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

Abstract

The purpose of the present invention is to provide a resin composition and an adhesive which can be cured under low-temperature conditions, have a cured product having excellent stress relaxation properties, and have a low self-exothermic temperature in a curing reaction. The present invention provides a resin composition comprising (A) a polyfunctional epoxy compound, (B) a polyfunctional thiol compound, (C) a monofunctional compound having, in the molecule, one group (c) comprising an unsaturated double bond and an electron-withdrawing group adjacent thereto, and (D) a curing catalyst.

Description

Technical Field

[0001] The present invention relates to a resin composition, an adhesive or a sealant containing the resin composition, a cured product thereof, and a semiconductor device and an electronic component containing the cured product thereof. Background Art

[0002] At present, in the assembly and installation of components used in semiconductor devices and electronic components, such as semiconductor chips, adhesives and sealants containing curable resin compositions, especially epoxy resin compositions, are often used for the purpose of maintaining reliability. In particular, in the case of semiconductor devices or electronic components containing components that deteriorate under high temperature conditions, their manufacturing processes all need to be carried out under low temperature conditions. Therefore, for adhesives and sealants used in the manufacture of such devices or components, it is required to show sufficient curability even under low temperature conditions. As such low-temperature curable epoxy resin compositions, curable compositions using thiol curing agents as curing agents are known (for example, Patent Documents 1 or 2).

[0003] When the temperature around an assembly formed by two parts made of different materials and bonded to each other by an adhesive changes (for example, temperature changes during use or temperature changes during the cooling process after heating and curing), thermal stresses are generated in these parts according to the thermal expansion coefficients of their materials. These thermal stresses are not uniform due to the difference in thermal expansion coefficients, so they cannot be offset, resulting in deformation of the assembly. The stress accompanying this deformation acts especially on the joint of the parts, that is, the cured product of the adhesive, and causes peeling of the joint, cracking of the cured product, etc., depending on the situation. Such peeling and cracking are particularly prone to occur when the cured product is brittle and lacks flexibility. Therefore, the adhesive used to bond parts made of different materials needs to have flexibility, that is, stress relaxation characteristics, that can follow the degree of deformation of the assembly caused by the thermal stress of the parts after curing.

[0004] Patent Document 3 discloses an epoxy resin composition that cures in a short time even under low temperature conditions, has a low glass transition temperature (Tg), and provides a cured product with excellent moisture resistance reliability after curing. The epoxy resin composition comprises: (A) at least one thiol curing agent comprising a multifunctional thiol compound having three or more thiol groups; (B) at least one multifunctional epoxy resin; (C) a crosslinking density modifier comprising at least one monofunctional epoxy resin; and (D) a latent curing catalyst, wherein the number (amount) of thiol groups and the number (amount) of epoxy groups possessed by these components are in a specific relationship. Patent Document 3 discloses that the cured product of the epoxy resin composition can follow the deformation caused by the thermal expansion of the components in an assembly formed by joining a plurality of components made of different materials.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Laid-Open No. 6-211969

[0008] Patent Document 2: Japanese Patent Application Laid-Open No. 6-211970

[0009] Patent Document 3: Japanese Patent Application Publication No. 2019-156965 Summary of the invention

[0010] Problems to be solved by the invention

[0011] Although the resin composition disclosed in Patent Document 3 is cured under low temperature conditions, its cured product can follow the deformation caused by the thermal expansion of the components, but as a subject, it is found that the self-exothermic temperature in the curing reaction is high. Even if the curing conditions are low temperature conditions, when the self-exothermic temperature of the resin composition is high, there is also concern about overheating of the adherend and its surrounding components to which the resin composition is applied. The subject of the present invention is to provide a resin composition that is cured under low temperature conditions, provides a cured product with a degree of flexibility that can follow the deformation of the assembly caused by the thermal stress of the components, that is, excellent stress relaxation, and the self-exothermic temperature in the curing reaction is low.

[0012] Means for solving problems

[0013] The results of the research found that the issue was resolved through the following specific methods.

[0014] A first embodiment of the present invention is the following resin composition.

[0015] (1) A resin composition comprising:

[0016] (A) a multifunctional epoxy compound;

[0017] (B) multifunctional thiol compounds;

[0018] (C) a monofunctional compound having in its molecule one group (c) comprising an unsaturated double bond and an electron withdrawing group adjacent thereto; and

[0019] (D) Curing catalyst.

[0020] (2) The resin composition according to (1) above, wherein the component (C) is selected from the group consisting of a monofunctional maleimide compound and a monofunctional (meth)acrylate compound.

[0021] (3) The resin composition according to (1) or (2) above, wherein the component (C) is a monofunctional (meth)acrylate compound having a molecular weight of 100 to 450.

[0022] (4) The resin composition according to any one of (1) to (3) above, wherein the ratio of the number of equivalents of groups (c) of the component (C) to the number of equivalents of epoxy groups of the component (A) ([number of equivalents of groups (c) of the component (C)] / [number of equivalents of epoxy groups of the component (A)]) is 0.05 to 2.

[0023] (5) The resin composition according to any one of (1) to (4) above, wherein the ratio of the number of epoxy group equivalents of the component (A) to the number of thiol group equivalents of the component (B) ([number of epoxy group equivalents of the component (A)] / [number of thiol group equivalents of the component (B)]) is 0.4 to 0.9.

[0024] (6) The resin composition according to any one of (1) to (5), wherein the ratio of the sum of the number of epoxy group equivalents of the component (A) and the number of group (c) equivalents of the component (C) to the number of thiol group equivalents of the component (B) (([number of epoxy group equivalents of the component (A)] + [number of group (c) equivalents of the component (C)]) / [number of thiol group equivalents of the component (B)]) is 0.7 to 1.5.

[0025] (7) The resin composition according to any one of (1) to (6) above, wherein the ratio of the number of equivalents of groups (c) in component (C) to the number of equivalents of thiol groups in component (B) ([number of equivalents of groups (c) in component (C)] / [number of equivalents of thiol groups in component (B)]) is 0.05 to 0.7.

[0026] (8) The resin composition according to any one of (1) to (7) above, wherein the amount of the component (A) is 51 parts by mass or more based on 100 parts by mass of the total amount of the thermosetting compound.

[0027] (9) The resin composition according to any one of (1) to (8) above, wherein the (A) polyfunctional epoxy compound comprises 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 relative to 100 parts by mass of the total amount of the (A) polyfunctional epoxy compound.

[0028] A second aspect of the present invention is (10) an adhesive or a sealant comprising the resin composition according to any one of (1) to (9) above.

[0029] 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.

[0030] A fourth embodiment of the present invention is (12) a semiconductor device or an electronic component including the cured product described in the above (11).

[0031] One embodiment of the resin composition, adhesive or sealant is (13) the resin composition according to any one of (1) to (9) above, or the adhesive or sealant according to (10) above, which is used for curing by heat alone.

[0032] Another embodiment of the present invention is (14) use of the resin composition according to any one of (1) to (9) above, or the adhesive or sealant according to (10) above, in curing by heat alone.

[0033] Effects of the Invention

[0034] According to a first embodiment of the present invention, a resin composition that cures under low temperature conditions and provides a cured product with excellent stress relaxation can be obtained. In addition, the resin composition can suppress overheating of an adherend and its surrounding components due to the low self-exothermic temperature in the curing reaction. In addition, according to a second embodiment of the present invention, an adhesive or sealant that cures under low temperature conditions, provides a cured product with excellent stress relaxation, and can suppress overheating of an adherend and its surrounding components can be obtained. In addition, according to a third embodiment of the present invention, a cured product with excellent stress relaxation can be obtained, and overheating of an adherend and its surrounding components of the cured product can be suppressed. According to a fourth embodiment of the present invention, a semiconductor device and an electronic component can be obtained, which include a cured product with excellent stress relaxation and overheating of an adherend and its surrounding components suppressed. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 Dumbbell-shaped test piece used for tensile testing. DETAILED DESCRIPTION

[0036] In this specification, in accordance with the customary practice in the field of synthetic resins, a name including the term "resin" generally referring to a polymer (particularly a synthetic polymer) is sometimes used for a component constituting a curable resin composition before curing, even though the component is not a polymer.

[0037] In the present specification, “a cured product having excellent stress relaxation properties” means a cured product having flexibility to such an extent that it can follow the deformation of an assembled product caused by thermal stress of a component.

[0038] In this specification, the "self-exothermic temperature" of a resin composition refers to the temperature of the resin composition itself during thermal curing. The maximum value of the self-exothermic temperature of the resin composition can be obtained as the maximum value (maximum exothermic temperature) of the sample temperature when thermogravimetric-differential thermal measurement (TG-DTA measurement) is performed under curing reaction conditions at a certain temperature.

[0039] [Resin composition]

[0040] A resin composition as a first embodiment of the present invention includes:

[0041] (A) a multifunctional epoxy compound;

[0042] (B) multifunctional thiol compounds;

[0043] (C) a monofunctional compound having in its molecule one group (c) comprising an unsaturated double bond and an electron withdrawing group adjacent thereto; and

[0044] (D) Curing catalyst.

[0045] According to the present embodiment, it is possible to obtain a resin composition that cures under low temperature conditions, provides a cured product having excellent stress relaxation properties, and has a low self-exothermic temperature during the curing reaction.

[0046] (A) Multifunctional Epoxy Compounds

[0047] The resin composition of the present embodiment includes (A) a polyfunctional epoxy compound (hereinafter also referred to as "component (A)"). The polyfunctional epoxy compound (A) is not particularly limited as long as it is a compound having at least two epoxy groups, and conventionally commonly used epoxy resins can be used as component (A). Epoxy resin is a general term for thermosetting resins that can be cured by cross-linking and networking using epoxy groups present in the molecule, and includes prepolymer compounds before curing. If the aspect of ensuring heat resistance is taken into consideration, as component (A), a compound having 2 to 6 epoxy groups is more preferred, and a compound having 2 epoxy groups is further preferred. The polyfunctional epoxy compound (A) can be in a liquid state or a solid state at 25°C, and is preferably in a liquid state at 25°C. In one embodiment, the amount of the (A) polyfunctional epoxy compound that is 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 100 parts by mass of the total amount of the (A) polyfunctional epoxy compound. In one embodiment, the (A) polyfunctional epoxy compound includes 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 the (A) polyfunctional epoxy compound that is 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 amount of the (A) polyfunctional epoxy compound.

[0048] (A) Polyfunctional epoxy compounds are roughly divided into aromatic polyfunctional epoxy compounds and polyfunctional epoxy compounds having no aromatic ring.

[0049] Aromatic polyfunctional epoxy compounds are polyfunctional epoxy compounds having a structure containing an aromatic ring such as a benzene ring. Among the epoxy resins frequently used in the past, such as bisphenol A type epoxy compounds, there are many such epoxy resins. Examples of aromatic polyfunctional epoxy compounds include:

[0050] -Bisphenol A type epoxy compounds;

[0051] - branched multifunctional bisphenol A type epoxy compounds such as p-glycidyloxyphenyl dimethyl trisphenol A diglycidyl ether;

[0052] -Bisphenol F type epoxy compounds;

[0053] -phenolic epoxy compounds;

[0054] -Tetrabromobisphenol A type epoxy compounds;

[0055] -Fluorene epoxy compounds;

[0056] -biphenyl aralkyl epoxides;

[0057] - Diepoxides such as 1,4-phenylenedimethanol diglycidyl ether;

[0058] -Biphenyl type epoxy compounds such as 3,3',5,5'-tetramethyl-4,4'-diglycidyloxybiphenyl;

[0059] - glycidylamine type epoxy compounds such as diglycidylaniline, diglycidyltoluidine, triglycidyl-p-aminophenol, tetraglycidyl-m-xylylenediamine; and

[0060] -Naphthalene ring-containing epoxy compounds, etc., but not limited to these. They can be used alone or in combination of two or more. From the viewpoint of compatibility with the (B) polyfunctional thiol compound, component (A) preferably contains an aromatic polyfunctional epoxy compound. As aromatic polyfunctional epoxy compounds, bisphenol F type epoxy compounds, bisphenol A type epoxy compounds and glycidylamine type epoxy compounds are preferred, among which the epoxy equivalent is more preferably 90 to 500 g / eq, and the epoxy equivalent is further preferably 90 to 400 g / eq. The aromatic polyfunctional epoxy compound can be subjected to oxyalkylene modification such as EO (ethylene oxide) modification and PO (propylene oxide) modification. The aromatic polyfunctional epoxy compound is preferably liquid at 25°C. The viscosity of the aromatic polyfunctional epoxy compound 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.

[0061] In this specification, the viscosity is expressed as a value measured in accordance with Japanese Industrial Standard JIS K6833 unless otherwise specified. Specifically, it can be obtained by measuring using an E-type viscometer at a rotation speed of 10 rpm. There are no particular restrictions on the equipment, rotor or measurement range used.

[0062] The polyfunctional epoxy compound having no aromatic ring includes, for example, an aliphatic polyfunctional epoxy compound and a polyfunctional epoxy compound having a heterocyclic ring.

[0063] Examples of aliphatic polyfunctional epoxy compounds include:

[0064] - 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 glycol diglycidyl ether, glycerol diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexane diglycidyl ether, and dicyclopentadiene diglycidyl ether;

[0065] - triepoxy compounds such as trimethylolpropane triglycidyl ether and glycerol triglycidyl ether;

[0066] - Alicyclic epoxy compounds such as vinyl (3,4-cyclohexene) dioxide and 2-(3,4-epoxycyclohexyl)-5,1-spiro-(3,4-epoxycyclohexyl)-m-dioxane;

[0067] - Hydrogenated bisphenol A type diepoxides such as hydrogenated bisphenol A diglycidyl ether;

[0068] - Glycidylamine-type epoxy compounds such as tetraglycidylbis(aminomethyl)cyclohexane;

[0069] -Hydantoin-type epoxy compounds such as 1,3-diglycidyl-5-methyl-5-ethylhydantoin; and

[0070] -1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane and the like, but not limited thereto.

[0071] The epoxy equivalent of the aliphatic polyfunctional epoxy compound is preferably 90 to 450 g / eq. The aliphatic polyfunctional epoxy compound is preferably liquid at 25° C. The viscosity of the aliphatic polyfunctional epoxy compound at 25° C. is preferably 10 to 10,000 mPa·s, more preferably 10 to 5,000 mPa·s.

[0072] Examples of the polyfunctional epoxy compound having a heterocyclic ring include isocyanurate epoxy compounds (manufactured by Nissan Chemical Co., Ltd., trade names: TEPIC-S, TEPIC-L, TEPIC-PAS, TEPIC-VL, TEPIC-FL, TEPIC-UC) and glycoluril epoxy compounds (manufactured by Shikoku Chemical Co., Ltd., trade name: TG-G).

[0073] The epoxy equivalent of the polyfunctional epoxy compound having a heterocyclic ring is preferably 80 to 450 g / eq. From the viewpoint of workability, the polyfunctional epoxy compound having a heterocyclic ring is preferably liquid at 25°C. The viscosity of the polyfunctional epoxy compound having a heterocyclic ring at 25°C is preferably 100 to 50,000 mPa·s, more preferably 100 to 5,000 mPa·s. On the other hand, from the viewpoint of adhesion, the polyfunctional epoxy compound having a heterocyclic ring is preferably solid at 25°C.

[0074] (B) Multifunctional thiol compounds

[0075] The resin composition of the present embodiment includes (B) a polyfunctional thiol compound (hereinafter also referred to as "component (B)"). In the present embodiment, the (B) polyfunctional thiol compound is a compound including two or more thiol groups, which react with the epoxy group in the (A) polyfunctional epoxy compound and the group (c) in the monofunctional compound having a group (c) containing an unsaturated double bond and an electron-withdrawing group adjacent thereto in the molecule (C). In the present embodiment, the (B) polyfunctional thiol compound preferably has three or more thiol groups. The (B) polyfunctional thiol compound more preferably includes a trifunctional thiol compound and / or a tetrafunctional thiol compound. Trifunctional and tetrafunctional thiol compounds are thiol compounds having three and four thiol groups, respectively. The thiol equivalent of the (B) polyfunctional thiol compound is preferably 90 to 200 g / eq, more preferably 90 to 150 g / eq, further preferably 90 to 140 g / eq, particularly preferably 90 to 130 g / eq.

[0076] Polyfunctional thiol compounds are roughly divided into thiol compounds having a hydrolyzable partial structure such as an ester bond in the molecule (ie, hydrolyzable thiol compounds) and thiol compounds not having such a partial structure (ie, non-hydrolyzable thiol compounds).

[0077] Examples of the hydrolyzable multifunctional thiol compound include trimethylolpropane tris(3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd., trade name: TMMP), tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate (manufactured by SC Organic Chemical Co., Ltd., trade name: TEMPIC), pentaerythritol tetrakis(3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd., trade name: PEMP), tetraethylene glycol bis(3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd., trade name: EGMP-4), dipentaerythritol hexa(3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd., trade name: DPMP), pentaerythritol tetrakis(3-mercaptobutyrate) (manufactured by Showa Denko K.K., trade name: KARENZ MT (registered trademark) PE1), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by Showa Denko K.K., trade name: KARENZMT (registered trademark) NR1), etc. These may be used alone or in combination of two or more.

[0078] Examples of the non-hydrolyzable polyfunctional thiol compound include 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril (manufactured by Shikoku Chemicals Co., Ltd., trade name: TS-G), 1,3,4,6-tetrakis(3-mercaptopropyl)glycoluril (manufactured by Shikoku Chemicals Co., Ltd., trade name: C3 TS-G), 1,3,4,6-tetrakis(mercaptomethyl) glycoluril, 1,3,4,6-tetrakis(mercaptomethyl)-3a-methyl glycoluril, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a-methyl glycoluril, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a-methyl glycoluril, 1,3,4,6-tetrakis(mercaptomethyl)-3a,6a-dimethyl glycoluril, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a,6a-dimethyl glycoluril, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a,6a-dimethyl glycoluril, 1,3,4,6-tetrakis(mercaptomethyl)-3a,6a-diphenyl glycoluril, 1,3,4,6 -Tetrakis(2-mercaptoethyl)-3a,6a-diphenyl glycoluril, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a,6a-diphenyl glycoluril, tris(3-mercaptopropyl) isocyanurate, 1,3,5-tris[3-(2-mercaptoethylthio)propyl]isocyanurate, 1,3,5-tris[2-(3-mercaptopropoxy)ethyl]isocyanurate, pentaerythritol tripropylthiol (manufactured by SC Organic Chemicals Co., Ltd., trade name: PEPT), 3-[2,3-bis(3-sulfanylpropoxy)propoxy]propane-1-thiol y]propan-1-thiol), 3-[2,2-bis[(3-mercaptopropoxy)methyl]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 1,1,5,5-tetrakis(mercaptomethylthio)-3-thiapentane, 1,1,6,6-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-dithianonane, 1,1,9,9-tetrakis(mercaptomethylthio)-5-(3,3-bis(mercaptomethylthio)-1-thiapropyl)3,7-dithianonane, tris(2,2-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-hexa(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-hexa(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- 9-[2-(1,3-dithiol)]methyl-3,5,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,6,8,10,12,16-hexathiaheptadecane, 3-[2-(1,3-dithiol)]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]-1,3-dithiolane 4-[3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiooctyl]-5-mercaptomethylthio-1,3-dithiolane, 2-[(3,4-bis(mercaptomethylthio)methyl-6-mercapto-2,5-dithiohexylthio)-5-mercaptomethylthio-1,3-dithiolane 2-[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]mercaptomethylthiomethyl-1,3-dithiacyclobutane, 2-[3,4,8,9-tetrakis(mercaptomethylthio)-11-mercapto-2,5,7,10-tetrathiaundecylthio]mercaptomethylthiomethyl-1,3-dithiacyclobutane, 2-[ 3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiaoctyl]mercaptomethylthiomethyl-1,3-dithiacyclopentane, 4-{1-[2-(1,3-dithiacyclopentane)]-3-mercapto-2-thiapropylthio}-5-[1,2-bis(mercaptomethylthio)-4-mercapto-3-thiabutylthio]-1,3-dithiacyclopentane, etc. These may be used alone or in combination of two or more.

[0079] (C) A monofunctional compound having in the molecule one group (c) containing an unsaturated double bond and an electron-withdrawing group adjacent thereto

[0080] The resin composition of the present embodiment includes a monofunctional compound (hereinafter also referred to as "component (C)") having a group (c) (hereinafter also referred to as "group (c)") containing an unsaturated double bond and an electron-withdrawing group adjacent thereto in the (C) molecule. In the present embodiment, the group (c) in the component (C), more specifically the unsaturated double bond in the group (c), reacts with the thiol group in the (B) polyfunctional thiol compound. In this specification, the term "monofunctional" is used with respect to the component (C) to mean that the molecule has one group (c) that reacts with the thiol group. Examples of electron-withdrawing groups include a carbonyl group and a cyano group, preferably a carbonyl group.

[0081] By including component (C), the rise of the self-exothermic temperature in the curing reaction of the resin composition is suppressed. The reason is not limited, but it is considered as follows. The unsaturated double bond of the group (c) in the component (C) is highly reactive because it is adjacent to the electron-withdrawing group, and reacts with the thiol group in the (B) multifunctional thiol compound before the epoxy group in the (A) multifunctional epoxy compound. Therefore, the exothermic peak accompanying the curing reaction is shifted, the reaction heat is dispersed, and the rise of the self-exothermic temperature is suppressed. On the other hand, it is believed that the reaction system of the resin composition described in Patent Document 3 is mainly based on the reaction of epoxy-thiol, so the reaction heat is not dispersed, and the self-exothermic temperature rises. The reaction of epoxy-thiol generates reaction heat caused by the ring-opening reaction of the epoxy group. In contrast, the reaction of component (C) is not accompanied by ring opening, so it is believed that the resin composition of this embodiment has a lower self-exothermic temperature than the resin composition described in Patent Document 3 that is mainly based on the reaction of epoxy-thiol. From the viewpoint of suppressing overheating of the adherend to which the resin composition of the present invention is applied and its peripheral members, the temperature difference between the curing temperature and the maximum value of the self-exothermic temperature (maximum exothermic temperature) is preferably 20° C. or less, more preferably 15° C. or less, and further preferably 10° C. or less. The maximum value of the self-exothermic temperature (maximum exothermic temperature) is preferably 100° C. or less, more preferably 95° C. or less, and further preferably 90° C. or less.

[0082] In addition, since the component (C) is monofunctional, no crosslinking is formed, and an increase in the internal stress of the cured product due to an excessively high crosslinking density can be suppressed, thereby imparting flexibility to the cured product of the obtained resin composition.

[0083] From the viewpoint of the viscosity of the resin composition, the component (C) is preferably in a liquid state at 25°C.

[0084] Examples of component (C) include monofunctional maleimide compounds, monofunctional (meth)acrylate compounds, and monofunctional acrylamide compounds. Group (c) includes maleimide groups and (meth)acryloyl groups. In the present embodiment, component (C) is preferably selected from monofunctional maleimide compounds and monofunctional (meth)acrylate compounds, and more preferably monofunctional (meth)acrylate compounds.

[0085] The monofunctional maleimide compound is a compound having one maleimide group as the group (c), and examples thereof include maleimide; maleimides containing aliphatic hydrocarbon groups such as methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, and cyclohexylmaleimide; maleimides containing aromatic rings such as phenylmaleimide, etc. These may be used alone or in combination of two or more.

[0086] The monofunctional (meth)acrylate compound is a compound having one (meth)acryloyl group as the group (c). Examples of the monofunctional (meth)acrylate compound include:

[0087] -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, phenoxy Esters of (meth)acrylic acid with monohydric alcohols such as diethylene glycol (meth)acrylate, phenoxypolyethylene 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-phenoxy (meth)acrylate Propyl acrylate, octyl acrylate, nonyl acrylate, isononyl acrylate, 3,3,5-trimethylcyclohexyl acrylate, cyclic trimethylolpropane formal acrylate, 1-naphthyl (meth)acrylate, 1-ethylcyclohexyl (meth)acrylate, 1-methylcyclohexyl (meth)acrylate, 1-ethylcyclopentyl (meth)acrylate, 1-methylcyclopentyl (meth)acrylate, 1-methylcyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentyl (meth)acrylate, nonylphenoxy polyethylene glycol (meth)acrylate, tetrahydrodicyclopentadienyl (meth)acrylate, 2-(o-phenylphenoxy)ethyl (meth)acrylate, isoborneol (meth)acrylate cyclohexyl (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-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, 2-isopropyladamantyl-2-yl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, (adamantyl-1-yloxy)methyl (meth)acrylate, 2-isopropyl-2-adamantyl (meth)acrylate, 1-methyl-1-ethyl-1-adamantyl methyl (meth)acrylate, 1,1-diethyl-1-adamantylmethyl ester, 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-oxatetrahydrofuran-3-yl (meth)acrylate, (5-oxatetrahydrofuran-2-yl)methyl (meth)acrylate, (2-oxa-1,3-dioxolan-4-yl)methyl (meth)acrylate, N-acryloyloxyethylhexahydrophthalimide, α-acryloyl-ω-methoxypoly(oxyethylene), mono(meth)acrylate of a polyol such as 1-ethoxyethyl (meth)acrylate, or esters of a monohydric alcohol and (meth)acrylic acid. These may be used alone or in combination of two or more. From the viewpoint of stress relaxation of the cured product, the molecular weight of the monofunctional (meth)acrylate compound is preferably 450 or less, more preferably 400 or less, further preferably 380 or less, further preferably 350 or less, and particularly preferably 300 or less. In order to prevent contamination of peripheral components due to volatilization, the monofunctional (meth)acrylate compound is preferably low-volatile, and its molecular weight is preferably 100 or more, more preferably 120 or more, further preferably 160 or more, particularly preferably 190 or more, and most preferably 200 or more. In a certain embodiment, the molecular weight of the monofunctional (meth)acrylate compound is preferably 100 to 450, more preferably 120 to 400, further preferably 140 to 380, particularly preferably 180 to 350, and most preferably 200 to 320. ,

[0088] Component (C) may have a group reactive with a thiol group, such as an epoxy group, in addition to group (c). In view of the flexibility of the obtained cured product, component (C) may preferably not contain a group reactive with a thiol group, such as an epoxy group.

[0089] In the present embodiment, from the viewpoint of achieving both flexibility and adhesive strength, the ratio of the number of equivalents of the group (c) of the component (C) to the number of equivalents of the epoxy group of the component (A) ([number of equivalents of the group (c) of the component (C)] / [number of equivalents of the epoxy group of the component (A)]) is preferably 0.05 to 2, more preferably 0.1 to 1.5, further preferably 0.15 to 1.25, and particularly preferably 0.2 to 1.

[0090] In the present embodiment, the ratio of the number of epoxy group equivalents of the component (A) to the number of thiol group equivalents of the component (B) ([number of epoxy group equivalents of the component (A)] / [number of thiol group equivalents of the component (B)]) is preferably 0.4 to 0.95, more preferably 0.45 to 0.9, further preferably 0.5 to 0.9, and particularly preferably 0.55 to 0.9.

[0091] In the present embodiment, from the viewpoint of curability and suppression of bleed-out, the ratio of the sum of the epoxy group equivalent number of component (A) and the group (c) equivalent number of component (C) to the thiol group equivalent number of component (B) (([epoxy group equivalent number of component (A)] + [group (c) equivalent number of component (C)]) / [thiol group equivalent number of component (B)]) is preferably 0.7 to 1.5, more preferably 0.75 to 1.4, further preferably 0.8 to 1.3, and most preferably 0.8 to 1.1. In particular, by adding a certain amount of component (B) to component (A) and component (C), the residue of unreacted components that cannot react with thiol groups can be suppressed, and the bleed-out caused by the unreacted components can be suppressed. In addition, it is also expected that the volatile components are suppressed. In this specification, "bleeding" refers to a phenomenon in which unreacted components ooze out from an adhesive coating or cured product over time when an adhesive comprising a curable resin composition is used to fix or bond parts. The oozing components themselves may also be referred to as "bleeding".

[0092] In the present embodiment, the ratio of the number of equivalents of groups (c) of component (C) to the number of equivalents of thiol groups of component (B) ([number of equivalents of groups (c) of component (C)] / [number of equivalents of thiol groups of component (B)]) is preferably 0.05 to 0.7, more preferably 0.1 to 0.6, and even more preferably 0.15 to 0.55.

[0093] When component (C) contains an epoxy group, it is preferred that the above-mentioned relationship of equivalent numbers is satisfied when the epoxy group equivalent number of component (C) is added to the epoxy group equivalent number of component (A).

[0094] In this specification, functional group equivalents such as thiol equivalent, epoxy equivalent, (meth)acryloyl equivalent, etc. represent the molecular weight of the compound per one functional group, and functional group equivalent numbers such as thiol equivalent number, epoxy equivalent number, (meth)acryloyl equivalent number, etc. represent the number (equivalent number) of functional groups per unit compound mass (feed amount).

[0095] The epoxy equivalent of component (A) is theoretically the number obtained by dividing the molecular weight of component (A) 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 equivalent number of component (A) is the number of epoxy groups (equivalent number) per unit mass (feed amount) of component (A), and is the quotient obtained by dividing the mass (g) of the epoxy compound as component (A) by the epoxy equivalent of the epoxy compound (when more than one epoxy compound is included, it is the sum of such quotients of each epoxy compound). When component (C) contains an epoxy group, its epoxy equivalent and epoxy equivalent number are determined by the same method.

[0096] The thiol equivalent of component (B) is theoretically the number obtained by dividing the molecular weight of component (B) by the number of thiol groups in one molecule. The actual thiol equivalent can be determined by, for example, obtaining the thiol value by potentiometric measurement. This method is well known and disclosed, for example, in paragraph 0079 of Japanese Patent Application Laid-Open No. 2012-153794. The thiol equivalent number of component (B) is the number (equivalent number) of thiol groups per unit mass (feed amount) of component (B), and is the quotient obtained by dividing the mass (g) of the polythiol compound of component (B) by the thiol equivalent of the polythiol compound (when more than one polythiol compound is included, it is the sum of such quotients of each polythiol compound).

[0097] When the group (c) is a (meth)acryloyl group, the (meth)acryloyl equivalent of the component (C) is theoretically equal to the number obtained by dividing the molecular weight of the (meth)acrylic acid ester compound by the number of acryloyl groups (or methacryloyl groups) in one molecule. The actual (meth)acryloyl equivalent can be measured by, for example, NMR. The (meth)acryloyl equivalent of the component (C) is the number (equivalent number) of (meth)acryloyl groups per unit mass (feed amount) of the component (C), and is the quotient obtained by dividing the mass (g) of the (meth)acrylic acid ester compound of the component (C) by the (meth)acrylic acid ester equivalent of the (meth)acrylic acid ester compound (when more than one (meth)acrylic acid ester compound is included, it is the sum of such quotients of each (meth)acrylic acid ester compound).

[0098] When group (c) is a maleimide group, the maleimide equivalent of component (C) is theoretically equal to the number obtained by dividing the molecular weight of the maleimide compound by the number of maleimide groups in one molecule. The actual maleimide equivalent can be measured by, for example, NMR. The maleimide equivalent number of component (C) is the number (equivalent number) of maleimide groups per unit mass (feed amount) of component (C), and is the quotient obtained by dividing the mass (g) of the maleimide compound as component (C) by the maleimide equivalent of the maleimide compound (when more than one maleimide compound is included, it is the sum of such quotients of each maleimide compound).

[0099] (D) Curing catalyst

[0100] The resin composition of the present embodiment includes (D) a curing catalyst (hereinafter, also referred to as "component (D)"). By using component (D), the resin composition of the present embodiment can be cured in a short time even under low temperature conditions. The curing catalyst used in the present embodiment is not particularly limited as long as it is a curing catalyst of the (A) multifunctional epoxy compound, and a known curing catalyst can be used.

[0101] Component (D) is preferably a latent curing catalyst. A latent curing catalyst refers to a compound that is inactive at room temperature and is activated by heating to function as a curing catalyst. Examples of latent curing catalysts 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 adduct type latent curing catalysts); reaction products of amine compounds and isocyanate compounds or urea compounds (urea-type adduct type latent curing catalysts), etc. As component (D), from the viewpoint of pot life and curability, a solid-dispersed amine adduct type latent curing catalyst is preferred.

[0102] 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, 2,4-diamino-6-(2'-methylimidazolyl-(1')')-ethyl-S-triazine-isocyanuric acid adduct, 2 -methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazole trimellitate, N-(2-methylimidazolyl-1-ethyl)-urea, N,N'-(2-methylimidazolyl-(1)-ethyl)-adipoyldiamide (Japanese: アジボイルジアミド, English: adipoyldiamide), etc., but are not limited to these.

[0103] Examples of epoxy compounds used as one of the raw materials for producing solid dispersion type amine adduct latent curing catalysts (amine-epoxy adduct type latent curing catalysts) include polyglycidyl ethers obtained by reacting polyphenols such as bisphenol A, bisphenol F, catechol, and resorcinol, or polyols such as glycerol and polyethylene glycol 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, m-aminophenol, etc. with epichlorohydrin; and polyfunctional epoxy compounds such as epoxidized phenol novolac resins, epoxidized cresol novolac resins, and epoxidized polyolefins; monofunctional epoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, and glycidyl methacrylate, etc., but are not limited thereto.

[0104] The amine compound used as another raw material for manufacturing the latent curing catalyst of the solid-dispersible amine adduct has only one or more active hydrogens capable of undergoing addition reaction with the epoxy group in the molecule and at least one or more functional groups selected from the group consisting of primary amino groups, secondary amino groups and tertiary amino groups in the molecule. Examples of such amine compounds are shown below, but are not limited to them. Such amine compounds include: 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; heterocyclic compounds containing nitrogen atoms such as 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline, piperidine, and piperazine, but are not limited to them.

[0105] Among them, compounds having a tertiary amino group in the molecule are raw materials for providing a latent curing catalyst having excellent curing accelerating ability. Examples of such compounds include: amine compounds such as dimethylaminopropylamine, diethylaminopropylamine, di-n-propylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, and N-methylpiperazine; primary or secondary amines having a tertiary amino group in the molecule such as imidazole compounds such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, and 2-phenylimidazole; 2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol, 1-(2-hydroxy-3-phenoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-ethyl-4-methylimidazole, 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazole, 1 The invention also includes, but is not limited to, alcohols, phenols, thiols, carboxylic acids and hydrazides having a tertiary amino group in the molecule, such as -(2-hydroxy-3-butoxypropyl)-2-ethyl-4-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-phenylimidazoline, 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazoline, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol, N-β-hydroxyethylmorpholine, 2-dimethylaminoethanethiol, 2-mercaptopyridine, 2-benzimidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 4-mercaptopyridine, N,N-dimethylaminobenzoic acid, N,N-dimethylglycine, nicotinic acid, isonicotinic acid, picolinic acid, N,N-dimethylglycine hydrazide, N,N-dimethylpropionic acid hydrazide, nicotinic acid hydrazide and isonicotinic acid hydrazide.

[0106] Examples of isocyanate compounds used as another raw material for manufacturing the solid-dispersible 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, toluene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, p-phenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, and bicycloheptane triisocyanate; compounds containing terminal isocyanate groups obtained by reacting the above-mentioned polyfunctional isocyanate compounds with active hydrogen compounds, etc., but are not limited to these. Examples of such terminal isocyanate group-containing compounds include, but are not limited to, an addition compound having a terminal isocyanate group obtained by the reaction of toluene diisocyanate and trimethylolpropane, an addition compound having a terminal isocyanate group obtained by the reaction of toluene diisocyanate and pentaerythritol, and the like.

[0107] In addition, examples of the urea compound include urea and thiourea, but are not limited to these.

[0108] The solid dispersion type latent curing catalyst that can be used in the present embodiment is, for example, the above-mentioned combination of (a) two components of an amine compound and an epoxy compound, (b) a combination of three components of the two components and an active hydrogen compound, or (c) a combination of two or three components of 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 of room temperature to 200° C., cooling and solidifying the reaction product, and then crushing it, or reacting these components in a solvent such as methyl ethyl ketone, dioxane, and tetrahydrofuran, removing the solvent from the reaction product, and then crushing its solid component.

[0109] Representative examples of commercially available products of latent curing catalysts include, as amine-epoxy adduct-type products (amine adducts), "Ajicure PN-23" (trade name of Ajinomoto Fine-Techno Co., Ltd.), "Ajicure PN-40" (trade name of Ajinomoto Fine-Techno Co., Ltd.), "Ajicure PN-50" (trade name of Ajinomoto Fine-Techno Co., Ltd.), "Hardner X-3661S" (trade name of ACR Corporation), "Hardner X-3670S" (trade name of ACR Corporation), "Novacure HX-3742" (trade name of Asahi Kasei Corporation), "Novacure HX-3721" (trade name of Asahi Kasei Corporation), "Novacure HXA9322HP" (trade name of Asahi Kasei Corporation), "Novacure HXA3922HP" (trade name of Asahi Kasei Corporation), "Novacure HXA3932HP" (trade name of Asahi Kasei Co., Ltd.), "Novacure HXA5945HP" (trade name of Asahi Kasei Co., Ltd.), "NovacureHXA5911HP" (trade name of Asahi Kasei Co., Ltd.), "Novacure HXA9382HP" (trade name of Asahi Kasei Co., Ltd.), etc.; as the urea type adduct, "Fujicure FXE-1000" (trade name of T&K TOKA Co., Ltd.), FujicureFXR1020" (trade name of T&K TOKA Co., Ltd.), "Fujicure FXR-1030" (trade name of T&K TOKA Co., Ltd.), "Fujicure FXR1121" (trade name of T&K TOKA Co., Ltd.), "Fujicure FXR1081" (trade name of T&K TOKA Co., Ltd.), "Fujicure FXR1061" (T&K TOKA Co., Ltd.), "Fujicure FXR1171" (T&K TOKA Co., Ltd. trade name), etc., but are not limited to these. Component (D) may be used alone or in combination of two or more.

[0110] The resin composition preferably contains the component (D) 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.

[0111] It should be noted that the component (D) may be provided in the form of a dispersion dispersed in the polyfunctional epoxy compound. It should be noted that when the component (D) in such a form is used, the amount of the polyfunctional epoxy compound in which the component (D) is dispersed is also included in the amount of the component (A) present in the resin composition of the present embodiment.

[0112] The resin composition of the present embodiment may contain optional components other than the above-mentioned components (A) to (D), for example, the optional components described below, as necessary.

[0113] The resin composition of the present embodiment may contain thermosetting compounds other than component (A) within a range that does not impair the effects of the present invention. In this specification, "thermosetting compounds other than component (A)" refers to polyfunctional thermosetting compounds other than component (A) that can react with the thiol group of component (B), excluding component (B). As thermosetting compounds other than component (A), for example, (E) polyfunctional (meth)acrylate compounds, phenol compounds, bismaleimide compounds, cyanate compounds, episulfide compounds, etc. can be cited. Episulfide compounds refer to compounds containing ethylene sulfide rings in which all or part of the oxygen atoms of the ethylene oxide ring of the epoxy compound are replaced by sulfur atoms. Examples of episulfide compounds include compounds containing two or more ethylene sulfide rings in the molecule and compounds containing one or more ethylene sulfide rings and ethylene oxide rings in the molecule. In the resin composition of the present embodiment, the amount of component (A) relative to 100 parts by mass of the total amount of the thermosetting compound (excluding 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.

[0114] (E) Multifunctional (meth)acrylate compounds

[0115] The resin composition of the present embodiment may contain (E) a polyfunctional (meth)acrylate compound (hereinafter also referred to as “component (E)”) within a range that does not impair the effects of the present invention.

[0116] Examples of the polyfunctional (meth)acrylate compound 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; polyacrylate and / or polymethacrylate of dipentaerythritol; tris(acryloyloxyethyl)isocyanurate; Caprolactone-modified tris(acryloyloxyethyl)isocyanurate; caprolactone-modified tris(methacryloyloxyethyl)isocyanurate; alkyl-modified dipentaerythritol polyacrylate and / or polymethacrylate; caprolactone-modified dipentaerythritol polyacrylate and / or polymethacrylate; ethoxylated bisphenol A diacrylate and / or ethoxylated bisphenol A dimethacrylate; dihydrocyclopentadiethyl acrylate and / or dihydrocyclopentadiethyl methacrylate, and polyester acrylate and / or polyester methacrylate, dimethylol-tricyclodecane diacrylate, poly(meth)acrylate of ditrimethylolpropane, polyurethane having two or more (meth)acryloyl groups in one molecule, polyester having two or more (meth)acryloyl groups in one molecule, etc., but not limited to these.

[0117] Any one of the above-mentioned polyfunctional (meth)acrylate compounds may be used alone, or two or more of them may be used in combination.

[0118] Examples of commercially available polyfunctional (meth)acrylate compounds include polyester acrylate (trade name: EBECRYL 810) manufactured by Daicel-Allnex Corporation, ditrimethylolpropane tetraacrylate (trade name: EBECRYL 140) manufactured by Daicel-Allnex Corporation, polyester acrylate (trade name: M7100) manufactured by Toagosei Co., Ltd., dimethylol-tricyclodecane diacrylate (trade name: Light Acrylate DCP-A) manufactured by Kyoeisha Chemical Co., Ltd., and neopentyl glycol-modified trimethylolpropane diacrylate (trade name: KAYARAD R-604) manufactured by Nippon Kayaku Co., Ltd.

[0119] (F) Filling

[0120] The resin composition of the present embodiment may contain a filler (F) (hereinafter also referred to as "component (F)") within a range that does not impair the effects of the present invention. By containing a filler (F) in the resin composition, the linear expansion coefficient of the cured product formed by curing the resin composition can be reduced, thereby improving heat cycle resistance. In addition, if the filler has a low elastic modulus, the stress generated in the cured product can be alleviated, and the long-term reliability can be improved. The filler (F) is roughly divided into an inorganic filler and an organic filler.

[0121] As long as the inorganic filler contains a granular body formed by an inorganic material and has the effect of reducing the linear expansion coefficient by addition, there is no particular limitation. As the inorganic material, silicon dioxide, talc, aluminum oxide, 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, boron nitride, etc. can be used. Any one of the inorganic fillers can be used, or two or more can be used in combination. As the inorganic filler, from the aspect of being able to increase the filling amount, a silicon dioxide filler is preferably used. Silica is preferably amorphous silicon dioxide. The surface of the inorganic filler can be surface treated with a coupling agent such as a silane coupling agent.

[0122] Examples of the organic filler include polytetrafluoroethylene (PTFE) fillers, silicone fillers, acrylic fillers, fillers having a urethane skeleton, fillers having a butadiene skeleton, styrene fillers, etc. The organic filler may be surface treated.

[0123] The shape of the filler is not particularly limited, and may be any of spherical, flaky, needle-shaped, and irregular shapes.

[0124] The average particle size of the filler is preferably 6.0 μm or less, more preferably 5.0 μm or less, and further preferably 4.0 μm or less. In this specification, unless otherwise specified, the average particle size refers to the volume-based median particle size (d ) measured by laser diffraction according to ISO-13320 (2009). 50). By making the average particle size of the filler below the upper limit, the sedimentation of the filler can be suppressed. It also suppresses the formation of coarse particles, suppresses the wear of the nozzle of the jet distributor, and suppresses the scattering of the resin composition sprayed from the nozzle of the jet distributor to the outside of the desired area. The lower limit of the average particle size of the filler is not particularly limited. From the perspective of the viscosity of the resin composition, it is preferably 0.005 μm or more, and more preferably 0.1 μm or more. In a certain mode of the present embodiment, the average particle size of the (F) filler 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 also be used in combination. For example, a filler having an average particle size of 0.005 μm or more and 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.

[0125] The content of the filler in the resin composition of the present embodiment is preferably 15 to 50% by mass, more preferably 20 to 45% by mass, and further preferably 20 to 40% by mass relative to the total mass of the resin composition. By setting the content of the filler to the above range, the heat cycle resistance is improved, and the viscosity of the resin composition is set to an appropriate range, thereby improving the applicability to distribution.

[0126] (G) Photoradical initiator

[0127] The resin composition of the present embodiment may contain (G) a photoradical initiator (hereinafter also referred to as "component (G)") within a range that does not impair the effects of the present invention. By containing the (G) photoradical initiator, the reaction of the component (B) with the component (C) and the optional component (E) by light irradiation is promoted.

[0128] (G) As a photoradical initiator, an alkylphenone type compound, an acylphosphine oxide type compound, etc. are mentioned, for example.

[0129] Examples of the alkylphenone compounds include benzyl dimethyl ketal such as 2,2-dimethoxy-1,2-diphenylethane-1-one (Omnirad 651 manufactured by IGM Resins BV as a commercial product); α-aminoalkylphenone such as 2-methyl-2-morpholino (4-thiomethylphenyl) propane-1-one (Omnirad 907 manufactured by IGM Resins BV as a commercial product); α-hydroxyalkylphenone such as 1-hydroxy-cyclohexyl-phenyl-ketone (Omnirad 184 manufactured by IGM Resins BV as a commercial product); 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butane-1-one (Omnirad 200 manufactured by IGM Resins BV as a commercial product); 379EG), 2-benzyl-2-(dimethylamino)-4′-morpholinobutyrophenone (commercially available product: Omnirad 369 manufactured by IGM Resins BV), and the like.

[0130] Examples of the acylphosphine oxide-based compounds include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (a commercial product is Omnirad TPO H manufactured by IGM Resins BV) and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (a commercial product is Omnirad 819 manufactured by IGM Resins BV).

[0131] (G) The photoradical initiator includes, in addition to the above-mentioned photoradical initiators, 2-hydroxy-2-methyl-1-phenylpropane-1-one, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropane-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, Benzoin phenyl ether, benzil dimethyl ketal, benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropyl thioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methyl phenyl glyoxylate, benzil, camphorquinone, etc.

[0132] From the viewpoint of light irradiation reactivity, the content of the (G) photoradical initiator is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 8 parts by mass, based on 100 parts by mass of the total of the monofunctional (meth)acrylate compound and the polyfunctional (meth)acrylate compound.

[0133] (H) Stabilizer

[0134] The resin composition of the present embodiment may contain (H) a stabilizer (hereinafter also referred to as "component (H)") as desired within a range that does not impair the effects of the present invention. The stabilizer can improve storage stability and extend the pot life of the resin composition of the present embodiment. As the stabilizer, any known stabilizer can be used, and from the perspective of having a high effect of improving storage stability, at least one selected from a liquid borate compound, an aluminum chelate, and an organic acid is preferred.

[0135] Examples of the liquid borate compound include 2,2'-oxybis(5,5'-dimethyl-1,3,2-oxaborinane), trimethyl borate, triethyl borate, tri-n-propyl borate, tri-isopropyl 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, tri(2-ethylhexyloxy)borane, bis(1,4,7,10-tetraoxaundecyl)(1,4,7,10,13-pentaoxatetradecyl)(1,4,7-trioxaundecyl)borane, tribenzyl borate, triphenyl borate, tri-o-cresyl borate, tri-m-cresyl borate, and triethanolamine borate. Liquid borate compounds are preferred because they are liquid at room temperature (25° C.) and can keep the viscosity of the composition 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.

[0136] The stabilizers may be used alone or in combination of two or more.

[0137] When a stabilizer is added, the amount thereof added is preferably 0.01 to 30% by mass, more preferably 0.05 to 25% by mass, and even more preferably 0.1 to 20% by mass, based on the total mass of the resin composition.

[0138] (I) Coupling agent

[0139] The resin composition of the present embodiment may contain (I) a coupling agent (hereinafter also referred to as "component (I)") as desired within a range that does not impair the effects of the present invention. The coupling agent has two or more different functional groups in the molecule, one of which is a functional group that chemically bonds to an inorganic material, and the other is a functional group that chemically bonds to an organic material. By making the resin composition contain a coupling agent, the bonding strength of the resin composition to a substrate and other materials is improved.

[0140] Examples of the (I) 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 to the inorganic material.

[0141] Examples of coupling agents include, but are not limited to, epoxy-based, amino-based, vinyl-based, methacrylic, acrylic, mercapto-based, and other types of coupling agents, depending on the type of functional group chemically bonded to the organic material. Among them, epoxy-based coupling agents containing epoxy groups are preferred from the viewpoint of moisture resistance reliability.

[0142] Specific examples of the epoxy-based silane coupling agent include 3-glycidoxypropyltrimethoxysilane (trade name: KBM403, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-glycidoxypropyltriethoxysilane (trade name: KBE-403, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-glycidoxypropylmethyldiethoxysilane (trade name: KBE-402, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-glycidoxypropylmethyldimethoxysilane (trade name: KBM402, manufactured by Shin-Etsu Chemical Co., Ltd.), 8-glycidoxyoctyltrimethoxysilane (trade name: KBM-4803, Shin-Etsu Chemical Co., Ltd.), and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (trade name: KBM-303, Shin-Etsu Chemical Co., Ltd.).

[0143] Specific examples of the methacrylic silane coupling agent include 3-methacryloxypropyltrimethoxysilane (trade name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropylmethyldimethoxysilane (trade name: KBM502, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropylmethyldiethoxysilane (trade name: KBE502, manufactured by Shin-Etsu Chemical Co., Ltd.), and 3-methacryloxypropyltriethoxysilane (trade name: KBE503, manufactured by Shin-Etsu Chemical Co., Ltd.).

[0144] Specific examples of the acrylic silane coupling agent include 3-acryloxypropyltrimethoxysilane (trade name: KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

[0145] In addition, in this embodiment, the methacrylic silane coupling agent and the acrylic silane coupling agent are different from the component (C) in that they have a functional group that chemically bonds to an inorganic material, and are not included in the component (C).

[0146] Specific examples of the mercapto-based silane coupling agent include 3-mercaptopropyltrimethoxysilane (trade name: KBM803, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-mercaptopropylmethyldimethoxysilane (trade name: KBM802, manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.

[0147] The coupling agents may be used alone or in combination of two or more.

[0148] When a coupling agent is added, the amount of the coupling agent added is preferably 0.01% by mass to 30% by mass, more preferably 0.1% by mass to 10% by mass, based on the total mass of the resin composition, from the viewpoint of improving the adhesive strength.

[0149] (J) Other additives

[0150] The resin composition of the present embodiment may further contain other additives as desired within the scope not impairing the main purpose of the present embodiment, such as carbon black, titanium black, ion capture agent, leveling agent, antioxidant, defoaming agent, viscosity modifier, flame retardant, colorant, solvent, etc. The type and addition amount of each additive are as shown in the conventional method.

[0151] The method for manufacturing the resin composition of the present embodiment is not particularly limited. For example, component (A) to component (D) and component (E), component (F), component (G), component (H), component (I), (J) and other additives as required are simultaneously or separately introduced into a suitable mixer, and stirred and mixed while being melted by heating as required to make a uniform composition, thereby obtaining the resin composition of the present embodiment. The mixer is not particularly limited, and a crusher, Henschel mixer, three-roll mill, ball mill, planetary mixer and bead mill equipped with a stirring device and a heating device can be used. In addition, these devices can also be used in appropriate combination.

[0152] The resin composition thus obtained is thermosetting, preferably cured within 5 hours, more preferably within 3 hours, and further preferably within 1 hour at a temperature of 80°C. When the curable composition of the present embodiment is used for the manufacture of a semiconductor module containing 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 addition, the resin composition of the present embodiment is low volatility. Volatility can be determined based on the heating loss. The heating loss is preferably less than 1%, more preferably less than 0.7%, and further preferably less than 0.5%. In one embodiment, the resin composition of the present embodiment is the above-mentioned resin composition for curing only by heat. The use of the above-mentioned resin composition in curing only by heat is also an embodiment of the present invention.

[0153] When the resin composition of the present embodiment includes the component (E) and the component (G), the resin composition may be cured by light (UV). For example, the resin composition may be pre-cured by light (UV) curing and then fully cured by heat curing.

[0154] The resin composition of the present embodiment can be used as an adhesive or a sealant for fixing, bonding or protecting members constituting a semiconductor device or an electronic component, or as a raw material thereof, for example.

[0155] [Adhesive or sealant]

[0156] The adhesive or sealant as the second embodiment of the present invention includes the resin composition of the first embodiment. The adhesive or sealant can well fix, bond or protect 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 semiconductor devices or electronic components. 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, integrated circuits, etc.

[0157] The adhesive or sealant of this embodiment can be cured under low temperature conditions and provide a cured product with excellent stress relaxation, so it has high productivity and is suitable for use in the manufacture of semiconductor devices and electronic components that are assembled by joining multiple components made of different materials. In addition, the adhesive or sealant of this embodiment is suitable for use in the manufacture of semiconductor modules with miniaturized electronic components, for example, because the self-exothermic temperature in the curing reaction is low. In one embodiment, the adhesive or sealant of this embodiment is the above-mentioned adhesive or sealant used for curing using only heat. The use of the above-mentioned adhesive or sealant in curing using only heat is also an embodiment of the present invention.

[0158] [Cured product of resin composition, adhesive or sealant]

[0159] 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. The cured product has excellent stress relaxation properties.

[0160] [Semiconductor devices, electronic components]

[0161] The semiconductor device or electronic component of the fourth embodiment of the present invention has high reliability, especially in a semiconductor device or electronic component assembled by bonding a plurality of components made of different materials, because it includes the cured product of the third embodiment. The term "semiconductor device" refers to all devices that can function by utilizing semiconductor characteristics, including electronic components, semiconductor circuits, modules assembled with these components, and electronic devices. 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, integrated circuits, and the like.

[0162] [Example]

[0163] The present invention is further described in detail below by way of examples and comparative examples, but the present invention is not limited to these examples. It should be noted that, in the following examples, parts and % represent parts by mass and % by mass unless otherwise specified.

[0164] [Examples 1 to 24, Comparative Examples 1 to 2]

[0165] Each resin composition was prepared by mixing each component in the amount shown in Table 1 using a three-roll mill. In Table 1, the amount of each component is expressed in parts by mass (unit: g). The components used in Examples and Comparative Examples are as follows.

[0166] (A) Polyfunctional epoxy compound (ingredient (A))

[0167] (A-1): A mixture of bisphenol F epoxy resin and bisphenol A epoxy resin (trade name: EXA-835LV, manufactured by DIC Corporation, epoxy equivalent: 165 g / eq)

[0168] (A-2): Liquid epoxy compound (trade name: jER YX7400, manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent: 450 g / eq)

[0169] (A-3): PO-modified bisphenol-type liquid epoxy resin (trade name: AER9000, manufactured by Asahi Kasei Corporation, epoxy equivalent: 380 g / eq)

[0170] (A-4): Bisphenol F type epoxy resin (trade name: jER4005P, manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent: 1004 g / eq)

[0171] (A-5): Epoxy resin in component (D-1) (mixture of bisphenol A epoxy resin and bisphenol F epoxy resin, epoxy equivalent: 180 g / eq)

[0172] (B) Polyfunctional thiol compound (ingredient (B))

[0173] (B-1): Pentaerythritol tetrakis (3-mercaptopropionate) (trade name: PEMP, manufactured by SC Organic Chemicals, thiol equivalent: 122 g / eq)

[0174] (B-2): 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril (trade name: TS-G, manufactured by Shikoku Chemical Industry Co., Ltd., thiol equivalent: 100 g / eq)

[0175] (B-3): 1,3,4,6-tetrakis(3-mercaptopropyl)glycoluril (trade name: C3 TS-G, manufactured by Shikoku Chemical Industry Co., Ltd., thiol equivalent: 114 g / eq)

[0176] (B-4): Trimethylolpropane tris(3-mercaptopropionate) (trade name: TMMP, manufactured by SC Organic Chemicals, mercaptan equivalent: 133 g / eq)

[0177] (B-5): Pentaerythritol tripropyl mercaptan (trade name: PEPT, manufactured by SC Organic Chemicals, mercaptan equivalent: 124 g / eq)

[0178] (C) A monofunctional compound having in its molecule one group (c) containing an unsaturated double bond and an electron-withdrawing group adjacent thereto (component (C))

[0179] (C-1): Dicyclopentanyl acrylate (trade name: FA513AS, manufactured by Showa Denko Materials Co., Ltd., (meth)acryloyl equivalent: 206 g / eq)

[0180] (C-2): Isobornyl acrylate (trade name: IBXA, manufactured by Kyoeisha Chemical Co., Ltd., (meth)acryloyl equivalent: 208 g / eq)

[0181] (C-3): 2-(o-phenylphenoxy)ethyl acrylate (trade name: HRD-01, manufactured by Nisshoku Techno Fine Chemical Co., Ltd., (meth)acryloyl equivalent: 268 g / eq)

[0182] (C-4): (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl acrylate (trade name: MEDOL-10, manufactured by Osaka Organic Chemical Industry Co., Ltd., (meth)acryloyl equivalent: 200 g / eq)

[0183] (C-5): Cyclic trimethylolpropane formal acrylate (trade name: Viscoat #200, manufactured by Osaka Organic Chemical Industry Co., Ltd., (meth)acryloyl equivalent: 200 g / eq)

[0184] (C-6): m-Phenoxybenzyl acrylate (trade name: Light Acrylate POB-A, manufactured by Kyoeisha Chemical Co., Ltd., (meth)acryloyl equivalent: 254 g / eq)

[0185] (C-7): Isostearyl acrylate (trade name: ISTA, manufactured by Osaka Organic Chemical Industry Co., Ltd., (meth)acryloyl equivalent: 325 g / eq)

[0186] (C-8): n-octyl acrylate (trade name: NOAA, manufactured by Osaka Organic Chemical Industry Co., Ltd., (meth)acryloyl equivalent: 184 g / eq)

[0187] (C-9): Methoxyethylene oxide-modified acrylate (trade name: Light Acrylate 130A, manufactured by Kyoeisha Chemical Co., Ltd., (meth)acryloyl equivalent: 428 g / eq)

[0188] (C-10): Butyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd., (meth)acryloyl equivalent: 128 g / eq)

[0189] (D) Curing catalyst (component (D))

[0190] (D-1): Amine-epoxy adduct type latent curing catalyst (trade name: Novacure HXA9322HP, manufactured by Asahi Kasei Corporation)

[0191] (D-2): Urea adduct type latent curing catalyst (trade name: Fujicure FXR1121, manufactured by T&K TOKA Co., Ltd.)

[0192] 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 particulate 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 the dispersion is treated as a part of component (A). Therefore, in Table 1, only the amount of the latent curing catalyst in (D-1) is shown in the column of component (D), and the amount of the epoxy resin in (D-1) is shown as component (A-5) in the column of component (A).

[0193] (E) Multifunctional (meth)acrylate compound (component (E))

[0194] (E-1): dimethyloltricyclodecane diacrylate (trade name: Light Acrylate DCP-A, manufactured by Kyoeisha Chemical Co., Ltd., (meth)acryloyl equivalent: 152 g / eq)

[0195] (F) Filler (ingredient (F))

[0196] (F-1): Silica filler 1 (trade name: SE2300, manufactured by Admatechs Co., Ltd., average particle size: 0.6 μm)

[0197] (F-2): Silica filler 2 (trade name: Admanano YA050C-SM1, manufactured by Admatechs Co., Ltd., average particle size: 50 nm)

[0198] (F-3): Cross-linked styrene monodisperse particles (trade name: SX350H, manufactured by Soken Chemical Co., Ltd., average particle size: 3.5 μm)

[0199] (G) Photoradical initiator (ingredient (G))

[0200] (G-1): α-aminoalkylphenone; 1-hydroxy-cyclohexyl-phenyl-ketone (trade name: Omnirad 184, manufactured by IGM Resins BV)

[0201] (H) Stabilizer (ingredient (H))

[0202] (H-1): triisopropyl borate (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0203] (H-2): N-nitroso-N-phenylhydroxylamine aluminum salt (trade name: Q1301, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0204] (Z) Monofunctional epoxy compound (ingredient (Z))

[0205] (Z-1): p-tert-butylphenyl glycidyl ether (trade name: ED509S, manufactured by ADEKA Co., Ltd., epoxy equivalent: 205 g / eq)

[0206] In Table 1, the symbols in the column "Equivalent Number Calculation" have the following meanings.

[0207] “((A) + (C) + (E) + (Z)) / (B)” represents the ratio of the sum of the epoxy group equivalent number of the component (A), the group (c) equivalent number of the component (C), the (meth)acryloyl group equivalent number of the component (E), and the epoxy group equivalent number of the component (Z) to the thiol group equivalent number of the component (B) (([epoxy group equivalent number of the component (A)] + [group (c) equivalent number of the component (C)] + [(meth)acryloyl group equivalent number of the component (E)] + [epoxy group equivalent number of the component (Z)]) / [thiol group equivalent number of the component (B)]).

[0208] “(A) / (B)” represents the ratio of the number of epoxy group equivalents of the component (A) to the number of thiol group equivalents of the component (B) ([number of epoxy group equivalents of the component (A)] / [number of thiol group equivalents of the component (B)]).

[0209] “(C) / (B)” represents the ratio of the number of equivalents of groups (c) of component (C) to the number of equivalents of thiol groups of component (B) ([number of equivalents of groups (c) of component (C)] / [number of equivalents of thiol groups of component (B)]).

[0210] “(E) / (B)” represents the ratio of the number of (meth)acryloyl group equivalents of the component (E) to the number of thiol group equivalents of the component (B) ([number of (meth)acryloyl group equivalents of the component (E)] / [number of thiol group equivalents of the component (B)]).

[0211] “(Z) / (B)” represents the ratio of the number of epoxy group equivalents of the component (Z) to the number of thiol group equivalents of the component (B) ([number of epoxy group equivalents of the component (Z)] / [number of thiol group equivalents of the component (B)]).

[0212] In Examples and Comparative Examples, properties of the resin compositions and cured products obtained by curing the resin compositions were measured as follows.

[0213] [Evaluation of Softness]

[0214] Each resin composition was applied to a Teflon (registered trademark) sheet with a thickness of 0.3 mm, and heat-cured in a blower dryer at 80° C. for 60 minutes to produce each cured product sheet. A dumbbell for tensile testing (shown in FIG. 1 ) was produced from the obtained cured product sheet. Figure 1), using a tensile tester (Autograph AGS-J, manufactured by Shimadzu Corporation), the elongation at break (unit: %) at a tensile speed of 5 mm / min was measured at room temperature (22°C). The evaluation of flexibility was performed with n=4. The measurement results are shown in Table 1.

[0215] The elongation at break obtained from the above test shows that Examples 1 to 24 containing component (C) have greater elongation at break than Comparative Example 1 not containing component (C). The elongation at break is preferably 40% or more, more preferably 70% or more, and even more preferably 100% or more.

[0216] [Evaluation of self-heating temperature]

[0217] Maximum sample temperature during TG-DTA measurement: (°C)

[0218] 20 mg of each resin composition was added to an aluminum container for TG-DTA, and the temperature was raised from 25°C to 80°C at 3°C / min using a thermogravimetric-differential thermal analyzer (TG-DTA, manufactured by Rigaku Corporation, trade name: Thermo plus EVO (registered trademark)), and the temperature of the resin composition was measured during the process of maintaining the temperature at 80°C for 10 minutes. The maximum exothermic temperature in the obtained temperature curve is shown in Table 1. The temperature differences between the curing temperature (80°C) and the above-mentioned maximum exothermic temperature of the resin composition are shown in Table 1.

[0219] The maximum exothermic temperature of the resin composition is preferably 100° C. or lower, more preferably 95° C. or lower, and further preferably 90° C. or lower.

[0220] [Evaluation of the Volatilization Amount during Thermal Curing]

[0221] 1 gram (1 g) of each resin composition was added to a SUS container with a diameter of 5 cm and a depth of 6 mm, and the entire bottom surface of the container was filled to make the surface area uniform. After measuring the weight of the entire container containing the resin composition, a heat curing treatment was performed at 80°C for 60 minutes in a blower dryer to cure the resin composition. After the heat curing treatment, the container was placed until the heat was cooled, and the weight of the entire container containing the cured product of the resin composition was measured. Then, according to the following formula (1), the volatile amount was calculated from the weight change before and after the heating treatment. The evaluation of the volatile amount during the heat curing treatment was performed with n=3.

[0222] [Volatilization amount (%)] = 100 × {[weight of the entire container containing the resin composition before heat curing treatment (g)] - [weight of the entire container after heat curing treatment (g)]} / [initial weight of the resin composition (g)] ···Formula (1)

[0223] The volatilization amount during the heat curing treatment obtained by the above test is preferably 1.0% or less, more preferably 0.7% or less, and further preferably 0.5% or less.

[0224]

Table 1-1

[0225]

[0226]

Table 1-2

[0227]

[0228]

Table 1-3

[0229]

[0230] It can be seen that the cured products of the resin compositions of Examples 1 to 24 all have high elongation at break and excellent flexibility (stress relaxation). The resin compositions of Examples 1 to 24 have low self-exothermic temperatures during the curing reaction. The resin compositions of Examples 1 to 24 have low volatilization amounts during thermal curing treatment.

[0231] On the other hand, the cured product of the resin composition of Comparative Example 1 not containing component (C) had a low elongation at break and did not meet the required stress relaxation criteria. In addition, the resin composition of Comparative Example 1 had a high self-exothermic temperature during the curing reaction.

[0232] The resin composition of Comparative Example 2 containing (Z) a monofunctional epoxy compound instead of the component (C) has a high self-exothermic temperature during the curing reaction.

[0233] Industrial Applicability

[0234] The present invention is a resin composition that can be cured under low temperature conditions, provides a cured product having excellent stress relaxation properties, and has a low self-exothermic temperature during the curing reaction. The resin composition is very useful as an adhesive or sealant used when manufacturing semiconductor devices and electronic components that are assembled by bonding multiple components made of different materials.

[0235] The disclosure of Japanese Patent Application No. 2022-173402 (filing date: October 28, 2022) is incorporated herein by reference in its entirety.

[0236] All references, patent applications, and technical standards mentioned herein are incorporated by reference to the same extent as if each individual reference, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A resin composition comprising: (A) a multifunctional epoxy compound; (B) a multifunctional thiol compound; (C) a monofunctional compound having in its molecule one group (c) comprising an unsaturated double bond and an electron withdrawing group adjacent thereto; and (D) Curing catalyst.

2. The resin composition according to claim 1, wherein Component (C) is selected from monofunctional maleimide compounds and monofunctional (meth)acrylate compounds.

3. The resin composition according to claim 1 or 2, wherein Component (C) is a monofunctional (meth)acrylate compound having a molecular weight of 100 to 450.

4. The resin composition according to any one of claims 1 to 3, wherein The ratio of the number of equivalents of groups (c) of component (C) to the number of equivalents of epoxy groups of component (A), i.e., [number of equivalents of groups (c) of component (C)] / [number of equivalents of epoxy groups of component (A)], is 0.05 to 2.

5. The resin composition according to any one of claims 1 to 4, wherein The ratio of the epoxy group equivalent number of the component (A) to the thiol group equivalent number of the component (B), that is, [epoxy group equivalent number of the component (A)] / [thiol group equivalent number of the component (B)], is 0.4 to 0.

9.

6. The resin composition according to any one of claims 1 to 5, wherein The ratio of the sum of the epoxy group equivalent number of the component (A) and the group (c) equivalent number of the component (C) to the thiol group equivalent number of the component (B), i.e., ([epoxy group equivalent number of the component (A)] + [group (c) equivalent number of the component (C)]) / [thiol group equivalent number of the component (B)] is 0.7 to 1.

5.

7. The resin composition according to any one of claims 1 to 6, wherein The ratio of the number of equivalents of groups (c) of component (C) to the number of equivalents of thiol groups of component (B), i.e., [number of equivalents of groups (c) of component (C)] / [number of equivalents of thiol groups of component (B)], is 0.05 to 0.

7.

8. The resin composition according to any one of claims 1 to 7, wherein The amount of the component (A) is 51 parts by mass or more relative to 100 parts by mass of the total amount of the thermosetting compound.

9. The resin composition according to any one of claims 1 to 8, wherein The (A) polyfunctional epoxy compound contains 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 based on 100 parts by mass of the total amount of the (A) polyfunctional epoxy compound. 10 . An adhesive or a sealant comprising the resin composition according to claim 1 .

11. A cured product, wherein: The resin composition according to any one of claims 1 to 9, or the adhesive or sealant according to claim 10 is cured. 12 . A semiconductor device or an electronic component comprising the cured product according to claim 11 .

13. The resin composition according to any one of claims 1 to 9, or the adhesive or sealant according to claim 10, which is used for curing by heat alone.

14. Use of the resin composition according to any one of claims 1 to 9, or the adhesive or sealant according to claim 10, in curing by heat alone.

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