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

Abstract

The present invention addresses the problem of providing a resin composition and an adhesive for supplying a cured product having excellent reactivity and excellent stress relief properties. Provided is a resin composition containing (A) a polyfunctional epoxy compound having an epoxy equivalent weight of less than 215 g / eq, (B) a polyfunctional epoxy compound having an epoxy equivalent weight of 215 g / eq or more, (C) a polyfunctional thiol compound, (D) a curing catalyst, and (E) a monofunctional compound having in a molecule one group (e) including an unsaturated double bond and an electron-withdrawing group adjacent thereto.

Description

Technical Field

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

[0002] At present, in the assembly and installation of components used in semiconductor devices and electronic components, such as semiconductor chips, for the purpose of maintaining reliability, adhesives and sealing materials containing curable resin compositions, especially epoxy resin compositions, are often used. In particular, in the case of semiconductor devices and 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 the adhesives and sealing materials used in the manufacture of such devices and 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-based 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, temperature changes during the cooling process after heating and curing), thermal stress will be generated in these parts corresponding to the thermal expansion coefficients of the materials. This thermal stress is not uniform due to the difference in thermal expansion coefficients, so it is not offset by each other, but causes deformation of the assembly. The stress accompanying this deformation acts particularly on the joint of the parts, that is, the cured product of the adhesive, and in some cases, peeling of the joint will occur, cracks will occur in the cured product, etc. 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 relief characteristics, to be able to 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 as an epoxy resin composition capable of providing a cured product that can follow the 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] 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. 2019-143134 Summary of the invention

[0010] Problems to be solved by the invention

[0011] In the epoxy resin composition described in patent document 3, by using an epoxy compound with a small epoxy equivalent and an epoxy compound with a large epoxy equivalent, stress relief characteristics are given to its cured product. However, it is found that in the case of such epoxy compounds with different epoxy equivalents, the start of the curing reaction of the resin composition slows down. It is believed that this is because, due to the use of an epoxy compound with a large epoxy equivalent, molecular motion is restricted compared with the case of using an epoxy compound with a small equivalent, and the reaction probability becomes low. Thus, the time for the viscosity of the resin composition produced before the start of the curing reaction to decrease with the temperature rises is prolonged, so that the problem of dripping and the infiltration and development beyond the intention may occur.

[0012] Therefore, an object of the present invention is to provide a resin composition and an adhesive having excellent reactivity even when an epoxy compound having a large epoxy equivalent is used.

[0013] Means for solving problems

[0014] Specific means for solving the above-mentioned problems are as follows.

[0015] A first embodiment of the present invention is the following resin composition.

[0016] (1) A resin composition comprising:

[0017] (A) a multifunctional epoxy compound having an epoxy equivalent weight of less than 215 g / eq,

[0018] (B) a polyfunctional epoxy compound having an epoxy equivalent of 215 g / eq or more,

[0019] (C) Multifunctional thiol compounds,

[0020] (D) a curing catalyst, and

[0021] (E) A monofunctional compound having one group (e) including an unsaturated double bond and an electron-withdrawing group adjacent thereto in the molecule.

[0022] (2) The resin composition according to (1) above, wherein the component (E) is liquid at 25°C.

[0023] (3) The resin composition according to (1) or (2) above, wherein the component (E) is selected from a monofunctional maleimide compound and a monofunctional (meth)acrylate compound.

[0024] (4) The resin composition according to any one of (1) to (3) above, wherein the content of the component (B) is 1 to 100 parts by mass based on 100 parts by mass of the component (A).

[0025] (5) The resin composition according to any one of (1) to (4), wherein the ratio of the sum of the epoxy group equivalents of the component (A) and the epoxy group equivalents of the component (B) to the thiol group equivalents of the component (C) (([epoxy group equivalents of the component (A)] + [epoxy group equivalents of the component (B)]) / [thiol group equivalents of the component (C)]) is 0.4 to 0.95.

[0026] (6) The resin composition according to any one of (1) to (5), wherein the ratio of the sum of the epoxy group equivalent number of the component (A), the epoxy group equivalent number of the component (B), and the group (e) equivalent number of the component (E) to the thiol group equivalent number of the component (C) (([epoxy group equivalent number of the component (A)] + [epoxy group equivalent number of the component (B)] + [group (e) equivalent number of the component (E)]) / [thiol group equivalent number of the component (C)]) is 0.7 to 1.5.

[0027] (7) The resin composition according to any one of (1) to (6) above, wherein the ratio of the number of equivalents of groups (e) of component (E) to the number of equivalents of thiol groups of component (C) ([number of equivalents of groups (e) of component (E)]) / [number of equivalents of thiol groups of component (C)]) is 0.05 to 0.7.

[0028] (8) The resin composition according to any one of (1) to (7) above, wherein the total amount of the component (A) and the component (B) is 51 parts by mass or more per 100 parts by mass of the total mass of the thermosetting compound.

[0029] (9) The resin composition according to any one of (1) to (8) above, 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 relative to 100 parts by mass of the total mass of component (A) and component (B).

[0030] A second aspect of the present invention is (10) an adhesive or a sealing material comprising the resin composition according to any one of (1) to (9) above.

[0031] A third embodiment of the present invention is (11) a cured product obtained by curing the resin composition according to any one of (1) to (9) above or the adhesive or sealing material according to (10) above.

[0032] A fourth aspect of the present invention is (12) a semiconductor device or an electronic component including the cured product described in the above (11).

[0033] One embodiment of the resin composition, adhesive or sealing material is (13) the resin composition according to any one of (1) to (9) or the adhesive or sealing material according to (10) for curing only by heat.

[0034] 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 sealing material described in (10) above for curing using only heat.

[0035] Effects of the Invention

[0036] According to the first embodiment of the present invention, a resin composition with excellent reactivity can be obtained. In addition, the total heat release in the curing reaction of the resin composition is small, and the overheating of the adherend and its surrounding components during short-time curing can be suppressed. In addition, according to the second embodiment of the present invention, an adhesive or sealing material with excellent reactivity can be obtained. In addition, according to the third embodiment of the present invention, a cured product with excellent stress relief can be obtained. According to the fourth embodiment of the present invention, since a cured product with excellent stress relief is included, a semiconductor device and an electronic component with excellent reliability can be obtained. DETAILED DESCRIPTION

[0037] 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) may be used for a component constituting a curable resin composition before curing, even though the component is not a polymer.

[0038] In this specification, the term “cured product having excellent stress relaxation properties” refers to a cured product having flexibility to the extent that it can follow the deformation of an assembled product due to thermal stress of a component.

[0039] In this specification, the "resin composition having excellent reactivity" refers to a resin composition having a low reaction starting temperature of the curing reaction.

[0040] [Resin composition]

[0041] A resin composition as a first embodiment of the present invention includes:

[0042] (A) a multifunctional epoxy compound having an epoxy equivalent weight of less than 215 g / eq,

[0043] (B) a polyfunctional epoxy compound having an epoxy equivalent of 215 g / eq or more,

[0044] (C) Multifunctional thiol compounds,

[0045] (D) a curing catalyst, and

[0046] (E) A monofunctional compound having one group (e) including 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.

[0047] (A) a polyfunctional epoxy compound having an epoxy equivalent of less than 215 g / eq and (B) a polyfunctional epoxy compound having an epoxy equivalent of more than 215 g / eq

[0048] The resin composition of the present embodiment comprises (A) a polyfunctional epoxy compound having an epoxy equivalent of less than 215 g / eq (hereinafter also referred to as "component (A)") and (B) a polyfunctional epoxy compound having an epoxy equivalent of 215 g / eq or more (hereinafter also referred to as "component (B)"). By using component (A) and component (B) in combination, it is possible to achieve both excellent bonding strength of the resin composition and excellent stress relief properties of the cured product. In addition, a resin composition having a viscosity suitable for workability can be obtained.

[0049] The multifunctional epoxy compounds as components (A) and (B) are not particularly limited as long as they are compounds having at least two epoxy groups, and conventionally commonly used epoxy resins can be used as components (A) and (B). It should be noted that the so-called 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, including prepolymer compounds before curing. If heat resistance is taken into consideration, compounds having 2 to 6 epoxy groups are more preferred as components (A) and (B), and compounds having 2 epoxy groups are further preferred.

[0050] The epoxy equivalent of component (A) is less than 215 g / eq, preferably 50 g / eq or more and less than 215 g / eq, more preferably 100 g / eq or more and less than 215 g / eq, and further preferably 130 g / eq or more and less than 185 g / eq.

[0051] The epoxy equivalent of the component (B) is 215 g / eq or more, preferably 215 to 1000 g / eq, more preferably 230 to 700 g / eq, further preferably 280 to 7000 g / eq, particularly preferably 280 to 440 g / eq.

[0052] The molecular weight of the component (A) is preferably 100 to 600, more preferably 200 to 600, and even more preferably 260 to 400. The molecular weight of the component (B) is preferably 400 to 3,000, more preferably 460 to 1,500, and even more preferably 560 to 1,000.

[0053] Component (A) and component (B) may be liquid or solid at 25°C, but are preferably liquid at 25°C. In one embodiment, 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, for example, 100 parts by mass, relative to 100 parts by mass of the total mass of component (A) and component (B). In one embodiment, component (A) and component (B) contain 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 mass of component (A) and component (B).

[0054] The polyfunctional epoxy compounds as the component (A) and the component (B) are roughly divided into aromatic polyfunctional epoxy compounds and polyfunctional epoxy compounds having no aromatic ring.

[0055] Aromatic polyfunctional epoxy compounds are polyfunctional epoxy compounds having a structure containing an aromatic ring such as a benzene ring. Such compounds are common in conventional epoxy resins such as bisphenol A type epoxy compounds. Examples of aromatic polyfunctional epoxy compounds include:

[0056] -Bisphenol A type epoxy compounds;

[0057] - branched multifunctional bisphenol A type epoxy compounds such as p-glycidyloxyphenyl dimethyl trisphenol A diglycidyl ether;

[0058] -Bisphenol F type epoxy compounds;

[0059] - Novolac epoxy compounds;

[0060] -Tetrabromobisphenol A type epoxy compounds;

[0061] -Fluorene epoxy compounds;

[0062] -biphenyl aralkyl epoxides;

[0063] - Diepoxides such as 1,4-phenylenedimethanol diglycidyl ether;

[0064] -Biphenyl type epoxy compounds such as 3,3',5,5'-tetramethyl-4,4'-diglycidyloxybiphenyl;

[0065] - glycidylamine type epoxy compounds such as diglycidylaniline, diglycidyltoluidine, triglycidyl-p-aminophenol, tetraglycidyl-m-xylylenediamine; and

[0066] -Epoxy compounds containing naphthalene rings, etc., but are not limited to them. They can be used alone or in combination of two or more. From the viewpoint of compatibility with the (C) polyfunctional thiol compound, component (A) and component (B) preferably contain 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. In addition, the aromatic polyfunctional epoxy compound can be modified by oxyalkylene such as EO (ethylene oxide) modification and PO (propylene oxide) modification. In addition, the aromatic polyfunctional epoxy compound is preferably liquid at 25°C. In addition, 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.

[0067] In this specification, unless otherwise specified, the viscosity is expressed as a value measured in accordance with Japanese Industrial Standard JIS K6833. 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, and measurement range used.

[0068] Examples of the polyfunctional epoxy compound not having an aromatic ring include aliphatic polyfunctional epoxy compounds and polyfunctional epoxy compounds having a heterocyclic ring.

[0069] Examples of aliphatic polyfunctional epoxy compounds include:

[0070] - 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, glycerol diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexane type diglycidyl ether, and dicyclopentadiene type diglycidyl ether;

[0071] - triepoxy compounds such as trimethylolpropane triglycidyl ether and glycerol triglycidyl ether;

[0072] - Alicyclic epoxy compounds such as vinyl (3,4-cyclohexene) dioxide and 2-(3,4-epoxycyclohexyl)-5,1-spiro-(3,4-epoxycyclohexyl)-1,3-dioxane;

[0073] - Hydrogenated bisphenol A type diepoxides such as hydrogenated bisphenol A diglycidyl ether;

[0074] - Glycidylamine-type epoxy compounds such as tetraglycidylbis(aminomethyl)cyclohexane;

[0075] -Hydantoin-type epoxy compounds such as 1,3-diglycidyl-5-methyl-5-ethylhydantoin; and

[0076] -1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane and the like, but the present invention is not limited thereto.

[0077] The aliphatic polyfunctional epoxy compound is preferably in a liquid state at 25° C. The viscosity at 25° C. is preferably 10 to 10,000 mPa·s, more preferably 10 to 5,000 mPa·s.

[0078] Examples of the polyfunctional epoxy compound having a heterocyclic ring include isocyanuric acid type epoxy resins (manufactured by Nissan Chemical Co., Ltd.: TEPIC-S, TEPIC-L, TEPIC-PAS, TEPIC-VL, TEPIC-FL, TEPIC-UC) and glycoluril type epoxy resins (manufactured by Shikoku Chemical Co., Ltd.: TG-G). From the viewpoint of operability, the polyfunctional epoxy compound having a heterocyclic ring is preferably in a liquid state at 25° C. In addition, the viscosity at 25° C. is preferably 100 to 50,000 mPa·s, and more preferably 100 to 5,000 mPa·s. On the other hand, from the viewpoint of adhesion, it is preferably solid at 25° C.

[0079] Examples of commercially available products of the multifunctional epoxy compound containing the component (A) include 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, and EXA -830LVP, EXA-830LVP, EXA-835LV, N-730A (manufactured by DIC Corporation), DENACOL (registered trademark) EP-4100, EP-4100G, EP-4100E, EP-4300E, EP-4530, EP-4901, EP-4901E (manufactured by ADEKA Corporation), EX-810, EX-811, EX-850, EX-821, EXA-920, EX-201, EX-212 (manufactured by Nagase ChemteX Corporation), etc., but are not limited to them.

[0080] Examples of commercially available polyfunctional epoxy compounds containing the 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.

[0081] The content of component (B) is preferably 1 to 1000 parts by mass, more preferably 1 to 100 parts by mass, relative to 100 parts by mass of component (A). From the viewpoint of stress relief, the content of component (B) is preferably 10 to 1000 parts by mass, more preferably 25 to 1000 parts by mass, and further preferably 50 to 1000 parts by mass, relative to 100 parts by mass of component (A). In addition, 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, more preferably 10 parts by mass or more and less than 50 parts by mass, relative to 100 parts by mass of component (A).

[0082] (C) Multifunctional thiol compounds

[0083] The resin composition of the present embodiment includes (C) a polyfunctional thiol compound (hereinafter also referred to as "component (C)"). In the present 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 the components (A) and (B), and 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 the present embodiment, the (C) polyfunctional thiol compound preferably has three or more thiol groups. The (C) polyfunctional thiol compound more preferably includes a trifunctional thiol compound and / or a tetrafunctional thiol compound. The so-called trifunctional and tetrafunctional thiol compounds are thiol compounds having three and four thiol groups, respectively. The thiol equivalent of the (C) 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.

[0084] Polyfunctional thiol compounds are roughly divided into thiol compounds having a hydrolyzable partial structure such as an ester bond in the molecule (ie, hydrolyzable) and thiol compounds not having such a partial structure (ie, non-hydrolyzable).

[0085] Examples of the hydrolyzable multifunctional thiol compound include trimethylolpropane tris(3-mercaptopropionate) (manufactured by SC Organic Chemicals: TMMP), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate (manufactured by SC Organic Chemicals: TEMPIC), pentaerythritol tetrakis(3-mercaptopropionate) (manufactured by SC Organic Chemicals: PEMP), tetraethylene glycol bis(3-mercaptopropionate) (manufactured by SC Organic Chemicals: EGMP-4), dipentaerythritol hexa(3-mercaptopropionate) (manufactured by SC Organic Chemicals: DPMP), pentaerythritol tetrakis(3-mercaptobutyrate) (manufactured by Showa Denko K.K.: KARENZ MT (registered trademark) PE1), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (Showa Denko K.K.: KARENZ MT (registered trademark) NR1), etc. These may be used alone or in combination of two or more.

[0086] On the other hand, examples of non-hydrolyzable polyfunctional thiol compounds include 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril (manufactured by Shikoku Chemicals Co., Ltd.: TS-G), (1,3,4,6-tetrakis(3-mercaptopropyl)glycoluril (manufactured by Shikoku Chemicals Co., Ltd.: 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 (SC Organic Chemicals Co., Ltd.: PEPT), 3-[2,3-bis(3-sulfanylpropoxy)propoxy]propane-1-thiol, 3-[2,2-bis[(3-mercaptopropoxy)methyl]butoxy]-1-propanethiol, pentaerythritol tetrapropylthiol, 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-dithiooctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithioundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithioundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithioundecane, 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-thiopentane, 1,1,6,6-tetrakis(mercaptomethylthio)-3,4-dithiohexane, 2,2-bis(mercaptomethylthio)ethanethiol, 3-mercaptomethylthio-1,7-dimercapto-2,6-dithioheptane, 3,6-bis(mercaptomethylthio)-1,9-dimercapto-2,5,8-trithiononane, 3-mercaptomethylthio-1,6-dimercapto-2,5-dithiohexane, 1,1,9,9-tetrakis(mercaptomethylthio)-5-(3,3-bis(mercaptomethylthio)-1-thiopropyl)3,7-dithiononane, tris(2,2-bis(mercaptomethylthio)ethyl)methane, tris(4,4-bis(mercaptomethylthio)-2-thiobutyl)methane, tetrakis(2,2-bis(mercaptomethylthio)ethyl)methane, tetrakis(4,4-bis(mercaptomethylthio)-2-thiobutyl)methane, 3,5,9,11-tetrakis(mercaptomethylthio)-1,13-dimercapto-2,6,8,12-tetrathiotridecane, 3,5,9,11,15,17-hexa(mercaptomethylthio)-1,19-dimercapto-2,6,8,12,14,18-hexathiononadecane, 9-(2,2-bis(mercaptomethylthio)ethyl)-3,5,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,6,8 ,10,12,16-hexathioheptadecane, 3,4,8,9-tetrakis(mercaptomethylthio)-1,11-dimercapto-2,5,7,10-tetrathioundecane, 3,4,8,9,13,14-hexa(mercaptomethylthio)-1,16-dimercapto-2,5,7,10,12,15-hexathiohexadecane, 8-[bis(mercaptomethylthio)methyl]-3,4,12,13-tetrakis(mercaptomethylthio)-1,15-dimercapto-2,5,7,9,11,14-hexathiopentadecane, 4,6-bis[3,5-bis(mercaptomethylthio)-7-mercapto-2,6-dithioheptylthio]-1,3-dithiane, 4-[3,5-bis(mercaptomethylthio)-7-mercapto-2,6-dithioheptylthio] 1,3-dithiophene, 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-tetrathia-undecane, 3-[2-(1,3-dithiobutyl)]methyl-7,9-bis(mercaptomethylthio)-1,11-dimercapto-2,4,6,10-tetrathia-undecane, 9-[2-(1,3-dithiobutyl)]methyl-3,5,13,15-tetra(mercaptomethylthio)-1,17-dimercaptophene 2,6,8,10,12,16-hexathioheptadecane, 3-[2-(1,3-dithiobutyl)]methyl-7,9,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,4,6,10,12,16-hexathioheptadecane, 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-tetrathioundecyl]-5-mercaptomethylthio-1,3-dithiolane, 4,5-bis[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiohexylthio]-1,3-dithiocyclopentane, 4-[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiohexylthio]-5-mercaptomethylthio-1,3-dithiocyclopentane, 4-[3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiooctyl]-5-mercaptomethylthio-1,3-dithiocyclopentane, 2-[bis[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiohexylthio]methyl]-1,3-dithiocyclopentane, 2-[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiohexylthio]methyl Thiomethyl-1,3-dithioethane, 2-[3,4,8,9-tetrakis(mercaptomethylthio)-11-mercapto-2,5,7,10-tetrathioundecylthio]thiomethylthiomethyl-1,3-dithioethane, 2-[3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiooctyl]thiomethylthiomethyl-1,3-dithioethane, 4-{1-[2-(1,3-dithioethane)]-3-mercapto-2-thiopropylthio}-5-[1,2-bis(mercaptomethylthio)-4-mercapto-3-thiobutylthio]-1,3-dithioethane, etc. These may be used alone or in combination of two or more.

[0087] (D) Curing catalyst

[0088] 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 multifunctional epoxy compound of component (A) and component (B), and a known catalyst can be used.

[0089] Component (D) is preferably a latent curing catalyst. The so-called latent curing catalyst is a compound that is inactive at room temperature and is activated by heating to act as a curing catalyst. Examples thereof include imidazole compounds that are solid at room temperature; solid-dispersed amine adduct-based latent curing catalysts such as reaction products of amine compounds and epoxy compounds (amine-epoxy adduct systems); reaction products of amine compounds and isocyanate compounds or urea compounds (urea-type adduct systems), etc. As component (D), solid-dispersed amine adduct-based latent curing catalysts are preferred from the perspective of usable time and curability.

[0090] 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-methyl-1-imidazolyl-(1))-ethyl-S-triazine, 2,4-diamino-6-(2′-methylimidazolyl-(1′))-ethyl-S-triazine, -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)-adipic acid diamide, etc., but are not limited to them.

[0091] Examples of epoxy compounds used as one of the raw materials for producing the solid-dispersible amine adduct-based latent curing catalyst (amine-epoxy adduct-based) 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, and the like with epichlorohydrin; and polyfunctional epoxy compounds such as epoxidized phenol novolac resins, epoxidized cresol novolac resins, and epoxidized polyolefins; and monofunctional epoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, and glycidyl methacrylate. However, the present invention is not limited to these.

[0092] The amine compound used as another raw material for manufacturing the solid dispersion type amine adduct system latent curing catalyst only needs to have one or more active hydrogen capable of addition reaction with the epoxy group in the molecule and at least one or more functional groups selected from primary amino group, secondary amino group and tertiary amino group in the molecule. Examples of such amine compounds are given below, but they are not limited to them. For example, 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; etc., but they are not limited to them.

[0093] In addition, 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-(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-Dimethylaminoethylsulfide Alcohols, phenols, thiols, carboxylic acids and hydrazides having a tertiary amino group in the molecule, such as alcohols, 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, isonicotinic acid hydrazide, etc., but are not limited to them.

[0094] In addition, in the solid dispersion type amine adduct-based latent curing catalyst, as the isocyanate compound used as another manufacturing raw material, for example, monofunctional isocyanate compounds such as n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, and benzyl isocyanate; polyfunctional isocyanate compounds such as hexamethylene diisocyanate, tolylene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4′-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, p-phenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, and dicycloheptane triisocyanate; and compounds containing terminal isocyanate groups obtained by reacting these polyfunctional isocyanate compounds with active hydrogen compounds, etc. can also be used. Examples of such terminal isocyanate group-containing compounds include, but are not limited to, addition compounds having terminal isocyanate groups obtained by reaction of tolylene diisocyanate and trimethylolpropane and addition compounds having terminal isocyanate groups obtained by reaction of tolylene diisocyanate and pentaerythritol.

[0095] Moreover, examples of the urea compound include urea and thiourea, but are not limited thereto.

[0096] The solid dispersion type latent curing catalyst that can be used in this embodiment is, for example, the above-mentioned (a) two components of an amine compound and an epoxy compound, (b) 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 collecting and mixing the components, reacting them at a temperature from room temperature to 200° C., cooling and solidifying them, and then crushing them, or reacting them in a solvent such as methyl ethyl ketone, dioxane, tetrahydrofuran, etc., removing the solvent, and then crushing the solid component.

[0097] Representative examples of commercially available products of latent curing catalysts include, for amine-epoxy adducts (amine adducts), "AMICURE PN-23" (trade name of Ajinomoto Fine-Techno Co., Ltd.), "AMICURE PN-40" (trade name of Ajinomoto Fine-Techno Co., Ltd.), "AMICURE PN-50" (trade name of Ajinomoto Fine-Techno Co., Ltd.), "Hardener X-3661S" (trade name of ACR Co., Ltd.), "Hardener X-3670S" (trade name of ACR Co., Ltd.), "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 Corporation), “NOVACURE HXA5945HP” (trade name of Asahi Kasei Corporation), “NOVACURE HXA5911HP” (trade name of Asahi Kasei Corporation), “NOVACURE HXA9382HP” (trade name of Asahi Kasei Corporation), and the like. In addition, as for the urea type adduct system, “FUJICURE FXE-1000” (trade name of T&K TOKA Corporation), “FUJICURE FXR 1020” (trade name of T&K TOKA Corporation), “FUJICURE FXR-1030” (trade name of T&K TOKA Corporation), “FUJICURE FXR1121” (trade name of T&K TOKA Corporation), “FUJICURE FXR1081” (trade name of T&K TOKA Corporation), “FUJICURE FXR1061” (trade name of T&K TOKA Corporation) and the like are exemplified. However, the present invention is not limited to these. As the component (D), any one kind may be used, or two or more kinds may be used in combination.

[0098] The content of component (D) is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, based on the total mass of the resin composition.

[0099] It should be noted that, among the components (D), there are components (D) provided in the form of a dispersion dispersed in an epoxy compound. It should be noted that when using the component (D) in such a form, the amount of the epoxy compound dispersed with the component (D) is also included in the amount of the component (A) or the component (B) in the resin composition of the present embodiment.

[0100] (E) A monofunctional compound having in the molecule one group (e) containing an unsaturated double bond and an electron-withdrawing group adjacent thereto

[0101] The resin composition of the present embodiment includes (E) a monofunctional compound (hereinafter also referred to as "component (E)") having in the molecule a group (e) including an unsaturated double bond and an electron-withdrawing group adjacent thereto (hereinafter also referred to as "group (e)"). In the present embodiment, the group (e) in the component (E), more specifically the unsaturated double bond in the group (e), reacts with the thiol group in the (C) polyfunctional thiol compound. In this specification, the term "monofunctional" is used for component (E) because it means that the molecule has one group (e) that reacts with the thiol group. Examples of electron-withdrawing groups include a carbonyl group and a cyano group, preferably a carbonyl group.

[0102] When the resin composition of the present embodiment is subjected to DSC measurement, the starting temperature of the exothermic peak is observed on the low temperature side compared to the composition not containing component (E). Here, the starting temperature can be defined as the curing reaction start temperature. It can be considered that the unsaturated double bond of the group (e) in the component (E) is highly reactive due to the adjacent electron-withdrawing group, and reacts with the thiol group in the multifunctional thiol compound (C) before the epoxy group in the multifunctional epoxy compound of component (A) and component (B), so the curing reaction start temperature is reduced. As a result, the viscosity reduction time of the resin composition generated before the start of the curing reaction and accompanying the temperature increase is shortened, dripping and unintended wetting and expansion are suppressed, and the shape retention of the coating is excellent.

[0103] In addition, when the resin composition of the present embodiment is subjected to DSC measurement under curing reaction conditions of 80° C., for example, the total heat release is smaller than that of a composition not containing component (E). It is believed that the epoxy-thiol reaction generates reaction heat due to the ring-opening reaction of epoxy, while the reaction of component (E) is not accompanied by ring opening, so the heat release is reduced. As a result, overheating of the adherend and its surrounding components during short-term curing can be suppressed.

[0104] In addition, since the component (E) 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, and flexibility can be imparted to the cured product of the obtained resin composition.

[0105] From the viewpoint of the viscosity of the resin composition, the component (E) is preferably in a liquid state at 25°C.

[0106] Examples of component (E) include monofunctional maleimide compounds, monofunctional (meth)acrylate compounds, and monofunctional acrylamide compounds. Group (e) includes maleimide groups and (meth)acryloyl groups. In the present embodiment, component (E) is preferably selected from monofunctional maleimide compounds and monofunctional (meth)acrylate compounds, and more preferably monofunctional (meth)acrylate compounds.

[0107] The monofunctional maleimide compound is a compound having one maleimide group as the group (e), and examples thereof include maleimide; maleimides containing aliphatic hydrocarbon groups such as methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, and cyclohexylmaleimide; and maleimides containing aromatic rings such as phenylmaleimide. These may be used alone or in combination of two or more.

[0108] 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:

[0109] 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, benzyl Esters of (meth)acrylic acid with monohydric alcohols such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenyl (meth)acrylate, 2-hydroxy-3-phenyl (meth)acrylate, 2-hydroxy-2-hydroxy-4-(2-hydroxy-2-propene)-4-ol; 2-hydroxy-2-hydroxy-3-phenyl (meth)acrylate, 2-hydroxy-2-propene-4-ol; ... Oxypropyl 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, dicyclopentadienyl (meth)acrylate, dicyclopentadienyloxyethyl (meth)acrylate, dicyclopentyl (meth)acrylate, nonylphenoxy polyethylene glycol (meth)acrylate, tetrahydrodicyclopentadienyl (meth)acrylate, 2-(o-phenylphenoxy)ethyl (meth)acrylate, isobornyl 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-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-1,3-dioxolan-4-yl)methyl (meth)acrylate, N-acryloyloxyethylhexahydrophthalimide, α-acryloyl-ω-methoxypoly(oxyethylene), 1-ethoxyethyl (meth)acrylate, etc., mono(meth)acrylate of a polyhydric alcohol or ester 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 relief 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 addition, 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 140 or more, and particularly preferably 160 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. ,

[0110] 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 resulting cured product, component (E) may preferably not contain a group reactive with a thiol group, such as an epoxy group.

[0111] In the present embodiment, from the viewpoint of achieving both flexibility and adhesive strength, the ratio of the sum of the epoxy group equivalents of the component (A) and the epoxy group equivalents of the component (B) to the thiol group equivalents of the component (C) (([epoxy group equivalents of the component (A)] + [epoxy group equivalents of the component (B)]) / [thiol group equivalents of the component (C)]) is preferably 0.4 to 0.95, more preferably 0.4 to 0.9, further preferably 0.45 to 0.9, further preferably 0.5 to 0.9, and particularly preferably 0.55 to 0.9.

[0112] 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 (C) ([number of epoxy group equivalents of the component (A)] / [number of thiol group equivalents of the component (C)]) is preferably 0.1 to 0.9, more preferably 0.15 to 0.85, further preferably 0.15 to 0.80, and particularly preferably 0.2 to 0.8.

[0113] In the present embodiment, the ratio of the sum of the epoxy equivalent number of component (A), the epoxy equivalent number of component (B), and the group (e) equivalent number of component (E) to the thiol group equivalent number of component (C) ([epoxy equivalent number of component (A)] + [epoxy equivalent number of component (B)] + [group (e) equivalent number of component (E)]) / [thiol group equivalent number of component (C)]) 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 (C) to component (A), component (B), and component (E), the remaining unreacted components that cannot react with the thiol group can be suppressed, and the bleeding caused by the unreacted components can be suppressed. In addition, it is also expected that the volatile components can be suppressed. It should be noted that in this specification, the so-called bleeding refers to the phenomenon that when an adhesive containing a curable resin composition is used for fixing or bonding parts, unreacted components seep out from the adhesive coating or cured product over time, and the seeped components themselves are sometimes also referred to as "bleeding".

[0114] In the present embodiment, the ratio of the number of equivalents of groups (e) of component (E) to the number of equivalents of thiol groups of component (C) ([number of equivalents of groups (e) of component (E)]) / [number of equivalents of thiol groups of 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.

[0115] When component (E) contains an epoxy group, it is preferred that the above-mentioned relationship of equivalent numbers is satisfied by adding the epoxy equivalent number of component (E) to the epoxy equivalent numbers of component (A) and component (B).

[0116] In this specification, the 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 the functional group equivalent number 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).

[0117] Theoretically, the epoxy equivalent of each component (A) and component (B) is the number obtained by dividing the molecular weight of each component (A) and component (B) by the number of epoxy groups in one molecule. The actual epoxy equivalent can be calculated using the method described in JIS K7236. The epoxy equivalent number of each component (A) and component (B) is the number (equivalent number) of epoxy groups per unit mass (feed amount) of each component (A) and component (B), and is the quotient obtained by dividing the mass (g) of each epoxy compound of component (A) and component (B) by the epoxy equivalent of the epoxy compound (when multiple epoxy compounds are included, it is the sum of such quotients for each epoxy compound). It should be noted that when component (E) contains an epoxy group, its epoxy equivalent and epoxy equivalent number are calculated in the same way.

[0118] The thiol equivalent of component (C) is theoretically a number obtained by dividing the molecular weight of component (C) by the number of thiol groups in one molecule. The actual thiol equivalent can be determined, for example, by determining the thiol value using a potential difference measurement. This method is well known and is disclosed, for example, in paragraph 0079 of Japanese Patent Application Laid-Open No. 2012-153794. The thiol equivalent number of component (C) is the number (equivalent number) of thiol groups per unit mass (feed amount) of component (C), and is a quotient obtained by dividing the mass (g) of the polythiol compound (C) by the thiol equivalent of the polythiol compound (the sum of such quotients for each polythiol compound when a plurality of polythiol compounds are included).

[0119] When the group (e) is a (meth)acryloyl group, the (meth)acryloyl equivalent of the component (E) 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, for example, by NMR. The (meth)acryloyl equivalent of the component (E) is the number (equivalent number) of (meth)acryloyl groups per unit mass (feed amount) of the component (E), and is the quotient obtained by dividing the mass (g) of the (meth)acrylic acid ester compound of the component (E) by the (meth)acrylic acid ester equivalent of the (meth)acrylic acid ester compound (when a plurality of (meth)acrylic acid ester compounds are included, the sum of such quotients for each (meth)acrylic acid ester compound).

[0120] When the group (e) is a maleimide group, the maleimide equivalent of the component (E) 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, for example, by NMR. The maleimide equivalent number of the component (E) is the number (equivalent number) of maleimide groups per unit mass (feed amount) of the component (E), and is the quotient obtained by dividing the mass (g) of the maleimide compound of the component (E) by the maleimide equivalent of the maleimide compound (when a plurality of maleimide compounds are included, the sum of such quotients for each maleimide compound).

[0121] If necessary, the resin composition of the present embodiment may contain an arbitrary component other than the above-mentioned components (A) to (E), for example, the following components.

[0122] The resin composition of the present embodiment may contain thermosetting compounds other than component (A) and component (B) within a range that does not impair the effects of the present invention. In this specification, the so-called "thermosetting compounds 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). As thermosetting compounds other than component (A) and component (B), for example, (F) polyfunctional (meth)acrylate compounds, phenol compounds, bismaleimide compounds, cyanate compounds, episulfide compounds, etc. can be cited. The so-called episulfide compound refers to a compound containing an oxirane ring in which all or part of the oxygen atoms of the oxirane ring of the epoxy compound are replaced by sulfur atoms. As examples of episulfide compounds, compounds containing two or more oxirane rings in the molecule and compounds containing one or more oxirane rings and an oxirane ring in the molecule can be cited. However, in the resin composition of the present embodiment, the total amount of component (A) and component (B) relative to 100 parts by mass of the total mass of the thermosetting compound (excluding component (C)), 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.

[0123] (F) Multifunctional (meth)acrylate compounds

[0124] 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 not impairing the effects of the present invention.

[0125] 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; Acids; polyacrylates and / or polymethacrylates of alkyl-modified dipentaerythritol; polyacrylates and / or polymethacrylates of caprolactone-modified dipentaerythritol; ethoxylated bisphenol A diacrylate and / or ethoxylated bisphenol A dimethacrylate; dihydrocyclopentadienyl acrylate and / or dihydrocyclopentadienyl methacrylate, as well as polyester acrylates and / or polyester methacrylates, dimethylol-tricyclodecane diacrylate, poly(meth)acrylates of bis(trimethylol)propane, polyurethanes having two or more (meth)acryloyl groups in one molecule, polyesters having two or more (meth)acryloyl groups in one molecule, and the like.

[0126] As the polyfunctional (meth)acrylate compound, any one of the above-mentioned polyfunctional (meth)acrylate compounds may be used, or two or more of them may be used in combination.

[0127] Examples of commercially available polyfunctional (meth)acrylate compounds include polyester acrylate (trade name: EBECRYL810) manufactured by Daicel Allnex Co., Ltd., bis(trimethylol)propane tetraacrylate (trade name: EBECRYL140) manufactured by Daicel Allnex Co., Ltd., 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.

[0128] (G) Filling

[0129] The resin composition of the present embodiment may contain a filler (G) (hereinafter also referred to as "component (G)") within a range that does not impair the effects of the present invention. By containing a filler (G) in the resin composition, the linear expansion coefficient of the cured product obtained by curing the resin composition can be reduced, and the heat cycle resistance can be improved. In addition, if the filler has a low elastic modulus, the stress generated in the cured product can be relieved, and the long-term reliability can be improved. The filler (G) is roughly divided into an inorganic filler and an organic filler.

[0130] The inorganic filler includes a granular body formed with an inorganic material, and is not particularly limited as long as it is an inorganic filler having the effect of reducing the linear expansion coefficient by addition. As the inorganic material, silicon dioxide, talc, aluminum oxide, aluminum nitride, calcium carbonate, aluminum silicate, magnesium silicate, magnesium carbonate, barium sulfate, barium carbonate, calcium 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, and two or more can be used in combination. As the inorganic filler, from the aspect of being able to increase the filling amount, a silica filler is preferably used. Silica is preferably amorphous silica. The surface of the inorganic filler can be surface treated by a coupling agent such as a silane coupling agent.

[0131] 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.

[0132] The shape of the filler is not particularly limited, and may be any of spherical, flaky, needle-shaped, and irregular shapes.

[0133] 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, the so-called average particle size, unless otherwise specified, refers to the volume-based median diameter (d50) measured by laser diffraction method in accordance with ISO-13320 (2009). By setting the average particle size of the filler to below the upper limit, the sedimentation of the filler can be suppressed, and the formation of coarse particles can be suppressed, and the wear of the nozzle of the spray sizing machine and the scattering of the resin composition sprayed from the nozzle of the spray sizing machine to the outside of the desired area can be suppressed. The lower limit of the average particle size of the filler is not particularly limited, but 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 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 can 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 and a filler having an average particle size of 0.1 μm to 6.0 μm may be used in combination.

[0134] 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 within the above range, the heat cycle resistance is improved, and the viscosity of the resin composition is set within an appropriate range, so that the applicability in sizing is improved.

[0135] (H) Photoradical initiator

[0136] The resin composition of the present 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. By containing the (H) photoradical initiator, the reaction of the component (C) with the component (E) and the optional component (F) by light irradiation is promoted.

[0137] Examples of the (H) photoradical initiator include alkylphenone compounds and acylphosphine oxide compounds.

[0138] 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-methylthiophenyl) propan-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)-1-butanone (Omnirad 500 manufactured by IGM Resins BV as a commercial product); 379EG), 2-benzyl-2-(dimethylamino)-4'-morpholinophenyl-butanone (commercially available product: Omnirad 369 manufactured by IGM Resins BV), and the like.

[0139] Examples of the acylphosphine oxide-based compounds include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (commercially available as Omnirad TPO H manufactured by IGM Resins BV) and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (commercially available as Omnirad 819 manufactured by IGM Resins BV).

[0140] Examples of the (H) photoradical initiator include, 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, and benzoin n-butyl ether. , benzoin phenyl ether, benzyl dimethyl ketal, benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, 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 benzoylformate, benzyl, camphorquinone, etc.

[0141] The content of the (H) 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, from the viewpoint of light irradiation reactivity.

[0142] (I) Stabilizer

[0143] If necessary, the resin composition of the present embodiment may contain (I) a stabilizer (hereinafter also referred to as "component (I)") within a range that does not impair the effects of the present invention. The stabilizer can improve the storage stability of the resin composition of the present embodiment and extend the usable time. Various known stabilizers can be used as the stabilizer, but from the perspective of the height of the effect of improving storage stability, it is preferably selected from at least one of a liquid borate compound, an aluminum chelate, and an organic acid.

[0144] 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 reduce the viscosity of the complex. As the aluminum chelate, for example, aluminum chelate A (manufactured by Kawaken Fine Chemical Co., Ltd.) can be used. As the organic acid, for example, barbituric acid can be used.

[0145] The stabilizer may be used alone or in combination of two or more.

[0146] 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.

[0147] (J) Coupling agent

[0148] If necessary, the resin composition of the present embodiment may contain (J) a coupling agent (hereinafter also referred to as "component (J)") 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 or the like is improved.

[0149] Examples of the (J) coupling agent include silane coupling agents, aluminum coupling agents, titanium coupling agents, and the like, depending on the type of functional group that chemically bonds to the inorganic material, but are not limited thereto.

[0150] As an example of a coupling agent, various coupling agents such as epoxy, amino, vinyl, methacrylic, acrylic, and mercapto can be cited according to the type of functional group chemically bonded to the organic material, but are not limited to them. Among them, from the viewpoint of moisture resistance reliability, epoxy coupling agents containing epoxy groups are preferred.

[0151] Specific examples of the epoxy 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.).

[0152] 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.).

[0153] 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.

[0154] In addition, in this embodiment, the methacrylic silane coupling agent and the acrylic silane coupling agent are different from the component (E) in that they have a functional group that chemically bonds to an inorganic material, and are not included in the component (E).

[0155] Specific examples of the mercapto-based silane coupling agent include 3-mercaptopropyltrimethoxysilane (trade name KBM803, manufactured by Shin-Etsu Chemical Co., Ltd.) and 3-mercaptopropylmethyldimethoxysilane (trade name KBM802, manufactured by Shin-Etsu Chemical Co., Ltd.).

[0156] The coupling agent may be used alone or in combination of two or more.

[0157] 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.

[0158] (K) Other additives

[0159] If necessary, the resin composition of the present embodiment may further contain other additives, such as carbon black, titanium black, ion trapping agent, leveling agent, antioxidant, defoaming agent, viscosity modifier, flame retardant, colorant, solvent, etc., within the scope that does not impair the gist of the present embodiment. The type and addition amount of each additive are as shown in the conventional method.

[0160] The method for manufacturing the resin composition of the present embodiment is not particularly limited. For example, components (A) to (E) and components (F), (G), (H), (I), (J), (K) and other additives used as needed are simultaneously or separately introduced into an appropriate mixer, and if necessary, they are melted by heating while stirring and mixing 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.

[0161] The resin composition thus obtained is thermosetting, preferably solidifies within 5 hours at a temperature of 80°C, more preferably solidifies within 3 hours, and further preferably solidifies within 1 hour. In the case of using the curable composition of the present embodiment in the manufacture of a semiconductor module containing components that degrade 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 embodiment, the resin composition of the present embodiment is a resin composition for curing using only heat. In addition, the application of the above-mentioned resin composition in curing using only heat is also an embodiment of the present invention.

[0162] When the resin composition of the present embodiment contains the component (F) and the component (H), the resin composition may be cured by light (UV). For example, the resin composition may be pre-cured by curing with light (UV) and then cured by curing with heat.

[0163] The resin composition of the present embodiment can be used as an adhesive or a sealing material or a raw material thereof for fixing, bonding or protecting members constituting a semiconductor device or an electronic component, for example.

[0164] [Adhesive or sealing material]

[0165] The adhesive or sealing material of the second embodiment of the present invention includes the resin composition of the first embodiment described above. The adhesive or sealing material can achieve good fixing, bonding or protection of engineering plastics (such as LCP (liquid crystal polymer), polyamide, polycarbonate, etc.), ceramics and metals (such as copper, nickel, etc.), and can be used to fix, bond or protect components constituting semiconductor devices or electronic components. As semiconductor devices or electronic components, for example, HDDs, semiconductor elements, sensor modules such as image sensor modules, camera modules, semiconductor modules, integrated circuits, etc. can be cited, but they are not limited to them.

[0166] The adhesive or sealing material of this embodiment has high productivity because it can provide a cured product with high reactivity and excellent stress relief properties, and is suitable for use in, for example, the manufacture of semiconductor devices and electronic components that are assembled by joining multiple components made of different materials. In addition, the adhesive or sealing material of this embodiment has a small total heat release during the curing reaction, and is suitable for use in, for example, the manufacture of semiconductor modules having miniaturized electronic components.

[0167] In one embodiment, the adhesive or sealing material of this embodiment is an adhesive or sealing material used for curing using only heat. In addition, the use of the above-mentioned adhesive or sealing material in curing using only heat is also an embodiment of the present invention.

[0168] [Cured product of resin composition, adhesive or sealing material]

[0169] 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 sealing material of the second embodiment. The cured product has excellent stress relaxation properties.

[0170] [Semiconductor devices, electronic components]

[0171] 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. Here, the so-called semiconductor device refers to all devices that can function by utilizing semiconductor characteristics, including electronic components, semiconductor circuits, modules assembled with them, electronic devices, etc. Semiconductor devices or electronic components can include, for example, HDDs, semiconductor elements, sensor modules such as image sensor modules, camera modules, semiconductor modules, integrated circuits, etc., but are not limited to them.

[0172] Example

[0173] Hereinafter, the present invention will be described in further detail using 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 indicated.

[0174] [Examples 1 to 20, Comparative Examples 1 to 3]

[0175] The resin composition was prepared by mixing the given amounts of the components using a three-roll mill according to the formulation shown in Table 1. 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.

[0176] (A) Epoxy compounds having an epoxy equivalent weight of less than 215 g / eq (ingredient (A))

[0177] (A-1) Bisphenol F epoxy resin / bisphenol A epoxy resin mixture (trade name: EXA-835LV, manufactured by DIC Corporation, epoxy equivalent: 165 g / eq)

[0178] (A-2): Epoxy resin in component (D-1) (mixture of bisphenol A epoxy resin and bisphenol F epoxy resin, epoxy equivalent: 180 g / eq)

[0179] (B) an epoxy compound having an epoxy equivalent of 215 g / eq or more (component (B))

[0180] (B-1) Polyether epoxy compound (trade name: AER-9000, manufactured by Asahi Kasei Corporation, epoxy equivalent: 380 g / eq, liquid at 25° C., viscosity: 1 Pa·s)

[0181] (B-2) Liquid epoxy compound (trade name: jER YX7400, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 450 g / eq, liquid at 25° C., viscosity: 170 mPa·s)

[0182] (B-3) Bisphenol A type epoxy resin (trade name: jER 1002, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 250 g / eq, solid at 25°C)

[0183] (C) Polyfunctional thiol compound (ingredient (C))

[0184] (C-1): Pentaerythritol tetrakis (3-mercaptopropionate) (trade name: PEMP, manufactured by SC Organic Chemicals, thiol equivalent: 122 g / eq)

[0185] (C-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)

[0186] (C-3): Pentaerythritol tripropyl mercaptan (trade name: PEPT, manufactured by SC Organic Chemicals, mercaptan equivalent: 124 g / eq)

[0187] (C-4): Trimethylolpropane tris(3-mercaptopropionate) (trade name: TMMP, manufactured by SC Organic Chemicals, mercaptan equivalent: 133 g / eq)

[0188] (D) Curing catalyst (component (D))

[0189] (D-1): Amine-epoxy adduct-based latent curing catalyst (trade name: NOVACURE HXA9322HP, manufactured by Asahi Kasei Corporation)

[0190] (D-2): Urea-type adduct-based latent curing catalyst (trade name: FUJICURE FXR1121, manufactured by T&K TOKA Co., Ltd.)

[0191] 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 substance constituting 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-2) in the column of component (A).

[0192] (E) a monofunctional compound having in the molecule one group (e) containing an unsaturated double bond and an electron-withdrawing group adjacent thereto (component (E))

[0193] (E-1): n-octyl acrylate (trade name: NOAA, manufactured by Osaka Organic Chemical Industry Co., Ltd., (meth)acrylate equivalent: 184 g / eq)

[0194] (E-2): (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl acrylate (trade name: MEDOL-10, manufactured by Osaka Organic Chemical Industry Co., Ltd., (meth)acrylate equivalent: 200 g / eq)

[0195] (E-3): Cyclic trimethylolpropane formal acrylate (trade name: VISCOAT#200, manufactured by Osaka Organic Chemical Industry Co., Ltd., (meth)acrylate equivalent: 200 g / eq)

[0196] (E-4): dicyclopentyl acrylate (trade name: FA513AS, manufactured by Showa Denko Materials Co., Ltd., (meth)acrylate equivalent: 206 g / eq)

[0197] (E-5): Isobornyl acrylate (trade name: IBXA, manufactured by Kyoeisha Chemical Co., Ltd., (meth)acrylate equivalent: 208 g / eq)

[0198] (E-6): 3-phenoxybenzyl acrylate (trade name: Light Acrylate POB-A, manufactured by Kyoeisha Chemical Co., Ltd., (meth)acrylate equivalent: 254 g / eq)

[0199] (E-7): 2-(o-phenylphenoxy)ethyl acrylate (trade name: HRD-01, manufactured by Nichikyu Techno FineChemica Co., Ltd., (meth)acrylate equivalent: 268 g / eq)

[0200] ·(E') monofunctional epoxy compound (ingredient (E'))

[0201] (E'-1): p-tert-butylphenyl glycidyl ether (trade name: ED509S, manufactured by ADEKA Co., Ltd., epoxy equivalent: 205 g / eq)

[0202] (G) Filler (ingredient (G))

[0203] (G-1): Silica filler (trade name: SE2300, manufactured by Admatechs Co., Ltd., average particle size: 0.6 μm)

[0204] In Table 1, the symbols in the column of "Equivalent Number Calculation" have the following meanings.

[0205] “((A) + (B) + (E)) / (C)” represents the ratio of the sum of the epoxy group equivalents of the component (A), the epoxy group equivalents of the component (B), and the group (e) equivalents of the component (E) to the thiol group equivalents of the component (C) (([epoxy group equivalents of the component (A)] + [epoxy group equivalents of the component (B)] + [group (e) equivalents of the component (E)]) / [thiol group equivalents of the component (C)]).

[0206] “((A) + (B)) / (C)” represents the ratio of the sum of the epoxy group equivalents of the component (A) and the epoxy group equivalents of the component (B) to the thiol group equivalents of the component (C) (([epoxy group equivalents of the component (A)] + [epoxy group equivalents of the component (B)]) / [thiol group equivalents of the component (C)]).

[0207] “(A) / (C)” represents the ratio of the number of epoxy group equivalents of the component (A) to the number of thiol group equivalents of the component (C) ([number of epoxy group equivalents of the component (A)] / [number of thiol group equivalents of the component (C)]).

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

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

[0210] “(E′) / (C)” represents the ratio of the number of epoxy equivalents of the component (E′) to the number of thiol group equivalents of the component (C) ([number of epoxy equivalents of the component (E′)] / [number of thiol group equivalents of the component (C)]).

[0211] In Examples and Comparative Examples, the properties of the resin compositions were measured as follows.

[0212] [DSC measurement]

[0213] (1) Starting temperature

[0214] 5 mg of each resin composition was placed in an aluminum pan for DSC, and after the lid was closed, a hole was opened in the lid, and a DSC curve of the process of heating from 25°C to 250°C at 5°C / min under a nitrogen atmosphere was obtained using a differential scanning calorimeter (DSC, manufactured by NETZSCH: DSC204 F1 Phoenix (registered trademark)). When multiple onset temperatures were observed in the obtained DSC curve, the value on the low temperature side was set as the onset temperature. This is shown in Table 1.

[0215] The onset temperature obtained by the above test shows the reactivity, and the higher the reactivity, the lower the onset temperature. The onset temperatures of Examples 1 to 20 are lower than those of Comparative Examples 1 to 3, indicating that the reactivity is high. The onset temperature is preferably 85°C or lower, more preferably 83°C or lower, and further preferably 80°C or lower.

[0216] (2) Exothermic peak area

[0217] Based on the data of the DSC curve obtained when the onset temperature in (1) above was determined, the exothermic peak area was calculated using analysis software (NETZSCH Proteus-Thermal Analysis Version 8.0.2). The results are shown in Table 1.

[0218] The exothermic peak area in the DSC curve obtained by the above test represents the heat released by the resin composition during curing. The smaller the area, the smaller the heat release, which can 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 further preferably 300 J / g.

[0219]

[0220]

[0221]

[0222] Comparison of the resin compositions of Examples 1 to 20, the resin composition of Comparative Example 1 not containing component (B) and component (E), and the resin composition of Comparative Example 3 containing component (B) and component (E') instead of component (E) revealed that the onset temperature increased due to the inclusion of component (B), the onset temperature could be lowered by the inclusion of component (E), and component (E') could not lower the onset temperature to the same extent as component (E).

[0223] In addition, from the comparison between the resin compositions of Examples 1 to 20, the resin composition of Comparative Example 1 not containing component (B) and component (E), and the resin composition of Comparative Example 2 not containing component (B) and containing component (E') instead of component (E), it can be seen that the exothermic peak area becomes larger by containing component (E'), while the exothermic peak area becomes smaller by containing component (E).

[0224] Industrial Applicability

[0225] The present invention provides a resin composition that provides a cured product having excellent reactivity and excellent stress relief properties, and is very useful as an adhesive or sealing material suitable for use in the manufacture of semiconductor devices and electronic components that are assembled by bonding a plurality of components made of different materials.

[0226] The entire contents of the disclosure of Japanese Patent Application No. 2022-173403 (filing date: October 28, 2022) are incorporated into this specification by reference.

[0227] All documents, patent applications, and technical standards described in this specification are incorporated herein by reference to the same extent as if each individual document, patent application, or technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A resin composition comprising: A: Multifunctional epoxy compounds with epoxy equivalent weight less than 215 g / eq, B: a polyfunctional epoxy compound having an epoxy equivalent of 215 g / eq or more, C: Multifunctional thiol compounds, D: Curing catalyst, and E: A monofunctional compound having one group e including an unsaturated double bond and an electron-withdrawing group adjacent thereto in the molecule.

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

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

4. The resin composition according to any one of claims 1 to 3, wherein The content of the component B is 1 to 100 parts by mass based on 100 parts by mass of the component A.

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

95.

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

5.

7. The resin composition according to any one of claims 1 to 6, wherein The ratio of the group e equivalent number of component E to the thiol group equivalent number of component C, ie, [group e equivalent number of component E] / [thiol group equivalent number of component C], is 0.05 to 0.

7.

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

9. The resin composition according to any one of claims 1 to 8, wherein Component A and Component B include 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 mass of Component A and Component B. 10 . An adhesive or a sealing material comprising the resin composition according to claim 1 . 11 . A cured product obtained by curing the resin composition according to claim 1 or the adhesive or sealing material according to claim 10 . 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 sealing material according to claim 10 for curing using only heat.

14. Use of the resin composition according to any one of claims 1 to 9 or the adhesive or sealing material according to claim 10 for curing using only heat.

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