid and the mixed liquid, the viscosities η 5B and η 5P at a rotation speed of 5 rpm and a temperature of 25 °C, the viscosities η 10B and η 10P at a rotation speed of 10 rpm and a temperature of 25 °C, and the thixotropy were measured. The measurement results are shown in Table 1. Note that the description "measurement impossible" in Table 1 indicates that the viscosities of the first liquid, second liquid, and mixed liquid obtained in each example and each comparative example were high and the measurement torque exceeded 100%, so correct measurement values could not be obtained.

[0104] (Flowability) 0.05 ml of the mixed solution was applied onto a glass plate such that the diameter of the mixed solution was 1 cm or less. Subsequently, the glass plate was held at an inclined angle of 45° and at a temperature of 60°C for 3 minutes. The distance that the mixed solution flowed during that time was measured as the flow distance (mm) and evaluated according to the following criteria. The evaluation results are shown in Table 1. A: The flow distance is 30 mm or more. B: The flow distance is 15 mm or more and less than 30 mm. C: The flow distance is less than 15 mm.

[0105] (Storage stability) The storage stabilities of the first liquid and the second liquid were evaluated by the following method. First, the first liquid was poured into a 120 mL capped plastic container to a height of 50 - 55 mm, capped, and the height of the filler sediment (hard cake) deposited at the bottom after 60°C × 240 hr was measured and evaluated according to the following criteria. A: The height of the hard cake is 0 mm. B: The height of the hard cake is more than 0 mm and less than 3 mm. C: The height of the hard cake is 3 mm or more. The storage stability of the second liquid was also evaluated in the same manner as the first liquid. The evaluation results are shown in Table 1.

[0106] (Casting workability) The casting workability of the mixed solution was evaluated according to the following criteria. A: All of the following (Requirement 1) - (Requirement 3) are satisfied. B: Any two of the following (Requirement 1) - (Requirement 3) are satisfied. C: Any one of the following (Requirement 1) - (Requirement 3) is satisfied, or none of them are satisfied. Requirement 1: The viscosity η of the mixed solution at 25°C 5P and the viscosity η 10P are both 50 Pa·s or less. Requirement 2: The evaluation result of the fluidity of the mixed solution is "A". Requirement 3: The evaluation results of the storage stabilities are both "A" for the first liquid and the second liquid.

[0107]

Table 1

[0108] In the two - component liquid resin composition of the example, the first liquid contains an epoxy resin (A), an inorganic filler (C), and an anti - settling agent (D), the second liquid contains an acid anhydride (B), an inorganic filler (C), and an anti - settling agent (D), the anti - settling agent (D) contains a dispersant, and the viscosity η 5A is 1.0 Pa·s or more and 50.0 Pa·s or less, thereby improving the performance balance between storage stability and fluidity.

Claims

1. A two-component liquid resin composition comprising a first liquid and a second liquid, wherein the first liquid contains an epoxy resin (A), an inorganic filler (C), and an anti-settling agent (D), the second liquid contains an acid anhydride (B), an inorganic filler (C), and an anti-settling agent (D), and the anti-settling agent (D) contains a dispersant. The viscosity η of the first liquid, measured using an E-type viscometer and a 3°×R14 cone rotor under the conditions of a rotation speed of 5 rpm and a temperature of 25°C ５Ａ A two-component liquid resin composition in which is 1.0 Pa·s or more and 50.0 Pa·s or less.

2. The viscosity η of the first liquid, measured using an E-type viscometer and a cone rotor of 3°×R14, under the conditions of a rotational speed of 10 rpm and a temperature of 25°C １０Ａ The two-component liquid resin composition according to claim 1, wherein the viscosity η is 1.0 Pa·s or more and 50.0 Pa·s or less

3. The viscosity η １０Ａ The viscosity η with respect to ５Ａ The viscosity ratio Ti Ａ (η ５Ａ / η １０Ａ ) is 0.4 or more and 1.5 or less. The two-component liquid resin composition according to claim 2.

4. The viscosity η of the second liquid, measured using an E-type viscometer and a 3°×R14 cone rotor under the conditions of a rotation speed of 5 rpm and a temperature of 25°C ５Ｂ The two-component liquid resin composition according to claim 1, wherein the viscosity η is 1.0 Pa·s or more and 70.0 Pa·s or less.

5. The viscosity η of the second liquid, measured using an E-type viscometer and a cone rotor of 3°×R14, under the conditions of a rotational speed of 10 rpm and a temperature of 25°C １０Ｂ The two-component liquid resin composition according to claim 4, wherein the viscosity η is 1.0 Pa·s or more and 50.0 Pa·s or less

6. The viscosity η １０Ｂ The viscosity η with respect to ５Ｂ The viscosity ratio Ti Ｂ (η ５Ｂ / η １０Ｂ ) is 0.5 or more and 4.0 or less. The two-component liquid resin composition according to claim 5.

7. The viscosity η of the mixed liquid of the first liquid and the second liquid, measured using an E-type viscometer and a 3°×R14 cone rotor under the conditions of a rotational speed of 5 rpm and a temperature of 25°C ５Ｐ The two-component liquid resin composition according to claim 1, wherein η is 1.0 Pa·s or more and 50.0 Pa·s or less.

8. The viscosity η of the mixed liquid of the first liquid and the second liquid, measured using an E-type viscometer and a cone rotor of 3°×R14 under the conditions of a rotation speed of 10 rpm and a temperature of 25°C １０Ｐ The two-component liquid resin composition according to claim 7, wherein the viscosity η is 10.0 Pa·s or more and 50.0 Pa·s or less.

9. The viscosity η １０Ｐ The viscosity η with respect to ５Ｐ The viscosity ratio Ti Ｐ (η ５Ｐ / η １０Ｐ ) is 0.5 or more and 2.0 or less. The two-component liquid resin composition according to claim 8.

10. The two-component liquid resin composition according to any one of Claims 1 to 9, wherein the dispersant contains an ester compound containing a long-chain hydrocarbon group.

11. The two-component liquid resin composition according to Claim 10, wherein the ester compound containing a long-chain hydrocarbon group contains one or more selected from the group consisting of polyhydroxycarboxylic acid esters, acidic phosphate esters, and carboxyl group-containing polymer modified products.

12. The two-component liquid resin composition according to any one of Claims 1 to 9, wherein the content of the anti-settling agent (D) is 0.01% by mass or more and 2.0% by mass or less when the total amount of the two-component liquid resin composition is 100% by mass.

13. The two-component liquid resin composition according to any one of Claims 1 to 9, wherein the epoxy resin (A) contains an alicyclic epoxy resin.

14. The two-component liquid resin composition according to Claim 13, wherein the content of the alicyclic epoxy resin is 50 parts by mass or more and 100 parts by mass or less when the content of the epoxy resin (A) is 100 parts by mass.

15. The two-component liquid resin composition according to any one of Claims 1 to 9, wherein the content of the epoxy resin (A) is 5% by mass or more and 30% by mass or less when the total amount of the two-component liquid resin composition is 100% by mass.

16. The two-component liquid resin composition according to any one of Claims 1 to 9, wherein the acid anhydride (B) contains one or more selected from the group consisting of methyl-5-norbornene-2,3-dicarboxylic anhydride, methylcyclohexane-1,2-dicarboxylic anhydride, and methyltetrahydrophthalic anhydride.

17. The two-component liquid resin composition according to any one of Claims 1 to 9, wherein the content of the acid anhydride (B) is 5% by mass or more and 20% by mass or less when the total amount of the two-component liquid resin composition is 100% by mass.

18. The two-component liquid resin composition according to any one of claims 1 to 9, wherein the inorganic filler (C) contains one or more selected from the group consisting of silica, alumina, aluminum hydroxide, and calcium carbonate.

19. The average particle diameter D at which the cumulative value becomes 50% in the volume frequency particle size distribution of the inorganic filler (C) measured by the laser diffraction scattering method ５０ is 0.5 μm or more and 100 μm or less, and the two-component liquid resin composition according to any one of claims 1 to 9.

20. The two-component liquid resin composition according to any one of claims 1 to 9, wherein the content of the inorganic filler (C) is 65% by mass or more and 85% by mass or less when the total amount of the two-component liquid resin composition is 100% by mass.

21. The two-component liquid resin composition according to any one of claims 1 to 9, further comprising a curing accelerator (E).

22. The two-component liquid resin composition according to claim 21, wherein the curing accelerator (E) contains one or more selected from the group consisting of tertiary amines, quaternary ammonium salts, imidazoles, organic phosphines, and Lewis acid catalysts.

23. The two-component liquid resin composition according to claim 21, wherein the content of the curing accelerator (E) is 0.01% by mass or more and 1.00% by mass or less when the total amount of the two-component liquid resin composition is 100% by mass.

24. The two-component liquid resin composition according to any one of claims 1 to 9, which can be used for encapsulating a power module comprising a substrate for a power module including a circuit layer and a power semiconductor element on the circuit layer of the substrate for the power module by an injection molding method.

25. A substrate for a power module including a circuit layer, a power semiconductor element on the circuit layer of the substrate for the power module, and a sealing material for sealing the substrate for the power module and the power semiconductor element, comprising: A power module, wherein the sealing material contains a cured product of the two-component liquid resin composition according to any one of claims 1 to 9.

26. The power module according to claim 25, wherein the power semiconductor element contains one or more selected from the group consisting of MOS transistors and insulated gate bipolar transistors (IGBTs).

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