resin composition

Abstract

To provide a resin composition capable of producing a cured product excellent in both adhesive strength and impact resistance; a resin sheet containing the resin composition; and electronic components and semiconductor devices containing the cured product of the resin composition. [Solution] A 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-1) an epoxy resin containing an aromatic skeleton; and the amount of (A-1) the epoxy resin containing an aromatic skeleton is 30% by mass or more with respect to 100% by mass of (A) the epoxy resin.

Description

Technical Field

[0001] The present invention relates to a resin composition. Furthermore, it relates to a resin sheet, an electronic component, and a semiconductor device.

Background Art

[0002] As a resin composition for bonding electronic components, a resin composition such as an epoxy resin composition may be used. Usually, bonding of electronic components is performed by a cured product of the resin composition.

[0003] Also, heretofore, an epoxy resin composition containing a thiol compound has been known (Patent Documents 1 and 2).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] In recent years, from the viewpoint of extending the product life, a resin composition that provides an adhesive (cured product) having impact resistance has been demanded. Generally, the more flexible the cured product is, the better the impact resistance of the cured product.

[0006] On the other hand, the more flexible the cured product is, the more the bonding ability of the cured product tends to decrease.

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

Means for Solving the Problems

[0008] The present inventors have intensively studied to solve the above problems. As a result, the present inventors have found that a resin composition containing (A) an epoxy resin, (B) a thiol compound having a specific structure, and (C) a curing accelerator; wherein (A) the epoxy resin contains an epoxy resin having an aromatic skeleton in a specific range of amounts can solve the above problems, and completed the present invention. That is, the present invention includes the following.

[0009] <1> (A) An epoxy resin, (B) a thiol compound represented by the following formula (I), and (C) a curing accelerator, a resin composition comprising: (A) The epoxy resin includes (A-1) an epoxy resin containing an aromatic skeleton, (A-1) The amount of the epoxy resin containing an aromatic skeleton is 30% by mass or more based on 100% by mass of (A) the epoxy resin, a resin composition. [Chemical formula] (In formula (I), Ring P is each independently a phenyl group or a naphthyl group, A is 1 to 5 in each ring P when ring P is a phenyl group, and 1 to 7 in each ring P when ring P is a naphthyl group, and each A is each independently -R 1 -SH, R 1 is each independently a C1-C6 alkylene group optionally substituted with one or more Ys, B is a group other than A on ring P, and each is independently a hydrogen atom, a C1-C6 alkyl group optionally substituted with one or more Ys, or a C1-C6 alkoxy group optionally substituted with one or more Ys, A and B, independently, are bonded at the ortho, meta, or para position relative to the position where ring P is bonded to the main chain if ring P is a phenyl group, and at the ortho, meta, para, ana, epi, cata, peri, pros, amphi, or 2,7 position relative to the position where ring P is bonded to the main chain. X is independently -CH2-, -O-, -N(-R 2 )-, or -S-, R 2 Each of these is independently a hydrogen atom, a C1-C6 alkyl group which may be substituted with one or more Y atoms, or a C1-C6 alkoxy group which may be substituted with one or more Y atoms. Y is independently a hydrogen atom, a C1-C6 alkyl group, or a C1-C6 alkoxy group. Each Z is independently a direct bond, -CH2-, -C2H4-, -C3H6-, -C4H8-, -O-, or -S-. n is an integer between 1 and 20. <2> (B) The thiol compound represented by formula (I) includes one or more selected from the group consisting of 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). <1> The resin composition described above. [ka] <3> (A-1) An epoxy resin containing an aromatic skeleton contains two or more aromatic rings, <1> or <2> The resin composition described above. <4> (A-1) An epoxy resin containing an aromatic skeleton contains 2 to 4 epoxy groups in one molecule. <1> ~ <3> A resin composition according to any one of the items. <5> (A-1) An epoxy resin containing an aromatic skeleton, including a glycidylamine type epoxy resin, <1> ~ <4> A resin composition according to any one of the items. <6> (A-1) An epoxy resin containing an aromatic skeleton comprises an epoxy resin containing two or more aromatic rings and a glycidylamine-type epoxy resin in combination. <1> ~ <5> A resin composition according to any one of the items. <7> (D) containing inorganic fillers, <1> ~ <6> A resin composition according to any one of the items. <8> The tensile modulus of the cured product obtained by curing the resin composition at 80°C for 60 minutes is between 1 MPa and 5000 MPa. <1> ~ <7> A resin composition according to any one of the items. <9> The thixotropy 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 between 1 and 10. <1> ~ <8> A resin composition according to any one of the items. <10> <1> ~ <9> An electronic component comprising a cured product of a resin composition according to any one of the items, and an electronic component mounted on the cured product. <11> <1> ~ <9> A semiconductor device comprising a cured product of a resin composition described in any one of the items. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a resin composition that can produce a cured product excellent in both adhesive strength and impact resistance; a resin sheet containing the resin composition; and electronic components and semiconductor devices containing the cured product of the resin composition. [Brief explanation of the drawing]

[0011] [Figure 1] Figure 1 is a schematic front view illustrating steps (1) and (2) of the manufacturing method for the laminated sample 10 used in the DuPont impact test. [Figure 2]FIG. 2 is a schematic front view for explaining step (3) of the method for manufacturing the laminated sample 10 used in the DuPont impact test. [Figure 3] FIG. 3 is a schematic front view for explaining step (4) of the method for manufacturing the laminated sample 10 used in the DuPont impact test. [Figure 4] FIG. 4 is a schematic front view for explaining the outline of the DuPont impact test. [Figure 5] FIG. 5 is a spectrum diagram showing the NMR data of the thiol compound (1) synthesized in Synthesis Example 1.

MODE FOR CARRYING OUT THE INVENTION

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

[0013] [[ID=二十一]]The aspects described in this specification may be used in combination with each other regardless of expressions such as "preferred" and "more preferred". For example, the description of a numerical range may use the upper and lower limits of each range, as well as a range combined with the numerical values of the examples.

[0014] <00001十七6>In this specification, the notation "Cp~Cq" (p and q are integers of 1 or more satisfying p < q) attached before the name of a group represents that the number of carbon atoms of the group is p or more and q or less. Therefore, for example, the notation "C1~C6 alkyl group" represents "an alkyl group having 1 to 6 carbon atoms".

[0015] In this specification, the term "may be substituted" with a substituent for a compound, group or ring means both the case where the hydrogen atom of the compound, group or ring is not substituted with a substituent and the case where some or all of the hydrogen atoms of the compound, group or ring are substituted with a substituent, unless otherwise specified.

[0016] In this specification, the term "aromatic ring" means a ring that obeys Hückel's rule, where the number of electrons in the π-electron system on the ring is 4n+2 (where n is a natural number), and includes monocyclic aromatic rings and fused aromatic rings formed by the fusion of two or more monocyclic aromatic rings. An aromatic ring can be an aromatic carbocyclic ring having only carbon atoms as ring constituent atoms, or an aromatic heterocyclic ring having heteroatoms such as oxygen, nitrogen, or sulfur atoms in addition to carbon atoms as ring constituent atoms. In this specification, the term "heteroatom" means an atom other than carbon and hydrogen atoms, such as oxygen, nitrogen, sulfur, or silicon atoms.

[0017] In this specification, "non-volatile components" as used in reference to a resin composition refer to components of the resin composition other than the organic solvents described later.

[0018] [Overview of Resin Compositions] 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. In the resin composition of the present invention, (A) the epoxy resin includes (A-1) an epoxy resin having an aromatic skeleton, and the amount of (A-1) the epoxy resin having an aromatic skeleton is 30% by mass or more with respect to 100% by mass of (A) the epoxy resin. In this specification, "(B) a thiol compound represented by formula (I)" may be referred to as "(B) a thiol compound having a specific structure."

[0019] [ka]

[0020] (In equation (I), The ring P is independently either a phenyl group or a naphthyl group. A exists in groups of 1 to 5 for each ring P when the ring P is a phenyl group, and in groups of 1 to 7 for each ring P when the ring P is a naphthyl group, and each A independently has -R 1 -SH is, R 1Each of these is an independent C1-C6 alkylene group which may be substituted with one or more Y groups. B is a group other than A on ring P, and each is independently a hydrogen atom, a C1-C6 alkyl group which may be substituted with one or more Y atoms, or a C1-C6 alkoxy group which may be substituted with one or more Y atoms. A and B, independently, are bonded at the ortho, meta, or para position relative to the position where ring P is bonded to the main chain if ring P is a phenyl group, and at the ortho, meta, para, ana, epi, cata, peri, pros, amphi, or 2,7 position relative to the position where ring P is bonded to the main chain. X is independently -CH2-, -O-, -N(-R 2 )-, or -S-, R 2 Each of these is independently a hydrogen atom, a C1-C6 alkyl group which may be substituted with one or more Y atoms, or a C1-C6 alkoxy group which may be substituted with one or more Y atoms. Y is independently a hydrogen atom, a C1-C6 alkyl group, or a C1-C6 alkoxy group. Each Z is independently a direct bond, -CH2-, -C2H4-, -C3H6-, -C4H8-, -O-, or -S-. n is an integer between 1 and 20.

[0021] According to the resin composition of the present invention, a cured product with excellent adhesive strength and impact resistance can be obtained.

[0022] The resin composition of the present invention may optionally further contain (D) an inorganic filler, (E) a curing agent, (F) other additives, and (G) an organic solvent. The components contained in the resin composition of the present invention will be described in detail below.

[0023] <(A) Epoxy resin> The resin composition of the present invention comprises (A) epoxy resin as component (A). (A) epoxy resin may be used alone or in combination of two or more types.

[0024] (A) As the epoxy resin, a curable resin having epoxy groups may 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, trisphenol-type epoxy resin, naphthol novolac-type epoxy resin, phenol novolac-type epoxy resin, tert-butyl-catechol-type epoxy resin, naphthalene-type epoxy resin, naphthol-type epoxy resin, anthracene-type epoxy resin, glycidylamine-type epoxy resin, glycidyl ester-type epoxy resin, cresol novolac-type epoxy resin, phenol aralkyl-type epoxy resin, biphenyl-type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro-ring-containing epoxy resin, cyclohexane-type epoxy resin, cyclohexanedimethanol-type epoxy resin, naphthylene ether-type epoxy resin, trimethylol-type epoxy resin, tetraphenylethane-type epoxy resin, isocyanurate-type epoxy resin, and phenolphthaleimidine-type epoxy resin.

[0025] (A) The epoxy resin preferably contains an epoxy resin that contains two or more epoxy groups per molecule. The proportion of the epoxy resin containing two or more epoxy groups per 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 the epoxy resin.

[0026] (A) The epoxy resin contains an epoxy resin containing an aromatic skeleton (hereinafter sometimes referred to as "component (A-1)"). Here, the aromatic skeleton means a skeleton that includes a chemical structure generally defined as an aromatic ring. The aromatic ring may be an aromatic carbocyclic ring or an aromatic heterocyclic ring. The aromatic ring may also be a monocyclic aromatic ring, a condensed aromatic ring formed by the condensation of two or more monocyclic aromatic rings, or a condensed aromatic ring formed by the condensation of one or more monocyclic aromatic rings with one or more monocyclic non-aromatic rings. Among these, the aromatic ring contained in component (A-1) is preferably an aromatic carbocyclic ring. The number of carbon atoms in the aromatic carbocyclic ring is preferably 6 or more and 10 or less.

[0027] (A-1) Examples of epoxy resins containing aromatic skeletons 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, trisphenol type epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, bisquilenol type epoxy resin, triphenylmethane type epoxy resin, and glycerol having an aromatic ring. Examples include ricidylamine-type epoxy resins, glycidyl ester-type epoxy resins having aromatic rings, cresol novolac-type epoxy resins, biphenyl-type epoxy resins, linear aliphatic epoxy resins containing aromatic rings, epoxy resins having a butadiene structure containing aromatic rings, alicyclic epoxy resins containing aromatic rings, heterocyclic epoxy resins, spiro-ring-containing epoxy resins containing aromatic rings, cyclohexanedimethanol-type epoxy resins containing aromatic rings, naphthylene ether-type epoxy resins, trimethylol-type epoxy resins containing aromatic rings, and tetraphenylethane-type epoxy resins containing aromatic rings. In particular, from the viewpoint of effectively improving the adhesive strength of the cured product of the resin composition, it is preferable that the epoxy resin containing an aromatic skeleton (A-1) includes a glycidylamine-type epoxy resin.

[0028] In the resin composition, the amount of epoxy resin containing the (A-1) aromatic skeleton 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, based on 100% by mass of the (A) epoxy resin. The upper limit of the amount of component (A-1) may be 100% by mass, less than 100% by mass, 95% by mass or less, or 90% by mass or less. When the amount of component (A-1) is within the above range, the adhesive strength in the cured product of the resin composition can be effectively improved.

[0029] The number of aromatic rings contained in component (A-1) is usually one or more, preferably two or more. That is, in one preferred embodiment, the epoxy resin containing the aromatic skeleton of (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.

[0030] The number of epoxy groups contained in component (A-1) is usually one or more, and is preferably two to four, from the viewpoint of achieving both adhesive strength and impact resistance of the cured product. That is, in a preferred embodiment, the epoxy resin containing the aromatic skeleton of (A-1) contains 2 to 4 epoxy groups per molecule.

[0031] (A-1) The epoxy resin containing the aromatic skeleton may be used as a single component or as a combination of two or more different components. In particular, from the viewpoint of effectively improving the impact resistance of the cured resin composition, it is preferable to use the epoxy resin containing the (A-1) aromatic skeleton as a combination of two or more different components.

[0032] In a preferred embodiment, the epoxy resin containing (A-1) an aromatic skeleton comprises a combination of an epoxy resin containing two or more aromatic rings and a glycidylamine-type epoxy resin. According to such an embodiment, the adhesive strength and impact resistance of the cured resin composition can be improved.

[0033] The amount of epoxy resin containing the (A-1) aromatic skeleton 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, 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, based on 100% by mass of the total of components (A), (B), and (C).

[0034] The amount of epoxy resin containing the (A-1) aromatic skeleton in the resin composition 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, based on 100% by mass of the nonvolatile components in the resin composition.

[0035] As described above, in the resin composition, the amount of epoxy resin containing the (A-1) aromatic skeleton is 30% by mass or more with respect to 100% by mass of the (A) epoxy resin. Therefore, as long as the content range is satisfied, the (A) epoxy resin may further contain epoxy resin that does not contain the (A-2) aromatic skeleton (hereinafter sometimes referred to as "component (A-2)"). The amount of epoxy resin that does not contain the (A-2) aromatic skeleton in the resin composition is less than 70% by mass with respect to 100% by mass of the (A) epoxy resin, 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 component (A-2) may be 0% by mass (i.e., no component (A-2)), or it may be greater than 0% by mass, 1% by mass or more, 5% by mass or more, or 10% by mass or more.

[0036] Epoxy resins include epoxy resins that are liquid at 20°C (hereinafter referred to as "liquid epoxy resins") and epoxy resins that are solid at 20°C (hereinafter referred to as "solid epoxy resins"). The resin composition preferably contains liquid epoxy resin as (A) epoxy resin, and more preferably contains only liquid epoxy resin.

[0037] As the liquid epoxy resin, a liquid epoxy resin containing two or more epoxy groups per molecule is preferred.

[0038] Preferred liquid epoxy resins 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, glycidylamine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resins such as alicyclic epoxy resins having an ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, and epoxy resins having a butadiene structure.

[0039] 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" (phenol novolac-type epoxy resin); Mitsubishi Chemical's "630," "630LSD," and "604" (glycidylamine-type epoxy resin); DIC's "N-730A" and Nippon Steel Chemical & Material's "ZX-1059" (bisphenol Examples include: a mixture of Type A epoxy resin and bisphenol F epoxy resin; "EXA-7250" (triphenylmethane type epoxy resin) from DIC Corporation; "EX-721" (glycidyl ester type epoxy resin) from Nagase ChemteX Corporation; "Celoxide 2021P" (alicyclic epoxy resin with an ester skeleton) from Daicel Corporation; "PB-3600" (epoxy resin with a butadiene structure) from Daicel Corporation; "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) from Nippon Steel Chemical & Material Corporation; and "Showfree PETG" (pentaerythritol type epoxy resin) from Resonaq Corporation. Liquid epoxy resins may be used individually or in combination of two or more types.

[0040] As for the solid epoxy resin, a solid epoxy resin containing two or more epoxy groups per molecule is preferred, a solid epoxy resin containing three or more epoxy groups per molecule is more preferred, and a solid epoxy resin containing three or more epoxy groups and an aromatic ring per molecule is even more preferred.

[0041] Preferred solid epoxy resins include bixylenol-type epoxy resin, naphthalene-type epoxy resin, naphthalene-type tetrafunctional epoxy resin, cresol novolac-type epoxy resin, dicyclopentadiene-type epoxy resin, trisphenol-type epoxy resin, naphthol-type epoxy resin, biphenyl-type epoxy resin, naphthylene ether-type epoxy resin, anthracene-type epoxy resin, bisphenol A-type epoxy resin, bisphenol AF-type epoxy resin, and tetraphenylethane-type epoxy resin, with biphenyl-type epoxy resin being more preferred.

[0042] 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 novolac-type epoxy resin); DIC's "N-695" (cresol novolac-type epoxy resin); DIC's "HP-7200", "HP-7200HH", and "HP-7200H" (dicyclopentadiene-type epoxy resin). );DIC Corporation's "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000", "HP6000L" (naphthylene ether type epoxy resin); Nippon Kayaku Co., Ltd.'s "EPPN-502H" (trisphenol type epoxy resin); Nippon Kayaku Co., Ltd.'s "NC7000L" (naphthol novolac type epoxy resin); Nippon Kayaku Co., Ltd.'s "NC3000H", "NC3000", "NC3000L", "NC310 0 (biphenyl-type epoxy resin); "ESN475V" (naphthalene-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ESN485" (naphthol novolac-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YL6121" (biphenyl-type epoxy resin), "YX4000", "YX4000H", "YX4000HK" (bixylenol-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; Osaka Gas Examples include "PG-100" and "CG-500" from Schemical Co., Ltd., "YL7760" (bisphenol AF type epoxy resin), "YL7800" (fluorene type epoxy resin), "1010" (solid bisphenol A type epoxy resin), "1031S" (tetraphenylethane type epoxy resin), and "WHR-991S" (phenolphthalein type epoxy resin) from Nippon Kayaku Co., Ltd. Solid epoxy resins may be used individually or in combination of two or more types.

[0043] (A) When using a combination of liquid epoxy resin and solid epoxy resin as the epoxy resin, their ratio (liquid epoxy resin:solid epoxy resin) is preferably 1:0.1 to 1:20 by mass, more preferably 1:0.15 to 1:10, and even more preferably 1:0.2 to 1:5.

[0044] (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, the crosslinking density of the cured resin composition can result in a cured product with sufficient crosslinking density. The epoxy equivalent is the mass of epoxy resin containing one equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

[0045] (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 on a polystyrene basis measured by gel permeation chromatography (GPC).

[0046] 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, based on 100% by mass of the total of components (A), (B), and (C). When the amount of epoxy resin (A) is within the above range, the adhesive strength and impact resistance of the cured product of the resin composition can be effectively improved.

[0047] The amount of the (A) epoxy resin in the resin composition is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more or 33% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 45% by mass or less, based on 100% by mass of the non-volatile components in the resin composition. When the amount of the (A) epoxy resin is within the above range, the adhesive strength and impact resistance of the cured product of the resin composition can be effectively improved.

[0048] <(B) Thiol compound represented by formula (I) (thiol compound having a specific structure)> The resin composition of the present invention contains, as the component (B), a thiol compound having a specific structure. 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 (A) epoxy resin to cure the resin composition. The thiol compound having a specific structure may be used alone or in combination of two or more.

[0049]

Chemical formula

[0050] (In formula (I), Ring P is independently a phenyl group or a naphthyl group, A is 1 to 5 in each ring P when ring P is a phenyl group, and 1 to 7 in each ring P when ring P is a naphthyl group. Each A is independently -R 1 -SH, R 1 is independently a C1-C6 alkylene group optionally substituted with one or more Ys, B is a group other than A on ring P, and is independently a hydrogen atom, a C1-C6 alkyl group optionally substituted with one or more Ys, or a C1-C6 alkoxy group optionally substituted with one or more Ys. A and B, independently, are bonded at the ortho, meta, or para position relative to the position where ring P is bonded to the main chain if ring P is a phenyl group, and at the ortho, meta, para, ana, epi, cata, peri, pros, amphi, or 2,7 position relative to the position where ring P is bonded to the main chain. X is independently -CH2-, -O-, -N(-R 2 )-, or -S-, R 2 Each of these is independently a hydrogen atom, a C1-C6 alkyl group which may be substituted with one or more Y atoms, or a C1-C6 alkoxy group which may be substituted with one or more Y atoms. Y is independently a hydrogen atom, a C1-C6 alkyl group, or a C1-C6 alkoxy group. Each Z is independently a direct bond, -CH2-, -C2H4-, -C3H6-, -C4H8-, -O-, or -S-. n is an integer between 1 and 20.

[0051] In formula (I), ring P is independently either a phenyl group or a naphthyl group. Ring P is preferably a phenyl group.

[0052] In formula (I), when ring P is a phenyl group, A is usually present in 1 to 5, preferably 1 to 3, more preferably 1 to 2, and even more preferably 1, elements per ring P. When ring P is a naphthyl group, A is usually present in 1 to 7, preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 to 2 elements per ring P.

[0053] Each A is independent of -R 1 -SH. 1 These are C1-C6 alkylene groups that may be substituted with one or more Y groups, independently of each other. 1The alkylene group is preferably an unsubstituted C2-C5 alkylene group; more preferably an unsubstituted C2-C3 alkylene group. The alkylene group may be linear or branched, and may be saturated or unsaturated. Furthermore, the alkylene group may or may not be substituted with Y. The definition of Y is as described below.

[0054] In formula (I), B is a group other than A on ring P. Therefore, the total number of groups A and B on one ring P is 5 if ring P is a phenyl group, and 7 if ring P is a naphthyl group. The number of groups A and B on one ring P is, for example, 1 to 2 A and 0 to 2 non-hydrogen B for each ring P; more preferably, 1 A and 0 to 1 non-hydrogen B for each ring P.

[0055] Each B is independently a hydrogen atom, an optionally substituted C1-C6 alkyl group, or an optionally substituted C1-C6 alkoxy group. The definition of Y is as described below. Preferably, each B is independently a hydrogen atom, an unsubstituted C1-C3 alkyl group, or an unsubstituted C1-C3 alkoxy group; more preferably, each B is independently a hydrogen atom, a methyl group, or a methoxy group; even more preferably, B is a hydrogen atom. All B may be hydrogen atoms. In another embodiment, one or two B present in each ring P may be a methyl group, a methoxy group, or a phenyl group, and all other B present in each ring P may be hydrogen atoms. When ring P is a phenyl group, typically 0 to 4, preferably 0 to 3, more preferably 1 to 2 B per ring P may be non-hydrogen atoms. When ring P is a naphthyl group, there are usually 0 to 6, preferably 0 to 5, more preferably 1 to 3, and even more preferably 1 to 2 B atoms other than hydrogen atoms for each ring P.

[0056] When ring P is a phenyl group, A and B can each be independently bonded to the ortho, meta, or para position relative to the position where ring P is bonded to the main chain. Preferably, A and B may each be independently bonded to the ortho or para position relative to the position where ring P is bonded to the main chain. In a more preferred embodiment, there is one A on ring P, and either no B other than a hydrogen atom is present on ring P, and A is bonded to the ortho or para position relative to the position where ring P is bonded to the main chain, and if a B other than a hydrogen atom is present, B is bonded to the ortho position relative to the position where ring P is bonded to the main chain. In particular, it is preferable that A is bonded to the ortho position relative to the position where ring P is bonded to the main chain.

[0057] When ring P is a naphthyl group, A and B can each independently bond to the ortho, meta, para, ana, epi, cat, peri, pros, amphi, or 2,7 positions relative to the position where ring P is attached to the main chain. Preferably, A and B can each independently bond to the ana, epi, cat, peri, amphi, or 2,7 positions relative to the position where ring P is attached to the main chain. In a more preferred embodiment, there is one A on ring P, and either no or one non-hydrogen B on ring P, and A is bonded to the amphi or 2,7 positions relative to the position where ring P is attached to the main chain, and if a non-hydrogen B is present, B is bonded to the amphi or 2,7 positions relative to the position where ring P is attached to the main chain.

[0058] In equation (I), X is independently -CH2-, -O-, and -N(-R 2 )-, or -S-. Here, R 2 Each of these is independently a hydrogen atom, a C1-C6 alkyl group which may be substituted with one or more Y atoms, or a C1-C6 alkoxy group which may be substituted with one or more Y atoms. 2X is preferably an unsubstituted C2-C5 alkylene group; more preferably an unsubstituted C2-C3 alkylene group. The alkylene group may be linear or branched, and may be saturated or unsaturated. Furthermore, the alkylene group may or may not be substituted with Y. The definition of Y is as described below. X is preferably -CH2- or -O-, and more preferably -O-.

[0059] 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.

[0060] In formula (I), Z is independently a direct bond, -CH2-, -C2H4-, -C3H6-, -C4H8-, -O-, or -S-. Z is preferably a direct bond, -CH2-, -O-, or -S-; more preferably a direct bond or -O-; and even more preferably a direct bond.

[0061] In equation (I), n is an integer between 1 and 20. Preferably, n is an integer between 1 and 10; more preferably, it is an integer between 2 and 5 or between 1 and 3.

[0062] (B) Specific examples of thiol compounds represented by formula (I) include the thiol compound represented by formula (I-1), the thiol compound represented by formula (I-2), the thiol compound represented by formula (I-3), the thiol compound represented by formula (I-4), the thiol compound represented by formula (I-5), and the thiol compound represented by formula (I-6). Among these, the thiol compound represented by formula (I-1) and the thiol compound represented by formula (I-3) are preferred; the thiol compound represented by formula (I-1) is particularly preferred.

[0063] [ka]

[0064] (B) There are no restrictions on the method for producing the thiol compound represented by formula (I). For example, the thiol compound represented by formula (I-1) can be produced by the following method. First, 2-allylphenol and 1,4-dibromobutane are mixed with tetra-n-butylammonium bromide as a phase transfer catalyst and methyl isobutyl ketone (MIBK) as a reaction solvent and dissolved. In one example, after mixing, the mixture is dissolved at a temperature of, for example, 50°C to 200°C, preferably 60°C to 150°C, more preferably 100°C ± 10 to 20°C, for a period of time of usually 1 minute to 12 hours, preferably 10 minutes to 5 hours, more preferably 30 minutes ± 10 to 20 minutes. The resulting solution is mixed with a base such as an aqueous KOH solution, and then the MIBK is returned to the system at a temperature range of, for example, 100°C to 150°C, preferably 110°C to 120°C, and the reaction is carried out while removing water by distillation. The reaction time is usually 1 to 24 hours, preferably 2 to 10 hours, and more preferably 6 hours ± 1 hour. After that, the temperature is lowered to about 60°C, distilled water is added and allowed to stand, and the lower by-product brine layer is discarded. Further distilled water and a base (such as sodium dihydrogen phosphate in an appropriate amount for neutralization) are added and allowed to stand and separate, and the lower by-product brine layer is discarded. Further, the same amount of distilled water is added and the mixture is washed and purified with water usually 1 to 5 times, preferably 2 to 3 times. After that, the mixture is heated to, for example, 50°C to 200°C, preferably 60°C to 150°C, and more preferably 120°C ± 10 to 20°C to perform azeotropic dehydration. The obtained solution is microfiltered to remove impurities, and MIBK and unreacted 2-allylphenol are distilled under reduced pressure to obtain a liquid resin. The obtained liquid resin, thioacetic acid, toluene, and azobisisobutyronitrile (AIBN) are mixed and reacted. The reaction temperature for this reaction is, for example, 50°C to 200°C, preferably 60°C to 150°C, and more preferably 80°C ± 10 to 20°C. The reaction time is, for example, 30 minutes to 24 hours, preferably 1 hour to 10 hours, and more preferably 4 hours ± 1 to 2 hours. After removing toluene from the resulting reactant, crystallization is performed with methanol, and the crystallized product is dried and recovered. The recovered dried crystallized product is mixed with a base such as NaOH and reacted. The reaction temperature for this reaction is, for example, 50°C to 200°C, preferably 60°C to 150°C, and more preferably 80°C ± 10 to 20°C.Furthermore, the reaction time is, for example, 30 minutes to 12 hours, preferably 1 hour to 5 hours, and more preferably 2 hours ± 1 hour. After neutralizing the reactants with an acid such as hydrochloric acid, the organic layer is separated and washed with water. Toluene is removed from the washed organic layer to obtain the desired thiol compound. For a specific manufacturing method, the method described in the specification of Japanese Patent Application No. 2023-057934 may be adopted.

[0065] 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, 47% by mass or more, or 49% by mass or more, based on 100% by mass of the total of components (A), (B), and (C), and preferably 85% by mass or less, more preferably 75% by mass or less, even more 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 the resin composition is within the above range, the adhesive strength and impact resistance of the cured product of the resin composition can be effectively improved.

[0066] 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, based on 100% by mass of the nonvolatile components in the resin composition. 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 product of the resin composition can be effectively improved.

[0067] In the resin composition, the mass ratio of the thiol compound represented by formula (I) (B) to the epoxy resin (A) (content of the thiol compound represented by formula (I) / content of the epoxy resin) is preferably 0.1 or more, more preferably 0.5 or more, even more preferably 1 or more, preferably 5 or less, more preferably 3 or less, even more preferably 2 or less or 1.7 or less. When the above mass ratio (content of the thiol compound represented by formula (I) / content of the epoxy resin) is within the above range, the adhesive strength and impact resistance of the cured product of the resin composition can be effectively improved.

[0068] In a resin composition, the ratio of the number of mercapto groups in the thiol compound represented by formula (I) (B) to the number of epoxy groups in the epoxy resin (A) is preferably within a specific range. The above ratio (mercapto groups / epoxy groups) is preferably 0.1 or more, more preferably 0.5 or more, even more preferably 0.8 or more or 0.9 or more, preferably 3 or less, more preferably 2 or less, even more preferably 1.5 or less, 1.3 or less or 1.1 or less. The "number of epoxy groups in the epoxy resin (A)" in the resin composition refers to the sum of all values ​​obtained by dividing the mass of the epoxy resin (A) present in the resin composition by its epoxy equivalent. The "number of mercapto groups in the thiol compound represented by formula (I) (B)" in the resin composition refers to the sum of all values ​​obtained by dividing the mass of the thiol compound represented by formula (I) (B) present in the resin composition by its mercapto group equivalent. The mercapto group equivalent refers to the mass of resin containing 1 equivalent of mercapto groups. When the above ratio (number of mercapto 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.

[0069] The resin composition may contain (E) other thiol compounds, described later, in combination with (B) a thiol compound represented by formula (I). In the resin composition in such embodiments, the ratio of the total number of mercapto groups of the thiol compound represented by formula (I) (B) to the total number of mercapto groups of the other thiol compound (E) to the number of epoxy groups of the epoxy resin (A) is preferably within a specific range. When the resin composition contains (E) other thiol compounds, the above ratio (total number of mercapto groups / number of epoxy groups) is preferably 0.1 or more, more preferably 0.5 or more, even more preferably 0.8 or more or 1 or more, preferably 5 or less, more preferably 3 or less, even more preferably 2 or less, and even more preferably 1.5 or less. When the above ratio (total number of mercapto groups / number of epoxy groups) is within the above range, the adhesive strength and impact resistance of the cured product of the resin composition can be effectively improved.

[0070] <(C) Curing accelerator> The resin composition of the present invention includes a curing accelerator as component (C). The curing accelerator (C) does not include components (A) and (B) described above. The curing accelerator (C) can act as a catalyst in the reaction of the epoxy resin (A) to accelerate the curing of the resin composition. The curing accelerator (C) may be used alone or in combination of two or more types.

[0071] (C) As a curing accelerator, a latent curing accelerator is preferably used. Latent curing accelerators generally do not contribute to the curing of (A) epoxy resin at room temperature (25°C), but have the function of accelerating the curing of (A) epoxy resin when heated.

[0072] The latent curing accelerator may be a liquid latent curing accelerator or a solid-dispersed latent curing accelerator, but a solid-dispersed latent curing accelerator is more preferred. A liquid latent curing accelerator is a liquid that is soluble in the resin composition at room temperature (25°C) and functions as a curing accelerator for (A) epoxy resin when heated. On the other hand, a solid-dispersed latent curing accelerator is a solid that is insoluble in the resin composition at room temperature (25°C) and becomes soluble in the resin composition when heated and functions as a curing accelerator for (A) epoxy resin.

[0073] Examples of solid-disperse latent curing accelerators include imidazole compounds that are solid at room temperature (25°C) and solid-disperse amine adduct-based latent curing accelerators.

[0074] Examples of imidazole compounds that are solid at room temperature (25°C) include 2-heptadecylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-undecylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4-benzyl-5-hydroxymethylimidazole, 2,4-diamino-6-[2-(2-methyl-1-imidazolyl)ethyl]-1,3,5-triazine, and 2,4-diamino-6 Examples include -[2-(2-methyl-1-imidazolyl)ethyl]-1,3,5-triazine isocyanurate adduct, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazole trimellitate, N-(2-methylimidazolyl-1-ethyl)urea, etc.

[0075] Suitable examples of solid-disperse amine adduct-based latent curing accelerators include amine epoxy adduct-based latent curing accelerators, urea adduct-based latent curing accelerators of amine compounds, and compounds obtained by the addition reaction of an isocyanate compound to the hydroxyl group of an epoxy adduct. Among these, amine epoxy adduct-based latent curing accelerators are preferred.

[0076] Examples of epoxy compounds that can be used as raw materials for the production of solid-disperse amine adduct-type latent curing accelerators include: polyglycidyl ethers obtained by reacting polyhydric phenols (bisphenol A, bisphenol F, catechol, resorcinol, etc.) or polyhydric alcohols (glycerin, polyethylene glycol, etc.) with epichlorohydrin; glycidyl ether esters obtained by reacting hydroxycarboxylic acids such as p-hydroxybenzoic acid and β-hydroxynaphthoic acid with epichlorohydrin; polyglycidyl esters obtained by reacting polycarboxylic acids such as phthalic acid and terephthalic acid with epichlorohydrin; glycidylamine compounds obtained by reacting 4,4'-diaminodiphenylmethane or m-aminophenol with epichlorohydrin; polyfunctional epoxy compounds such as epoxidized phenol novolac resins, epoxidized cresol novolac resins, and epoxidized polyolefins; and monofunctional epoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, and glycidyl methacrylate.

[0077] Amine compounds that can be used as raw materials for the production of solid-dispersible amine adduct-type latent curing accelerators may be compounds that have one or more active hydrogen atoms capable of addition reactions with epoxy groups in their molecule, and have at least one functional group selected from primary amino groups, secondary amino groups, and tertiary amino groups in their molecule. Examples of such amine compounds include aliphatic amine compounds such as diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, and 4,4'-diamino-dicyclohexylmethane; aromatic amine compounds such as 4,4'-diaminodiphenylmethane and 2-methylaniline; and nitrogen-containing heterocyclic compounds such as 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline, piperidine, and piperazine.

[0078] Among the amine compounds mentioned above, amine compounds having a tertiary amino group in the molecule are raw materials that provide latent curing accelerators with excellent curing acceleration ability. Examples of amine compounds having a tertiary amino group in the molecule include primary or secondary amines having a tertiary amino group in the molecule; alcohols, phenols, thiols, carboxylic acids, and hydrazides having a tertiary amino group in the molecule. Examples of primary or secondary amines having a tertiary amino group in the molecule include amine compounds such as dimethylaminopropylamine, diethylaminopropylamine, di-n-propylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, and N-methylpiperazine; and imidazole compounds such as 2-methylimidazole, 2-ethylimidal, 2-ethyl-4-methylimidazole, and 2-phenylimidazole.Furthermore, examples of alcohols, phenols, thiols, carboxylic acids, and hydrazides having a tertiary amino group in the molecule include 2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol, 1-(2-hydroxy-3-phenoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-ethyl-4-methylimidazole, 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3 Examples include (phenoxypropyl)-2-phenylimidazoline, 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazoline, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol, N-β-hydroxyethylmorpholine, 2-dimethylaminoethanethiol, 2-mercaptopyridine, 2-benzimidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 4-mercaptopyridine, N,N-dimethylaminobenzoic acid, N,N-dimethylglycine, nicotinic acid, isonicotinic acid, picolinic acid, N,N-dimethylglycine hydrazide, N,N-dimethylpropionic acid hydrazide, nicotinic acid hydrazide, and isonicotinic acid hydrazide.

[0079] When producing a latent curing accelerator by addition reaction between an epoxy compound and an amine compound, an active hydrogen compound having two or more active hydrogen atoms in its molecule may be reacted further. Examples of such active hydrogen compounds include polyhydric phenols such as bisphenol A, bisphenol F, bisphenol S, hydroquinone, catechol, resorcinol, pyrogallol, and phenol novolac resins; polyhydric alcohols such as trimethylolpropane; polyhydric carboxylic acids such as adipic acid and phthalic acid; and 1,2-dimercaptoethane, 2-mercaptoethanol, 1-mercapto-3-phenoxy-2-propanol, mercaptoacetic acid, anthranilic acid, and lactic acid.

[0080] Examples of isocyanate compounds that can be used as raw materials for the production of solid-dispersible amine adduct-type latent curing accelerators include monofunctional isocyanate compounds such as n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, and benzyl isocyanate; polyfunctional isocyanate compounds such as hexamethylene diisocyanate, toluene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, and bicycloheptane triisocyanate; and terminal isocyanate group-containing compounds obtained by the reaction of these polyfunctional isocyanate compounds with active hydrogen compounds. Specific examples of compounds containing terminal isocyanate groups include adducts having terminal isocyanate groups obtained by the reaction of toluene diisocyanate and trimethylolpropane, and adducts having terminal isocyanate groups obtained by the reaction of toluene diisocyanate and pentaerythritol.

[0081] Examples of urea compounds that can be used as raw materials for the manufacture of solid-disperse amine adduct-type latent curing accelerators include urea and thiourea.

[0082] The above-mentioned solid-dispersed amine adduct-based latent curing accelerator may be manufactured, for example, by mixing the above-mentioned raw materials, reacting them at a temperature from room temperature to 200°C, then cooling and solidifying them before grinding; or by reacting the above-mentioned raw materials in a solvent such as methyl ethyl ketone, dioxane, or tetrahydrofuran, removing the solvent, and then grinding the solid component.

[0083] Examples of commercially available solid-disperse amine adduct-based latent curing accelerators include, for example, "Amicure PN-FJ," "Amicure PN-23," and "Amicure PN-H" from Ajinomoto Fine Techno Co., Ltd.; "Hardener X-3661S" and "Hardener X-3670S" from ACR Co., Ltd.; "FXR-1081," "Fujicure FXR-1000," and "Fujicure FXR-1030" from T&K Toka Co., Ltd.; and "Novacure HX-3721," "HX-3722," and "Novacure HX-3742" from Asahi Kasei Corporation.

[0084] 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, based on 100% by mass of the total of components (A), (B), and (C).

[0085] 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, based on 100% by mass of the nonvolatile components in the resin composition.

[0086] In the resin composition, the mass ratio of (B) the thiol compound represented by formula (I) to (C) the curing accelerator (content of (B) the thiol compound represented by formula (I) / content of (C) the curing accelerator) is preferably 10 or more, more preferably 15 or more, even more preferably 20 or more, preferably 50 or less, more preferably 40 or less, even more preferably 35 or less or 33 or less. When the above mass ratio (content of (B) the thiol compound represented by formula (I) / content of (C) the curing accelerator) is within the above range, the adhesive strength and impact resistance of the cured product of the resin composition can be effectively improved.

[0087] The total 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, even more preferably 70% by mass or more, even more preferably 80% by mass or more, and even more preferably 90% by mass or more, based on 100% by mass of the nonvolatile components in the resin composition. The upper limit is usually 100% by mass or less, and may be 99% by mass or less. When the total amount of components (A) to (C) is within the above range, the adhesive strength and impact resistance of the cured product of the resin composition can be effectively improved.

[0088] <(D) Inorganic filler> The resin composition of the present invention may optionally contain (D) an inorganic filler. The (D) inorganic filler, as a component, is a particle of an inorganic material. Therefore, the (D) inorganic filler is included in the resin composition in granular form and is usually included in the cured product while maintaining that granular state. The (D) inorganic filler may be used alone or in combination of two or more types.

[0089] (D) Inorganic materials are typically inorganic compounds used to form the inorganic filler. (D) Examples of materials for the inorganic filler include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is preferred. Examples of silica include fumed silica, amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. In one preferred embodiment, the (D) inorganic filler includes fumed silica.

[0090] Fumed silica can be classified into hydrophilic and hydrophobic types. Hydrophilic fumed silica is obtained by flame hydrolysis of silicon tetrachloride and has hydrophilic silanol groups on its surface. Commercially available hydrophilic fumed silica products include "200," "300," and "380" from Nippon Aerosil Co., Ltd. Hydrophobic fumed silica is obtained by treating the above-mentioned 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" from Nippon Aerosil Co., Ltd. These fumed silicas may be used individually or in combination of two or more types.

[0091] Examples of surface treatment agents for hydrophobic fumed silica include organosilane compounds such as dimethylsilane, trimethylsilane, alkylsilane, methacryloxysilane, and organochlorosilane; organosiloxane compounds such as polydimethylsiloxane; and organosilazane compounds such as hexamethyldisilazane.

[0092] (D) The average particle size range of the fumed silica as an inorganic filler 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 range, the adhesive strength and impact resistance of the cured resin composition can be effectively improved.

[0093] (D) The average particle size of the inorganic filler can be measured by the laser diffraction-scattering method based on Mie scattering theory. Specifically, a particle size distribution of the inorganic filler (D) can be created on a volume basis using a laser diffraction-scattering particle size distribution analyzer, and the average particle size can be measured as the median diameter from this particle size distribution. Preferably, the measurement sample is the inorganic filler (D) dispersed in water using ultrasound. Suitable laser diffraction-scattering particle size distribution analyzers include the "LA-960" from Horiba, Ltd. and the "SALD-2200" from Shimadzu Corporation.

[0094] (D) The specific surface area range of fumed silica as an inorganic filler is preferably 1 m². 2 / g or more, comfortably 10m 2 / g or more, more preferably 50m 2 / g or more, more preferably 100m 2 / g or more or 150m 2 It is 1 / 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 It is less than or equal to / g. When the specific surface area of ​​fumed silica is within the above range, the adhesive strength and impact resistance of the cured resin composition can be effectively improved.

[0095] (D) The specific surface area of ​​the inorganic filler can be measured by adsorbing nitrogen gas onto the sample surface using a specific surface area measuring device (Macsorb HM-1210, manufactured by Mountec Co., Ltd.) according to the BET method, and then calculating the specific surface area using the BET multipoint method.

[0096] Other commercially available inorganic fillers besides fumed silica include "SP60-05" and "SP507-05" from Nippon Steel Chemical & Material Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", "YA010C", "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1" from Admatex Co., Ltd.; "UFP-30", "DAW-03", and "FB-105FD" from Denka Co., Ltd.; "Silfil NSS-3N", "Silfil NSS-4N", and "Silfil NSS-5N" from Tokuyama Corporation; and "Cellspheres" and "MGH-005" from Taiheiyo Cement Corporation.

[0097] The average particle size range of the inorganic filler (D) other than 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 inorganic filler (D) other than fumed silica is within the above range, the adhesive strength and impact resistance of the cured resin composition can be effectively improved.

[0098] The specific surface area range of the inorganic filler other than fumed silica (D) is preferably 0.05 m². 2 / g or more, more preferably 0.1m 2 / g or more, more preferably 1m 2 / g or more, 3m 2 / g or more or 5m 2 It is 100m or more / g, preferably 100m 2 / g or less, more preferably 80m 2 / g or less, more preferably 60mg 2 / g or less, 50m 2 / g or less or 40m 2 It is less than or equal to / g. When the specific surface area of ​​the inorganic filler other than fumed silica (D) is within the above range, the adhesive strength and impact resistance of the cured resin composition can be effectively improved.

[0099] (D) Inorganic fillers other than fumed silica may be treated with a surface treatment agent to improve moisture resistance and dispersibility. Examples of surface treatment agents include aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, titanate coupling agents, etc. One type of surface treatment agent may be used alone, or two or more types may be used in any combination.

[0100] Examples of commercially available surface treatment agents include Shin-Etsu Chemical Co., Ltd.'s "KBM403" (3-glycidoxypropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM803" (3-mercaptopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM5783" (N-phenyl-3-aminooctyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd.'s "KBM103" (phenyltrimethoxysilane), and Shin-Etsu Chemical Co., Ltd.'s "KBM-4803" (long-chain epoxy type silane coupling agent).

[0101] The degree of surface treatment by the surface treatment agent is preferably within a specific range from the viewpoint of improving the dispersibility of the inorganic filler (D). When the inorganic filler (D) is treated with a surface treatment agent, 100 parts by mass of the inorganic filler is preferably surface-treated with 0.2 to 5 parts by mass of the surface treatment agent, more preferably with 0.2 to 3 parts by mass of the surface treatment agent, and even more preferably with 0.3 to 2 parts by mass of the surface treatment agent.

[0102] The degree of surface treatment by a surface treatment agent can be evaluated by the amount of carbon per unit surface area of ​​the (D) inorganic filler. When the (D) inorganic filler is treated with a surface treatment agent, the amount of carbon per unit surface area of ​​the (D) inorganic filler is 0.02 mg / m² from the viewpoint of improving the dispersibility of the (D) inorganic filler. 2The above is preferred, and 0.1 mg / m² 2 The above is more preferable, 0.2 mg / m² 2 The above is even more preferable. On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin composition, (D) the upper limit of the amount of carbon per unit surface area of ​​the inorganic filler is 1.0 mg / m 2 The following is preferred: 0.8 mg / m² 2 The following is more preferable: 0.5 mg / m² 2 The following is even more preferable.

[0103] (D) The amount of carbon per unit surface area of ​​the inorganic filler can be measured after cleaning the inorganic filler with a solvent (e.g., methyl ethyl ketone (MEK)) after surface treatment. Specifically, a sufficient amount of MEK as the solvent is added to the inorganic filler that has been surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solids, the amount of carbon per unit surface area of ​​the inorganic filler can be measured using a carbon analyzer. As a carbon analyzer, a Horiba "EMIA-320V" or similar can be used.

[0104] When the resin composition contains (D) an inorganic filler, the amount of (D) an inorganic filler in the resin composition is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, 6% by mass or more, or 7% by mass or more, with respect to 100% by mass of the nonvolatile components in the resin composition, preferably 30% by mass or less, more preferably 25% by mass or less, even more preferably 20% by mass or less, even more preferably 15% by mass or less, 13% by mass or less, or 10% by mass or less. When the amount of (D) an inorganic filler is within the above range, the adhesive strength and impact resistance of the cured product of the resin composition can be effectively improved.

[0105] When the resin composition contains (D) an inorganic filler, the mass ratio of (B) the thiol compound represented by formula (I) to (D) the inorganic filler (content of (B) the thiol compound represented by formula (I) / content of (D) the inorganic filler) is preferably 1 or more, more preferably 3 or more, even more preferably 5 or more, preferably 30 or less, more preferably 25 or less, even more preferably 20 or less, even more preferably 15 or less, 13 or less, or 10 or less. When the above mass ratio (content of (B) the thiol compound represented by formula (I) / content of (D) the inorganic filler) is within the above range, the adhesive strength and impact resistance of the cured product of the resin composition can be effectively improved.

[0106] <(E) Other Thiol Compounds> The resin composition of the present invention may optionally contain (E) other thiol compounds. The (E) other thiol compound is a thiol compound not represented by the above formula (I). That is, the (E) other thiol compound is a thiol compound other than the (B) component. The (E) other thiol compound may be used alone or in combination of two or more types.

[0107] (E) Other thiol compounds may be compounds having one or more mercapto groups in one molecule and not represented by formula (I) above. In particular, (E) other thiol compounds are preferably polythiol compounds having two or more mercapto groups in one molecule.

[0108] The polythiol compound may be a commercially available product or one manufactured by a known method (for example, the method described in Japanese Patent Publication No. 2012-153794 or International Publication No. 2001 / 00698).

[0109] Examples of polythiol compounds include partial esters of polyols and mercaptoorganic acids, and complete esters of polyols and mercaptoorganic acids. Here, a partial ester is an ester of a polyol and a carboxylic acid in which some of the hydroxyl groups of the polyol form ester bonds. A complete ester is one in which all of the hydroxyl groups of the polyol form ester bonds.

[0110] Examples of polyols used in the synthesis of polythiol compounds include ethylene glycol, trimethylolethane, trimethylolpropane, pentaerythritol, and dipentaerythritol.

[0111] Examples of mercapto-organic acids used in the synthesis of polythiol compounds include mercaptoaliphatic monocarboxylic acids such as mercaptoacetic acid, mercaptopropionic acid (e.g., 3-mercaptopropionic acid), and mercaptobutyric acid (e.g., 3-mercaptobutyric acid, 4-mercaptobutyric acid); esters containing mercapto and carboxyl groups obtained by the esterification reaction of hydroxy acids with mercapto-organic acids; mercaptoaliphatic dicarboxylic acids such as mercaptosuccinic acid and dimercaptosuccinic acid (e.g., 2,3-dimercaptosuccinic acid); and mercaptoaromatic monocarboxylic acids such as mercaptobenzoic acid (e.g., 4-mercaptobenzoic acid). The number of carbon atoms in the mercaptoaliphatic monocarboxylic acid is preferably 2 to 8, more preferably 2 to 6, even more preferably 2 to 4, and particularly preferably 3. In particular, the mercapto organic acids used in the synthesis of polythiol compounds are preferably mercaptoaliphatic monocarboxylic acids having 2 to 8 carbon atoms, more preferably mercaptoacetic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, and 4-mercaptobutyric acid, and even more preferably 3-mercaptopropionic acid.

[0112] Specific examples of partial esters of polyols and mercapto-organic acids include trimethylolethane bis(mercaptoacetate), trimethylolethane bis(3-mercaptopropionate), trimethylolethane bis(3-mercaptobutyrate), trimethylolethane bis(4-mercaptobutyrate), trimethylolpropane bis(mercaptoacetate), trimethylolpropane bis(3-mercaptopropionate), trimethylolpropane bis(3-mercaptobutyrate), trimethylolpropane bis(4-mercaptobutyrate), pentaerythritol tris(mercaptoacetate), pentaerythritol tris(3-mercaptopropionate), pentaerythritol tris(3-mercaptobutyrate), and pentaerythritol. Examples include Tris(4-mercaptobutyrate), dipentaerythritol tetrakis(mercaptoacetate), dipentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol tetrakis(3-mercaptobutyrate), and dipentaerythritol tetrakis(4-mercaptobutyrate).

[0113] Specific examples of complete esters of polyols and mercapto-organic acids include ethylene glycol bis(mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), ethylene glycol bis(3-mercaptobutyrate), ethylene glycol bis(4-mercaptobutyrate), trimethylolethane tris(mercaptoacetate), trimethylolethane tris(3-mercaptopropionate), trimethylolethane tris(3-mercaptobutyrate), trimethylolethane tris(4-mercaptobutyrate), trimethylolpropane tris(mercaptoacetate), trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), trimethylolpropane tris(4-mercaptobutyrate), and pentaerythritol. Examples include tetrakis (mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakis (4-mercaptobutyrate), dipentaerythritol hexakis (mercaptoacetate), dipentaerythritol hexakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptobutyrate), and dipentaerythritol hexakis (4-mercaptobutyrate).

[0114] From the viewpoint of storage stability, partial and complete esters of polyols and mercapto organic acids are preferably those with the lowest possible amount of basic impurities, and more preferably those that do not require the use of basic substances in their manufacture.

[0115] Furthermore, as the polythiol compound, it is also possible to use a polythiol compound produced using a basic substance as a reaction catalyst in the manufacturing process, such as alkane polythiol compounds such as 1,4-butanedithiol, 1,6-hexanedithiol, and 1,10-decanedithiol; polyethers containing terminal mercapto groups; polythioethers containing terminal mercapto groups; polythiol compounds obtained by the reaction of an epoxy compound with hydrogen sulfide; and polythiol compounds having terminal mercapto groups obtained by the reaction of a polythiol compound with an epoxy compound. It is preferable to use a polythiol compound produced using a basic substance after dealkalization treatment to reduce the alkali metal ion concentration to 50 ppm by mass or less.

[0116] Dealkalization treatments for polythiol compounds produced using basic substances include, but are not limited to, methods such as: dissolving the polythiol compound in an organic solvent such as acetone or methanol, neutralizing it by adding an acid such as dilute hydrochloric acid or dilute sulfuric acid, and then desalting it by extraction and washing; adsorbing the basic substance using an ion exchange resin; or purifying the polythiol compound by distillation.

[0117] Furthermore, as the polythiol compound, 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-tetrakis(2-mercaptoethyl)glycoluryl, and 4,4'-isopropylidenediphenyl bis(3-mercaptopropyl) ether may be used.

[0118] In polythiol compounds, the number of mercapto groups in one molecule is preferably two or more, more preferably three or more, preferably six or fewer, more preferably five or fewer, and even more preferably four or fewer. Among these, it is particularly preferable that the polythiol compound has three or four mercapto groups in one molecule.

[0119] (E) The mercapto group equivalent of the other thiol compound 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, even more preferably 500 g / eq. or less, and even more preferably 300 g / eq. or less. The mercapto group equivalent is the mass of the other thiol compound (E) per equivalent of mercapto group.

[0120] (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 on a polystyrene basis measured by gel permeation chromatography (GPC).

[0121] If the resin composition contains (E) other thiol compounds, the ratio of the number of mercapto groups of (E) other thiol compounds to the number of epoxy groups of (A) epoxy resin ((E) other thiol compound mercapto groups / (A) epoxy resin epoxy groups) is preferably within a specific range. The above ratio ((E) other thiol compound mercapto groups / (A) epoxy resin epoxy groups) is preferably 0.01 or more, more preferably 0.05 or more, even more preferably 0.1 or more, preferably 2 or less, more preferably 1.5 or less, and even more preferably 1 or less. The "(E) other thiol compound mercapto groups" in the resin composition refers to the sum of all values ​​obtained by dividing the mass of the (E) other thiol compounds present in the resin composition by their mercapto group equivalents.

[0122] If the resin composition contains (E) other thiol compounds, the amount of (E) other thiol compounds in the resin composition is, for example, 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, and even more preferably 3% by mass or more, based on 100% by mass of the nonvolatile components in the resin composition, 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 (E) other thiol compounds is within the above range, the adhesive strength and impact resistance of the cured product of the resin composition can be effectively improved.

[0123] <(F) Preservative stabilizer> The resin composition of the present invention may optionally contain (F) a preservative stabilizer. The (F) preservative stabilizer does not include those corresponding to the above-mentioned components (A) to (E). Although (A) epoxy resin and (B) thiol compounds having a specific structure have high reactivity, the (F) preservative stabilizer can suppress unintended reactions between (A) epoxy resin and (B) thiol compounds having a specific structure, thereby improving the pot life (storage stability) of the resin composition. The (F) preservative stabilizer may be used alone or in combination of two or more types.

[0124] (F) Examples of preservatives and stabilizers include borate compounds, titanate compounds, aluminate compounds, zirconate compounds, isocyanate compounds, carboxylic acids, acid anhydrides, mercapto organic acids, etc.

[0125] Examples of borate compounds include trimethyl borate, triethyl borate (TEB), tri-n-propyl borate, triisopropyl borate, tri-n-butyl borate, tripentyl borate, triallyl borate, trihexyl borate, tricyclohexyl borate, trioctyl borate, trinonyl borate, tridecyl borate, tridodecyl borate, trihexadecyl borate, trioctadecyl borate, tris(2-ethylhexyloxy)borane, bis(1,4,7,10-tetraoxowndecyl)(1,4,7,10,13-pentaoxatetradecyl)(1,4,7-trioxowndecyl)borane, trimenzyl borate, triphenyl borate, tri-o-tolyl borate, tri-m-tolyl borate, and triethanolamine borate.

[0126] Examples of titanate compounds include tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, and tetraoctyl titanate.

[0127] Examples of aluminate compounds include triethylaluminate, tripropylaluminate, triisopropylaluminate, tributylaluminate, and trioctylaluminate.

[0128] Examples of zirconate compounds include tetraethyl zirconate, tetrapropyl zirconate, tetraisopropyl zirconate, and tetrabutyl zirconate.

[0129] Examples of isocyanate compounds include n-butyl isocyanate, isopropyl isocyanate, 2-chloroethyl isocyanate, phenyl isocyanate, p-chlorophenyl isocyanate, benzyl isocyanate, hexamethylene diisocyanate, 2-ethylphenyl isocyanate, 2,6-dimethylphenyl isocyanate, tolylene diisocyanate (e.g., 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate), 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, tolidine diisocyanate, isophorone diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate, and bicycloheptane triisocyanate.

[0130] Examples of carboxylic acids include saturated aliphatic monobasic acids such as formic acid, acetic acid, propionic acid, butyric acid, caproic acid, and caprylic acid; unsaturated aliphatic monobasic acids such as acrylic acid, methacrylic acid, and crotonic acid; halogenated fatty acids such as monochloroacetic acid and dichloroacetic acid, monobasic oxyacids such as glycolic acid and lactic acid; aliphatic aldehyde acids and ketonic acids such as glyoxalic acid and violet acid; aliphatic polybasic acids such as oxalic acid, malonic acid, succinic acid, and maleic acid; aromatic monobasic acids such as benzoic acid, halogenated benzoic acid, toluic acid, phenylacetic acid, cinnamic acid, and mandelic acid; and aromatic polybasic acids such as phthalic acid and trimesic acid.

[0131] Examples of acid anhydrides include aliphatic polybasic acid anhydrides such as succinic anhydride, dodecinyl succinic anhydride, maleic anhydride, adducts of methylcyclopentadiene and maleic anhydride, hexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride; and aromatic polybasic acid anhydrides such as phthalic anhydride, trimellitic anhydride, and pyrrolimellitic anhydride.

[0132] Examples of mercapto-organic acids include mercaptoaliphatic monocarboxylic acids such as mercaptoacetic acid, mercaptopropionic acid, mercaptobutyric acid, mercaptosuccinic acid, and dimercaptosuccinic acid; mercaptoaliphatic monocarboxylic acids obtained by esterification reactions of hydroxy organic acids and mercapto-organic acids; and mercapto-aromatic monocarboxylic acids such as mercaptobenzoic acid.

[0133] (F) As preservatives and stabilizers, borate compounds are preferred from the viewpoint of high versatility and safety, and effectively improving preservation stability. Among these, triethyl borate, tri-n-propyl borate, triisopropyl borate, and tri-n-butyl borate are more preferred, and triethyl borate is even more preferred.

[0134] If the resin composition contains (F) a preservative stabilizer, the amount of (F) 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, based on 100% by mass of the nonvolatile components in the resin composition.

[0135] <(G) Other additives> The resin composition of the present invention may contain (G) other additives as optional components. The (G) other additives do not include those corresponding to the above-mentioned components (A) to (F). Examples of (G) other additives include thermoplastic resins; polymerization initiators; organometallic compounds such as organocumeric compounds, organozinc compounds, and organocobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium dioxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; thickeners such as bentonite and montmorillonite; silicone-based defoamers, acrylic-based defoamers, fluorine-based defoamers, and vinyl resin-based defoamers. Examples include defoaming agents such as benzotriazole-based UV absorbers; UV absorbers such as benzotriazole-based UV absorbers; adhesion improvers such as urea silane; adhesion fertilizers such as triazole-based adhesion fertilizers, tetrazole-based adhesion fertilizers, and triazine-based adhesion fertilizers; antioxidants such as hindered phenol-based antioxidants; fluorescent whitening agents such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; flame retardants such as phosphorus-based flame retardants (e.g., phosphate ester compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus), nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, and inorganic flame retardants (e.g., antimony trioxide); etc. (G) Other additives may be used individually or in combination of two or more types.

[0136] <(H) Organic solvents> The resin composition of the present invention may further contain an optional volatile component, an organic solvent (H), in combination with the 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. (H) Examples of organic solvents include ketone solvents such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, and anisole; alcohol solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, and methoxypropyl acetate. Examples of solvents include ether ester solvents such as methyl ionate; 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.

[0137] The amount of (H) organic solvent in the resin composition is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less, 1% by mass or less, 0.5% by mass or less, 0.1% by mass or less, or 0.01% by mass or less, and even more preferably 0% by mass, based on 100% by mass of the nonvolatile components in the resin composition. That is, in a preferred embodiment, the resin composition does not contain (H) organic solvent.

[0138] [Method for producing resin compositions] The resin composition of the present invention can be produced, for example, by mixing components that may be included in the resin composition. The above-mentioned components may be mixed some or all at the same time, or they may be mixed sequentially. The temperature may be set appropriately during the mixing of each component, and thus heating and / or cooling may be performed temporarily or throughout the process. Furthermore, stirring or shaking may be performed during the mixing of each component.

[0139] [Properties of resin compositions and their cured products] The resin composition of the present invention may be in solid or liquid form. Furthermore, the liquid resin composition may be in paste form containing no or only a small amount of (H) organic solvent, or in varnish form containing many (H) organic solvents.

[0140] A cured product of the resin composition of the present invention can be obtained by curing the resin composition. Normally, heat is applied when a resin composition is cured, so among the components contained in the resin composition, volatile components such as (H) organic solvents may volatilize due to the heat during curing. Therefore, the cured product obtained by curing the resin composition may contain non-volatile components such as components (A) to (G) or their reaction products.

[0141] The cured product of the resin composition of the present invention can have good adhesive strength. Therefore, the cured product of the resin composition can have good tensile shear adhesive strength. In one example, two epoxy glass test pieces are bonded together via the resin composition, and the resin composition is heated at 120°C for 30 minutes to obtain a laminated sample comprising epoxy glass test piece / cured resin composition / epoxy glass test piece in this order. Using this laminated sample, a tensile shear adhesive strength measurement test is performed in accordance with JIS-K-6850. The tensile shear adhesive strength measured in this test is preferably 3 N / mm 2 More preferably 6 N / mm 2 More preferably 10 N / mm 2 That concludes the explanation. A higher upper limit for tensile shear adhesive strength is preferable, for example, 50 N / mm². 2 The following or 40 N / mm² 2 The following are possible:

[0142] The cured resin composition of the present invention can have good impact resistance. Therefore, when the cured resin composition is subjected to a DuPont impact test, the cured material can have a high impact fracture height. Details of the DuPont impact test are described below. In one example, an epoxy glass test piece and a stainless steel test piece are bonded together via the resin composition, and the resin composition is heated at 120°C for 30 minutes to obtain a laminated sample comprising the epoxy glass test piece / cured resin composition / stainless steel test piece in this order. The obtained laminated sample is placed in a DuPont impact tester with the epoxy glass test piece side facing upwards, and a DuPont impact test is performed using a 50g weight. At this time, the height at which the fracture of the cured resin composition is confirmed (impact fracture height) is preferably 300mm or more, more preferably 350mm or more, even more preferably 400mm or more, and even more preferably 450mm or more. The upper limit of the impact fracture height is preferably higher, for example, 10m or less or 8m or less.

[0143] The cured product of the resin composition of the present invention may have good mechanical properties. For example, the cured product of the resin composition preferably has a low modulus of elasticity, and therefore 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 limit to the lower limit of the tensile modulus of elasticity, for example, 0.1 MPa or more, preferably 1 MPa or more, more preferably 5 MPa or more, and may be 10 MPa or more, 100 MPa or more, or 1,000 MPa or more. Furthermore, the cured product contained in an electronic component or semiconductor device may have a tensile modulus of elasticity within the above range.

[0144] The tensile modulus of the cured resin composition can be measured by a tensile test under the conditions of a temperature of 25°C, a relative humidity of 50%, and a tensile speed of 5 mm / min. The specific measurement method can be the one described later in the examples.

[0145] When the resin composition of the present invention is in liquid form, the resin composition may have a viscosity within a specific range. For 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.

[0146] In one example, the viscosity of the resin composition measured using an E-type viscometer under conditions of 25°C and 10 rpm is preferably 0.1 Pa·s or higher, more preferably 1 Pa·s or higher, even more preferably 3 Pa·s or higher, preferably 100 Pa·s or lower, more preferably 50 Pa·s or lower, even more preferably 30 Pa·s or lower, or 20 Pa·s or lower.

[0147] When the resin composition of the present invention is in liquid form, it may have good thixotropy. The thixotropy of the resin composition can be expressed by the thixotropy 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 thixotropy index calculated in this case is preferably 1 or higher, more preferably 1.5 or higher, even more preferably 2 or higher, preferably 10 or lower, more preferably 8.5 or lower, and even more preferably 7.5 or lower.

[0148] <DuPont impact test of cured resin composition> As mentioned earlier, the impact fracture height of a cured resin composition can be measured by the DuPont impact test. Before explaining the details of the DuPont impact test, the manufacturing method of the laminated sample 10 used in the DuPont impact test will be explained using the drawings.

[0149] The laminated sample 10 used in the DuPont impact test can be manufactured, for example, using a resin composition. For example, the laminated sample 10 is (1) A step of forming a first resin composition layer 12 on one side of the first test piece 11 so as to correspond to the adhesive portion 13 of the laminated sample. (2) A step of forming a second resin composition layer 12' on one side of the second test piece 11' so as to correspond to the adhesive portion 13 of the laminated sample. (3) A step of bonding the first test piece 11 and the second test piece 11' so that the first resin composition layer 12 and the second resin composition layer 12' are bonded together, (4) A step of 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', It can be manufactured by a method that includes these elements in this order.

[0150] Figure 1 is a schematic front view illustrating step (1) of the manufacturing method for a laminated sample 10 used in a DuPont impact test. Step (1) is the step of forming a first resin composition layer 12 on one side of the first test piece 11 using a resin composition so as to correspond to the adhesive portion 13 of the laminated sample, which will be described later. There are no particular restrictions on the method of forming the first resin composition layer 12; the resin composition can be applied to one side of the first test piece 11 using a die coater or the like to form the first resin composition layer 12. Alternatively, if necessary, the resin composition may be dissolved in an organic solvent to prepare a resin varnish, and the resin varnish may be applied to one side of the first test piece 11. If a resin varnish is used, drying may be performed after application if necessary.

[0151] Drying may be carried out by methods such as heating or blowing hot air. The drying conditions are not particularly limited, but the resin composition layer should be dried so that the content of organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. 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.

[0152] The first test piece 11 (and the second test piece 11' described later) may, for example, have the same dimensions along the thickness direction. The shape of the main surface of the first test piece 11 can be, for example, a rectangle, square, circle, approximately rectangular, approximately circular, etc. Among these, the shape of the main surface of the first test piece 11 is preferably a rectangle, square, or approximately rectangular, with a rectangle being more preferable. Furthermore, it is preferable that the first test piece 11 and the second test piece 11' have the same dimensions. Hereinafter, the description will be based on a configuration in which the first test piece 11 and the second test piece 11' described later each have main surfaces of the same dimensions, and the shape of the main surface is rectangular.

[0153] In step (1), the location where the resin composition layer 12 is formed can be appropriately set according to the shape of the adhesive portion 13 of the laminated sample 10. Figure 1 shows a case where the resin composition layer 12 is formed in a region at a distance d from the short side 11E, so as to include one of the short sides 11E of the first test piece. Here, when the length of the long side of the first test piece is L, it is preferable that the distance d is close to L / 2.

[0154] The thickness of the resin composition layer 12 (and the resin composition layer 12' described later) can be appropriately set within a range in which the impact resistance of the laminated sample 10 can be evaluated. For example, the thickness of the resin composition layer 12 (and the resin composition layer 12' described later) can be approximately 1 mm.

[0155] Step (2) is the step of forming a second resin composition layer 12' on one side of the second test piece 11' using the resin composition so as to correspond to the adhesive portion 13 of the laminated sample described later. There are no particular restrictions on the method of forming the second resin composition layer 12', and it is the same as the method of forming the first resin composition layer 12 in step (1). The location where the resin composition layer 12' is formed is, for example, as shown in Figure 1, in a region at a distance d from the short side 11'E so as to include one of the short sides 11'E of the second test piece. The thickness of the resin composition layer 12' is the same as that of the resin composition 12. The materials of the first test piece 11 and the second test piece 11' will be described later.

[0156] Figure 2 is a schematic front view illustrating step (3) of the manufacturing method for the laminated sample 10 used in the DuPont impact test. Step (3) is the step of bonding the first test piece 11 and the second test piece 11' after steps (1) and (2) so that the first resin composition layer 12 and the second resin composition layer 12' are joined together. Figure 2 shows the first test piece 11 and the second test piece 11' bonded together so that the first resin composition layer 12 and the second resin composition layer 12' are joined by an overlap joint.

[0157] In the bonding process of step (3), the first test piece 11 and the second test piece 11' may be compressed together by applying pressure to either one or both of the first test piece 11 and the second test piece 11' as needed. The compression of the first test piece 11 and the second test piece 11' may be done using an instrument such as a clip, or by using a machine such as a press.

[0158] Figure 3 is a schematic front view illustrating step (4) of the manufacturing method for a laminated sample 10 used in a DuPont impact test. Step (4) is a step 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' after step (3). In step (4), the first resin composition layer 12 and the second resin composition layer 12' cure together, forming an adhesive portion 13 made of cured resin composition layers. Therefore, in step (4), a laminated sample 10 can be obtained having the second test piece 11' / adhesive portion 13 made of cured resin composition layers / first test piece 11 in this order.

[0159] Next, we will explain the details of the DuPont impact test using the laminated sample 10 obtained in the above steps (1) to (4). Figure 4 is a schematic front view illustrating the overview of the DuPont impact test. As shown in Figure 4, in the DuPont impact test, the laminated sample 10 containing the cured resin composition is placed in a fixing jig 40, and the striking die 20 is placed on the laminated sample 10. Then, a weight 30 is dropped onto the striking die 20 from a predetermined height h relative to the striking die 20, as shown by arrow A1. The height at which the adhesive portion 13 of the laminated sample is broken by the energy of the impact when the dropped weight 30 collides with the striking die 20 can be measured as the impact fracture height. The higher the impact fracture height, the better the impact resistance of the laminated sample 10. The DuPont impact test can be performed in accordance with JIS K5600-5-3. For the specific measurement method of the impact fracture height, the method described in the <Test Example 2: Impact Resistance Evaluation Test> section of the examples described later may be adopted.

[0160] In a DuPont impact test, the laminated sample 10 may be installed 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). Alternatively, the installation direction of the laminated sample 10 may be selected depending on the materials of the first test piece 11 and the second test piece 11', so that either test piece is on top. Figure 4 shows an example where the laminated sample 10 is installed in the fixing jig 40 with the first test piece 11 on the bottom (i.e., the second test piece 11' on top).

[0161] Examples of materials for the test specimens constituting the laminated sample 10 include glass materials, 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 the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, molybdenum, titanium, tungsten, iron, tin, and indium. The metallic material may be a single metal or an alloy material. Examples of alloy materials include those containing two or more metals selected from the above group. Examples of ceramic materials include metal oxides, transition metal oxides, metal nitrides, and boride ceramics. Here, metal oxides and transition metal oxides may include composite oxides.

[0162] The material of the upper test piece of the laminated sample 10 (the second test piece 11' in Figure 4) is preferably a glass material, from the viewpoint of sufficiently transmitting impact to the adhesive portion 13 of the laminated sample and more accurately evaluating the impact resistance of the laminated sample 10. In the section "Test Example 2: Impact Resistance Evaluation Test" of the examples described later, an example is given in which epoxy glass is used as the material of the upper test piece.

[0163] The material of the lower test piece of the laminated sample 10 (the first test piece 11 in Figure 4) is preferably a metallic material, from the viewpoint of more accurately evaluating the impact resistance of the laminated sample 10 without mitigating the impact transmitted to the adhesive portion 13 of the laminated sample. In the section "<Test Example 2: Impact Resistance Evaluation Test>" of the examples described later, an example is given in which stainless steel with electroless nickel plating on the surface is used as the material of the lower test piece.

[0164] In DuPont impact testing, the arrangement of the striking die 20 is not particularly limited, but from the viewpoint of more accurately evaluating the impact resistance of the laminated sample 10, it is preferable to arrange the striking die 20 so that its tip 20T is included on the vertical line of the center position C of the adhesive portion 13 in the laminated sample.

[0165] [Uses of resin compositions] The resin composition of the present invention can produce a cured product with excellent adhesive strength and impact resistance. Taking advantage of these excellent benefits, the resin composition is preferably used as an adhesive resin composition where both adhesive strength and impact resistance are required.

[0166] 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 used in electrical products (e.g., computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, camera modules, medical equipment, and televisions, etc.) and vehicles (e.g., motorcycles, automobiles, trains, ships, and aircraft, etc.). Generally, semiconductor devices include electronic components. Generally, such electronic components include electronic components and components other than the electronic components. Specific examples of electronic components include, but are not limited to, semiconductor chips, power semiconductors, modules containing electronic components such as LED-PKGs (e.g., camera modules), and semiconductor chip packages. In one example, the resin composition of the present invention is used to bond a first electronic component and a second electronic component constituting an electronic component. In particular, the resin composition of the present invention is more preferably used to bond components 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 component and a second electronic component constituting a camera module.

[0167] Another preferred application of the resin composition is a resin composition for bonding a substrate and electronic components in a semiconductor device. Specifically, the resin composition of the present invention may be used as the bonding resin composition in a method for manufacturing a semiconductor device, which includes bonding a substrate such as a circuit board, housing, and frame to an electronic component such as a semiconductor module. As mentioned above, the resin composition of the present invention is preferably used to bond components of a camera module. Therefore, in a more preferred embodiment, the resin composition of the present invention is used to bond a substrate constituting a camera module to an electronic component constituting a camera module.

[0168] [Electronic components] An electronic component according to one embodiment of the present invention comprises a cured product of a resin composition and an electronic component mounted on the cured product.

[0169] As described above, the resin composition of the present invention is used to bond a first electronic component and a second electronic component that constitute an electronic member. Therefore, in one example, the electronic member includes a first electronic component, a second electronic component, and an adhesive portion that bonds the first electronic component and the second electronic component.

[0170] The electronic component can be manufactured by a method that includes, for example, the steps of: 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 together via the resin composition; and curing the resin composition. For example, the resin composition may be applied using an application device such as a syringe or dispenser, and pressed as necessary to apply the resin composition to a uniform thickness.

[0171] The curing of the resin composition is usually carried out by thermal curing. The thermal curing conditions for the resin composition layer may vary depending on the type of resin composition. For example, the curing temperature is preferably 50°C to 240°C, more preferably 60°C to 220°C, and even more preferably 70°C to 210°C. The curing time may be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 100 minutes. The process of curing the resin composition may also include preheating the resin composition at a temperature lower than the curing temperature before thermal curing.

[0172] [Semiconductor device] A semiconductor device according to one embodiment of the present invention includes a cured product of the resin composition described above. Examples of such a semiconductor device include a semiconductor device equipped with the electronic components described above. Specific examples of semiconductor devices are as described above.

[0173] Furthermore, in semiconductor devices, the resin composition described above may be used to bond the components of the semiconductor device. For example, a semiconductor device may comprise a substrate, a cured resin composition provided on the substrate, and electronic components or electronic members mounted on the cured resin composition. Examples of substrates include circuit boards, heat sinks, frames, etc. In such a semiconductor device, electronic components or electronic members are bonded to the substrate by the cured resin composition. From the viewpoint of utilizing good adhesive strength, the bonding surface of the substrate (the surface that joins with the cured resin composition) may be formed of a material that is difficult to bond. [Examples]

[0174] The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these examples. In the following description, "parts" and "%" refer to "parts by mass" and "mass%" respectively, unless otherwise specified. Unless otherwise specified, the temperature and pressure conditions were room temperature (25°C) and atmospheric pressure (1 atm).

[0175] [Methods for measuring high-performance liquid chromatography and mass spectrometry (LC / MS measurement)] (Measurement conditions for high-performance liquid chromatography and mass spectrometry) The sample was diluted to 1 mg / mL with tetrahydrofuran (THF), and measured by high-performance liquid chromatography and mass spectrometry (LC / MS) under the following conditions. High-performance liquid chromatography (HPLC): ACQUITY UPLC (manufactured by Waters Japan Co., Ltd.) Mass Spectrum (MS): SQ Detector2 (manufactured by Waters Japan) Column: ACQUITY UPLC BEH C8 1.7um, 2.1mm x 50mm (manufactured by Waters Japan Co., Ltd.) Mobile phase A: 2 mmol ammonium acetate aqueous solution Mobile phase B: 2-propanol / acetonitrile (50:50) Mobile phase mixing time and mixing ratio (A%): 0-0.5 min (95%) → 1 min-8.5 min (75%) → 9-11 min (5%) → 11.1 min (95%) → 13 min (95%) Flow rate: 0.30mL / min Analysis time: 13 minutes Column temperature: 40°C, Ion mode: ESI (Electron Spray Ionization) positive Ionic polarity: Positive detection mode Desolvent gas flow rate: 700 L / hr, 250°C Corn gas: 70L / hr Ion source heater: 150℃

[0176] [Method for measuring NMR] The NMR data for the thiol compounds prepared in Synthesis Example 1 below were measured using a JEOL LA-500 (manufactured by JEOL).

[0177] <Synthesis Example 1: Synthesis of Thiol Compounds Represented by Formula (I-1)> (1) Synthesis of diallyl compounds having a butylene chain In a 2-liter four-necked round-bottom flask equipped with a stirrer, thermometer, condenser, dropping funnel, and Dean-Stark trap, 140.9 g (1.05 mol) of 2-allylphenol (reagent), 108.0 g (0.5 mol) of 1,4-dibromobutane (reagent), 3.1 g of tetra-n-butylammonium bromide as an interlayer transfer catalyst, and 300 g of methyl isobutyl ketone (MIBK) as the reaction solvent were charged. The mixture was heated to 100°C and maintained for 30 minutes to allow complete dissolution. To the resulting solution, 175 g (1.5 mol) of 48% KOH aqueous solution was added dropwise over 1 hour. The water and MIBK were separated by azeotropic distillation using the added KOH aqueous solution in the Dean-Stark trap, and the reaction was continued while only MIBK was returned to the reaction system. The reaction was further continued at 118°C for 6 hours while only MIBK was returned to the system and the water was removed by distillation. Subsequently, the temperature was lowered to 60°C, 100g of distilled water was added and allowed to stand, and the lower by-product brine layer was discarded. Next, 100g of distilled water and an appropriate amount of sodium dihydrogen phosphate for neutralization were added and the mixture was allowed to stand and separated, and the lower by-product brine layer was discarded. After further purification by washing with the same amount of distilled water twice, the mixture was heated to 118°C and azeotropic dehydration was performed. The obtained solution was then microfiltered using filter paper No. 5C (manufactured by Kiriyama Seisakusho Co., Ltd.) and a Kiriyama funnel (manufactured by Kiriyama Seisakusho Co., Ltd.) to remove impurities, and then MIBK and unreacted 2-allylphenol were removed by vacuum distillation at a maximum temperature of 180°C to obtain 145g of liquid resin.

[0178] The obtained liquid resin was measured according to the LC / MS measurement method described above, and spectral peaks corresponding to a proton adduct (m / z=323) and an ammonium adduct (m / z=340) were detected. From this analytical data, it was confirmed that the obtained liquid resin is a diallyl compound with the following structure.

[0179] [ka]

[0180] (2) Synthesis of thiol compounds represented by formula (I-1) In a 1 L four-necked flask, the diallyl compound obtained in (1) above (100 g, 0.31 mol, 1.0 eq.), thioacetic acid (51.9 g, 0.682 mol, 2.2 eq.), toluene (360 mL), and azobisisobutyronitrile (AIBN, 5.09 g, 0.031 mol, 0.1 eq.) were added and reacted at 80 °C for 4 hours. The resulting reaction product was concentrated under reduced pressure to remove toluene, and then crystallized with methanol (500 g). The crystallized material was vacuum-dried, and 110.36 g of the dried crystallized material was recovered. In a 3 L four-necked flask, the recovered dried crystallized material (110.36 g) and 32% by mass NaOH (550 g) were added and reacted at 80 °C for 2 hours. After neutralizing the reaction product with 1 N HCl (380 mL), the organic layer was separated and washed with water. Toluene was removed from the water-washed organic layer by vacuum concentration to obtain 89.0 g of the target thiol compound (yield 74%).

[0181] The obtained thiol compound was measured according to the LC / MS measurement method described above, and spectral peaks corresponding to the proton adduct at m / z=391 and the ammonium adduct at m / z=408 were detected. From these analytical data and the NMR spectrum shown in Figure 5, it was confirmed that the obtained thiol compound has the structure represented by the following formula (I-1).

[0182] [ka]

[0183] <Example 1: Preparation of Resin Composition 1> 100.0 parts of glycidylamine-type epoxy resin (Mitsubishi Chemical Corporation "604") and 20.0 parts of fumed silica (Nippon Aerosil Co., Ltd. "200") were added to a dedicated plastic container to obtain a mixture. Next, the mixture was thoroughly mixed using a mixer (Sinky Corporation "ARE-310") at 25°C and 2000 rpm for approximately 30 to 60 seconds. Then, the mixture after being subjected to the mixer was kneaded using three rollers to obtain a fumed silica epoxy resin dispersion. Next, 5.0 parts of a curing accelerator (Ajinomoto Fine Techno Co., Ltd. "Amicure PN-FJ") was added to the dispersion, and the mixture was thoroughly mixed using a mixer (Sinky Corporation "ARE-310") at 25°C and 2000 rpm for approximately 30 to 60 seconds 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 using a mixer (Sinky Co., Ltd. "ARE-310") at 25°C and 2000 rpm for approximately 20 seconds. The resulting mixture was degassed for 2 minutes by stirring at 1000 rpm under vacuum using a stirring and degassing machine (Kyoritsu Seiki Co., Ltd. "HM-200W") to obtain resin composition 1.

[0184] <Example 2: Preparation of Resin Composition 2> In Example 1, 1) 100.0 parts of glycidylamine type epoxy resin (Mitsubishi Chemical Corporation's "604") were replaced with 75.0 parts of glycidylamine type epoxy resin (Mitsubishi Chemical Corporation's "604") and 25.0 parts of bisphenol A type epoxy resin (Mitsubishi Chemical Corporation's "828"). 2) The amount of the thiol compound obtained in Synthesis Example 1 was changed from 162.8 parts to 147.1 parts. Resin composition 2 was obtained in the same manner as in Example 1, except for the matters described above.

[0185] <Example 3: Preparation of Resin Composition 3> In Example 1, 1) 100.0 parts of glycidylamine type epoxy resin (Mitsubishi Chemical Corporation's "604") were replaced with 50.0 parts of glycidylamine type epoxy resin (Mitsubishi Chemical Corporation's "604") and 50.0 parts of bisphenol A type epoxy resin (Mitsubishi Chemical Corporation's "828"). 2) The amount of the thiol compound obtained in Synthesis Example 1 was changed from 162.8 parts to 133.0 parts. Resin composition 3 was obtained in the same manner as in Example 1, except for the matters described above.

[0186] <Example 4: Preparation of Resin Composition 4> In Example 1, 1) 100.0 parts of glycidylamine type epoxy resin (Mitsubishi Chemical Corporation's "604") were replaced with 25.0 parts of glycidylamine type epoxy resin (Mitsubishi Chemical Corporation's "604") and 75.0 parts of bisphenol A type epoxy resin (Mitsubishi Chemical Corporation's "828"). 2) The amount of the thiol compound obtained in Synthesis Example 1 was changed from 162.8 parts to 118.0 parts. Resin composition 4 was obtained in the same manner as in Example 1, except for the matters described above.

[0187] <Example 5: Preparation of resin composition 5> In Example 1, 1) 100.0 parts of glycidylamine type epoxy resin (Mitsubishi Chemical Corporation's "604") were replaced with 100.0 parts of bisphenol A type epoxy resin (Mitsubishi Chemical Corporation's "828"). 2) The amount of the thiol compound obtained in Synthesis Example 1 was changed from 162.8 parts to 103.2 parts. Resin composition 5 was obtained in the same manner as in Example 1, except for the matters described above.

[0188] <Example 6: Preparation of resin composition 6> In Example 1, 1) 100.0 parts of glycidylamine type epoxy resin (Mitsubishi Chemical Corporation's "604") were replaced with 75.0 parts of bisphenol A type epoxy resin (Mitsubishi Chemical Corporation's "828") and 25.0 parts of another glycidylamine type epoxy resin (Mitsubishi Chemical Corporation's "604"). 2) The amount of the thiol compound obtained in Synthesis Example 1 was changed from 162.8 parts to 127.1 parts. Resin composition 6 was obtained in the same manner as in Example 1, except for the matters described above.

[0189] <Example 7: Preparation of Resin Composition 7> In Example 1, 1) 100.0 parts of glycidylamine type epoxy resin (Mitsubishi Chemical Corporation's "604") were replaced with 75.0 parts of bisphenol A type epoxy resin (Mitsubishi Chemical Corporation's "828") and 25.0 parts of phenol novolac type epoxy resin (DIC Corporation's "N-730A"). 2) The amount of the thiol compound obtained in Synthesis Example 1 was changed from 162.8 parts to 105.4 parts. Resin composition 7 was obtained in the same manner as in Example 1, except for the matters described above.

[0190] <Example 8: Preparation of resin composition 8> In Example 1, 1) 100.0 parts of glycidylamine type epoxy resin (Mitsubishi Chemical Corporation's "604") were replaced with 75.0 parts of bisphenol A type epoxy resin (Mitsubishi Chemical Corporation's "828") and 25.0 parts of triphenylmethane type epoxy resin (DIC Corporation's "EXA-7250"). 2) The amount of the thiol compound obtained in Synthesis Example 1 was changed from 162.8 parts to 107.5 parts. Resin composition 8 was obtained in the same manner as in Example 1, except for the matters described above.

[0191] <Example 9: Preparation of resin composition 9> In Example 1, 1) 100.0 parts of glycidylamine type epoxy resin (Mitsubishi Chemical Corporation's "604") were replaced with 75.0 parts of bisphenol A type epoxy resin (Mitsubishi Chemical Corporation's "828") and 25.0 parts of pentaerythritol type epoxy resin (Resonac Corporation's "Showfree PETG"). 2) The amount of the thiol compound obtained in Synthesis Example 1 was changed from 162.8 parts to 128.7 parts. Resin composition 9 was obtained in the same manner as in Example 1, except for the matters described above.

[0192] <Comparative Example 1: Preparation of Resin Composition 10> In Example 1, 1) 100.0 parts of glycidylamine type epoxy resin (Mitsubishi Chemical Corporation's "604") were replaced with 25.0 parts of glycidylamine type epoxy resin (Mitsubishi Chemical Corporation's "604") and 75.0 parts of 1,4-glycidylcyclohexane type epoxy resin (Nippon Steel Chemical & Material Corporation's "ZX1658GS"). 2) The amount of the thiol compound obtained in Synthesis Example 1 was changed from 162.8 parts to 150.6 parts. Resin composition 10 was obtained in the same manner as in Example 1, except for the matters described above.

[0193] <Comparative Example 2: Preparation of Resin Composition 11> In Example 1, 1) 100.0 parts of glycidylamine-type epoxy resin (Mitsubishi Chemical Corporation's "604") were replaced with 100.0 parts of 1,4-glycidylcyclohexane-type epoxy resin (Nippon Steel Chemical & Material Corporation's "ZX1658GS"). 2) The amount of the thiol compound obtained in Synthesis Example 1 was changed from 162.8 parts to 146.6 parts. Resin composition 11 was obtained in the same manner as in Example 1, except for the matters described above.

[0194] <Comparative Example 3: Preparation of Resin Composition 12> In Example 1, 1) 100.0 parts of glycidylamine type epoxy resin (Mitsubishi Chemical Corporation's "604") were replaced with 25.0 parts of glycidylamine type epoxy resin (Mitsubishi Chemical Corporation's "604") and 75.0 parts of bisphenol A type epoxy resin (Mitsubishi Chemical Corporation's "828"). 2) 162.8 parts of the thiol compound obtained in Synthesis Example 1 were replaced with 90.8 parts of another thiol compound (BD-1, manufactured by Resonaq). Resin composition 12 was obtained in the same manner as in Example 1, except for the matters described above.

[0195] <Comparative Example 4: Preparation of Resin Composition 13> In Example 1, 1) 100.0 parts of glycidylamine type epoxy resin (Mitsubishi Chemical Corporation's "604") were replaced with 25.0 parts of glycidylamine type epoxy resin (Mitsubishi Chemical Corporation's "604") and 75.0 parts of bisphenol A type epoxy resin (Mitsubishi Chemical Corporation's "828"). 2) The thiol compound obtained in Synthesis Example 1 was not used. 3) The amount of curing accelerator (Amicure PN-FJ, manufactured by Ajinomoto Fine Techno Co., Ltd.) was changed from 5.0 parts to 10.0 parts. Resin composition 13 was obtained in the same manner as in Example 1, except for the matters described above.

[0196] Details of each component listed in Tables 1 to 3 below are as follows:

[0197] (A-1) Epoxy resin containing an aromatic skeleton • "828": Bisphenol A type epoxy resin (bifunctional), manufactured by Mitsubishi Chemical Corporation, "jER828", epoxy group equivalent weight approximately 189 g / eq.

[0198] • "604": A glycidylamine-type epoxy resin (tetrafunctional) having the structure represented by the following formula (a-2), manufactured by Mitsubishi Chemical Corporation, "jER604", epoxy equivalent weight approximately 120 g / eq.

[0199] [ka]

[0200] · "630": A glycidylamine-type epoxy resin (3-functional) having a structure represented by the following formula (a-3), "jER630" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 95 g / eq.

[0201]

Chemical formula

[0202] · "N-730A": A phenol novolak-type epoxy resin (average 2.6-functional), manufactured by DIC, an epoxy resin with an average of 2.6 functional groups, epoxy equivalent of about 174 g / eq. · "EXA-7250": A triphenylmethane-type epoxy resin (5-functional or more), manufactured by DIC, epoxy equivalent of about 162 g / eq.

[0203] (A-2) An epoxy resin that does not contain an aromatic skeleton · "ZX1658GS": A 1,4-glycidylcyclohexane-type epoxy resin (2-functional) having a structure represented by the following formula (a-1), "ZX1658GS" manufactured by Nippon Steel Chemical & Material Co., Ltd., epoxy group equivalent of about 133 g / eq.

[0204]

Chemical formula

[0205] · "PETG": A pentaerythritol-type epoxy resin (4-functional) having a structure represented by the following formula (a-4), "Sho-Free PETG" manufactured by Resonaak, a 4-functional epoxy resin

[0206]

Chemical formula

[0207] (B) A thiol compound having a specific structure (a thiol compound having a structure represented by formula (I)) · "Synthesis Example 1": Thiol compound 1 obtained in Synthesis Example 1, mercapto group equivalent 195 g / eq.

[0208] (B’) Other thiol compounds (thiol compounds not having the structure represented by formula (I)) · "BD-1": 1,4-bis(3-mercaptobutyryloxy)butane, manufactured by Resonaac Co., mercapto group equivalent 147 g / eq.

[0209] (C) Curing accelerator · "PNFJ": Solid dispersion type amine adduct based latent curing accelerator, "Amicure PN-FJ" manufactured by Ajinomoto Fine-Techno Co., Inc.

[0210] (D) Inorganic filler [[ID=...]] · "A200": Fumed silica, "200" manufactured by Nippon Aerosil Co., average particle diameter of 0.1 μm, specific surface area of 200 m 2 / g

[0211] <Test Example 1: Adhesive strength evaluation test> Two epoxy glass test pieces measuring 100 mm x 25 mm x 1.6 mm thick (Paltec Co., Ltd. "EL-3762") were prepared, and any oil was wiped off with a cloth dampened with ethanol. The resin compositions obtained in each example and comparative example were applied to the flat surface (one side) of each epoxy glass test piece. The resin composition was applied to an area approximately 12.5 mm from one of the short sides of the epoxy glass test piece (i.e., half the area of ​​the epoxy glass test piece), with a thickness of approximately 1 mm. Next, the two epoxy glass test pieces, with their resin composition-coated surfaces overlapping, were joined together with a joint and secured with two clips. At this time, some of the resin composition seeped out from the area between the two epoxy glass test pieces, so the seeped resin composition was immediately wiped off with a cloth. The compressed epoxy glass test pieces were evenly arranged in an oven and heated at 120°C for 30 minutes to cure the resin composition. As a result, the two epoxy glass test pieces were bonded together by the cured resin composition, obtaining a laminated sample A comprising epoxy glass test piece / cured resin composition / epoxy glass test piece in that order. Three laminated samples A were prepared for each resin composition.

[0212] Using the obtained laminated sample A, a tensile shear bond strength measurement test was performed in accordance with JIS-K-6850, and the shear bond strength (tensile shear bond strength) was measured. Specifically, using a Tensilon universal testing machine (TOYO BALDWIN "UTM-5T"), one epoxy glass test piece was pulled against the other epoxy glass test piece in a direction parallel to the plane of the epoxy glass test piece, and the maximum load (N) at which the cured resin composition broke was measured. The measurement was performed at a temperature of 25°C, relative humidity of 50%, and a pulling speed of 5 mm / min. The measured maximum load (N) and the bond area (mm²) of the two test pieces were measured. 2 The shear bond strength was calculated based on the following formula. Tables 1-3, described later, show the average of the measurements taken from the three laminated samples A. Tensile shear bond strength (N / mm²) 2 )=Maximum load (N) / Adhesive area (mm2 )

[0213] The shear bond strength obtained from the above procedure was evaluated according to the following criteria. Good: Shear bond strength is 10 N / mm². 2 That's all. Yes: Shear bond strength of 3 N / mm 2 More than 10N / mm 2 It is less than. Defect: Shear bond strength is 3 N / mm 2 It is less than.

[0214] <Test Example 2: Impact Resistance Evaluation Test> One 100mm x 25mm x 1.6mm thick epoxy glass test piece (Paltec Co., Ltd. "EL-3762") and one 100mm x 25mm x 1.6mm thick stainless steel test piece (Taiyu Kikai Co., Ltd. "SUS304", a stainless steel plate with electroless nickel plating on the surface) were prepared, and oil was wiped off with a cloth dampened with ethanol. The resin composition obtained in each example and comparative example was applied to one flat surface of the epoxy glass test piece. The resin composition obtained in each example and comparative example was also applied to one flat surface of the stainless steel test piece. The resin composition was applied to an area approximately 12.5mm from the short side of one of the epoxy glass and stainless steel test pieces (i.e., half the area of ​​the epoxy glass and stainless steel test pieces) with a thickness of approximately 1mm, so as to include one of the short sides of the epoxy glass and stainless steel test pieces. Next, the surface of the epoxy glass test piece coated with the resin composition and the surface of the stainless steel test piece coated with the resin composition were joined together with an overlapping joint so that the applied resin compositions overlapped, and then clamped with two clips. At this time, some of the resin composition seeped out from the area between the epoxy glass test piece and the stainless steel test piece, so the seeped resin composition was immediately wiped off with a cloth. The clamped epoxy glass test piece and stainless steel test piece were evenly arranged in an oven and heated at 120°C for 30 minutes to cure the resin composition. As a result, the epoxy glass test piece and the cold-rolled stainless steel sheet were bonded together by the cured resin composition, and a laminated sample B was obtained comprising the epoxy glass test piece / cured resin composition / stainless steel test piece in this order. Three laminated samples B were prepared for each resin composition.

[0215] Using the obtained laminated sample B, a DuPont impact test of a cured sample was performed in accordance with JIS K5600-5-3 using a DuPont drop impact tester (Yasuda Seiki Seisakusho Co., Ltd. "No. 517"), and the impact fracture height was measured. Specifically, with the epoxy glass test piece surface of laminated sample B facing upwards, both sides of laminated sample B were fixed to the tester at a point 1.5 cm from the center of the adhesive joint of laminated sample B. At this time, it was confirmed that there was a hollow space between the stainless steel test piece side of laminated sample B and the support base of the tester at the bottom of the adhesive joint of laminated sample B. A 50g weight was used for the test, and a striking die with a tip radius R=1 / 4 inch was used. The weight was dropped so that the impact was transmitted to the center of the adhesive joint of laminated sample B. In the first impact test, the weight was dropped from a height of 50 mm. In subsequent impact tests, if the adhesive joint of the laminated sample was not fractured, the height was increased by 50 mm at a time, and the weight was dropped again. The height at which fracture of the adhesive joint (cured resin composition) was observed was measured as the impact fracture height. Tables 1-3, described later, show the average of the measurements taken from three laminated samples B.

[0216] The impact fracture height obtained from the above operation was evaluated according to the following criteria. Good: The impact fracture height is 350 mm or more. Acceptable: The impact fracture height is 300mm or more but less than 350mm. Defect: Impact fracture height is less than 300mm.

[0217] <Test Example 3: Measurement of Tensile Modulus of a Hardened Material> A PET film (Toray Industries' "NS-80A") with a mold release treatment on its surface was prepared. On the mold release surface of this PET film, the resin compositions obtained in each of the examples and comparative examples were coated using a bar coater and heat-cured at 80°C for 60 minutes to obtain a cured product with a thickness of 70 μm. The obtained cured product was punched out using a cutter (Dumbell's "Super Dumbell Cutter (Model: SDMK-5889-01)") to prepare test pieces for measuring the tensile modulus. The PET film was peeled off from the test pieces. The tensile modulus was measured by conducting a tensile test using a tabletop precision universal testing machine (Shimadzu Corporation's "AUTOGRAPH AGS-X") under the conditions of a temperature of 25°C, a relative humidity of 50%, and a pulling speed of 5 mm / min.

[0218] <Test Example 4: Measurement of Viscosity> The viscosities of the resin compositions obtained in each of the examples and comparative examples were measured. Specifically, using an E-type viscometer (Tokyo Keiki Co., Ltd.'s "RE-85U", 3°×R14 rotor), the first viscosity measurement was performed for 2 minutes under the conditions of a measurement temperature of 25°C, an amount of 0.40 ml of the varnish-like resin composition, and a rotation speed of 1 rpm. Also, the second viscosity measurement was performed in the same manner except that the rotation speed was changed from 1 rpm to 10 rpm. From the measured viscosity η1 at a rotation speed of 1 rpm and the measured viscosity η 10 Based on the following formula, the thixotropy index (T.I.(1 / 10)) was calculated. T.I.(1 / 10) = (Measured viscosity η1 at a rotation speed of 1 rpm) / (Measured viscosity η at a rotation speed of 10 rpm) 10 )

[0219]

Table 1

[0220]

Table 2

[0221]

Table 3

[0222] 10 Layered Samples 11 First test specimen 11E One short side of the first test specimen 11' Second test specimen 11'E One short side of the second test specimen 12 First resin composition layer 12' Second resin composition layer 13. Adhesion area of ​​the laminated sample 20-shot type 20T firing type tip 30 weights 40 Fixing fixtures

Claims

1. A resin composition comprising (A) an epoxy resin, (B) a thiol compound represented by the following formula (I), and (C) a curing accelerator, (A) The epoxy resin includes (A-1) an epoxy resin containing an aromatic skeleton, (A-1) A resin composition in which the amount of epoxy resin containing an aromatic skeleton is 30% by mass or more relative to 100% by mass of epoxy resin (A). 【Chemistry 1】 (In equation (I), Ring P is independently either a phenyl group or a naphthyl group. A is present in 1 to 5 groups for each ring P when the ring P is a phenyl group, and in 1 to 7 groups for each ring P when the ring P is a naphthyl group, and each A is independently -R １ -SH, R １ Each of these is an independent C1-C6 alkylene group which may be substituted with one or more Y groups. B is a group other than A on ring P, and each is independently a hydrogen atom, a C1-C6 alkyl group which may be substituted with one or more Y atoms, or a C1-C6 alkoxy group which may be substituted with one or more Y atoms. A and B, independently, are bonded at the ortho, meta, or para position relative to the position where ring P is bonded to the main chain if ring P is a phenyl group, and at the ortho, meta, para, ana, epi, cata, peri, pros, amphi, or 2,7 position relative to the position where ring P is bonded to the main chain. Each X is independently -CH ２ -, -O-, -N(-R ２ ) -, or -S-, R ２ Each of these is independently a hydrogen atom, a C1-C6 alkyl group which may be substituted with one or more Y atoms, or a C1-C6 alkoxy group which may be substituted with one or more Y atoms. Y is independently a hydrogen atom, a C1-C6 alkyl group, or a C1-C6 alkoxy group. Z is, independently of each other, a direct bond, -CH ２ -, -C ２ H ４ -, -C ３ H ６ -, -C ４ H ８ -, -O-, or -S-, and n is an integer between 1 and 20.

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

3. (A-1) The resin composition according to claim 1, wherein the epoxy resin containing an aromatic skeleton contains two or more aromatic rings.

4. (A-1) The resin composition according to claim 1, wherein the epoxy resin containing an aromatic skeleton contains 2 to 4 epoxy groups in one molecule.

5. (A-1) The resin composition according to claim 1, wherein the epoxy resin containing an aromatic skeleton includes a glycidylamine type epoxy resin.

6. (A-1) The resin composition according to claim 1, wherein the epoxy resin containing an aromatic skeleton comprises a combination of an epoxy resin containing two or more aromatic rings and a glycidylamine-type epoxy resin.

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

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

9. The resin composition according to claim 1, wherein the thixotropy 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 1 or more and 10 or less.

10. An electronic component comprising a cured product of a 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 a resin composition according to any one of claims 1 to 9.

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