Resin composition

Abstract

A resin composition containing (A) an epoxy resin, (B) a thiol compound containing a specific structure, and (C) a curing accelerator, the epoxy resin (A) containing (A-1) an epoxy resin containing an aromatic skeleton, the amount of (A-1) the epoxy resin containing an aromatic skeleton being 30 mass% or more with respect to 100 mass% of the epoxy resin (A).

Description

Technical Field

[0001] This invention relates to resin compositions, and further to resin sheets, electronic components, and semiconductor devices. Background Technology

[0002] Resin compositions used for bonding electronic components can include epoxy resin compositions and other resin compositions. Typically, electronic components are bonded through the cured product of the resin composition.

[0003] In addition, epoxy resin compositions containing thiol compounds are known to date (Patent Documents 1 and 2).

[0004] Existing technical documents Patent documents Patent Document 1: Japanese Patent No. 7413678 Patent Document 2: Japanese Patent Application Publication No. 2022-151779. Summary of the Invention

[0005] The problem that the invention aims to solve In recent years, from the perspective of extending the lifespan of products, there has been a demand for resin compositions that provide adhesives (cured products) with impact resistance. Generally, the more flexible the cured product, the better its impact resistance.

[0006] On the other hand, the softer the cured material, the more likely it is to have reduced adhesive ability.

[0007] The present invention was made in view of the aforementioned problems, and its object is to provide: a resin composition that yields a cured product with excellent adhesive strength and impact resistance; a resin sheet comprising the resin composition; and electronic components and semiconductor devices comprising the cured product of the resin composition.

[0008] Methods for solving problems The inventors conducted in-depth research to solve the aforementioned problems. As a result, the inventors discovered that the following resin composition can solve the aforementioned problems, thereby completing the present invention, the resin composition comprising: (A) an epoxy resin, (B) a thiol compound containing a specific structure and (C) a curing accelerator, wherein (A) the epoxy resin comprises: a specific range of amounts of (A-1) an epoxy resin containing an aromatic backbone.

[0009] That is, the present invention includes the following contents.

[0010] <1> A resin composition comprising (A) an epoxy resin, (B) a thiol compound represented by formula (I) below, and (C) a curing accelerator. Among them, (A) epoxy resin includes: (A-1) epoxy resin containing an aromatic backbone, Compared to 100% by mass of epoxy resin (A), the amount of epoxy resin (A-1) containing an aromatic backbone is 30% by mass or more. In formula (I), Each ring P is independently either phenyl or naphthyl. When ring P is phenyl, there are 1 to 5 atoms relative to each ring P; when ring P is naphthyl, there are 1 to 7 atoms relative to each ring P, and each a atom is independently -R. 1 -SH, R 1 Each is independently a C1-C6 alkylene group that can be substituted by one or more Y atoms. B is a group on ring P other than A, each of which is independently a hydrogen atom, a C1-C6 alkyl group that can be substituted by one or more Y atoms, or a C1-C6 alkoxy group that can be substituted by one or more Y atoms. When ring P is phenyl, A and B are independently bonded to the ortho, meta, or para positions relative to the position of ring P bonded to the main chain. When ring P is naphthyl, A and B are independently bonded to the ortho, meta, para, ana-, epi-, cata-, peri-, pros-, amphi-, or 2,7 positions relative to the position of ring P bonded to the main chain. X can be independently -CH2-, -O-, or -N(-R) 2 )- or -S-, R 2 Each is independently a hydrogen atom, a C1-C6 alkyl group that can be substituted with one or more Y atoms, or a C1-C6 alkoxy group that can be substituted with one or more Y atoms. Y can be independently a hydrogen atom, a C1-C6 alkyl group, or a C1-C6 alkoxy group. Z can be directly bonded, -CH2-, -C2H4-, -C3H6-, -C4H8-, -O-, or -S-. n is an integer from 1 to 20.

[0011] <2> <1> The resin composition thereof, wherein (B) the thiol compound represented by formula (I) comprises one or more selected from the following: 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). .

[0012] The resin composition described in <3>, <1> or <2>, wherein (A-1) the epoxy resin containing an aromatic skeleton contains two or more aromatic rings.

[0013] The resin composition of any one of <4> <1> to <3>, wherein (A-1) the epoxy resin containing an aromatic skeleton contains 2 to 4 epoxy groups in 1 molecule.

[0014] The resin composition of any one of <5> <1> to <4>, wherein (A-1) the epoxy resin containing an aromatic backbone comprises a glycidylamine type epoxy resin.

[0015] The resin composition of any one of <6> <1> to <5>, wherein (A-1) the epoxy resin composition containing an aromatic skeleton comprises: an epoxy resin containing two or more aromatic rings and a glycidylamine type epoxy resin.

[0016] The resin composition of any one of <7>, <1> to <6>, comprises (D) an inorganic filler.

[0017] The resin composition of any one of <8>, <1> to <7>, wherein the tensile modulus of the cured product obtained by curing the resin composition at 80°C for 60 minutes is 1 MPa or more and 5000 MPa or less.

[0018] The resin composition of any one of <9> <1> to <8>, wherein the thixotropic index calculated by dividing the viscosity measured by an E-type viscometer at 25°C and 1 rpm by the viscosity measured by an E-type viscometer at 25°C and 10 rpm is 1 or more and 10 or less.

[0019] <10> An electronic component comprising: a cured resin composition as described in any one of <1> to <9> and an electronic component mounted on the cured resin composition.

[0020] <11> A semiconductor device comprising a cured product of the resin composition described in any one of <1> to <9>.

[0021] Invention Effects According to the present invention, a resin composition capable of producing a cured product with excellent adhesive strength and impact resistance can be provided; a resin sheet comprising the resin composition; and electronic components and semiconductor devices comprising the cured product of the resin composition. Attached Figure Description

[0022] [ Figure 1 ] Figure 1 This is a schematic front view illustrating steps (1) and (2) of the manufacturing method of the laminated specimen 10 used in the DuPont impact test.

[0023] [ Figure 2 ] Figure 2 This is a schematic front view illustrating step (3) of the manufacturing method of the laminated specimen 10 used in the DuPont impact test.

[0024] [ Figure 3 ] Figure 3 This is a schematic front view illustrating step (4) of the manufacturing method of the laminated specimen 10 used in the DuPont impact test.

[0025] [ Figure 4 ] Figure 4 This is a schematic front view used to illustrate the overview of DuPont's impact test.

[0026] [ Figure 5 ] Figure 5 This is a spectrum representing the NMR data of the thiol compound (1) synthesized in Synthesis Example 1. Detailed Implementation

[0027] The present invention will now be described in detail with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples described below, and may be implemented by any modifications without departing from the scope of the claims and their equivalents.

[0028] The solutions described in this specification can be used in combination with each other, without regard to expressions such as "preferred" or "more preferred". For example, the description of numerical ranges can use a range formed by combining the upper and lower limits of each range and the numerical values ​​of the embodiments.

[0029] In this specification, the designation "Cp~Cq" (where p and q are integers of 1 or more satisfying p < q) preceding the group name indicates that the group has p or more carbon atoms and q or less. Therefore, for example, the designation "C1~C6 alkylene" indicates "an alkylene group with 1 or more and 6 or less carbon atoms." Similarly, the designation "C1~C6 alkyl" indicates "an alkyl group with 1 or more and 6 or less carbon atoms." Furthermore, the designation "C1~C6 alkoxy" indicates "an alkoxy group with 1 or more and 6 or less carbon atoms."

[0030] In this specification, unless otherwise stated, the term "substitutable" refers to both the case where the hydrogen atoms of the compound, group, or ring are not substituted by a substituent and the case where some or all of the hydrogen atoms of the compound, group, or ring are substituted by a substituent.

[0031] In this specification, the term "aromatic ring" refers to a ring that follows Hückel's rule, containing 4r+2 electrons (where r is an integer greater than or equal to 1) in its π-electron system. This includes monocyclic aromatic rings and fused aromatic rings composed of two or more monocyclic aromatic rings. An aromatic ring can be an aromatic carbon ring with only carbon atoms as ring-forming atoms, or an aromatic heterocycle with heteroatoms such as oxygen, nitrogen, and sulfur atoms as ring-forming atoms in addition to carbon atoms. In this specification, the term "heteroatom" refers to atoms other than carbon and hydrogen atoms, such as oxygen, nitrogen, sulfur, and silicon atoms.

[0032] In this specification, the term "non-volatile component" in relation to the resin composition refers to components other than the organic solvents described later in the description of the resin composition.

[0033] [Summary of the Resin Composition] The resin composition of the present invention comprises: (A) an epoxy resin, (B) a thiol compound represented by formula (I), and (C) a curing accelerator. Furthermore, in the resin composition of the present invention, (A) the epoxy resin comprises: (A-1) an epoxy resin having an aromatic backbone, wherein the amount of (A-1) the epoxy resin having an aromatic backbone is 30% by mass or more relative to 100% by mass of (A) the epoxy resin. In this specification, "(B) the thiol compound represented by formula (I)" is sometimes referred to as "(B) a thiol compound having a specific structure".

[0034] In formula (I), Each ring P is independently either phenyl or naphthyl. When ring P is phenyl, there are 1 to 5 atoms relative to each ring P; when ring P is naphthyl, there are 1 to 7 atoms relative to each ring P, and each a atom is independently -R. 1 -SH, R 1 Each is independently a C1-C6 alkylene group that can be substituted by one or more Y atoms. B is a group on ring P other than A, each of which is independently a hydrogen atom, a C1-C6 alkyl group that can be substituted by one or more Y atoms, or a C1-C6 alkoxy group that can be substituted by one or more Y atoms. When ring P is phenyl, A and B are independently bonded at the ortho, meta, or para positions relative to the position of ring P bonded to the main chain. When ring P is naphthyl, A and B are independently bonded at the ortho, meta, para, remote, epitope, telomere, forced, equatorial, transposition, or 2,7 positions relative to the position of ring P bonded to the main chain. X can be independently -CH2-, -O-, or -N(-R) 2 )- or -S-, R 2 Each is independently a hydrogen atom, a C1-C6 alkyl group that can be substituted with one or more Y atoms, or a C1-C6 alkoxy group that can be substituted with one or more Y atoms. Y can be independently a hydrogen atom, a C1-C6 alkyl group, or a C1-C6 alkoxy group. Z can be directly bonded, -CH2-, -C2H4-, -C3H6-, -C4H8-, -O-, or -S-. n is an integer from 1 to 20.

[0035] According to the resin composition of the present invention, a cured product with excellent adhesive strength and impact resistance can be obtained.

[0036] As needed, the resin composition of the present invention may further comprise: (D) inorganic filler, (E) curing agent, (F) other additives, and (G) organic solvent. The components comprised in the resin composition of the present invention will be described in detail below.

[0037] <(A) Epoxy Resin> The resin composition of the present invention comprises (A) epoxy resin as component (A). Epoxy resin (A) may be used alone or in combination of two or more types.

[0038] As epoxy resin (A), a curable resin having epoxy groups can be used. Examples of epoxy resins include: bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, triphenol type epoxy resin, naphthol phenolic varnish type epoxy resin, phenolic phenolic varnish type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, and glycidyl ester type epoxy resin. Epoxy resins include: cresol phenolic varnish-type epoxy resins, phenol aralkyl type epoxy resins, biphenyl type epoxy resins, linear aliphatic epoxy resins, epoxy resins with butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spirocyclic epoxy resins, cyclohexane type epoxy resins, cyclohexane-diethanol type epoxy resins, naphthyl ether type epoxy resins, tris(hydroxymethyl) type epoxy resins, tetraphenylethane type epoxy resins, isocyanurate type epoxy resins, and phenol benzopyrrolidone type epoxy resins, etc.

[0039] (A) The epoxy resin preferably includes epoxy resin containing two or more epoxy groups in one molecule. The proportion of epoxy resin containing two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more, relative to 100% by mass of epoxy resin.

[0040] (A) The epoxy resin comprises: (A-1) an epoxy resin containing an aromatic backbone (hereinafter, sometimes referred to as "(A-1) component"). Here, the aromatic backbone refers to a backbone containing a chemical structure generally defined as an aromatic ring. This aromatic ring can be an aromatic carbide ring or an aromatic heterocycle. Furthermore, the aromatic ring can be a monocyclic aromatic ring, a fused aromatic ring formed by the fusion of two or more monocyclic aromatic rings, or a fused aromatic ring formed by the fusion of one or more monocyclic non-aromatic rings onto one or more monocyclic aromatic rings. Preferably, the aromatic ring contained in component (A-1) is an aromatic carbide ring. The aromatic carbide ring preferably has 6 or more and 10 or fewer carbon atoms.

[0041] Examples of epoxy resins containing an aromatic backbone (A-1) include: bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, triphenol type epoxy resin, naphthol phenolic varnish type epoxy resin, phenol phenolic varnish type epoxy resin, tert-butyl-catechol type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, bixylenol type epoxy resin, triphenylmethane type epoxy resin, and glycidylamine type epoxy resin with an aromatic ring. Epoxy resins include glycidyl ester type epoxy resins with aromatic rings, cresol phenolic varnish type epoxy resins, biphenyl type epoxy resins, linear aliphatic epoxy resins containing aromatic rings, butadiene-structured epoxy resins containing aromatic rings, alicyclic epoxy resins containing aromatic rings, heterocyclic epoxy resins, spirocyclic epoxy resins containing aromatic rings, cyclohexanediol type epoxy resins containing aromatic rings, naphthyl ether type epoxy resins, trimethylolpropionic acid type epoxy resins containing aromatic rings, and tetraphenylethane type epoxy resins containing aromatic rings. Among these, from the viewpoint of effectively improving the adhesive strength of the cured resin composition, (A-1) epoxy resins containing an aromatic backbone preferably include glycidylamine type epoxy resins.

[0042] In the resin composition, relative to 100% by mass of epoxy resin (A), the amount of epoxy resin (A-1) containing an aromatic backbone is 30% by mass or more, preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more. The upper limit of the amount of this (A-1) component can be 100% by mass, or it can be less than 100% by mass, 95% by mass or less, or 90% by mass or less. When the amount of the (A-1) component is within the above-mentioned range, the adhesive strength of the cured resin composition can be effectively improved.

[0043] The number of aromatic rings contained in component (A-1) is usually one or more, preferably two or more. That is, in a preferred embodiment, the epoxy resin containing an aromatic skeleton in component (A-1) contains two or more aromatic rings. When component (A-1) contains two or more aromatic rings, these two or more aromatic rings may be the same or different. The number of epoxy groups contained in component (A-1) is usually more than one, and from the viewpoint of balancing the adhesive strength and impact resistance of the cured product, it is preferable to have more than two and less than four. That is, in a preferred embodiment, the epoxy resin containing an aromatic skeleton in (A-1) contains 2 to 4 epoxy groups per molecule.

[0044] (A-1) Epoxy resins containing an aromatic backbone may be used as a single component or in combination of two or more different components. From the viewpoint of effectively improving the impact resistance of the cured resin composition, (A-1) epoxy resins containing an aromatic backbone preferably use a combination of two or more different components.

[0045] In a preferred embodiment, (A-1) the epoxy resin composition containing an aromatic backbone comprises: an epoxy resin containing two or more aromatic rings and a glycidylamine type epoxy resin. According to the embodiments described, the cured resin composition can exhibit improved bond strength and impact resistance.

[0046] Relative to the total of 100% by mass of components (A), (B), and (C), the amount of epoxy resin containing an aromatic skeleton in (A-1) of the resin composition is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, even more preferably 35% by mass or more, preferably 60% by mass or less, more preferably 55% by mass or less, and even more preferably 50% by mass or less.

[0047] The amount of epoxy resin containing an aromatic skeleton in (A-1) of the resin composition relative to the non-volatile components in 100% by mass is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 25% by mass or more, even more preferably 30% by mass or more, preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 45% by mass or less.

[0048] As described above, in the resin composition, the amount of epoxy resin containing an aromatic backbone (A-1) is 30% by mass or more relative to 100% by mass of epoxy resin (A). Therefore, as long as the range of the stated content is met, epoxy resin (A-2) may further contain epoxy resin without an aromatic backbone (hereinafter, sometimes referred to as "(A-2) component"). The amount of epoxy resin without an aromatic backbone (A-2) in the resin composition is less than 70% by mass relative to 100% by mass of epoxy resin (A-1), preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less. The lower limit of the amount of the (A-2) component can be 0% by mass (i.e., no (A-2) component), or it can be more than 0% by mass, more than 1% by mass, more than 5% by mass, or more than 10% by mass.

[0049] The epoxy resin includes epoxy resin that is liquid at 20°C (hereinafter referred to as "liquid epoxy resin") and epoxy resin that is solid at 20°C (hereinafter referred to as "solid epoxy resin"). For the resin composition, as epoxy resin (A), it is preferable to include liquid epoxy resin, and more preferably, it includes only liquid epoxy resin.

[0050] As a liquid epoxy resin, it is preferred to have a liquid epoxy resin containing two or more epoxy groups in one molecule.

[0051] As liquid epoxy resins, preferred types include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenolic varnish type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexane type epoxy resin, cyclohexanediethanol type epoxy resin, and epoxy resin with butadiene structure.

[0052] Specific examples of liquid epoxy resins include: DIC's "HP-4032", "HP-4032-D", and "HP-4032-SS" (naphthalene-type epoxy resin); Mitsubishi Chemical's "828US", "828", "828EL", and "825" (bisphenol A type epoxy resin); Mitsubishi Chemical's "807" and "1750" (bisphenol F type epoxy resin); Mitsubishi Chemical's "152" (phenolic varnish type epoxy resin); Mitsubishi Chemical's "630", "630LSD", and "604" (glycidylamine type epoxy resin); DIC's "N-730A"; Nippon Steel Chemical Materials Co., Ltd.'s "ZX-1059" (a mixture of bisphenol A and bisphenol F type epoxy resins); and DIC's "EXA-7250". (Triphenylmethane type epoxy resin); Nagase ChemteX's "EX-721" (glycidyl ester type epoxy resin); Daicel's "Celloxide 2021P" (alicyclic epoxy resin with ester backbone); Daicel's "PB-3600" (epoxy resin with butadiene structure); Nippon Steel Chemical Materials Co., Ltd.'s "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin); Resonac's "ShofreePETG" (pentaerythritol type epoxy resin), etc. Liquid epoxy resins can be used alone or in combination of two or more.

[0053] As a solid epoxy resin, it is preferred to have a solid epoxy resin containing two or more epoxy groups in one molecule, more preferably to have a solid epoxy resin containing three or more epoxy groups in one molecule, and even more preferably to have a solid epoxy resin containing three or more epoxy groups and an aromatic ring in one molecule.

[0054] As solid epoxy resins, preferred types include xylenol-type epoxy resins, naphthalene-type epoxy resins, naphthalene-type tetrafunctional epoxy resins, cresol-phenolic varnish-type epoxy resins, dicyclopentadiene-type epoxy resins, triphenol-type epoxy resins, naphthol-type epoxy resins, biphenyl-type epoxy resins, naphthylene ether-type epoxy resins, anthracene-type epoxy resins, bisphenol A-type epoxy resins, bisphenol AF-type epoxy resins, and tetraphenylethane-type epoxy resins, with biphenyl-type epoxy resins being more preferred.

[0055] Specific examples of solid epoxy resins include: DIC's "HP4032H" (naphthalene-type epoxy resin); DIC's "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resins); DIC's "N-690" (cresol-phenolic varnish type epoxy resin); DIC's "N-695" (cresol-phenolic varnish type epoxy resin); DIC's "HP-7200," "HP-7200HH," and "HP-7200H" (dicyclopentadiene type epoxy resin); DIC's "EXA-7311," "EXA-7311-G3," "EXA-7311-G4," "EXA-7311-G4S," "HP6000," and "HP6000L" (naphthyl ether type epoxy resin); and Nippon Kayaku Co., Ltd.'s "EPPN-502H." (Pyrophenol type epoxy resin); "NC7000L" (Naphthol phenolic varnish type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC3000H", "NC3000", "NC3000L", and "NC3100" (Biphenyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "ESN475V" (Naphthyl type epoxy resin) manufactured by Nippon Steel Chemical Materials Co., Ltd.; "ESN485" (Naphthol phenolic varnish type epoxy resin) manufactured by Nippon Steel Chemical Materials Co., Ltd.; "YL6121" (Biphenyl type epoxy resin), "YX4000", "YX4000H", and "YX4000HK" (Bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "YX8800" (Anthracene type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.; "YL7760" manufactured by Mitsubishi Chemical Co., Ltd. (Bisphenol AF type epoxy resin); Mitsubishi Chemical's "YL7800" (fluorene type epoxy resin); Mitsubishi Chemical's "1010" (solid bisphenol A type epoxy resin); Mitsubishi Chemical's "1031S" (tetraphenylethane type epoxy resin); Nippon Kayaku Co., Ltd.'s "WHR-991S" (phenol benzopyrrolidone type epoxy resin), etc. Solid epoxy resins can be used alone or in combination of two or more.

[0056] When liquid epoxy resin and solid epoxy resin are used in combination as epoxy resin (A), their mass ratio (liquid epoxy resin: solid epoxy resin) is preferably 1:0.1 to 1:20, more preferably 1:0.15 to 1:10, and even more preferably 1:0.2 to 1:5.

[0057] (A) The epoxy equivalent of the epoxy resin is preferably 50 g / eq. or more, more preferably 80 g / eq. or more, even more preferably 110 g / eq. or more, preferably 5,000 g / eq. or less, more preferably 3,000 g / eq. or less, even more preferably 2,000 g / eq. or less, and even more preferably 1,000 g / eq. or less. When the epoxy equivalent of the epoxy resin is within the above range, a cured body with sufficient crosslinking density of the resin composition can be obtained. The epoxy equivalent is the mass of epoxy resin containing 1 equivalent of epoxy groups. This epoxy equivalent can be determined according to JIS K7236.

[0058] (A) The weight-average molecular weight (Mw) of the epoxy resin is preferably 100 or more, more preferably 150 or more, even more preferably 200 or more, preferably 5,000 or less, more preferably 3,000 or less, and even more preferably 1,500 or less. The weight-average molecular weight of the epoxy resin is the weight-average molecular weight converted from polystyrene as determined by gel permeation chromatography (GPC).

[0059] Relative to the total of 100% by mass of components (A), (B), and (C), the amount of epoxy resin (A) in the resin composition is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 35% by mass or more, preferably 60% by mass or less, more preferably 55% by mass or less, and even more preferably 50% by mass or less. When the amount of epoxy resin (A) is within the above range, the adhesive strength and impact resistance of the cured resin composition can be effectively improved.

[0060] Relative to the non-volatile components in 100% by mass of the resin composition, the amount of epoxy resin (A) in the resin composition is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more or 33% by mass or more, preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 45% by mass or less. When the amount of epoxy resin (A) is within the above range, the adhesive strength and impact resistance of the cured resin composition can be effectively improved.

[0061] <(B) Thiol compounds represented by formula (I) (thiol compounds with specific structures)> The resin composition of the present invention comprises (B) a thiol compound having a specific structure as component (B). The thiol compound having a specific structure is represented by the following formula (I). The thiol compound having a specific structure can react with the epoxy resin (A) to cure the resin composition. One thiol compound having a specific structure can be used alone, or two or more can be used in combination.

[0062] In formula (I), Each ring P is independently either phenyl or naphthyl. When ring P is phenyl, there are 1 to 5 atoms relative to each ring P; when ring P is naphthyl, there are 1 to 7 atoms relative to each ring P, and each a atom is independently -R. 1 -SH, R 1 Each is independently a C1-C6 alkylene group that can be substituted by one or more Y atoms. B is a group on ring P other than A, each of which is independently a hydrogen atom, a C1-C6 alkyl group that can be substituted by one or more Y atoms, or a C1-C6 alkoxy group that can be substituted by one or more Y atoms. When ring P is phenyl, A and B are independently bonded at the ortho, meta, or para positions relative to the position of ring P bonded to the main chain. When ring P is naphthyl, A and B are independently bonded at the ortho, meta, para, remote, epitope, telomere, forced, equatorial, transposition, or 2,7 positions relative to the position of ring P bonded to the main chain. X can be independently -CH2-, -O-, or -N(-R) 2 )- or -S-, R 2 Each is independently a hydrogen atom, a C1-C6 alkyl group that can be substituted with one or more Y atoms, or a C1-C6 alkoxy group that can be substituted with one or more Y atoms. Y can be independently a hydrogen atom, a C1-C6 alkyl group, or a C1-C6 alkoxy group. Z can be directly bonded, -CH2-, -C2H4-, -C3H6-, -C4H8-, -O-, or -S-. n is an integer from 1 to 20.

[0063] In formula (I), each ring P is independently phenyl or naphthyl. Ring P is preferably phenyl.

[0064] In formula (I), when ring P is phenyl, there are typically 1 to 5 A atoms relative to each ring P, preferably 1 to 3, more preferably 1 to 2, and even more preferably 1. When ring P is naphthyl, there are typically 1 to 7 A atoms relative to each ring P, preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 to 2.

[0065] Each A is independently -R 1 -SH. R 1 Each is independently a C1-C6 alkylene group that can be substituted by one or more Y atoms. R 1Preferably, it is an unsubstituted C2-C5 alkylene group; more preferably, it is an unsubstituted C2-C3 alkylene group. This alkylene group can be straight-chain or branched, and can be saturated or unsaturated. Furthermore, the alkylene group may or may not be substituted with Y. The definition of Y is described below.

[0066] In formula (I), B is a group on ring P other than A. Therefore, when ring P is phenyl, the total number of groups A and B on one ring P is 5, and when ring P is naphthyl, the total number of groups A and B on one ring P is 7. Regarding the number of groups A and B on one ring P, for example, relative to each ring P, A is 1 to 2, and B (excluding hydrogen atoms) is 0 to 2; more preferably, relative to each ring P, A is 1, and B (excluding hydrogen atoms) is 0 to 1.

[0067] Each of the B atoms is independently a hydrogen atom, a C1-C6 alkyl group that may be substituted with one or more Y atoms, or a C1-C6 alkoxy group that may be substituted with one or more Y atoms. The definition of Y is as described below. Preferably, each of the B atoms is independently a hydrogen atom, an unsubstituted C1-C3 alkyl group, or an unsubstituted C1-C3 alkoxy group; more preferably, each of the B atoms is independently a hydrogen atom, a methyl group, or a methoxy group; even more preferably, B atoms are hydrogen atoms. All B atoms may be hydrogen atoms. Alternatively, as another option, one or two B atoms present on each ring P may be methyl, methoxy, or phenyl, and all other B atoms present on each ring P may be hydrogen atoms. When ring P is phenyl, typically 0 to 4, preferably 0 to 3, more preferably 1 to 2 B atoms relative to each ring P may not be hydrogen atoms. When ring P is naphthyl, typically 0 to 6, preferably 0 to 5, more preferably 1 to 3, more preferably 1 to 2 B atoms relative to each ring P may not be hydrogen atoms.

[0068] When ring P is phenyl, A and B can 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 be independently bonded to the ortho or para position relative to the position where ring P is bonded to the main chain. As a more preferred embodiment, if there is one A on ring P and one B (excluding hydrogen atoms) is absent or present on ring P, the A is bonded to the ortho or para position relative to the position where ring P is bonded to the main chain, and if there is a B (excluding hydrogen atoms) relative to the position where ring P is bonded to the main chain, the B is bonded to the ortho position. 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.

[0069] When ring P is naphthyl, A and B can be independently bonded to the ortho, meta, para, remote, epitope, salient, forced, transposition, or 2,7 position relative to the position of ring P bonded to the main chain. Preferably, A and B can be independently bonded to the remote, epitope, salient, forced, transposition, or 2,7 position relative to the position of ring P bonded to the main chain. As a more preferred embodiment, if there is one A on ring P, and there is no B or one B other than a hydrogen atom on ring P, the A is bonded to the transposition or 2,7 position relative to the position of ring P bonded to the main chain, and the B is bonded to the transposition or 2,7 position relative to the position of ring P bonded to the main chain.

[0070] In equation (I), X is independently -CH2-, -O-, or -N(-R) 2 )- or -S-. Here, R 2 Each is independently a hydrogen atom, a C1-C6 alkyl group that can be substituted with one or more Y atoms, or a C1-C6 alkoxy group that can be substituted with one or more Y atoms. R 2 Preferably, it is an unsubstituted C2-C5 alkylene group; more preferably, it is an unsubstituted C2-C3 alkylene group. This alkylene group can be straight-chain or branched, and can be saturated or unsaturated. Furthermore, the alkylene group may or may not be substituted with Y. The definition of Y is described below. X is preferably -CH2- or -O-, more preferably -O-.

[0071] 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.

[0072] In formula (I), Z is independently direct-bonded, -CH2-, -C2H4-, -C3H6-, -C4H8-, -O-, or -S-. Z is preferably direct-bonded, -CH2-, -O-, or -S-; more preferably direct-bonded or -O-; and even more preferably direct-bonded.

[0073] In formula (I), n is an integer from 1 to 20. n is preferably an integer from 1 to 10; more preferably an integer from 2 to 5 or from 1 to 3.

[0074] Specific examples of thiols represented by formula (I) in (B) include: thiols represented by formula (I-1), thiols represented by formula (I-2), thiols represented by formula (I-3), thiols represented by formula (I-4), thiols represented by formula (I-5), and thiols represented by formula (I-6). Among these, thiols represented by formula (I-1) and thiols represented by formula (I-3) are preferred; thiols represented by formula (I-1) are particularly preferred.

[0075] There are no limitations on the method for producing the thiol compound represented by formula (I) in (B). For example, the thiol compound represented by formula (I-1) can be produced by the following method. First, 2-allylphenol and 1,4-dibromobutane, as starting materials, are mixed with tetra-n-butylammonium bromide as a phase transfer catalyst and methyl isobutyl ketone (MIBK) as a reaction solvent to dissolve them. In one example, after mixing, the mixture is typically maintained at 50°C to 200°C, preferably 60°C to 150°C, more preferably 100°C ± 10 to 20°C (i.e., 80°C to 120°C or 90°C to 110°C) for 1 minute to 12 hours, preferably 10 minutes to 5 hours, more preferably 30 minutes ± 10 to 20 minutes (i.e., 10 minutes to 50 minutes or 20 minutes to 40 minutes) to dissolve it. The resulting solution is mixed with an alkali such as KOH aqueous solution, and then the reaction is carried out at a temperature range of, for example, 100°C to 150°C, preferably 110°C to 120°C, while distilling off water. The reaction time is usually 1 hour to 24 hours, preferably 2 hours to 10 hours, more preferably 6 hours ± 1 hour (i.e., 5 hours to 7 hours). Afterward, the temperature is lowered to about 60°C, distilled water is added and the mixture is allowed to stand, discarding the lower byproduct brine layer. Then, distilled water and an alkali (a suitable amount of sodium dihydrogen phosphate, etc. for neutralization) are added and the mixture is allowed to stand and separate, discarding the lower byproduct brine layer. Then, an equal amount of distilled water is added, and the mixture is usually washed and purified 1 to 5 times, preferably 2 to 3 times. Afterward, the mixture is heated to, for example, 50°C to 200°C, preferably 60°C to 150°C, more preferably 120°C ± 10 to 20°C (i.e., 100°C to 140°C or 110°C to 130°C) for azeotropic dehydration. The resulting solution is precisely filtered 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 is, for example, 50°C to 200°C, preferably 60°C to 150°C, more preferably 80°C ± 10 to 20°C (i.e., 60°C to 100°C or 70°C to 90°C). The reaction time is, for example, 30 minutes to 24 hours, preferably 1 hour to 10 hours, more preferably 4 hours ± 1 to 2 hours (i.e., 2 hours to 6 hours or 3 hours to 5 hours). After removing toluene from the resulting reactants, crystallization is performed with methanol, the crystals are dried, and recovered. The recovered dried crystals are mixed with an alkali such as NaOH and reacted. The reaction temperature is, for example, 50°C to 200°C, preferably 60°C to 150°C, and more preferably 80°C ± 10 to 20°C (i.e., 60°C to 100°C or 70°C to 90°C). The reaction time is, for example, 30 minutes to 12 hours, preferably 1 hour to 5 hours, and more preferably 2 hours ± 1 hour (i.e., 1 hour to 3 hours). After neutralization with an acid such as hydrochloric acid, the organic layer is separated and washed with water.The target thiol compound can be obtained by removing toluene from the organic layer after washing with water. The specific manufacturing method can be found in the specification described in Japanese Patent Application No. 2023-057934.

[0076] Relative to the total of 100% by mass of components (A), (B), and (C), the amount of the thiol compound represented by formula (I) in the resin composition is preferably 30% by mass or more, more preferably 40% by mass or more, further preferably 45% by mass or more, 47% by mass or more, or 49% by mass or more, preferably 85% by mass or less, more preferably 75% by mass or less, further preferably 65% ​​by mass or less, 63% by mass or less, or 61% by mass or less. When the amount of the thiol compound represented by formula (I) in (B) is within the above-mentioned range, the adhesive strength and impact resistance of the cured resin composition can be effectively improved.

[0077] Relative to the non-volatile components in 100% by mass of the resin composition, the amount of the thiol compound represented by formula (I) in the resin composition is preferably 30% by mass or more, more preferably 40% by mass or more, even more preferably 45% by mass or more, preferably 85% by mass or less, more preferably 70% by mass or less, even more preferably 60% by mass or less or 57% by mass or less. When the amount of the thiol compound represented by formula (I) is within the above range, the adhesive strength and impact resistance of the cured resin composition can be effectively improved.

[0078] In the resin composition, the mass ratio of the thiol compound represented by formula (I) of (B) to the epoxy resin of (A) (the content of the thiol compound represented by formula (I) of (B) / the content of the epoxy resin of (A)) is preferably 0.1 or more, more preferably 0.5 or more, further preferably 1 or more, preferably 5 or less, more preferably 3 or less, further preferably 2 or less, or 1.7 or less. When the above-mentioned mass ratio (the content of the thiol compound represented by formula (I) of (B) / the content of the epoxy resin of (A)) is within the above-mentioned range, the adhesive strength and impact resistance of the cured resin composition can be effectively improved.

[0079] In the resin composition, the ratio (thiol group number / epoxy group number) of the thiol compound represented by formula (I) in (B) to the epoxy group number of the epoxy resin in (A) is preferably within a specific range. This ratio (thiol group number / epoxy group number) is preferably 0.1 or more, more preferably 0.5 or more, further preferably 0.8 or more or 0.9 or more, preferably 3 or less, more preferably 2 or less, and further preferably 1.5 or less, 1.3 or less, or 1.1 or less. The "epoxy group number of the epoxy resin in (A)" in the resin composition represents the sum of all values ​​obtained by dividing the mass of the epoxy resin present in the resin composition by its epoxy equivalent. Furthermore, the "thiol group number of the thiol compound represented by formula (I) in (B)" in the resin composition represents the sum of all values ​​obtained by dividing the mass of the thiol compound represented by formula (I) in the resin composition by its thiol equivalent. Additionally, the thiol equivalent represents the mass of the resin containing 1 equivalent of thiol groups. When the ratio (thiol group number / epoxy group number) is within the above range, the adhesive strength and impact resistance of the cured resin composition can be effectively improved.

[0080] The resin composition may include, in combination with the thiol compound represented by formula (I) (B), other thiol compounds (E) described later. In the resin composition of the embodiments involved, the ratio of the total number of thiol groups of the thiol compound represented by formula (I) (B) and the total number of thiol groups of the other thiol compounds (E) to the number of epoxy groups of the epoxy resin (A) (total number of thiol groups / number of epoxy groups) is preferably within a specific range. When the resin composition includes other thiol compounds (E), the ratio (total number of thiol groups / number of epoxy groups) is preferably 0.1 or more, more preferably 0.5 or more, further preferably 0.8 or more or 1 or more, preferably 5 or less, more preferably 3 or less, further preferably 2 or less, and even more preferably 1.5 or less. When the ratio (total number of thiol groups / number of epoxy groups) is within the above range, the adhesive strength and impact resistance of the cured resin composition can be effectively improved.

[0081] <(C) Curing Accelerator> The resin composition of the present invention includes a curing accelerator (C) as component (C). The curing accelerator (C) does not include components equivalent to components (A) and (B) described above. The curing accelerator (C) acts as a catalyst on the reaction of the epoxy resin (A), promoting the curing of the resin composition. One type of curing accelerator (C) may be used alone, or two or more may be used in combination.

[0082] As a curing accelerator for (C), a latent curing accelerator is preferred. Latent curing accelerators generally do not contribute to the curing of epoxy resin (A) at room temperature (25°C), but they have the function of promoting the curing of epoxy resin (A) when heated.

[0083] Latent curing accelerators can be either liquid latent curing accelerators or solid-dispersed latent curing accelerators, but solid-dispersed latent curing accelerators are more preferred. Liquid latent curing accelerators refer to liquids that are soluble in the resin composition at room temperature (25°C), indicating compounds that function as curing accelerators for epoxy resin (A) upon heating. On the other hand, solid-dispersed latent curing accelerators refer to solids that are insoluble in the resin composition at room temperature (25°C), but become soluble in the resin composition upon heating and function as curing accelerators for epoxy resin (A).

[0084] Examples of solid-dispersed latent curing accelerators include imidazole compounds and solid-dispersed amine adduct systems that are solid at room temperature (25°C).

[0085] Examples of imidazole compounds that are solid at room temperature (25°C) include: 2-heptadecylimidazolium, 2-phenyl-4,5-dihydroxymethylimidazolium, 2-undecylimidazolium, 2-phenyl-4-methyl-5-hydroxymethylimidazolium, 2-phenyl-4-benzyl-5-hydroxymethylimidazolium, 2,4-diamino-6-[2-(2-methyl-1-imidazolyl)ethyl]-1,3,5-triazine, 2,4-diamino-6-[2-(2-methyl-1-imidazolyl)ethyl]-1,3,5-triazine-isocyanuric acid adduct, 2-methylimidazolium, 2-phenylimidazolium, 2-phenyl-4-methylimidazolium, 1-cyanoethyl-2-phenylimidazolium, 1-cyanoethyl-2-methylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, N-(2-methylimidazolyl-1-ethyl)urea, etc.

[0086] Preferred examples of solid-dispersed 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 adding isocyanate compounds to the hydroxyl groups of epoxy adducts. Among these, amine-epoxy adduct-based latent curing accelerators are preferred.

[0087] Examples of epoxy compounds that can be used as latent curing accelerators for solid-dispersed amine adduct systems include: polyglycidyl ethers obtained by reacting polyphenols (bisphenol A, bisphenol F, catechol, resorcinol, etc.) or polyols (glycerol, polyethylene glycol, etc.) with epichlorohydrin; glycidyl ether esters obtained by reacting hydroxycarboxylic acids such as p-hydroxybenzoic acid and β-hydroxynaphthyl acid with epichlorohydrin; polyglycidyl esters obtained by reacting polycarboxylic acids such as phthalic acid and terephthalic acid with epichlorohydrin; glycidyl amine compounds obtained by reacting 4,4'-diaminodiphenylmethane or m-aminophenol with epichlorohydrin; polyfunctional epoxy compounds such as epoxidized phenolic varnish resins, epoxidized cresol varnish resins, and epoxidized polyolefins; and monofunctional epoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, and glycidyl methacrylate.

[0088] Amine compounds that can be used as one of the raw materials for manufacturing latent curing accelerators of solid-dispersed amine adduct systems can be compounds having one or more active hydrogen atoms in the molecule that can undergo addition reactions with epoxy groups, and having at least one functional group selected from primary, secondary, and tertiary amines in the molecule. Examples of the amine compounds involved include, for example, 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-methylimidazolium, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline, piperidine, and piperazine.

[0089] Among the aforementioned amine compounds, those containing a tertiary amino group within the molecule are raw materials for providing latent curing accelerators with excellent curing-promoting abilities. Examples of amine compounds containing a tertiary amino group within the molecule include: primary or secondary amines; alcohols, phenols, thiols, carboxylic acids, and hydrazides. Examples of primary or secondary amines containing a tertiary amino group within the molecule include: dimethylaminopropylamine, diethylaminopropylamine, di-n-propylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, N-methylpiperazine, etc.; and imidazole compounds such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, etc. In addition, examples of alcohols, phenols, thiols, carboxylic acids, and hydrazides containing a tertiary amino group within 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-butoxypropyl)-2-ethyl-4-methylimidazole, 1 -(2-hydroxy-3-phenoxypropyl)-2-phenylimidazoline, 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazoline, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol, N-β-hydroxyethylmorpholine, 2-dimethylaminoethanethiol, 2-mercaptopyridine, 2-benzimidazole, 2-mercaptopyridine, 2-mercaptopyridine, 2-mercaptopyridine, 2-mercaptopyridine, 2-mercaptopyridine, 4-mercaptopyridine, N,N-dimethylaminobenzoic acid, N,N-dimethylglycine, nicotinic acid, isonicotinic acid, methylpyridine acid, N,N-dimethylglycine hydrazide, N,N-dimethylpropionic acid hydrazide, nicotinic acid hydrazide, isonicotinic acid hydrazide.

[0090] When producing latent curing accelerators by adding epoxy compounds to amine compounds, active hydrogen compounds with two or more active hydrogen atoms in the molecule can also be reacted. Examples of such active hydrogen compounds include: polyphenols such as bisphenol A, bisphenol F, bisphenol S, hydroquinone, catechol, resorcinol, pyrogallol, and phenolic varnish resins; polyols such as trimethylolpropane; polycarboxylic 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.

[0091] Isocyanate compounds that can be used as raw materials for manufacturing latent curing accelerators for solid-dispersed amine adduct systems include, for example, 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, phenyl diisocyanate, terephthalene diisocyanate, 1,3,6-hexamethylene triisocyanate, and bicycloheptane triisocyanate; and compounds containing terminal isocyanate groups obtained by reacting these polyfunctional isocyanate compounds with active hydrogen compounds. Specific examples of compounds containing terminal isocyanate groups include: addition compounds with terminal isocyanate groups obtained by the reaction of toluene diisocyanate with trimethylolpropane, and addition compounds with terminal isocyanate groups obtained by the reaction of toluene diisocyanate with pentaerythritol.

[0092] Urea compounds that can be used as raw materials for manufacturing latent curing accelerators for solid-dispersed amine adduct systems include, for example, urea and thiourea.

[0093] The aforementioned solid-dispersed amine adduct is a latent curing accelerator, which can be manufactured, for example, by the following methods: mixing the above-mentioned raw materials, reacting them at a temperature of room temperature to 200°C, cooling and curing them, and then pulverizing them; or reacting the above-mentioned raw materials in solvents such as methyl ethyl ketone, dimethyl ether, and tetrahydrofuran, removing the solvent, and then pulverizing the solid components.

[0094] Commercially available solid-dispersed amine adduct latent curing accelerators include, for example: "Amicure PN-FJ", "Amicure PN-23", and "Amicure PN-H" manufactured by Ajinomoto Fine-Techno Co., Inc.; "Hardener X-3661S" and "Hardener X-3670S" manufactured by ACR Corporation; "FXR-1081", "Fujicure FXR-1000", and "Fujicure FXR-1030" manufactured by T&K TOKA Corporation; and "Novocure HX-3721", "HX-3722", and "Novocure HX-3742" manufactured by Asahi Kasei Corporation.

[0095] Relative to the total of 100% by mass of components (A), (B), and (C), the amount of curing accelerator (C) in the resin composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 1.5% by mass or more or 1.8% by mass or more, preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.

[0096] The amount of (C) curing accelerator in the resin composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 1.5% by mass or more or 1.7% by mass or more, preferably 8% by mass or less, more preferably 6% by mass or less, even more preferably 4% by mass or less, and even more preferably 2.5% by mass or less, relative to the non-volatile components in 100% by mass of the resin composition.

[0097] In the resin composition, the mass ratio of the thiol compound represented by formula (I) (B) to the curing accelerator (C) (content of the thiol compound represented by formula (I) / content of the curing accelerator (C)) is preferably 10 or more, more preferably 15 or more, further preferably 20 or more, preferably 50 or less, more preferably 40 or less, and even more preferably 35 or less or 33 or less. When the above-mentioned mass ratio (content of the thiol compound represented by formula (I) / content of the curing accelerator (C)) is within the above-mentioned range, the adhesive strength and impact resistance of the cured resin composition can be effectively improved.

[0098] Relative to the non-volatile components in 100% by mass of the resin composition, the combined amount of (A) epoxy resin, (B) thiol compound represented by formula (I), and (C) curing accelerator in the resin composition is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, even more preferably 80% by mass or more, and even more preferably 90% by mass or more. The upper limit is typically 100% by mass or less, and can be 99% by mass or less. When the combined amount of components (A) to (C) is within the above-mentioned range, the adhesive strength and impact resistance of the cured resin composition can be effectively improved.

[0099] <(D) Inorganic filler materials> The resin composition of the present invention may optionally include (D) inorganic filler material. The (D) inorganic filler material, as component (D), is particulate inorganic material. Therefore, the (D) inorganic filler material is contained in the resin composition in particulate form, and typically, it is contained in the cured product to maintain this particulate state. One type of (D) inorganic filler material may be used alone, or two or more may be used in combination.

[0100] Inorganic compounds are typically used as inorganic materials to form the (D) inorganic filler. Examples of materials that can be used as (D) inorganic fillers 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 zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is preferred. Examples of silica include: fumed silica, amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. In a preferred embodiment, the (D) inorganic filler comprises fumed silica.

[0101] Fumed silica includes hydrophilic fumed silica and hydrophobic fumed silica. Hydrophilic fumed silica is obtained by flame hydrolysis of silicon tetrachloride and has hydrophilic silanol groups on its surface. Commercially available hydrophilic fumed silica includes products such as "200", "300", and "380" manufactured by NIPPON AEROSIL CO., LTD. Hydrophobic fumed silica is obtained by treating the aforementioned hydrophilic fumed silica with a surface treatment agent to make it hydrophobic. Commercially available hydrophobic fumed silica products include: "R972", "R972V", "R974", "R976", "R976S", "RX50", "RX200", "RX300", "RY200S", "RY200", "RY300", "R202", "R805", and "R7200" manufactured by NIPPON AEROSIL CO., LTD. These fumed silicas can be used alone or in combination of two or more.

[0102] Among hydrophobic fumed silica, examples of surface treatment agents include: organosilane compounds such as dimethylsilane, trimethylsilane, alkylsilane, methacryloxysilane, and organochlorosilane; organosiloxane compounds such as polydimethylsiloxane; and organosilazane compounds such as hexamethyldisilazane.

[0103] The average particle size of the fumed silica used as the inorganic filler in (D) is preferably 0.01 μm or more, more preferably 0.05 μm or more, even more preferably 0.07 μm or more, even more preferably 0.09 μm or more, preferably 100 μm or less, more preferably 50 μm or less, even more preferably 10 μm or less, and even more preferably 1 μm or less. When the average particle size of the fumed silica is within the above-mentioned range, the adhesive strength and impact resistance of the cured resin composition can be effectively improved.

[0104] The average particle size of (D) inorganic filler materials can be determined by laser diffraction / scattering based on the Mie scattering theory. Specifically, a particle size distribution of the (D) inorganic filler material can be prepared on a volume basis using a laser diffraction scattering particle size distribution measuring device, and the average particle size, which is the median particle size, can be determined based on this particle size distribution. The sample used for measurement is preferably a sample obtained by ultrasonically dispersing the (D) inorganic filler material in water. As a laser diffraction scattering particle size distribution measuring device, the "LA-960" manufactured by Horiba Corporation and the "SALD-2200" manufactured by Shimadzu Corporation can be used.

[0105] The preferred specific surface area range for fumed silica, used as an inorganic filler material in (D), is 1 m². 2 / g or more, preferably 10m 2 / g or more, more preferably 50m 2 / g or more, and more preferably 100m 2 / g or more or 150m 2 / g or more, preferably 500m 2 / g or less, more preferably 400m 2 / g or less, more preferably 300m 2 / g or less or 250m 2 / g or less. When the specific surface area of ​​fumed silica is within the range described, the bond strength and impact resistance of the cured resin composition can be effectively improved.

[0106] (D) The specific surface area of ​​inorganic filler materials can be determined as follows: using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) according to the BET method, nitrogen gas is adsorbed onto the sample surface, and the specific surface area is calculated using the BET multi-point method.

[0107] Commercially available (D) inorganic filler materials other than fumed silica include: "SP60-05" and "SP507-05" manufactured by Nippon Steel Chemical Materials Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", "YA010C", "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1" manufactured by Admatechs Co., Ltd.; "UFP-30", "DAW-03", and "FB-105FD" manufactured by DENKA Co., Ltd.; "SILFIL NSS-3N", "SILFIL NSS-4N", and "SILFIL NSS-5N" manufactured by Tokuyama Co., Ltd.; and "CellSpheres" and "MGH-005" manufactured by Pacific Cement Co., Ltd.

[0108] The average particle size of the (D) inorganic filler material, excluding fumed silica, is preferably 0.01 μm or more, more preferably 0.05 μm or more, even more preferably 0.07 μm or more, even more preferably 0.09 μm or more, preferably 100 μm or less, more preferably 50 μm or less, even more preferably 10 μm or less, and even more preferably 1 μm or less. When the average particle size of the (D) inorganic filler material, excluding fumed silica, is within the above-mentioned range, the adhesive strength and impact resistance of the cured resin composition can be effectively improved.

[0109] The specific surface area of ​​(D) inorganic filler materials other than fumed silica is preferably in the range of 0.05 m². 2 / g or more, more preferably 0.1m 2 / g or more, further preferably 1m 2 / g or more, 3m 2 / g or more or 5m 2 / g or more, preferably 100m 2 / g or less, preferably 80m 2 / g or less, more preferably 60m 2 / g or less, 50m 2 / g or less or 40m 2 / g or less. When the specific surface area of ​​the (D) inorganic filler material other than fumed silica is within the range described, the bond strength and impact resistance of the cured resin composition can be effectively improved.

[0110] From the perspective of improving moisture resistance and dispersibility, (D) inorganic fillers other than fumed silica can be treated with surface treatment agents. 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. A single surface treatment agent can be used, or two or more can be used in combination.

[0111] Commercially available surface treatment agents include, for example, "KBM403" (3-epoxypropoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBM5783" (N-phenyl-3-aminooctyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., and "KBM-4803" (long-chain epoxy silane coupling agent) manufactured by Shin-Etsu Chemical Industry Co., Ltd.

[0112] From the viewpoint of improving the dispersibility of the (D) inorganic filler material, it is preferable to control the degree of surface treatment by the surface treatment agent within a specific range. When the (D) inorganic filler material is treated with a surface treatment agent, it is preferable to use 0.2 to 5 parts by mass of the surface treatment agent for 100 parts by mass of the inorganic filler material, more preferably 0.2 to 3 parts by mass of the surface treatment agent, and even more preferably 0.3 to 2 parts by mass of the surface treatment agent.

[0113] The degree of surface treatment by the surface treatment agent can be evaluated by the carbon content per unit surface area of ​​the (D) inorganic filler. When the (D) inorganic filler is treated with a surface treatment agent, from the viewpoint of improving the dispersibility of the (D) inorganic filler, the carbon content per unit surface area of ​​the (D) inorganic filler is preferably 0.02 mg / m². 2 More preferably 0.1 mg / m 2 The above is further optimized to 0.2 mg / m². 2 That's all. On the other hand, from the viewpoint of suppressing the increase in melt viscosity of the resin composition, the upper limit of the carbon content per unit surface area of ​​the (D) inorganic filler material is preferably 1.0 mg / m². 2 Below, 0.8 mg / m² is more preferred. 2The following is a further preferred dosage: 0.5 mg / m² 2 the following.

[0114] The carbon content per unit surface area of ​​the inorganic filler material (D) can be determined after washing the surface-treated inorganic filler material with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the surface-treated inorganic filler material, and ultrasonic washing is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid components, the carbon content per unit surface area of ​​the inorganic filler material can be determined using a carbon analyzer. A carbon analyzer such as the "EMIA-320V" manufactured by Horiba Seisakusho Co., Ltd. can be used.

[0115] When the resin composition contains (D) inorganic filler, the amount of (D) inorganic filler in the resin composition is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, 6% by mass or more, or 7% by mass or more, preferably 30% by mass or less, more preferably 25% by mass or less, further preferably 20% by mass or less, and even more preferably 15% by mass or less, 13% by mass or less, or 10% by mass or less when the amount of (D) inorganic filler is within the above range, the adhesive strength and impact resistance of the cured resin composition can be effectively improved.

[0116] When the resin composition contains inorganic filler (D), the mass ratio of the thiol compound represented by formula (I) to the inorganic filler (D) (content of the thiol compound represented by formula (I) / content of the inorganic filler (D)) is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, preferably 30 or less, more preferably 25 or less, further preferably 20 or less, and even more preferably 15 or less, 13 or less, or 10 or less. When the above-mentioned mass ratio (content of the thiol compound represented by formula (I) / content of the inorganic filler (D)) is within the above-mentioned range, the adhesive strength and impact resistance of the cured resin composition can be effectively improved.

[0117] <(E) Other Thiol Compounds> The resin composition of the present invention may include (E) other thiol compounds as optional components. The (E) other thiol compounds as component (E) are not the thiol compounds represented by formula (I) above. That is, the (E) other thiol compounds are thiol compounds other than component (B). One (E) other thiol compound may be used alone, or two or more may be used in combination.

[0118] As other thiols (E), compounds having one or more thiol groups in one molecule and not represented by formula (I) above may be used. Among them, other thiols (E) are preferably polythiols having two or more thiol groups in one molecule.

[0119] The polythiol compounds may be commercially available products or compounds manufactured by known methods (e.g., the methods described in Japanese Patent Application Publication No. 2012-153794 or International Publication No. 2001 / 00698).

[0120] Examples of polythiol compounds include partial esters of polyols and thiol-containing organic acids, and complete esters of polyols and thiol-containing organic acids. Here, a partial ester refers to an ester of a polyol and a carboxylic acid in which some of the hydroxyl groups of the polyol form ester bonds. Conversely, a complete ester refers to an ester of a polyol and a carboxylic acid in which all the hydroxyl groups of the polyol form ester bonds.

[0121] Examples of polyols used in the synthesis of polythiol compounds include ethylene glycol, trimethylolethane, trimethylolpropane, pentaerythritol, and dipentaerythritol.

[0122] Examples of thiol organic acids used in the synthesis of polythiol compounds include: thiol aliphatic monocarboxylic acids (monocarboxylic acids) such as thioglycolic acid, thiol propionic acid (e.g., 3-mercaptopropionic acid), and thiol butyric acid (e.g., 3-mercaptobutyric acid, 4-mercaptobutyric acid); esters containing thiol and carboxyl groups obtained by esterification of hydroxy acids with thiol organic acids; thiol aliphatic dicarboxylic acids such as thiol succinic acid and dimercaptosuccinic acid (e.g., 2,3-dimercaptosuccinic acid); and thiol aromatic monocarboxylic acids such as thiol benzoic acid (e.g., 4-mercaptobenzoic acid). The number of carbon atoms in the thiol aliphatic monocarboxylic acid is preferably 2 to 8, more preferably 2 to 6, further preferably 2 to 4, and particularly preferably 3. The thiol organic acid used to synthesize polythiol compounds is preferably a thiol aliphatic monocarboxylic acid with 2 to 8 carbon atoms, more preferably thioacetic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid and 4-mercaptobutyric acid, and even more preferably 3-mercaptopropionic acid.

[0123] Specific examples of partial esters of polyols and thiol organic acids include: trimethylolethane bis(thiolacetate), trimethylolethane bis(3-mercaptopropionate), trimethylolethane bis(3-mercaptobutyrate), trimethylolethane bis(4-mercaptobutyrate), trimethylolpropane bis(thiolacetate), trimethylolpropane bis(3-mercaptopropionate), trimethylolpropane bis(3-mercaptobutyrate), trimethylolpropane bis(4-mercaptobutyrate), pentaerythritol tri(thiolacetate), pentaerythritol tri(3-mercaptopropionate), pentaerythritol tri(3-mercaptobutyrate), pentaerythritol tri(4-mercaptobutyrate), dipentaerythritol tetra(thiolacetate), dipentaerythritol tetra(3-mercaptopropionate), dipentaerythritol tetra(3-mercaptobutyrate), dipentaerythritol tetra(4-mercaptobutyrate), etc.

[0124] Specific examples of complete esters of polyols and thiol organic acids include: ethylene glycol bis(thiol acetate), ethylene glycol bis(3-thiol propionate), ethylene glycol bis(3-thiol butyrate), ethylene glycol bis(4-thiol butyrate), trimethylolethane tri(thiol acetate), trimethylolethane tri(3-thiol propionate), trimethylolethane tri(3-thiol butyrate), trimethylolethane tri(4-thiol butyrate), trimethylolpropane tri(thiol acetate), trimethylolpropane Tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), trimethylolpropane tris(4-mercaptobutyrate), pentaerythritol tetra(mercaptoacetate), pentaerythritol tetra(3-mercaptopropionate), pentaerythritol tetra(3-mercaptobutyrate), pentaerythritol tetra(4-mercaptobutyrate), dipentaerythritol hexa(mercaptoacetate), dipentaerythritol hexa(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptobutyrate), dipentaerythritol hexa(4-mercaptobutyrate), etc.

[0125] From the perspective of preservation stability, partial and complete esters of polyols and thiol organic acids are preferred to have as little basic impurities as possible, and more preferably esters that do not require the use of basic substances in manufacturing.

[0126] In addition, polythiols such as alkane polythiols (1,4-butanedithiol, 1,6-hexanedithiol, 1,10-decanedithiol), polyethers containing terminal thiol groups, polysulfides containing terminal thiol groups, polythiols obtained by reacting epoxides with hydrogen sulfide, and polythiols with terminal thiol groups obtained by reacting polythiols with epoxides can also be manufactured using alkaline substances as reaction catalysts in their manufacturing process. Polythiols manufactured using alkaline substances are preferably subjected to dealkalization treatment to ensure that the concentration of alkali metal ions is below 50 ppm by mass before use.

[0127] Examples of dealkali treatment for polythiol compounds produced using alkaline substances include: dissolving the polythiol compound in organic solvents such as acetone and methanol, neutralizing it by adding acids such as dilute hydrochloric acid and dilute sulfuric acid, and then desalting it by extraction, washing, etc.; using ion exchange resins to adsorb alkaline substances; purifying polythiol compounds by distillation, etc., but not limited to these methods.

[0128] In addition, as polythiol compounds, for example, tris[(3-mercaptopropionyloxy)ethyl]isocyanurate, 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, tris(3-mercaptopropyl)isocyanurate, bis(3-mercaptopropyl)isocyanurate, 1,3,4,6-tetra(2-mercaptoethyl)glycourea and 4,4'-isopropylidene diphenyl bis(3-mercaptopropyl) ether, etc.

[0129] In polythiol compounds, the number of thiol groups per molecule is preferably 2 or more, more preferably 3 or more, more preferably 6 or less, more preferably 5 or less, and even more preferably 4 or less. Particularly preferred polythiol compounds have 3 or 4 thiol groups per molecule.

[0130] (E) The mercapto equivalent of other thiols is preferably 50 g / eq. or more, more preferably 100 g / eq. or more, preferably 3,000 g / eq. or less, more preferably 1,000 g / eq. or less, further preferably 500 g / eq. or less, and even more preferably 300 g / eq. or less. Mercapto equivalent is the mass of (E) other thiols per 1 equivalent of mercaptols.

[0131] (E) The weight-average molecular weight (Mw) of the other thiol compounds is preferably 100 or more, more preferably 250 or more, even more preferably 300 or more, preferably 5,000 or less, more preferably 3,000 or less, and even more preferably 1,500 or less. (E) The weight-average molecular weight of the other thiol compounds is the weight-average molecular weight converted from polystyrene as determined by gel permeation chromatography (GPC).

[0132] When the resin composition contains other thiols (E), the ratio of the number of thiol groups in the other thiols (E) to the number of epoxy groups in the epoxy resin (A) (number of thiol groups in the other thiols (E) / number of epoxy groups in the epoxy resin) is preferably within a specific range. This ratio (number of thiol groups in the other thiols (E) / number of epoxy groups in the epoxy resin) is preferably 0.01 or more, more preferably 0.05 or more, further preferably 0.1 or more, preferably 2 or less, more preferably 1.5 or less, and even more preferably 1 or less. The term "number of thiol groups in the other thiols (E)" in the resin composition refers to the sum of all values ​​obtained by dividing the mass of the other thiols (E) present in the resin composition by their thiol equivalent.

[0133] When the resin composition contains other thiols (E), the amount of other thiols (E) in the resin composition relative to 100% by mass of the non-volatile components is, for example, 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, even more preferably 3% by mass or more, for example, 25% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less. When the amount of other thiols (E) is within the above range, the adhesive strength and impact resistance of the cured resin composition can be effectively improved.

[0134] <(F) Preservative Stabilizer> The resin composition of the present invention may optionally include a (F) preservation stabilizer. The (F) preservation stabilizer, as component (F), does not include components equivalent to components (A) to (E) described above. While the (A) epoxy resin and (B) a thiol compound having a specific structure are highly reactive, the (F) preservation stabilizer inhibits undesirable reactions between the (A) epoxy resin and the (B) thiol compound having a specific structure, thereby improving the pot life (storage stability) of the resin composition. One (F) preservation stabilizer may be used alone, or two or more may be used in combination.

[0135] Examples of (F) preservation stabilizers include: borate esters, titanate esters, aluminate esters, zirconate esters, isocyanate esters, carboxylic acids, acid anhydrides, mercapto organic acids, etc.

[0136] Examples of borate esters 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, tri(dodecyl) borate, tri(hexadecyl) borate, tri(octadecyl) borate, tri(2-ethylhexyloxy)borane, bis(1,4,7,10-tetraoxaundecyl)(1,4,7,10,13-pentaoxatetradecyl)(1,4,7-trioxaundecyl)borane, tribenzyl borate, triphenyl borate, tri-o-tolyl borate, tri-m-tolyl borate, triethanolamine borate, etc.

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

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

[0139] Examples of zirconate ester compounds include tetraethyl zirconate, tetrapropyl zirconate, tetraisopropyl zirconate, and tetrabutyl zirconate.

[0140] Examples of isocyanate compounds include: n-butyl isocyanate, isopropyl isocyanate, 2-chloroethyl isocyanate, phenyl isocyanate, p-chlorophenyl isocyanate, benzyl isocyanate, hexamethylene diisocyanate, 2-ethylphenyl isocyanate, 2,6-dimethylphenyl isocyanate, toluene diisocyanate (e.g., 2,4-toluene diisocyanate, 2,6-toluene diisocyanate), 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, benzyltoluidine diisocyanate, isophorone diisocyanate, phenyldimethyl diisocyanate, p-phenylene diisocyanate, and bicycloheptane triisocyanate.

[0141] Examples of carboxylic acids include: saturated aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, hexanoic acid, and octanoic acid; unsaturated aliphatic monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; halogenated fatty acids such as monochloroacetic acid and dichloroacetic acid; monocarboxylic hydroxy acids such as glycolic acid and lactic acid; aliphatic aldehyde acids and keto acids such as glyoxylic acid and gluconic acid; aliphatic polycarboxylic acids such as oxalic acid, malonic acid, succinic acid, and maleic acid; aromatic monocarboxylic acids such as benzoic acid, halobenzoic acid, toluic acid, phenylacetic acid, cinnamic acid, and mandelic acid; and aromatic polycarboxylic acids such as phthalic acid and pyromellitic acid.

[0142] Examples of acid anhydrides include: succinic anhydride, dodecyl succinic anhydride, maleic anhydride, adducts of methylcyclopentadiene and maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and other aliphatic polyacid anhydrides; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and other aromatic polyacid anhydrides.

[0143] Examples of thiol organic acids include: thiol aliphatic monocarboxylic acids such as thioacetic acid, thiol propionic acid, thiol butyric acid, thiol succinic acid, and dimercaptosuccinic acid; thiol aliphatic monocarboxylic acids obtained by esterification of hydroxy organic acids with thiol organic acids; and thiol aromatic monocarboxylic acids such as mercaptobenzoic acid.

[0144] As a (F) preservation stabilizer, borate ester compounds are preferred from the viewpoint of high versatility and safety, and effective improvement of 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.

[0145] When the resin composition contains a (F) preservation stabilizer, the amount of the (F) preservation stabilizer in the resin composition relative to 100% by mass of the non-volatile components in the resin composition is, for example, 0.001% by mass or more, 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.

[0146] <(G) Other Additives> The resin composition of the present invention may include (G) other additives as optional components. The (G) other additives, which are components (G), do not include components equivalent to (A) to (F) above. Examples of (G) other additives include: thermoplastic resins; polymerization initiators; organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium dioxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; homogenizing agents such as organosilicon homogenizers and acrylic polymer homogenizers; thickeners such as Benton and montmorillonite; defoamers such as organosilicon defoamers, acrylic defoamers, fluorinated defoamers, and vinyl resin defoamers; benzo[a]trimethylammonium chloride... Ultraviolet absorbers such as azole-based UV absorbers; adhesive enhancers such as ureasilanes; adhesive enhancers such as triazole-based, tetraazole-based, and triazine-based adhesive enhancers; antioxidants such as hindered phenolic antioxidants; fluorescent whitening agents such as stilbene derivatives; surfactants such as fluorinated and organosilicon surfactants; flame retardants such as phosphorus-based (e.g., phosphate esters, phosphononitriles, phosphonic acid compounds, red phosphorus), nitrogen-based (e.g., melamine sulfate), halogen-based, and inorganic (e.g., antimony trioxide). (G) Other additives may be used alone or in combination of two or more.

[0147] <(H) organic solvent> In the resin composition of the present invention, an organic solvent (H) may be further included as an optional volatile component, in combination with non-volatile components such as components (A) to (G) described above. The organic solvent (H) may be used alone or in combination of two or more in any ratio. Examples of organic solvents (H) 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-dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, and anisole; alcohol solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; and 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, and carbitol acetate. Ether ester solvents such as diglycolacetate, γ-butyrolactone, and methyl methoxypropionate; 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.

[0148] Relative to the non-volatile components in 100% by mass of the resin composition, the amount of (H) organic solvent in the resin composition is preferably 10% by mass or less, more preferably 5% by mass or less, further 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, and even more preferably 0% by mass. That is, in the preferred embodiment, the resin composition does not contain (H) organic solvent.

[0149] [Method for manufacturing the resin composition] The resin composition of the present invention can be manufactured, for example, by mixing components that may be included in the resin composition. The aforementioned components may be mixed partially or entirely simultaneously, or sequentially. During the mixing of the components, a suitable temperature can be set, thus allowing for temporary or continuous heating and / or cooling. Furthermore, stirring or agitation may be performed during the mixing of the components.

[0150] [Properties of the resin composition and its cured product] The resin composition of the present invention can be solid or liquid. Furthermore, the liquid resin composition can be a paste containing little or no (H) organic solvent, or a varnish containing a large amount of (H) organic solvent.

[0151] By curing the resin composition of the present invention, a cured product of the resin composition can be obtained. Generally, since heating occurs during the curing of the resin composition, volatile components such as (H) organic solvents contained in the resin composition can be volatilized by the heat during curing. Therefore, the cured product obtained by curing the resin composition may contain non-volatile components such as (A) to (G) or their reaction products.

[0152] The cured resin composition of the present invention exhibits good adhesive strength. Therefore, the cured resin composition exhibits good tensile shear bond strength. In one example, two epoxy glass test pieces are bonded together with the resin composition, and the resin composition is heated at 120°C for 30 minutes to obtain a laminated specimen consisting of an epoxy glass test piece, a cured resin composition, and an epoxy glass test piece in sequence. Using this laminated specimen, a tensile shear bond strength test is performed according to JIS-K-6850. The tensile shear bond strength measured in this test is preferably 3 N / mm². 2 The above is preferred to be 6 N / mm. 2 The above is further optimized to 10 N / mm. 2 The higher the upper limit of the tensile shear bond strength, the better; for example, it could be 50 N / mm. 2 Below or 40N / mm 2 the following.

[0153] The cured resin composition of the present invention exhibits good impact resistance. Therefore, when the cured resin composition is subjected to a DuPont impact test, it can achieve a high impact fracture height. Details regarding the DuPont impact test are described below. In one example, an epoxy glass test piece and a stainless steel test piece are bonded together with the resin composition, and the resin composition is heated at 120°C for 30 minutes to obtain a laminated specimen consisting of an epoxy glass test piece, a cured resin composition, and a stainless steel test piece. The resulting laminated specimen is placed on a DuPont impact testing machine with the epoxy glass test piece side of the laminated specimen facing upwards, and a DuPont impact test is performed using a 50g hammer. At this time, it is confirmed that the fracture height (impact fracture height) of the cured resin composition is preferably 300 mm or more, more preferably 350 mm or more, further preferably 400 mm or more, and even more preferably 450 mm or more. The higher the upper limit of the impact fracture height, the better; for example, it can be 10 m or less or 8 m or less.

[0154] The cured resin composition of the present invention can have good mechanical properties. For example, it is preferable that the cured resin composition has a low modulus of elasticity, thus exhibiting excellent flexibility and toughness. In one example, the tensile modulus of elasticity of the cured product obtained by curing the resin composition at 80°C for 60 minutes is preferably 5,000 MPa or less, more preferably 4,000 MPa or less, and even more preferably 3,000 MPa or less. There is no particular limitation on the lower limit of the tensile modulus of elasticity; for example, it can be 0.1 MPa or more, preferably 1 MPa or more, more preferably 5 MPa or more, 10 MPa or more, 100 MPa or more, or 1,000 MPa or more. In addition, the cured product contained in electronic components or semiconductor devices may also have a tensile modulus of elasticity within the above-mentioned range.

[0155] The tensile modulus of elasticity of the cured resin composition can be determined by a tensile test at a temperature of 25°C, a relative humidity of 50%, and a tensile speed of 5 mm / min. Specific determination methods can be described later in the examples.

[0156] When the resin composition of the present invention is in a liquid state, the resin composition may have a specific range of viscosity. In one example, the viscosity of the resin composition measured using an E-type viscometer at 25°C and 1 rpm is preferably 1 Pa·s or more, more preferably 5 Pa·s or more, even more preferably 10 Pa·s or more, preferably 500 Pa·s or less, more preferably 250 Pa·s or less, even more preferably 100 Pa·s or less, or 75 Pa·s or less.

[0157] In another example, the viscosity of the resin composition, measured using an E-type viscometer at 25°C and 10 rpm, is preferably 0.1 Pa·s or more, more preferably 1 Pa·s or more, even more preferably 3 Pa·s or more, preferably 100 Pa·s or less, more preferably 50 Pa·s or less, even more preferably 30 Pa·s or less or 20 Pa·s or less.

[0158] When the resin composition of the present invention is in a liquid state, it exhibits good thixotropic properties. The thixotropic properties of the resin composition can be expressed by the thixotropic index (TI). In one example, the viscosity of the resin composition measured using an E-type viscometer at 25°C and 1 rpm is divided by the viscosity of the resin composition measured using an E-type viscometer at 25°C and 10 rpm. The thixotropic index calculated in this way is preferably 1 or more, more preferably 1.5 or more, further preferably 2 or more, preferably 10 or less, more preferably 8.5 or less, and even more preferably 7.5 or less.

[0159] <DuPont Impact Test of Cured Resin Compositions> As described above, the impact failure height of the cured resin composition can be determined by the DuPont impact test. Before detailing the DuPont impact test, the method for manufacturing the laminated specimen 10 used in the DuPont impact test will be described here using the accompanying drawings.

[0160] The laminated specimen 10 used in the DuPont impact test can be manufactured, for example, using a resin composition. For instance, the laminated specimen 10 can be manufactured by a method comprising the following steps in sequence: Step (1): A first resin composition layer 12 is formed on one side of the first test piece 11 in a manner corresponding to the adhesive portion 13 of the laminated sample. Step (2) involves forming a second resin composition layer 12' on one side of the second test piece 11' in a manner corresponding to the adhesive portion 13 of the laminated sample; Step (3) involves bonding the first test piece 11 and the second test piece 11' together with the first resin composition layer 12 and the second resin composition layer 12'; and Step (4) involves bonding the first test piece 11 and the second test piece 11' by curing the first resin composition layer 12 and the second resin composition layer 12'.

[0161] Figure 1 This is a schematic front view illustrating step (1) of the manufacturing method of the laminated specimen 10 used in the DuPont impact test. Step (1) is a step in which a first resin composition layer 12 is formed on one side of the first test piece 11 in a manner corresponding to the adhesive portion 13 of the laminated specimen described later, using a resin composition. There are no particular limitations on the method of forming the first resin composition layer 12; a coating machine or the like can be used to apply the resin composition to one side of the first test piece 11 to form the first resin composition layer 12. Alternatively, a resin varnish can be prepared by dissolving the resin composition in an organic solvent as needed, and then applied to one side of the first test piece 11. When using a resin varnish, drying can be performed after coating as needed.

[0162] Drying can be carried out, for example, by heating or blowing hot air. There are no particular limitations on the drying conditions; drying is generally carried out when the content of organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Although the drying conditions vary depending on the components contained in the resin composition, the resin composition layer 12 can be formed by drying at 50°C to 150°C for 3 to 10 minutes.

[0163] As the first test piece 11 (and the second test piece 11' described later), test pieces having the same dimensions in the thickness direction can be used, for example. Regarding the shape of the main surface of the first test piece 11, examples include: rectangle, square, circle, approximately rectangular, approximately circular, etc. Preferably, the main surface shape of the first test piece 11 is rectangular, square, or approximately rectangular, and more preferably rectangular. Furthermore, the first test piece 11 and the second test piece 11' preferably have the same dimensions. Hereinafter, a scheme using the first test piece 11 and the second test piece 11' described later, each having a main surface of the same size and a rectangular shape, will be described.

[0164] In step (1), the portion of the resin composition layer 12 formed can be appropriately set according to the shape of the adhesive portion 13 of the laminated sample 10. Figure 1 The diagram shows a test piece formed by forming a resin composition layer 12 in a region at a distance d from the short side 11E, including one short side 11E of the first test piece. Here, when the length of the long side of the first test piece is set to L, the closer the distance d is to L / 2, the better.

[0165] The thickness of the resin composition layer 12 (and the resin composition layer 12' described later) in the laminated specimen 10 can be appropriately set within a range that allows for the evaluation of impact resistance. In one example, the thickness of the resin composition layer 12 (and the resin composition layer 12' described later) can be set to about 1 mm.

[0166] Step (2) is a step in which a second resin composition layer 12' is formed on one side of the second test piece 11' in a manner corresponding to the adhesive portion 13 of the laminated sample described later, using a resin composition. There are no particular limitations on the method for forming the second resin composition layer 12', and it is the same as the method for forming the first resin composition layer 12 in step (1). Regarding the location where the resin composition layer 12' is formed, for example, as... Figure 1 As shown, the second test piece is formed in a region at a distance d from the short side 11'E, in a manner that includes one short side 11'E. It should be noted that the thickness of the resin composition layer 12' is the same as that of the resin composition 12. Furthermore, the materials of the first test piece 11 and the second test piece 11' are described later.

[0167] Figure 2 This is a schematic front view illustrating step (3) of the manufacturing method of the laminated specimen 10 used in the DuPont impact test. Step (3) is a step after steps (1) and (2) in which the first test piece 11 and the second test piece 11' are bonded together in a manner that the first resin composition layer 12 and the second resin composition layer 12' are joined. Figure 2The image shows a test piece formed by bonding a first test piece 11 and a second test piece 11' together with a first resin composition layer 12 and a second resin composition layer 12' using an overlapping joint.

[0168] In the bonding process of step (3), pressure can also be applied to either or both of the first test piece 11 and the second test piece 11' to press the first test piece 11 and the second test piece 11' together as needed. The pressing of the first test piece 11 and the second test piece 11' can be done using clamps or other tools, or using a press or other machinery.

[0169] Figure 3 This is a schematic front view illustrating step (4) of the manufacturing method of the laminated specimen 10 used in the DuPont impact test. Step (4) is a step after step (3) in which the first test piece 11 and the second test piece 11' are bonded together by curing the first resin composition layer 12 and the second resin composition layer 12'. In step (4), the first resin composition layer 12 and the second resin composition layer 12' are cured together to form an adhesive portion 13 composed of the cured resin composition layers. Therefore, in step (4), a laminated specimen 10 consisting of the second test piece 11', the adhesive portion 13 composed of the cured resin composition layers, and the first test piece 11 can be obtained in sequence.

[0170] Next, details of the DuPont impact test of the laminated specimen 10 obtained in the above steps (1) to (4) will be explained. Figure 4 This is a schematic front view used to illustrate the overview of DuPont's impact testing. For example... Figure 4 As shown, in the DuPont impact test, a laminated specimen 10 containing a cured resin composition is placed on a fixture 40, and a punch 20 is placed on the laminated specimen 10. Then, a hammer 30 is dropped onto the punch 20 from a predetermined height h relative to the punch 20, as indicated by arrow A1. The height at which the bonded portion 13 of the laminated specimen is broken due to the energy of the impact is measured as the impact failure height. A higher impact failure height indicates better impact resistance of the laminated specimen 10. The DuPont impact test can be performed according to JIS K5600-5-3. The specific method for measuring the impact failure height can be the method described in the <Test Example 2: Evaluation Test of Impact Resistance> section of the embodiments described later.

[0171] In DuPont impact testing, the stacked specimen 10 can be positioned with the first test piece 11 on top (i.e., the second test piece 11' on the bottom) or with the first test piece 11 on the bottom (i.e., the second test piece 11' on top). Furthermore, the orientation of the stacked specimen 10 can be selected based on the materials of the first and second test pieces 11', choosing which test piece is positioned on top. Figure 4 The example shown is an example in which the stacked sample 10 is placed on the fixing fixture 40 with the first test piece 11 as the bottom side (i.e., the second test piece 11' as the top side).

[0172] Examples of materials that can be used to form the test piece of the laminated sample 10 include: glass, single-crystal silicon, metallic materials, and ceramic materials. Examples of glass materials include: epoxy glass, alkali-free glass, quartz glass, and borosilicate glass. Examples of metallic materials include: materials containing one or more metals selected from gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, molybdenum, titanium, tungsten, iron, tin, and indium. Metallic materials can be single metals or alloys. Examples of alloy materials include: materials containing two or more metals selected from the above. Examples of ceramic materials include: metal oxides, transition metal oxides, metal nitrides, and boride ceramics. Here, composite oxides are excluded from metal oxides and transition metal oxides.

[0173] From the viewpoint of fully transmitting impact to the adhesive portion 13 of the laminated specimen and more accurately evaluating the impact resistance of the laminated specimen 10, the upper test piece of the laminated specimen 10 ( Figure 4 The material of the second test piece 11' is preferably glass. In the "Test Example 2: Impact Resistance Evaluation Test" section of the embodiments described later, epoxy glass is used as an example of the material of the upper test piece.

[0174] From the viewpoint of more accurately evaluating the impact resistance of the laminated specimen 10 by not mitigating the impact transmitted to the adhesive portion 13 of the laminated specimen, the test piece on the lower side of the laminated specimen 10 ( Figure 4 The material of the first test piece 11) is preferably a metallic material. In the “Test Example 2: Impact Resistance Evaluation Test” section of the embodiments described later, stainless steel with electroless nickel plating on the surface is used as an example of the material of the test piece on the lower side.

[0175] In the DuPont impact test, there are no particular restrictions on the configuration of the punch 20. From the viewpoint of more accurately evaluating the impact resistance of the laminated specimen 10, it is preferable to configure the punch 20 in a manner that includes the front end 20T of the punch 20 on the vertical line of the center position C of the adhesive portion 13 in the laminated specimen.

[0176] [Uses of the resin composition] The resin composition of the present invention provides cured products with both excellent adhesive strength and impact resistance. Taking advantage of these superior properties, the resin composition is preferably used as an adhesive composition for applications requiring both adhesive strength and impact resistance.

[0177] The resin composition of the present invention is preferably used as an adhesive for semiconductor devices. Specific examples of semiconductor devices include various semiconductor devices for electronic products (e.g., computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, camera modules, medical devices, and televisions) and vehicles (e.g., motorcycles, automobiles, electric trains, ships, and airplanes). Typically, semiconductor devices include electronic components. Furthermore, these electronic components typically include electronic parts and constituent elements other than those electronic parts. Specific examples of electronic parts include modules (e.g., camera modules) containing electronic parts such as semiconductor chips, power semiconductors, and LED-PKGs, and semiconductor chip packages, but are not limited to these. In one example, the resin composition of the present invention is used to bond a first electronic part and a second electronic part constituting an electronic component. More preferably, the resin composition of the present invention is used to bond constituent parts of a camera module. That is, in a more preferred embodiment, the resin composition of the present invention is used to bond a first electronic part constituting a camera module and a second electronic part constituting a camera module.

[0178] Another preferred application of the resin composition is as a resin composition used for bonding substrates and electronic components in semiconductor devices. Specifically, the resin composition of the present invention can also be used as the bonding resin composition in a method for manufacturing a semiconductor device, including bonding substrates such as circuit boards, frames, and housings to electronic components such as semiconductor modules. As described above, the resin composition of the present invention is preferably used for bonding constituent parts of a camera module. Therefore, in a more preferred embodiment, the resin composition of the present invention is used for bonding a substrate constituting a camera module and electronic components constituting a camera module.

[0179] [Electronic Components] An electronic component according to one embodiment of the present invention comprises: a cured resin composition and an electronic component mounted on the cured composition.

[0180] As described above, the resin composition of the present invention is used to bond a first electronic component and a second electronic component constituting an electronic component. Therefore, in one example, the electronic component includes: a first electronic component, a second electronic component, and an adhesive portion for bonding the first electronic component and the second electronic component.

[0181] Electronic components can be manufactured, for example, by a method comprising the following steps: applying a resin composition to one or both of a first electronic component and a second electronic component; bonding the first electronic component and the second electronic component through the resin composition; and curing the resin composition. For example, the resin composition can also be applied using a coating device such as a syringe or dispenser, and pressure can be applied as needed to apply the resin composition to a uniform thickness.

[0182] The curing of resin compositions is typically performed by heat curing. The heat curing conditions for the resin composition layer can 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. Furthermore, the curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 100 minutes. Additionally, the process of curing the resin composition may include preheating the resin composition at a temperature below the curing temperature before heat curing.

[0183] [Semiconductor Devices] One embodiment of the present invention relates to a semiconductor device comprising a cured product of the above-described resin composition. Examples of the semiconductor device include semiconductor devices incorporating the above-described electronic components. Specific examples of semiconductor devices are as described above.

[0184] Furthermore, in semiconductor devices, the aforementioned resin composition can also be used to bond constituent elements of the semiconductor device. For example, a semiconductor device may include: a substrate, a cured resin composition disposed on the substrate, and electronic components or parts mounted on the cured resin composition. Examples of substrates include: circuit boards, heat sinks, frames, etc. In the semiconductor device in question, electronic components or parts are bonded to the substrate by the cured resin composition. From the viewpoint of effectively utilizing good adhesive strength, the bonding surface of the substrate (the surface that bonds with the cured resin composition) may also be formed of a difficult-to-bond material. Example

[0185] The present invention will be specifically described below with reference to embodiments. However, the present invention is not limited to these embodiments. In the following description, unless otherwise explicitly stated, "parts" and "%" refer to "parts by mass" and "% by mass," respectively. In addition, the temperature and pressure conditions, unless otherwise specified, are room temperature (25°C) and atmospheric pressure (1 atm).

[0186] [High Performance Liquid Chromatography and Mass Spectrometry Determination Methods (LC / MS Determination)] (Determination conditions for high performance liquid chromatography and mass spectrometry) The sample was diluted with tetrahydrofuran (THF) to 1 mg / mL and determined by high performance liquid chromatography and mass spectrometry (LC / MS) under the following conditions.

[0187] High Performance Liquid Chromatography (HPLC): ACQUITY UPLC (manufactured by Nihon Waters KK) Mass spectrometry (MS): SQ Detector 2 (manufactured by Nihon Waters KK) Column: ACQUITY UPLC BEH C8 1.7um, 2.1mm × 50mm (manufactured by Nihon Waters KK) 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 min ~ 0.5 min (95%) → 1 min ~ 8.5 min (75%) → 9 min ~ 11 min (5%) → 11.1 min (95%) → 13 min (95%) Flow rate: 0.30 mL / min Analysis time: 13 minutes Column temperature: 40℃ Ion mode: ESI (electrospray ionization) positive Ion polarity: Positive detection mode Desolventizing gas flow rate: 700 L / h, 250℃ Cone gas: 70L / hour Ion source heater: 150℃ [NMR Measurement Methods] The NMR data of the thiol compounds prepared in Synthesis Example 1 below were determined using a JEOL LA-500 (manufactured by JEOL Corporation).

[0188] <Synthetic Example 1: Synthesis of the thiol compound represented by formula (I-1)> (1) Synthesis of diallyl compounds with butylene chains A 2L four-necked round-bottom flask equipped with a stirrer, thermometer, condenser, dropping funnel, and Dean-Stark separator was filled with 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 a reaction solvent. The mixture was heated to 100°C and maintained for 30 minutes to allow it to dissolve completely. Over one hour, 175 g (1.5 mol) of a 48% KOH aqueous solution was added dropwise to the resulting solution. The water and MIBK were separated into water and MIBK by azeotropic distillation of the added KOH aqueous solution within the Dean-Stark separator, with only MIBK being returned to the reaction system while the reaction continued. The reaction was then continued for 6 hours at 118°C, with only MIBK being returned to the system and water being distilled off. Next, the temperature was lowered to 60°C, 100g of distilled water was added, and the mixture was allowed to stand, discarding the lower layer of byproduct brine. Then, 100g of distilled water and an appropriate amount of sodium dihydrogen phosphate for neutralization were added, and the mixture was allowed to stand and separate, discarding the lower layer of byproduct brine. An equal volume of distilled water was then added, and the mixture was washed twice for purification. The solution was then heated to 118°C for azeotropic dehydration. Using filter paper No. 5C (manufactured by Kiriyama Corporation) and a Kiriyama funnel (manufactured by Kiriyama Corporation), the resulting solution was precisely filtered to remove impurities. Then, MIBK and unreacted 2-allylphenol were distilled under reduced pressure at a maximum temperature of 180°C to obtain 145g of liquid resin.

[0189] The LC / MS analysis of the obtained liquid resin, performed according to the aforementioned method, revealed spectral peaks at m / z=323 for the proton adduct and m / z=340 for the ammonium adduct. Based on this analytical data, the obtained liquid resin was confirmed to be a diallyl compound with the structure described below.

[0190] (2) Synthesis of the thiol compound represented by formula (I-1) Add the diallyl compound (100 g, 0.31 mol, 1.0 eq.) obtained in (1) above, 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.) to a 1 L four-necked flask, and react at 80 °C for 4 hours. After removing toluene by vacuum concentration, the resulting reactant was crystallized with methanol (500 g). The crystals were dried under vacuum, and 110.36 g of the dried crystals were recovered. Add the recovered dried crystals (110.36 g) and 32% NaOH (550 g) to a 3 L four-necked flask, and react at 80 °C for 2 hours. After neutralization with 1 N HCl (380 mL), the organic layer was separated and washed with water. Toluene was removed from the washed organic layer by vacuum concentration, yielding 89.0 g of the target thiol compound (74% yield).

[0191] The LC / MS analysis of the obtained thiol compounds yielded spectral peaks at m / z = 391 for the proton adduct and m / z = 408 for the ammonium adduct. Based on these analytical data and... Figure 5 The NMR spectra shown confirm that the obtained thiol compound has the structure represented by the following formula (I-1).

[0192] <Example 1: Preparation of Resin Composition 1> 100.0 parts of glycidylamine-type epoxy resin (“604” manufactured by Mitsubishi Chemical Co., Ltd.) and 20.0 parts of fumed silica (“200” manufactured by NIPPON AEROSIL CO., LTD.) were added to a dedicated plastic container to obtain a mixture. Next, using a mixer (“ARE-310” manufactured by THINKY Co., Ltd.), the mixture was thoroughly mixed at 25°C and 2000 rpm for approximately 30 to 60 seconds. Then, the mixture supplied to the mixer was kneaded using three rollers to obtain a fumed silica epoxy resin dispersion. Next, 5.0 parts of a curing accelerator (“Amicure PN-FJ” manufactured by Ajinomoto Fine-Techno Co., Inc.) were added to this dispersion, and the mixture was thoroughly mixed at 25°C and 2000 rpm for approximately 30 to 60 seconds using a mixer (“ARE-310” manufactured by THINKY Co., Ltd.) to obtain a liquid masterbatch. Next, 162.8 parts of the thiol compound obtained in Synthesis Example 1 were added to the liquid masterbatch, and the mixture was mixed for about 20 seconds at 25°C and 2000 rpm using a mixer (THINKY Corporation's "ARE-310"). The mixture was then degassed under vacuum at 1000 rpm for 2 minutes using a stirring degassing machine (Kyoritsu Seiki Corporation's "HM-200W") to obtain resin composition 1.

[0193] <Example 2: Preparation of Resin Composition 2> In Example 1, 1) Change 100.0 parts of glycidylamine epoxy resin (“604” manufactured by Mitsubishi Chemical Corporation) to 75.0 parts of glycidylamine epoxy resin (“604” manufactured by Mitsubishi Chemical Corporation) and 25.0 parts of bisphenol A epoxy resin (“828” manufactured by Mitsubishi Chemical Corporation).

[0194] 2) The amount of the thiol compound obtained in Synthesis Example 1 was changed from 162.8 parts to 147.1 parts.

[0195] Apart from the above, the same procedure as in Example 1 was followed to obtain resin composition 2.

[0196] <Example 3: Preparation of Resin Composition 3> In Example 1, 1) Change 100.0 parts of glycidylamine type epoxy resin (“604” manufactured by Mitsubishi Chemical Corporation) to 50.0 parts of glycidylamine type epoxy resin (“604” manufactured by Mitsubishi Chemical Corporation) and 50.0 parts of bisphenol A type epoxy resin (“828” manufactured by Mitsubishi Chemical Corporation).

[0197] 2) The amount of the thiol compound obtained in Synthesis Example 1 was changed from 162.8 parts to 133.0 parts.

[0198] Apart from the above, the same procedure as in Example 1 was followed to obtain resin composition 3.

[0199] <Example 4: Preparation of Resin Composition 4> In Example 1, 1) Change 100.0 parts of glycidylamine epoxy resin (“604” manufactured by Mitsubishi Chemical Corporation) to 25.0 parts of glycidylamine epoxy resin (“604” manufactured by Mitsubishi Chemical Corporation) and 75.0 parts of bisphenol A epoxy resin (“828” manufactured by Mitsubishi Chemical Corporation).

[0200] 2) The amount of the thiol compound obtained in Synthesis Example 1 was changed from 162.8 parts to 118.0 parts.

[0201] Apart from the above, the same procedure as in Example 1 was followed to obtain resin composition 4.

[0202] <Example 5: Preparation of Resin Composition 5> In Example 1, 1) Change 100.0 parts of glycidylamine type epoxy resin (“604” manufactured by Mitsubishi Chemical Corporation) to 100.0 parts of bisphenol A type epoxy resin (“828” manufactured by Mitsubishi Chemical Corporation).

[0203] 2) The amount of the thiol compound obtained in Synthesis Example 1 was changed from 162.8 parts to 103.2 parts.

[0204] Apart from the above, the same procedure as in Example 1 was followed to obtain resin composition 5.

[0205] <Example 6: Preparation of Resin Composition 6> In Example 1, 1) Replace 100.0 parts of glycidylamine type epoxy resin (“604” manufactured by Mitsubishi Chemical Corporation) with 75.0 parts of bisphenol A type epoxy resin (“828” manufactured by Mitsubishi Chemical Corporation) and 25.0 parts of other glycidylamine type epoxy resin (“604” manufactured by Mitsubishi Chemical Corporation).

[0206] 2) The amount of the thiol compound obtained in Synthesis Example 1 was changed from 162.8 parts to 127.1 parts.

[0207] Apart from the above, the same procedure as in Example 1 was followed to obtain resin composition 6.

[0208] <Example 7: Preparation of Resin Composition 7> In Example 1, 1) Replace 100.0 parts of glycidylamine type epoxy resin (“604” manufactured by Mitsubishi Chemical Corporation) with 75.0 parts of bisphenol A type epoxy resin (“828” manufactured by Mitsubishi Chemical Corporation) and 25.0 parts of phenolic varnish type epoxy resin (“N-730A” manufactured by DIC Corporation).

[0209] 2) The amount of the thiol compound obtained in Synthesis Example 1 was changed from 162.8 parts to 105.4 parts.

[0210] Apart from the above, the same procedure as in Example 1 was followed to obtain resin composition 7.

[0211] <Example 8: Preparation of Resin Composition 8> In Example 1, 1) Replace 100.0 parts of glycidylamine type epoxy resin (“604” manufactured by Mitsubishi Chemical Corporation) with 75.0 parts of bisphenol A type epoxy resin (“828” manufactured by Mitsubishi Chemical Corporation) and 25.0 parts of triphenylmethane type epoxy resin (“EXA-7250” manufactured by DIC Corporation).

[0212] 2) The amount of the thiol compound obtained in Synthesis Example 1 was changed from 162.8 parts to 107.5 parts.

[0213] Apart from the above, the same procedure as in Example 1 was followed to obtain resin composition 8.

[0214] <Example 9: Preparation of Resin Composition 9> In Example 1, 1) Replace 100.0 parts of glycidylamine type epoxy resin (“604” manufactured by Mitsubishi Chemical Corporation) with 75.0 parts of bisphenol A type epoxy resin (“828” manufactured by Mitsubishi Chemical Corporation) and 25.0 parts of pentaerythritol type epoxy resin (“Shofree PETG” manufactured by Resonac Corporation).

[0215] 2) The amount of the thiol compound obtained in Synthesis Example 1 was changed from 162.8 parts to 128.7 parts.

[0216] Apart from the above, the same procedure as in Example 1 was followed to obtain resin composition 9.

[0217] <Comparative Example 1: Preparation of Resin Composition 10> In Example 1, 1) Replace 100.0 parts of glycidylamine type epoxy resin (“604” manufactured by Mitsubishi Chemical Corporation) with 25.0 parts of glycidylamine type epoxy resin (“604” manufactured by Mitsubishi Chemical Corporation) and 75.0 parts of 1,4-glycidylcyclohexane type epoxy resin (“ZX1658GS” manufactured by Nippon Steel Chemical Materials Co., Ltd.

[0218] 2) The amount of the thiol compound obtained in Synthesis Example 1 was changed from 162.8 parts to 150.6 parts.

[0219] Apart from the above, the same procedure as in Example 1 was followed to obtain resin composition 10.

[0220] <Comparative Example 2: Preparation of Resin Composition 11> In Example 1, 1) Change 100.0 parts of glycidylamine type epoxy resin ("604" manufactured by Mitsubishi Chemical Co., Ltd.) to 100.0 parts of 1,4-glycidylcyclohexane type epoxy resin ("ZX1658GS" manufactured by Nippon Steel Chemical Materials Co., Ltd.).

[0221] 2) The amount of the thiol compound obtained in Synthesis Example 1 was changed from 162.8 parts to 146.6 parts.

[0222] Apart from the above, the same procedure as in Example 1 was followed to obtain resin composition 11.

[0223] <Comparative Example 3: Preparation of Resin Composition 12> In Example 1, 1) Change 100.0 parts of glycidylamine epoxy resin (“604” manufactured by Mitsubishi Chemical Corporation) to 25.0 parts of glycidylamine epoxy resin (“604” manufactured by Mitsubishi Chemical Corporation) and 75.0 parts of bisphenol A epoxy resin (“828” manufactured by Mitsubishi Chemical Corporation).

[0224] 2) Replace 162.8 parts of the thiol compound obtained in Synthesis Example 1 with 90.8 parts of another thiol compound (“BD-1” manufactured by Resonac).

[0225] Apart from the above, the same procedure as in Example 1 was followed to obtain resin composition 12.

[0226] <Comparative Example 4: Preparation of Resin Composition 13> In Example 1, 1) Change 100.0 parts of glycidylamine epoxy resin (“604” manufactured by Mitsubishi Chemical Corporation) to 25.0 parts of glycidylamine epoxy resin (“604” manufactured by Mitsubishi Chemical Corporation) and 75.0 parts of bisphenol A epoxy resin (“828” manufactured by Mitsubishi Chemical Corporation).

[0227] 2) Do not use the thiol compound obtained in Synthesis Example 1.

[0228] 3) The amount of curing accelerator (Amicure PN-FJ manufactured by Ajinomoto Fine-Techno Co., Inc.) was changed from 5.0 parts to 10.0 parts.

[0229] Apart from the above, the same procedure as in Example 1 was followed to obtain resin composition 13.

[0230] The details of each component listed in Tables 1 to 3 below are as follows.

[0231] (A-1) Epoxy resin containing an aromatic backbone • "828": Bisphenol A type epoxy resin (2-functional), "jER828" manufactured by Mitsubishi Chemical Corporation, with an epoxy equivalent of approximately 189 g / eq. • "604": A glycidylamine type epoxy resin (4-functional) having the structure represented by the following formula (a-2), "jER604" manufactured by Mitsubishi Chemical Corporation, with an epoxy equivalent of approximately 120 g / eq. • "630": A glycidylamine type epoxy resin (3-functional) having the structure represented by the following formula (a-3), "jER630" manufactured by Mitsubishi Chemical Corporation, with an epoxy equivalent of approximately 95 g / eq. • “N-730A”: Phenolic varnish-type epoxy resin (average 2.6 functionality), manufactured by DIC Corporation, an epoxy resin with an average functionality of 2.6 and an epoxy equivalent of approximately 174 g / eq. • "EXA-7250": Triphenylmethane type epoxy resin (5 or more functionalities), manufactured by DIC, with an epoxy equivalent of approximately 162 g / eq. (A-2) Epoxy resins without aromatic backbones • "ZX1658GS": A 1,4-glycidylcyclohexane type epoxy resin (2-functional) having the structure represented by the following formula (a-1), manufactured by Nippon Steel Chemical Materials Co., Ltd., with an epoxy equivalent of approximately 133 g / eq. • "PETG": A pentaerythritol-type epoxy resin (4-functional) having the structure represented by the following formula (a-4), such as "Shofree PETG" manufactured by Resonac, a 4-functional epoxy resin. (B) Thiol compounds with specific structures (thiol compounds with the structure represented by formula (I)) • Synthesis Example 1: Thiol compound 1 obtained in Synthesis Example 1 has a mercapto equivalent of 195 g / eq. (B') Other thiols (thiols that do not have the structure represented by formula (I)) • "BD-1": 1,4-bis(3-mercaptobutyryloxy)butane, manufactured by Resonac, mercapto equivalent 147 g / eq. (C) Curing accelerator • "PNFJ": A solid-dispersed amine adduct-based latent curing accelerator, manufactured by Ajinomoto Fine-TechnoCo., Inc. as "Amicure PN-FJ". (D) Inorganic filler materials • "A200": Fumed silica, manufactured by NIPPON AEROSIL CO., LTD., with an average particle size of 0.1 μm and a specific surface area of ​​200 m². 2 / g <Example 1: Evaluation Test of Bond Strength> Prepare two 100mm × 25mm × 1.6mm thick epoxy glass test pieces (PALTEK "EL-3762"), and wipe off any oil with an ethanol-moistened cloth. Apply the resin composition obtained in the various examples and comparative examples to each flat (single-sided) surface of the epoxy glass test piece. For the area where the resin composition is applied, apply a layer of approximately 1mm thick covering a short side of the epoxy glass test piece, extending approximately 12.5mm from that short side (i.e., half of the epoxy glass test piece). Next, overlap the coated resin compositions on the two epoxy glass test pieces using an overlap joint, and press them together with two clamps. At this point, some of the resin composition seeps out from between the two epoxy glass test pieces; immediately wipe away this seeped resin composition with a cloth. Arrange the pressed epoxy glass test pieces evenly in an oven and heat at 120°C for 30 minutes to cure the resin composition. Thus, two epoxy glass test pieces are bonded together by the cured resin composition to obtain a laminated sample A consisting of an epoxy glass test piece, a cured resin composition, and an epoxy glass test piece.

[0232] For one resin composition, three laminated samples A were prepared.

[0233] Using the obtained laminated specimen A, the tensile shear bond strength was determined according to JIS-K-6850. Specifically, using a TENSILON universal testing machine (TOYO BALDWIN "UTM-5T"), one epoxy glass specimen was stretched relative to another in a direction parallel to the plane of the epoxy glass specimens, and the maximum load (N) at which the cured resin composition failed was determined. The test was conducted at a temperature of 25°C, a relative humidity of 50%, and a tensile speed of 5 mm / min. The maximum load (N) and the bond area (mm²) of the two specimens were used to determine the bond strength. 2 The shear bond strength was calculated based on the following formula. Tables 1-3, described below, show the average values ​​of the measurements taken from three laminated specimens A.

[0234] Tensile shear bond strength (N / mm) 2 = Maximum load (N) / Bonding area (mm²) 2 ) The shear bond strength obtained in the above operation shall be evaluated according to the following criteria.

[0235] Good: Shear bond strength is 10 N / mm 2 above.

[0236] Available: Shear bond strength is 3 N / mm 2 Above and less than 10 N / mm 2 .

[0237] Defect: Shear bond strength less than 3 N / mm 2 .

[0238] <Example 2: Impact Resistance Evaluation Test> Prepare one 100mm × 25mm × 1.6mm thick epoxy glass test piece (PALTEK "EL-3762") and one 100mm × 25mm × 1.6mm thick stainless steel test piece (Tayu Machinery Co., Ltd. "SUS304", a stainless steel sheet with non-electrolytic nickel plating on the surface), and wipe off the oil with a waste cloth moistened with ethanol. Coat a single side of the epoxy glass test piece with the resin composition obtained in the various examples and comparative examples. Coat a single side of the stainless steel test piece with the resin composition obtained in the various examples and comparative examples. For the coating area of ​​the resin composition, coat an area approximately 1mm thick at a distance of approximately 12.5mm from the short side (i.e., half the area of ​​the epoxy glass test piece and the stainless steel test piece) in a manner that includes one short side of both the epoxy glass test piece and the stainless steel test piece. Next, the surfaces of the epoxy glass test piece and the stainless steel test piece coated with the resin composition were overlapped using an lap joint and pressed together with two clamps. At this point, some of the resin composition seeped out from between the epoxy glass test piece and the stainless steel test piece; this seeped resin composition was immediately wiped away with a waste cloth. The pressed surfaces of the epoxy glass test piece and the stainless steel test piece were then evenly arranged in an oven and heated at 120°C for 30 minutes to cure the resin composition. Thus, the epoxy glass test piece and the cold-rolled stainless steel sheet were bonded together by the cured resin composition, resulting in a laminated sample B consisting of an epoxy glass test piece, a cured resin composition, and a stainless steel test piece.

[0239] For one resin composition, three laminated samples B were prepared.

[0240] Using the obtained laminated specimen B, a DuPont impact test was performed on the cured specimen according to JIS K5600-5-3 using a DuPont drop impact testing machine (Manufactured by Yasuda Seiki Co., Ltd., "No. 517"), and the impact failure height was determined. Specifically, with the epoxy glass test piece of laminated specimen B as the top side, both sides of laminated specimen B were fixed to the testing machine at a position 1.5 cm from the center of the bonded portion of laminated specimen B. At this time, it was confirmed that there was a hollow space between the stainless steel test piece side of laminated specimen B and the test machine's support platform at the bottom of the bonded portion of laminated specimen B. The hammer used for the test was 50g, and the punch was of the type with a front radius R = 1 / 4 inch. The hammer was dropped so that the impact was transmitted to the center of the bonded portion of laminated specimen B. In the first impact test, the hammer was dropped from a height of 50 mm. In subsequent impact tests, if the bonded portion of the laminated specimen was not damaged, the height was increased by 50 mm before the hammer was dropped. The height at which the bond (cured resin composition) breaks is confirmed is used as the impact failure height. The average values ​​of the measurements taken from three laminated specimens B are listed in Tables 1-3 below.

[0241] The impact damage height obtained in the above operation shall be evaluated according to the following criteria.

[0242] Good: Impact damage height is above 350mm.

[0243] Allowed: Impact damage height is 300mm or more but less than 350mm.

[0244] Undesirable: Impact damage height less than 300mm.

[0245] <Experimental Example 3: Determination of the Tensile Modulus of Elasticity of Cured Products> A PET film (NS-80A manufactured by Toray Industries, Inc.) with a release agent treatment on its surface was prepared. The resin compositions obtained in the various examples and comparative examples were applied to the release surface of the PET film using a bar coating method, and then heat-cured at 80°C for 60 minutes to obtain a cured product with a thickness of 70 μm. The cured product was then cut using a cutter (SuperDumbbell Cutter (model: SDMK-5889-01) manufactured by Dumbbell Corporation) to prepare test pieces for measuring the tensile modulus of elasticity. The PET film was peeled off the test pieces. Tensile tests were performed using a benchtop precision universal testing machine (AUTOGRAPH AGS-X manufactured by Shimadzu Corporation) at a temperature of 25°C, a relative humidity of 50%, and a tensile speed of 5 mm / min, thereby determining the tensile modulus of elasticity.

[0246] <Experimental Example 4: Viscosity Determination> The viscosity of the resin compositions obtained in each example and comparative example was measured. Specifically, an E-type viscometer (RE-85U, manufactured by Toki Sangyo Co., Ltd., 3°×R14 rotor) was used to perform a first viscosity measurement for 2 minutes at a measurement temperature of 25°C, an amount of 0.40 ml of varnish-like resin composition, and a rotation speed of 1 rpm. A second viscosity measurement was performed, except that the rotation speed was changed from 1 rpm to 10 rpm. The viscosity η1 measured at 1 rpm and the viscosity η2 measured at 10 rpm were compared. 10 The thixotropic index (TI(1 / 10)) is calculated based on the following formula.

[0247] TI(1 / 10) = (viscosity measured at 1 rpm η1) / (viscosity measured at 10 rpm η) 10 ) [Table 1] [Table 1. Composition and results of Examples 1-5] [Table 2] [Table 2. Composition and Results of Examples 6-9] [Table 3] [Table 3. Composition and Results of Comparative Examples 1-4] .

[0248] Marker description 10-layer stacked specimen 11 First test piece 11E The short side of the first test piece 11' Second test piece 11'E One short side of the second test piece 12 First resin composition layer 12' Second resin composition layer 13. Adhesive portion of the laminated specimen 20 punches 20T punch tip 30 hammers 40 Fixture.

Claims

1. A resin composition comprising (A) an epoxy resin, (B) a thiol compound represented by formula (I) below, and (C) a curing accelerator. in, (A) Epoxy resins include: (A-1) epoxy resins containing an aromatic backbone. Compared to 100% by mass of epoxy resin (A), the amount of epoxy resin (A-1) containing an aromatic backbone is 30% by mass or more. In formula (I), Each ring P is independently either phenyl or naphthyl. When ring P is phenyl, there are 1 to 5 atoms relative to each ring P; when ring P is naphthyl, there are 1 to 7 atoms relative to each ring P, and each a atom is independently -R. 1 -SH, R 1 Each is independently a C1-C6 alkylene group that can be substituted by one or more Y atoms. B is a group on ring P other than A, each of which is independently a hydrogen atom, a C1-C6 alkyl group that can be substituted by one or more Y atoms, or a C1-C6 alkoxy group that can be substituted by one or more Y atoms. When ring P is phenyl, A and B are independently bonded at the ortho, meta, or para positions relative to the position of ring P bonded to the main chain. When ring P is naphthyl, A and B are independently bonded at the ortho, meta, para, remote, epitope, telomere, forced, equatorial, transposition, or 2,7 positions relative to the position of ring P bonded to the main chain. X can be independently -CH2-, -O-, or -N(-R) 2 )- or -S-, R 2 Each is independently a hydrogen atom, a C1-C6 alkyl group that can be substituted with one or more Y atoms, or a C1-C6 alkoxy group that can be substituted with one or more Y atoms. Y can be independently a hydrogen atom, a C1-C6 alkyl group, or a C1-C6 alkoxy group. Z can be directly bonded, -CH2-, -C2H4-, -C3H6-, -C4H8-, -O-, or -S-. n is an integer from 1 to 20.

2. The resin composition of claim 1, wherein, (B) The thiol compound represented by formula (I) comprises one or more of the following: 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). 。 3. The resin composition of claim 1, wherein, (A-1) Epoxy resins containing an aromatic skeleton contain more than two aromatic rings.

4. The resin composition of claim 1, wherein, (A-1) Epoxy resins containing an aromatic skeleton contain 2 to 4 epoxy groups per molecule.

5. The resin composition of claim 1, wherein, (A-1) Epoxy resins containing an aromatic backbone include glycidylamine type epoxy resins.

6. The resin composition of claim 1, wherein, (A-1) Epoxy resin compositions containing an aromatic skeleton include: epoxy resins containing two or more aromatic rings and glycidylamine type epoxy resins.

7. The resin composition of claim 1, comprising (D) an inorganic filler.

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

9. The resin composition of claim 1, wherein, The thixotropic index calculated by dividing the viscosity measured using an E-type viscometer at 25°C and 1 rpm by the viscosity measured using an E-type viscometer at 25°C and 10 rpm is greater than or equal to 10.

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

11. A semiconductor device comprising a cured product of the resin composition according to any one of claims 1 to 9.

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