Resin composition

Abstract

To provide a resin composition or the like which can give a cured product having high thermal conductivity, high insulation performance, and excellent mechanical strength.SOLUTION: The resin composition contains (A) an epoxy resin, (B) a thermally conductive filler having a volume resistivity of 109 Ω m or more, and (C) a thiol compound. The component (C) contains at least (C-1) a non-ester type thiol compound. The component (C-1) is trifunctional or higher. The component (B) contains (B-1) a thermally conductive filler having a particle diameter of 10 μm or more, (B-2) a thermally conductive filler having a particle diameter of 1 μm or more and less than 10 μm, and (B-3) a thermally conductive filler having a particle diameter of less than 1 μm.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin composition and a method for producing the same, and further to a resin sheet, a circuit board, a semiconductor chip package, and an electronic component using the resin composition. [Background technology]

[0002] In recent years, electronic devices have become smaller and more sophisticated, and the mounting density of semiconductor elements on printed wiring boards has tended to increase. Coupled with the increasing functionality of the mounted semiconductor elements, there is a demand for technology to efficiently dissipate the heat generated by the semiconductor elements.

[0003] For example, Patent Documents 1 and 2 disclose that heat can be dissipated by using a resin composition containing a specific alumina or the like as an adhesive to bond a component from which heat dissipation is desired, such as a circuit board, to a thermally conductive material. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2016-104832 [Patent Document 2] Patent No. 7056649 Summary of the Invention [Problem to be solved by the invention]

[0005] In recent years, there has been a demand for cured adhesives with high thermal conductivity to more efficiently dissipate the heat generated by semiconductor elements. For example, when used as an underfill to remove heat generated from silicon chips, high insulation properties are required to prevent conduction between bumps. In addition, from the perspective of impact resistance, low elastic modulus and high elongation are required.

[0006] However, one possible way to improve the thermal conductivity of the cured adhesive is to highly fill it with a thermally conductive filler such as alumina and increase the contact area with the component from which heat dissipation is desired, but this can result in a high modulus of elasticity of the cured adhesive. Furthermore, increasing the contact area between the thermally conductive fillers results in the resin component not blending completely with the thermally conductive filler, and the thermally conductive fillers are in contact with each other, making it impossible to obtain sufficient elongation in the cured adhesive. Therefore, conventional technologies have not always been able to achieve adhesives with sufficient thermal conductivity. Hereinafter, elongation and modulus of elasticity may be collectively referred to as "mechanical strength."

[0007] The present invention has been made in view of the above, and aims to provide a resin composition that can give a cured product having high thermal conductivity, insulating performance, and excellent mechanical strength, and a method for producing the same; and a resin sheet, a circuit board, a semiconductor chip package, and an electronic component that use the resin composition. [Means for solving the problem]

[0008] In order to achieve the objects of the present invention, the present inventors conducted extensive research and found that by using a thermally conductive filler with adjusted particle size and volume resistivity, and further incorporating an epoxy resin and a thiol compound in combination, it is possible to obtain a cured product with high thermal conductivity, insulating performance, and elongation, and a low elastic modulus, and thus completed the present invention.

[0009] That is, the present invention includes the following. [1] (A) epoxy resin, (B) Volume resistivity is 10 9 A thermally conductive filler having a thermal conductivity of Ω·m or more, and (C) A resin composition containing a thiol compound, The component (C) contains at least a non-ester thiol compound (C-1), The component (C-1) has three or more functional groups, A resin composition, wherein component (B) comprises (B-1) a thermally conductive filler having a particle size of 10 μm or more, (B-2) a thermally conductive filler having a particle size of 1 μm or more and less than 10 μm, and (B-3) a thermally conductive filler having a particle size of less than 1 μm. [2] The resin composition according to [1], wherein the content of the component (B-1) is 50% by volume or more and 95% by volume or less, when the total volume of the component (B) is 100% by volume. [3] The resin composition according to [1] or [2], wherein the content of the component (B-2) is 1% by volume or more and 40% by volume or less, when the total volume of the component (B) is taken as 100% by volume. [4] The resin composition according to any one of [1] to [3], wherein the content of the component (B-3) is 0.01% by volume or more and 10% by volume or less, when the total volume of the component (B) is taken as 100% by volume. [5] The resin composition according to any one of [1] to [4], further comprising (D) a dispersant having an unsaturated aliphatic skeleton in which all carbon atoms contained in one molecule have 8 to 60 carbon atoms and 8 to 54 carbon atoms. [6] The resin composition according to any one of [1] to [5], wherein the content of component (A) is 1% by mass or more and 25% by mass or less, when the non-volatile components of the resin composition are taken as 100% by mass. [7] The resin composition according to any one of [1] to [6], wherein the content of component (B) is 50% by mass or more and 95% by mass or less, when the non-volatile components of the resin composition are 100% by mass. [8] The resin composition according to any one of [1] to [7], wherein the content of component (C) is 1% by mass or more and 20% by mass or less, when the non-volatile components of the resin composition are taken as 100% by mass. [9] (A) Epoxy resin, (B) Volume resistivity is 10 9 A thermally conductive filler having a thermal conductivity of Ω·m or more, and (C) A resin composition containing a thiol compound, The component (C) contains at least a non-ester thiol compound (C-1), The component (C-1) has three or more functional groups, (B) The 10% particle size of the component is 0.1 μm or more and 5 μm or less, The average particle size of component (B) is 3 μm or more and 20 μm or less, A resin composition, wherein the 90% particle size of component (B) is 10 μm or more and 40 μm or less.

[10] A resin sheet having a support and a resin composition layer provided on the support, the resin composition comprising the resin composition according to any one of [1] to [9].

[11] A circuit board comprising an insulating layer formed from a cured product of the resin composition according to any one of [1] to [9].

[12] A semiconductor chip package comprising the circuit board according to

[11] and a semiconductor chip mounted on the circuit board.

[13] An electronic component comprising: a heat sink; a cured product of the resin composition according to any one of [1] to [9] provided on the heat sink; and an electronic component mounted on the cured product.

[14] A method for producing the resin composition according to any one of [1] to [9], (A) epoxy resin, (B-1b) a thermally conductive filler having an average particle size of 10 μm or more; (B-2b) a thermally conductive filler having an average particle size of 1 μm or more and less than 10 μm; (B-3b) a thermally conductive filler having an average particle size of less than 1 μm, and (C) a thiol compound, The component (C) contains at least a non-ester thiol compound (C-1), A method for producing a resin composition, wherein the component (C-1) is trifunctional or higher. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a resin composition and a method for producing the same that can give a cured product having high thermal conductivity, insulating performance, and excellent mechanical strength; and it is also possible to provide a resin sheet, a circuit board, a semiconductor chip package, and an electronic component that use the resin composition. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention will be described in detail below with reference to preferred embodiments thereof. However, the present invention is not limited to the following embodiments and examples, and can be implemented with any modifications within the scope of the claims of the present invention and their equivalents.

[0012] [Resin composition] The resin composition of the first embodiment comprises (A) an epoxy resin, (B) a polymer having a volume resistivity of 10 9 The resin composition of the second embodiment contains (A) an epoxy resin, (B) a thermally conductive filler having a volume resistivity of 10 Ω·m or more, and (C) a thiol compound, wherein the component (C) contains at least (C-1) a non-ester type thiol compound, the component (C-1) is trifunctional or more, and the component (B) contains (B-1) a thermally conductive filler having a particle size of 10 μm or more, (B-2) a thermally conductive filler having a particle size of 1 μm or more but less than 10 μm, and (B-3) a thermally conductive filler having a particle size of less than 1 μm. 9 The resin composition contains a thermally conductive filler having a thermal conductivity of Ω·m or greater and (C) a thiol compound, wherein the (C) component contains at least a (C-1) non-ester thiol compound, the (C-1) component being trifunctional or greater, the 10% particle size (D10) of the (B) component being 0.1 μm or greater and 5 μm or less, the average particle size (D50) of the (B) component being 3 μm or greater and 20 μm or less, and the 90% particle size (D90) of the (B) component being 10 μm or greater and 40 μm or less. By including components (A) to (C), these resin compositions can yield cured products with high thermal conductivity, insulating properties, and excellent mechanical strength. Furthermore, the resin composition can also yield cured products with typically high adhesive strength, moisture resistance, and excellent adhesive strength retention.

[0013] In addition to the components (A) to (C), the resin compositions of the first and second embodiments may further contain, as necessary, (D) a dispersant having an unsaturated aliphatic skeleton in which the total number of carbon atoms contained in one molecule is 8 to 60 and the number of carbon atoms is 8 to 54, (E) a curing accelerator, (F) a storage stabilizer, (G) a silane coupling agent, (H) an optional additive, and (I) a solvent. Each component contained in the resin composition will be described in detail below. Here, the resin compositions of the first and second embodiments will sometimes be collectively referred to as the "resin composition."

[0014] <(A) Epoxy resin> The resin composition contains an epoxy resin (A) as component (A). By including the epoxy resin (A) in the resin composition, a cured product exhibiting good mechanical strength and insulating performance can be obtained. The epoxy resin (A) may be used alone or in combination of two or more.

[0015] (A) Epoxy resins include, for example, bixylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol novolac type epoxy resins, phenol novolac type epoxy resins, tert-butyl-catechol type epoxy resins, naphthalene type epoxy resins, naphthol type epoxy resins, anthracene type epoxy resins, glycidylamine type epoxy resins, and glycidyl ester type Examples of epoxy resins include epoxy resins, glycidyl cyclohexane-type epoxy resins, alkyl diglycidyl ether-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, cyclohexane-type epoxy resins, cyclohexane dimethanol-type epoxy resins, naphthylene ether-type epoxy resins, trimethylol-type epoxy resins, tetraphenylethane-type epoxy resins, and phenolphthalimidine-type epoxy resins.

[0016] The resin composition preferably contains, as component (A), an epoxy resin having two or more epoxy groups per molecule. From the viewpoint of significantly achieving the desired effects of the present invention, the proportion of the epoxy resin having two or more epoxy groups per molecule relative to 100% by mass of the epoxy resin (A) is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

[0017] Epoxy resins include epoxy resins that are liquid at a temperature of 20°C (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at a temperature of 20°C (hereinafter sometimes referred to as "solid epoxy resins"). The resin composition may contain, as component (A), only a liquid epoxy resin, only a solid epoxy resin, or a combination of a liquid epoxy resin and a solid epoxy resin. Of these, it is preferable to contain only a liquid epoxy resin, from the viewpoint of significantly achieving the effects of the present invention.

[0018] The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule.

[0019] Preferred liquid epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, alicyclic epoxy resins having an ester skeleton, cyclohexane type epoxy resins, cyclohexane dimethanol type epoxy resins, glycidyl amine type epoxy resins, and epoxy resins having a butadiene structure, glycidyl cyclohexane type epoxy resins, phenolphthalimidine type epoxy resins, and alkyl diglycidyl ether type epoxy resins, and more preferred are bisphenol A type epoxy resins, bisphenol F type epoxy resins, and cyclohexane dimethanol type epoxy resins.

[0020] Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resins) manufactured by DIC Corporation; "828US", "jER828EL", "825", and "Epikote 828EL" (bisphenol A type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "jER807" and "1750" (bisphenol F type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630" and "630LSD" (glycidyl amine type epoxy resins) manufactured by Mitsubishi Chemical Corporation; and "ZX1" manufactured by Nippon Steel Chemical & Material Co., Ltd. Examples of epoxy resins that can be used include "EX-721" (a glycidyl ester epoxy resin) manufactured by Nagase ChemteX Corporation, "Celloxide 2021P" (an alicyclic epoxy resin having an ester skeleton) manufactured by Daicel Corporation, "PB-3600" (an epoxy resin having a butadiene structure) manufactured by Daicel Corporation, "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane epoxy resins) manufactured by Nippon Steel Chemical & Material Co., Ltd., and "YED216D" (an alkyl diglycidyl ether epoxy resin) manufactured by Mitsubishi Chemical Corporation. These may be used alone or in combination of two or more.

[0021] As the solid epoxy resin, a solid epoxy resin having two or more epoxy groups in one molecule is preferred, a solid epoxy resin having three or more epoxy groups in one molecule is more preferred, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is even more preferred.

[0022] Preferred solid epoxy resins include bixylenol-type epoxy resins, naphthalene-type epoxy resins, naphthalene-type tetrafunctional epoxy resins, cresol novolac-type epoxy resins, dicyclopentadiene-type epoxy resins, trisphenol-type epoxy resins, naphthol-type epoxy resins, biphenyl-type epoxy resins, naphthylene ether-type epoxy resins, anthracene-type epoxy resins, bisphenol A-type epoxy resins, bisphenol AF-type epoxy resins, and tetraphenylethane-type epoxy resins.

[0023] Specific examples of solid epoxy resins include "HP4032H" (naphthalene type epoxy resin), "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin), "N-690" (cresol novolac type epoxy resin), "N-695" (cresol novolac type epoxy resin), "HP-7200", "HP-7200HH", "HP-7200H" (dicyclopentadiene type epoxy resin), "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000", "HP6000L" (naphthylene ether type epoxy resin), manufactured by DIC Corporation; "EPPN-502H" (trisphenol type epoxy resin), "NC7000L" (naphthol novolac type epoxy resin), "NC3000H", "NC3000", "NC3000L" manufactured by Nippon Kayaku Co., Ltd.; Examples include "NC3100" (biphenyl-type epoxy resin); "ESN475V" (naphthalene-type epoxy resin) and "ESN485" (naphthol novolac-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H", "YL6121" (biphenyl-type epoxy resin), "YX4000HK" (bixylenol-type epoxy resin), and "YX8800" (anthracene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.; "YL7760" (bisphenol AF-type epoxy resin), "YL7800" (fluorene-type epoxy resin), "jER1010" (solid bisphenol A-type epoxy resin), and "jER1031S" (tetraphenylethane-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; and "WHR-991S" (phenolphthalimidine-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. These may be used alone or in combination of two or more.

[0024] When a liquid epoxy resin and a solid epoxy resin are used in combination as component (A), the ratio by mass between them (liquid epoxy resin:solid epoxy resin) is preferably 1:0.1 to 1:20, more preferably 1:0.15 to 1:10, and particularly preferably 1:0.2 to 1:5. When the ratio by mass between the liquid epoxy resin and the solid epoxy resin is within this range, the desired effects of the present invention can be significantly achieved.

[0025] The epoxy equivalent of component (A) is preferably 50 g / eq. to 5000 g / eq., more preferably 50 g / eq. to 3000 g / eq., even more preferably 80 g / eq. to 2000 g / eq., and even more preferably 110 g / eq. to 1000 g / eq. By keeping it within this range, a cured product of the resin composition can be obtained with sufficient crosslink density. The epoxy equivalent is the mass of an epoxy resin containing one equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

[0026] The weight average molecular weight (Mw) of the component (A) is preferably 100 to 5000, more preferably 150 to 3000, and even more preferably 200 to 1500. The weight average molecular weight of the epoxy resin is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

[0027] The content of component (A) is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, based on 100% by mass of the nonvolatile components in the resin composition, and the upper limit is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less.

[0028] The content of component (A) is preferably 35% by mass or more, more preferably 40% by mass or more, and even more preferably 45% by mass or more, when the resin component in the resin composition is taken as 100% by mass, and the upper limit is preferably 65% ​​by mass or less, more preferably 60% by mass or less, and even more preferably 55% by mass or less.

[0029] In the present invention, the content of each component in the resin composition is a value when the nonvolatile components in the resin composition are 100 mass %, unless otherwise specified. The nonvolatile components refer to the components other than the solvent that constitute the resin composition. In addition, in the present invention, the resin component in the resin composition refers to the nonvolatile components of the resin composition that have a volume resistivity of 10 9 This represents the components excluding thermally conductive fillers with a conductivity of Ω·m or more.

[0030] <(B) Volume resistivity is 10 9 Thermally conductive filler with a thermal conductivity of Ω·m or more The resin composition contains, as the component (B), a resin having a volume resistivity of 10 9 It contains a thermally conductive filler with a resistance of Ω·m or more. By adding component (B) to the resin composition, it is possible to obtain a cured product with excellent thermal conductivity, mechanical properties, and insulating performance.

[0031] From the viewpoint of obtaining a cured product with excellent insulating properties, the volume resistivity of component (B) is set to 10 9 Ω·m or more, preferably 10 10 Ω·m or more, preferably 10 11 The upper limit is not particularly limited, but it is 10 15 Ω·m or less. The volume resistivity of component (B) is 10 9 Since the resistance is Ω·m or more, cases where component (B) is silicon carbide are excluded.

[0032] From the viewpoint of obtaining a cured product with high thermal conductivity, the thermal conductivity of component (B) is preferably 20 W / m K or more, more preferably 30 W / m K or more, even more preferably 50 W / m K or more, or 100 W / m K or more. There is no particular upper limit, but it can be set to 1000 W / m K or less.

[0033] Component (B) is contained in the resin composition in the form of particles, and is not particularly limited as long as its volume resistivity and thermal conductivity are within the above-mentioned ranges. Examples of materials for component (B) include silica, boron nitride, aluminum nitride, and aluminum oxide (alumina). In particular, from the viewpoint of significantly achieving the effects of the present invention, component (B) preferably contains one or more selected from silica, aluminum nitride, and aluminum oxide, and more preferably contains aluminum oxide.

[0034] The aspect ratio of component (B) is preferably 10 or less, more preferably 5 or less, and even more preferably 2 or less. The lower limit is preferably 1 or more, more preferably 1.1 or more, and even more preferably 1.2 or more, or more than 1.2. The aspect ratio is the value obtained by dividing the length of the major axis of the particles of component (B) by the length of the minor axis.

[0035] The component (B) in the resin composition of the first embodiment contains (B-1) a thermally conductive filler having a particle size of 10 μm or more, (B-2) a thermally conductive filler having a particle size of 1 μm or more but less than 10 μm, and (B-3) a thermally conductive filler having a particle size of less than 1 μm. Components (B-1) to (B-3) may be the same material or different materials.

[0036] The content of component (B-1), when the total volume of component (B) is taken as 100%, is preferably 50% by volume or more, more preferably 55% by volume or more, even more preferably 60% by volume or more, 65% by volume or more, or 80% by volume or more. The upper limit is preferably 95% by volume or less, more preferably 90% by volume or less, and even more preferably 85% by volume or less.

[0037] The content of component (B-2), when the total volume of component (B) is taken as 100%, is preferably 1% by volume or more, more preferably 5% by volume or more, and even more preferably 10% by volume or more, and the upper limit is preferably 40% by volume or less, more preferably 35% by volume or less, and even more preferably 30% by volume or less.

[0038] The content of component (B-3), based on the total volume of component (B) taken as 100%, is preferably 0.01% by volume or more, more preferably 0.05% by volume or more, and even more preferably 0.1% by volume or more, and the upper limit is preferably 10% by volume or less, more preferably 5% by volume or less, and even more preferably 4.5% by volume or less, or 4% by volume or less.

[0039] The amounts of components (B-1), (B-2), and (B-3) contained in component (B) can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, a particle size distribution of component (B) is created on a volume basis using a laser diffraction / scattering particle size distribution analyzer, and the amounts of components (B-1) to (B-3) can be measured from that particle size distribution. A preferred measurement sample is component (B) dispersed in water using ultrasonic waves. Examples of laser diffraction / scattering particle size distribution analyzers that can be used include the LA-500 manufactured by Horiba, Ltd. and the SALD-2200 manufactured by Shimadzu Corporation.

[0040] Component (B) can be obtained by mixing (B-1b) a thermally conductive filler with an average particle size of 10 μm or more, (B-2b) a thermally conductive filler with an average particle size of 1 μm or more but less than 10 μm, and (B-3b) a thermally conductive filler with an average particle size of less than 1 μm in appropriate amounts. However, component (B-1b) may contain particle sizes of 10 μm or more and particle sizes of less than 10 μm. Similarly, component (B-2b) may contain particle sizes of more than 10 μm and less than 1 μm in addition to particle sizes of 1 μm or more but less than 10 μm, and component (B-3b) may contain particle sizes of 1 μm or more in addition to particle sizes less than 1 μm. Therefore, the amount of component (B-1b) does not match the amount of component (B-1), the amount of component (B-2b) does not match the amount of component (B-2), and the amount of component (B-3b) does not match the amount of component (B-3). Therefore, to obtain a component (B) containing specific amounts of components (B-1), (B-2), and (B-3), it is usually necessary to understand the particle size distribution of each of components (B-1b) to (B-3b) and then set the amount based on those particle size distributions. Details of components (B-1b) to (B-3b) will be described later.

[0041] The component (B) in the resin composition of the first embodiment includes components (B-1) to (B-3). Therefore, the average particle size (D50) of component (B) is preferably 3 μm or more, more preferably 5 μm or more, and even more preferably 8 μm or more, and is preferably 20 μm or less, more preferably 18 μm or less, and even more preferably 16 μm or less.

[0042] The average particle size can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, a particle size distribution of the thermally conductive filler is created on a volume basis using a laser diffraction / scattering particle size distribution analyzer, and the median diameter is used as the average particle size. A preferred measurement sample is one in which each component is dispersed in water using ultrasonic waves. Examples of laser diffraction / scattering particle size distribution analyzers that can be used include the LA-500 manufactured by Horiba, Ltd. and the SALD2200 manufactured by Shimadzu Corporation.

[0043] The volume-based particle size distribution of component (B) typically follows a normal distribution. Therefore, component (B) may have a 10% particle size (D10) smaller than the average particle size (D50) of component (B), and a 90% particle size (D90) larger than the average particle size (D50) of component (B). Here, the 10% particle size (D10) refers to the particle size at which the cumulative volume from the smaller particle size side in the volume-based particle size distribution is 10%. Furthermore, the 90% particle size (D90) refers to the particle size at which the cumulative volume from the smaller particle size side in the volume-based particle size distribution is 90%. The 10% particle size (D10) and 90% particle size (D90) of component (B) can be measured from the volume-based particle size distribution measured by the laser diffraction / scattering method described above.

[0044] The 10% particle size (D10) of component (B) in the resin composition of the first embodiment is preferably 0.1 μm or more, more preferably 0.5 μm or more, even more preferably 1 μm or more, and is preferably 5 μm or less, more preferably 4 μm or less, even more preferably 3 μm or less, or 2 μm or less. The 10% particle size (D10) can be measured in the same manner as the average particle size (D50).

[0045] The 90% particle size (D90) of component (B) in the resin composition of the first embodiment is preferably 10 μm or more, more preferably 15 μm or more, even more preferably 20 μm or more, and preferably 40 μm or less, more preferably 35 μm or less, even more preferably 30 μm or less. The 90% particle size (D90) can be measured in the same manner as the average particle size (D50).

[0046] The difference (D50-D10) between the average particle size (D50) and the 10% particle size (D10) of the (B) component in the resin composition of the first embodiment is preferably 3 μm or more, more preferably 5 μm or more, even more preferably 7 μm or more, and is preferably 20 μm or less, more preferably 15 μm or less, even more preferably 12 μm or less.

[0047] The difference (D90-D50) between the average particle size (D50) and the 90% particle size (D90) of component (B) in the resin composition of the first embodiment is preferably 5 μm or more, more preferably 7 μm or more, even more preferably 10 μm or more, and is preferably 20 μm or less, more preferably 17 μm or less, even more preferably 15 μm or less.

[0048] The difference (D90-D10) between the 10% particle size (D10) and the 90% particle size (D90) of component (B) in the resin composition of the first embodiment is preferably 10 μm or more, more preferably 15 μm or more, even more preferably 20 μm or more, and is preferably 35 μm or less, more preferably 30 μm or less, even more preferably 25 μm or less.

[0049] The ratio (D50 / D10) of the average particle size (D50) to the 10% particle size (D10) of the (B) component in the resin composition of the first embodiment is preferably 3 or more, more preferably 4 or more, and even more preferably 5 or more, and is preferably 15 or less, more preferably 10 or less, and even more preferably 8 or less.

[0050] The ratio (D90 / D50) of the average particle size (D50) to the 10% particle size (D90) of component (B) in the resin composition of the first embodiment is preferably 1.1 or more, more preferably 1.3 or more, and even more preferably 1.5 or more, and is preferably 8 or less, more preferably 5 or less, and even more preferably 3 or less.

[0051] The ratio (D90 / D10) of the 10% particle size (D10) to the 90% particle size (D90) of the (B) component in the resin composition of the first embodiment is preferably 3 or more, more preferably 4 or more, and even more preferably 5 or more, and is preferably 25 or less, more preferably 20 or less, and even more preferably 17 or less.

[0052] The component (B) in the resin composition of the second embodiment preferably contains (B-1) a thermally conductive filler having a particle size of 10 μm or more, (B-2) a thermally conductive filler having a particle size of 1 μm or more but less than 10 μm, and (B-3) a thermally conductive filler having a particle size of less than 1 μm. The components (B-1) to (B-3) are as described above.

[0053] The 10% particle size (D10) of component (B) in the resin composition of the second embodiment is 0.1 μm or more, preferably 0.5 μm or more, and more preferably 1 μm or more. The upper limit is 5 μm or less, preferably 4 μm or less, more preferably 3 μm or less, or 2 μm or less. The method for measuring the 10% particle size (D10) is as described above.

[0054] The average particle size (D50) of component (B) in the resin composition of the second embodiment is 3 μm or more, preferably 5 μm or more, and more preferably 8 μm or more. The upper limit is 20 μm or less, preferably 18 μm or less, and more preferably 16 μm or less. The method for measuring the average particle size (D50) is as described above.

[0055] The 90% particle size (D90) of the (B) component in the resin composition of the second embodiment is 10 μm or more, preferably 15 μm or more, and more preferably 20 μm or more. The upper limit is 40 μm or less, preferably 35 μm or less, and more preferably 30 μm or less. The method for measuring the 90% particle size (D90) is as described above.

[0056] The preferred ranges of the 10% particle size (D10), 90% particle size (D90), D50-D10, D90-D50, D90-D10, D50 / D10, D90 / D50, and D90 / D10 of the component (B) in the resin composition of the second embodiment are the same as those of the component (B) in the resin composition of the first embodiment.

[0057] The specific surface area of ​​the component (B) in the resin compositions of the first and second embodiments is preferably 0.01 m from the viewpoint of obtaining a cured product with excellent thermal conductivity. 2 / g or more, more preferably 0.025m 2 / g or more, more preferably 0.05m 2 / g or more. The upper limit is preferably 30m 2 / g or less, more preferably 25m 2 / g or less, more preferably 20m 2 / g or less. The specific surface area of ​​component (B) can be measured by the nitrogen BET method. Specifically, it can be measured using an automatic specific surface area measuring device, such as the "Macsorb HM-1210" manufactured by Mountech Co., Ltd.

[0058] In order to enhance moisture resistance and dispersibility, the component (B) (or the components (B-1) to (B-3) when the components (B-1) to (B-3) are included) may be treated with one or more surface treatment agents such as an aminosilane coupling agent, an epoxysilane coupling agent, a mercaptosilane coupling agent, a silane coupling agent, an alkoxysilane compound, an organosilazane compound, or a titanate coupling agent. Examples of commercially available surface treatment agents include Shin-Etsu Chemical Co., Ltd.'s "KBM403" (3-glycidoxypropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM803" (3-mercaptopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM5783" (N-phenyl-3-aminooctyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd.'s "KBM103" (phenyltrimethoxysilane), and Shin-Etsu Chemical Co., Ltd.'s "KBM-4803" (long-chain epoxy-type silane coupling agent).

[0059] From the viewpoint of improving the dispersibility of component (B), the degree of surface treatment with the surface treatment agent is preferably 0.2 to 5 parts by mass, more preferably 0.2 to 3 parts by mass, and even more preferably 0.3 to 2 parts by mass, per 100 parts by mass of each component.

[0060] The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of ​​each component. From the viewpoint of improving the dispersibility of each component, the amount of carbon per unit surface area of ​​each component is set to 0.02 mg / m 2 More than 0.1 mg / m is preferable. 2 More preferably, 0.2 mg / m or more 2 On the other hand, from the viewpoint of suppressing an increase in melt viscosity, it is more preferable that the content is 1 mg / m 2 Preferably less than 0.8 mg / m 2 Less than 0.5 mg / m is more preferable. 2The following is even more preferred:

[0061] The carbon content per unit surface area of ​​component (B) can be measured after each surface-treated component is washed with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to component (B) that has been surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. The supernatant is removed, the solid content is dried, and then the carbon content per unit surface area of ​​each component can be measured using a carbon analyzer. An "EMIA-320V" manufactured by Horiba, Ltd., or the like can be used as the carbon analyzer.

[0062] The content (mass%) of component (B) is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, or even 80% by mass or more, based on 100% by mass of the nonvolatile components in the resin composition, and the upper limit is preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less.

[0063] The content (vol %) of component (B) is preferably 30% by volume or more, more preferably 40% by volume or more, and even more preferably 50% by volume or more, based on 100% by volume of the nonvolatile components in the resin composition, and the upper limit is preferably 80% by volume or less, more preferably 75% by volume or less, and even more preferably 70% by volume or less, or 65% by volume or less.

[0064] The volume content (vol %) of each component contained in the resin composition can be calculated from the mass of the component contained in the resin composition. Specifically, the volume of each component is calculated by dividing the mass by the specific gravity, and the volume content (vol %) can be calculated from the volume of each component thus calculated.

[0065] <(C) Thiol Compound> The resin composition contains a thiol compound (C) as component (C). This thiol compound (C) does not include compounds corresponding to the aforementioned components (A) and (B). Component (C) reacts with component (A) to cure the resin composition. By incorporating a combination of components (C) and (A) into the resin composition, the mechanical strength (elongation and modulus of elasticity) of the cured resin composition can be improved. Furthermore, incorporating component (C) into the resin composition reduces the viscosity of the resin composition, improving workability and enabling the resin composition to be cured at low temperatures. For resin compositions requiring high thermal conductivity, conventionally, curing agents such as acid anhydride-based liquid curing agents and phenol-based liquid curing agents have been used as components that react with component (A) to cure the resin composition. However, these curing agents have a high curing temperature, slowing the curing reaction. As a result, component (B) settles during heat curing of the resin composition, making it difficult to uniformly distribute component (B) throughout the resin composition. In the present invention, component (C) is used instead of the curing agent. Component (C) has a lower curing temperature than the curing agent, resulting in a faster curing rate. This prevents the sedimentation of component (B), enabling component (B) to be uniformly distributed throughout the resin composition. As a result, the mechanical strength of the cured product can be improved. Component (C) may be used alone or in combination of two or more types.

[0066] As component (C), a compound having a thiol group that can react with component (A) to cure the resin composition can be used. From the viewpoint of improving crosslink density, component (C) preferably has two or more thiol groups per molecule (bifunctional or more), more preferably three or more thiol groups (trifunctional or more), and preferably six or less thiol groups (hexafunctional or less), more preferably five or less thiol groups (pentafunctional or less).

[0067] The (C) component can be divided into (C-1) a trifunctional or higher non-ester thiol compound that does not have an ester structure (-C(=O)-O-), (C-2) an ester thiol compound that has an ester structure, and (C-3) a bifunctional non-ester thiol compound that does not have an ester structure (-C(=O)-O-). From the viewpoint of obtaining a cured product that has excellent moisture resistance and retention of adhesive strength, the (C) component contains at least the (C-1) component, and preferably uses the (C-1) component and the (C-2) component in combination. Note that the (C-1), (C-2), and (C-3) components may be collectively referred to as the (C) component.

[0068] Examples of the (C-1) component include alkyl isocyanurate-type thiol compounds, hydrocarbon-type thiol compounds, ether-type thiol compounds, alcohol-type thiol compounds, and alkyl glycoluril-type thiol compounds. Of these, alkyl isocyanurate-type thiol compounds are preferred as the (C-1) component, from the viewpoints of improving the compatibility of the (B) component with the resin component, improving wettability with the (B) component, and improving adhesion strength and elongation. The (C-1) component has three or more thiol groups per molecule (trifunctional or more), preferably six or fewer (hexafunctional or fewer), and more preferably five or fewer (pentafunctional or fewer), from the viewpoint of improving crosslink density.

[0069] An alkyl isocyanurate thiol compound is a compound in which an alkyl group is bonded to each of the nitrogen atoms at the 1-, 3-, and 5-positions of isocyanuric acid and which has one or more mercapto groups. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3, 2, or 3, or 3. Examples of alkyl isocyanurate thiol compounds include trifunctional alkyl isocyanurate thiol compounds such as tris(3-mercaptopropyl)isocyanurate, tris(2-mercaptopropyl)isocyanurate, and tris(2-mercaptoethyl)isocyanurate.

[0070] The hydrocarbon thiol compound is a compound in which one or more hydrogen atoms bonded to the same or different non-aromatic carbon atoms of a hydrocarbon are substituted with a mercapto group. Examples of the hydrocarbon thiol compound include trifunctional hydrocarbon thiol compounds such as 2-mercaptomethyl-1,3-propanedithiol, 2-ethyl-2-(mercaptomethyl)-1,3-propanedithiol, 2-mercaptomethyl-1,4-butanedithiol, and 1,2,3-propanetrithiol; and tetrafunctional hydrocarbon thiol compounds such as tetrakis(mercaptomethyl)methane and 2,2-bis(mercaptomethyl)-1,3-propanedithiol.

[0071] An ether-type thiol compound is a compound in which one or more hydrogen atoms bonded to the same or different non-aromatic carbon atoms of a hydrocarbon are replaced with mercapto groups, and one or more CH2 (secondary carbons) in the molecule are replaced with O. Examples of ether-type thiol compounds include (2-mercaptoethyl)(2,3-dimercaptopropyl) ether, trimethylolpropane tris(2-mercaptoethyl) ether, trimethylolethane tris(2-mercaptoethyl) ether, trimethylolpropane tris(3-mercaptopropyl) ether, trimethylolethane tris(3-mercaptopropyl) ether, trimethylolpropane tris(4-mercaptobutyl) ether, trimethylolethane tris(4-mercaptobutyl) ether, glycerin tris(3-mercaptopropyl) ether, glycerin tris(4-mercaptobutyl) ether, trimethylolpropane tris(2-mercaptopropyl) ether, trimethylolethane tris(2-mercaptopropyl) ether, trimethylolpropane tris(3-mercaptobutyl) ether, trimethylolethane Examples of such ether-type thiol compounds include trifunctional ether-type thiol compounds such as tantalum tris(3-mercaptobutyl) ether, glycerin tris(2-mercaptopropyl) ether, and glycerin tris(3-mercaptobutyl) ether; tetrafunctional ether-type thiol compounds such as bis(2,3-dimercaptopropyl) ether, pentaerythritol tetrakis(2-mercaptoethyl) ether, pentaerythritol tetrakis(3-mercaptopropyl) ether, pentaerythritol tetrakis(4-mercaptobutyl) ether, pentaerythritol tetrakis(2-mercaptopropyl) ether, and pentaerythritol tetrakis(3-mercaptobutyl) ether; and polyfunctional ether-type thiol compounds having five or more functionalities such as dipentaerythritol hexakis(3-mercaptopropyl) ether and dipentaerythritol hexakis(2-mercaptopropyl) ether.

[0072] An alcohol-type thiol compound is a compound in which one or more hydrogen atoms bonded to the same or different non-aromatic carbon atoms of a hydrocarbon are substituted with a mercapto group and one or more hydrogen atoms are substituted with a hydroxy group, and further in which one or more CH2 (secondary carbon) positions within the molecule may be replaced with O and / or S, and one or more CH2 (secondary carbon) and / or CH (tertiary carbon) positions may be replaced with NH and / or N. Examples of such compounds include bifunctional alcohol-type thiol compounds such as 1,3-dimercapto-2-propanol, 2,3-dimercapto-1-propanol, and 2,2-bis(mercaptomethyl)-1,3-propanediol; and trifunctional alcohol-type thiol compounds such as pentaerythritol tris(3-mercaptopropyl) ether and 3-mercapto-2,2-bis(mercaptomethyl)-1-propanol.

[0073] An alkyl glycoluril thiol compound is a compound having an alkyl group bonded to at least one of the 1-, 3-, 4-, 6-, 3a-, and 6a-positions of glycoluril (i.e., tetrahydroimidazo[4,5-d]imidazole-2,5(1H,3H)-dione) and one or more mercapto groups. Examples of alkyl glycoluril thiol compounds include trifunctional alkyl glycoluril thiol compounds such as 1,3,4-tris(2-mercaptoethyl)glycoluril and 1,3,4-tris(3-mercaptopropyl)glycoluril; and tetrafunctional alkyl glycoluril thiol compounds such as 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril and 1,3,4,6-tetrakis(3-mercaptopropyl)glycoluril.

[0074] Component (C-1) may be a commercially available product, such as "TMPIC" manufactured by Ajinomoto Fine-Techno Co., Inc., "SS32" manufactured by Kawaguchi Chemical Industry Co., Ltd., "TS-G" and "C3TS-G" manufactured by Shikoku Chemical Industry Co., Ltd., and "MR93" manufactured by Daito Kogyo Co., Ltd.

[0075] Examples of the component (C-2) include carboxylic acid ester type thiol compounds, carboxylic acid ester isocyanurate type thiol compounds, etc. Among these, carboxylic acid ester type thiol compounds are preferred as the component (C-2).

[0076] A carboxylic acid ester type thiol compound is a compound in which one or more hydrogen atoms bonded to the same or different non-aromatic carbon atoms of a hydrocarbon are substituted with a mercapto group, and at least one CH2 (secondary carbon) in the molecule is substituted with C(=O)-O. Examples of the carboxylic acid ester type thiol compound include monofunctional carboxylic acid ester type thiol compounds such as octyl thioglycolate, 3-mercaptopropionic acid, and ethylene glycol bisthioglycolate;Bis(2-mercaptoethyl) succinate, bis(2-mercaptoethyl) phthalate, bis(3-mercaptopropyl) phthalate, bis(4-mercaptobutyl) phthalate, ethylene glycol bis(mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), ethylene glycol bis(4-mercaptobutyrate), propylene glycol bis(3-mercaptopropionate), propylene glycol bis(4-mercaptobutyrate), diethylene Glycol bis(3-mercaptopropionate), diethylene glycol bis(4-mercaptobutyrate), tetraethylene glycol bis(3-mercaptopropionate), 1,4-butanediol bis(mercaptoacetate), 1,4-butanediol bis(3-mercaptopropionate), 1,4-butanediol bis(4-mercaptobutyrate), 1,8-octanediol bis(3-mercaptopropionate), 1,8-octanediol bis(4-mercaptopropionate) bis(1-mercaptoethyl) phthalate, bis(2-mercaptopropyl) phthalate, bis(3-mercaptobutyl) phthalate, ethylene glycol bis(2-mercaptopropionate), ethylene glycol bis(3-mercaptobutyrate), propylene glycol bis(2-mercaptopropionate), propylene glycol bis(3-mercaptobutyrate), diethylene glycol bis(2-mercaptopropionate), diethylene glycol bifunctional carboxylic acid ester-type thiol compounds such as tetraethylene glycol bis(3-mercaptobutyrate), tetraethylene glycol bis(2-mercaptopropionate), 1,4-butanediol bis(2-mercaptopropionate), 1,4-butanediol bis(3-mercaptobutyrate), 1,8-octanediol bis(2-mercaptopropionate), 1,8-octanediol bis(3-mercaptobutyrate), and 1,4-bis(3-mercaptobutyryloxy)butane;Trimethylolpropane tris(3-mercaptobutyrate), bis(2-mercaptoethyl) thiomalate, trimethylolpropane tris(mercaptoacetate), trimethylolethane tris(mercaptoacetate), trimethylolpropane tris(3-mercaptopropionate), trimethylolethane tris(3-mercaptopropionate), trimethylolpropane tris(4-mercaptobutyrate), trimethylol Trimethylolethane tris(4-mercaptobutyrate), glycerin tris(3-mercaptopropionate), glycerin tris(4-mercaptobutyrate), trimethylolpropane tris(2-mercaptopropionate), trimethylolethane tris(2-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), trimethylolethane tris(3-mercaptobutyrate), glycerin tris(2- trifunctional carboxylic acid ester-type thiol compounds such as 2,3-dimercaptosuccinic acid bis(2-mercaptoethyl) bis(mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(4-mercaptobutyrate), pentaerythritol tetrakis(2-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate; and polyfunctional carboxylic acid ester-type thiol compounds having five or more functionalities such as dipentaerythritol hexakis(3-mercaptopropionate) and dipentaerythritol hexakis(2-mercaptopropionate). Among these, the carboxylic acid ester type thiol compound is preferably either a trifunctional carboxylic acid ester type thiol compound or a tetrafunctional carboxylic acid ester type thiol compound from the viewpoint of improving adhesion strength and elongation.

[0077] A carboxylic acid ester isocyanurate type thiol compound is a compound in which an alkyl group is bonded to each of the nitrogen atoms at the 1st, 3rd, and 5th positions of isocyanuric acid (i.e., 1,3,5-triazine-2,4,6(1H,3H,5H)-trione) and which has one or more mercapto groups. Examples of carboxylic acid ester type thiol compounds include trifunctional carboxylic acid ester isocyanurate type thiol curing agents such as tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate, tris[2-(4-mercaptobutyryloxy)ethyl]isocyanurate, tris[2-(2-mercaptopropionyloxy)ethyl]isocyanurate, tris[2-(3-mercaptobutyryloxy)ethyl]isocyanurate, and 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione.

[0078] The component (C-2) may be a commercially available product, such as "OTG," "PEMP," "EGTG," "TMTG," "PETG," "3-MPA," or "TMTP" manufactured by Yodo Chemical Co., Ltd.; "TEMPIC," "DPMP," "PE-1," "BD-1," "NR-1," or "TPMB" manufactured by Sakai Chemical Industry Co., Ltd.; "TEMB" manufactured by Showa Denko KK; or "PE1" manufactured by Resonac Corporation.

[0079] Examples of the component (C-3) include alkyl isocyanurate-type thiol compounds, hydrocarbon-type thiol compounds, ether-type thiol compounds, thioether-type thiol compounds, amine-type thiol compounds, alcohol-type thiol compounds, and alkyl glycoluril-type thiol compounds.

[0080] A hydrocarbon thiol compound is a compound in which one or more hydrogen atoms bonded to the same or different non-aromatic carbon atoms of a hydrocarbon are substituted with a mercapto group. Examples of hydrocarbon thiol compounds include bifunctional hydrocarbon thiol compounds such as 1,4-butanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, 1,10-decanedithiol, 2,2-dimethylpropane-1,3-dithiol, 1,4-cyclohexanedithiol, 1,2-cyclohexanedithiol, and p-xylene-α,α'-dithiol.

[0081] An ether-type thiol compound is a compound in which one or more hydrogen atoms bonded to the same or different non-aromatic carbon atoms of a hydrocarbon are substituted with a mercapto group, and one or more CH2 (secondary carbon) in the molecule are substituted with O. Examples of ether-type thiol compounds include bifunctional ether-type thiol compounds such as 3,6-dioxa-1,8-octanedithiol, 3,4-dimethoxybutane-1,2-dithiol, 2,3-dimercaptopropyl methyl ether, and bis(2-mercaptoethyl) ether.

[0082] A thioether-type thiol compound is a compound in which one or more hydrogen atoms bonded to the same or different non-aromatic carbon atoms of a hydrocarbon are substituted with mercapto groups, and one or more CH2 (secondary carbons) in the molecule are substituted with S, and one or more CH2 (secondary carbons) in the molecule may also be substituted with O. The thioether-type thiol compound is preferably an aliphatic thioether-type thiol compound. Examples of thioether-type thiol compounds include bifunctional thioether-type thiol compounds such as 3,6-dithia-1,8-octanedithiol.

[0083] An amine-type thiol compound is a compound in which one or more hydrogen atoms bonded to the same or different non-aromatic carbon atoms of a hydrocarbon are substituted with a mercapto group, and one or more CH2 (secondary carbon) and / or CH (tertiary carbon) in the molecule are replaced with NH and / or N, and one or more CH2 (secondary carbon) in the molecule may be replaced with O and / or S. Examples of such compounds include bifunctional amine-type thiol compounds such as bis[4-(3-phenoxy-2-mercaptopropylamino)phenyl]methane, bis{4-[3-(4-methylphenoxy)-2-mercaptopropylamino]phenyl}methane, and 1,4-bis(3-phenoxy-2-mercaptopropylamino)benzene.

[0084] An alcohol-type thiol compound is a compound in which one or more hydrogen atoms bonded to the same or different non-aromatic carbon atoms of a hydrocarbon are substituted with a mercapto group and one or more hydrogen atoms are substituted with a hydroxy group, and further, one or more CH2 (secondary carbon) in the molecule may be substituted with O and / or S, and one or more CH2 (secondary carbon) and / or CH (tertiary carbon) may be substituted with NH and / or N. Examples of such compounds include bifunctional alcohol-type thiol compounds such as 1,3-dimercapto-2-propanol, 2,3-dimercapto-1-propanol, and 2,2-bis(mercaptomethyl)-1,3-propanediol.

[0085] An alkyl glycoluril thiol compound is a compound having an alkyl group bonded to at least one of the 1-, 3-, 4-, 6-, 3a-, and 6a-positions of glycoluril (i.e., tetrahydroimidazo[4,5-d]imidazole-2,5(1H,3H)-dione) and one or more mercapto groups. Examples of alkyl glycoluril thiol compounds include bifunctional alkyl glycoluril thiol compounds such as 1,3-bis(2-mercaptoethyl)glycoluril, 1,3-bis(3-mercaptopropyl)glycoluril, 1,4-bis(2-mercaptoethyl)glycoluril, 1,4-bis(3-mercaptopropyl)glycoluril, 1,6-bis(2-mercaptoethyl)glycoluril, and 1,6-bis(3-mercaptopropyl)glycoluril.

[0086] The (C) thiol compound is preferably in a liquid state. "Liquid" means that the compound has fluidity at room temperature (20°C) and atmospheric pressure (0.1 MPa). Preferably, the viscosity measured using an E-type viscometer at atmospheric pressure, 25°C, and a cone rotation speed of 2.0 rpm is 200,000 mPa s or less. An example of an E-type viscometer is the E-type viscometer RE-85U (cone rotor: 3°×R14) (manufactured by Toki Sangyo Co., Ltd.).

[0087] The molecular weight of the (C) thiol compound is not particularly limited, but is preferably at least 100, more preferably at least 150, even more preferably at least 200, and particularly preferably at least 250. The upper limit of the molecular weight of the (C) thiol compound is not particularly limited, but is preferably at most 1,500, more preferably at most 1,000, even more preferably at most 800, and particularly preferably at most 700.

[0088] The thiol equivalent of the (C) thiol compound is not particularly limited, but is preferably 50 to 1,000 g / eq., more preferably 50 to 500 g / eq., even more preferably 50 to 300 g / eq., and particularly preferably 50 to 200 g / eq. The thiol equivalent is the mass of the thiol compound per equivalent of a thiol group.

[0089] The ratio of the (A) epoxy resin to the (C) thiol compound, expressed as the ratio of [total number of epoxy groups in the (A) epoxy resin] to [total number of thiol groups in the (C) thiol compound], is preferably in the range of 1:0.1 to 1:5, more preferably 1:0.1 to 1:3, and even more preferably 1:0.5 to 1:2. The total number of epoxy groups in the epoxy resins is the sum of the solid mass of each (A) epoxy resin divided by the epoxy equivalent, for all epoxy resins. The total number of thiol groups in the (C) thiol compound is the sum of the solid mass of each (C) thiol compound divided by the thiol group equivalent, for all (C) components. By maintaining the ratio of the (A) epoxy resin to the (C) thiol compound within this range, the mechanical strength of the cured resin composition is further improved.

[0090] The content of component (C) is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, and is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, when the non-volatile components in the resin composition are taken as 100% by mass.

[0091] The content of component (C) is preferably 25% by mass or more, more preferably 30% by mass or more, and even more preferably 35% by mass or more, and is preferably 60% by mass or less, more preferably 55% by mass or less, and even more preferably 50% by mass or less, when the resin component in the resin composition is taken as 100% by mass.

[0092] The content of component (C-1) is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 3% by mass or more, and is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less, when the non-volatile components in the resin composition are taken as 100% by mass.

[0093] The content of the (C-1) component is preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more, and is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, when the resin component in the resin composition is taken as 100% by mass.

[0094] The content of component (C-2) is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 3% by mass or more, and is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less, when the non-volatile components in the resin composition are taken as 100% by mass.

[0095] The content of the (C-2) component is preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more, and is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, when the resin component in the resin composition is taken as 100% by mass.

[0096] The content of component (C-3) is preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 1.5% by mass or more, and is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less, when the non-volatile components in the resin composition are taken as 100% by mass.

[0097] The content of the (C-3) component is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 8% by mass or more, or 20% by mass or more, and is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less, when the resin component in the resin composition is taken as 100% by mass.

[0098] <(D) A dispersant in which all carbon atoms contained in one molecule are 8 to 60 and which has an unsaturated aliphatic skeleton having 8 to 54 carbon atoms> The resin composition may further contain, as an optional component, (D) a dispersant in which the total number of carbon atoms contained in each molecule is 8 to 60 and the total number of carbon atoms is 8 to 54. This dispersant in which the total number of carbon atoms contained in each molecule is 8 to 60 and the total number of carbon atoms is 8 to 54 does not include components (A) to (C). One type of component (D) may be used alone, or two or more types may be used in combination.

[0099] The component (D) can be a compound having 8 to 60 carbon atoms per molecule, and at least one unsaturated aliphatic skeleton having 8 to 54 carbon atoms per molecule. The total number of carbon atoms per molecule of component (D) is 8 or more, preferably 10 or more, more preferably 12 or more, and even more preferably 15 or more. The upper limit is 60 or less, preferably 54 or less, more preferably 50 or less, and even more preferably 40 or less, 30 or less, 20 or less, or 18 or less.

[0100] The number of carbon atoms in the unsaturated aliphatic skeleton of component (D) is 8 or more, preferably 10 or more, more preferably 12 or more, and even more preferably 15 or more. The upper limit is 54 or less, preferably 50 or less, more preferably 40 or less, and even more preferably 30 or less, 20 or less, or 18 or less. This number of carbon atoms does not include the number of carbon atoms in the carbonyl group and the number of carbon atoms in the substituents described below. One unsaturated aliphatic skeleton may be present in one molecule of component (D), but two or more may be present.

[0101] The unsaturated aliphatic skeleton refers to a skeleton containing a linear, branched, or cyclic non-aromatic unsaturated aliphatic hydrocarbon group. Examples of the unsaturated aliphatic hydrocarbon group include an alkenyl group, an alkapolyenyl group, and an alkynyl group, with an alkenyl group being preferred. Furthermore, the unsaturated aliphatic hydrocarbon group is preferably linear.

[0102] The number of unsaturated aliphatic skeletons contained in one molecule of component (D) is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6, or 1 to 3. The number of unsaturated aliphatic skeletons refers to the number of unsaturated aliphatic hydrocarbon groups.

[0103] The alkenyl group may be linear, branched, or cyclic, with linear being preferred. The alkenyl group has 8 or more carbon atoms, preferably 10 or more, more preferably 12 or more, and even more preferably 15 or more. The upper limit is 54 or less, preferably 50 or less, more preferably 40 or less, and even more preferably 30 or less, 20 or less, or 18 or less. Examples of the alkenyl group include an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, a hexadecenyl group, a heptadecenyl group, an octadecenyl group, a nonadecenyl group, and an icosenyl group.

[0104] The alkapolyenyl group may be linear, branched, or cyclic, with linear being preferred. The number of double bonds in the alkapolyenyl group is usually 2 or more, and may be 3 or more, and is preferably 10 or less, more preferably 6 or less, and particularly preferably 4 or less. The number of carbon atoms in the alkapolyenyl group is 8 or more, preferably 10 or more, more preferably 12 or more, and even more preferably 15 or more. The upper limit is 54 or less, preferably 50 or less, more preferably 40 or less, and even more preferably 30 or less, 20 or less, or 18 or less. Examples of the alkapolyenyl group include alkadienyl groups such as octadienyl, nonadienyl, decadienyl, undecadienyl, dodecadienyl, tridecadienyl, tetradecadienyl, pentadecadienyl, hexadecadienyl, heptadecadienyl, octadecadienyl, nonadecadienyl, and icosadienyl groups; and alkatrienyi groups such as heptatrienyl, octatrienyl, nonatrienyl, decatrienyl, undecatrienyl, dodecatrienyl, tridecatrienyl, tetradecatrienyl, pentadecatrienyl, hexadecatrienyl, heptadecatrienyl, octadecatrienyl, nonadecatrienyl, and icosatrienyl groups.

[0105] The alkynyl group may be linear, branched, or cyclic, with linear being preferred. The alkynyl group has 8 or more carbon atoms, preferably 10 or more, more preferably 12 or more, and even more preferably 15 or more. The upper limit is 54 or less, preferably 50 or less, more preferably 40 or less, and even more preferably 30 or less, 20 or less, or 18 or less. Examples of the alkynyl group include an octynyl group, a nonynyl group, a decynyl group, an undecynyl group, a dodecynyl group, a tridecynyl group, a tetradecynyl group, a pentadecynyl group, a hexadecynyl group, a heptadecynyl group, an octadecynyl group, a nonadecynyl group, and an icosynyl group.

[0106] The unsaturated aliphatic hydrocarbon group may have a substituent. The substituent is not particularly limited, and examples thereof include a halogen atom, —OH, and —OC.1-6 an alkyl group, -N(C 1-6 alkyl)2, C 1-6 alkyl group, C 6-10 an aryl group, -NH2, -CN, -C(O)O-C 1-6 alkyl group, -COOH, -C(O)H, -NO2, etc. Here, the term "C p-q "(p and q are positive integers and satisfy p < q.) represents that the number of carbon atoms of the organic group described immediately after this term is p to q. For example, the expression "C 1-6 alkyl group" indicates an alkyl group having 1 to 6 carbon atoms. The above substituents may further have substituents (hereinafter sometimes referred to as "secondary substituents"). As the secondary substituents, the same ones as the above substituents may be used unless otherwise specified.

[0107] Component (D) is a fatty acid ester formed by ester-bonding a fatty acid having an unsaturated aliphatic skeleton and a polyhydric alcohol. That is, component (D) preferably is a fatty acid ester having an unsaturated aliphatic skeleton with 8 to 60 carbon atoms in total per molecule and 8 to 54 carbon atoms.

[0108] Examples of the fatty acid having an unsaturated aliphatic skeleton include myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, eicosenoic acid, erucic acid, nervonic acid, linoleic acid, α-linolenic acid, eicosadienoic acid, docosadienoic acid, linolenic acid, α-linolenic acid, γ-linolenic acid, pinolenic acid, eleostearic acid, α-eleostearic acid, β-eleostearic acid, mead acid, dihomo-γ-linolenic acid, eicosatrienoic acid, stearidonic acid, arachidonic acid, eicosatetraenoic acid, adrenic acid, bosseopentaenoic acid, eicosapentaenoic acid, osbond acid, sardine acid, tetracosapentaenoic acid, tetracosapentaenoic acid, docosahexaenoic acid, nisinic acid, etc. Among them, oleic acid is preferable as the fatty acid having an unsaturated aliphatic skeleton.

[0109] The dihydric or higher alcohol is preferably a dihydric to decahydric alcohol, more preferably a dihydric to hexahydric alcohol, and even more preferably a dihydric to pentahydric alcohol. Examples of such alcohols include glycols such as ethylene glycol, propylene glycol, and diethylene glycol; trihydric alcohols such as glycerin; tetrahydric alcohols such as sorbitol and pentaerythritol; and hexahydric alcohols such as sorbitol. Among these, the dihydric or higher alcohol is preferably any of propylene glycol, glycerin, and sorbitan, and more preferably propylene glycol.

[0110] Component (D) may be a commercially available product, such as "PO-100V," "SP-O30V," "OL-200V," "OL-200VM," or "O-80V," manufactured by Riken Vitamin Co., Ltd.

[0111] The molecular weight of component (D) is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more, and is preferably 2000 or less, more preferably 1500 or less, and even more preferably 1000 or less.

[0112] The content of component (D) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, based on 100% by mass of the nonvolatile components of the resin composition, and the upper limit is preferably 1% by mass or less, more preferably 0.5% by mass or less, and even more preferably 0.3% by mass or less.

[0113] The content of component (D) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more, when the nonvolatile components of the resin components of the resin composition are taken as 100% by mass, and the upper limit is preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less.

[0114] <(E) Curing accelerator> The resin composition may further contain a curing accelerator (E) as an optional component in combination with the above-described components (A) to (C). The curing accelerator (E) as component (E) does not include components (A) to (D) described above. The curing accelerator (E) functions as a curing catalyst that accelerates the curing of the epoxy resin (A). One type of curing accelerator (E) may be used alone, or two or more types may be used in combination in any ratio.

[0115] As the (E) curing accelerator, a latent curing accelerator is preferably used. A latent curing accelerator is an important component, particularly when preparing a one-component resin composition, and does not contribute to the curing of the (A) epoxy resin at room temperature (25°C), but has the function of accelerating the curing of the (A) epoxy resin when heated.

[0116] The latent curing accelerator may be a liquid latent curing accelerator or a solid dispersion type latent curing accelerator, but a solid dispersion type latent curing accelerator is more preferred.

[0117] A liquid latent curing accelerator is a compound that is a liquid that is soluble in epoxy resin at room temperature (25°C) and functions as a curing accelerator for epoxy resin when heated. Examples of liquid latent curing accelerators include, but are not limited to, ionic liquids.

[0118] Examples of cations that constitute ionic liquids include ammonium-based cations such as imidazolium ions, piperidinium ions, pyrrolidinium ions, pyrazonium ions, guanidinium ions, pyridinium ions, and hydrocarbon group (alkyl group, phenyl group, combinations thereof, etc.)-substituted cations thereof; phosphonium-based cations such as tetraalkylphosphonium ions; and sulfonium-based cations such as trialkylsulfonium ions.

[0119] Examples of anions that constitute ionic liquids include halide anions such as fluoride ion, chloride ion, bromide ion, and iodide ion; alkyl sulfate anions such as methanesulfonate ion; fluorine-containing compound anions such as trifluoromethanesulfonate ion, hexafluorophosphonate ion, trifluorotris(pentafluoroethyl)phosphonate ion, bis(trifluoromethanesulfonyl)imide ion, trifluoroacetate ion, and tetrafluoroborate ion; phenol ion, 2-methoxyphenol ion, Examples include phenolic anions such as 2,6-di-tert-butylphenol ion; acidic amino acid ions such as aspartate ion and glutamate ion; neutral amino acid ions such as glycine ion, alanine ion and phenylalanine ion; N-acyl amino acid ions such as N-benzoylalanine ion, N-acetylphenylalanine ion, N-acetylglycine ion and N-acetylglycine ion; and carboxylic acid anions such as formate ion, lactate ion, tartrate ion, hippurate ion, N-methyluric acid and benzoate ion.

[0120] A solid dispersion type latent curing accelerator is a compound that is a solid that is insoluble in epoxy resin at room temperature (25°C), but becomes soluble in epoxy resin when heated, and functions as a curing accelerator for epoxy resin.

[0121] Examples of solid-dispersed latent curing accelerators include, but are not limited to, imidazole compounds that are solid at room temperature (25°C) and solid-dispersed amine adduct latent curing accelerators.

[0122] Examples of imidazole compounds that are solid at room temperature (25° C.) include 2-heptadecylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-undecylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4-benzyl-5-hydroxymethylimidazole, 2,4-diamino-6-[2-(2-methyl-1-imidazolyl)ethyl]-1,3,5-triazine, 2,4-diamino-6-[2-(2-methyl Examples of suitable imidazole derivatives include, but are not limited to, N-(2-methylimidazolyl-1-ethyl)urea, N-(2-methylimidazolyl-1-ethyl)-1,3,5-triazine·isocyanuric acid adduct, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole-trimellitate, 1-cyanoethyl-2-phenylimidazole-trimellitate, and N-(2-methylimidazolyl-1-ethyl)urea.

[0123] Suitable examples of the solid-dispersion amine adduct latent curing accelerator include at least one selected from the group consisting of amine epoxy adduct latent curing accelerators, urea adduct latent curing accelerators of amine compounds, and compounds obtained by addition reaction of an isocyanate compound with the hydroxyl group of an epoxy adduct, and amine epoxy adduct latent curing accelerators are preferred.

[0124] Examples of epoxy compounds that can be used as one of the raw materials for producing epoxy adducts of amine compounds include, but are not limited to, polyglycidyl ethers obtained by reacting epichlorohydrin with polyhydric phenols such as bisphenol A, bisphenol F, catechol, and resorcinol, or polyhydric alcohols such as glycerin and polyethylene glycol; glycidyl ether esters obtained by reacting epichlorohydrin with hydroxycarboxylic acids such as p-hydroxybenzoic acid and β-hydroxynaphthoic acid; polyglycidyl esters obtained by reacting epichlorohydrin with polycarboxylic acids such as phthalic acid and terephthalic acid; glycidyl amine compounds obtained by reacting epichlorohydrin with 4,4'-diaminodiphenylmethane or m-aminophenol; polyfunctional epoxy compounds such as epoxidized phenol novolac resins, epoxidized cresol novolac resins, and epoxidized polyolefins; and monofunctional epoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, and glycidyl methacrylate.

[0125] The amine compound used as a raw material for producing the solid dispersion amine adduct latent curing accelerator has at least one active hydrogen atom capable of addition reaction with an epoxy group in the molecule, and at least one functional group selected from primary amino groups, secondary amino groups, and tertiary amino groups in the molecule. Examples of such amine compounds include aliphatic amine compounds such as diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, and 4,4'-diamino-dicyclohexylmethane; aromatic amine compounds such as 4,4'-diaminodiphenylmethane and 2-methylaniline; and nitrogen-containing heterocyclic compounds such as 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline, piperidine, and piperazine. However, these are not limited thereto.

[0126] Among these, compounds having a tertiary amino group in the molecule are particularly useful as raw materials for providing latent curing accelerators with excellent curing acceleration capabilities. Examples of such compounds include primary or secondary amines having a tertiary amino group in the molecule, such as amine compounds such as dimethylaminopropylamine, diethylaminopropylamine, di-n-propylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, and N-methylpiperazine, and imidazole compounds such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, and 2-phenylimidazole; 2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol, and 1-(2-hydroxy-3-phenoxypropyl)-2-methylimidazole. Imidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-ethyl-4-methylimidazole, 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-butoxypropyl)-2-ethyl-4-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-phenylimidazoline, 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazoline, 2-(dimethylaminomethyl) Phenol, 2,4,6-tris(dimethylaminomethyl)phenol, N-β-hydroxyethylmorpholine, 2-dimethylaminoethanethiol, 2-mercaptopyridine, 2-benzimidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 4-mercaptopyridine, N,N-dimethylaminobenzoic acid, N,N-dimethylglycine, nicotinic acid, isonicotinic acid, picolinic acid, N,N-dimethylglycine hydrazide, N,N-dimethyl Examples include alcohols, phenols, thiols, carboxylic acids and hydrazides having a tertiary amino group in the molecule, such as ethylpropionic acid hydrazide, nicotinic acid hydrazide, isonicotinic acid hydrazide, etc.

[0127] When producing a latent curing accelerator by addition reaction of an epoxy compound with an amine compound, an active hydrogen compound having two or more active hydrogen atoms in the molecule can also be reacted. Examples of such active hydrogen compounds include polyhydric phenols such as bisphenol A, bisphenol F, bisphenol S, hydroquinone, catechol, resorcinol, pyrogallol, and phenol novolac resin, polyhydric alcohols such as trimethylolpropane, polycarboxylic acids such as adipic acid and phthalic acid, 1,2-dimercaptoethane, 2-mercaptoethanol, 1-mercapto-3-phenoxy-2-propanol, mercaptoacetic acid, anthranilic acid, and lactic acid, but are not limited thereto.

[0128] Examples of isocyanate compounds that can be used as raw materials for producing the solid dispersion-type amine adduct latent curing accelerator include monofunctional isocyanate compounds such as n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, and benzyl isocyanate; polyfunctional isocyanate compounds such as hexamethylene diisocyanate, toluylene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, and bicycloheptane triisocyanate; and terminal isocyanate group-containing compounds obtained by reacting these polyfunctional isocyanate compounds with active hydrogen compounds. Examples of such a terminal isocyanate group-containing compound include, but are not limited to, an addition compound having a terminal isocyanate group obtained by reacting toluylene diisocyanate with trimethylolpropane, and an addition compound having a terminal isocyanate group obtained by reacting toluylene diisocyanate with pentaerythritol.

[0129] Furthermore, examples of urea compounds used as raw materials for producing the solid dispersion-type amine adduct latent curing accelerator include, but are not limited to, urea and thiourea.

[0130] The solid-dispersion amine adduct latent curing accelerator can be easily obtained, for example, by appropriately mixing the above-mentioned production raw materials, reacting them at a temperature of from room temperature to 200°C, cooling to solidify them, and then pulverizing them; or by reacting them in a solvent such as methyl ethyl ketone, dioxane, or tetrahydrofuran, removing the solvent, and then pulverizing the solid content.

[0131] Commercially available solid dispersion type amine adduct latent curing accelerators include, for example, "Amicure PN-FJ" (manufactured by Ajinomoto Fine-Techno Co., Ltd.), "Amicure PN-23" (manufactured by Ajinomoto Fine-Techno Co., Ltd.), "Amicure PN-H" (manufactured by Ajinomoto Fine-Techno Co., Ltd.), "Hardener X-3661S" (manufactured by ACS Co., Ltd.), "Hardener X-3670S" (manufactured by ACS Co., Ltd.), "FXR-1081" (manufactured by T&K TOKA Co., Ltd.), "Fujicure FXR-1000" (manufactured by T&K TOKA Co., Ltd.), "Fujicure FXR-1030" (manufactured by T&K TOKA Co., Ltd.), "Novacure HX-3721" (manufactured by Asahi Kasei Corporation), "HX-3722" (manufactured by Asahi Kasei Corporation), and "Novacure HX-3742" (manufactured by Asahi Kasei Corporation).

[0132] The content of the (E) curing accelerator is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.2% by mass or more, and is preferably 3% by mass or less, more preferably 1% by mass or less, and even more preferably 0.5% by mass or less, based on 100% by mass of the non-volatile components in the resin composition.

[0133] The content of the (E) curing accelerator is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, based on 100% by mass of the resin component in the resin composition, and the upper limit is preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 5% by mass or less.

[0134] <(F) Storage stabilizer> The resin composition may further contain a storage stabilizer (F) as an optional component in combination with the above-described components (A) to (C). The storage stabilizer (F) as component (F) does not include those corresponding to the above-described components (A) to (E). The storage stabilizer (F) is used to improve the life of the resin composition. One type of storage stabilizer (F) may be used alone, or two or more types may be used in combination in any ratio.

[0135] (F) Storage stabilizers include, for example, borate compounds, titanate compounds, aluminate compounds, zirconate compounds, isocyanate compounds, carboxylic acids, acid anhydrides, and organic mercapto acids.

[0136] Examples of borate compounds include trimethyl borate, triethyl borate (TEB), tri-n-propyl borate, triisopropyl borate, tri-n-butyl borate, tripentyl borate, triallyl borate, trihexyl borate, tricyclohexyl borate, trioctyl borate, trinonyl borate, tridecyl borate, tridodecyl borate, trihexadecyl borate, trioctadecyl borate, tris(2-ethylhexyloxy)borane, bis(1,4,7,10-tetraoxaundecyl)(1,4,7,10,13-pentaoxatetradecyl)(1,4,7-trioxaundecyl)borane, tribenzyl borate, triphenyl borate, tri-o-tolyl borate, tri-m-tolyl borate, and triethanolamine borate.

[0137] Examples of titanate compounds include tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, and tetraoctyl titanate.

[0138] Examples of the aluminate compound include triethyl aluminate, tripropyl aluminate, triisopropyl aluminate, tributyl aluminate, and trioctyl aluminate.

[0139] Examples of the zirconate compound include tetraethyl zirconate, tetrapropyl zirconate, tetraisopropyl zirconate, and tetrabutyl zirconate.

[0140] Examples of isocyanate compounds include n-butyl isocyanate, isopropyl isocyanate, 2-chloroethyl isocyanate, phenyl isocyanate, p-chlorophenyl isocyanate, benzyl isocyanate, hexamethylene diisocyanate, 2-ethylphenyl isocyanate, 2,6-dimethylphenyl isocyanate, and tolylene diisocyanate (e.g., 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate). isocyanate), 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, tolidine diisocyanate, isophorone diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate, bicycloheptane triisocyanate, and the like.

[0141] Examples of carboxylic acids include saturated aliphatic monobasic acids such as formic acid, acetic acid, propionic acid, butyric acid, caproic acid, and caprylic acid; unsaturated aliphatic monobasic acids such as acrylic acid, methacrylic acid, and crotonic acid; halogenated fatty acids such as monochloroacetic acid and dichloroacetic acid; monobasic oxyacids such as glycolic acid and lactic acid; aliphatic aldehyde acids and ketone acids such as glyoxalic acid and acetic acid; aliphatic polybasic acids such as oxalic acid, malonic acid, succinic acid, and maleic acid; aromatic monobasic acids such as benzoic acid, halogenated benzoic acids, toluic acid, phenylacetic acid, cinnamic acid, and mandelic acid; and aromatic polybasic acids such as phthalic acid and trimesic acid.

[0142] Examples of acid anhydrides include aliphatic or aliphatic polybasic acid anhydrides such as succinic anhydride, dodecynylsuccinic anhydride, maleic anhydride, an adduct of methylcyclopentadiene and maleic anhydride, hexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride; and aromatic polybasic acid anhydrides such as phthalic anhydride, trimellitic anhydride, and pyrrolimellitic anhydride.

[0143] Examples of mercapto organic acids include mercapto aliphatic monocarboxylic acids such as mercaptoacetic acid, mercaptopropionic acid, mercaptobutyric acid, mercaptosuccinic acid, and dimercaptosuccinic acid; mercapto aliphatic monocarboxylic acids obtained by an esterification reaction between a hydroxy organic acid and a mercapto organic acid; and mercapto aromatic monocarboxylic acids such as mercaptobenzoic acid.

[0144] As the (F) storage stabilizer, among these, from the viewpoints of versatility, high safety, and improving storage stability, borate compounds are preferred, triethyl borate, tri-n-propyl borate, triisopropyl borate, and tri-n-butyl borate are more preferred, and triethyl borate is even more preferred.

[0145] The content of the (F) storage stabilizer is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, and even more preferably 0.05% by mass or more, based on 100% by mass of the nonvolatile components in the resin composition. The upper limit is preferably 1% by mass or less, more preferably 0.5% by mass or less, and even more preferably 0.3% by mass or less.

[0146] The content of the (F) storage stabilizer is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and even more preferably 0.3% by mass or more, based on 100% by mass of the resin component in the resin composition, and the upper limit is preferably 3% by mass or less, more preferably 1.5% by mass or less, and even more preferably 1% by mass or less.

[0147] <(G) Silane coupling agent> The resin composition may further contain a silane coupling agent (G) as an optional component in combination with the above-described components (A) to (C). The silane coupling agent (G) as component (G) does not include those corresponding to the above-described components (A) to (F). The silane coupling agent (G) may be used alone, or two or more types may be combined in any ratio.

[0148] The (G) silane coupling agent is not a surface treatment agent that treats the surface of the (B) component, but a silane coupling agent that does not treat the surface of the (B) component. The (G) silane coupling agent may be the same as or different from the surface treatment agent that treats the surface of the (B) component. Furthermore, the (G) silane coupling agent may be used alone or in combination of two or more. The (G) silane coupling agent is as described above.

[0149] The content of the (G) silane coupling agent is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, and even more preferably 0.05% by mass or more, based on 100% by mass of the nonvolatile components in the resin composition. The upper limit is preferably 1% by mass or less, more preferably 0.5% by mass or less, and even more preferably 0.3% by mass or less.

[0150] The content of the (G) silane coupling agent is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and even more preferably 0.3% by mass or more, based on 100% by mass of the resin component in the resin composition, and the upper limit is preferably 3% by mass or less, more preferably 1.5% by mass or less, and even more preferably 1% by mass or less.

[0151] <(H) Optional Additives> The resin composition may further contain (H) an optional additive as an optional non-volatile component in addition to the above-mentioned components (A) to (C). As the optional additive (F), for example, silicon carbide or the like having a volume resistivity of 10 9Thermally conductive fillers with a conductivity of less than Ω·m; curing agents (excluding those corresponding to component (C)); thermoplastic resins; polymerization initiators; organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; thickeners such as bentone and montmorillonite; antifoaming agents such as silicone-based antifoaming agents, acrylic-based antifoaming agents, fluorine-based antifoaming agents, and vinyl resin-based antifoaming agents; benzotriazole-based ultraviolet absorbers UV absorbers such as urea silanes; adhesion improvers such as triazole adhesion promoters, tetrazole adhesion promoters, and triazine adhesion promoters; antioxidants such as hindered phenol antioxidants; fluorescent brighteners such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; flame retardants such as phosphorus-based flame retardants (e.g., phosphate ester compounds, phosphazene compounds, phosphinic acid compounds, and red phosphorus), nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, and inorganic flame retardants (e.g., antimony trioxide); photopolymerization initiation aids such as tertiary amines; photosensitizers such as pyrarizones, anthracenes, coumarins, xanthones, and thioxanthones; and the like. (H) Optional additives may be used alone or in combination of two or more. It should be noted that the optional additives may be used in combination of two or more types, each of which has a volume resistivity of 10 9 The content of the thermally conductive filler having a volume resistivity of less than Ω·m is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less, 0.5% by mass or less, 0.1% by mass or less, or 0% by mass, when the nonvolatile components in the resin composition are taken as 100% by mass. 9 It is particularly preferable that the thermally conductive filler having a conductivity of less than Ω·m is not contained.

[0152] <(I) Solvent> In addition to the nonvolatile components (A) to (H), the composition may further contain a solvent (I) as an optional volatile component. The solvent may be used alone or in combination of two or more types in any ratio.

[0153] (I) As the solvent, an organic solvent is usually used. Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, and anisole; alcohol solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, and methoxypropion. ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, diethylene glycol monobutyl ether (butyl carbitol); amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile, propionitrile; aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane, methylcyclohexane; and aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene.

[0154] The amount of (I) solvent is preferably 3% by mass or less, more preferably 1% by mass or less, even more preferably 0.5% by mass or less, even more preferably 0.1% by mass or less, and even more preferably 0.01% by mass or less, relative to 100% by mass of non-volatile components in the resin composition, and it is particularly preferable that no solvent is included (0% by mass).

[0155] <Physical properties and applications of resin compositions> The cured product obtained by thermally curing the resin composition at 80°C for 60 minutes exhibits excellent thermal conductivity. This results in an insulating layer with high thermal conductivity. The thermal conductivity is preferably 1.0 W / m·K or higher, more preferably 1.5 W / m·K or higher, and even more preferably 2.0 W / m·K or higher. The upper limit of the thermal conductivity is not particularly limited, but it can be set to 10 W / m·K or lower. The thermal conductivity can be measured according to the method described in the Examples below.

[0156] The cured product obtained by thermally curing the resin composition at 80°C for 60 minutes exhibits high elongation. That is, an insulating layer exhibiting high elongation is obtained. The elongation of the cured product is preferably 2% or more, more preferably 3% or more, and even more preferably 3.5% or more, or 4% or more. There is no particular upper limit, but it can be 10% or less. The elongation can be measured according to the method described in the examples below.

[0157] The cured product obtained by thermally curing the resin composition at 80°C for 60 minutes exhibits a low modulus of elasticity. That is, an insulating layer exhibiting a low modulus of elasticity is obtained. The modulus of elasticity of the cured product is preferably less than 6000 MPa, more preferably 5500 MPa or less, and even more preferably 5000 MPa or less. The lower limit is not particularly limited, but may be 0.1 MPa or more. The modulus of elasticity can be measured according to the method described in the Examples below. Since the cured product exhibits a low modulus of elasticity, a cured product with excellent impact resistance can be obtained.

[0158] The cured product obtained by thermally curing the resin composition at 80°C for 60 minutes exhibits high volume resistivity. In other words, it provides an insulating layer with excellent insulating performance. The volume resistivity is preferably 1.0 x 10 14The upper limit of the volume resistivity is not particularly limited, but is preferably 1.0×10 15 The volume resistivity can be measured according to the method described in the examples below.

[0159] The cured product obtained by thermally curing the resin composition at 80°C for 60 minutes usually exhibits high adhesive strength. That is, it produces an insulating layer with excellent adhesive strength. The adhesive strength is measured by applying the resin composition to the polished surface of a mild steel plate to obtain a test piece. Two test pieces are attached together so that the resin compositions overlap, and then pressed together, and the resin composition is thermally cured at 80°C for 60 minutes. The tensile shear adhesive strength of the test piece obtained by thermally curing the resin composition is measured in accordance with JIS-K-6850. At this time, the tensile shear adhesive strength is preferably 4 N / mm 2 More than 5N / mm 2 That's all. There is no particular upper limit, but the maximum is 20N / mm 2 The adhesive strength can be measured according to the method described in the examples below.

[0160] The cured product obtained by thermally curing the resin composition at 80°C for 60 minutes usually exhibits high moisture resistance. That is, it results in an insulating layer with excellent moisture resistance. The test piece used to measure the adhesive strength is left at 85°C and 85% RH for 250 hours. After leaving the test piece, the tensile shear adhesive strength is measured. At this time, the tensile shear adhesive strength of the test piece after leaving it is preferably 3 / mm 2 More preferably, 4N / mm 2 That's all. There is no particular upper limit, but the maximum is 20N / mm 2 The moisture resistance can be measured according to the method described in the examples below.

[0161] A cured product obtained by thermally curing a resin composition at 80°C for 60 minutes typically exhibits high adhesion strength retention. That is, an insulating layer with excellent adhesion strength retention is obtained. The adhesion strength retention can be determined by dividing the tensile shear adhesion strength measured in the moisture resistance evaluation by the tensile shear adhesion strength measured in the adhesion strength evaluation. The adhesion strength retention is preferably 60% or more, more preferably 80% or more. There is no particular upper limit, but it can be 100% or less. The adhesion strength retention can be determined according to the method described in the Examples below.

[0162] The resin composition of the present invention can produce a cured product with high thermal conductivity, insulating properties, and elongation, and a low elastic modulus. Therefore, the resin composition of the present invention can be suitably used as a resin composition for bonding a heat sink to an electronic component (a resin composition for heat sink adhesion), a resin composition for forming an insulating layer of a semiconductor chip package (a resin composition for an insulating layer of a semiconductor chip package), or a resin composition for forming an insulating layer of a circuit board (including a printed wiring board) (a resin composition for an insulating layer of a circuit board). It can also be suitably used as a resin composition for forming an interlayer insulating layer on which a conductor layer is formed by plating (a resin composition for an interlayer insulating layer of a circuit board on which a conductor layer is formed by plating). It can also be suitably used as a resin composition for encapsulating a semiconductor chip (a resin composition for semiconductor chip encapsulation) or a resin composition for forming wiring on a semiconductor chip (a resin composition for forming semiconductor chip wiring).

[0163] [Method of producing resin composition] The method for producing a resin composition of the present invention includes a step of mixing (A) an epoxy resin, (B-1b) a thermally conductive filler having an average particle size of 10 μm or more, (B-2b) a thermally conductive filler having an average particle size of 1 μm or more and less than 10 μm, (B-3b) a thermally conductive filler having an average particle size of less than 1 μm, and (C) a thiol compound, wherein the (C) component includes at least (C-1) a non-ester type thiol compound, and the (C-1) component is trifunctional or higher.

[0164] As described above, the component (B) contained in the resin composition includes components (B-1) to (B-3), and the component (B) can be obtained by mixing (B-1b) a thermally conductive filler having an average particle size of 10 μm or more, (B-2b) a thermally conductive filler having an average particle size of 1 μm or more but less than 10 μm, and (B-3b) a thermally conductive filler having an average particle size of less than 1 μm in an appropriate quantitative ratio.

[0165] As can be seen from the range of the average particle size, (B-1b) thermally conductive filler having an average particle size of 10 μm or more includes (B-1) thermally conductive filler having a particle size of 10 μm or more.

[0166] The average particle diameter (D50) of the thermally conductive filler (B-1b) having an average particle diameter of 10 μm or more is 10 μm or more, preferably 13 μm or more, more preferably 15 μm or more, and even more preferably 20 μm or more, and is preferably 45 μm or less, more preferably 40 μm or less, and even more preferably 35 μm or less. The method for measuring the average particle diameter is as described above.

[0167] The 10% particle size (D10) of the thermally conductive filler (B-1b) having an average particle size of 10 μm or more is preferably 1 μm or more, more preferably 2 μm or more, even more preferably 3 μm or more, and preferably 10 μm or less, more preferably 9 μm or less, even more preferably 8 μm or less. The method for measuring the average particle size is as described above. The 10% particle size D10 represents the particle size at which the integrated volume accumulated from the smallest particle size in the volume-based particle size distribution is 10%, and can be measured in the same manner as the average particle size (D50).

[0168] The average particle diameter (D90) of the thermally conductive filler (B-1b) having an average particle diameter of 10 μm or more is preferably 20 μm or more, more preferably 25 μm or more, even more preferably 30 μm or more, and preferably 60 μm or less, more preferably 50 μm or less, and even more preferably 40 μm or less. The method for measuring the average particle diameter is as described above. The 10% particle diameter D90 represents the particle diameter at which the integrated volume accumulated from the smallest particle diameter in the volume-based particle diameter distribution is 90%, and can be measured in the same manner as the average particle diameter (D50).

[0169] The content (volume %) of component (B-1b) used in the production method of the resin composition is preferably 65% ​​by volume or more, more preferably 70% by volume or more, even more preferably 75% by volume or more, or 80% by volume or more, and is preferably 95% by volume or less, more preferably 90% by volume or less, and even more preferably 85% by volume or less, when the total amount of components (B-1b) to (B-3b) (the total content of components (B)) is taken as 100% by volume. By producing the resin composition by mixing components (B-1b) so that the content falls within this range, it is possible to keep the content of component (B-1) within the above range.

[0170] The content (% by mass) of component (B-1b) used in the method for producing a resin composition is preferably 65% ​​by mass or more, more preferably 70% by mass or more, even more preferably 75% by mass or more, or 80% by mass or more, and is preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less, when the total amount of components (B-1b) to (B-3b) (the total content of components (B)) is taken as 100% by mass. By producing a resin composition by mixing components (B-1b) so that the content falls within this range, it is possible to keep the content of component (B-1) within the above range.

[0171] The content (mass %) of the (B-1b) component used in the resin composition production method is preferably 50 mass % or more, more preferably 55 mass % or more, and even more preferably 60 mass % or more, and is preferably 85 mass % or less, more preferably 80 mass % or less, and even more preferably 75 mass % or less, when the nonvolatile components in the resin composition are taken as 100 mass %. By producing the resin composition by mixing so that the content of the (B-1b) component falls within this range, it is possible to keep the content of the (B-1) component within the above range.

[0172] The content (vol %) of the (B-1b) component used in the method for producing the resin composition is preferably 30 vol % or more, more preferably 35 vol % or more, and even more preferably 40 vol % or more, when the non-volatile components in the resin composition are taken as 100 vol %, and is preferably 65 vol % or less, more preferably 60 vol % or less, and even more preferably 55 vol % or less.

[0173] The component (B-1b) may be a commercially available product, such as "AS-20," "AS-10," "AS-30," or "AS-40" manufactured by Resonac Corporation, "AA-10" or "AA-18" manufactured by Sumitomo Chemical Co., Ltd., "SSC-A15" manufactured by Shinano Electric Refining Co., Ltd., or "DAW-45" manufactured by Denka Company, Limited.

[0174] As can be seen from the range of average particle size, (B-2b) thermally conductive filler having an average particle size of 1 μm or more and less than 10 μm includes (B-2) thermally conductive filler having a particle size of 1 μm or more and less than 10 μm.

[0175] (B-2b) The thermally conductive filler having an average particle size of 1 μm or more and less than 10 μm has an average particle size (D50) of 1 μm or more, preferably 1.3 μm or more, more preferably 1.5 μm or more, and even more preferably 2 μm or more. The upper limit is less than 10 μm, preferably 7 μm or less, more preferably 5 μm or less, and even more preferably 4 μm or less. The method for measuring the average particle size is as described above.

[0176] The 10% particle size (D10) of the thermally conductive filler (B-2b) having an average particle size of 1 μm or more and less than 10 μm is preferably 0.3 μm or more, more preferably 0.4 μm or more, even more preferably 0.5 μm or more, and preferably 2.0 μm or less, more preferably 1.9 μm or less, even more preferably 1.8 μm or less. The method for measuring the average particle size is as described above.

[0177] The average particle diameter (D90) of the (B-2b) thermally conductive filler having an average particle diameter of 1 μm or more and less than 10 μm is preferably 3 μm or more, more preferably 4 μm or more, and even more preferably 5 μm or more, and is preferably 10 μm or less, more preferably 9 μm or less, and even more preferably 8 μm or less. The method for measuring the average particle diameter is as described above.

[0178] The content (volume %) of component (B-2b) used in the production method of the resin composition is preferably 1% by volume or more, more preferably 5% by volume or more, and even more preferably 10% by volume or more, and is preferably 30% by volume or less, more preferably 25% by volume or less, and even more preferably 20% by volume or less, when the total amount of components (B-1b) to (B-3b) is taken as 100% by volume. By producing the resin composition by mixing components (B-2b) so that the content falls within this range, it is possible to keep the content of component (B-2) within the above range.

[0179] The content (mass %) of component (B-2b) used in the production method of the resin composition is preferably 1 mass % or more, more preferably 5 mass % or more, and even more preferably 10 mass % or more, and is preferably 30 mass % or less, more preferably 25 mass % or less, and even more preferably 20 mass % or less, when the total amount of components (B-1b) to (B-3b) is taken as 100 mass %. By producing the resin composition by mixing components (B-2b) so that the content falls within this range, it is possible to keep the content of component (B-2) within the above range.

[0180] The content (mass %) of the (B-2b) component used in the resin composition production method is preferably 1 mass % or more, more preferably 3 mass % or more, and even more preferably 5 mass % or more, and is preferably 25 mass % or less, more preferably 20 mass % or less, and even more preferably 15 mass % or less, when the nonvolatile components in the resin composition are taken as 100 mass %. By producing the resin composition by mixing so that the content of the (B-2b) component falls within this range, it is possible to keep the content of the (B-2) component within the above range.

[0181] The content (vol %) of the (B-2b) component used in the method for producing the resin composition is preferably 5 vol % or more, more preferably 10 vol % or more, and even more preferably 15 vol % or more, when the non-volatile components in the resin composition are taken as 100 vol %, and is preferably 45 vol % or less, more preferably 40 vol % or less, and even more preferably 35 vol % or less.

[0182] The component (B-2b) may be a commercially available product, such as "CB-P02" manufactured by Resonac, "HF-01Dc" manufactured by Tokuyama, "SO-C6" manufactured by Admattex, and "AA-2" and "AA-5" manufactured by Sumitomo Chemical.

[0183] When the non-volatile components of the resin composition produced are taken as 100 mass%, the content (mass%) of the (B-1b) component is taken as b1, and the content (mass%) of the (B-2b) component is taken as b2. Then, b1 / b2 is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more, and is preferably 25 or less, more preferably 20 or less, and even more preferably 15 or less.

[0184] As can be seen from the range of the average particle size, (B-3b) thermally conductive filler having an average particle size of less than 1 μm includes (B-3) thermally conductive filler having a particle size of less than 1 μm.

[0185] The average particle diameter (D50) of the thermally conductive filler (B-3b) having an average particle diameter of less than 1 μm is less than 1 μm, preferably 0.8 μm or less, more preferably 0.7 μm or less, and even more preferably 0.5 μm or less. The lower limit is preferably 0.01 μm or more, more preferably 0.05 μm or more, and even more preferably 0.1 μm or more. The method for measuring the average particle diameter is as described above.

[0186] The 10% particle size (D10) of the thermally conductive filler (B-3b) having an average particle size of less than 1 μm is preferably 0.01 μm or more, more preferably 0.05 μm or more, even more preferably 0.1 μm or more, and is preferably 0.3 μm or less, more preferably 0.25 μm or less, even more preferably 0.2 μm or less. The average particle size is measured by the method described above.

[0187] The average particle diameter (D90) of the thermally conductive filler (B-3b) having an average particle diameter of less than 1 μm is preferably 0.65 μm or more, more preferably 0.7 μm or more, even more preferably 0.75 μm or more, and is preferably 0.9 μm or less, more preferably 0.85 μm or less, even more preferably 0.8 μm or less. The method for measuring the average particle diameter is as described above.

[0188] The content (volume %) of component (B-3b) used in the production method of the resin composition is preferably 0.01 volume % or more, more preferably 0.05 volume % or more, and even more preferably 0.1 volume % or more, and is preferably 5 volume % or less, more preferably 4.5 volume % or less, and even more preferably 4 volume % or less, when the total amount of components (B-1b) to (B-3b) is taken as 100 volume %. By producing the resin composition by mixing components (B-3b) so that the content falls within this range, it becomes possible to keep the content of component (B-3) within the above range.

[0189] The content (mass %) of component (B-3b) used in the production method of the resin composition is preferably 0.01 mass % or more, more preferably 0.05 mass % or more, and even more preferably 0.1 mass % or more, and is preferably 5 mass % or less, more preferably 4.5 mass % or less, and even more preferably 4 mass % or less, when the total amount of components (B-1b) to (B-3b) is taken as 100 mass %. By producing the resin composition by mixing components (B-3b) so that the content falls within this range, it is possible to keep the content of component (B-3) within the above range.

[0190] The content (mass%) of the (B-3b) component used in the resin composition production method is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, even more preferably 0.1 mass% or more, 0.5 mass% or more, or 1 mass% or more, and is preferably 20 mass% or less, more preferably 15 mass% or less, even more preferably 10 mass% or less, or 5 mass% or less, when the nonvolatile components in the resin composition are taken as 100 mass%. By producing a resin composition by mixing components (B-3b) so that the content falls within this range, it is possible to keep the content of the (B-3) component within the above range.

[0191] The content (vol %) of the (B-3b) component used in the method for producing the resin composition is preferably 0.05 vol % or more, more preferably 0.5 vol % or more, and even more preferably 1 vol % or more, when the non-volatile components in the resin composition are taken as 100 vol %, and is preferably 8 vol % or less, more preferably 7 vol % or less, and even more preferably 6 vol % or less.

[0192] The component (B-3b) may be a commercially available product, such as "ASFP20" manufactured by Resonac Corporation, or "AA-03," "AA-05," or "AA-07" manufactured by Sumitomo Chemical Co., Ltd.

[0193] When the content (mass%) of the (B-1b) component is b1 and the content (mass%) of the (B-3b) component is b3, where the non-volatile components of the resin composition produced are taken as 100 mass%, b1 / b3 is preferably 1 or more, more preferably 2 or more, even more preferably 3 or more, 5 or more, 10 or more, or 20 or more, and is preferably 1000 or less, more preferably 50 or less, and even more preferably 40 or less.

[0194] When the content (mass%) of the (B-2b) component is b2 and the content (mass%) of the (B-3b) component is b3, where the non-volatile components of the resin composition produced are taken as 100 mass%, b2 / b3 is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more, and is preferably 500 or less, more preferably 200 or less, and even more preferably 100 or less, 50 or less, 30 or less, 20 or less, or 10 or less.

[0195] The method for producing a resin composition includes mixing an epoxy resin (A) as component (A) and a thiol compound (C) as component (C) in addition to components (B-1b) to (B-3b). Component (C) contains at least a non-esterified thiol compound (C-1), and component (C-1) is trifunctional or higher. The epoxy resin (A) and the thiol compound (C) are as described above, and the amounts of the epoxy resin (A) and the thiol compound (C) mixed in the method for producing a resin composition are the same as the contents of the epoxy resin (A) and the thiol compound (C) contained in the resin composition.

[0196] When the content (mass%) of the (B-1b) component when the non-volatile components of the resin composition to be produced are taken as 100 mass%, b1 is the content (mass%) of the (C) component when the non-volatile components of the resin composition to be produced are taken as 100 mass%, and c is the content (mass%) of the (C) component when the non-volatile components of the resin composition to be produced are taken as 100 mass%, then b1 / c is preferably 1 or more, more preferably 3 or more, and even more preferably 5 or more, and is preferably 25 or less, more preferably 20 or less, and even more preferably 15 or less, or 10 or less.

[0197] When the content (mass%) of the (B-2b) component when the non-volatile components of the resin composition to be produced are taken as 100 mass%, is b2, and when the content (mass%) of the (C) component when the non-volatile components of the resin composition to be produced are taken as 100 mass%, is c, b2 / c is preferably 0.1 or more, more preferably 0.3 or more, and even more preferably 0.5 or more, and is preferably 15 or less, more preferably 10 or less, and even more preferably 5 or less.

[0198] When the content (mass%) of the (B-3b) component when the non-volatile components of the resin composition to be produced are taken as 100 mass%, is b3, and when the content (mass%) of the (C) component when the non-volatile components of the resin composition to be produced are taken as 100 mass%, is c, b3 / c is preferably 0.01 or more, more preferably 0.05 or more, and even more preferably 0.1 or more, and is preferably 5 or less, more preferably 4 or less, and even more preferably 3 or less, or 1 or less.

[0199] When the content (mass%) of the (B-1b) component when the non-volatile components of the resin composition to be produced are taken as 100 mass%, b1 is the content (mass%) of the (C-1) component when the non-volatile components of the resin composition to be produced are taken as 100 mass%, and c1 is the content (mass%) of the (C-1) component when the non-volatile components of the resin composition to be produced are taken as 100 mass%, then b1 / c1 is preferably 1 or more, more preferably 5 or more, and even more preferably 10 or more, and is preferably 35 or less, more preferably 30 or less, and even more preferably 25 or less, 20 or less, or 15 or less.

[0200] When the content (mass%) of the (B-2b) component when the non-volatile components of the resin composition to be produced are taken as 100 mass%, b2 is the content (mass%) of the (B-2b) component when the non-volatile components of the resin composition to be produced are taken as 100 mass%, and c1 is the content (mass%) of the (C-1) component when the non-volatile components of the resin composition to be produced are taken as 100 mass%, then b2 / c1 is preferably 0.5 or more, more preferably 1 or more, and even more preferably 1.5 or more, and is preferably 10 or less, more preferably 8 or less, and even more preferably 5 or less.

[0201] When the content (mass%) of the (B-3b) component when the non-volatile components of the resin composition to be produced are taken as 100 mass%, is b3, and the content (mass%) of the (C-1) component when the non-volatile components of the resin composition to be produced are taken as 100 mass%, c1, the ratio b3 / c1 is preferably 0.01 or more, more preferably 0.05 or more, and even more preferably 0.1 or more, and is preferably 5 or less, more preferably 3 or less, and even more preferably 1 or less.

[0202] When the content (mass%) of the (B-1b) component when the non-volatile components of the resin composition to be produced are taken as 100 mass%, b1 is the content (mass%) of the (C-2) component when the non-volatile components of the resin composition to be produced are taken as 100 mass%, and c1 is the content (mass%) of the (C-2) component when the non-volatile components of the resin composition to be produced are taken as 100 mass%, then b1 / c2 is preferably 1 or more, more preferably 5 or more, and even more preferably 10 or more, and is preferably 50 or less, more preferably 45 or less, and even more preferably 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, or 15 or less.

[0203] When the content (mass%) of the (B-2b) component when the non-volatile components of the resin composition to be produced are taken as 100 mass%, b2 is the content (mass%) of the (B-2b) component when the non-volatile components of the resin composition to be produced are taken as 100 mass%, and c1 is the content (mass%) of the (C-2) component when the non-volatile components of the resin composition to be produced are taken as 100 mass%, then b2 / c2 is preferably 0.5 or more, more preferably 1 or more, and even more preferably 1.5 or more, and is preferably 10 or less, more preferably 8 or less, and even more preferably 5 or less.

[0204] When the content (mass%) of the (B-3b) component when the non-volatile components of the resin composition to be produced are taken as 100 mass%, is b3, and the content (mass%) of the (C-2) component when the non-volatile components of the resin composition to be produced are taken as 100 mass%, c1, the ratio b3 / c2 is preferably 0.01 or more, more preferably 0.05 or more, and even more preferably 0.1 or more, and is preferably 5 or less, more preferably 3 or less, and even more preferably 1 or less.

[0205] In the method for producing the resin composition, in addition to the above-described components (A) to (C), optional components (D) to (I) may be further mixed in. Components (D) to (I) are as described above, and the amounts of components (D) to (I) mixed in the method for producing the resin composition are the same as the contents of components (D) to (I) contained in the resin composition.

[0206] The resin composition can be produced, for example, by adding the ingredients to a preparation vessel in any order and / or simultaneously, partially or entirely, and mixing them. The temperature can be appropriately set during the process of adding and mixing each ingredient, and heating and / or cooling may be performed temporarily or throughout the process. Stirring or shaking may be performed during the process of adding and mixing each ingredient. The resin composition may be stirred or shaken using a stirring or shaking device such as a mixer during or after the addition and mixing to achieve uniform dispersion. Simultaneously with the stirring or shaking, degassing may be performed under low-pressure conditions, such as under vacuum. The mixing temperature may be, for example, 10 to 40°C. The stirring speed during mixing may be, for example, 100 to 10,000 rpm. The mixing time may be, for example, 10 seconds to 10 minutes.

[0207] [Resin sheet] The resin sheet of the present invention includes a support and a resin composition layer formed from the resin composition of the present invention and provided on the support.

[0208] From the viewpoint of thinning, the thickness of the resin composition layer is preferably 200 μm or less, more preferably 150 μm or less, and even more preferably 100 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but can usually be 1 μm or more, 5 μm or more, 10 μm or more, etc.

[0209] Examples of the support include films made of plastic materials, metal foils, and release papers, with films made of plastic materials and metal foils being preferred.

[0210] When a film made of a plastic material is used as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"), polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, with inexpensive polyethylene terephthalate being particularly preferred.

[0211] When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, with copper foil being preferred. The copper foil may be a foil made of a single metal, copper, or an alloy of copper and another metal (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.).

[0212] The surface of the support that is to be bonded to the resin composition layer may be subjected to a matte treatment, a corona treatment, or an antistatic treatment.

[0213] The support may also be a support with a release layer, which has a release layer on the surface that bonds to the resin composition layer. Examples of the release agent used in the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. Commercially available products may also be used as the support with a release layer, including, for example, "SK-1," "AL-5," and "AL-7" manufactured by Lintec Corporation, "Lumirror T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Limited, and "Uni-Peel" manufactured by Unitika Limited, which are PET films having a release layer primarily composed of an alkyd resin-based release agent.

[0214] The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably 10 μm to 60 μm. When a support with a release layer is used, it is preferable that the thickness of the entire support with a release layer is in the above range.

[0215] In one embodiment, the resin sheet may further include other layers as necessary. Examples of such other layers include a protective film conforming to the support and provided on the surface of the resin composition layer that is not bonded to the support (i.e., the surface opposite the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, adhesion of dust and the like to the surface of the resin composition layer and scratches can be suppressed.

[0216] The resin sheet can be produced, for example, by preparing a resin composition-containing varnish by dissolving the resin composition in an organic solvent, applying this resin composition-containing varnish to a support using a die coater or the like, and then drying it to form a resin composition layer.

[0217] The organic solvent is the same as the solvent that may be contained in the resin composition, as described above.

[0218] Drying may be carried out by known methods such as heating or hot air blowing. Drying conditions are not particularly limited, but drying is carried out so that the content of organic solvent in the resin composition layer becomes 10% by mass or less, preferably 5% by mass or less. Although it varies depending on the boiling point of the organic solvent in the resin composition-containing varnish, for example, when a resin composition-containing varnish containing 30% by mass to 60% by mass of organic solvent is used, the resin composition layer can be formed by drying at 50°C to 150°C for 3 to 10 minutes.

[0219] The resin sheet can be stored in a rolled state. When the resin sheet has a protective film, it can be used by peeling off the protective film.

[0220] [Circuit board] The circuit board of the present invention includes an insulating layer formed from a cured product of the resin composition of the present invention. The method for manufacturing a circuit board of the present invention comprises the steps of: (1) a step of preparing a substrate with a wiring layer, the substrate having a substrate and a wiring layer provided on at least one surface of the substrate; (2) applying a resin composition onto the substrate with the wiring layer so that the wiring layer is embedded therein, and then thermally curing the resin composition to form an insulating layer; (3) A process for connecting wiring layers to each other is included. The method for manufacturing a circuit board may also include (4) the step of removing the base material.

[0221] Step (3) is not particularly limited as long as it can connect the wiring layers to each other, but it is preferably at least one of the steps of forming a via hole in an insulating layer to form a wiring layer, and polishing or grinding the insulating layer to expose the wiring layer.

[0222] <Process (1)> Step (1) is a step of preparing a substrate with a wiring layer, which has a substrate and a wiring layer provided on at least one surface of the substrate. Typically, a substrate with a wiring layer has a first metal layer and a second metal layer, which are part of the substrate, on both sides of the substrate, and a wiring layer on the surface of the second metal layer opposite the substrate-side surface. Specifically, a dry film (photosensitive resist film) is laminated on the substrate, and a patterned dry film is formed by exposing and developing the film under specified conditions using a photomask. The developed patterned dry film is used as a plating mask to form a wiring layer by electroplating, and then the patterned dry film is peeled off.

[0223] Examples of the substrate include glass epoxy substrates, metal substrates (such as stainless steel and cold-rolled steel sheet (SPCC)), polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates, and the substrate surface may have a metal layer such as copper foil formed thereon. Furthermore, a peelable metal layer such as a first metal layer and a second metal layer (for example, an ultra-thin copper foil with a carrier foil manufactured by Mitsui Mining & Smelting Co., Ltd., product name "Micro Thin") may be formed thereon.

[0224] The dry film is not particularly limited as long as it is a photosensitive dry film made of a photoresist composition, and examples thereof include dry films of novolac resin, acrylic resin, etc. Commercially available dry films may also be used.

[0225] The substrate and the dry film may be laminated by a vacuum lamination method. In the vacuum lamination method, the thermocompression temperature is preferably in the range of 60°C to 160°C, more preferably 80°C to 140°C, the thermocompression pressure is preferably in the range of 0.098MPa to 1.77MPa, more preferably 0.29MPa to 1.47MPa, and the thermocompression time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. The lamination is preferably carried out under reduced pressure conditions of 13 hPa or less.

[0226] After laminating the dry film on the substrate, the dry film is exposed to light and developed under predetermined conditions using a photomask to form a desired pattern.

[0227] Regarding the lines (circuit width) and spaces (width between circuits) of the wiring layer, the line and space (L / S) is not particularly limited, but is preferably 20 / 20 μm or less (i.e., a pitch of 40 μm or less), more preferably 10 / 10 μm or less, even more preferably 5 / 5 μm or less, even more preferably 1 / 1 μm or less, and particularly preferably 0.5 / 0.5 μm or more. The pitch does not need to be uniform throughout the wiring layer. The minimum pitch of the wiring layer may be 40 μm or less, 36 μm or less, or 30 μm or less.

[0228] After forming the pattern of the dry film, a wiring layer is formed and the dry film is peeled off. Here, the wiring layer can be formed by a plating method using the dry film with the desired pattern formed as a plating mask.

[0229] The conductive material used for the wiring layer is not particularly limited. In a preferred embodiment, the wiring layer contains one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The wiring layer may be a single metal layer or an alloy layer. Examples of alloy layers include those formed from an alloy of two or more metals selected from the above group (e.g., nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy). Among these, from the viewpoints of versatility in wiring layer formation, cost, ease of patterning, etc., single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or alloy layers of nickel-chromium alloy, copper-nickel alloy, or copper-titanium alloy are preferred. Single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or alloy layers of nickel-chromium alloy are more preferred, and single metal layers of copper are even more preferred.

[0230] The thickness of the wiring layer depends on the desired design of the wiring board, but is preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm, and even more preferably 10 to 20 μm or 15 to 20 μm. When the step (3) involves polishing or grinding the insulating layer to expose the wiring layer and connect the wiring layers to each other, it is preferable that the thickness of the wiring that connects the layers be different from that of the wiring that does not connect the layers. The thickness of the wiring layer can be adjusted by repeating the above-mentioned pattern formation. The thickness of the thickest wiring layer (conductive pillar) among the wiring layers depends on the desired design of the wiring board, but is preferably 2 μm or more and 100 μm or less. The wiring that connects the layers to each other may be convex.

[0231] After the wiring layer is formed, the dry film is peeled off. The dry film can be peeled off using, for example, an alkaline peeling solution such as a sodium hydroxide solution. If necessary, unnecessary wiring patterns can be removed by etching or the like to form a desired wiring pattern. The pitch of the wiring layer to be formed is as described above.

[0232] <Process (2)> In step (2), a resin composition is applied onto the substrate with a wiring layer so that the wiring layer is embedded, and then thermally cured to form an insulating layer. More specifically, a resin composition is applied onto the wiring layer of the substrate with a wiring layer obtained in step (1) above, and then thermally cured to form an insulating layer.

[0233] The wiring layer and the resin composition can be applied, for example, by injecting the resin composition with a syringe and pressing the resin composition to form a resin composition layer of uniform thickness.

[0234] After applying a resin composition onto the substrate with a wiring layer so that the wiring layer is embedded, the resin composition layer is thermally cured to form an insulating layer. The thermal curing conditions for the resin composition layer vary depending on the type of resin composition, but for example, the curing temperature can be in the range of 50°C to 240°C, and the curing time can be in the range of 5 minutes to 120 minutes. Before thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature.

[0235] After the resin composition layer is thermally cured to form the insulating layer, the surface of the insulating layer may be polished. The polishing method is not particularly limited, and the surface of the insulating layer may be polished by a known method, for example, using a surface grinder.

[0236] <Process (3)> Step (3) is a step of connecting the wiring layers to each other. Specifically, it is a step of forming a via hole in an insulating layer and forming a conductor layer to connect the wiring layers to each other. Alternatively, it is a step of polishing or grinding the insulating layer to expose the wiring layer to connect the wiring layers to each other.

[0237] When a process of forming a via hole in an insulating layer and forming a conductor layer to connect wiring layers to each other is adopted, the formation of the via hole is not particularly limited, and examples thereof include laser irradiation, etching, mechanical drilling, etc., but laser irradiation is preferred. This laser irradiation can be performed using any suitable laser processing machine that uses a carbon dioxide laser, YAG laser, excimer laser, etc. as a light source.

[0238] The conditions for laser irradiation are not particularly limited, and laser irradiation can be carried out by any suitable process according to a conventional method depending on the selected means.

[0239] The shape of the via hole, that is, the shape of the outline of the opening when viewed in the extending direction, is not particularly limited, but is generally circular (approximately circular).

[0240] After the via holes are formed, a so-called desmearing process, which is a process for removing smears from the via holes, may be performed. When the conductive layer described below is formed by a plating process, the via holes may be subjected to, for example, a wet desmearing process, and when the conductive layer is formed by a sputtering process, a dry desmearing process such as a plasma treatment process may be performed. The desmearing process may also serve as a roughening treatment process.

[0241] Before forming the conductor layer, the via hole and the insulating layer may be subjected to a roughening treatment. The roughening treatment may be performed using a known procedure and conditions that are usually used. An example of a dry roughening treatment is a plasma treatment, and an example of a wet roughening treatment is a method in which a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid are performed in this order.

[0242] The arithmetic mean roughness (Ra) of the insulating layer surface after roughening treatment is preferably 350 nm or more, more preferably 400 nm or more, and even more preferably 450 nm or more. The upper limit is preferably 700 nm or less, more preferably 650 nm or less, and even more preferably 600 nm or less. The arithmetic mean roughness (Ra) can be measured, for example, using a non-contact surface roughness meter.

[0243] After the via holes are formed, a conductor layer is formed. The conductor material constituting the conductor layer is not particularly limited, and the conductor layer can be formed by any suitable conventional method such as plating, sputtering, or vapor deposition, and is preferably formed by plating. In a preferred embodiment, for example, a conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer using a conventional technique such as a semi-additive method or a full-additive method. The conductor layer may have a single-layer structure or a multi-layer structure in which two or more single metal layers or alloy layers made of different types of metals or alloys are laminated.

[0244] In detail, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer, exposing a portion of the plating seed layer corresponding to the desired wiring pattern. An electrolytic plating layer is formed on the exposed plating seed layer by electrolytic plating. At this time, via holes may be filled by electrolytic plating along with the formation of the electrolytic plating layer to form filled vias. After the electrolytic plating layer is formed, the mask pattern is removed. Thereafter, unnecessary plating seed layer is removed by etching or the like, thereby forming a conductor layer having the desired wiring pattern. Note that when forming the conductor layer, the dry film used to form the mask pattern is the same as the dry film described above.

[0245] The conductor layer may include not only linear wiring but also, for example, electrode pads (lands) on which external terminals can be mounted, etc. The conductor layer may also be composed of only electrode pads.

[0246] Alternatively, the conductor layer may be formed by forming an electrolytic plating layer and a filled via without using a mask pattern after forming a plating seed layer, and then patterning by etching.

[0247] When a process of polishing or grinding an insulating layer to expose a wiring layer and connect the wiring layers to each other is adopted, the method of polishing or grinding the insulating layer is not particularly limited as long as it can expose the wiring layer and the polished or ground surface is horizontal. Conventional polishing or grinding methods can be applied, such as chemical mechanical polishing using a chemical mechanical polishing device, mechanical polishing using a buff, or surface grinding using a rotating grinding wheel. As with the process of forming via holes in an insulating layer and forming a conductor layer to connect the wiring layers to each other, a smear removal process and a roughening process may be performed, and a conductor layer may be formed. Furthermore, it is not necessary to expose the entire wiring layer; only a portion of the wiring layer may be exposed.

[0248] <Process (4)> Step (4) is a step of removing the substrate to form the circuit board of the present invention. The method for removing the substrate is not particularly limited. In a preferred embodiment, the substrate is peeled from the circuit board at the interface between the first and second metal layers, and the second metal layer is etched away with, for example, a copper chloride aqueous solution. If necessary, the substrate may be peeled off while the conductor layer is protected with a protective film.

[0249] [Semiconductor chip package] A first aspect of the semiconductor chip package of the present invention is a semiconductor chip package in which a semiconductor chip is mounted on the circuit board. The semiconductor chip package can be manufactured by bonding the semiconductor chip to the circuit board.

[0250] The bonding conditions are not particularly limited as long as the terminal electrodes of the semiconductor chip are conductively connected to the circuit wiring of the circuit board, and known conditions used in flip-chip mounting of semiconductor chips may be used. Alternatively, the semiconductor chip and the circuit board may be bonded via an insulating adhesive.

[0251] In a preferred embodiment, the semiconductor chip is pressure-bonded to the circuit board under pressure conditions such as a pressure-bonding temperature in the range of 120°C to 240°C (preferably 130°C to 200°C, more preferably 140°C to 180°C) and a pressure-bonding time in the range of 1 second to 60 seconds (preferably 5 seconds to 30 seconds).

[0252] In another preferred embodiment, the semiconductor chip is bonded to the circuit board by reflow. The reflow conditions can be, for example, in the range of 120°C to 300°C.

[0253] After bonding the semiconductor chip to the circuit board, it is also possible to obtain a semiconductor chip package by, for example, filling the semiconductor chip with a molded underfill material. The method of filling with the molded underfill material can be carried out by a known method. The molded underfill material may be a resin composition.

[0254] A second aspect of the semiconductor chip package of the present invention is, for example, a semiconductor chip package (fan-out type WLP). The semiconductor chip package (fan-out type WLP) is a semiconductor chip package in which the sealing layer is manufactured using the resin composition of the present invention. The semiconductor chip package includes a semiconductor chip, a sealing layer formed so as to cover the periphery of the semiconductor chip, a rewiring formation layer (insulating layer) on the side of the semiconductor chip opposite to the side covered by the sealing layer, a conductor layer (rewiring layer), a solder resist layer, and bumps. A method for manufacturing such a semiconductor chip package is as follows: (A) a step of laminating a temporary fixing film on a substrate; (B) a step of temporarily fixing a semiconductor chip on a temporary fixing film; (C) applying the resin composition of the present invention onto a semiconductor chip and thermally curing it to form an encapsulating layer; (D) peeling the substrate and the temporary fixing film from the semiconductor chip; (E) a step of forming a rewiring formation layer (insulating layer) on the surface from which the base material and the temporary fixing film of the semiconductor chip have been peeled off; (F) forming a conductor layer (rewiring layer) on the rewiring formation layer (insulating layer); and (G) forming a solder resist layer on the conductor layer. The method for manufacturing a semiconductor chip package also includes: (H) The method may include a step of dicing the plurality of semiconductor chip packages into individual semiconductor chip packages.

[0255] <Process (A)> Step (A) is a step of laminating a temporary fixing film on a substrate. The lamination conditions for the substrate and the temporary fixing film are the same as the lamination conditions for the substrate and the dry film in the above-mentioned step (1), and the preferred ranges are also the same.

[0256] The material used for the substrate is not particularly limited. Examples of the substrate include silicon wafers, glass wafers, glass substrates, metal substrates such as copper, titanium, stainless steel, and cold-rolled steel sheets (SPCC), substrates such as FR-4 substrates in which glass fibers are impregnated with epoxy resin or the like and then thermoset, and substrates made of bismaleimide triazine resins such as BT resin.

[0257] The material of the temporary fixing film is not particularly limited as long as it can be peeled off from the semiconductor chip in the step (D) described below and can temporarily fix the semiconductor chip. Commercially available products can be used as the temporary fixing film. Examples of commercially available products include Riva Alpha manufactured by Nitto Denko Corporation.

[0258] <Process (B)> Step (B) is a step of temporarily fixing semiconductor chips on a temporary fixing film. Temporarily fixing semiconductor chips can be performed using known devices such as a flip chip bonder or a die bonder. The layout and number of semiconductor chips can be appropriately set depending on the shape and size of the temporary fixing film, the number of semiconductor packages to be produced, etc., and for example, the semiconductor chips can be temporarily fixed by arranging them in a matrix of multiple rows and multiple columns.

[0259] <Process (C)> Step (C) is a step of applying the resin composition of the present invention onto a semiconductor chip and thermally curing it to form an encapsulating layer.

[0260] The conditions for applying the resin composition and for thermal curing are the same as those for applying the resin composition and for thermal curing in step (2) of the method for producing a circuit board described above.

[0261] <Process (D)> Step (D) is a step of peeling the substrate and the temporary fixing film from the semiconductor chip. The peeling method can be appropriately changed depending on the material of the temporary fixing film, etc. Examples include a method of heating the temporary fixing film to foam (or expand) it and peeling it off, and a method of irradiating the temporary fixing film with ultraviolet light from the substrate side to reduce the adhesive strength of the temporary fixing film and peeling it off.

[0262] In the method of heating and foaming (or expanding) the temporary fixing film to peel it off, the heating conditions are usually 100°C to 250°C for 1 second to 90 seconds or 5 minutes to 15 minutes. In the method of irradiating ultraviolet light from the substrate side to reduce the adhesive strength of the temporary fixing film to peel it off, the irradiation dose of ultraviolet light is usually 10 mJ / cm. 2 ~1000mJ / cm 2 is.

[0263] <Process (E)> Step (E) is a step of forming a rewiring formation layer (insulating layer) on the surface of the semiconductor chip from which the base material and the temporary fixing film have been peeled off.

[0264] The material for forming the rewiring formation layer (insulating layer) is not particularly limited as long as it has insulating properties when the rewiring formation layer (insulating layer) is formed, and from the viewpoint of ease of manufacturing the semiconductor chip package, photosensitive resins and thermosetting resins are preferred.

[0265] After forming the rewiring formation layer (insulating layer), via holes may be formed in the rewiring formation layer (insulating layer) to connect the semiconductor chip to a conductor layer (described later) between layers.

[0266] When forming a via hole, if the material forming the rewiring formation layer (insulating layer) is a photosensitive resin, first, active energy rays are irradiated onto the surface of the rewiring formation layer (insulating layer) through a mask pattern, and the outermost wiring layer in the irradiated area is photocured.

[0267] Examples of active energy rays include ultraviolet rays, visible light rays, electron beams, and X-rays, with ultraviolet rays being particularly preferred. The dose and duration of ultraviolet light irradiation can be appropriately changed depending on the photosensitive resin. The exposure method may be either a contact exposure method in which a mask pattern is brought into close contact with the rewiring formation layer (insulating layer) and then exposed, or a non-contact exposure method in which a mask pattern is brought into close contact with the rewiring formation layer (insulating layer) and then exposed using parallel light.

[0268] Next, the rewiring formation layer (insulating layer) is developed, and the unexposed portions are removed to form via holes. Either wet development or dry development is suitable for development. A known developer can be used as the developer for wet development.

[0269] Examples of the development method include a dipping method, a puddle method, a spray method, a brushing method, and a scraping method, and from the viewpoint of resolution, the puddle method is preferred.

[0270] When the material for forming the rewiring formation layer (insulating layer) is a thermosetting resin, the formation of the via hole is not particularly limited, and examples thereof include laser irradiation, etching, mechanical drilling, etc., but laser irradiation is preferred. Laser irradiation can be performed using any suitable laser processing machine that uses a carbon dioxide laser, UV-YAG laser, excimer laser, etc. as a light source.

[0271] The conditions for laser irradiation are not particularly limited, and laser irradiation can be carried out by any suitable process according to a conventional method depending on the selected means.

[0272] The shape of the via hole, i.e., the shape of the outline of the opening when viewed in the extension direction, is not particularly limited, but is generally circular (approximately circular). The top diameter of the via hole (the diameter of the opening on the surface of the rewiring formation layer (insulating layer)) is preferably 50 μm or less, more preferably 30 μm or less, and even more preferably 20 μm or less. The lower limit is not particularly limited, but is preferably 10 μm or more, more preferably 15 μm or more, and even more preferably 20 μm or more.

[0273] <Process (F)> Step (F) is a step of forming a conductor layer (rewiring layer) on a rewiring formation layer (insulating layer). The method of forming the conductor layer on the rewiring formation layer (insulating layer) is the same as the method of forming the conductor layer after forming via holes in the insulating layer in step (3) in the circuit board manufacturing method, and the preferred range is also the same. Note that steps (E) and (F) may be repeated to alternately stack (build up) the conductor layer (rewiring layer) and the rewiring formation layer (insulating layer).

[0274] <Process (G)> Step (G) is a step of forming a solder resist layer on the conductor layer.

[0275] The material for forming the solder resist layer is not particularly limited as long as it has insulating properties when the solder resist layer is formed, and photosensitive resins and thermosetting resins are preferred from the viewpoint of ease of manufacturing the semiconductor chip package.

[0276] In step (G), bumping processing may be performed to form bumps, if necessary. The bumping processing can be performed by a known method such as solder balls or solder plating. In addition, via holes can be formed in the bumping processing in the same manner as in step (E).

[0277] <Process (H)> The method for manufacturing a semiconductor chip package may include a step (H) in addition to the steps (A) to (G). The step (H) is a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages.

[0278] The method for dicing the semiconductor chip package into individual semiconductor chip packages is not particularly limited, and any known method can be used.

[0279] A third aspect of the semiconductor chip package of the present invention is a semiconductor chip package (fan-out type WLP) in which, for example, a rewiring formation layer (insulating layer) and a solder resist layer are produced from the resin composition of the present invention.

[0280] [Semiconductor Devices] Semiconductor devices that can be equipped with the semiconductor chip package of the present invention include various semiconductor devices used in electrical appliances (e.g., computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical equipment, and televisions) and vehicles (e.g., motorcycles, automobiles, trains, ships, and aircraft).

[0281] [Electronic materials] The electronic component of the present invention comprises a heat sink, a cured product of the resin composition of the present invention provided on the heat sink, and an electronic component mounted on the cured product. The cured product of the resin composition has high thermal conductivity, insulating properties, and excellent mechanical strength. For example, by providing the cured product of the resin composition on the heat sink so as to be adhered to the heat sink and then mounting the electronic component on the cured product, the heat dissipation efficiency of the electronic component to the heat sink is improved. The cured product can be formed by a method similar to that of step (C) described above.

[0282] Examples of electronic components include semiconductor chips, power semiconductors, LED-PKGs, etc. Examples of electronic members include circuit boards, semiconductor chip packages, semiconductor devices, etc. [Example]

[0283] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the following description, "parts" and "%" representing amounts mean "parts by mass" and "% by mass", respectively, unless otherwise specified.

[0284] [Preparation of Resin Composition] The resin compositions of Examples 1 to 12 and Comparative Examples 1 to 7 were prepared by mixing the components according to the formulation shown in the table below. Specifically, the materials were weighed out in the amounts shown in the table below into dedicated plastic containers. Then, using a planetary centrifugal vacuum mixer, Awatori Rentaro (Thinky Corporation; ARE-310), the mixture was thoroughly mixed at 2000 rpm at room temperature and degassed for one minute to obtain the desired resin composition. In the table, the amount of each component is indicated in parts by mass.

[0285] [Table 1] [Table 2] *1: Indicates the content when the non-volatile components of the resin composition are taken as 100% by mass. *2: Indicates the content when the non-volatile components of the resin composition are taken as 100% by volume. *3: (B) Indicates the content when the total component is 100% by mass. *4: (B) Indicates the content when the total volume of the component is 100%.

[0286] The abbreviations in the table are as follows: Component (A) ZX1059: Manufactured by Nippon Steel Chemical & Material Co., Ltd., bisphenol epoxy resin (a 1:1 mixture of bisphenol A and bisphenol F), epoxy equivalent weight approximately 169g / eq. ZX1658GS: Manufactured by Nippon Steel Chemical & Material Co., Ltd., cyclohexanedimethanol epoxy resin, epoxy equivalent weight approximately 120g / eq. (B) Component AS-20: Aluminum oxide filler manufactured by Resonac, with an average particle size of 22 μm DAW-45: Aluminum oxide filler manufactured by Denka, with an average particle size of 45 μm CB-P02: Aluminum oxide filler manufactured by Resonac, with an average particle size of 3.0 μm HF-01Dc: Tokuyama Corporation, aluminum nitride filler with an average particle size of 2.0 μm SO-C6: Silica filler manufactured by Admattex, average particle size 1.8-2.3μm ASFP20: Aluminum nitride filler manufactured by Resonac, with an average particle size of 0.3 μm (H) Component SSC-15A: Silicon carbide filler with an average particle size of 15 μm, manufactured by Shinano Electric Refining Co., Ltd. (C) Component TMPIC: Ajinomoto Fine-Techno Co., Inc., tris(3-mercaptopropyl) isocyanurate, trifunctional, total thiol equivalent weight 117g / eq. TMTP: Yodo Chemical Co., Ltd., trimethylolpropane tris(3-mercaptopropionate), total thiol equivalent: 140g / eq. PE1: Resonaq, pentaerythritol tetrakis(3-mercaptobutyrate), total thiol equivalent: 136g / eq. MR93: Daito Sangyo Co., Ltd., aliphatic thioether, bifunctional, total thiol equivalent: 91g / eq. (D) Component PO-100V: Riken Vitamin Co., Ltd., propylene glycol monooleate (unsaturated aliphatic skeleton with one carbon atom) SP-O30V: Riken Vitamin Co., Ltd., sorbitan trioleate (unsaturated aliphatic skeleton with 3 carbon atoms) (E) Component PN-FJ: Amine epoxy adduct latent hardener manufactured by Ajinomoto Fine-Techno Co., Ltd. (F) Component TEB: Triethyl borate, manufactured by Tokyo Chemical Industry Co., Ltd. (G) Component KBM-403: Shin-Etsu Silicone Co., Ltd., 3-glycidoxypropyltrimethoxysilane

[0287] [Calculation of particle size distribution of component (B)] Components (B-1b) to (B-3b) were precisely weighed out in the amounts shown in the table above and mixed. 50 mg of this mixed powder and 40 g of pure water were weighed into a vial and dispersed ultrasonically for 20 minutes. Using a laser diffraction particle size distribution analyzer (HORIBA, Ltd., LA-500), the particle size distribution was measured using a batch cell method, and the D10, D50, and D90 of component (B) were calculated.

[0288] [Evaluation of mechanical strength (elongation and elastic modulus)] Each resin composition was applied to a release PET film (NS-80A, manufactured by Toray Industries, Inc.) using a bar coater and then heat-cured at 80°C for 60 minutes to obtain a cured product. The resulting cured product, 100 μm thick, was punched out with a dumbbell (trade name "Super Dumbbell Cutter (Model: SDMK-5889-01)", manufactured by Dumbbell Co., Ltd.) to prepare a test piece for measuring tensile strength. The PET film was peeled off from the test piece. A tensile test was performed using a Tensilon universal testing machine (manufactured by Orientec Co., Ltd., RTM-500) at a temperature of 25°C, humidity of 60%, and a tensile speed of 5 mm / min to measure elongation and elastic modulus, and the results were evaluated according to the following criteria. Elongation rating: 〇: Elongation is 2.0% or more ×: Elongation less than 2.0% Elasticity evaluation: ○: Elastic modulus less than 6000 MPa ×: Elastic modulus is 6000 MPa or more

[0289] [Measurement and evaluation of thermal conductivity] Each resin composition was placed in a designated container and thermally cured in a heat circulation oven at 80°C for 60 minutes to produce cylindrical cured products measuring 10 mm in thickness and 36 mm in diameter. The thermal conductivity of the resulting cylindrical cured products was measured using a Kyoto Electronics Manufacturing Co., Ltd. "TPS-2500" under a constant temperature environment of 25°C and 40% RH using the hot disc method, and evaluated according to the following criteria. 〇: Thermal conductivity is 1.5W / m K or more ×: Thermal conductivity is less than 1.5 W / m K

[0290] [Evaluation of volume resistivity] Each resin composition was applied to a 38 μm-thick polyethylene terephthalate film that had been subjected to a release treatment, and then heated at 80° C. for 60 minutes to heat cure, producing a cured film. Test pieces measuring 10 cm square were cut out from the resulting cured film, and the volume resistivity of these test pieces was measured in accordance with JIS K 6271-1 using a digital ultra-high resistivity meter (R8340A, manufactured by Advantest Corporation), and evaluated according to the following criteria. 〇: Volume resistivity is 1.0×10 14 Ω m or more ×: Volume resistivity is 1.0×10 14 Less than Ω·m

[0291] [Evaluation of adhesive strength (initial tensile shear adhesive strength)] Two test pieces of mild steel plate (JIS G3141, SPCC) were prepared, and oil was wiped off with a cloth moistened with acetone. Furthermore, the adhesive surface of the mild steel plate was polished with an endless belt #120. The resin composition was uniformly applied to the polished surface of the mild steel plate to a thickness of approximately 1 mm to obtain a test piece. The two test pieces were attached and clamped with two clips so that the coated surfaces overlapped by approximately 12 mm. Any exuded resin composition was immediately wiped off with a cloth. The test pieces were evenly arranged in an oven and heated to 80°C for 60 minutes for curing and bonding. Two test pieces were prepared for each resin. The tensile shear adhesive strength of the obtained test pieces was measured in accordance with JIS-K-6850 using a Tensilon universal testing machine (UTM-5T, manufactured by Toyo Baldwin Corporation) (measurement environment: temperature 25°C / humidity 60%, tensile speed: 5 mm / min). Based on the maximum load (N) at which the test piece broke, the adhesive area (mm 2 ) was measured, and the tensile shear adhesive strength A was calculated using the following formula and evaluated according to the following criteria. Tensile shear adhesive strength A (N / mm 2 )=Maximum load (N) / Adhesive area (mm 2 ) 〇: Tensile shear adhesive strength A is 5N / mm 2 End △: Tensile shear adhesive strength A is 4N / mm 2 More than 5N / mm 2 less than ×: Tensile shear adhesive strength A is 4N / mm 2 less than

[0292] [Moisture resistance evaluation] Two test pieces were prepared separately using the same procedure as for the evaluation of initial tensile shear adhesive strength. After leaving them in a constant temperature and humidity tester set at 85°C and 85% RH for 250 hours, the resulting test pieces were measured for tensile shear adhesive strength in accordance with JIS-K-6850 using a Tensilon universal testing machine (UTM-5T manufactured by TOYO BALDWIN), in the same manner as for the measurement of initial adhesive strength (measurement environment: temperature 25°C / humidity 60%, tensile speed: 5 mm / min). The adhesive area (mm 2 ) was measured, and the tensile shear adhesive strength B was calculated in the same manner as in the evaluation of adhesiveness, and evaluated according to the following evaluation criteria. Tensile shear adhesive strength B (N / mm 2 )=Maximum load (N) / Adhesive area (mm 2 ) 〇: Tensile shear adhesive strength B is 4N / mm 2 End △: Tensile shear adhesive strength B is 3N / mm 2 More than 4N / mm 2 less than ×: Tensile shear adhesive strength B is 3N / mm 2 Less than

[0293] [Measurement of tensile shear adhesive strength retention (adhesive strength retention)] To evaluate the effect of humidity on adhesive strength, the tensile shear strength retention rate was calculated. The tensile shear strength retention rate was calculated from the above tensile shear adhesive strength A and tensile shear adhesive strength B as follows, and evaluated according to the following evaluation criteria. Tensile shear strength retention rate = [Tensile shear adhesive strength B] / [Tensile shear adhesive strength A] x 100 〇: Tensile shear strength retention rate is 80% or more △: Tensile shear strength retention rate is 60% or more but less than 80% ×: Tensile shear strength retention rate is less than 60%

[0294] [Table 3] [Table 4]

[0295] In Comparative Example 7, the resin composition could not be cured, so it was not possible to evaluate the elastic modulus, elongation, thermal conductivity, volume resistivity, adhesive strength, moisture resistance, and adhesive strength retention.

Claims

1. (A) an epoxy resin, (B) Volume resistivity is 10 ９ A thermally conductive filler having a thermal conductivity of Ω·m or more, and (C) A resin composition containing a thiol compound, The component (C) contains at least a non-ester thiol compound (C-1), The component (C-1) is trifunctional or more functional, A resin composition, wherein the component (B) comprises (B-1) a thermally conductive filler having a particle size of 10 μm or more, (B-2) a thermally conductive filler having a particle size of 1 μm or more and less than 10 μm, and (B-3) a thermally conductive filler having a particle size of less than 1 μm.

2. 2. The resin composition according to claim 1, wherein the content of the component (B-1) is 50% by volume or more and 95% by volume or less, when the total volume of the component (B) is 100% by volume.

3. 2. The resin composition according to claim 1, wherein the content of the component (B-2) is 1% by volume or more and 40% by volume or less, when the total volume of the component (B) is 100% by volume.

4. 2. The resin composition according to claim 1, wherein the content of the component (B-3) is 0.01% by volume or more and 10% by volume or less, when the total volume of the component (B) is 100% by volume.

5. The resin composition according to claim 1, further comprising (D) a dispersant having an unsaturated aliphatic skeleton in which all carbon atoms contained in one molecule have 8 to 60 carbon atoms and the number of carbon atoms is 8 to 54 carbon atoms.

6. The resin composition according to claim 1, wherein the content of the component (A) is 1% by mass or more and 25% by mass or less, when the total nonvolatile components of the resin composition is 100% by mass.

7. The resin composition according to claim 1, wherein the content of the component (B) is 50% by mass or more and 95% by mass or less, when the nonvolatile components of the resin composition are 100% by mass.

8. The resin composition according to claim 1, wherein the content of the component (C) is 1% by mass or more and 20% by mass or less, when the nonvolatile components of the resin composition are 100% by mass.

9. (A) an epoxy resin, (B) Volume resistivity is 10 ９ A thermally conductive filler having a thermal conductivity of Ω·m or more, and (C) A resin composition containing a thiol compound, The component (C) contains at least a non-ester thiol compound (C-1), The component (C-1) is trifunctional or more functional, The 10% particle size of the (B) component is 0.1 μm or more and 5 μm or less, The average particle size of component (B) is 3 μm or more and 20 μm or less, A resin composition, wherein the 90% particle size of component (B) is 10 μm or more and 40 μm or less.

10. A resin sheet having a support and a resin composition layer provided on the support, the resin composition comprising the resin composition according to any one of claims 1 to 9.

11. A circuit board comprising an insulating layer formed from a cured product of the resin composition according to any one of claims 1 to 9.

12. A semiconductor chip package comprising the circuit board according to claim 11 and a semiconductor chip mounted on the circuit board.

13. An electronic component comprising: a heat sink; a cured product of the resin composition according to any one of claims 1 to 9 provided on the heat sink; and an electronic component mounted on the cured product.

14. A method for producing the resin composition according to any one of claims 1 to 9, (A) an epoxy resin, (B-1b) a thermally conductive filler having an average particle size of 10 μm or more; (B-2b) a thermally conductive filler having an average particle size of 1 μm or more and less than 10 μm; (B-3b) a thermally conductive filler having an average particle size of less than 1 μm, and (C) a thiol compound, The component (C) contains at least a non-ester thiol compound (C-1), A method for producing a resin composition, wherein the component (C-1) is trifunctional or higher.

Images