Resin composition, adhesive, sealing material, cured product, semiconductor device, and electronic component

Abstract

The present invention addresses the problem of providing: a resin composition which has excellent reactivity and from which a cured product having excellent stress relaxation properties is formed; and an adhesive.　Provided is a resin composition comprising: (A) a polyfunctional epoxy compound having an epoxy equivalent of less than 215 g / eq; (B) a polyfunctional epoxy compound having an epoxy equivalent of at least 215 g / eq; (C) a polyfunctional thiol compound; (D) a curing catalyst; and (E) a monofunctional compound having one group (e), which includes an unsaturated double bond and an electron-withdrawing group adjacent thereto, in a molecule.

Description

Resin compositions, adhesives, sealing materials, cured products, semiconductor devices and electronic components

[0001] The present invention relates to a resinous composition, an adhesive or sealing material containing the same, a cured product thereof, and a semiconductor device and an electronic component containing the cured product.

[0002] Currently, adhesives, sealants, etc. containing curable resin compositions, particularly epoxy resin compositions, are often used to assemble and mount components used in semiconductor devices and electronic components, such as semiconductor chips, in order to maintain reliability, etc. In particular, in the case of semiconductor devices and electronic components that include components that deteriorate under high-temperature conditions, all manufacturing processes must be carried out under low-temperature conditions. Therefore, adhesives and sealants used in the manufacture of such devices and components are required to exhibit sufficient curability even under low-temperature conditions. As such low-temperature-curing epoxy resin compositions, curable compositions using a thiol-based curing agent as a curing agent are known (e.g., Patent Documents 1 and 2).

[0003] When the ambient temperature of an assembly formed by bonding two parts made of different materials together with an adhesive changes (for example, during use or during the cooling process after heating and curing), thermal stresses are generated in each of the parts according to the thermal expansion coefficients of the materials. Because these thermal stresses are not uniform due to the differences in the thermal expansion coefficients, they do not cancel each other out, resulting in deformation of the assembly. The stresses associated with this deformation act particularly on the joint between the parts, i.e., the cured adhesive, and in some cases can cause separation of the joint or cracks in the cured adhesive. Such separation and cracks are particularly likely to occur when the cured adhesive is brittle and lacks flexibility. Therefore, adhesives for bonding parts made of different materials must have sufficient flexibility, i.e., stress relaxation properties, after curing to accommodate deformation of the assembly due to thermal stresses in the parts.

[0004] Patent Document 3 discloses an epoxy resin composition capable of providing a cured product that can follow deformation of a substrate, the epoxy resin composition comprising: (A1) a first epoxy resin that is liquid at 25°C and has an epoxy equivalent of 250 to 1000; (A2) a second epoxy resin that has an epoxy equivalent lower than that of the first epoxy resin; (B) a thiol compound having two or more thiol groups in the molecule; and (C) an inorganic filler.

[0005] JP 6-211969 JP 6-211970 JP 2019-143134

[0006] In the epoxy resin composition described in Patent Document 3, stress relaxation properties are imparted to the cured product by using a combination of an epoxy compound with a low epoxy equivalent weight and an epoxy compound with a high epoxy equivalent weight. However, it has been found that when such epoxy compounds with different epoxy equivalent weights are used in combination, the initiation of the curing reaction of the resin composition is delayed. This is thought to be because the use of an epoxy compound with a high epoxy equivalent weight restricts molecular motion and reduces the reaction probability compared to when an epoxy compound with a low equivalent weight is used. As a result, the viscosity of the resin composition decreases with increasing temperature over a longer period of time before the initiation of the curing reaction, which can lead to problems such as dripping and unintended spreading.

[0007] Therefore, an object of the present invention is to provide a resin composition and an adhesive that are excellent in reactivity even when an epoxy compound with a large epoxy equivalent is used.

[0008] Specific means for solving the above problems are as follows. A first embodiment of the present invention is the following resin composition. (1) A resin composition comprising: (A) a polyfunctional epoxy compound having an epoxy equivalent of less than 215 g / eq; (B) a polyfunctional epoxy compound having an epoxy equivalent of 215 g / eq or more; (C) a polyfunctional thiol compound; (D) a curing catalyst; and (E) a monofunctional compound having, in the molecule, one group (e) containing an unsaturated double bond and an electron-withdrawing group adjacent thereto. (2) The resin composition according to (1) above, wherein component (E) is liquid at 25°C. (3) The resin composition according to (1) or (2) above, wherein component (E) is selected from a monofunctional maleimide compound and a monofunctional (meth)acrylate compound. (4) The resin composition according to any one of (1) to (3) above, wherein the content of component (B) is 1 to 100 parts by mass per 100 parts by mass of component (A). (5) The resin composition according to any one of (1) to (4) above, wherein the ratio of the sum of the number of epoxy group equivalents of component (A) and the number of epoxy group equivalents of component (B) to the number of thiol group equivalents of component (C) (([number of epoxy group equivalents of component (A)] + [number of epoxy group equivalents of component (B)]) / [number of thiol group equivalents of component (C)]) is 0.4 to 0.95. (6) The resin composition according to any one of (1) to (5) above, wherein the ratio of the sum of the number of epoxy group equivalents of component (A), the number of epoxy group equivalents of component (B), and the number of group (e) equivalents of component (E) to the number of thiol group equivalents of component (C) (([number of epoxy group equivalents of component (A)] + [number of epoxy group equivalents of component (B)] + [number of group (e) equivalents of component (E)]) / [number of thiol group equivalents of component (C)]) is 0.7 to 1.5. (7) The resin composition according to any one of (1) to (6) above, wherein the ratio of the number of group (e) equivalents of component (E) to the number of thiol group equivalents of component (C) ([number of group (e) equivalents of component (E)]) / [number of thiol group equivalents of component (C)]) is 0.05 to 0.7. (8) The resin composition according to any one of (1) to (7), wherein the total amount of component (A) and component (B) is 51 parts by mass or more relative to 100 parts by mass of the total mass of the thermosetting compound.(9) The resin composition according to any one of (1) to (8), wherein component (A) and component (B) contain a polyfunctional epoxy compound that is liquid at 25°C, and the amount of the polyfunctional epoxy compound that is liquid at 25°C is 50 parts by mass or more per 100 parts by mass of the combined total mass of component (A) and component (B).

[0009] A second embodiment of the present invention is (10) an adhesive or sealant comprising the resin composition described in any one of (1) to (9) above. A third embodiment of the present invention is (11) a cured product obtained by curing the resin composition described in any one of (1) to (9) above, or the adhesive or sealant described in (10) above. A fourth embodiment of the present invention is (12) a semiconductor device or electronic component comprising the cured product described in (11) above. One aspect of the resin composition, adhesive, or sealant is (13) the resin composition described in any one of (1) to (9) above, or the adhesive or sealant described in (10) above, for use in curing by heat alone. Another embodiment of the present invention is (14) use of the resin composition described in any one of (1) to (9) above, or the adhesive or sealant described in (10) above, for curing by heat alone.

[0010] According to the first embodiment of the present invention, a resin composition with excellent reactivity can be obtained. Furthermore, this resin composition has a small total heat generation during the curing reaction, making it possible to prevent overheating of the adherend and its surrounding components during short-term curing. According to the second embodiment of the present invention, an adhesive or sealant with excellent reactivity can be obtained. Furthermore, according to the third embodiment of the present invention, a cured product with excellent stress relaxation properties can be obtained. According to the fourth embodiment of the present invention, since the resin composition contains a cured product with excellent stress relaxation properties, semiconductor devices and electronic components with excellent reliability can be obtained.

[0011] In this specification, following the convention in the field of synthetic resins, a name including the term "resin," which normally refers to a polymer (especially a synthetic polymer), may be used for a component constituting a curable resin composition before curing, even though the component is not a polymer. In this specification, a "cured product having excellent stress relaxation properties" refers to a cured product that has a degree of flexibility that allows it to follow deformation of an assembly caused by thermal stress of parts. In this specification, a "resin composition with excellent reactivity" refers to a resin composition that has a low reaction initiation temperature for the curing reaction.

[0012] [Resin Composition] The resin composition according to the first embodiment of the present invention comprises: (A) a polyfunctional epoxy compound having an epoxy equivalent of less than 215 g / eq, (B) a polyfunctional epoxy compound having an epoxy equivalent of 215 g / eq or more, (C) a polyfunctional thiol compound, (D) a curing catalyst, and (E) a monofunctional compound having one group (e) containing an unsaturated double bond and an electron-withdrawing group adjacent thereto in the molecule. According to this embodiment, a resin composition having excellent reactivity can be obtained.

[0013] (A) A multifunctional epoxy compound having an epoxy equivalent of less than 215 g / eq and (B) a multifunctional epoxy compound having an epoxy equivalent of 215 g / eq or more The resin composition of this embodiment contains a combination of (A) a multifunctional epoxy compound having an epoxy equivalent of less than 215 g / eq (hereinafter also referred to as "component (A)") and (B) a multifunctional epoxy compound having an epoxy equivalent of 215 g / eq or more (hereinafter also referred to as "component (B)"). The combined use of component (A) and component (B) achieves both excellent adhesive strength of the resin composition and excellent stress relaxation properties of the cured product. Furthermore, a resin composition having a viscosity suitable for workability can be obtained.

[0014] The polyfunctional epoxy compounds used as components (A) and (B) are not particularly limited as long as they have at least two epoxy groups, and conventionally used epoxy resins can be used as components (A) and (B). The term "epoxy resin" refers to a general term for thermosetting resins that can be cured by forming a crosslinked network with the epoxy groups present in the molecule, and includes prepolymer compounds before curing. Considering the need to ensure heat resistance, compounds having 2 to 6 epoxy groups are more preferred for components (A) and (B), and compounds having 2 epoxy groups are even more preferred.

[0015] The epoxy equivalent of component (A) is less than 215 g / eq, preferably from 50 to less than 215 g / eq, more preferably from 100 to less than 215 g / eq, and even more preferably from 130 to less than 185 g / eq. The epoxy equivalent of component (B) is 215 g / eq or more, preferably from 215 to 1000 g / eq, more preferably from 230 to 700 g / eq, even more preferably from 280 to 7000 g / eq, and particularly preferably from 280 to 440 g / eq.

[0016] The molecular weight of component (A) is preferably 100 to 600, more preferably 200 to 600, and even more preferably 260 to 400. The molecular weight of component (B) is preferably 400 to 3000, more preferably 460 to 1500, and even more preferably 560 to 1000. Components (A) and (B) may be liquid or solid at 25°C, but are preferably liquid at 25°C. In one aspect, the amount of components (A) and (B) that are liquid at 25°C is preferably 50 parts by mass or more, for example, 60 parts by mass or more, for example, 70 parts by mass or more, for example, 80 parts by mass or more, for example, 90 parts by mass or more, for example, 100 parts by mass, relative to the total mass of components (A) and (B). In one embodiment, component (A) and component (B) comprise a polyfunctional epoxy compound that is liquid at 25°C and a polyfunctional epoxy compound that is solid at 25°C, and the amount of component (A) and component (B) that are liquid at 25°C is preferably 50 parts by mass or more, for example, 60 parts by mass or more, for example, 70 parts by mass or more, for example, 80 parts by mass or more, for example, 90 parts by mass or more, relative to 100 parts by mass of the total combined mass of component (A) and component (B).

[0017] The polyfunctional epoxy compounds as components (A) and (B) are roughly classified into aromatic polyfunctional epoxy compounds and polyfunctional epoxy compounds having no aromatic ring.

[0018] Aromatic polyfunctional epoxy compounds are polyfunctional epoxy compounds having a structure containing an aromatic ring such as a benzene ring. Many of the epoxy resins that have been frequently used so far, such as bisphenol A epoxy compounds, are of this type. Examples of aromatic polyfunctional epoxy compounds include, but are not limited to, bisphenol A type epoxy compounds; branched polyfunctional bisphenol A type epoxy compounds such as p-glycidyloxyphenyldimethyltrisbisphenol A diglycidyl ether; bisphenol F type epoxy compounds; novolac type epoxy compounds; tetrabromobisphenol A type epoxy compounds; fluorene type epoxy compounds; biphenyl aralkyl epoxy compounds; diepoxy compounds such as 1,4-phenyldimethanol diglycidyl ether; biphenyl type epoxy compounds such as 3,3',5,5'-tetramethyl-4,4'-diglycidyloxybiphenyl; glycidylamine type epoxy compounds such as diglycidylaniline, diglycidyltoluidine, triglycidyl-p-aminophenol, and tetraglycidyl-m-xylylenediamine; and naphthalene ring-containing epoxy compounds. These may be used alone or in combination of two or more. From the viewpoint of compatibility with the (C) polyfunctional thiol compound, it is preferable that component (A) and component (B) contain an aromatic polyfunctional epoxy compound. Examples of the aromatic polyfunctional epoxy compound include bisphenol F epoxy compounds, bisphenol A epoxy compounds, and glycidylamine epoxy compounds. The aromatic polyfunctional epoxy compound may be oxyalkylene-modified, such as EO (ethylene oxide)-modified or PO (propylene oxide)-modified. The aromatic polyfunctional epoxy compound is preferably liquid at 25°C. The viscosity at 25°C is preferably 0.1 to 100 Pa·s, more preferably 0.5 to 100 Pa·s, and particularly preferably 1 to 100 Pa·s.

[0019] In this specification, unless otherwise specified, viscosity is expressed as a value measured in accordance with Japanese Industrial Standard JIS K6833. Specifically, viscosity can be determined by measuring using an E-type viscometer at a rotation speed of 10 rpm. There are no particular limitations on the equipment, rotor, or measurement range used.

[0020] The polyfunctional epoxy compound having no aromatic ring includes, for example, an aliphatic polyfunctional epoxy compound and a polyfunctional epoxy compound having a heterocycle.

[0021] Examples of aliphatic polyfunctional epoxy compounds include: diepoxy compounds such as (poly)ethylene glycol diglycidyl ether, (poly)propylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, polytetramethylene ether glycol diglycidyl ether, glycerin diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexane-type diglycidyl ether, and dicyclopentadiene-type diglycidyl ether; triepoxy compounds such as trimethylolpropane triglycidyl ether and glycerin triglycidyl ether; alicyclic epoxy compounds such as vinyl(3,4-cyclohexene) dioxide and 2-(3,4-epoxycyclohexyl)-5,1-spiro-(3,4-epoxycyclohexyl)-m-dioxane; Examples of the aliphatic polyfunctional epoxy compound include, but are not limited to, hydrogenated bisphenol A diepoxy compounds such as hydrogenated bisphenol A diglycidyl ether; glycidylamine epoxy compounds such as tetraglycidyl bis(aminomethyl)cyclohexane; hydantoin epoxy compounds such as 1,3-diglycidyl-5-methyl-5-ethylhydantoin; and epoxy compounds having a silicone skeleton such as 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane. The aliphatic polyfunctional epoxy compound is preferably liquid at 25°C. Furthermore, the viscosity at 25°C is preferably 10 to 10,000 mPa·s, and more preferably 10 to 5,000 mPa·s.

[0022] Examples of polyfunctional epoxy compounds having a heterocycle include isocyanuric acid type epoxy resins (manufactured by Nissan Chemical Industries, Ltd.: TEPIC-S, TEPIC-L, TEPIC-PAS, TEPIC-VL, TEPIC-FL, TEPIC-UC) and glycoluril type epoxy resins (manufactured by Shikoku Chemical Industries, Ltd.: TG-G). From the viewpoint of workability, polyfunctional epoxy compounds having a heterocycle are preferably liquid at 25°C. Furthermore, those having a viscosity at 25°C of 100 to 50,000 mPa·s are preferred, and those having a viscosity of 100 to 5,000 mPa·s are more preferred. On the other hand, from the viewpoint of adhesion, those that are solid at 25°C are preferred.

[0023] Commercially available products containing the polyfunctional epoxy compound of component (A) include, for example, jER (registered trademark) 825, 827, 828, 828EL, 828XA, 828US, 806, 806H, 807, 152, 871, 872, YL980, YL983U, YX8000, and YX8034 (manufactured by Mitsubishi Chemical Corporation), EPICLON (registered trademark) 840, 840S, 850, 850S, 850CRP, 850-LC, 830, 835, EXA-830LVP, and EXA Examples of the ethylene glycol ether ester include, but are not limited to, ethylene glycol ether esters EXA-830LVP, EXA-835LV, and N-730A (manufactured by DIC Corporation), Denacol (registered trademark) EP-4100, EP-4100G, EP-4100E, EP-4300E, EP-4530, EP-4901, and EP-4901E (manufactured by ADEKA Corporation), and EX-810, EX-811, EX-850, EX-821, EXA-920, EX-201, and EX-212 (manufactured by Nagase ChemteX Corporation).

[0024] Commercially available products containing the polyfunctional epoxy compound of component (B) include jER (registered trademark) 834, 1001, 1002, 1003, 1055, 1004, 1004AF, 4005P, 4007P, and YX4000H (manufactured by Mitsubishi Chemical Corporation), and EPICLON (registered trademark) 860, 1050, 1055, 2050, 3050, 4050, 7050, HM-091, HP-7200L, HP-7200, HP-7200H, HP-4700, and HP-4770 (manufactured by DIC Corporation), but are not limited to these.

[0025] The content of component (B) is preferably 1 to 1,000 parts by mass, and more preferably 1 to 100 parts by mass, per 100 parts by mass of component (A). From the viewpoint of stress relaxation property, the content of component (B) is preferably 10 to 1,000 parts by mass, more preferably 25 to 1,000 parts by mass, and even more preferably 50 to 1,000 parts by mass, per 100 parts by mass of component (A). Furthermore, from the viewpoint of improving reactivity, the content of component (B) is preferably 1 part by mass or more and less than 100 parts by mass, and more preferably 10 parts by mass or more and less than 50 parts by mass, per 100 parts by mass of component (A).

[0026] (C) Polyfunctional Thiol Compound The resin composition of this embodiment contains (C) a polyfunctional thiol compound (hereinafter also referred to as "component (C)"). In this embodiment, the (C) polyfunctional thiol compound is a compound containing two or more thiol groups, and the thiol groups react with the epoxy groups in components (A) and (B) and with the group (e) in the monofunctional compound (E) having one group (e) containing an unsaturated double bond and an electron-withdrawing group adjacent thereto in the molecule. In this embodiment, the (C) polyfunctional thiol compound preferably has three or more thiol groups. The (C) polyfunctional thiol compound more preferably contains a trifunctional thiol compound and / or a tetrafunctional thiol compound. Trifunctional and tetrafunctional thiol compounds refer to thiol compounds having three and four thiol groups, respectively. The thiol equivalent of the polyfunctional thiol compound (C) is preferably 90 to 200 g / eq, more preferably 90 to 150 g / eq, even more preferably 90 to 140 g / eq, and particularly preferably 90 to 130 g / eq.

[0027] Polyfunctional thiol compounds are broadly classified into thiol compounds having a hydrolyzable partial structure such as an ester bond in the molecule (i.e., hydrolyzable) and thiol compounds not having such a partial structure (i.e., non-hydrolyzable). Examples of hydrolyzable polyfunctional thiol compounds include trimethylolpropane tris(3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: TMMP), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate (manufactured by SC Organic Chemical Co., Ltd.: TEMPIC), pentaerythritol tetrakis(3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: PEMP), tetraethylene glycol bis(3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: PEMP), and tetraethylene glycol bis(3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: TEMP). Examples of such an ester include dipentaerythritol hexakis(3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: EGMP-4), dipentaerythritol hexakis(3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: DPMP), pentaerythritol tetrakis(3-mercaptobutyrate) (manufactured by Showa Denko K.K.: Karenz MT (registered trademark) PE1), and 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by Showa Denko K.K.: Karenz MT (registered trademark) NR1). These may be used alone or in combination of two or more.

[0028] On the other hand, examples of non-hydrolyzable polyfunctional thiol compounds include 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril (manufactured by Shikoku Chemical Industry Co., Ltd.: TS-G), 1,3,4,6-tetrakis(3-mercaptopropyl)glycoluril (manufactured by Shikoku Chemical Industry Co., Ltd.: C3 TS-G), 1,3,4,6-tetrakis(mercaptomethyl)glycoluril, 1,3,4,6-tetrakis(mercaptomethyl)-3a-methylglycoluril, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a-methylglycoluril, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a-methylglycoluril, 1,3,4,6-tetrakis(mercaptomethyl)-3a,6a-dimethylglycoluril, and 1,3,4,6-tetrakis(mercaptomethyl)-3a,6a-dimethylglycoluril. 1,3,4,6-tetrakis(2-mercaptoethyl)-3a,6a-dimethylglycoluril, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a,6a-dimethylglycoluril, 1,3,4,6-tetrakis(mercaptomethyl)-3a,6a-diphenylglycoluril, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a,6a-diphenylglycoluril, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a,6a-diphenylglycoluril, Tris(3-mercaptopropyl)isocyanurate, 1,3,5-tris[3-(2-mercaptoethylsulfanyl)propyl]isocyanurate, 1,3,5-tris[2-(3-mercaptopropoxy)ethyl]isocyanurate, pentaerythritol trippropanethiol (manufactured by SC Organic Chemicals Co., Ltd.: PEPT), 3-[2,3-bis(3-sulfanylpropoxy)propoxy]propane-1-thiol, 3-[2,2-bis[(3-mercaptopropoxy)methyl]isocyanurate [Butoxy]-1-propanethiol, pentaerythritol tetrapropanethiol, 1,2,3-tris(mercaptomethylthio)propane, 1,2,3-tris(2-mercaptoethylthio)propane, 1,2,3-tris(3-mercaptopropylthio)propane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercaptopropylthiomethyl)methane, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 1,1,5,5-tetrakis(mercaptomethylthio)-3-thiapentane, 1,1,6,6-tetrakis(mercaptomethylthio)propane tetrakis(mercaptomethylthio)-3,4-dithiahexane, 2,2-bis(mercaptomethylthio)ethanethiol, 3-mercaptomethylthio-1,7-dimercapto-2,6-dithiaheptane, 3,6-bis(mercaptomethylthio)-1,9-dimercapto-2,5,8-trithianonane, 3-mercaptomethylthio-1,6-dimercapto-2,5-dithiahexane, 1,1,9,9-tetrakis(mercaptomethylthio)-5-(3,3-bis(mercaptomethylthio)-1-thiapropyl)3,7-dithianonane, tris(2,2-bis(mercaptomethylthio) tris(4,4-bis(mercaptomethylthio)ethyl)methane, tris(4,4-bis(mercaptomethylthio)-2-thiabutyl)methane, tetrakis(2,2-bis(mercaptomethylthio)ethyl)methane, tetrakis(4,4-bis(mercaptomethylthio)-2-thiabutyl)methane, 3,5,9,11-tetrakis(mercaptomethylthio)-1,13-dimercapto-2,6,8,12-tetrathiatridecane, 3,5,9,11,15,17-hexakis(mercaptomethylthio)-1,19-dimercapto-2,6,8,12,14,18-hexathianonadecane 9-(2,2-bis(mercaptomethylthio)ethyl)-3,5,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,6,8,10,12,16-hexathiaheptadecane, 3,4,8,9-tetrakis(mercaptomethylthio)-1,11-dimercapto-2,5,7,10-tetrathiaundecane, 3,4,8,9,13,14-hexakis(mercaptomethylthio)-1,16-dimercapto-2,5,7,10,12,15-hexathiahexadecane, 8-[bis(mercaptomethylthio)methyl]-3,4,12,13-tetrakis(mercaptomethylthio)-1,15-dimercapto-2,5,7,9,11,14-hexathiapentadecane, 4,6-bis[3,5-bis(mercaptomethylthio)-7-mercapto-2,6-dithiaheptylthio]-1,3-dithiane, 4-[3,5-bis(mercaptomethylthio)-7-mercapto-2,6-dithiaheptylthio]-6-mercaptomethylthio-1,3-dithiane, 1,1-bis[4-(6-mercaptomethylthio)-1,3-dithianylthio]-1,3-bis(mercaptomethylthio)propane 1-[4-(6-mercaptomethylthio)-1,3-dithianylthio]-3-[2,2-bis(mercaptomethylthio)ethyl]-7,9-bis(mercaptomethylthio)-2,4,6,10-tetrathiaundecane, 3-[2-(1,3-dithietanyl)]methyl-7,9-bis(mercaptomethylthio)-1,11-dimercapto-2,4,6,10-tetrathiaundecane, 9-[2-(1,3-dithietanyl)]methyl-3,5,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,6,8,10,1 2,16-Hexathiaheptadecane, 3-[2-(1,3-dithietanyl)]methyl-7,9,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,4,6,10,12,16-hexathiaheptadecane, 4,6-bis[4-(6-mercaptomethylthio)-1,3-dithianylthio]-6-[4-(6-mercaptomethylthio)-1,3-dithianylthio]-1,3-dithiane, 4-[3,4,8,9-tetrakis(mercaptomethylthio)-11-mercapto-2,5,7,10-tetrathiaundecyl]-5 -mercaptomethylthio-1,3-dithiolane, 4,5-bis[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]-1,3-dithiolane, 4-[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]-5-mercaptomethylthio-1,3-dithiolane, 4-[3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiaoctyl]-5-mercaptomethylthio-1,3-dithiolane, 2-{bis[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]methyl}-1,3-dithietane, 2-[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]mercaptomethylthiomethyl-1,3-dithietane, 2-[3,4,8,9-tetrakis(mercaptomethylthio)-11-mercapto-2,5,7,10-tetrathiaundecylthio]mercaptomethylthiomethyl-1,3 -dithietane, 2-[3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiaoctyl]mercaptomethylthiomethyl-1,3-dithietane, 4-{1-[2-(1,3-dithietanyl)]-3-mercapto-2-thiapropylthio}-5-[1,2-bis(mercaptomethylthio)-4-mercapto-3-thiabutylthio]-1,3-dithiolane, etc. These may be used alone or in combination of two or more.

[0029] (D) Curing Catalyst The resin composition of this embodiment contains (D) a curing catalyst (hereinafter also referred to as "component (D)"). By using component (D), the resin composition of this embodiment can be cured in a short time even under low temperature conditions. The curing catalyst used in this embodiment is not particularly limited as long as it is a curing catalyst for the polyfunctional epoxy compounds of components (A) and (B), and known curing catalysts can be used.

[0030] Component (D) is preferably a latent curing catalyst. A latent curing catalyst is a compound that is inactive at room temperature but is activated by heating to function as a curing catalyst. Examples include imidazole compounds that are solid at room temperature; solid-dispersed amine adduct latent curing catalysts such as reaction products of amine compounds and epoxy compounds (amine-epoxy adducts); and reaction products of amine compounds and isocyanate compounds or urea compounds (urea adducts). From the viewpoints of pot life and curability, solid-dispersed amine adduct latent curing catalysts are preferred as component (D).

[0031] Examples of imidazole compounds that are solid at room temperature 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-methylimidazolyl-(1))-ethyl-S-triazine, and 2,4-diamino-6-(2'-methylimidazolyl-(1)')-ethyl-S-triazine. Examples of the methylimidazole include, but are not limited to, isocyanuric acid adducts, 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, and N,N'-(2-methylimidazolyl-(1)-ethyl)-adiboyldiamide.

[0032] Examples of epoxy compounds used as one of the raw materials for producing a solid dispersion type amine adduct latent curing catalyst (amine-epoxy adduct) include polyglycidyl ethers obtained by reacting epichlorohydrin with polyhydric phenols such as bisphenol A, bisphenol F, catechol, and resorcinol, or polyhydric alcohols such as glycerin and polyethylene glycol; glycidyl ether esters obtained by reacting epichlorohydrin with hydroxycarboxylic acids such as p-hydroxybenzoic acid and β-hydroxynaphthoic acid; phthalic acid, terephthalic acid, and the like; Examples of epoxy compounds include, but are not limited to, polyglycidyl esters obtained by reacting a polycarboxylic acid such as carboxylic acid with epichlorohydrin; glycidylamine compounds obtained by reacting 4,4'-diaminodiphenylmethane or m-aminophenol with epichlorohydrin; and polyfunctional epoxy compounds such as epoxidized phenol novolac resin, epoxidized cresol novolac resin, and epoxidized polyolefin; and monofunctional epoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, and glycidyl methacrylate.

[0033] The amine compound used as another raw material for producing the solid dispersion-type amine adduct latent curing catalyst may be any compound as long as it has one or more active hydrogen atoms in the molecule capable of addition reacting with an epoxy group and at least one functional group selected from a primary amino group, a secondary amino group, and a tertiary amino group in the molecule. Examples of such amine compounds include, but are not limited to, aliphatic amines 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.

[0034] Among these, compounds having a tertiary amino group in the molecule are particularly useful as raw materials for providing latent curing catalysts with excellent curing acceleration capabilities. Examples of such compounds include amine compounds such as dimethylaminopropylamine, diethylaminopropylamine, di-n-propylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, and N-methylpiperazine, as well as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, and 2-phenylimidazole. primary or secondary amines having a tertiary amino group in the molecule, such as imidazole compounds such as imidazole; 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 ... 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-butoxypropyl)-2-ethyl-4-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-phenylimidazoline, 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazoline, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol, N-β-hydroxyethylmorpholine, 2-dimethylaminoethanethiol, 2-mercaptopyridine, 2-benzimidazole Examples of the tertiary amino acid include, but are not limited to, alcohols, phenols, thiols, carboxylic acids, and hydrazides having a tertiary amino group in the molecule, such as thiazole, 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.

[0035] Further, examples of the isocyanate compound used as another manufacturing raw material for the solid dispersion type amine adduct latent curing catalyst include monofunctional isocyanate compounds such as n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, and benzyl isocyanate; polyfunctional isocyanate compounds such as hexamethylene diisocyanate, toluylene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, and bicycloheptane triisocyanate; and terminal isocyanate group-containing compounds obtained by reacting these polyfunctional isocyanate compounds with active hydrogen compounds. Examples of such a terminal isocyanate group-containing compound include, but are not limited to, an addition compound having a terminal isocyanate group obtained by reacting toluylene diisocyanate with trimethylolpropane, and an addition compound having a terminal isocyanate group obtained by reacting toluylene diisocyanate with pentaerythritol.

[0036] Examples of urea compounds include, but are not limited to, urea and thiourea.

[0037] The solid-dispersed latent curing catalyst that can be used in this embodiment is, for example, the above-mentioned combination of two components: (a) an amine compound and an epoxy compound, (b) a combination of three components: these two components and an active hydrogen compound, or (c) a combination of two or three components: an amine compound and an isocyanate compound and / or a urea compound. These can be easily prepared by mixing the components, reacting them at a temperature from room temperature to 200°C, cooling them to solidify them, and then pulverizing them, or by reacting them in a solvent such as methyl ethyl ketone, dioxane, or tetrahydrofuran, removing the solvent, and then pulverizing the solid content.

[0038] Representative examples of commercially available latent curing catalysts include amine-epoxy adducts (amine adducts), such as "Amicure PN-23" (product name of Ajinomoto Fine-Techno Co., Ltd.), "Amicure PN-40" (product name of Ajinomoto Fine-Techno Co., Ltd.), "Amicure PN-50" (product name of Ajinomoto Fine-Techno Co., Ltd.), "Hardener X-3661S" (product name of ACR Co., Ltd.), "Hardener X-3670S" (product name of ACR Co., Ltd.), "Novacure HX-3742" (product name of Asahi Kasei Corporation), and " Examples of such urea-type adducts include Novacure HX-3721 (product name of Asahi Kasei Corporation), Novacure HXA9322HP (product name of Asahi Kasei Corporation), Novacure HXA3922HP (product name of Asahi Kasei Corporation), Novacure HXA3932HP (product name of Asahi Kasei Corporation), Novacure HXA5945HP (product name of Asahi Kasei Corporation), Novacure HXA5911HP (product name of Asahi Kasei Corporation), and Novacure HXA9382HP (product name of Asahi Kasei Corporation). Examples of the component (D) include, but are not limited to, "Fujicure FXR1020" (T&K TOKA Corporation), "Fujicure FXR-1030" (T&K TOKA Corporation), "Fujicure FXR1121" (T&K TOKA Corporation), "Fujicure FXR1081" (T&K TOKA Corporation), "Fujicure FXR1061" (T&K TOKA Corporation), and "Fujicure FXR1171" (T&K TOKA Corporation). Component (D) may be used singly or in combination of two or more.

[0039] The component (D) is preferably contained in an amount of 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, based on the total mass of the resin composition.

[0040] Component (D) may be provided in the form of a dispersion in an epoxy compound. When component (D) in such a form is used, it should be noted that the amount of the epoxy compound in which it is dispersed is also included in the amount of component (A) or component (B) in the resin composition of this embodiment.

[0041] (E) Monofunctional Compound Having One Group (e) Containing an Unsaturated Double Bond and an Adjacent Electron-Withdrawing Group in the Molecule The resin composition of this embodiment contains (E) a monofunctional compound (hereinafter also referred to as "component (E)") having one group (e) (hereinafter also referred to simply as "group (e)") in the molecule containing an unsaturated double bond and an adjacent electron-withdrawing group. In this embodiment, the group (e) in component (E), more specifically the unsaturated double bond in group (e), reacts with the thiol group in (C) the polyfunctional thiol compound. In this specification, the term "monofunctional" is used to refer to component (E) having one group (e) in the molecule that reacts with a thiol group. Examples of the electron-withdrawing group include a carbonyl group and a cyano group, with a carbonyl group being preferred.

[0042] When the resin composition according to this embodiment is subjected to DSC measurement, the onset temperature of the exothermic peak is observed to be lower than that of a resin composition not containing component (E). Here, the onset temperature can be defined as the curing reaction initiation temperature. The unsaturated double bond of group (e) in component (E) is highly reactive due to the adjacent electron-withdrawing groups, and reacts with the thiol group in the polyfunctional thiol compound (C) before the epoxy groups in the polyfunctional epoxy compounds of components (A) and (B). This is thought to have lowered the curing reaction initiation temperature. This shortens the time for the viscosity reduction of the resin composition that occurs before the curing reaction begins, suppresses dripping and unintended wetting and spreading, and provides excellent shape retention for coated products. Furthermore, when the resin composition according to this embodiment is subjected to DSC measurement under curing reaction conditions, such as at 80°C, the total heat generation is lower than that of a resin composition not containing component (E). The epoxy-thiol reaction generates reaction heat due to the ring-opening reaction of the epoxy, whereas the reaction of component (E) does not involve ring-opening, which is thought to have reduced the heat generation. This makes it possible to prevent overheating of the adherend and its surrounding components during short-time curing. Furthermore, because component (E) is monofunctional, it does not form crosslinks, and therefore it is possible to prevent an increase in internal stress in the cured product due to excessive crosslink density, thereby imparting flexibility to the cured product of the resulting resin composition.

[0043] From the viewpoint of the viscosity of the resin composition, component (E) is preferably liquid at 25°C.

[0044] Examples of component (E) include a monofunctional maleimide compound, a monofunctional (meth)acrylate compound, and a monofunctional acrylamide compound. Examples of group (e) include a maleimide group and a (meth)acryloyl group. In this embodiment, component (E) is preferably selected from a monofunctional maleimide compound and a monofunctional (meth)acrylate compound, and more preferably a monofunctional (meth)acrylate compound.

[0045] The monofunctional maleimide compound is a compound having one maleimide group as the group (e), and examples thereof include maleimide; aliphatic hydrocarbon group-containing maleimides such as methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, and cyclohexylmaleimide; aromatic ring-containing maleimides such as phenylmaleimide, etc. These may be used alone or in combination of two or more.

[0046] The monofunctional (meth)acrylate compound is a compound having one (meth)acryloyl group as the group (e). Examples of the monofunctional (meth)acrylate compound include: -ethyl (meth)acrylate, trifluoroethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, isobornyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, phenoxyethyl (meth)acrylate, benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene Esters of monohydric alcohols and (meth)acrylic acid, such as glycol (meth)acrylate, butoxydiethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, 2-ethylhexyldiethylene glycol (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, and 3-phenoxybenzyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, octyl acrylate, nonyl acrylate, isononyl acrylate, 3,3,5-Trimethylcyclohexyl acrylate, cyclic trimethylolpropane formal acrylate, 1-naphthalenemethyl (meth)acrylate, 1-ethylcyclohexyl (meth)acrylate, 1-methylcyclohexyl (meth)acrylate, 1-ethylcyclopentyl (meth)acrylate, 1-methylcyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, nonyl phenoxy polyethylene glycol (meth)acrylate, tetrahydrodicyclopentadienyl (meth)acrylate, 2-(o-phenylphenoxy)ethyl (meth)acrylate, isobornylcyclohexyl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, 1-adamantyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, 2-methyl-2-adamantanyl (meth)acrylate, 2- Ethyl-2-adamantanyl (meth)acrylate, 2-isopropyladamantan-2-yl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, (adamantan-1-yloxy)methyl (meth)acrylate, 2-isopropyl-2-adamantyl (meth)acrylate, 1-methyl-1-ethyl-1-adamantylmethanol (meth)acrylate, 1,1-diethyl-1-adamantylmethanol (meth)acrylate, 2-cyclohexylpropane-2-yl (meth)acrylate, 1-isopropylcyclohexyl (meth)acrylate, 1-methylcyclohexyl (meth)acrylate, 1-ethylcyclopentyl (meth)acrylate, 1-methylcyclohexyl (meth)acrylate, tetrahydropyranyl (meth)acrylate, tetrahydro-2-furanyl (meth)acrylate, 2-oxotetrahydrofuran-3-yl (meth)acrylate, (5-oxotetrahydrofuran-2-yl)methyl (meth)acrylate, (2-oxo-1,Examples of suitable mono(meth)acrylates include monohydric alcohols and esters of monohydric alcohols and (meth)acrylic acid, such as (3-dioxolan-4-yl)methyl (meth)acrylate, N-acryloyloxyethyl hexahydrophthalimide, α-acryloyl-ω-methoxypoly(oxyethylene), and 1-ethoxyethyl (meth)acrylate. These may be used alone or in combination of two or more. From the viewpoint of the stress relaxation properties of the cured product, the monofunctional (meth)acrylate compound preferably has a molecular weight of 450 or less, more preferably 400 or less, even more preferably 380 or less, even more preferably 350 or less, and particularly preferably 300 or less. Furthermore, to prevent contamination of surrounding components due to volatilization, the monofunctional (meth)acrylate compound preferably has low volatility, and its molecular weight is preferably 100 or more, more preferably 120 or more, even more preferably 140 or more, and particularly preferably 160 or more. In one embodiment, the molecular weight of the monofunctional (meth)acrylate compound is preferably 100 to 450, more preferably 120 to 400, even more preferably 140 to 380, particularly preferably 180 to 350, and most preferably 200 to 320.

[0047] Component (E) may have a group reactive with a thiol group, such as an epoxy group, in addition to group (e). However, from the viewpoint of flexibility of the obtained cured product, it may be preferable that component (E) does not contain a group reactive with a thiol group, such as an epoxy group.

[0048] In the present embodiment, from the viewpoint of achieving both flexibility and adhesive strength, the ratio of the sum of the number of epoxy group equivalents of component (A) and the number of epoxy group equivalents of component (B) to the number of thiol group equivalents of component (C) (([number of epoxy group equivalents of component (A)] + [number of epoxy group equivalents of component (B)]) / [number of thiol group equivalents of component (C)]) is preferably 0.4 to 0.95, more preferably 0.4 to 0.9, still more preferably 0.45 to 0.9, even more preferably 0.5 to 0.9, and particularly preferably 0.55 to 0.9. In the present embodiment, the ratio of the number of epoxy group equivalents of component (A) to the number of thiol group equivalents of component (C) ([number of epoxy group equivalents of component (A)] / [number of thiol group equivalents of component (C)]) is preferably 0.1 to 0.9, more preferably 0.15 to 0.85, even more preferably 0.15 to 0.80, and particularly preferably 0.2 to 0.8. In this embodiment, the ratio of the sum of the number of epoxy group equivalents of component (A), the number of epoxy group equivalents of component (B), and the number of group (e) equivalents of component (E) to the number of thiol group equivalents of component (C) (([number of epoxy group equivalents of component (A)] + [number of epoxy group equivalents of component (B)] + [number of group (e) equivalents of component (E)]) / [number of thiol group equivalents of component (C)]) is preferably 0.7 to 1.5, more preferably 0.75 to 1.4, even more preferably 0.8 to 1.3, and most preferably 0.8 to 1.1. In particular, by blending a certain amount of component (C) with components (A), (B), and (E), it is possible to suppress the remaining unreacted components that cannot react with thiol groups, and thus suppress bleeding of the unreacted components. It is also expected that volatile components will be suppressed. In this specification, bleeding refers to a phenomenon in which unreacted components seep out from the adhesive coating or cured product over time when an adhesive containing a curable resin composition is used to fix or bond parts, and the exuded components themselves are sometimes referred to as "bleed."In this embodiment, the ratio of the number of equivalents of group (e) in component (E) to the number of equivalents of thiol groups in component (C) ([number of equivalents of group (e) in component (E)] / [number of equivalents of thiol groups in component (C)]) is preferably 0.05 to 0.7, more preferably 0.1 to 0.6, and even more preferably 0.15 to 0.55. Note that, when component (E) contains an epoxy group, it is preferable to add the number of equivalents of epoxy group in component (E) to the number of equivalents of components (A) and (B) so that the above-mentioned relational expression of equivalents is satisfied.

[0049] In this specification, functional group equivalents such as thiol equivalent, epoxy equivalent, and (meth)acryloyl equivalent refer to the molecular weight of a compound per functional group, and functional group equivalents such as the number of thiol group equivalents, the number of epoxy group equivalents, and the number of (meth)acryloyl equivalents refer to the number of functional groups (number of equivalents) per mass (charged amount) of a compound.

[0050] Theoretically, the epoxy equivalent of each of components (A) and (B) is the molecular weight of each of components (A) and (B) divided by the number of epoxy groups in one molecule. The actual epoxy equivalent can be determined by the method described in JIS K7236. The epoxy group equivalent of each of components (A) and (B) is the number of epoxy groups (equivalents) per mass (charge amount) of each of components (A) and (B), and is the quotient obtained by dividing the mass (g) of each epoxy compound in components (A) and (B) by the epoxy equivalent of that epoxy compound (if multiple epoxy compounds are contained, the sum of such quotients for each epoxy compound). If component (E) contains epoxy groups, its epoxy equivalent and epoxy group equivalent can be determined in a similar manner.

[0051] Theoretically, the thiol equivalent of component (C) is the molecular weight of component (C) divided by the number of thiol groups in one molecule. The actual thiol equivalent can be determined, for example, by determining the thiol value by potentiometric measurement. This method is widely known and is disclosed, for example, in paragraph 0079 of JP 2012-153794 A. The thiol group equivalent of component (C) is the number of thiol groups (equivalents) per mass (charge amount) of component (C), and is the quotient obtained by dividing the mass (g) of the polythiol compound (C) by the thiol equivalent of that polythiol compound (when multiple polythiol compounds are included, the sum of such quotients for each polythiol compound).

[0052] When group (e) is a (meth)acryloyl group, the (meth)acryloyl equivalent of component (E) is theoretically equal to the molecular weight of the (meth)acrylate compound divided by the number of acryloyl groups (or methacryloyl groups) in one molecule. The actual (meth)acryloyl equivalent can be measured, for example, by NMR. The (meth)acryloyl group equivalent of component (E) is the number of (meth)acryloyl groups (equivalents) per mass (charged amount) of component (E), and is the quotient obtained by dividing the mass (g) of the (meth)acrylate compound of component (E) by the (meth)acryloyl equivalent of that (meth)acrylate compound (when multiple (meth)acrylate compounds are contained, the sum of such quotients for each (meth)acrylate compound).

[0053] When group (e) is a maleimide group, the maleimide equivalent of component (E) is theoretically equal to the molecular weight of the maleimide compound divided by the number of maleimide groups in one molecule. The actual maleimide equivalent can be measured, for example, by NMR. The maleimide group equivalent of component (E) is the number of maleimide groups (equivalents) per mass (charged amount) of component (E), and is the quotient obtained by dividing the mass (g) of the maleimide compound of component (E) by the maleimide equivalent of that maleimide compound (when multiple maleimide compounds are contained, the sum of such quotients for each maleimide compound).

[0054] If desired, the resin composition of the present embodiment may contain optional components other than the above components (A) to (E), such as those described below, as necessary.

[0055] The resin composition of this embodiment may contain a thermosetting compound other than component (A) and component (B) as long as the effects of the present invention are not impaired. In this specification, "thermosetting compound other than component (A) and component (B)" refers to a polyfunctional thermosetting compound other than component (A) and component (B) that can react with the thiol group of component (C), and does not include component (C). Examples of thermosetting compounds other than component (A) and component (B) include (F) polyfunctional (meth)acrylate compounds, phenolic compounds, bismaleimide compounds, cyanate compounds, episulfide compounds, etc. An episulfide compound is a compound containing a thiirane ring in which all or some of the oxygen atoms in the oxirane ring of an epoxy compound are replaced with sulfur atoms. Examples of episulfide compounds include compounds containing two or more thiirane rings in the molecule and compounds containing at least one thiirane ring and at least one oxirane ring in the molecule. However, in the resin composition of this embodiment, the total amount of component (A) and component (B) is preferably 50 parts by mass or more, for example, 51 parts by mass or more, for example, 55 parts by mass or more, for example, 60 parts by mass or more, for example, 65 parts by mass or more, for example, 70 parts by mass or more, for example, 75 parts by mass or more, for example, 80 parts by mass or more, for example, 85 parts by mass or more, for example, 90 parts by mass or more, relative to 100 parts by mass of the total mass of the thermosetting compound (excluding component (C)).

[0056] (F) Polyfunctional (meth)acrylate compound The resin composition of the present embodiment may contain (F) a polyfunctional (meth)acrylate compound (hereinafter also referred to as "component (F)") within a range that does not impair the effects of the present invention.

[0057] Examples of polyfunctional (meth)acrylate compounds include diacrylate and / or dimethacrylate of tris(2-hydroxyethyl)isocyanurate; tris(2-hydroxyethyl)isocyanurate triacrylate and / or trimethacrylate; trimethylolpropane triacrylate and / or trimethacrylate, or oligomers thereof; pentaerythritol triacrylate and / or trimethacrylate, or oligomers thereof; dipentaerythritol polyacrylate and / or polymethacrylate; tris(acryloxyethyl)isocyanurate; caprolactone-modified tris(acryloxyethyl)isocyanurate; caprolactone-modified tris(methacryloxyethyl)isocyanurate; alkyl-modified tris(acryloxyethyl)isocyanurate; Examples of the polyfunctional (meth)acrylate compound include polyacrylates and / or polymethacrylates of caprolactone-modified dipentaerythritol, polyacrylates and / or polymethacrylates of caprolactone-modified dipentaerythritol, ethoxylated bisphenol A diacrylate and / or ethoxylated bisphenol A dimethacrylate, dihydrocyclopentadiethyl acrylate and / or dihydrocyclopentadiethyl methacrylate, polyester acrylate and / or polyester methacrylate, dimethylol-tricyclodecane diacrylate, poly(meth)acrylate of ditrimethylolpropane, polyurethanes having two or more (meth)acryloyl groups per molecule, and polyesters having two or more (meth)acryloyl groups per molecule. The polyfunctional (meth)acrylate compound may be any one of the above-mentioned polyfunctional (meth)acrylate compounds, or two or more of them may be used in combination.

[0058] Commercially available polyfunctional (meth)acrylate compounds include, for example, polyester acrylate (product name: EBECRYL810) manufactured by Daicel-Allnex Corporation, ditrimethylolpropane tetraacrylate (product name: EBECRYL140) manufactured by Daicel-Allnex Corporation, polyester acrylate (product name: M7100) manufactured by Toagosei Co., Ltd., dimethylol-tricyclodecane diacrylate (product name: Light Acrylate DCP-A) manufactured by Kyoeisha Chemical Co., Ltd., and neopentyl glycol-modified trimethylolpropane diacrylate (product name: Kayarad R-604) manufactured by Nippon Kayaku Co., Ltd.

[0059] (G) Filler The resin composition of this embodiment may contain a (G) filler (hereinafter also referred to as "component (G)") within a range that does not impair the effects of the present invention. By containing a (G) filler in the resin composition, the linear expansion coefficient of the cured product obtained by curing the resin composition can be reduced, and thermal cycle resistance can be improved. Furthermore, if the filler has a low elastic modulus, it can alleviate stress generated in the cured product, improving long-term reliability. (G) fillers are broadly classified into inorganic fillers and organic fillers.

[0060] The inorganic filler is not particularly limited as long as it is made of granular material formed from an inorganic material and has the effect of lowering the linear expansion coefficient when added. Examples of inorganic materials that can be used include silica, talc, alumina, aluminum nitride, calcium carbonate, aluminum silicate, magnesium silicate, magnesium carbonate, barium sulfate, barium carbonate, lime sulfate, aluminum hydroxide, calcium silicate, potassium titanate, titanium oxide, zinc oxide, silicon carbide, silicon nitride, and boron nitride. One or more inorganic fillers may be used, or two or more may be used in combination. As the inorganic filler, silica filler is preferably used because it allows for a high loading. Amorphous silica is preferred as the silica. The surface of the inorganic filler may be surface-treated with a coupling agent such as a silane coupling agent.

[0061] Examples of the organic filler include polytetrafluoroethylene (PTFE) filler, silicone filler, acrylic filler, filler having a urethane skeleton, filler having a butadiene skeleton, styrene filler, etc. The organic filler may be surface-treated.

[0062] The shape of the filler is not particularly limited, and may be any of spherical, flaky, needle-like, irregular, etc.

[0063] The average particle size of the filler is preferably 6.0 μm or less, more preferably 5.0 μm or less, and even more preferably 4.0 μm or less. In this specification, unless otherwise specified, the average particle size refers to the volume-based median diameter (d ５０ ) By setting the average particle size of the filler to the upper limit or less, sedimentation of the filler can be suppressed, and the formation of coarse particles can be suppressed, which can prevent wear on the jet dispenser nozzle and scattering of the resin composition ejected from the jet dispenser nozzle outside the desired area. The lower limit of the average particle size of the filler is not particularly limited, but from the viewpoint of the viscosity of the resin composition, it is preferably 0.005 μm or more, and more preferably 0.1 μm or more. In one aspect of this embodiment, the average particle size of the filler (F) is preferably 0.01 μm to 5.0 μm, and more preferably 0.1 μm to 3.0 μm. Fillers with different average particle sizes may be used in combination. For example, a filler having an average particle size of 0.005 μm or more but less than 0.1 μm may be used in combination with a filler having an average particle size of 0.1 μm to 6.0 μm.

[0064] The content of the filler in the resin composition of this embodiment is preferably 15 to 50 mass %, more preferably 20 to 45 mass %, and even more preferably 20 to 40 mass %, relative to the total mass of the resin composition. By setting the filler content within this range, thermal cycle resistance is improved, and the viscosity of the resin composition is set within an appropriate range, improving applicability to dispensing.

[0065] (H) Photoradical Initiator The resin composition of this embodiment may contain (H) a photoradical initiator (hereinafter also referred to as "component (H)") within a range that does not impair the effects of the present invention. The inclusion of (H) photoradical initiator promotes the reaction of component (C), component (E), and optional component (F) upon irradiation with light. Examples of (H) photoradical initiators include alkylphenone-based compounds and acylphosphine oxide-based compounds.

[0066] Examples of alkylphenone compounds include benzyl dimethyl ketals such as 2,2-dimethoxy-1,2-diphenylethan-1-one (commercially available as Omnirad 651 from IGM Resins B.V.); α-aminoalkylphenones such as 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one (commercially available as Omnirad 907 from IGM Resins B.V.); α-hydroxyalkylphenones such as 1-hydroxy-cyclohexyl-phenyl-ketone (commercially available as Omnirad 184 from IGM Resins B.V.); 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one (commercially available as Omnirad 184 from IGM Resins B.V.); 379EG), 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone (commercially available as Omnirad 369 manufactured by IGM Resins BV), and the like.

[0067] Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (commercially available as Omnirad TPO H manufactured by IGM Resins B.V.), bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (commercially available as Omnirad 819 manufactured by IGM Resins B.V.), and the like.

[0068] (H) Examples of the photoradical initiator include, in addition to the above-mentioned photoradical initiators, 2-hydroxy-2-methyl-1-phenylpropan-1-one, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin phenyl ether, benzoin methyl ether, benzoin ethyl ... diethyl benzoyl dimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methylphenyl glyoxylate, benzyl, and camphorquinone.

[0069] From the viewpoint of photoirradiation reactivity, the content of the (H) photoradical initiator is preferably 0.1 to 10 parts by mass, and more preferably 0.2 to 8 parts by mass, relative to 100 parts by mass in total of the monofunctional (meth)acrylate compound and the polyfunctional (meth)acrylate compound.

[0070] (I) Stabilizer The resin composition of this embodiment may contain (I) a stabilizer (hereinafter also referred to as "component (I)"), if desired, to the extent that the effects of the present invention are not impaired. The stabilizer can improve the storage stability of the resin composition of this embodiment and extend its pot life. Various known stabilizers can be used as the stabilizer, but at least one selected from the group consisting of liquid boric acid ester compounds, aluminum chelates, and organic acids is preferred because of its high effect of improving storage stability.

[0071] Examples of liquid boric acid ester compounds include 2,2'-oxybis(5,5'-dimethyl-1,3,2-oxaborinane), trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, tri-n-butyl borate, tripentyl borate, triallyl borate, trihexyl borate, tricyclohexyl borate, trioctyl borate, trinonyl borate, tridecyl borate, tridodecyl borate, trihexadecyl borate, trioctadecyl borate, tris(2-ethylhexyloxy)borane, bis(1,4,7,10-tetraoxaundecyl)(1,4,7,10,13-pentaoxatetradecyl)(1,4,7-trioxaundecyl)borane, tribenzyl borate, triphenyl borate, tri-o-tolyl borate, tri-m-tolyl borate, and triethanolamine borate. Liquid borate ester compounds are preferred because they are liquid at room temperature (25°C), allowing the viscosity of the formulation to be kept low. As the aluminum chelate, for example, Aluminum Chelate A (manufactured by Kawaken Fine Chemicals Co., Ltd.) can be used. As the organic acid, for example, barbituric acid can be used. The stabilizers may be used alone or in combination of two or more.

[0072] When a stabilizer is added, the amount added is preferably 0.01 to 30 mass %, more preferably 0.05 to 25 mass %, and even more preferably 0.1 to 20 mass %, relative to the total mass of the resin composition.

[0073] (J) Coupling Agent If desired, the resin composition of this embodiment may contain (J) a coupling agent (hereinafter also referred to as "component (J)") to the extent that the effects of the present invention are not impaired. The coupling agent has two or more different functional groups in the molecule, one of which is a functional group that chemically bonds with inorganic materials and the other is a functional group that chemically bonds with organic materials. By including a coupling agent in the resin composition, the adhesive strength of the resin composition to substrates and the like is improved.

[0074] Examples of the (J) coupling agent include, but are not limited to, silane coupling agents, aluminum coupling agents, and titanium coupling agents, depending on the type of functional group that chemically bonds with the inorganic material.

[0075] Examples of coupling agents include, but are not limited to, various coupling agents such as epoxy, amino, vinyl, methacrylic, acrylic, and mercapto coupling agents depending on the type of functional group that chemically bonds with the organic material. Among these, epoxy coupling agents containing an epoxy group are preferred from the viewpoint of moisture resistance reliability.

[0076] Specific examples of epoxy-based silane coupling agents include 3-glycidoxypropyltrimethoxysilane (product name: KBM403, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-glycidoxypropyltriethoxysilane (product name: KBE-403, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-glycidoxypropylmethyldiethoxysilane (product name: KBE-402, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-glycidoxypropylmethyldimethoxysilane (product name: KBM402, manufactured by Shin-Etsu Chemical Co., Ltd.), 8-glycidoxyoctyltrimethoxysilane (product name: KBM-4803, manufactured by Shin-Etsu Chemical Co., Ltd.), and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (product name: KBM-303, manufactured by Shin-Etsu Chemical Co., Ltd.).

[0077] Specific examples of methacrylic silane coupling agents include 3-methacryloxypropyltrimethoxysilane (product name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropylmethyldimethoxysilane (product name: KBM502, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropylmethyldiethoxysilane (product name: KBE502, manufactured by Shin-Etsu Chemical Co., Ltd.), and 3-methacryloxypropyltriethoxysilane (product name: KBE503, manufactured by Shin-Etsu Chemical Co., Ltd.).

[0078] A specific example of the acrylic silane coupling agent is 3-acryloxypropyltrimethoxysilane (product name: KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.).

[0079] In this embodiment, methacrylic silane coupling agents and acrylic silane coupling agents differ from component (E) in that they have functional groups that chemically bond with inorganic materials, and are therefore not included in component (E).

[0080] Specific examples of mercapto-based silane coupling agents include 3-mercaptopropyltrimethoxysilane (product name: KBM803, manufactured by Shin-Etsu Chemical Co., Ltd.) and 3-mercaptopropylmethyldimethoxysilane (product name: KBM802, manufactured by Shin-Etsu Chemical Co., Ltd.).

[0081] The coupling agents may be used alone or in combination of two or more.

[0082] When a coupling agent is added, the amount of the coupling agent added is preferably 0.01% by mass to 30% by mass, and more preferably 0.1% by mass to 10% by mass, relative to the total mass of the resin composition, from the viewpoint of improving adhesive strength.

[0083] (K) Other Additives If desired, the resin composition of this embodiment may further contain other additives, such as carbon black, titanium black, an ion trapping agent, a leveling agent, an antioxidant, an antifoaming agent, a viscosity modifier, a flame retardant, a colorant, a solvent, etc., within the scope of this embodiment. The type and amount of each additive are as usual.

[0084] The method for producing the resin composition of this embodiment is not particularly limited. For example, the resin composition of this embodiment can be obtained by simultaneously or separately introducing components (A) to (E), and, if necessary, components (F), (G), (H), (I), (J), (K), and other additives, into an appropriate mixer, and stirring and mixing them while melting them by heating if necessary, to form a homogeneous composition. The mixer is not particularly limited, but examples include a Raikai mixer, a Henschel mixer, a three-roll mill, a ball mill, a planetary mixer, and a bead mill equipped with a stirrer and a heater. These devices may also be used in appropriate combinations.

[0085] The resin composition obtained in this manner is thermosetting, and preferably cures within 5 hours, more preferably within 3 hours, and even more preferably within 1 hour at a temperature of 80°C. When the curable composition of this embodiment is used to manufacture a semiconductor module including components that deteriorate under high temperature conditions, the composition is preferably thermally cured at a temperature of 50 to 90°C for 30 to 120 minutes. In one aspect, the resin composition of this embodiment is a resin composition for use in curing by heat alone. Use of the above resin composition in curing by heat alone is also one embodiment of the present invention.

[0086] When the resin composition of the present embodiment contains the component (F) and the component (H), the resin composition can also be cured by light (UV). For example, the resin composition can be pre-cured by light (UV) curing and then fully cured by heat curing.

[0087] The resin composition of the present embodiment can be used, for example, as an adhesive or sealant for fixing, joining, or protecting components that constitute a semiconductor device or electronic component, or as a raw material thereof.

[0088] [Adhesive or Sealant] An adhesive or sealant according to a second embodiment of the present invention comprises the resin composition of the first embodiment described above. This adhesive or sealant provides excellent fixation, bonding, or protection for engineering plastics (e.g., LCP (liquid crystal polymer), polyamide, polycarbonate, etc.), ceramics, and metals (e.g., copper, nickel, etc.), and can be used to fix, bond, or protect components constituting a semiconductor device or electronic component. Examples of semiconductor devices or electronic components include, but are not limited to, HDDs, semiconductor elements, sensor modules such as image sensor modules, camera modules, semiconductor modules, and integrated circuits. The adhesive or sealant according to this embodiment is highly reactive and can provide a cured product with excellent stress relaxation properties, making it highly productive and suitable for use, for example, in the manufacture of semiconductor devices and electronic components in which multiple components made of different materials are joined and assembled. Furthermore, the adhesive or sealant according to this embodiment generates a small total amount of heat during the curing reaction, making it suitable for use, for example, in the manufacture of semiconductor modules equipped with miniaturized electronic components. In one aspect, the adhesive or sealant according to this embodiment is an adhesive or sealant that is cured using heat alone. The use of the adhesive or sealant described above in a heat only cure is also an embodiment of the present invention.

[0089] [Cured product of resin composition, adhesive, or sealant] The cured product of the third embodiment of the present invention is a cured product obtained by curing the resin composition of the first embodiment or the adhesive or sealant of the second embodiment. This cured product has excellent stress relaxation properties.

[0090] [Semiconductor Device, Electronic Component] The semiconductor device or electronic component of the fourth embodiment of the present invention includes the cured product of the third embodiment described above, and therefore has high reliability, particularly in semiconductor devices or electronic components assembled by joining multiple components made of different materials. Here, the term "semiconductor device" refers to any device that can function by utilizing semiconductor properties, including electronic components, semiconductor circuits, modules incorporating these, electronic devices, etc. Examples of semiconductor devices or electronic components include, but are not limited to, HDDs, semiconductor elements, sensor modules such as image sensor modules, camera modules, semiconductor modules, and integrated circuits.

[0091] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following examples, parts and % represent parts by mass and % by mass unless otherwise specified.

[0092] [Examples 1 to 20, Comparative Examples 1 to 3] Resin compositions were prepared by mixing predetermined amounts of each component using a three-roll mill according to the formulations shown in Table 1. In Table 1, the amount of each component is expressed in parts by mass (unit: g). The components used in the examples and comparative examples are as follows.

[0093] (A) Epoxy compound having an epoxy equivalent of less than 215 g / eq (component (A)) (A-1) Bisphenol F epoxy resin / bisphenol A epoxy resin mixture (product name: EXA-835LV, manufactured by DIC Corporation, epoxy equivalent: 165 g / eq) (A-2): Epoxy resin in component (D-1) (mixture of bisphenol A epoxy resin and bisphenol F epoxy resin, epoxy equivalent: 180 g / eq)

[0094] (B) Epoxy compound having an epoxy equivalent of 215 g / eq or more (component (B)) (B-1) Polyether type epoxy compound (product name: AER-9000, manufactured by Asahi Kasei Corporation, epoxy equivalent: 380 g / eq, liquid at 25°C, viscosity: 1 Pa·s) (B-2) Liquid epoxy compound (product name: jER YX7400, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 450 g / eq, liquid at 25°C, viscosity: 170 mPa·s) (B-3) Bisphenol A type epoxy resin (product name: jER 1002, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 250 g / eq, solid at 25°C)

[0095] (C) Polyfunctional thiol compounds (component (C)) (C-1): Pentaerythritol tetrakis(3-mercaptopropionate) (product name: PEMP, manufactured by SC Organic Chemicals, thiol equivalent: 122 g / eq) (C-2): 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril (product name: TS-G, manufactured by Shikoku Chemicals Corporation, thiol equivalent: 100 g / eq) (C-3): Pentaerythritol trippropanethiol (product name: PEPT, manufactured by SC Organic Chemicals, thiol equivalent: 124 g / eq) (C-4): Trimethylolpropane tris(3-mercaptopropionate) (product name: TMMP, manufactured by SC Organic Chemicals, thiol equivalent: 133 g / eq)

[0096] (D) Curing catalyst (component (D)) (D-1): Amine-epoxy adduct latent curing catalyst (product name: Novacure HXA9322HP, manufactured by Asahi Kasei Corporation) (D-2): Urea adduct latent curing catalyst (product name: Fujicure FXR1121, manufactured by T&K TOKA Corporation)

[0097] The latent curing catalyst (D-1) is provided in the form of a dispersion (latent curing catalyst / mixture of bisphenol A epoxy resin and bisphenol F epoxy resin = 33 / 67 (mass ratio)) in which fine particle latent curing catalyst is dispersed in an epoxy resin (a mixture of bisphenol A epoxy resin and bisphenol F epoxy resin (epoxy equivalent: 180 g / eq)). The epoxy resin constituting this dispersion is treated as constituting a part of component (A). Therefore, in Table 1, the amount of only the latent curing catalyst in (D-1) is shown in the column for component (D), and the amount of the epoxy resin in (D-1) is shown as component (A-2) in the column for component (A).

[0098] (E) Monofunctional compounds having one group (e) containing an unsaturated double bond and an electron-withdrawing group adjacent thereto in the molecule (component (E)) (E-1): n-octyl acrylate (product name: NOAA, manufactured by Osaka Organic Chemical Industry Ltd., (meth)acrylate equivalent: 184 g / eq) (E-2): (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl acrylate (product name: MEDOL-10, manufactured by Osaka Organic Chemical Industry Ltd., (meth)acrylate equivalent: 200 g / eq) (E-3): cyclic trimethylolpropane formal acrylate (product name: Biscoat #200, manufactured by Osaka Organic Chemical Industry Ltd., (meth)acrylate equivalent: 200 g / eq) (E-4): dicyclopentanyl acrylate (product name: FA513AS, manufactured by Showa Denko Materials Co., Ltd., (meth)acrylate equivalent: 206 g / eq) (E-5): isobornyl acrylate (product name: IBXA, manufactured by Kyoeisha Chemical Co., Ltd., (meth)acrylate equivalent: 208 g / eq) (E-6): m-phenoxybenzyl acrylate (product name: Light Acrylate POB-A, manufactured by Kyoeisha Chemical Co., Ltd., (meth)acrylate equivalent: 254 g / eq) (E-7): 2-(o-phenylphenoxy)ethyl acrylate (product name: HRD-01, manufactured by Nisshoku Techno Fine Chemical Co., Ltd., (meth)acrylate equivalent: 268 g / eq) (E') monofunctional epoxy compound (component (E')) (E'-1): p-tert-butylphenyl glycidyl ether (product name: ED509S, manufactured by ADEKA Corporation, epoxy equivalent: 205 g / eq)

[0099] (G) Filler (Component (G)) (G-1): Silica filler (product name: SE2300, manufactured by Admatechs Co., Ltd., average particle size: 0.6 μm)

[0100] In Table 1, the symbols in the "Equivalent Calculation" column have the following meanings: "((A) + (B) + (E)) / (C)" represents the ratio of the sum of the epoxy group equivalents of component (A), the epoxy group equivalents of component (B), and the group (e) equivalents of component (E) to the thiol group equivalents of component (C) (([epoxy group equivalents of component (A)] + [epoxy group equivalents of component (B)] + [group (e) equivalents of component (E)]) / [thiol group equivalents of component (C)]). "((A) + (B)) / (C)" represents the ratio of the sum of the number of epoxy group equivalents of component (A) and the number of epoxy group equivalents of component (B) to the number of thiol group equivalents of component (C) (([number of epoxy group equivalents of component (A)] + [number of epoxy group equivalents of component (B)]) / [number of thiol group equivalents of component (C)]). "(A) / (C)" represents the ratio of the number of epoxy group equivalents of component (A) to the number of thiol group equivalents of component (C) ([number of epoxy group equivalents of component (A)] / [number of thiol group equivalents of component (C)]). "(B) / (C)" represents the ratio of the number of epoxy group equivalents of component (B) to the number of thiol group equivalents of component (C) ([number of epoxy group equivalents of component (B)] / [number of thiol group equivalents of component (C)]). "(E) / (C)" represents the ratio of the number of equivalents of the group (e) of component (E) to the number of equivalents of the thiol group of component (C) ([number of equivalents of the group (e) of component (E)] / [number of equivalents of the thiol group of component (C)]). "(E') / (C)" represents the ratio of the number of epoxy equivalents of component (E') to the number of equivalents of the thiol group of component (C) ([number of epoxy equivalents of component (E')] / [number of equivalents of the thiol group of component (C)]).

[0101] In the examples and comparative examples, the properties of the resin compositions were measured as follows.

[0102] [DSC Measurement] (1) Onset Temperature 5 mg of each resin composition was placed in a DSC aluminum pan, the pan was covered with a lid, and holes were drilled in the lid. A DSC curve was obtained using a differential scanning calorimeter (DSC, manufactured by NETZSCH: DSC204 F1 Phoenix (registered trademark)) in a nitrogen atmosphere while the temperature was raised from 25°C to 250°C at a rate of 5°C / min. If multiple onset temperatures were observed in the obtained DSC curve, the lower value was taken as the onset temperature. This is shown in Table 1. The onset temperature obtained by the above test indicates reactivity, and the higher the reactivity, the lower the onset temperature. Compared to Comparative Examples 1 to 3, Examples 1 to 20 had lower onset temperatures, indicating higher reactivity. The onset temperature is preferably 85°C or lower, more preferably 83°C or lower, and even more preferably 80°C or lower. (2) Exothermic Peak Area From the DSC curve data obtained when determining the onset temperature (1) above, the exothermic peak area was calculated using analysis software (NETZSCH Proteus-Thermal Analysis version 8.0.2). This is shown in Table 1. The exothermic peak area in the DSC curve obtained by the above test represents the amount of heat generated by the resin composition during curing; the smaller the area, the smaller the amount of heat generated, making it possible to suppress overheating of peripheral components during short-term curing. The exothermic peak area in the DSC curve is preferably 420 J / g or less, more preferably 350 J / g or less, and even more preferably 300 J / g.

[0103]

[0104]

[0105]

[0106] Comparison of the resin compositions of Examples 1 to 20 with the resin composition of Comparative Example 1, which does not contain component (B) and component (E), and the resin composition of Comparative Example 3, which contains component (B) and contains component (E') instead of component (E), reveals that the inclusion of component (B) increases the onset temperature, that the inclusion of component (E) can lower the onset temperature, and that component (E') cannot lower the onset temperature as much as component (E). Furthermore, comparison of the resin compositions of Examples 1 to 20 with the resin composition of Comparative Example 1, which does not contain component (B) and component (E), and the resin composition of Comparative Example 2, which does not contain component (B) and contains component (E') instead of component (E), reveals that the inclusion of component (E') increases the exothermic peak area, whereas the inclusion of component (E) reduces the exothermic peak area.

[0107] The present invention relates to a resin composition that provides a cured product having excellent reactivity and excellent stress relaxation properties, and is extremely useful as an adhesive or sealant suitable for use in the manufacture of semiconductor devices and electronic components that are assembled by joining multiple parts made of different materials.

[0108] The disclosure of Japanese Patent Application No. 2022-173403 (filing date: October 28, 2022) is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards mentioned herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. (A) Polyfunctional epoxy compounds having an epoxy equivalent of less than 215 g / eq, (B) A polyfunctional epoxy compound having an epoxy equivalent of 215 g / eq or more. (C) Polyfunctional thiol compound, (D) Curing catalyst, and (E) Monofunctional compounds having one group (e) in the molecule that contains an unsaturated double bond and an adjacent electron-withdrawing group. A resin composition containing the following:

2. The resin composition according to claim 1, wherein component (E) is liquid at 25°C.

3. The resin composition according to claim 1, wherein component (E) is selected from a monofunctional maleimide compound and a monofunctional (meth)acrylate compound.

4. The resin composition according to claim 1, wherein the content of component (B) is 1 to 100 parts by mass per 100 parts by mass of component (A).

5. The resin composition according to claim 1, wherein the ratio of the sum of the number of epoxy group equivalents of component (A) and the number of epoxy group equivalents of component (B) to the number of thiol group equivalents of component (C) (([Epoxy group equivalents of component (A)] + [Epoxy group equivalents of component (B)]) / [Number of thiol group equivalents of component (C)]) is 0.4 to 0.

95.

6. The resin composition according to claim 1, wherein the ratio of the sum of the number of epoxy group equivalents of component (A), the number of epoxy group equivalents of component (B), and the number of group (e) equivalents of component (E) to the number of thiol group equivalents of component (C) (([Epoxy group equivalents of component (A)] + [Epoxy group equivalents of component (B)] + [Number of group (e) equivalents of component (E)]) / [Number of thiol group equivalents of component (C)]) is 0.7 to 1.

5.

7. The resin composition according to claim 1, wherein the ratio of the number of group (e) equivalents of component (E) to the number of thiol group equivalents of component (C) ([number of group (e) equivalents of component (E)]) / [number of thiol group equivalents of component (C)]) is 0.05 to 0.

7.

8. The resin composition according to claim 1, wherein the total amount of component (A) and component (B) is 51 parts by mass or more per 100 parts by mass of the total mass of the thermosetting compound.

9. The resin composition according to claim 1, wherein component (A) and component (B) contain a polyfunctional epoxy compound that is liquid at 25°C, and the amount of the polyfunctional epoxy compound that is liquid at 25°C is 50 parts by mass or more with respect to 100 parts by mass of the total mass of component (A) and component (B).

10. An adhesive or sealant comprising the resin composition according to any one of claims 1 to 9.

11. A cured product obtained by curing the resin composition according to any one of claims 1 to 9.

12. A semiconductor device or electronic component comprising the cured product described in claim 11.

13. A resin composition according to any one of claims 1 to 9, for use in curing by heat alone.

14. Use of the resin composition according to any one of claims 1 to 9 in curing by heat alone.