Curable resin composition, cured product, electronic component, and method for manufacturing electronic component

Abstract

To provide a curable resin composition having excellent injection properties and coverage properties. The present invention also provides a cured product of the composition, an electronic component including the cured product, and a method for producing the electronic component.SOLUTION: (B), and inorganic particles (100nm) having a mean particle size of more than C1 and 50 μm or less and inorganic particles (100nm) having a mean particle size of 1 to C2 as the inorganic particles (C), and having a viscosity at 25 °C of 90 to 200Pa·s.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a curable resin composition, a cured product thereof, an electronic component including the cured product, and a method for producing the electronic component. [Background technology]

[0002] Multilayer ceramic capacitors (MLCCs) generally have a structure (laminated structure) in which many dielectric layers and internal electrode layers are stacked. External electrodes are formed on both ends of the laminated structure by applying a paste containing a conductive material such as nickel and glass frit, followed by drying and heating.

[0003] MLCCs are mounted on a substrate by soldering the external electrodes to the lands on the substrate, and then sealing the top of the MLCC and the gap between the MLCC and the substrate (the gap) with a curable resin composition such as an epoxy resin composition (see, for example, Patent Documents 1 and 2). Therefore, MLCC encapsulants are required to have (1) the ability to "inject" into the gap between the MLCC and the substrate, and (2) the ability to seal the entire laminate consisting of the MLCC and the substrate (hereinafter referred to as "coverage ability"). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2002-190564 [Patent Document 2] JP 2019-137866 A Summary of the Invention [Problem to be solved by the invention]

[0005] From the viewpoint of "injectability," MLCC encapsulants are required to have low viscosity. However, if the viscosity of the MLCC encapsulant is low, coverage tends to be low as well, resulting in the problem of the corners of the MLCC becoming visible. Furthermore, from the viewpoint of "coverage," MLCC encapsulants are required to have a certain degree of viscosity. However, if the viscosity of the MLCC encapsulant is high, it becomes difficult to inject it into the gap between the MLCC and the substrate.

[0006] In recent years, the miniaturization and high density of electronic components has led to the miniaturization of MLCCs, and as a result, the gap between the MLCC and the substrate has become narrower. As mentioned above, injection and coverage are contradictory properties, making it even more difficult to achieve both of these properties.

[0007] Accordingly, an object of the present invention is to provide a curable resin composition having excellent injectability and coverage, a cured product of the composition, an electronic component including the cured product, and a method for producing the same. [Means for solving the problem]

[0008] As a result of extensive research into achieving the above object, the present inventors have found that the problem can be solved by using a composition containing two different types of inorganic fillers. The present invention was completed based on these findings.

[0009] That is, in the present invention, Thermosetting resin (A), Hardener (B), The inorganic particles (C) include inorganic particles (C1) having an average particle size of more than 100 nm and 50 μm or less and inorganic particles (C2) having an average particle size of 1 to 100 nm, Viscosity at 25°C is 90 to 200 Pa·s. A curable resin composition is provided.

[0010] The TI value (5 rpm / 50 rpm) of the curable resin composition at 25° C. is preferably 1.5 to 5.0.

[0011] The content of the inorganic particles (C1) relative to the curable resin composition (100% by mass) is preferably 30 to 80% by mass.

[0012] The content of the inorganic particles (C2) relative to the curable resin composition (100% by mass) is preferably 0.5 to 20% by mass.

[0013] The curable resin composition is preferably a sealing material for a multilayer ceramic capacitor.

[0014] The curable resin composition is preferably used to seal the multilayer ceramic capacitor, the substrate, and the gap between the multilayer ceramic capacitor and the substrate in an electronic component having a gap width of 10 to 300 μm.

[0015] The present invention also provides a cured product of the curable resin composition.

[0016] The present invention also provides an electronic component comprising the above-mentioned cured product.

[0017] In the present invention, a substrate and a multilayer ceramic capacitor mounted on the substrate; a gap formed between the substrate and the multilayer ceramic capacitor; the substrate, the multilayer ceramic capacitor, and the cured product that seals the gap; An electronic component comprising the above is also provided.

[0018] In the present invention, a method for manufacturing a laminate includes a step of supplying the curable resin composition onto a laminate including a substrate, a multilayer ceramic capacitor mounted on the substrate, and a gap between the substrate and the multilayer ceramic capacitor; a step of filling the gap with the curable resin composition to form a molded body, and curing the molded body to seal the gap, thereby obtaining a sealed body; A method for manufacturing an electronic component including the method is also provided. [Effects of the Invention]

[0019] The curable resin composition of the present invention has both excellent injectability and coverage, and therefore electronic components comprising a cured product of the curable resin composition exhibit high reliability. [Brief explanation of the drawings]

[0020] [Figure 1] FIG. 1 is a diagram illustrating "Evaluation 3: Evaluation of injectability" in the Examples. [Figure 2] 1A and 1B are diagrams illustrating "Evaluation 4: Evaluation of coverage" in the examples. (a) is a diagram illustrating a case where the evaluation is "good". (b) is a diagram illustrating a case where the evaluation is "positive". (c) is a diagram illustrating a case where the evaluation is "negative". DETAILED DESCRIPTION OF THE INVENTION

[0021] The curable resin composition of the present invention comprises a thermosetting resin (A), a curing agent (B), and inorganic particles (C) including inorganic particles (C1) having an average particle size of more than 100 nm and not more than 50 μm and inorganic particles (C2) having an average particle size of 1 to 100 nm, and has a viscosity of 90 to 200 Pa·s at 25° C. In addition to the thermosetting resin (A), the curing agent (B), and the inorganic particles (C), the curable resin composition may also contain at least one selected from the group consisting of a curing accelerator (D) and a coupling agent (E).

[0022] ·Thermosetting resin (A) The thermosetting resin (A) is not particularly limited, but examples thereof include epoxy resins, silicone resins, melamine resins, urea resins, alkyd resins, polyurethanes, etc. Among these, epoxy resins are preferred from the viewpoints of electrical insulation, heat resistance, and cost. The thermosetting resin (A) can be used alone or in combination of two or more.

[0023] The epoxy resin is not particularly limited, and examples thereof include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and bisphenol AF type epoxy resin; bixylenol type epoxy resin, cyclohexane type epoxy resin, dicyclopentadiene type epoxy resin, trisphenolmethane type epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, and anthracene type epoxy resin. type epoxy resins, oxazolidone ring-containing epoxy resins, glycidylamine type epoxy resins, glycidyl ester type epoxy resins, cresol novolac type epoxy resins, biphenyl type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resins, trimethylol type epoxy resins, tetraphenylmethane type epoxy resins, aminophenol type epoxy resins, and silicone-modified epoxy resins.

[0024] Among these, from the viewpoints of viscosity and moisture resistance, bisphenol-type epoxy resins, naphthalene-type epoxy resins, aminophenol-type epoxy resins, cyclohexane-type epoxy resins, and glycidylamine-type epoxy resins are preferred, and bisphenol F-type epoxy resins, bisphenol A-type epoxy resins, naphthalene-type epoxy resins, and aminophenol-type epoxy resins are more preferred.

[0025] The number of epoxy groups in the epoxy resin is not particularly limited as long as it is one or more, but is preferably two or more (i.e., a polyfunctional epoxy resin). The epoxy resin may be liquid or solid at room temperature (25°C), but is preferably liquid from the viewpoint of the viscosity of the curable resin composition. Even a solid epoxy resin can be preferably used if it is used in combination with a liquid epoxy resin to form a liquid mixture.

[0026] Specific examples of liquid epoxy resins include "YDF-8170" and "YDF870GS" (both bisphenol F type epoxy resins), "YDF-8125" (bisphenol A type epoxy resin), "ZX-1658" and "ZX-1658GS" (all liquid 1,4-glycidylcyclohexane) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "HP-4032", "HP-4032D", and "HP-4032SS" (all naphthalene type epoxy resins) manufactured by DIC Corporation; "jER828US" and "jER828EL" (both bisphenol A type epoxy resins) and "jER80" manufactured by Mitsubishi Chemical Corporation. 6," "jER807" (all bisphenol F type epoxy resins), "jER152" (phenol novolac type epoxy resin), "jER630," "jER630LSD" (all aminophenol type epoxy resins), "YX7400N" (aliphatic epoxy resin / polytetramethylene glycol diglycidyl ether); "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; "EX-721" (glycidyl ester type epoxy resin) and "EX-171" (lauryl alcohol (EO)) manufactured by Nagase ChemteX Corporation. 15 glycidyl ether); ADEKA Corporation's "ADEKA RESIN EP4005" (bisphenol A type epoxy resin containing a polypropylene glycol structure), "EP-3950L" (aminophenol type epoxy resin), and "EP3980S" (glycidylamine type epoxy resin); Asahi Kasei Corporation's "AER9000" (PO-modified bisphenol type epoxy resin), "AER4001", "AER4004", and "AER4152" (all oxazolidone ring-containing epoxy resins); Dow Chemical Company's "DER852" and "DER858" (all oxazolidone ring-containing epoxy resins); Nippon Kayaku Co., Ltd.'s "FAE-2500" and "EPPN-501HY" (all trisphenolmethane type epoxy resins); and Daicel Corporation's "Celloxide 2021P" (alicyclic epoxy resin).

[0027] Specific examples of solid epoxy resins include "HP-4032H" (naphthalene-type epoxy resin), "HP-4700", and "HP-4710" (all naphthalene-type tetrafunctional epoxy resins), "N-690" (cresol novolac-type epoxy resin), "N-695" (cresol novolac-type epoxy resin), "HP-7200", "HP-7200L", "HP-7200HH", "HP-7200H", and "HP-7200HHH" (all dicyclopentadiene-type epoxy resins), all manufactured by DIC Corporation. ene-type epoxy resins), "EXA850CRP", "EXA7311", "EXA7311-G3", "EXA7311-G4", "EXA7311-G4S", and "HP6000" (all naphthylene ether-type epoxy resins); "EPPN-502H" (trisphenolmethane-type epoxy resin), "NC-7000-L" (naphthol novolac-type epoxy resin), "NC-3000-H", "NC-3000", "NC-3000-L", and "NC-310" manufactured by Nippon Kayaku Co., Ltd. 0" (all biphenyl-type epoxy resins); "ESN475V" (naphthol-type epoxy resin) and "ESN485" (naphthol novolac-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H" and "YL6121" (both biphenyl-type epoxy resins), "YX4000HK" (bixylenol-type epoxy resin), "YL7760" (bisphenol AF-type epoxy resin), and "YX8800" (anthracene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation. "PG-100" and "CG-500" manufactured by Osaka Gas Chemicals Co., Ltd.; and "YL7800" (fluorene-type epoxy resin), "jER1010" (solid bisphenol A-type epoxy resin), "jER1031S" (tetraphenylethane-type epoxy resin), "jER157S70" (bisphenol novolac-type epoxy resin), "YX4000HK" (bixylenol-type epoxy resin), and "YX8800" (anthracene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation.

[0028] The epoxy equivalent of the epoxy resin is not particularly limited, but is preferably 40 to 500 g / eq, more preferably 60 to 300 g / eq, and even more preferably 80 to 200 g / eq.

[0029] The silicone resin is not particularly limited, but examples thereof include dimethylpolysiloxane, methylphenylpolysiloxane, vinylpolysiloxane, phenoxypolysiloxane, and fluorosilicone resin. The melamine resin is not particularly limited, but examples thereof include melamine formaldehyde resin. The urea resin is not particularly limited, but examples thereof include urea formaldehyde resin. The alkyd resin is not particularly limited, but examples thereof include condensates of polyhydric alcohols and polybasic acids or their anhydrides. The polyurethane is not particularly limited as long as it is a resin having a urethane bond, but examples thereof include polyester polyurethane, polyether polyurethane, and MDI type polyurethane.

[0030] The content of the thermosetting resin (A) relative to the curable resin composition (100% by mass) is not particularly limited, but is, for example, preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and particularly preferably 20% by mass or more. Also, for example, it is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 35% by mass or less, and particularly preferably 30% by mass or less.

[0031] Hardener (B) The curing agent (B) is not particularly limited as long as it initiates, progresses, or accelerates the polymerization of the epoxy resin, and examples thereof include amine-based curing agents, acid anhydride-based curing agents, and phenol-based curing agents. The curing agent (B) can be used alone or in combination of two or more.

[0032] Examples of the amine-based curing agent include aromatic amines such as 4,4'-diamino-3,3'-diethyldiphenylmethane, diethyltoluenediamine, dimethylthiotoluenediamine, methylenedianiline, m-phenylenediamine, 4,4'-diaminodiphenylsulfone, and 3,3'-diaminodiphenylsulfone. Examples of the acid anhydride-based curing agent include alkylated tetrahydrophthalic anhydrides such as methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, phthalic anhydride, dodecenyl succinic anhydride, and methylnadic anhydride. Examples of the phenol-based curing agent include phenol novolac resin, cresol novolac resin, naphthol-modified phenolic resin, dicyclopentadiene-modified phenolic resin, and p-xylene-modified phenolic resin.

[0033] The equivalent weight (molecular weight per functional group) of the curing agent (B) is not particularly limited, but is, for example, preferably 10 to 600 g / eq, more preferably 30 to 300 g / eq, and even more preferably 50 to 180 g / eq.

[0034] When the curable resin composition contains an epoxy resin as the thermosetting resin (A), the content of the curing agent (B) relative to the epoxy resin is not particularly limited, but for example, the equivalent ratio (curing agent equivalent / epoxy equivalent) is preferably 0.5 to 1.5, and more preferably 0.8 to 1.2.

[0035] The content of the curing agent (B) relative to the curable resin composition (100% by mass) is not particularly limited, but is preferably 3% by mass or more, more preferably 5% by mass or more, even more preferably 8% by mass or more, and particularly preferably 10% by mass or more. Also, it is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, and particularly preferably 25% by mass or less. By having the content of the curing agent (B) within the above range, curability tends to be improved. Furthermore, injectability and coverage tend to be excellent.

[0036] The content of the curing agent (B) relative to the thermosetting resin (A) (100% by mass) is not particularly limited, but is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and particularly preferably 45% by mass or more. Also, it is preferably 300% by mass or less, more preferably 200% by mass or less, even more preferably 150% by mass or less, and particularly preferably 100% by mass or less. By having the content of the curing agent (B) within the above range, curability tends to be improved. Furthermore, injectability and coverage tend to be excellent.

[0037] ·Inorganic particles (C) The curable resin composition contains inorganic particles (C). The inorganic particles (C) include inorganic particles (C1) having an average particle size of more than 100 nm and not more than 50 μm and inorganic particles (C2) having an average particle size of 1 to 100 nm.

[0038] The inorganic particles (C) are not particularly limited, and examples thereof include silica (silicon dioxide), silicon carbide, silicon nitride, alumina (aluminum oxide), aluminum nitride, aluminum hydroxide, aluminum silicate, magnesium silicate, calcium silicate, calcium carbonate, barium sulfate, barium carbonate, titanium oxide, lime sulfate, potassium titanate, magnesium carbonate, zinc oxide, boron nitride, zirconia (zirconium oxide), and the like, as well as surface-treated materials of these materials. The inorganic particles (C) can be used singly or in combination of two or more.

[0039] The shape of the inorganic particles (C) is not particularly limited, and examples thereof include spherical (e.g., spherical, nearly spherical), polyhedral, rod-like (e.g., cylindrical, prismatic), tabular, scaly, and irregular shapes. Among these, spherical shapes are preferred from the viewpoint of achieving a high loading.

[0040] The average particle size of the inorganic particles (C) is not particularly limited, but is preferably 1 nm to 50 μm, more preferably 0.1 to 10 μm, and even more preferably 0.2 to 5 μm. In this specification, the method for measuring the average particle size of the inorganic particles (C) is not particularly limited, but can be measured, for example, using a laser diffraction / scattering particle size distribution analyzer (product name: LS 13 320, manufactured by Beckman Coulter, Inc.).

[0041] The content of the inorganic particles (C) relative to the curable resin composition (100% by mass) is not particularly limited, but is preferably, for example, 30% by mass or more, more preferably 40% by mass or more, even more preferably 45% by mass or more, and particularly preferably 50% by mass or more. Also, for example, it is preferably, for example, 80% by mass or less, more preferably 70% by mass or less, even more preferably 65% ​​by mass or less, and particularly preferably 60% by mass or less. When the content of the inorganic particles (C) is within the above range, the gap filling ability and workability of the curable resin composition tend to be improved.

[0042] The content of the inorganic particles (C) relative to the thermosetting resin (A) (100% by mass) contained in the curable resin composition is not particularly limited, but is preferably 100% by mass or more, more preferably 130% by mass or more, even more preferably 150% by mass or more, and particularly preferably 170% by mass or more. Also, for example, it is preferably 500% by mass or less, more preferably 400% by mass or less, even more preferably 300% by mass or less, and particularly preferably 260% by mass or less. When the content of the inorganic particles (C) is within the above range, the gap filling ability and workability of the curable resin composition tend to be improved.

[0043] The inorganic particles (C1) are preferably those (1) having the property of suppressing volumetric shrinkage (cure shrinkage) caused by the curing reaction of the curable resin composition, (2) having the property of suppressing volumetric change (thermal shrinkage) caused by heating of the cured product, i.e., having the effect of lowering the linear expansion coefficient of the cured product when added, or (3) having both of these properties. That is, the inorganic particles (C1) are preferably inorganic fillers.

[0044] The material of the inorganic particles (C1) is not particularly limited as long as it is one of the examples of the inorganic particles (C), but from the viewpoint of achieving a high loading, silica or surface-treated silica is preferred. The shape of the inorganic particles (C1) is not particularly limited, but from the viewpoint of achieving a high loading, a spherical shape is preferred.

[0045] In order to maintain the viscosity of the curable resin composition within an appropriate range, the inorganic particles (C1) are preferably surface-treated with a coupling agent having a functional group such as an epoxy group, a (meth)acryloyl group, or an amino group (particularly a phenylamino group). Examples of the coupling agent include silane coupling agents such as 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane. The surface treatment of the inorganic particles (C1) can be carried out using one of the above coupling agents alone or in combination of two or more.

[0046] The average particle size of the inorganic particles (C1) is not particularly limited as long as it is more than 100 nm and not more than 50 μm, but is, for example, preferably 200 nm to 10 μm, more preferably 300 nm to 5 μm, and even more preferably 400 nm to 2 μm. When the average particle size of the inorganic particles (C1) is within the above range, the particle size is not too large, and therefore the filling ability of the curable resin composition tends to be high even in narrow gaps.

[0047] The content of the inorganic particles (C1) relative to the curable resin composition (100% by mass) is not particularly limited, but is preferably, for example, 30% by mass or more, more preferably 35% by mass or more, even more preferably 40% by mass or more, and particularly preferably 45% by mass or more. Also, for example, it is preferably 80% by mass or less, more preferably 70% by mass or less, even more preferably 60% by mass or less, and particularly preferably 55% by mass or less. By having the content of the inorganic particles (C1) within the above range, the injectability and coverage tend to be excellent.

[0048] The content of inorganic particles (C1) relative to the thermosetting resin (A) (100% by mass) contained in the curable resin composition is not particularly limited, but is, for example, preferably 120% by mass or more, more preferably 140% by mass or more, even more preferably 150% by mass or more, and particularly preferably 160% by mass or more. Also, for example, it is preferably 450% by mass or less, more preferably 350% by mass or less, even more preferably 280% by mass or less, and particularly preferably 240% by mass or less. By having the content of inorganic particles (C1) within the above range, injectability and coverage tend to be excellent.

[0049] The content of the inorganic particles (C1) relative to the inorganic particles (C) (100% by mass) contained in the curable resin composition is not particularly limited, but is, for example, preferably 80% by mass or more, more preferably 85% by mass or more, even more preferably 88% by mass or more, and particularly preferably 90% by mass or more. Also, for example, it is preferably 99% by mass or less, more preferably 97% by mass or less, even more preferably 96% by mass or less, and particularly preferably 95% by mass or less. By having the content of the inorganic particles (C1) within the above range, injectability and coverage tend to be excellent.

[0050] The inorganic particles (C2) preferably have the property of imparting thixotropy to the curable resin composition, that is, the inorganic particles (C2) are preferably a thixotropic material.

[0051] The material for the inorganic particles (C2) is not particularly limited as long as it is one of the examples for the inorganic particles (C), but from the viewpoint of achieving a high loading, silica or surface-treated silica is preferred. The shape of the inorganic particles (C2) is not particularly limited, but from the viewpoint of achieving a high loading, a spherical shape is preferred.

[0052] From the viewpoint of imparting thixotropy to the curable resin composition, the inorganic particles (C2) are preferably surface-treated with a modified silicone oil such as dimethylsilicone oil, or with a coupling agent having a functional group such as an alkylsilyl group (e.g., dimethylsilyl, butylsilyl, hexylsilyl, or octylsilyl), a (meth)acryloylsilyl group, a methylpolysiloxane group, or a dimethylpolysiloxane group. Examples of the coupling agent include silane coupling agents such as polydimethylsiloxane, organosiloxane, hexamethyldisilazane, hexadecylsilane, and dimethyldichlorosilane. The above coupling agents can be used alone or in combination to surface-treat the inorganic particles (C2).

[0053] The average particle size of the inorganic particles (C2) is not particularly limited as long as it is 1 to 100 nm, but is, for example, preferably 3 to 80 nm, more preferably 5 to 60 nm, even more preferably 7 to 40 nm, still more preferably 9 to 30 nm, and particularly preferably 10 to 20 nm. When the average particle size of the inorganic particles (C2) is within the above range, the curable resin composition exhibits thixotropy and tends to be excellent in injectability and coverage.

[0054] The specific surface area of ​​inorganic particles (C2) is 50 to 300 m 2 / g, and 70 to 200m 2 / g, and more preferably 75 to 180m 2 / g is particularly preferred.

[0055] Specific examples of inorganic particles (C2) include "Aerosil R202," "Aerosil R805," "Aerosil R812," "Aerosil R812S," "Aerosil R816," "Aerosil R972," and "Aerosil R974," all manufactured by Nippon Aerosil Co., Ltd.; and "TS-720," manufactured by Cabot Corporation.

[0056] The content of the inorganic particles (C2) relative to the curable resin composition (100% by mass) is not particularly limited, but is preferably 0.5% by mass or more, more preferably 1.5% by mass or more, even more preferably 2% by mass or more, and particularly preferably 2.5% by mass or more. It is also preferably 20% by mass or less, more preferably 12% by mass or less, even more preferably 10% by mass or less, even more preferably 8% by mass or less, and particularly preferably 6% by mass or less. When the content of the inorganic particles (C2) is within the above range, the curable resin composition exhibits thixotropy and tends to have excellent injectability and coverage.

[0057] The content of the inorganic particles (C2) relative to the thermosetting resin (A) (100% by mass) contained in the curable resin composition is not particularly limited, but is, for example, preferably 4% by mass or more, more preferably 6% by mass or more, even more preferably 8% by mass or more, and particularly preferably 10% by mass or more. Also, for example, it is preferably 40% by mass or less, more preferably 35% by mass or less, even more preferably 30% by mass or less, and particularly preferably 25% by mass or less. When the content of the inorganic particles (C2) is within the above range, the curable resin composition exhibits thixotropy and tends to have excellent injectability and coverage.

[0058] The content of the inorganic particles (C2) relative to the inorganic particles (C) (100% by mass) contained in the curable resin composition is not particularly limited, but is, for example, preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 3% by mass or more, and particularly preferably 4% by mass or more. Also, for example, it is preferably 20% by mass or less, more preferably 16% by mass or less, even more preferably 12% by mass or less, and particularly preferably 10% by mass or less. When the content of the inorganic particles (C2) is within the above range, the curable resin composition exhibits thixotropy and tends to have excellent injectability and coverage.

[0059] Curing accelerator (D) The curing accelerator (D) has the property of accelerating the curing of the thermosetting resin. The curing accelerator is not particularly limited, but examples thereof include imidazole-based curing accelerators, tertiary amine-based curing accelerators, and phosphorus-based curing accelerators. Among these, imidazole-based curing accelerators are preferred from the viewpoint of reliability. The curing accelerator (D) can be used alone or in combination of two or more.

[0060] Examples of imidazole curing accelerators include imidazole compounds such as 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine. Commercially available products include 2-ethyl-4-methylimidazole (product name "2E4MZ"), 2-phenyl-4-methylimidazole (product name "2P4MZ"), 2-phenyl-4-methyl-5-hydroxymethylimidazole (product name "2P4MHZ-PW"), 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine (product name "2MZA-PW"), "2MZ-OK", "2MA-OK", and "2PHZ", all manufactured by Shikoku Chemical Industry Co., Ltd. Encapsulated imidazole, also known as microencapsulated imidazole or epoxy adduct imidazole, may also be used. Commercially available products include "HX3941HP", "HXA3942HP", "HXA3922HP", "HXA3792", "HX3748", "HX3721", "HX3722", "HX3088", "HX3741", "HX3742", and "HX3613" (all manufactured by Asahi Kasei Corporation), "PN-23J", "PN-40J", and "PN-50" (manufactured by Ajinomoto Fine-Techno Co., Ltd.), and "FXR-1121" (manufactured by Fuji Chemical Industry Co., Ltd.).

[0061] Examples of tertiary amine curing accelerators include benzyldimethylamine, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol, tetramethylguanidine, triethanolamine, N,N'-dimethylpiperazine, triethylenediamine, 1,8-diazabicyclo[5.4.0]undecene, 1,5-diazabicyclo[4.3.0]nonene, and salts thereof. Examples of the salts include formate, octylate, p-toluenesulfonate, o-phthalate, phenol salt, or phenol novolac resin salt of 1,8-diazabicyclo[5.4.0]undecene, and formate, octylate, p-toluenesulfonate, o-phthalate, phenol salt, or phenol novolac resin salt of 1,5-diazabicyclo[4.3.0]nonene.

[0062] Examples of phosphorus-based curing accelerators include phosphorus compounds such as triphenylphosphine, tri-p-tolylphosphine, tetraphenylphosphonium tetraphenylborate, triphenylphosphine triphenylborane, and 1,2-bis-(diphenylphosphino)ethane.

[0063] The content of the curing accelerator (D) relative to the curable resin composition (100% by mass) is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.3% by mass or more, and particularly preferably 0.6% by mass or more. Also, it is preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 2% by mass or less, and particularly preferably 1.5% by mass or less. By keeping the content of the curing accelerator (D) within the above range, curability tends to be improved.

[0064] The content of the curing accelerator (D) relative to the thermosetting resin (A) (100% by mass) contained in the curable resin composition is not particularly limited, but is, for example, preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, and particularly preferably 2% by mass or more. Also, for example, it is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 8% by mass or less, and particularly preferably 6% by mass or less. When the content of the curing accelerator (D) is within the above range, curability tends to be improved.

[0065] Coupling agent (E) The coupling agent (E) is not particularly limited, and examples thereof include silane coupling agents having a vinyl group, an epoxy group, a styryl group, a (meth)acrylic group, an amino group, an isocyanurate group, a ureido group, a mercapto group, a sulfide group, an isocyanate group, etc. The coupling agent (E) may be used alone or in combination of two or more.

[0066] Examples of the silane coupling agent include 3-glycidyloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 8-glycidoxyoctyltrimethoxysilane, 8-methacryloxyoctyltrimethoxysilane, and 8-phenylaminooctyltrimethoxysilane.

[0067] Specific examples of coupling agents include KBM-303, KBM-402, KBM-403, KBE-402, KBE-403, KBM-4803, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-5803, KBM-602, KBM-603, KBM-903, KBE-903, KBE-9103P, KBM-573, KBM-575, KBM-802, and KBM-803 (product names, all manufactured by Shin-Etsu Chemical Co., Ltd.).

[0068] The content of the coupling agent (E) relative to the curable resin composition (100% by mass) is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, and particularly preferably 0.15% by mass or more. The content is also not particularly limited, but is preferably 2.0% by mass or less, more preferably 1.5% by mass or less, even more preferably 1.0% by mass or less, and particularly preferably 0.5% by mass or less.

[0069] Other ingredients (F) The curable resin composition may contain components other than the thermosetting resin (A), curing agent (B), inorganic particles (C), curing accelerator (D), and coupling agent (E) (hereinafter referred to as "other components (F)"). Examples of other components (F) include thermoplastic resins, elastomers, surfactants, ion trapping agents, leveling agents, antioxidants, antifoaming agents, flame retardants, colorants such as carbon black, reactive diluents, and solvents. However, it is preferable not to include reactive diluents because they volatilize during heat curing and lead to the formation of voids. The other components (F) may be used alone or in combination of two or more.

[0070] The content of the other component (F) relative to the curable resin composition (100% by mass) is not particularly limited as long as it does not impair the effects of the present invention, but is, for example, preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 1% by mass or less, and particularly preferably 0.1% by mass or less. Also, for example, it is preferably 0.01% by mass or more.

[0071] (Properties and Production Method of Curable Resin Composition) The viscosity of the curable resin composition at 25°C is not particularly limited as long as it is 90 to 200 Pa·s, but is preferably 95 to 180 Pa·s, and more preferably 100 to 160 Pa·s. When the viscosity is within the above range, the injectability and coverage of the curable resin composition into gaps tend to be improved. The viscosity can be measured, for example, by the method described in the Examples below.

[0072] The TI value (thixotropic index, 5 rpm / 50 rpm) of the curable resin composition at 25°C is not particularly limited, but is preferably 1.5 to 5.0, more preferably 1.7 to 4.5, and even more preferably 2.0 to 4.0. The TI value (5 rpm / 50 rpm) can be measured, for example, by the method described in the Examples below.

[0073] The curable resin composition can be prepared by a known, commonly used method. For example, the curable resin composition can be obtained by introducing components such as the thermosetting resin (A) simultaneously or separately into an appropriate mixer and, if necessary, heating the components to melt them while stirring and mixing them. When the thermosetting resin (A) is solid, it is preferable to heat it to liquefy or fluidize it before mixing. If it is difficult to uniformly disperse the inorganic particles (C) in the curable resin composition, the curable resin composition may be prepared by heating and mixing the thermosetting resin (A) and the inorganic particles (C) to uniformly disperse the inorganic particles (C) in the thermosetting resin (A), cooling the mixture as necessary, and then mixing components such as the curing agent (B).

[0074] The mixer is not particularly limited, and examples thereof include a roll mill equipped with a stirrer and a heater, a Raikai mixer, a Henschel mixer, a tumbler, a planetary mixer, etc. The mixing ratio of each component is appropriately set depending on the content of each component in the curable resin composition.

[0075] The curable resin composition can be preferably used as a material for sealing a multilayer ceramic capacitor (a sealing material for a multilayer ceramic capacitor). By using the curable resin composition as a sealing material for a multilayer ceramic capacitor, highly reliable electrical components can be manufactured. More specifically, for an electronic component in which the gap width between the multilayer ceramic capacitor and the substrate is 10 to 300 μm (preferably 10 to 150 μm), the curable resin composition is preferably used as a sealing material for a multilayer ceramic capacitor for sealing the multilayer ceramic capacitor, the substrate, and the gap.

[0076] Furthermore, the use of the curable resin composition is not limited to the above-mentioned sealing material for multilayer ceramic capacitors, and it can also be used, for example, as a composition for sealing semiconductor elements or an adhesive for fixing, joining, or protecting components that constitute electronic components.

[0077] A cured product is formed by curing the curable resin composition. The curing method is not particularly limited, but for example, the curing can be carried out by subjecting the curable resin composition to a heat treatment. The temperature of the heat treatment is not particularly limited, but for example, 60 to 200°C is preferred, and 80 to 180°C is more preferred. The time of the heat treatment is not particularly limited, but for example, 0.1 to 5 hours is preferred, and 0.5 to 3 hours is more preferred.

[0078] The electronic component of the present invention includes a cured product of the curable resin composition. Specifically, the electronic component includes a substrate, a multilayer ceramic capacitor mounted on the substrate, a gap formed between the substrate and the multilayer ceramic capacitor, and the substrate, the multilayer ceramic capacitor, and the cured product sealing the gap. That is, in the electronic component, the substrate, the multilayer ceramic capacitor, and the gap formed therebetween are sealed with the cured product (sealant) of the curable resin composition.

[0079] The electronic component includes a step of supplying the curable resin composition onto a laminate including a substrate, a multilayer ceramic capacitor mounted on the substrate, and a gap between the substrate and the multilayer ceramic capacitor (supply step); a step of filling the gap with the curable resin composition to form a molded body, and curing the molded body to seal the gap to obtain a sealed body (sealing step); It can be produced by a method comprising:

[0080] The method for filling the gap with the curable resin composition is not particularly limited, but for example, the curable resin composition is applied to one end of the gap between the substrate or the multilayer ceramic capacitor while heating the substrate to 50 to 120°C, and the curable resin composition is filled into the gap between the substrate and the multilayer ceramic capacitor by capillary action. After filling the gap with the curable resin composition, the substrate is heated at a predetermined temperature for a predetermined time, specifically at the temperature and for the time described in the heat treatment for forming the cured product, thereby sealing the gap. [Example]

[0081] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0082] Curable resin compositions of the examples and comparative examples were prepared by mixing components such as the thermosetting resin (A) in the blending ratios shown in Table 1. The numerical values ​​for each component in Table 1 indicate parts by mass.

[0083] Each component in Table 1 will be explained below. ·Thermosetting resin (A) YDF-8170 (product name): Bisphenol F epoxy resin, liquid at 25°C, epoxy equivalent 158g / eq, manufactured by Nippon Steel Chemical & Material Co., Ltd. RE410S (product name): Bisphenol A epoxy resin, liquid at 25°C, epoxy equivalent 178g / eq, manufactured by Nippon Kayaku Co., Ltd. Hardener (B) MEH-8005 (product name): Phenolic curing agent, equivalent weight 139-143g / eq, manufactured by UBE Corporation HN-2200 (product name): 3-methyl-1,2,3,6-tetrahydrophthalic anhydride or 4-methyl-1,2,3,6-tetrahydrophthalic anhydride, acid anhydride curing agent, active hydrogen equivalent 168g / eq, manufactured by Resonac Corporation Ethacure 100 Plus (product name): Diethyltoluenediamine, amine-based curing agent, equivalent weight 89g / eq, manufactured by Mitsui Chemicals Fine Co., Ltd. ·Inorganic particles (C1) SE2200-SME (product name): Average particle size 0.6 μm, silica surface treated with 3-methacryloxypropyltrimethoxysilane, manufactured by Admatechs Co., Ltd. ·Inorganic particles (C2) Aerosil R805 (product name): Caprylyl silylated silica (silica with alkylsilyl groups), specific surface area calculated by the BET method: 125-175 m 2 / g, average particle size 12nm, Nippon Aerosil Co., Ltd. Aerosil R202 (product name): Dimethicone silylated silica (silica particles with dimethylpolysiloxane), specific surface area calculated by the BET method: 80-120 m 2 / g, average particle size 12nm, Nippon Aerosil Co., Ltd. Aerosil R972 (product name): Dimethylsilylated silica (silica particles with dimethylsilyl groups), specific surface area calculated by the BET method: 90-130 m 2 / g, average particle size 16nm, Nippon Aerosil Co., Ltd. Curing accelerator (D) 2P4MZ (product name): 2-phenyl-4-methylimidazole, imidazole-based curing accelerator, manufactured by Shikoku Chemicals Corporation 2P4MHZ (product name): 2-phenyl-4-methyl-5-hydroxymethylimidazole, imidazole-based curing accelerator, manufactured by Shikoku Chemicals Corporation Coupling agent (E) KBM-403 (product name): 3-glycidyloxypropyltrimethoxysilane, coupling agent, Shin-Etsu Chemical Co., Ltd. Other (F) Black 4 / Product name "Special Black 4 powder": Colorant, manufactured by Orion Engineered Carbons Co., Ltd. IXE-500: Ion trapping agent, Toagosei Co., Ltd.

[0084] (Evaluation 1: Viscosity evaluation) The viscosity (Pa s) at 25°C immediately after preparation of the curable resin compositions of the Examples and Comparative Examples was measured using a Brookfield HB-DV viscometer (model number: HB-DV1) when the curable resin compositions were rotated at 50 rpm for 1 minute at a liquid temperature of 25°C. The results are shown in Table 1 under "Viscosity at 25°C (Pa s)."

[0085] (Evaluation 2: Measurement of TI value) The TI values ​​(thixotropic index, 5 rpm / 50 rpm) at 25°C of the curable resin compositions of the Examples and Comparative Examples were measured and calculated. Specifically, immediately after measuring the "viscosity at 25°C" in Evaluation 1, the viscosity was measured when rotated at 5 rpm for 1 minute, and the TI value was calculated using the following formula. The results are shown in Table 1 under "TI value (5 rpm / 50 rpm)." TI value (5 rpm / 50 rpm) = viscosity at 5 rpm / viscosity at 50 rpm

[0086] (Evaluation 3: Injectability evaluation) Preparation of test specimens A glass plate was attached to the resin substrate with tape to obtain a test specimen with a gap between the resin substrate and the glass plate, measuring 50 μm in height, 1 cm in width, and 2 cm in distance.

[0087] Testing and evaluation The test piece was placed on a hot plate set at 60° C., and about 0.2 g of the curable resin composition of the Examples and Comparative Examples was applied to the sample application area, followed by leaving it for 10 minutes.

[0088] The gap filling test will be described using Figure 1. In Figure 1, 1 represents a test piece. 2 represents a glass plate, 2' represents a resin substrate, 3 represents a tape, 4 represents a gap, and 5 represents an evaluation sample. (a) is a plan view of the test piece 1, with the longitudinal direction of the test piece 1 being vertical and the lateral direction being horizontal. (b) is a side view of the test piece 1 from the longitudinal direction. (c) is a side view of the test piece 1 from the lateral direction. The glass plate 2 is laminated to the resin substrate 2' via tape 3. As shown in (b), the edge of the glass plate 2 is the application area (sample application area) of the evaluation sample 5. The gap 4 is a space surrounded by the glass plate 2 on its upper surface, the resin substrate 2' on its lower surface, and two tapes 3 on its sides. In the gap 4, the distance between the glass plate 2 and the resin substrate 2' (gap height) is 50 μm, and the distance between the two tapes 3 (gap width) is 1 cm. The longitudinal distance of the gap 4 (gap distance) is 2 cm. The test piece 1 is placed on a hot plate (not shown), and the evaluation sample 5 is applied to the sample application area. The applied evaluation sample 5 moves downwards (a) along the gap 4 due to capillary action. After leaving it for 10 minutes, the distance traveled by the evaluation sample 5 injected into the gap (the distance it penetrated into the gap) was measured with a CCD camera and evaluated according to the following criteria. The results are shown in the "Injectability" column of Table 1. ◯: The distance traveled by the evaluation sample (curable resin composition) is 1000 μm or more ×: The distance traveled by the evaluation sample (curable resin composition) is less than 1000 μm

[0089] (Evaluation 4: Coverage evaluation) A test specimen was prepared by mounting a multilayer ceramic capacitor (MLCC, manufactured by Murata Manufacturing Co., Ltd.) with a long side of 2.0 mm and a short side of 1.2 mm on a ceramic substrate. The gap width between the MLCC and the ceramic substrate in the test specimen was 150 μm. The test specimen was placed on a hot plate with a stage temperature set to 60°C and left for 5 minutes. After that, 0.05 g of the curable resin composition of the examples and comparative examples was applied to the MLCC and left for 10 minutes. The test piece was observed with a CCD and evaluated according to the following criteria. The results are shown in the "Coverage" section of Table 1. ○: The entire MLCC is sealed (Figure 2(a)) △: The entire MLCC is sealed, but the corners of the MLCC are not sealed sufficiently and are transparent (Fig. 2(b), 15) ×: The entire MLCC was not sealed, and the curable resin composition remained on the MLCC (Figure 2(c)).

[0090] [Table 1] [Explanation of symbols]

[0091] 1 test piece 2 glass plates 2' Resin substrate 3 Tape 4. Gap 5 Evaluation sample 11 Curable resin composition 12 MLCC (Multilayer Ceramic Capacitor) 13 External electrode 14 PCB 15 MLCC corner

Claims

1. thermosetting resin (A), a curing agent (B), and The inorganic particles (C) include inorganic particles (C1) having an average particle size of more than 100 nm and 50 μm or less and inorganic particles (C2) having an average particle size of 1 to 100 nm, The viscosity at 25°C is 90 to 200 Pa s. Curable resin composition.

2. 2. The curable resin composition according to claim 1, wherein the TI value (5 rpm / 50 rpm) at 25° C. is 1.5 to 5.

0.

3. 3. The curable resin composition according to claim 1, wherein the content of the inorganic particles (C1) relative to the curable resin composition (100% by mass) is 30 to 80% by mass.

4. 3. The curable resin composition according to claim 1, wherein the content of the inorganic particles (C2) relative to the curable resin composition (100% by mass) is 0.5 to 20% by mass.

5. The curable resin composition according to claim 1 or 2, which is a sealing material for a multilayer ceramic capacitor.

6. 3. The curable resin composition according to claim 1, which is used for sealing a multilayer ceramic capacitor, a substrate, and a gap between a multilayer ceramic capacitor and a substrate in an electronic component having a gap width of 10 to 300 μm.

7. A cured product of the curable resin composition according to claim 1 or 2.

8. An electronic component comprising the cured product of claim 7.

9. A substrate; a multilayer ceramic capacitor mounted on the substrate; a gap formed between the substrate and the multilayer ceramic capacitor; The cured product according to claim 7 that seals the substrate, the multilayer ceramic capacitor, and the gap; An electronic component comprising:

10. a step of supplying the curable resin composition according to claim 1 or 2 onto a laminate including a substrate, a multilayer ceramic capacitor mounted on the substrate, and a gap between the substrate and the multilayer ceramic capacitor; a step of filling the gap with the curable resin composition to form a molded body, and curing the molded body to seal the gap, thereby obtaining a sealed body; A method for manufacturing an electronic component, comprising:

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