resin composition

Abstract

The present invention provides a resin composition that can produce a cured product with excellent thermal conductivity and adhesive strength. [Solution] A resin composition comprising (A) a liquid epoxy resin, (B) an inorganic filler, and (C) a primary thiol compound having a specific structure, wherein the amount of (B) the inorganic filler is 20% by volume or more relative to 100% by volume of the non-volatile components of the resin composition.

Description

Technical Field

[0001] The present invention relates to a resin composition; and a resin sheet, an electronic member, and a semiconductor device using the resin composition.

Background Art

[0002] As a resin composition for adhesion or sealing of electronic components, a resin composition such as an epoxy resin composition may be used. Usually, the electronic components are adhered or sealed by a cured product of the resin composition.

[0003] On the other hand, in the field of electronic components in recent years, the speed and density have been increasing, and along with this progress, the amount of heat generated by the electronic components has been significantly increasing. From the viewpoint of efficient discharge of heat generated from the electronic components, improvement in thermal conductivity is required for the cured product of the resin composition. From such a viewpoint of improving thermal conductivity, development of a resin composition containing an inorganic filler has been attempted (Patent Document 1).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] Generally, an inorganic filler has a higher thermal conductivity than a resin component. Therefore, a high thermal conductivity can be expected for the cured product of a resin composition containing an inorganic filler. Therefore, the present inventor has attempted to fill the resin composition with a high concentration of an inorganic filler from the viewpoint of improving thermal conductivity.

[0006] However, resin compositions containing inorganic fillers at high concentrations tend to have a reduced adhesive ability. In particular, the adhesiveness to adhesive surfaces formed of difficult-to-bond materials such as nickel and liquid crystal polymer (LCP) is likely to be significantly inferior. Here, the "difficult-to-bond material" refers to a material for which it is difficult to achieve high adhesive strength with conventional general adhesives.

[0007] The present invention was devised in view of the above problems, and an object thereof is to provide a resin composition capable of obtaining a cured product excellent in both thermal conductivity and adhesive strength; a resin sheet containing the resin composition; and an electronic member and a semiconductor device containing a cured product of the resin composition.

Means for Solving the Problems

[0008] The present inventor diligently studied to solve the above problems. As a result, the present inventor found that a resin composition containing a combination of (A) a liquid epoxy resin, (B) an inorganic filler in a specific range of amounts, and (C) a first thiol compound having a specific structure can solve the above problems, and completed the present invention. That is, the present invention includes the following.

[0009] <1> A resin composition containing (A) a liquid epoxy resin, (B) an inorganic filler, and (C) a first thiol compound represented by the following formula (I), wherein the amount of (B) the inorganic filler is 20% by volume or more with respect to 100% by volume of the nonvolatile components of the resin composition.

Chemical formula

[0010] According to the present invention, it is possible to provide a resin composition capable of obtaining a cured product excellent in both thermal conductivity and adhesive strength; a resin sheet containing the resin composition; and an electronic member and a semiconductor device containing the cured product of the resin composition. [Brief Description of the Drawings]

[0011] [Figure 1] It is a spectral diagram showing the NMR data of the thiol compound (1) synthesized in Synthesis Example 1. [Figure 2] It is a spectral diagram showing the NMR data of the thiol compound (2) synthesized in Synthesis Example 2. [Modes for Carrying Out the Invention]

[0012] Hereinafter, the present invention will be described in detail with reference to embodiments and examples. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily modified and implemented without departing from the scope of the claims and their equivalents.

[0013] In the aspects described in this specification, regardless of expressions such as "preferred" and "more preferred", they may be used in combination with each other. For example, the description of a numerical range may use the upper and lower limits of each range, as well as a range combined with the numerical values of the examples. Further, terms such as "containing" and "including" may be read as "consisting essentially of" or "consisting only of".

[0014] In this specification, the notation "Cp~Cq" (p and q are natural numbers satisfying p < q) attached before the name of a group represents that the number of carbon atoms of the group is p or more and q or less. Therefore, for example, the notation "C1~C6 alkyl group" represents "an alkyl group having 1 to 6 carbon atoms". <00​In this specification, the term “may be substituted” with a substituent means, unless otherwise specified, both cases where the hydrogen atoms of the compound, group, or ring are not substituted with substituents, and cases where some or all of the hydrogen atoms of the compound, group, or ring are substituted with substituents.

[0016] <Overview of Resin Composition> A resin composition according to one embodiment of the present invention comprises (A) a liquid epoxy resin, (B) an inorganic filler, and (C) a primary thiol compound represented by formula (I). Hereinafter, "(C) the primary thiol compound represented by formula (I)" may be referred to as "(C) primary thiol compound". In the resin composition according to this embodiment, the amount of (B) the inorganic filler is within a specific range.

[0017] [ka]

[0018] (In equation (I), The ring P is independently either a phenyl group or a naphthyl group. A exists in groups of 1 to 5 for each ring P when the ring P is a phenyl group, and in groups of 1 to 7 for each ring P when the ring P is a naphthyl group, and each A independently has -R 1 -SH is, R 1 Each of these is an independent C1-C6 alkylene group which may be substituted with one or more Y groups. B is a group other than A on ring P, and each is independently a hydrogen atom, a C1-C6 alkyl group which may be substituted with one or more Y atoms, or a C1-C6 alkoxy group which may be substituted with one or more Y atoms. A and B, independently, are bonded at the ortho, meta, or para position relative to the position where ring P is bonded to the main chain if ring P is a phenyl group, and at the ortho, meta, para, ana, epi, cata, peri, pros, amphi, or 2,7 position relative to the position where ring P is bonded to the main chain. X is, independently of each other, -CH2-, -O-, -N(-R 2 )-, or -S-, R 2 is, independently of each other, a hydrogen atom, a C1-C6 alkyl group which may be substituted with one or more Ys, or a C1-C6 alkoxy group which may be substituted with one or more Ys, Y is, independently of each other, a hydrogen atom, a C1-C6 alkyl group, or a C1-C6 alkoxy group, Z is, independently of each other, a direct bond, -CH2-, -O-, or -S-, n is an integer from 1 to 20.)

[0019] According to the resin composition of the present embodiment, a cured product excellent in both thermal conductivity and adhesive strength can be obtained. Further, such a cured product can usually have excellent mechanical strength and high moisture resistance.

[0020] <(A) Liquid epoxy resin> The resin composition according to the present embodiment contains an (A) liquid epoxy resin as the component (A). The (A) liquid epoxy resin represents an epoxy resin that is liquid at a temperature of 20°C.

[0021] (A) The liquid epoxy resin preferably contains a liquid epoxy resin having two or more epoxy groups in one molecule. The proportion of the liquid epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, and may be 100% by mass, based on 100% by mass of the (A) liquid epoxy resin.

[0022] (A) Examples of liquid epoxy resins include bisphenol A type liquid epoxy resin, bisphenol E type liquid epoxy resin, bisphenol F type liquid epoxy resin, bisphenol AF type liquid epoxy resin, naphthalene type liquid epoxy resin, glycidyl ester type liquid epoxy resin, glycidylamine type liquid epoxy resin, phenol novolac type liquid epoxy resin, trimethylolpropane type liquid epoxy resin, neopentyl glycol type liquid epoxy resin, alicyclic liquid epoxy resin having an ester skeleton, cyclohexane type liquid epoxy resin, cyclohexanedimethanol type liquid epoxy resin, t-butylpyrocatechol type epoxy resin, and liquid epoxy resin having a butadiene structure. (A) Liquid epoxy resins may be used individually or in combination of two or more types.

[0023] (A)Specific examples of liquid epoxy resins include DIC's "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type liquid epoxy resin); DIC's "HP-820" (t-butylpyrocatechol-type epoxy resin); Mitsubishi Chemical's "828US", "828EL", "jER828EL", "825", and "Epicote 828EL" (bisphenol A-type liquid epoxy resin); Mitsubishi Chemical's "jER807" and "1750" (bisphenol F-type liquid epoxy resin); three "jER152" (phenol novolac type liquid epoxy resin) manufactured by Hishi Chemical Co., Ltd.; "630", "630LSD", and "604" (glycidylamine type liquid epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ED-523T" (glycyrol type liquid epoxy resin) manufactured by ADEKA Corporation; "EP-3950L" and "EP-3980S" (glycidylamine type liquid epoxy resin) manufactured by ADEKA Corporation; "EP-4088S" (dicyclopentadiene type liquid epoxy resin) manufactured by ADEKA Corporation; and "Z" manufactured by Nippon Steel Chemical & Material Co., Ltd. X1059 (a mixture of bisphenol A type liquid epoxy resin and bisphenol F type liquid epoxy resin); R1710 (bisphenol E type liquid epoxy resin) manufactured by Printec Co., Ltd.; EX-721 (glycidyl ester type liquid epoxy resin) manufactured by Nagase ChemteX Co., Ltd.; Celoxide 2021P (alicyclic liquid epoxy resin with an ester skeleton) manufactured by Daicel Corporation; PB-3600 manufactured by Daicel Corporation, JP-100 and JP-200 (liquid epoxy with a butadiene structure) manufactured by Nippon Soda Co., Ltd. Examples of epoxy resins include: Nippon Steel Chemical & Material's "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type liquid epoxy resin); Adeka's "ED-503" and "ED-503G" (hexanediol type liquid epoxy resin); Adeka's "ED-505" (trimethylolpropane type liquid epoxy resin); Adeka's "ED-506" (polypropylene glycol type liquid epoxy resin); and Adeka's "ED-523T" (neopentyl glycol type liquid epoxy resin).

[0024] (A) The liquid epoxy resin preferably has a low viscosity within a specific range. (A) The viscosity range of the liquid epoxy resin is preferably 15,000 mPa·s or less, more preferably 10,000 mPa·s or less, even more preferably 5,000 mPa or less, and particularly preferably 3,000 mPa·s or less. There is no particular limit to the lower limit, and it may be, for example, 5 mPa·s or more, 10 mPa·s or more, etc. (A) The viscosity of the liquid epoxy resin can be measured using an E-type viscometer (for example, "RE-25U" manufactured by Toki Sangyo, using a 1° 34' × R24 cone rotor) under conditions of 25°C and 20 rpm.

[0025] (A) The epoxy equivalent range of the liquid epoxy resin 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 particularly preferably 110 g / eq. to 1000 g / eq. The epoxy equivalent represents the mass of epoxy resin containing one equivalent of epoxy groups. The epoxy equivalent can be measured according to JIS K7236.

[0026] (A) The weight-average molecular weight (Mw) range of the liquid epoxy resin is preferably 100 to 5000, more preferably 150 to 3000, and even more preferably 200 to 1500. (A) Unless otherwise specified, the weight-average molecular weight of resins such as liquid epoxy resins represents the weight-average molecular weight in terms of polystyrene, measured by gel permeation chromatography (GPC).

[0027] (A) The amount of liquid epoxy resin is preferably 1% by mass or more, more preferably 5% by mass or more, particularly preferably 10% by mass or more, preferably 40% by mass or less, more preferably 30% by mass or less, and particularly preferably 20% by mass or less, based on 100% by mass of the nonvolatile components in the resin composition. Unless otherwise specified, the nonvolatile components in the resin composition refer to the components of the resin composition excluding (H) the solvent. (A) When the amount of liquid epoxy resin is within the above range, the thermal conductivity and adhesive strength of the cured product of the resin composition can be effectively improved, and furthermore, the mechanical strength and moisture resistance of the cured product can usually be made particularly good.

[0028] (A) The amount of liquid epoxy resin is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less, based on 100% by mass of the resin components in the resin composition. Unless otherwise specified, the resin components of the resin composition refer to the non-volatile components of the resin composition excluding (B) inorganic fillers. When the amount of (A) liquid epoxy resin is within the above range, the thermal conductivity and adhesive strength of the cured product of the resin composition can be effectively improved, and moreover, the mechanical strength and moisture resistance of the cured product can usually be made particularly good.

[0029] <(B) Inorganic filler> The resin composition according to this embodiment includes (B) an inorganic filler as component (B). The inorganic filler (B) is a particle of an inorganic material. Therefore, the inorganic filler (B) is included in the resin composition in granular form and is usually included in the cured product while maintaining that granular state. Generally, inorganic materials have higher thermal conductivity than resin components. Therefore, the cured product of the resin composition containing this inorganic filler (B) can have high thermal conductivity.

[0030] (B) Inorganic materials are usually inorganic compounds used to form the inorganic filler. (B) Examples of materials for the inorganic filler include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. (B) The inorganic filler may be used alone or in combination of two or more types.

[0031] (B) The inorganic filler preferably has a high thermal conductivity. Specifically, the range of the thermal conductivity of (B) the inorganic filler is preferably 1.0 W / mK or higher, more preferably 2.0 W / mK or higher, even more preferably 5.0 W / mK or higher, even more preferably 10 W / mK or higher, and particularly preferably 15 W / mK or higher. The upper limit is usually 1000 W / mK or lower, and preferably 300 W / mK or lower. When the thermal conductivity of (B) the inorganic filler is within the above range, the thermal conductivity of the cured resin composition can be effectively increased.

[0032] (B) The thermal conductivity of inorganic fillers can be measured by the laser flash method.

[0033] Examples of inorganic fillers (B) having high thermal conductivity include particles of one or more inorganic materials selected from the group consisting of silica, boron nitride, aluminum nitride, aluminum oxide (alumina), and silicon carbide. Among these, particles of one or more inorganic materials selected from the group consisting of silica, aluminum nitride, aluminum oxide, and silicon carbide are preferred; particles of aluminum oxide are particularly preferred.

[0034] (B) The average particle size D50 of the inorganic filler is preferably 0.01 μm or more, more preferably 0.1 μm or more, even more preferably 1.0 μm or more, particularly preferably 10 μm or more, preferably 100 μm or less, more preferably 50 μm or less, and even more preferably 30 μm or less. (B) When the average particle size D50 of the inorganic filler is within the above range, the thermal conductivity and adhesive strength of the cured resin composition can be effectively improved, and moreover, the mechanical strength and moisture resistance of the cured product can usually be made particularly good.

[0035] (B) The average particle size D50 of the inorganic filler can be measured by the laser diffraction-scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler (B) is created on a volume basis using a laser diffraction-scattering particle size distribution analyzer, and the average particle size D50 can be measured as the median diameter from this particle size distribution. The measurement sample preferably uses the inorganic filler (B) dispersed in water using ultrasound. Suitable laser diffraction-scattering particle size distribution analyzers include the "LA-960" manufactured by Horiba, Ltd. and the "SALD-2200" manufactured by Shimadzu Corporation.

[0036] (B) The specific surface area range of the inorganic filler is preferably 0.1 m². 2 / g or more, more preferably 0.2m 2 / g or more, more preferably 0.3m 2 / g or more, preferably 10m 2 / g or less, more preferably 7m 2 / g or less, more preferably 5m 2 / g or less, particularly preferably 2m 2 (B) When the specific surface area of ​​the inorganic filler is within the above range, the thermal conductivity and adhesive strength of the cured resin composition can be effectively improved, and moreover, the mechanical strength and moisture resistance of the cured product can usually be made particularly good.

[0037] (B) The specific surface area of ​​the inorganic filler can be measured by adsorbing nitrogen gas onto the sample surface using a specific surface area measuring device (Macsorb HM-1210, manufactured by Mountec Co., Ltd.) according to the BET method, and then calculating the specific surface area using the BET multipoint method.

[0038] (B) The inorganic filler may be treated with a surface treatment agent to improve moisture resistance and dispersibility. Examples of surface treatment agents include aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, titanate coupling agents, etc. One type of surface treatment agent may be used alone, or two or more types may be used in any combination.

[0039] 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).

[0040] (B) From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment by the surface treatment agent is preferably within a specific range. Specifically, 100 parts by mass of the inorganic filler is preferably surface-treated with 0.2 to 5 parts by mass of the surface treatment agent, more preferably with 0.2 to 3 parts by mass of the surface treatment agent, and even more preferably with 0.3 to 2 parts by mass of the surface treatment agent.

[0041] The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of ​​the inorganic filler (B). From the viewpoint of improving the dispersibility of the inorganic filler (B), the amount of carbon per unit surface area of ​​the inorganic filler (B) should be 0.02 mg / m². 2 The above is preferred, and 0.1 mg / m² 2 The above is more preferable, 0.2 mg / m² 2 The above is even more preferable. On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin composition, 1.0 mg / m² 2 The following is preferred: 0.8 mg / m² 2 The following is more preferable: 0.5 mg / m² 2 The following is even more preferable.

[0042] (B) The amount of carbon per unit surface area of ​​the inorganic filler can be measured after cleaning the inorganic filler with a solvent (e.g., methyl ethyl ketone (MEK)) following surface treatment. Specifically, a sufficient amount of MEK as the solvent is added to the inorganic filler that has been surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solids, the amount of carbon per unit surface area of ​​the inorganic filler can be measured using a carbon analyzer. As a carbon analyzer, a Horiba "EMIA-320V" or similar can be used.

[0043] (B) The amount (volume %) of the inorganic filler is usually 20% or more relative to 100% by volume of the non-volatile components in the resin composition. (B) When the amount of inorganic filler is within this range, the thermal conductivity and adhesive strength of the cured resin composition can be improved, and furthermore, the mechanical strength and moisture resistance of the cured product can usually be improved. Also, (B) the amount (volume %) of the inorganic filler is preferably 30% or more, more preferably 40% or more, preferably 70% or less, more preferably 60% or less, and particularly preferably 50% or less, relative to 100% by volume of the non-volatile components in the resin composition. (B) When the amount of inorganic filler is within the above range, the above effects can be significantly obtained.

[0044] The volume content (volume %) of each component in a resin composition can be calculated from the mass of each component. Specifically, the volume of each component can be determined by dividing its mass by its specific gravity, and then the volume content (volume %) can be calculated from the volume of each component.

[0045] (B) The amount (mass%) of the inorganic filler is preferably 30% by mass or more, more preferably 40% by mass or more, particularly preferably 50% by mass or more, preferably 90% by mass or less, more preferably 80% by mass or less, and particularly preferably 70% by mass or less, based on 100% by mass of the nonvolatile components in the resin composition. (B) When the amount of inorganic filler is within the above range, the thermal conductivity and adhesive strength of the cured product of the resin composition can be effectively improved, and furthermore, the mechanical strength and moisture resistance of the cured product can usually be made particularly good.

[0046] <(C) Primary Thiol Compound> The resin composition according to this embodiment contains a (C) primary thiol compound as component (C). The (C) primary thiol compound is represented by the following formula (I). The (C) primary thiol compound can react with (A) liquid epoxy resin to cure the resin composition. Since the (C) primary thiol compound has high reactivity with (A) liquid epoxy resin, the resin composition according to this embodiment can usually be cured at a lower curing temperature than conventional resins.

[0047] [ka]

[0048] In formula (I), ring P is independently either a phenyl group or a naphthyl group. Ring P is preferably a phenyl group.

[0049] In formula (I), when ring P is a phenyl group, A is usually present in 1 to 5, preferably 1 to 3, more preferably 1 to 2, and even more preferably 1, elements per ring P. When ring P is a naphthyl group, A is usually present in 1 to 7, preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 to 2 elements per ring P.

[0050] Each A is independent of -R 1 -SH. 1 These are C1-C6 alkylene groups that may be substituted with one or more Y groups, independently of each other. 1 The alkylene group is preferably an unsubstituted C2-C5 alkylene group; more preferably an unsubstituted C2-C3 alkylene group. The alkylene group may be linear or branched, and may be saturated or unsaturated. Furthermore, the alkylene group may or may not be substituted with Y. The definition of Y is as described below.

[0051] In formula (I), B is a group other than A on ring P. Therefore, the total number of groups A and B on one ring P is 5 if ring P is a phenyl group, and 7 if ring P is a naphthyl group. The number of groups A and B on one ring P is, for example, 1 to 2 A and 0 to 2 non-hydrogen B for each ring P; more preferably, 1 A and 0 to 1 non-hydrogen B for each ring P.

[0052] Each B is independently a hydrogen atom, an optionally substituted C1-C6 alkyl group, or an optionally substituted C1-C6 alkoxy group. The definition of Y is as described below. Preferably, each B is independently a hydrogen atom, an unsubstituted C1-C3 alkyl group, or an unsubstituted C1-C3 alkoxy group; more preferably, each B is independently a hydrogen atom, a methyl group, or a methoxy group; even more preferably, B is a hydrogen atom. All B may be hydrogen atoms. In another embodiment, one or two B present in each ring P may be a methyl group, a methoxy group, or a phenyl group, and all other B present in each ring P may be hydrogen atoms. When ring P is a phenyl group, typically 0 to 4, preferably 0 to 3, and more preferably 1 to 2 B may be non-hydrogen atoms for each ring P. When ring P is a naphthyl group, there are usually 0 to 6, preferably 0 to 5, more preferably 1 to 3, and even more preferably 1 to 2 B atoms other than hydrogen atoms for each ring P.

[0053] When ring P is a phenyl group, A and B can each be independently bonded to the ortho, meta, or para position relative to the position where ring P is bonded to the main chain. Preferably, A and B can each be independently bonded to the ortho or para position relative to the position where ring P is bonded to the main chain. In a more preferred embodiment, there is one A on ring P, and either no B other than a hydrogen atom is present on ring P, and A is bonded to the ortho or para position relative to the position where ring P is bonded to the main chain, and if a B other than a hydrogen atom is present, B is bonded to the ortho position relative to the position where ring P is bonded to the main chain. In particular, it is preferable that A is bonded to the ortho position relative to the position where ring P is bonded to the main chain.

[0054] When ring P is a naphthyl group, A and B can each independently bond to the ortho, meta, para, ana, epi, cat, peri, pros, amphi, or 2,7 positions relative to the position where ring P is attached to the main chain. Preferably, A and B can each independently bond to the ana, epi, cat, peri, amphi, or 2,7 positions relative to the position where ring P is attached to the main chain. In a more preferred embodiment, there is one A on ring P, and either no or one non-hydrogen B on ring P, and A is bonded to the amphi or 2,7 positions relative to the position where ring P is attached to the main chain, and if a non-hydrogen B is present, B is bonded to the amphi or 2,7 positions relative to the position where ring P is attached to the main chain.

[0055] In equation (I), X is independently -CH2-, -O-, and -N(-R 2 )-, or -S-. Here, R 2 Each of these is independently a hydrogen atom, a C1-C6 alkyl group which may be substituted with one or more Y atoms, or a C1-C6 alkoxy group which may be substituted with one or more Y atoms. 2X is preferably an unsubstituted C2-C5 alkylene group; more preferably an unsubstituted C2-C3 alkylene group. The alkylene group may be linear or branched, and may be saturated or unsaturated. Furthermore, the alkylene group may or may not be substituted with Y. The definition of Y is as described below. X is preferably -CH2- or -O-, and more preferably -O-.

[0056] In formula (I), Y is independently a hydrogen atom, a C1-C6 alkyl group, or a C1-C6 alkoxy group. Y is preferably a hydrogen atom, a methyl group, or an ethyl group; more preferably a hydrogen atom.

[0057] In formula (I), Z is independently a direct bond, -CH2-, -C2H4-, -C3H6-, -C4H8-, -O-, or -S-. Z is preferably a direct bond, -CH2-, -O-, or -S-; more preferably a direct bond or -O-; even more preferably a direct bond.

[0058] In equation (I), n is an integer between 1 and 20. Preferably, n is an integer between 1 and 10; more preferably, it is an integer between 2 and 5 or between 1 and 3.

[0059] (C)Specific examples of primary thiol compounds include the thiol compound represented by formula (I-1), the thiol compound represented by formula (I-2), the thiol compound represented by formula (I-3), the thiol compound represented by formula (I-4), the thiol compound represented by formula (I-5), and the thiol compound represented by formula (I-6). Among these, the thiol compound represented by formula (I-1) and the thiol compound represented by formula (I-3) are preferred; the thiol compound represented by formula (I-1) is particularly preferred.

[0060] [ka]

[0061] (C) The primary thiol compound may be used alone or in combination of two or more types.

[0062] (C) There are no restrictions on the method for producing the primary thiol compound. For example, the thiol compound represented by formula (I-1) can be produced by the following method. First, 2-allylphenol and 1,4-dibromobutane are mixed with tetra-n-butylammonium bromide as a phase transfer catalyst and methyl isobutyl ketone (MIBK) as a reaction solvent and dissolved. In one example, after mixing, the mixture is dissolved at a temperature of usually 50°C to 200°C, preferably 60°C to 150°C, more preferably 100°C ± 10 to 20°C, for usually 1 minute to 12 hours, preferably 10 minutes to 5 hours, more preferably 30 minutes ± 10 to 20 minutes. The resulting solution is mixed with a base such as an aqueous KOH solution, and the reaction is carried out by returning only MIBK to the system at a temperature of usually 100°C to 150°C, preferably 110°C to 120°C, while removing water by distillation. The reaction time is usually 1 to 24 hours, preferably 2 to 10 hours, and more preferably 6 hours ± 1 hour. After that, the temperature is lowered to about 60°C, distilled water is added and allowed to stand, and the lower by-product brine layer is discarded. Further distilled water and a base (such as sodium dihydrogen phosphate in an appropriate amount for neutralization) are added and allowed to stand and separate, and the lower by-product brine layer is discarded. Further, the same amount of distilled water is added and the mixture is washed and purified with water usually 1 to 5 times, preferably 2 to 3 times. After that, the mixture is heated to, for example, 50°C to 200°C, preferably 60°C to 150°C, and more preferably 120°C ± 10 to 20°C to perform azeotropic dehydration. The obtained solution is microfiltered to remove impurities, and MIBK and unreacted 2-allylphenol are distilled under reduced pressure to obtain a liquid resin. The obtained liquid resin, thioacetic acid, toluene, and azobisisobutyronitrile (AIBN) are mixed and reacted. The reaction temperature for this reaction is, for example, 50°C to 200°C, preferably 60°C to 150°C, and more preferably 80°C ± 10 to 20°C. The reaction time is, for example, 30 minutes to 24 hours, preferably 1 hour to 10 hours, and more preferably 4 hours ± 1 to 2 hours. After removing toluene from the resulting reactant, crystallization is performed with methanol, and the crystallized product is dried and recovered. The recovered dried crystallized product is mixed with a base such as NaOH and reacted. The reaction temperature for this reaction is, for example, 50°C to 200°C, preferably 60°C to 150°C, and more preferably 80°C ± 10 to 20°C.Furthermore, the reaction time is, for example, 30 minutes to 12 hours, preferably 1 hour to 5 hours, and more preferably 2 hours ± 1 hour. After neutralizing the reactants with an acid such as hydrochloric acid, the organic layer is separated and washed with water. Toluene is removed from the washed organic layer to obtain the desired thiol compound. For a specific manufacturing method, the method described in the specification of Japanese Patent Application No. 2023-057934 may be adopted.

[0063] (C) The amount of the primary thiol compound is preferably 1% by mass or more, more preferably 5% by mass or more, particularly preferably 8% by mass or more, preferably 30% by mass or less, more preferably 20% by mass or less, and particularly preferably 15% by mass or less, based on 100% by mass of the nonvolatile components in the resin composition. (C) When the amount of the primary thiol compound is within the above range, the thermal conductivity and adhesive strength of the cured product of the resin composition can be effectively improved, and furthermore, the mechanical strength and moisture resistance of the cured product can usually be made particularly good.

[0064] (C) The amount of the primary thiol compound is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, particularly preferably 35% by mass or more, preferably 60% by mass or less, more preferably 50% by mass or less, particularly preferably 40% by mass or less, based on 100% by mass of the resin components in the resin composition. (C) When the amount of the primary thiol compound is within the above range, the thermal conductivity and adhesive strength of the cured product of the resin composition can be effectively improved, and moreover, the mechanical strength and moisture resistance of the cured product can usually be made particularly good.

[0065] The mass ratio of (C) the primary thiol compound to (A) the liquid epoxy resin ((C) primary thiol compound / (A) liquid epoxy resin) is preferably 0.1 or higher, more preferably 0.3 or higher, even more preferably 0.5 or higher, particularly preferably 0.8 or higher, preferably 2.0 or lower, more preferably 1.5 or lower, even more preferably 1.0 or lower, and particularly preferably 0.9 or lower. When the mass ratio ((C) primary thiol compound / (A) liquid epoxy resin) is within the above range, the thermal conductivity and adhesive strength of the cured resin composition can be effectively improved, and moreover, the mechanical strength and moisture resistance of the cured product can usually be made particularly good.

[0066] The mass ratio of (C) the primary thiol compound to (B) the inorganic filler ((C) primary thiol compound / (B) inorganic filler) is preferably 0.01 or higher, more preferably 0.05 or higher, even more preferably 0.08 or higher, particularly preferably 0.12 or higher, preferably 0.8 or lower, more preferably 0.5 or lower, and particularly preferably 0.2 or lower. When the mass ratio ((C) primary thiol compound / (B) inorganic filler) is within the above range, the thermal conductivity and adhesive strength of the cured resin composition can be effectively improved, and moreover, the mechanical strength and moisture resistance of the cured product can usually be made particularly good.

[0067] In the resin composition, the ratio of the number of mercapto groups in (C) the primary thiol compound to the number of epoxy groups in (A) the liquid epoxy resin (mercapto group / epoxy group) is preferably within a specific range. The range of the ratio (mercapto group / epoxy group) is preferably 0.1 or more, more preferably 0.2 or more, even more preferably 0.3 or more, preferably 2.0 or less, more preferably 1.5 or less, even more preferably 1.0 or less, and particularly preferably 0.8 or less. The "number of epoxy groups in (A) the liquid epoxy resin" in the resin composition refers to the sum of all values ​​obtained by dividing the mass of the nonvolatile components of (A) the liquid epoxy resin present in the resin composition by its epoxy equivalent. The "number of mercapto groups in (C) the primary thiol compound" in the resin composition refers to the sum of all values ​​obtained by dividing the mass of the nonvolatile components of (C) the primary thiol compound present in the resin composition by its mercapto group equivalent. The mercapto group equivalent represents the mass of resin containing 1 equivalent of mercapto groups. When the aforementioned ratio (mercapto group / epoxy group) is within the aforementioned range, the thermal conductivity and adhesive strength of the cured resin composition can be effectively improved, and moreover, the mechanical strength and moisture resistance of the cured product can usually be made particularly good.

[0068] The resin composition may contain any thiol compound, such as a thiol-based curing agent described later, in combination with (C) the primary thiol compound. In the resin composition according to this embodiment, the ratio of the number of epoxy groups in (A) the liquid epoxy resin to the total number of mercapto groups of the thiol compound, including (C) the primary thiol compound and any other thiol compound (epoxy groups / mercapto groups) is preferably within a specific range. The range of the ratio (epoxy groups / mercapto groups) is preferably 0.1 or more, more preferably 0.4 or more, even more preferably 0.8 or more, particularly preferably greater than 1.0, preferably 2.0 or less, more preferably 1.8 or less, even more preferably 1.6 or less, and even more preferably 1.4 or less. The "total number of mercapto groups of the thiol compound" in the resin composition refers to the sum of all values ​​obtained by dividing the mass of the nonvolatile components of the thiol compounds (including (C) the primary thiol compound and any other thiol compound) present in the resin composition by their mercapto group equivalents. When the aforementioned ratio (mercapto group / epoxy group) is within the aforementioned range, the thermal conductivity and adhesive strength of the cured resin composition can be effectively improved, and moreover, the mechanical strength and moisture resistance of the cured product can usually be made particularly good.

[0069] The total amount of (A) liquid epoxy resin, (B) inorganic filler, and (C) primary thiol compound is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, and even more preferably 90% by mass or more, based on 100% by mass of the nonvolatile components in the resin composition. The upper limit is usually 100% by mass or less, and may be 99% by mass or less.

[0070] <(D) Hardener> The resin composition according to this embodiment may contain (D) a curing agent as an optional component. The curing agent (D) as component (D) represents a curable resin that can react with the liquid epoxy resin (A) to cure the resin composition. The curing agent (D) does not include components (A) to (C) described above. The curing agent (D) may be used alone or in combination of two or more types.

[0071] (D) Examples of curing agents include active ester curing agents, phenol curing agents, carbodiimide curing agents, cyanate curing agents, benzoxazine curing agents, acid anhydride curing agents, amine curing agents, and thiol curing agents. Among these, thiol curing agents are preferred.

[0072] As a thiol-based curing agent, (A) a thiol compound that can react with a liquid epoxy resin to cure the resin composition may be used. This thiol-based curing agent usually has one or more mercapto groups in one molecule. From the viewpoint of improving crosslinking density, the number of mercapto groups in one molecule of the thiol-based curing agent is preferably two or more, more preferably three or more. The upper limit is preferably six or less, more preferably five or less.

[0073] Among thiol curing agents, those containing a cyclic skeleton are preferred; (D-1) Thiol compounds having three or more mercapto groups in one molecule, containing a cyclic skeleton, and not represented by formula (I) are even more preferred. Hereinafter, "(D-1) Thiol compounds having three or more mercapto groups in one molecule, containing a cyclic skeleton, and not represented by formula (I)" may be referred to as "(D-1) secondary thiol compounds." When (D-1) secondary thiol compounds are used, the moisture resistance of the cured resin composition can be particularly effectively improved. Therefore, (D) curing agents preferably contain (D-1) secondary thiol compounds, and may contain only (D-1) secondary thiol compounds.

[0074] (D-1) As the secondary thiol compound, a non-ester type thiol compound that does not contain an ester structure (-C(=O)-O-) may be used, or an ester type thiol compound that contains an ester structure may be used, or both may be used in combination.

[0075] (D-1) Examples of non-ester type thiol compounds that can be used as secondary thiol compounds include alkyl isocyanurate type thiol compounds and alkyl glycoluryl type thiol compounds.

[0076] Alkyl isocyanurate type thiol compounds are compounds that contain a structure in which an alkyl group is bonded to the nitrogen atoms at positions 1, 3, and 5 of isocyanuric acid, and that also have a mercapto group. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 6, even more preferably 1 to 3, even more preferably 2 or 3, and even more preferably 3. Among such alkyl isocyanurate type thiol compounds, those having 3 or more mercapto groups in one molecule can be used as (D-1) secondary thiol compounds. Examples of alkyl isocyanurate type thiol compounds that can be used as (D-1) secondary thiol compounds include trifunctional alkyl isocyanurate type thiol compounds such as tris(3-mercaptopropyl)isocyanurate, tris(2-mercaptopropyl)isocyanurate, tris(2-mercaptoethyl)isocyanurate, and 1,3,5-tris[3-(2-mercaptoethylsulfanyl)propyl]isocyanut.

[0077] Alkyl glycoluryl-type thiol compounds are compounds that contain a structure in which an alkyl group is bonded to at least one of the positions 1, 3, 4, 6, 3a, and 6a of glycoluryl (i.e., tetrahydroimidazo[4,5-d]imidazole-2,5(1H,3H)-dione), and that have a mercapto group. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 6, even more preferably 1 to 3, even more preferably 2 or 3, and even more preferably 3. Among such alkyl glycoluryl-type thiol compounds, those having 3 or more mercapto groups in one molecule can be used as (D-1) secondary thiol compounds. (D-1) Examples of alkyl glycoluryl type thiol compounds that can be used as secondary thiol compounds include trifunctional alkyl glycoluryl type thiol compounds such as 1,3,4-tris(2-mercaptoethyl) glycoluryl and 1,3,4-tris(3-mercaptopropyl) glycoluryl; and tetrafunctional alkyl glycoluryl type thiol compounds such as 1,3,4,6-tetrakis(2-mercaptoethyl) glycoluryl and 1,3,4,6-tetrakis(3-mercaptopropyl) glycoluryl.

[0078] (D-1) Examples of ester-type thiol compounds that can be used as secondary thiol compounds include carboxylic acid ester isocyanurate-type thiol compounds.

[0079] A carboxylic acid ester isocyanurate type thiol compound is a compound that contains a structure in which an alkyl group is bonded to the nitrogen atoms at positions 1, 3, and 5 of isocyanuric acid (i.e., 1,3,5-triazine-2,4,6(1H,3H,5H)-trione), and also contains a mercapto group. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 6, even more preferably 1 to 3, even more preferably 2 or 3, and even more preferably 3. Among such carboxylic acid ester isocyanurate type thiol compounds, those having 3 or more mercapto groups in one molecule can be used as (D-1) secondary thiol compounds. (D-1) Examples of carboxylic acid ester type thiol compounds that can be used as secondary thiol compounds include trifunctional carboxylic acid ester isocyanurate type thiol compounds 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.

[0080] Among those mentioned above, non-ester type thiol compounds are preferred as the (D-1) secondary thiol compound. Therefore, the (D-1) secondary thiol compound preferably includes a non-ester type thiol compound, and may contain only a non-ester type thiol compound. When a non-ester type thiol compound is used, the moisture resistance of the resin composition can be improved particularly effectively.

[0081] Furthermore, among non-esterified thiol compounds, alkyl isocyanurate type thiol compounds are preferred as the (D-1) secondary thiol compound. Therefore, the (D-1) secondary thiol compound preferably includes an alkyl isocyanurate type thiol compound, and may contain only an alkyl isocyanurate type thiol compound. When an alkyl isocyanurate type thiol compound is used, the wettability between the (B) inorganic filler and the resin component can be improved, effectively increasing the elongation and adhesive strength of the cured product.

[0082] (D-1) Commercially available products may be used as the secondary thiol compound. Examples of commercially available products include "TMPIC" (tris(3-mercaptopropyl)isocyanurate) from Ajinomoto Fine Techno Co., Ltd.; "SS32" (1,3,5-tris[3-(2-mercaptoethylsulfanyl)propyl]isocyanut) from Kawaguchi Chemical Industry Co., Ltd.; "TS-G" (tetrahydro-1,3,4,6-tetrakis(3-mercaptoethyl)-imidazo[4,5-d]imidazole-2,5(1H,3H)-dione) and "C3TS-G" (tetrahydro-1,3,4,6-tetrakis(3-mercaptopropyl)-imidazo[4,5-d]imidazole-2,5(1H,3H)-dione) from Shikoku Chemicals, Ltd.; and "TEMPIC" (tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate) from Sakai Chemical Industry Co., Ltd.

[0083] In the resin composition, the equivalent ratio of (C) primary thiol compound to (D-1) secondary thiol compound is preferably within a specific range. The equivalent ratio can be expressed as the ratio of the number of mercapto groups in (C) primary thiol compound to the number of mercapto groups in (D-1) secondary thiol compound ((C) / (D-1)). Specifically, the range of the equivalent ratio is preferably 0.1 or more, more preferably 1.0 or more, even more preferably 1.5 or more, particularly preferably 2.0 or more, preferably 50.0 or less, more preferably 30.0 or less, and even more preferably 10.0 or less. The "number of mercapto groups in (D-1) secondary thiol compound" in the resin composition refers to the sum of all values ​​obtained by dividing the mass of the nonvolatile component of (D-1) secondary thiol compound present in the resin composition by its mercapto group equivalent. When the equivalent ratio is within the aforementioned range, the thermal conductivity and adhesive strength of the cured resin composition can be effectively improved, and moreover, the mechanical strength and moisture resistance of the cured product can usually be made particularly good.

[0084] In a resin composition, the ratio of the number of mercapto groups in the (D-1) secondary thiol compound to the number of epoxy groups in the (A) liquid epoxy resin (mercapto group / epoxy group) is preferably within a specific range. The range of the ratio (mercapto group / epoxy group) is preferably 0.01 or more, more preferably 0.05 or more, even more preferably 0.1 or more, preferably 2.0 or less, more preferably 1.0 or less, even more preferably 0.5 or less, and particularly preferably 0.3 or less. When the ratio (mercapto group / epoxy group) is within the above range, the thermal conductivity and adhesive strength of the cured product of the resin composition can be effectively improved, and moreover, the mechanical strength and moisture resistance of the cured product can usually be made particularly good.

[0085] (D-1) The amount of the secondary thiol compound is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and particularly preferably 3% by mass or less, based on 100% by mass of the nonvolatile components in the resin composition. (D-1) When the amount of the secondary thiol compound is within the above range, the thermal conductivity and adhesive strength of the cured product of the resin composition can be effectively improved, and moreover, the mechanical strength and moisture resistance of the cured product can usually be made particularly good.

[0086] (D-1) The amount of the secondary thiol compound is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 2% by mass or more, preferably 30% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass or less, based on 100% by mass of the resin components in the resin composition. (D-1) When the amount of the secondary thiol compound is within the above range, the thermal conductivity and adhesive strength of the cured product of the resin composition can be effectively improved, and moreover, the mechanical strength and moisture resistance of the cured product can usually be made particularly good.

[0087] (D-1) The curing agent (D), such as a secondary thiol compound, may be in liquid or solid form at 20°C.

[0088] (D-1) The weight-average molecular weight range of the curing agent (D), such as a secondary thiol compound, is preferably 100 or more, more preferably 150 or more, even more preferably 200 or more, and particularly preferably 250 or more. The upper limit of the weight-average molecular weight of the curing agent (D) may be, for example, 5,000 or less, 3,000 or less, 1,500 or less, 1,000 or less, 800 or less, 700 or less, etc.

[0089] (D-1) The active group equivalent of the curing agent (D), such as a secondary thiol compound, is preferably 50 g / eq. or more, but may be 60 g / eq. or more, 80 g / eq. or more, or 110 g / eq. or more. The upper limit of the active group equivalent of the curing agent (D) may be, for example, 3,000 g / eq. or less, 1,000 g / eq. or less, 500 g / eq. or less, 300 g / eq. or less, or 200 g / eq. or less. The active group equivalent represents the mass of resin per equivalent of active group. Furthermore, the active group of the curing agent (D) represents a group that can react with the epoxy group of the liquid epoxy resin (A), and examples include mercapto groups, phenolic hydroxyl groups, and active ester groups.

[0090] In a resin composition, the ratio of the number of active groups in the curing agent (D) to the number of epoxy groups in the liquid epoxy resin (A) is preferably within a specific range. The range of the ratio (active groups / epoxy groups) is preferably 0.01 or more, more preferably 0.05 or more, even more preferably 0.1 or more, preferably 2.0 or less, more preferably 1.0 or less, even more preferably 0.5 or less, and particularly preferably 0.3 or less. The "number of active groups in the curing agent (D)" in the resin composition refers to the sum of all values ​​obtained by dividing the mass of the nonvolatile components of the curing agent (D) present in the resin composition by the equivalent amount of its active groups. When the ratio (active groups / epoxy groups) is within the above range, the thermal conductivity and adhesive strength of the cured product of the resin composition can be effectively improved, and furthermore, the mechanical strength and moisture resistance of the cured product can usually be made particularly good.

[0091] (D) The amount of curing agent is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and particularly preferably 3% by mass or less, based on 100% by mass of the nonvolatile components in the resin composition. (D) When the amount of curing agent is within the above range, the thermal conductivity and adhesive strength of the cured product of the resin composition can be effectively improved, and moreover, the mechanical strength and moisture resistance of the cured product can usually be made particularly good.

[0092] (D) The amount of curing agent is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 2% by mass or more, preferably 30% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass or less, based on 100% by mass of the resin components in the resin composition. (D) When the amount of curing agent is within the above range, the thermal conductivity and adhesive strength of the cured product of the resin composition can be effectively improved, and moreover, the mechanical strength and moisture resistance of the cured product can usually be made particularly good.

[0093] <(E) Preservative stabilizer> The resin composition according to this embodiment may contain (E) a preservative stabilizer as an optional component. The (E) preservative stabilizer does not include those corresponding to the components (A) to (D) described above. Generally, (A) liquid epoxy resin and (B) primary thiol compound have high reactivity, but the (E) preservative stabilizer can suppress unintended reactions between (A) liquid epoxy resin and (B) primary thiol compound, thereby improving the pot life of the resin composition. The (E) preservative stabilizer may be used alone or in combination of two or more types.

[0094] (E) Examples of preservatives and stabilizers include borate compounds, titanate compounds, aluminate compounds, zirconate compounds, isocyanate compounds, carboxylic acids, acid anhydrides, mercapto organic acids, etc.

[0095] 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-tetraoxowndecyl)(1,4,7,10,13-pentaoxatetradecyl)(1,4,7-trioxowndecyl)borane, trimenzyl borate, triphenyl borate, tri-o-tolyl borate, tri-m-tolyl borate, and triethanolamine borate.

[0096] Examples of titanate compounds include tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, and tetraoctyl titanate.

[0097] Examples of aluminate compounds include triethylaluminate, tripropylaluminate, triisopropylaluminate, tributylaluminate, and trioctylaluminate.

[0098] Examples of zirconate compounds include tetraethyl zirconate, tetrapropyl zirconate, tetraisopropyl zirconate, and tetrabutyl zirconate.

[0099] 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, tolylene diisocyanate (e.g., 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate), 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, tolidine diisocyanate, isophorone diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate, and bicycloheptane triisocyanate.

[0100] 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 ketonic acids such as glyoxalic acid and violet acid; aliphatic polybasic acids such as oxalic acid, malonic acid, succinic acid, and maleic acid; aromatic monobasic acids such as benzoic acid, halogenated benzoic acid, toluic acid, phenylacetic acid, cinnamic acid, and mandelic acid; and aromatic polybasic acids such as phthalic acid and trimesic acid.

[0101] Examples of acid anhydrides include aliphatic polybasic acid anhydrides such as succinic anhydride, dodecinyl succinic anhydride, maleic anhydride, adducts of methylcyclopentadiene and maleic anhydride, hexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride; and aromatic polybasic acid anhydrides such as phthalic anhydride, trimellitic anhydride, and pyrrolimellitic anhydride.

[0102] Examples of mercapto-organic acids include mercaptoaliphatic monocarboxylic acids such as mercaptoacetic acid, mercaptopropionic acid, mercaptobutyric acid, mercaptosuccinic acid, and dimercaptosuccinic acid; mercaptoaliphatic monocarboxylic acids obtained by esterification reactions of hydroxy organic acids with mercapto-organic acids; and mercaptoaromatic monocarboxylic acids such as mercaptobenzoic acid.

[0103] (E) As preservatives and stabilizers, borate compounds are preferred from the viewpoint of high versatility and safety, and effectively improving preservation stability. Among these, triethyl borate, tri-n-propyl borate, triisopropyl borate, and tri-n-butyl borate are more preferred, and triethyl borate is even more preferred.

[0104] (E) The amount of the preservative stabilizer is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, even more preferably 0.05% by mass or more, preferably 1% by mass or less, more preferably 0.5% by mass or less, and even more preferably 0.3% by mass or less, based on 100% by mass of the nonvolatile components in the resin composition.

[0105] (E) The range of the amount of preservative stabilizer is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, even more preferably 0.3% by mass or more, preferably 3% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less, based on 100% by mass of the resin component in the resin composition.

[0106] <(F) Curing accelerator> The resin composition according to this embodiment may contain (F) a curing accelerator as an optional component. The curing accelerator (F) as component (F) does not include components (A) to (E) described above. The curing accelerator (F) can act as a catalyst in the reaction of the liquid epoxy resin (A) to accelerate the curing of the resin composition. The curing accelerator (F) may be used alone or in combination of two or more types.

[0107] (F) As a curing accelerator, a latent curing accelerator is preferably used. Latent curing accelerators generally do not contribute to the curing of (A) liquid epoxy resin at room temperature (25°C), but have the function of accelerating the curing of (A) liquid epoxy resin when heated.

[0108] The latent curing accelerator may be a liquid latent curing accelerator or a solid-dispersed latent curing accelerator, but a solid-dispersed latent curing accelerator is more preferred. A liquid latent curing accelerator refers to a compound that is a liquid soluble in (A) liquid epoxy resin at room temperature (25°C) and functions as a curing accelerator for (A) liquid epoxy resin when heated. On the other hand, a solid-dispersed latent curing accelerator is a solid that is insoluble in (A) liquid epoxy resin at room temperature (25°C) and becomes soluble in (A) liquid epoxy resin when heated and functions as a curing accelerator for (A) liquid epoxy resin.

[0109] Examples of solid-disperse latent curing accelerators include imidazole compounds that are solid at room temperature (25°C) and solid-disperse amine adduct-based latent curing accelerators.

[0110] 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, and 2,4-diamino-6 Examples include -[2-(2-methyl-1-imidazolyl)ethyl]-1,3,5-triazine isocyanurate adduct, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazole trimellitate, N-(2-methylimidazolyl-1-ethyl)urea, etc.

[0111] Suitable examples of solid-disperse amine adduct-based latent curing accelerators include amine epoxy adduct-based latent curing accelerators, urea adduct-based latent curing accelerators of amine compounds, and compounds obtained by the addition reaction of an isocyanate compound to the hydroxyl group of an epoxy adduct. Among these, amine epoxy adduct-based latent curing accelerators are preferred.

[0112] Examples of epoxy compounds that can be used as raw materials for the production of solid-disperse amine adduct-type latent curing accelerators include: polyglycidyl ethers obtained by reacting polyhydric phenols (bisphenol A, bisphenol F, catechol, resorcinol, etc.) or polyhydric alcohols (glycerin, polyethylene glycol, etc.) with epichlorohydrin; glycidyl ether esters obtained by reacting hydroxycarboxylic acids such as p-hydroxybenzoic acid and β-hydroxynaphthoic acid with epichlorohydrin; polyglycidyl esters obtained by reacting polycarboxylic acids such as phthalic acid and terephthalic acid with epichlorohydrin; glycidylamine compounds obtained by reacting 4,4'-diaminodiphenylmethane or m-aminophenol with epichlorohydrin; 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.

[0113] Amine compounds that can be used as raw materials for the production of solid-dispersible amine adduct-type latent curing accelerators may be compounds that have one or more active hydrogen atoms capable of addition reactions with epoxy groups in their molecule, and that have at least one functional group selected from primary amino groups, secondary amino groups, and tertiary amino groups in their 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.

[0114] Among the aforementioned amine compounds, amine compounds having a tertiary amino group in the molecule are raw materials that provide latent curing accelerators with excellent curing acceleration ability. Examples of amine compounds having a tertiary amino group in the molecule include primary or secondary amines having a tertiary amino group in the molecule; alcohols, phenols, thiols, carboxylic acids, and hydrazides having a tertiary amino group in the molecule. Examples of primary or secondary amines having a tertiary amino group in the molecule include amine compounds such as dimethylaminopropylamine, diethylaminopropylamine, di-n-propylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, and N-methylpiperazine; and imidazole compounds such as 2-methylimidazole, 2-ethylimidal, 2-ethyl-4-methylimidazole, and 2-phenylimidazole.Furthermore, examples of alcohols, phenols, thiols, carboxylic acids, and hydrazides having a tertiary amino group in the molecule include 2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol, 1-(2-hydroxy-3-phenoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-ethyl-4-methylimidazole, 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3 Examples include (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-dimethylpropionic acid hydrazide, nicotinic acid hydrazide, and isonicotinic acid hydrazide.

[0115] When producing a latent curing accelerator by addition reaction between an epoxy compound and an amine compound, an active hydrogen compound having two or more active hydrogen atoms in its molecule may be reacted further. Examples of such active hydrogen compounds include polyhydric phenols such as bisphenol A, bisphenol F, bisphenol S, hydroquinone, catechol, resorcinol, pyrogallol, and phenol novolac resins; polyhydric alcohols such as trimethylolpropane; polyhydric carboxylic acids such as adipic acid and phthalic acid; and 1,2-dimercaptoethane, 2-mercaptoethanol, 1-mercapto-3-phenoxy-2-propanol, mercaptoacetic acid, anthranilic acid, and lactic acid.

[0116] Examples of isocyanate compounds that can be used as raw materials for the production of solid-dispersible amine adduct-type latent curing accelerators include monofunctional isocyanate compounds such as n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, and benzyl isocyanate; polyfunctional isocyanate compounds such as hexamethylene diisocyanate, toluene 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 the reaction of these polyfunctional isocyanate compounds with active hydrogen compounds. Specific examples of compounds containing terminal isocyanate groups include adducts having terminal isocyanate groups obtained by the reaction of toluene diisocyanate and trimethylolpropane, and adducts having terminal isocyanate groups obtained by the reaction of toluene diisocyanate and pentaerythritol.

[0117] Examples of urea compounds that can be used as raw materials for the manufacture of solid-disperse amine adduct-based latent curing accelerators include urea and thiourea.

[0118] The above-mentioned solid-dispersed amine adduct-based latent curing accelerator may be manufactured, for example, by mixing the above-mentioned raw materials, reacting them at a temperature from room temperature to 200°C, then cooling and solidifying them before grinding; or by reacting the above-mentioned raw materials in a solvent such as methyl ethyl ketone, dioxane, or tetrahydrofuran, removing the solvent, and then grinding the solid component.

[0119] Examples of commercially available solid-disperse amine adduct-type latent curing accelerators include "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 ACR Co., Ltd.), "Hardener X-3670S" (manufactured by ACR 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).

[0120] (F) The amount of the curing accelerator is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, particularly preferably 1.0% by mass or more, preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less, based on 100% by mass of the nonvolatile components in the resin composition.

[0121] (F) The amount of the curing accelerator is preferably 0.1% by mass or more, more preferably 1.0% by mass or more, even more preferably 2.0% by mass or more, preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less, based on 100% by mass of the resin component in the resin composition.

[0122] <(G) Any additives> The resin composition according to this embodiment may further contain (G) any additive as an optional non-volatile component. The optional additive (G) as component (G) does not include those corresponding to components (A) to (F) described above. Examples of optional additives (G) include (A) any epoxy resin other than liquid epoxy resin; thermoplastic resin; polymerization initiator; 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 dioxide, 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 bentonite and montmorillonite; silicone-based defoaming agents, acrylic-based defoaming agents, and fluorine-based defoaming agents. Examples include: defoaming agents such as vinyl resin-based defoaming agents; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion improvers such as urea silane; adhesion improvers such as triazole-based adhesion improvers, tetrazole-based adhesion improvers, and triazine-based adhesion improvers; antioxidants such as hindered phenol-based antioxidants; fluorescent whitening agents 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, red phosphorus), nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, and inorganic flame retardants (e.g., antimony trioxide); etc. (G) Any additive may be used alone or in combination of two or more types.

[0123] <(H) Solvent> The resin composition according to this embodiment may further contain (H) a solvent as an optional volatile component in combination with the nonvolatile components such as components (A) to (G) described above. The solvent may be used alone, or two or more types may be used in any ratio.

[0124] (H) As the solvent, organic solvents are usually used. Examples of organic solvents 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 Examples of solvents include ether ester solvents such as methyl acid; ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butyl carbitol); amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; and aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene.

[0125] The amount of (H) solvent is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less, 1% by mass or less, 0.5% by mass or less, 0.1% by mass or less, or 0.01% by mass or less, based on 100% by mass of the nonvolatile components in the resin composition. Among these, the amount of (H) solvent is particularly preferably 0% by mass. That is, it is particularly preferable that the resin composition according to this embodiment does not contain (H) solvent.

[0126] <Properties of resin compositions and their cured products> The resin composition according to this embodiment may be in solid or liquid form. Furthermore, the liquid resin composition may be in paste form containing no (H) solvent or only a small amount of it, or in varnish form containing a large amount of (H) solvent.

[0127] A cured product of the resin composition according to this embodiment can be obtained by curing the resin composition. Normally, heat is applied when a resin composition is cured, so volatile components such as (H) solvents among the components contained in the resin composition may volatilize due to the heat during curing. Therefore, the cured product obtained by curing the resin composition may contain non-volatile components such as components (A) to (G) or their reaction products.

[0128] The cured product of the resin composition can have high thermal conductivity. Generally, cured products can have high thermal conductivity. For example, the range of thermal conductivity of a cured product obtained by curing a resin composition at 80°C for 60 minutes is preferably 0.5 W / mK or higher, more preferably 1.0 W / mK or higher, and even more preferably 1.2 W / mK or higher. The upper limit is usually 10 W / mK or lower, and may be, for example, 8 W / mK or lower or 6 W / mK or lower. Furthermore, cured products contained in electronic components or semiconductor devices may have thermal conductivity within the above range.

[0129] The thermal conductivity of the cured material can be measured by the hot disk method using a thermophysical property measuring device under constant temperature conditions of 25°C and 40% RH. The specific measurement method can be described later in the examples.

[0130] The cured product of the resin composition can have high adhesive strength. Typically, the cured product can have high shear adhesive strength. In particular, the cured product can exhibit high adhesive strength to difficult-to-bond materials (e.g., nickel, liquid crystal polymers, etc.) to which it was difficult to obtain high adhesive strength with conventional resin compositions.

[0131] In one example, two nickel test pieces are bonded together via a resin composition, and the resin composition is cured to obtain a laminated sample comprising a test piece / cured material / test piece in that order. Using this laminated sample, a tensile shear adhesive strength measurement test is performed in accordance with JIS-K-6850. The range of shear adhesive strength measured in this test is usually 10 MPa or higher, preferably 12 MPa or higher, and more preferably 14 MPa or higher. The upper limit is preferably higher, for example, 30 MPa or lower or 20 MPa or lower.

[0132] In another example, two test pieces made of liquid crystal polymer are bonded together via a resin composition, and the resin composition is cured to obtain a laminated sample comprising a test piece / cured material / test piece in that order. Using this laminated sample, a tensile shear adhesive strength measurement test is performed in accordance with JIS-K-6850. The range of shear adhesive strength measured in this test is usually 4.0 MPa or higher, preferably 4.5 MPa or higher, and more preferably 5.0 MPa or higher. The upper limit is preferably higher, for example, 20 MPa or lower or 10 MPa or lower.

[0133] The shear adhesive strength of the cured material can be measured by performing a measurement test in accordance with JIS-K-6850 as described above, under measurement conditions of 25°C, 60% relative humidity, and a tensile speed of 5 mm / min. This measurement can also be performed using a laminated sample containing a cured material prepared by curing the resin composition at 80°C for 60 minutes. The specific measurement method can be adopted as described later in the examples.

[0134] Cured resin compositions typically possess excellent mechanical properties. For example, it is preferable that the cured product has a low modulus of elasticity, and therefore excellent flexibility and toughness. In one example, the range of the tensile modulus of elasticity of a cured product obtained by curing a resin composition at 80°C for 60 minutes is preferably 5,000 MPa or less, more preferably 3,000 MPa or less, and even more preferably 2,000 MPa or less. The lower limit is preferably 10 MPa or more, and may be 100 MPa or more or 200 MPa or more. Furthermore, cured products contained in electronic components or semiconductor devices may have a tensile modulus within the above range.

[0135] The tensile modulus of the cured material can be measured by a tensile test under the conditions of a temperature of 25°C, humidity of 60%, and a tensile speed of 5 mm / min. The specific measurement method can be the one described later in the examples.

[0136] Furthermore, for example, it is preferable that the cured product has a high elongation at the breaking point. In one example, the range of elongation at the breaking point of a cured product obtained by curing a resin composition at 80°C for 60 minutes is preferably 3% or more, more preferably 10% or more, and even more preferably 15% or more. The upper limit is preferable as it is higher, and may be, for example, 300% or less, 290% or less, or 280% or less. Also, a cured product contained in an electronic component or semiconductor device may have an elongation at the breaking point within the above range.

[0137] The elongation at the breaking point of the cured material can be measured by a tensile test under the conditions of 25°C, 60% humidity, and a tensile speed of 5 mm / min. The specific measurement method can be the one described later in the examples.

[0138] Cured resin compositions typically exhibit excellent moisture resistance. For example, it is preferable that the cured product exhibits minimal reduction in adhesive strength during storage tests conducted in a high-temperature, high-humidity environment. In one example, when a storage test is conducted in an environment of 85°C and 85% RH for 250 hours, the strength retention rate is preferably 60% or more, more preferably 80% or more, and usually 100% or less.

[0139] The aforementioned strength preservation rate is determined by the shear bond strength S measured before the preservation test. A And the shear bond strength S measured after the storage test. BUsing the above, the following formula (M1) can be used to calculate the shear bond strength. Furthermore, the shear bond strength can be measured in accordance with JIS-K-6850 using a laminated sample with an appropriate test specimen (e.g., mild steel plate (JIS G3141, SPCC)). This measurement can be performed using a laminated sample containing a cured product obtained by curing the resin composition at 80°C for 60 minutes. The specific measurement method can be the one described later in the examples. Strength retention rate (%)=S B / S A ×100 (M1)

[0140] <Method for producing resin compositions> The resin composition according to this embodiment can be manufactured, for example, by mixing components that may be included in the resin composition. The above-mentioned components may be mixed some or all at the same time, or they may be mixed sequentially. The temperature may be set appropriately during the mixing of each component, and thus heating and / or cooling may be performed temporarily or throughout the process. Furthermore, stirring or shaking may be performed during the mixing of each component.

[0141] <Uses of resin compositions> The resin composition according to this embodiment can produce a cured product with excellent thermal conductivity and adhesive strength. Taking advantage of these excellent benefits, it is preferable to use this resin composition as an adhesive resin composition where both thermal conductivity and adhesive strength are required.

[0142] A preferred application of the resin composition is a resin composition for bonding a heat sink to an electronic component in an electronic component such as a semiconductor module. Specifically, the resin composition may be used as the bonding resin composition in a method for manufacturing a camera module, which involves bonding one or more of a circuit board, an electronic component, and a heat sink. Examples of electronic components include semiconductor chips, power semiconductors, and LED packages.

[0143] Furthermore, examples of preferred applications for the resin composition include resin compositions for bonding substrates and electronic components in semiconductor devices. Specifically, the resin composition according to this embodiment may be used as the bonding resin composition in a method for manufacturing a semiconductor device, which includes bonding substrates such as circuit boards, housings, and frames to electronic components such as camera modules.

[0144] Generally, cured resin compositions have insulating properties. Therefore, by utilizing this insulating property, the above-mentioned resin compositions may be used as resin compositions for forming cured layers on circuit boards. For example, an insulating layer and a sealing layer may be formed as the cured layer. Here, examples of circuit boards include, but are not limited to, printed wiring boards and semiconductor chip packages.

[0145] <Resin sheet> A resin sheet according to one embodiment of the present invention comprises a support and a resin composition layer formed on the support. The resin composition layer contains the above-mentioned resin composition, and preferably contains only the above-mentioned resin composition.

[0146] From the viewpoint of thinning, the thickness of the resin composition layer of the resin sheet 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 may be, for example, 1 μm or more, 3 μm or more, 5 μm or more, etc.

[0147] Examples of support materials include plastic film, metal foil, and release paper, with plastic film and metal foil being preferred.

[0148] When using a plastic film as a support, examples of plastic materials 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, triacetylcellulose (TAC), polyether sulfide (PES), polyether ketones, and polyimides. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0149] When using metal foil as a support, examples of metal foil include copper foil and aluminum foil, with copper foil being preferred. As for copper foil, foil made of single-metal copper may be used, or foil made of an alloy of copper with another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.

[0150] The support may have surface treatments such as matte finish, corona treatment, or antistatic treatment applied to the surface that bonds with the resin composition layer.

[0151] As the support, a support with a release layer may be used, which has a release layer on the surface that is bonded to the resin composition layer. Examples of release agents 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-based release agents, polyolefin-based release agents, urethane-based release agents, and silicone-based release agents. Commercially available products may be used as the support with a release layer, for example, PET films having a release layer mainly composed of a silicone-based release agent or an alkyd resin-based release agent, such as "PET501010", "SK-1", "AL-5", and "AL-7" from Lintec Corporation; "Lumirror T60" from Toray Industries, Inc.; "Purex" from Teijin Ltd.; and "Unipeel" from Unitika Corporation.

[0152] The thickness of the support is not particularly limited, but is preferably 1 μm or more, more preferably 5 μm or more, even more preferably 10 μm or more, preferably 75 μm or less, more preferably 60 μm or less, and even more preferably 50 μm or less. When using a support with a release layer, it is preferable that the overall thickness of the support with the release layer is within the above range.

[0153] The resin sheet may include any components as needed. For example, the resin sheet may include a protective film to protect the resin composition layer. The protective film is usually provided on the side of the resin composition layer that is not bonded to the support (i.e., the side opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. When a protective film is provided, the adhesion of dust and scratches to the surface of the resin composition layer can be suppressed.

[0154] A resin sheet can be used, for example, to form a resin composition layer on a suitable substrate. A method for forming a resin composition layer using a resin sheet typically involves laminating the resin sheet and the substrate. The lamination of the resin sheet and the substrate is carried out so that the resin composition layer of the resin sheet and the substrate are bonded together. This lamination may be carried out, for example, by heat-pressing the resin sheet onto the substrate from the support side. Specifically, a resin sheet and a substrate may be laminated, and the support may be peeled off as needed to form a resin composition layer on the substrate.

[0155] A resin sheet can be manufactured, for example, by a method that includes forming a resin composition layer on a support. Specifically, a resin sheet may be manufactured by coating a liquid resin composition onto a support and then drying it as needed to form a resin composition layer.

[0156] The resin composition can be applied using a coating device such as a die coater. Drying can be carried out by drying methods such as heating or hot air blowing. The drying conditions are not particularly limited, but the solvent content in the resin composition layer is usually 10% by mass or less, preferably 5% by mass or less. Although this may vary depending on the boiling point of the solvent, for example, when using a resin composition containing 30% to 60% by mass of solvent, the resin composition layer can be formed by drying at 50°C to 150°C for 3 to 10 minutes.

[0157] The manufactured resin sheets can be stored by rolling them up. If the resin sheets have a protective film, they can usually be used after removing the protective film.

[0158] <Electronic Components> The resin composition described above has excellent adhesive strength and is therefore preferable for use as an adhesive in electronic components such as semiconductor modules. Generally, electronic components include electronic components and other components. Therefore, the resin composition described above may be used to bond electronic components to other components.

[0159] In particular, from the viewpoint of utilizing the high thermal conductivity of the cured resin composition, it is preferable to use the resin composition to bond electronic components and heat sinks. An electronic component using a resin composition to bond electronic components and heat sinks in this way comprises, for example, a heat sink, a cured resin composition provided on the heat sink, and an electronic component mounted on the cured resin composition. In such an electronic component, the heat generated by the electronic component is efficiently transferred to the heat sink through the cured resin composition, so that heat dissipation from the electronic component can be performed efficiently.

[0160] Such electronic components can be manufactured, for example, by a method including the steps of: applying a resin composition to one or both of an electronic component and a heat sink; bonding the electronic component and the heat sink via the resin composition; and curing the resin composition. The application of the resin composition may be carried out by, for example, the method described in the method for manufacturing a resin sheet. Alternatively, for example, the resin composition may be applied using an application device such as a syringe or dispenser, and pressed as necessary to apply the resin composition to a uniform thickness.

[0161] The curing of the resin composition is usually carried out by thermal curing. The thermal curing conditions for the resin composition layer may vary depending on the type of resin composition. For example, the curing temperature is preferably 50°C to 240°C, more preferably 60°C to 220°C, and even more preferably 70°C to 210°C. The curing time may be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 100 minutes. The process of curing the resin composition may also include preheating the resin composition at a temperature lower than the curing temperature before thermal curing.

[0162] Examples of the aforementioned electronic components include, but are not limited to, modules containing semiconductor chips (e.g., camera modules) and semiconductor chip packages.

[0163] <Semiconductor device> A semiconductor device according to one embodiment of the present invention includes a cured product of the resin composition described above. Examples of such a semiconductor device include a semiconductor device equipped with the electronic components described above.

[0164] Furthermore, in semiconductor devices, the resin composition may be used to bond the components of the semiconductor device. For example, a semiconductor device may comprise a substrate, a cured resin composition provided on the substrate, and electronic components or electronic members mounted on the cured resin. Examples of substrates include circuit boards, heat sinks, frames, etc. In such a semiconductor device, the electronic components or electronic members are bonded to the substrate by the cured resin composition. From the viewpoint of utilizing high adhesive strength to difficult-to-bond materials such as nickel and liquid crystal polymers, the bonding surface of the substrate (the surface that joins with the cured resin) may be formed from a difficult-to-bond material.

[0165] Specific examples of the semiconductor devices mentioned above include various types of semiconductor devices used in electrical products (e.g., computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical equipment, and televisions, etc.) and vehicles (e.g., motorcycles, automobiles, trains, ships, and aircraft, etc.). [Examples]

[0166] The present invention will be described in detail below with reference to examples. However, the present invention is not limited to the following examples. In the following description, "parts" and "%" representing quantities are based on mass unless otherwise specified. Furthermore, the operations described below were carried out in an atmospheric environment at normal temperature and pressure (23°C, 1 atm) unless otherwise specified.

[0167] <Methods for measuring high-performance liquid chromatography and mass spectrometry (LC / MS measurement)> The sample was diluted to 1 mg / mL with tetrahydrofuran (THF), and measured by high-performance liquid chromatography and mass spectrometry (LC / MS) under the following conditions. High-performance liquid chromatography (HPLC): ACQUITY UPLC (manufactured by Waters Japan Co., Ltd.) Mass Spectrum (MS): SQ Detector2 (manufactured by Waters Japan) Column: ACQUITY UPLC BEH C8 1.7um, 2.1mm×50mm (manufactured by Waters Japan) Mobile phase A: 2 mmol ammonium acetate aqueous solution Mobile phase B: 2-propanol / acetonitrile (50:50) Mobile phase mixing time and mixing ratio (A%): 0 - 0.5 min (95%) → 1 - 8.5 min (75%) → 9 - 11 min (5%) → 11.1 min (95%) → 13 min (95%) Flow rate: 0.30 mL / min Analysis time: 13 min Column temperature: 40°C, Ion mode: ESI (electrospray ionization method) positive Ion polarity: Positive detection mode Desolvation gas flow rate: 700 L / hr, 250°C Cone gas: 70 L / hr Ion source heater: 150°C

[0168] <NMR measurement method> The NMR data of each synthesized sample was collected using JEOL LA-500 (manufactured by JEOL Ltd.).

[0169] <Synthesis Example 1. Synthesis of thiol compound (1)> (1) Synthesis of aliphatic skeleton diallyl compound (1): In a 2-liter four-necked round-bottom flask equipped with a stirrer, thermometer, condenser, dropping funnel, and Dean-Stark trap, 140.9 g (1.05 mol) of 2-allylphenol (reagent), 108.0 g (0.5 mol) of 1,4-dibromobutane (reagent), 3.1 g of tetra-n-butylammonium bromide as a phase transfer catalyst, and 300 g of methyl isobutyl ketone (MIBK) as the reaction solvent were charged. The mixture was heated to 100°C and maintained for 30 minutes to allow complete dissolution. To the resulting solution, 175 g (1.5 mol) of 48% KOH aqueous solution was added dropwise over 1 hour. The water and MIBK were separated by azeotropic distillation using the added KOH aqueous solution, and the reaction was continued while only MIBK was returned to the reaction system. The reaction was further continued at 118°C for 6 hours while only MIBK was returned to the system and the water was removed by distillation. Subsequently, the temperature was lowered to 60°C, 100g of distilled water was added and allowed to stand, and the lower by-product brine layer was discarded. Next, 100g of distilled water and an appropriate amount of sodium dihydrogen phosphate for neutralization were added and separated by standing, and the lower by-product brine layer was discarded. After further purification by washing with the same amount of distilled water twice, the solution was heated to 118°C and azeotropic dehydration was performed. The obtained solution was microfiltered using filter paper No. 5C (manufactured by Kiriyama Seisakusho Co., Ltd.) and a Kiriyama funnel (manufactured by Kiriyama Seisakusho Co., Ltd.) to remove impurities, and then MIBK and unreacted 2-allylphenol were removed by vacuum distillation at a maximum temperature of 180°C to obtain 145g of liquid resin. The obtained liquid resin was measured according to the LC / MS measurement method described above. As a result, spectral peaks corresponding to the proton adduct at m / z=323 and the ammonium adduct at m / z=340 were detected. From the analysis data, it was confirmed that the obtained liquid resin was a diallyl compound (1) shown in the following formula (c-1).

[0170] [ka]

[0171] (2) Synthesis of thiol compound (1): In a 1 L four-necked flask, the diallyl compound (1) (100 g, 0.31 mol, 1.0 eq), thioacetic acid (51.9 g, 0.682 mol, 2.2 eq), toluene (360 mL), and azobisisobutyronitrile (AIBN, 5.09 g, 0.031 mol, 0.1 eq) were added and reacted at 80°C for 4 hours. The resulting reaction was concentrated under reduced pressure to remove toluene, and then crystallized with methanol (500 g). The crystallized material was vacuum-dried, and 110.36 g of the dried crystallized material was recovered. In a 3 L four-necked flask, the recovered dried crystallized material (110.36 g) and 32% by mass NaOH (550 g) were added and reacted at 80°C for 2 hours. After neutralizing the reaction with 1N HCl (380 mL), the organic layer was separated and washed with water. Toluene was removed from the water-washed organic layer by vacuum concentration to obtain 89.0 g of the target thiol compound (1) (yield 74%). The obtained thiol compound (1) was measured according to the LC / MS measurement method described above. As a result, spectral peaks corresponding to the proton adduct at m / z=391 and the ammonium adduct at m / z=408 were detected. From these analytical data and the NMR spectrum results shown in Figure 1, it was confirmed that the obtained thiol compound (1) has the structure shown in formula (I-1).

[0172] [ka]

[0173] <Synthesis Example 2. Synthesis of Thiol Compound (2)> (1) Synthesis of aliphatic diallyl compounds (2): Except for replacing 108.0 g (0.5 mol) of 1,4-dibromobutane (reagent) with 150.0 g (0.5 mol) of 1,10-dibromodecane, 165 g of liquid resin was obtained by the same method as in step (1) of Synthesis Example 1. The obtained liquid resin was measured according to the LC / MS measurement method described above. As a result, spectral peaks corresponding to the proton adduct at m / z=407 and the ammonium adduct at m / z=424 were detected. From this analytical data, it was confirmed that the obtained liquid resin is the diallyl compound (2) shown in the following formula (c-2).

[0174] [ka]

[0175] (2) Synthesis of thiol compound (2): 109 g of the target thiol compound (2) was obtained by the same method as in step (2) of Example 1, except that 100 g (0.31 mol) of diallyl compound (1) was replaced with 125.9 g (0.31 mol) of diallyl compound (2) synthesized in step (1) of Example 2. The obtained thiol compound (2) was measured according to the LC / MS measurement method described above. As a result, spectral peaks corresponding to the proton adduct at m / z=475 and the ammonium adduct at m / z=492 were detected. From the analytical data and the NMR spectrum shown in Figure 2, it was confirmed that the obtained thiol compound (2) has the structure shown in formula (I-3).

[0176] [ka]

[0177] <Examples 1-12 and Comparative Examples 1-4> (Manufacturing of thermally conductive resin compositions) Resin compositions were prepared by mixing each component according to the formulations shown in Tables 1 to 4. In Tables 1 to 4, the unit of the amount of each component is parts by mass. Specifically, the amounts of materials shown in the tables were weighed into a dedicated plastic container. Then, using a rotating / revolving vacuum mixer (Sinky Co., Ltd. "Awatori Rentaro ARE-310"), the mixture was thoroughly mixed at 2000 rpm at room temperature, and then degassed for 1 minute to obtain the desired resin composition. The details of the materials used are as follows:

[0178] <(A) Liquid epoxy resin> "ZX1059": Bisphenol-type epoxy resin (1:1 mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin), manufactured by Nippon Steel Chemical & Material Co., Ltd., epoxy equivalent weight approximately 165 g / eq., viscosity 2250 mPa·s, density 1.18 g / cm³. 3 . "HP-820": t-butylpyrocatechol type epoxy resin, manufactured by DIC Corporation, epoxy equivalent weight approximately 214 g / eq., viscosity 1500 mPa·s, density 1.2 g / cm³. 3 .

[0179] <(B) Inorganic filler> "AS-20": Manufactured by Resonaq Corporation, aluminum oxide filler with an average particle size of 22 μm, thermal conductivity of 20 W / mK to 30 W / mK, and specific surface area of ​​0.6 m². 2 / g, density 3.9g / cm 3 . "SSC-A15": Manufactured by Shinano Electric Refining Co., Ltd., silicon carbide filler with an average particle size of 15.0 μm, thermal conductivity of 270 W / mK, and specific surface area of ​​0.3 m². 2 / g~0.5m 2 / g, density 3.2g / cm 3 . "AlN-1501": Manufactured by Resonaq Corporation, aluminum nitride filler with an average particle size of 13 μm, thermal conductivity of 140 W / mK-250 W / mK, specific surface area of ​​0.9 m². 2 / g, density 3.2g / cm 3 . "SO-C5": Manufactured by Admatex, silica filler with an average particle size of 1.3 μm to 1.7 μm, thermal conductivity of 2 W / mK, and specific surface area of ​​3.0 m². 2 / g~5.0m 2 / g, density 2.2g / cm 3 .

[0180] <(C) Primary Thiol Compound> "Thiol compound (1)": Thiol compound (1) synthesized in Synthesis Example 1, 3,3'-((butane-1,4-diylbis(oxy))bis(2,1-phenylene))bis(propane-1-thiol), compound of formula (I-1), mercapto group equivalent 195 g / eq., density 1.2 g / cm³ 3 . "Thiol compound (2)": Thiol compound (2) synthesized in Synthesis Example 2, 3,3'-((decane-1,10-diylbis(oxy))bis(2,1-phenylene))bis(propane-1-thiol), compound of formula (I-3), mercapto group equivalent 245 g / eq., density 1.2 g / cm³ 3 .

[0181] <(D) Hardener> "TMPIC": Tris(3-mercaptopropyl) isocyanurate, manufactured by Ajinomoto Fine Techno Co., Ltd., mercapto group equivalent 117 g / eq., density 1.2 g / cm³ 3 . "C3TSG": Tetrahydro-1,3,4,6-tetrakis(3-mercaptopropyl)-imidazo[4,5-d]imidazole-2,5(1H,3H)-dione, manufactured by Shikoku Chemicals Co., Ltd., mercapto group equivalent 114 g / eq., density 1.28 g / cm³ 3 .

[0182] <(E) Preservative stabilizer> "TEB": Triethyl borate, manufactured by Tokyo Chemical Industry Co., Ltd., density 0.86 g / cm³ 3 .

[0183] <(F) Curing accelerator> "FXR-1081": Modified aliphatic polyamine resin, manufactured by T&K TOKA, density 1.1 g / cm³ 3 .

[0184] <Evaluation test of shear bond strength> Two test specimens with flat surfaces were prepared, and any oil was wiped off with a cloth dampened with acetone. The resin composition was uniformly applied to the flat surface of each test specimen to a thickness of approximately 1 mm. The two test specimens were joined together, with the surfaces coated with the resin composition overlapping by approximately 12 mm in width, and then clamped together with two clips. At this time, some of the resin composition seeped out from the area between the two test specimens, so this seeped-out resin composition was immediately wiped off with a cloth. The test specimens were evenly arranged in an oven and heated at 80°C for 60 minutes to cure the resin composition. As a result, the two test specimens were bonded together by the cured resin composition, and a laminated sample was obtained comprising the test specimen / cured resin / test specimen in this order. For each resin composition, two laminated samples were prepared.

[0185] Using the obtained laminated samples, tensile shear adhesive strength was measured in accordance with JIS-K-6850. Specifically, using a Tensilon universal testing machine (TOYO BALDWIN "UTM-5T"), one test piece was pulled parallel to the plane relative to the other test piece, and the maximum load (N) at which the cured resin composition broke was measured. The measurement was performed at a temperature of 25°C, relative humidity of 60%, and a pulling speed of 5 mm / min. The measured maximum load (N) and the adhesive area (mm²) of the two test pieces were measured. 2 The shear bond strength was calculated using the following formula (M2) from the above. The average of the measured values ​​from the two laminated samples is shown in the table below. Shear bond strength (N / mm²) 2 )=Maximum load (N) / Adhesive area (mm 2 ) (M2)

[0186] The shear bond strength was measured using nickel test specimens. The shear bond strength obtained using nickel test specimens was evaluated according to the following criteria. Good: Shear bond strength is 10.0 MPa or higher. Defect: Shear bond strength is less than 10.0 MPa.

[0187] Furthermore, the shear bonding strength was measured using test specimens made of LCP (Zyder CM-301B, manufactured by ENEOS Sun Energy Co., Ltd.). The shear bonding strength obtained using LCP test specimens was evaluated according to the following criteria. Good: Shear bond strength is 4.0 MPa or higher. Defect: Shear bond strength is less than 4.0 MPa.

[0188] <Evaluation test of mechanical strength (elongation at breaking point and tensile modulus)> A PET film (Toray Industries, Ltd. "NS-80A") with a mold release agent applied to its surface was prepared. A resin composition was applied to this PET film using a bar coat and heated and cured at 80°C for 60 minutes to obtain a cured product with a thickness of 100 μm. The obtained cured product was punched out with a cutter (Dumbbell Co., Ltd. "Super Dumbbell Cutter (Model: SDMK-5889-01)") to prepare test pieces for tensile strength measurement. The PET film was peeled off the test pieces. Tensile tests were performed using a Tensilon universal tester (Orientec Co., Ltd., RTM-500) under conditions of temperature 25°C, humidity 60%, and tensile speed 5 mm / min to measure the elongation at the breaking point and the tensile modulus of elasticity.

[0189] The measured elongation at the fracture point was evaluated according to the following criteria. Good: Elongation at fracture is 3.0% or higher. Poor: Judgment score extension is less than 3.0%.

[0190] The measured tensile modulus was evaluated according to the following criteria. Good: Tensile modulus is less than 5000 MPa. Defective: Tensile modulus of elasticity is 5000 MPa or higher.

[0191] <Evaluation test of thermal conductivity> A resin composition was placed in a cylindrical container and heat-cured in a heat-circulating oven at 80°C for 60 minutes to produce a cylindrical cured product with a thickness of 10 mm and a diameter of φ36 mm. The thermal conductivity of the obtained cylindrical cured product was measured using the hot disk method with a thermophysical property measuring device (Kyoto Electronics Manufacturing Co., Ltd. "TPS-2500") under constant temperature conditions of 25°C and relative humidity of 40% RH.

[0192] The measured thermal conductivity was evaluated according to the following criteria. Good: Thermal conductivity is 1.0 W / mK or higher. Acceptable: Thermal conductivity of 0.5 W / m or more and less than 1.0 W / mK. Defect: Thermal conductivity is less than 0.5 W / m.

[0193] <Evaluation test for moisture resistance> (Initial shear bond strength measurement test) Two flat mild steel plates (JIS G3141, SPCC) were prepared, and the oil was wiped off with a cloth dampened with acetone. Furthermore, the flat surfaces of the mild steel plates were polished with an endless belt #120 to obtain test specimens.

[0194] The resin composition was uniformly applied to the polished surface of each of the two test specimens to a thickness of approximately 1 mm. The polished surfaces of the two test specimens were joined together so that the polished surfaces coated with the resin composition overlapped by a width of approximately 12 mm, and then clamped together with two clips. At this time, some of the resin composition seeped out from the area between the two test specimens, so the seeped resin composition was immediately wiped off with a cloth. The test specimens were evenly arranged in an oven and heated at 80°C for 60 minutes to cure the resin composition. As a result, the two test specimens were bonded together by the cured resin composition, and a laminated sample was obtained consisting of a test specimen / cured resin / test specimen in that order. For each resin composition, two laminated samples were prepared.

[0195] Using the obtained laminated samples, a tensile shear adhesive strength measurement test was performed using the same method as described in the <Evaluation Test of Shear Adhesion Strength> section above, and the shear adhesive strength (tensile shear adhesive strength) was measured. The average of the measured values ​​of the two laminated samples thus measured is called the "initial shear adhesive strength".

[0196] The measured initial shear bond strength was evaluated according to the following criteria. Good: Initial shear bonding strength is 10 N / mm². 2 That's all. Defect: Initial shear bonding strength is 10 N / mm². 2 less than.

[0197] (Measurement test of shear bond strength after storage) Two laminated samples were prepared using the same procedure as described above (for measuring initial shear bonding strength), with the test specimen / cured material / test specimen in that order. These laminated samples were then subjected to a storage test in a constant temperature and humidity testing chamber set to 85°C and 85% RH for 250 hours.

[0198] Using the laminated samples after the storage test, a tensile shear adhesive strength measurement test was performed using the same method as described in the <Evaluation Test of Shear Adhesion Strength> above, and the shear adhesive strength (tensile shear adhesive strength) was measured. The average of the measured values ​​of the two laminated samples thus measured is called the "shear adhesive strength after storage".

[0199] (Evaluation of strength retention rate of shear bonding) To evaluate the effect of humidity on the adhesive strength of cured resin compositions, the strength retention rate was calculated. The strength retention rate is defined as the initial shear adhesive strength S A and shear bond strength S after storage B The value was calculated using the following formula (M1). Strength retention rate (%)=S B / S A ×100 (M1)

[0200] The strength retention rate of the calculated shear bond strength was evaluated according to the following criteria. Good: Strength retention rate is 80% or higher. Acceptable: Strength retention rate is 60% or more but less than 80%. Defective: Strength retention rate is less than 60%.

[0201] <Result> The results of the above-mentioned examples and comparative examples are shown in the table below. In the table below, the meanings of the abbreviations are as follows. "LCP": Liquid Crystal Polymer "Elongation": Elongation at the breaking point "Elastic modulus": Tensile elastic modulus In the moisture resistance section, "Initial": Initial shear bonding strength

[0202] [Table 1]

[0203] [Table 2]

[0204] [Table 3]

[0205] [Table 4]

Claims

1. A resin composition comprising (A) a liquid epoxy resin, (B) an inorganic filler, and (C) a primary thiol compound represented by the following formula (I), (B) A resin composition in which the amount of inorganic filler is 20% by volume or more relative to 100% by volume of the non-volatile components of the resin composition. 【Chemistry 1】 (In equation (I), Ring P is independently either a phenyl group or a naphthyl group. A is present in 1 to 5 groups for each ring P when the ring P is a phenyl group, and in 1 to 7 groups for each ring P when the ring P is a naphthyl group, and each A is independently -R １ -SH, R １ Each of these is an independent C1-C6 alkylene group which may be substituted with one or more Y groups. B is a group other than A on ring P, and each is independently a hydrogen atom, a C1-C6 alkyl group which may be substituted with one or more Y atoms, or a C1-C6 alkoxy group which may be substituted with one or more Y atoms. A and B, independently, are bonded at the ortho, meta, or para position relative to the position where ring P is bonded to the main chain if ring P is a phenyl group, and at the ortho, meta, para, ana, epi, cata, peri, pros, amphi, or 2,7 position relative to the position where ring P is bonded to the main chain. Each X is independently -CH ２ -, -O-, -N(-R ２ ) -, or -S-, R ２ Each of these is independently a hydrogen atom, a C1-C6 alkyl group which may be substituted with one or more Y atoms, or a C1-C6 alkoxy group which may be substituted with one or more Y atoms. Y is independently a hydrogen atom, a C1-C6 alkyl group, or a C1-C6 alkoxy group. Z is, independently of each other, a direct bond, -CH ２ -, -C ２ H ４ -, -C ３ H ６ -, -C ４ H ８ -, -O-, or -S-, and n is an integer between 1 and 20.

2. (C) The resin composition according to claim 1, wherein the primary thiol compound comprises one or more selected from the group consisting of a thiol compound represented by the following formula (I-1), a thiol compound represented by the following formula (I-2), a thiol compound represented by the following formula (I-3), a thiol compound represented by the following formula (I-4), a thiol compound represented by the following formula (I-5), and a thiol compound represented by the following formula (I-6). 【Chemistry 2】

3. (D) The resin composition according to claim 1, comprising a curing agent.

4. (D) The curing agent contains (D-1) a secondary thiol compound, (D-1) The resin composition according to claim 3, wherein the secondary thiol compound has three or more mercapto groups in one molecule, contains a cyclic skeleton, and is not represented by formula (I).

5. The resin composition according to claim 4, wherein the equivalent ratio of (C) the primary thiol compound to (D-1) the secondary thiol compound is 0.1 or more and 50.0 or less.

6. (B) The resin composition according to claim 1, wherein the thermal conductivity of the inorganic filler is 1.0 W / mK or more and 300 W / mK or less.

7. (B) The specific surface area of ​​the inorganic filler is 0.1 m². ２ / g or more 10m ２ The resin composition according to claim 1, wherein the amount is less than or equal to / g.

8. (E) The resin composition according to claim 1, comprising a preservative stabilizer.

9. (F) The resin composition according to claim 1, comprising a curing accelerator.

10. The resin composition according to claim 1, wherein the thermal conductivity of the cured product obtained by curing the resin composition at 80°C for 60 minutes is 0.5 W / mK or more and 10 W / mK or less.

11. The resin composition according to claim 1, wherein the tensile modulus of the cured product obtained by curing the resin composition at 80°C for 60 minutes is 10 MPa or more and 5000 MPa or less.

12. The resin composition according to claim 1, wherein the elongation at the breaking point of the cured product obtained by curing the resin composition at 80°C for 60 minutes is 3% or more and 300% or less.

13. A support and a resin composition layer formed on the support, A resin sheet in which the resin composition layer comprises the resin composition according to any one of claims 1 to 12.

14. An electronic component comprising a heat sink, a cured resin composition according to any one of claims 1 to 12 provided on the heat sink, and an electronic component mounted on the cured resin composition.

15. A semiconductor device comprising a cured product of a resin composition according to any one of claims 1 to 12.

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