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

Abstract

The purpose of the present invention is to provide a resin composition and an adhesive which are capable of reducing odor from a thiol-based curing agent and providing a cured product in which odor is reduced. The present invention provides a resin composition comprising: (A) a thiol-based curing agent having two or more thiol groups; (B) a main agent having two or more reactive groups (b) capable of reacting with thiol groups; (C) an odor masking agent having one reactive group (c) capable of reacting with a thiol group; and (D) a thermally latent curing catalyst, the amount of (A) the thiol-based curing agent being 10-60 mass% with respect to the total mass of the resin composition, and the component (C) being a monofunctional compound having one group including an unsaturated double bond and an electron withdrawing group adjacent thereto in the molecule.

Description

Technical Field

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

[0002] At present, adhesives, sealants, etc. containing curable resin compositions are often used in the assembly and mounting of components used in semiconductor devices, such as semiconductor chips, for the purpose of maintaining reliability, etc. As such resin compositions, curable compositions containing epoxy resins or acrylic resins as main agents and thiol-based curing agents as curing agents are known (for example, Patent Documents 1 and 2).

[0003] In adhesives, when a large amount of thiol curing agents are added to the composition ratio, odor may become a problem. In particular, in adhesives that require thermal curing, low molecular weight thiol compounds contained in the thiol curing agents or generated as byproducts or decomposition products during the curing reaction tend to volatilize during heating, causing odor problems. The cured product after the curing reaction also emits an odor of low molecular weight thiol compound residues.

[0004] Some methods are known, including a method of using an acrylic polymer to adsorb the odor of a thiol compound, a method of using an aldehyde to capture the odor of a thiol compound, and a method of using an aromatic component such as eucalyptus to mask the odor of a thiol compound. For example, Patent Document 3 discloses a method of mixing mercaptosilane with one or more deodorants selected from eucalyptus oil, 1,8-cineole, and propylene oxide in an epoxy resin composition for semiconductor sealing to mask the odor based on a mercapto group.

[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 Publication No. 2009-51954

[0009] Patent Document 3: Japanese Patent Application Publication No. 2003-268205 Summary of the invention

[0010] Problems to be solved by the invention

[0011] Generally, the aromatic components used in odor masking do not have reactive groups that can bond with the curable components of the adhesive, or are components with too low molecular weight. Therefore, even if the adhesive is cured, they are not introduced into the cured product through bonding, resulting in defects such as degassing and bleeding. In addition, although propylene oxide is described as an example of a deodorant in Patent Document 3, it has a reactive group, but it is a dangerous special flammable substance with a low boiling point (34°C) and flash point (-37°C). Therefore, safer deodorants are desired.

[0012] An object of the present invention is to provide a resin composition capable of reducing odor derived from a curing agent in a thermosetting adhesive containing a thiol-based curing agent, and a cured product thereof having reduced odor.

[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 thiol-based curing agent having two or more thiol groups;

[0017] (B) a main agent having two or more reactive groups (b) that can react with thiol groups;

[0018] (C) an odor masking agent having one reactive group (c) that can react with a thiol group; and

[0019] (D) thermal latent curing catalyst,

[0020] The amount of the thiol curing agent (A) is 10 to 60% by mass relative to the total mass of the resin composition.

[0021] The component (C) is a monofunctional compound having one group 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 (C) is a monofunctional (meth)acrylate compound having a molecular weight of 100 to 400.

[0023] (3) The resin composition according to (1) or (2) above, wherein the component (B) contains a polyfunctional epoxy compound, and the amount of the polyfunctional epoxy compound in the total mass of the component (B) is 51 to 100% by mass.

[0024] (4) The resin composition according to any one of (1) to (3) above, wherein the ratio of the number of equivalents of reactive groups (c) reactive with thiol groups in the component (C) to the number of equivalents of thiol groups in the component (A) ([the number of equivalents of reactive groups (c) reactive with thiol groups in the component (C)] / [the number of equivalents of thiol groups in the component (A)]) is 0.01 to 0.7.

[0025] (5) The resin composition according to any one of (1) to (4), wherein the ratio of the sum of the equivalent number of reactive groups (b) reactive with thiol groups of the component (B) and the equivalent number of reactive groups (c) reactive with thiol groups of the component (C) to the equivalent number of thiol groups of the component (A) (([equivalent number of reactive groups (b) reactive with thiol groups of the component (B)] + [equivalent number of reactive groups (c) reactive with thiol groups of the component (C)]) / [equivalent number of thiol groups of the component (A)]) is 0.5 to 1.5.

[0026] A second aspect of the present invention is (6) an adhesive or a sealant including the resin composition according to any one of (1) to (5) above.

[0027] A third aspect of the present invention is (7) a cured product, wherein the resin composition according to any one of (1) to (5) above, or the adhesive or sealant according to (6) above is cured.

[0028] A fourth aspect of the present invention is (8) a semiconductor device including the cured product described in the above (7).

[0029] One embodiment of the resin composition, adhesive or sealant is (9) the resin composition according to any one of (1) to (5) above, or the adhesive or sealant according to (6) above, which is used for curing by heat alone.

[0030] Another embodiment of the present invention is (10) use of the resin composition according to any one of (1) to (5) above, or the adhesive or sealant according to (6) above, in curing by heat alone.

[0031] Effects of the Invention

[0032] According to the first embodiment of the present invention, a resin composition can be provided, which can reduce the odor from the thiol-based curing agent and provide a cured product with reduced odor. According to the second embodiment of the present invention, an adhesive or sealant can be provided, which can reduce the odor from the thiol-based curing agent and provide a cured product with reduced odor. In addition, according to the third embodiment of the present invention, a cured product with reduced odor can be provided. According to the fourth embodiment of the present invention, a semiconductor device including a cured product with reduced odor can be provided. DETAILED DESCRIPTION

[0033] 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.

[0034] [Resin composition]

[0035] A resin composition as a first embodiment of the present invention includes:

[0036] (A) a thiol-based curing agent having two or more thiol groups;

[0037] (B) a main agent having two or more reactive groups (b) that can react with thiol groups;

[0038] (C) an odor masking agent having one reactive group (c) that can react with a thiol group; and

[0039] (D) thermal latent curing catalyst,

[0040] in,

[0041] The amount of the thiol curing agent (A) is 10 to 60% by mass relative to the total mass of the resin composition, and

[0042] Component (C) is a monofunctional compound having one group including an unsaturated double bond and an electron withdrawing group adjacent thereto in the molecule.

[0043] According to the present embodiment, it is possible to provide a resin composition capable of reducing the odor derived from a thiol-based curing agent and a cured product having reduced odor.

[0044] (A) Thiol-based curing agent having two or more thiol groups

[0045] The resin composition of the present embodiment includes (A) a thiol-based curing agent having two or more thiol groups (hereinafter also referred to as "(A) thiol-based curing agent" or "component (A)"). In the present embodiment, the (A) thiol-based curing agent is a compound having two or more thiol groups, and the thiol groups react with a reactive group (b) that can react with a thiol group in the component (B) described later, and a reactive group (c) that can react with a thiol group in the component (C) described later. In the present embodiment, the (A) thiol-based curing agent preferably has three or more thiol groups. The (A) thiol-based curing agent more preferably includes a trifunctional thiol compound and / or a tetrafunctional thiol compound. Trifunctional and tetrafunctional thiol compounds refer to thiol compounds having three and four thiol groups, respectively. The thiol equivalent of the thiol-based curing agent (A) 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.

[0046] 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).

[0047] Examples of the hydrolyzable multifunctional thiol compound include trimethylolpropane tris(3-mercaptopropionate), tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, pentaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), and 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione. These may be used alone or in combination of two or more.

[0048] Examples of the non-hydrolyzable polyfunctional thiol compound include 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril, 1,3,4,6-tetrakis(3-mercaptopropyl)glycoluril, 1,3,4,6-tetrakis(mercaptomethyl)glycoluril, 1,3,4,6-tetrakis(mercaptomethyl)-3a-methylglycoluril, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a-methylglycoluril, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a-methylglycoluril, 1,3,4,6-tetrakis(mercaptomethyl)-3a,6a-dimethylglycoluril, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a,6a-dimethylglycoluril, 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)propane-1-thiol )propoxy]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-3,6,9-trithiaundecane, tetra( 1,1,5,5-tetrakis(mercaptomethylthio)-3-thiapentane, 1,1,6,6-tetrakis(mercaptomethylthio)-3,4-dithiahexanes, 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-dithiahexanes, 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)methane 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-(1,3-dithiacyclobutyl)]methyl-7,9-bis(mercaptomethylthio)-1,11-dimercapto-2,4,6,10 -tetrathiaundecane, 9-[2-(1,3-dithiacyclobutyl)]methyl-3,5,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,6,8,10,12,16-hexathiaheptadecane, 3-[2-(1,3-dithiacyclobutyl)]methyl-7,9,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,4,6,10,12,16-hexathiaheptadecane, 4,6-bis[4-(6-mercaptomethylthio)-1,3-dithianylthio]-6-[4-(6-mercaptomethylthio)-1,3-dithianylthio]-1,3-dithiane, 4-[3,4,8,9-tetrakis(mercaptomethylthio)-11-mercapto-2,5,7,10-tetrathiaundecyl]-5-mercaptomethylthio-1,3-dithiolane, 4,5-bis[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]-1,3-dithiolane, 4-[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]-5-mercaptomethylthio-1,3- dithiolane, 4-[3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiooctyl]-5-mercaptomethylthio-1,3-dithiolane, 2-{bis[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]methyl}-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 1,3-dithiocyclopentane, 4-{1-[2-(1,3-dithiocyclobutyl)]-3-mercapto-2-thiapropylthio}-5-[1,2-bis(mercaptomethylthio)-4-mercapto-3-thiabutylthio]-1,3-dithiocyclopentane, etc. These may be used alone or in combination of two or more.

[0049] The amount of (A) thiol curing agent is 10 to 60% by mass relative to the total mass of the resin composition. Since (A) thiol curing agent is formulated in a certain amount, it is usually easy to cause odor problems, but the composition of the resin composition of this embodiment can reduce odor. In one embodiment, the amount of (A) thiol curing agent is 15 to 60% by mass relative to the total mass of the resin composition. In one embodiment, the amount of (A) thiol curing agent is 15 to 60% by mass relative to the total mass of the resin composition excluding the filler (E) described later.

[0050] (B) A main agent having two or more reactive groups (b) that can react with a thiol group

[0051] The resin composition of the present embodiment includes a main agent (hereinafter also referred to as "(B) main agent" or "component (B)") having two or more reactive groups (b) (hereinafter also referred to as "groups (b)") that can react with thiol groups. Component (B) is a polyfunctional compound that can be cured by having two or more reactive groups (b) that react with thiol groups in component (A) to form a crosslinked network. Examples of such polyfunctional compounds include polyfunctional epoxy compounds having two or more epoxy groups and polyfunctional (meth)acrylate compounds having two or more (meth)acryloyloxy groups. In one embodiment, component (B) is a polyfunctional epoxy compound. In one embodiment, component (B) is a polyfunctional (meth)acrylate compound. In one embodiment, component (B) includes a polyfunctional epoxy compound. In one embodiment, component (B) includes both a polyfunctional epoxy compound and a polyfunctional (meth)acrylate compound. From the viewpoint of improving the adhesive strength, the amount of the polyfunctional epoxy compound in the total mass of the component (B) is preferably 50 to 100 mass%, preferably 51 to 100 mass%, more preferably 60 to 100 mass%, further preferably 80 to 100 mass%, and particularly preferably 90 to 100 mass%. It should be noted that, when the reactive group (b) reactive with a thiol group of the component (B) contains an epoxy group and other reactive groups in one molecule (for example, when the component (B) is a (meth)acrylate compound having an epoxy group and a (meth)acryloyloxy group), the mass of the polyfunctional epoxy compound is estimated as the value obtained by dividing the mass (charge amount) of the compound by the number of all reactive groups (b) in one molecule and multiplying it by the number of epoxy groups in one molecule.

[0052] The polyfunctional epoxy compound 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 (B). Epoxy resin is a general term for thermosetting resins that can be cured by crosslinking and networking using epoxy groups present in the molecule, including prepolymer compounds before curing. In view of ensuring heat resistance, as component (B), 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 may be liquid or solid at 25°C, and is preferably liquid at 25°C. In one embodiment, the amount of the 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 mass of the polyfunctional epoxy compound. In one embodiment, the 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. The amount of the 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 polyfunctional epoxy compound.

[0053] Polyfunctional epoxy compounds are roughly divided into aromatic polyfunctional epoxy compounds and polyfunctional epoxy compounds having no aromatic ring.

[0054] 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:

[0055] -Bisphenol A type epoxy compounds;

[0056] - branched multifunctional bisphenol A type epoxy compounds such as p-glycidyloxyphenyl dimethyl trisphenol A diglycidyl ether;

[0057] -Bisphenol F type epoxy compounds;

[0058] -phenolic epoxy compounds;

[0059] -Tetrabromobisphenol A type epoxy compounds;

[0060] -Fluorene epoxy compounds;

[0061] -biphenyl aralkyl epoxides;

[0062] - Diepoxides such as 1,4-phenylenedimethanol diglycidyl ether;

[0063] -Biphenyl type epoxy compounds such as 3,3',5,5'-tetramethyl-4,4'-diglycidyloxybiphenyl;

[0064] - glycidylamine type epoxy compounds such as diglycidylaniline, diglycidyltoluidine, triglycidyl-p-aminophenol, tetraglycidyl-m-xylylenediamine; and

[0065] -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 (A) polyfunctional thiol compound, the polyfunctional epoxy compound as component (B) preferably includes 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.

[0066] 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 is no particular limitation on the equipment, rotor or measurement range used.

[0067] 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.

[0068] Examples of aliphatic polyfunctional epoxy compounds include:

[0069] - 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;

[0070] - triepoxy compounds such as trimethylolpropane triglycidyl ether and glycerol triglycidyl ether;

[0071] - Alicyclic epoxy compounds such as vinyl (3,4-cyclohexene) dioxide and 2-(3,4-epoxycyclohexyl)-5,1-spiro-(3,4-epoxycyclohexyl)-m-dioxane;

[0072] - Hydrogenated bisphenol A type diepoxides such as hydrogenated bisphenol A diglycidyl ether;

[0073] - Glycidylamine-type epoxy compounds such as tetraglycidylbis(aminomethyl)cyclohexane;

[0074] -Hydantoin-type epoxy compounds such as 1,3-diglycidyl-5-methyl-5-ethylhydantoin; and

[0075] -1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane and the like, but not limited thereto.

[0076] 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 5 to 10,000 mPa·s, more preferably 10 to 5,000 mPa·s.

[0077] 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).

[0078] 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.

[0079] The polyfunctional (meth)acrylate compound is not particularly limited as long as it is a compound having at least two (meth)acryloyloxy groups. A compound having 2 to 6 (meth)acryloyloxy groups is preferred, and a compound having two (meth)acryloyloxy groups is more preferred.

[0080] 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. From the viewpoint of reactivity, the polyfunctional (meth)acrylate compound as the component (B) is preferably an acrylate compound, and substantially no methacrylate compound is contained.

[0081] 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.

[0082] From the viewpoint of preparation and dispensability of the resin composition, the polyfunctional (meth)acrylate compound preferably has a viscosity of 0.01 to 100 Pa·s.

[0083] Commercially available products of the multifunctional (meth)acrylate compound include, for example, polyester acrylate (trade name: EBECRYL810) manufactured by Daicel-Allnex Co., Ltd., ditrimethylolpropane 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. The multifunctional (meth)acrylate compound may be used alone or in combination of two or more.

[0084] The polyfunctional compound having two or more reactive groups (b) that can react with a thiol group may include an episulfide compound. An 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 with sulfur atoms. Examples of episulfide compounds include 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. Among them, from the viewpoint of the workability of the resin composition, the amount of the compound containing an oxirane ring in the total mass of the component (B) is preferably 20% by mass or less, for example, 15% by mass or less, for example, 10% by mass or less, for example, 5% by mass or less.

[0085] (C) Odor masking agent having one reactive group (c) reactive with a thiol group

[0086] The resin composition of the present embodiment contains (C) an odor masking agent (hereinafter also referred to as "component (C)") having one reactive group (c) (hereinafter also referred to as "group (c)") that can react with a thiol group. In this specification, "odor masking agent" refers to a compound that reacts with a thiol group from component (A) to mask the odor from component (A). As component (C), there is no particular limitation as long as it is an odor masking agent as described above and has a monofunctional compound having one group containing an unsaturated double bond and an electron-withdrawing group adjacent to the molecule. The group containing an unsaturated double bond and an electron-withdrawing group adjacent to the unsaturated double bond is equivalent to the reactive group (c) that can react with a thiol group. Examples of electron-withdrawing groups include a carbonyl group and a cyano group, preferably a carbonyl group. The carbonyl group also includes a carbonyloxy group.

[0087] Examples of component (C) include monofunctional maleimide compounds, monofunctional (meth)acrylate compounds, and monofunctional acrylamide compounds. Group (c) includes maleimide groups, (meth)acryloyl groups, and (meth)acryloyloxy 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.

[0088] 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.

[0089] The monofunctional (meth)acrylate compound is a compound having one (meth)acryloyloxy group as the group (c). Examples of the monofunctional (meth)acrylate compound include:

[0090] -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, Esters of (meth)acrylic acid with monohydric alcohols such as tetrahydrofurfuryl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, phenoxydiethylene 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-phenoxypropyl (meth)acrylate, Octyl acrylate, Nonyl acrylate, Isononyl acrylate, 3,3,5-trimethylcyclohexyl acrylate, Cyclic trimethylolpropane formal acrylate, 1-naphthylmethyl (meth)acrylate, 1-ethylcyclohexyl (meth)acrylate, 1-methylcyclohexyl (meth)acrylate, 1-ethylcyclopentyl (meth)acrylate, 1-methylcyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, (methyl ) dicyclopentenyloxyethyl acrylate, dicyclopentyl (meth)acrylate, nonylphenoxy polyethylene glycol (meth)acrylate, tetrahydrodicyclopentadienyl (meth)acrylate, 2-(o-phenylphenoxy)ethyl (meth)acrylate, isobornylcyclohexyl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, 1-adamantyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantane (meth)acrylate 2-isopropyladamantan-2-yl (meth)acrylate, 3-hydroxy-1-adamantanyl (meth)acrylate, (adamantan-1-yloxy)methyl (meth)acrylate, 2-isopropyl-2-adamantanyl (meth)acrylate, 1-methyl-1-ethyl-1-adamantanyl methyl (meth)acrylate, 1,1-diethyl-1-adamantanyl methyl (meth)acrylate, 2-cyclohexylpropane-2-yl (meth)acrylate, 1-isopropylcyclohexyl (meth)acrylate, 1-methylcyclohexyl (meth)acrylate, 1-ethylcyclopentyl (meth)acrylate, Mono(meth)acrylates of polyols such as 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), and 1-ethoxyethyl(meth)acrylate, or esters of monohydric alcohols and (meth)acrylic acid. These may be used alone or in combination of two or more. ;

[0091] From the viewpoint of odor masking effect, the molecular weight of component (C) is preferably 400 or less, more preferably 350 or less, and even more preferably 300 or less. In order to prevent adverse effects on the human body due to volatilization and contamination of the heat curing furnace, component (C) is preferably low-volatile, and its molecular weight is preferably 100 or more, and even more preferably 130 or more. In one embodiment, the molecular weight of component (C) is preferably 100 to 400, more preferably 100 to 350, and even more preferably 130 to 300.

[0092] By including the component (C), the odor from the component (A) is masked. The reason for this is not limited, but it is considered to be as follows.

[0093] Low molecular weight thiol compounds contained in component (A) or produced as by-products or decomposition products in the curing reaction are easy to volatilize, which may cause odor problems. It should be noted that most substances related to olfaction have a molecular weight of about 20 to 400. In a certain embodiment, it is believed that the molecular weight of the sulfur-containing compound produced by the reaction of component (C) with the low molecular weight thiol compound via group (c) increases, becomes less volatile, and the odor is suppressed. In particular, when component (C) is a monofunctional (meth)acrylate compound or a monofunctional maleimide compound, the reactivity of the (meth)acryloyl group, the (meth)acryloyloxy group, and the maleimide group is high, and the capture ability of the low molecular weight thiol compound is high.

[0094] In addition, the monofunctional (meth)acrylate compound as described above has a unique ester odor because it contains a carbonyl group and has a small molecular weight to a certain extent. The ester odor can mask the odor from the component (A).

[0095] In addition, since the component (C) is introduced into the cured product of the resin composition via the group (c), outgassing, bleeding, etc. from the cured product after heat treatment are suppressed compared with fragrance components generally used for odor masking.

[0096] In the present embodiment, from the viewpoint of reducing odor and curing properties, the ratio of the equivalent number of reactive groups (c) reactive with thiol groups of the component (C) to the equivalent number of thiol groups of the component (A) ([equivalent number of reactive groups (c) reactive with thiol groups of the component (C)] / [equivalent number of thiol groups of the component (A)]) is preferably 0.01 to 0.7, more preferably 0.05 to 0.65, further preferably 0.1 to 0.6, and particularly preferably 0.15 to 0.55.

[0097] In addition, from the viewpoint of the properties of the cured product, the ratio of the equivalent number of reactive groups (b) reactive with thiol groups of component (B) to the equivalent number of thiol groups of component (A) ([equivalent number of reactive groups (b) reactive with thiol groups of component (B)] / [equivalent number of thiol groups of component (A)]) is preferably 0.5 to 0.99, more preferably 0.55 to 0.95, further preferably 0.60 to 0.90, and particularly preferably 0.60 to 0.85. In the case of component (B) having an epoxy group and another reactive group as the reactive group (b) reactive with thiol groups in one molecule (for example, in the case of component (B) being a (meth)acrylate compound having an epoxy group and a (meth)acryloyloxy group), it is preferred that both the epoxy group and the other reactive group be calculated as the group (b) so as to satisfy the above-mentioned relationship of the equivalent number.

[0098] In the present embodiment, the ratio of the sum of the equivalent number of reactive groups (b) reactive with thiol groups of the component (B) and the equivalent number of reactive groups (c) reactive with thiol groups of the component (C) to the equivalent number of thiol groups of the component (A) (([equivalent number of reactive groups (b) reactive with thiol groups of the component (B)] + [equivalent number of reactive groups (c) reactive with thiol groups of the component (C)]) / [equivalent number of thiol groups of the component (A)]) is preferably 0.5 to 1.5, more preferably 0.7 to 1.3, and even more preferably 0.8 to 1.1.

[0099] In this specification, functional group equivalents such as thiol equivalent, epoxy equivalent, (meth)acryloyloxy 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)acryloyloxy equivalent number, etc. represent the number (equivalent number) of functional groups per unit compound mass (feed amount).

[0100] The thiol equivalent of component (A) is theoretically the number obtained by dividing the molecular weight of component (A) 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 (A) is the number (equivalent number) of thiol groups per unit mass (feed amount) of component (A), and is the quotient obtained by dividing the mass (g) of the multifunctional thiol compound of (A) by the thiol equivalent of the multifunctional thiol compound (when more than one multifunctional thiol compound is included, it is the sum of such quotients of each multifunctional thiol compound).

[0101] When component (B) is a multifunctional epoxy compound, the epoxy equivalent of component (B) is theoretically the number obtained by dividing the molecular weight of component (B) by the number of epoxy groups in one molecule. The actual epoxy equivalent can be calculated by the method described in JIS K7236. The epoxy equivalent number of component (B) is the number of epoxy groups (equivalent number) per unit mass (feed amount) of component (B), and is the quotient obtained by dividing the mass (g) of the epoxy compound as component (B) 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).

[0102] When component (B) is a multifunctional (meth)acrylate compound, and / or component (C) is a monofunctional (meth)acrylate compound, the (meth)acryloyloxy equivalent of component (B) and / or component (C) is theoretically equal to the number obtained by dividing the molecular weight of the (meth)acrylate compound by the number of acryloyloxy groups (or methacryloyloxy groups) in one molecule. The actual (meth)acryloyloxy equivalent can be measured by, for example, NMR. The (meth)acryloyloxy equivalent of component (B) and / or component (C) is the number (equivalent number) of (meth)acryloyloxy groups per unit mass (feed amount) of component (B) and / or component (C), and is the quotient obtained by dividing the mass (g) of the (meth)acrylate compound of component (B) and / or component (C) by the (meth)acryloyloxy equivalent of the (meth)acrylate compound (when more than one (meth)acrylate compound is included, it is the sum of such quotients of each (meth)acrylate compound).

[0103] In the case where component (C) is a monofunctional maleimide compound, 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 group 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).

[0104] (D) Thermal Latent Curing Catalyst

[0105] The resin composition of the present embodiment includes (D) a thermal latent curing catalyst (hereinafter also referred to as "component (D)"). By using component (D), the resin composition of the present embodiment can be made into a one-component resin composition and can be cured in a short time even under low temperature conditions.

[0106] 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-dispersible 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), solid-dispersible amine adduct type latent curing catalysts are preferred from the viewpoints of pot life and curability.

[0107] 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.

[0108] 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.

[0109] 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.

[0110] 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.

[0111] 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.

[0112] In addition, examples of the urea compound include urea and thiourea, but are not limited to these.

[0113] 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.

[0114] 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.

[0115] 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.

[0116] 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 (B) present in the resin composition of the present embodiment.

[0117] 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.

[0118] (E) Filling

[0119] The resin composition of the present embodiment may contain a filler (E) (hereinafter also referred to as "component (E)") within a range that does not impair the effects of the present invention. By containing a filler (E) in the resin composition, the linear expansion coefficient of the cured product obtained 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, thereby improving long-term reliability. The filler (E) is roughly divided into an inorganic filler and an organic filler.

[0120] 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.

[0121] 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.

[0122] The shape of the filler is not particularly limited, and may be any of spherical, flaky, needle-shaped, and irregular shapes.

[0123] 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.

[0124] 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.

[0125] (F) Stabilizer

[0126] The resin composition of the present embodiment may contain (F) a stabilizer (hereinafter also referred to as "component (F)") 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.

[0127] 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.

[0128] The stabilizers may be used alone or in combination of two or more.

[0129] 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.

[0130] (G) Other additives

[0131] The resin composition of the present embodiment may further contain other additives as desired within the scope that does not impair the main purpose of the present embodiment, such as photo-radical initiator, coupling agent, carbon black, titanium black, ion trapping 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.

[0132] The method for manufacturing the resin composition of the present embodiment is not particularly limited. For example, components (A) to (D) and other additives such as components (E), (F), and (G) 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.

[0133] The resin composition thus obtained is thermosetting and preferably cures 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. The resin composition of the present embodiment is particularly capable of reducing the odor from component (A) that is easily generated during thermal curing, and can provide a cured product with reduced odor. In one embodiment, the resin composition of the present embodiment is the above-mentioned resin composition for curing using only heat. The use of the above-mentioned resin composition in curing using only heat is also an embodiment of the present invention.

[0134] When the resin composition of the present embodiment contains a polyfunctional (meth)acrylate compound and a photoradical initiator, 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.

[0135] 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.

[0136] [Adhesive or sealant]

[0137] 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 include, but are not limited to, HDDs, semiconductor elements, sensor modules such as image sensor modules, camera modules, semiconductor modules, integrated circuits, etc.

[0138] The adhesive or sealant of this embodiment can reduce the odor from component (A) that is easily generated during heat curing, and can provide a cured product with reduced odor. 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.

[0139] [Cured product of resin composition, adhesive or sealant]

[0140] 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 odor derived from the component (A) is reduced in the cured product.

[0141] [Semiconductor devices]

[0142] The semiconductor device of the fourth embodiment of the present invention 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 incorporating these components, and electronic devices. Examples of semiconductor devices 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.

[0143] [Example]

[0144] 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.

[0145] [Examples 1 to 21, Comparative Examples 1 to 5]

[0146] 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.

[0147] (A) Thiol-based curing agent having two or more thiol groups (component (A))

[0148] (A-1) Thiol-based curing agent containing 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril as a main component

[0149] (A-2) A thiol-based curing agent containing pentaerythritol tetrakis(3-mercaptobutyrate) as a main component

[0150] (A-3) A thiol-based curing agent containing pentaerythritol tetrakis (3-mercaptopropionate) as a main component

[0151] (A-4) A thiol-based curing agent containing pentaerythritol tripropyl mercaptan as a main component

[0152] (A-5) A thiol-based curing agent containing 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione as a main component

[0153] (B) A main agent having two or more reactive groups (b) that can react with a thiol group (component (B))

[0154] (B-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)

[0155] (B-2): Epoxy resin in component (D-1) (mixture of bisphenol A epoxy resin and bisphenol F epoxy resin, epoxy equivalent: 180 g / eq)

[0156] (C) Odor masking agent having one reactive group (c) reactive with a thiol group (ingredient (C))

[0157] (C-1): Butyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd., (meth)acryloyloxy equivalent: 128 g / eq)

[0158] (C-2): n-octyl acrylate (trade name: NOAA, manufactured by Osaka Organic Chemical Industry Co., Ltd., (meth)acryloyloxy equivalent: 184 g / eq)

[0159] (C-3): Cyclic trimethylolpropane formal acrylate (trade name: Viscoat #200, manufactured by Osaka Organic Chemical Industry Co., Ltd., (meth)acryloyloxy equivalent: 200 g / eq)

[0160] (C-4): Dicyclopentanyl acrylate (trade name: FA513AS, manufactured by Showa Denko Materials Co., Ltd., (meth)acryloyloxy equivalent: 206 g / eq)

[0161] (C-5): Isobornyl acrylate (trade name: IBXA, manufactured by Kyoeisha Chemical Co., Ltd., (meth)acryloyloxy equivalent: 208 g / eq)

[0162] (C-6): N-acryloyloxyethyl hexahydrophthalimide (trade name: ARONIX M-140, manufactured by Toagosei Co., Ltd., (meth)acryloyloxy equivalent: 251 g / eq)

[0163] (C-7): m-Phenoxybenzyl acrylate (trade name: Light Acrylate POB-A, manufactured by Kyoeisha Chemical Co., Ltd., (meth)acryloyloxy equivalent: 254 g / eq)

[0164] (C-8): 2-(o-phenylphenoxy)ethyl acrylate (trade name: HRD-01, manufactured by Nisshoku Techno Fine Chemical Co., Ltd., (meth)acryloyloxy equivalent: 268 g / eq)

[0165] (C-9): Isostearyl acrylate (trade name: ISTA, manufactured by Osaka Organic Chemical Industry Co., Ltd., (meth)acryloyloxy equivalent: 325 g / eq)

[0166] (C-10): Methoxyethylene oxide-modified acrylate (trade name: Light Acrylate 130A, manufactured by Kyoeisha Chemical Co., Ltd., (meth)acryloyloxy equivalent: 428 g / eq)

[0167] (D) Thermal latent curing catalyst (ingredient (D))

[0168] (D-1): Amine-epoxy adduct type latent curing catalyst (trade name: Novacure HXA9322HP, manufactured by Asahi Kasei Corporation)

[0169] In Table 1, the symbols in the column "Equivalent Number Calculation" have the following meanings.

[0170] “((B) + (C)) / (A)” represents the ratio of the sum of the equivalent number of reactive groups (b) reactive with thiol groups of component (B) and the equivalent number of reactive groups (c) reactive with thiol groups of component (C) to the equivalent number of thiol groups of component (A) (([equivalent number of reactive groups (b) reactive with thiol groups of component (B)] + [equivalent number of reactive groups (c) reactive with thiol groups of component (C)]) / [equivalent number of thiol groups of component (A)]).

[0171] “(B) / (A)” represents the ratio of the number of equivalents of reactive groups (b) reactive with thiol groups in component (B) to the number of equivalents of thiol groups in component (A) ([the number of equivalents of reactive groups (b) reactive with thiol groups in component (B)] / [the number of equivalents of thiol groups in component (A)]).

[0172] “(C) / (A)” represents the ratio of the number of equivalents of reactive groups (c) reactive with thiol groups in component (C) to the number of equivalents of thiol groups in component (A) ([the number of equivalents of reactive groups (c) reactive with thiol groups in component (C)] / [the number of equivalents of thiol groups in component (A)]).

[0173] In Examples and Comparative Examples, properties of the resin compositions and their cured products were measured as follows.

[0174] [Group selection test]

[0175] Based on the "Calculation Method of Odor Index and Odor Emission Intensity" announced by the Environment Agency, a selection test was conducted to determine the panelists (i.e., people who use their sense of smell to determine the presence or absence of odor). People who can olfactorily distinguish five standard odors were selected as panelists using the panel selection standard concentration group (manufactured by Daiichi Pharmaceutical Industry Co., Ltd.).

[0176] Group 1: Men in their 30s

[0177] Group 2: Women in their 20s

[0178] Group 3: Women in their 20s

[0179] Group 4: Men in their 40s

[0180] Group 5: Women in their 20s

[0181] Group 6: Women in their 40s

[0182] Group 7: Male in their 40s

[0183] Group 8: Women in their 30s

[0184] Group 9: Male in their 20s

[0185] Group 10: Men in their 30s

[0186] [Odor evaluation]

[0187] 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. A 100 mL disposable cup (Azwan) was prepared, and a hole with a diameter of 5 mm was opened in the central part of the side, and the hole was covered with a polyimide tape. The disposable cup was covered on the SUS container with the resin composition added in such a way that the openings overlapped with each other, and the surroundings were adhered with a heat-resistant tape to make a closed state. Then, the sealed container was heated at 80°C / 60 minutes with an air supply dryer, thereby heat-treating the resin composition. Then, 50 mL of air inside the container was taken out from the hole opened in advance on the container and filled into a smell bag containing 3 L of odorless air. The odor was determined by each panel member smelling the odor of the diluted air inside the container in the odor bag.

[0188] The odor used as the benchmark is composed only of (A) a thiol curing agent, (B) a main agent, and (D) a thermal latent curing catalyst, as in Comparative Examples 1 to 5. Then, it was confirmed whether the odor from the thiol curing agent of the corresponding comparative example was masked by the (C) odor masking agent contained in the resin composition of Examples 1 to 21. The judgment criteria for the masking effect are the five levels shown below. The average score of each resin composition was calculated by excluding one upper limit and one lower limit judgment value (△ and ▲ in Table 1) from the scores judged by each group. The results are shown in Table 1.

[0189] 5: The mercaptan odor is strong, and the odor is the same as that of the comparative example or stronger than that of the comparative example.

[0190] 4: The odor of mercaptan has become slightly lighter, and the masking effect can be felt.

[0191] 3: The odor of mercaptan and the odor of the masking agent are present to the same extent, and the masking effect is felt.

[0192] 2: The odor of mercaptan is almost gone, and the masking effect is felt.

[0193] 1: No mercaptan odor is detected, and the masking effect is very strongly detected.

[0194] It can be seen that in each resin composition, a strong odor of thiol was confirmed in Comparative Examples 1 to 5, while in Examples 1 to 21, the odor was determined to be reduced compared with the Comparative Examples. The average score in the odor determination is preferably 4.5 points or less, more preferably 4.0 points or less, and even more preferably 3.5 points or less.

[0195]

Table 1-1

[0196]

[0197]

Table 1-2

[0198]

[0199]

Table 1-3

[0200]

[0201] Industrial Applicability

[0202] The present invention is a resin composition capable of reducing odor from a thiol-based curing agent and providing a cured product having reduced odor. The resin composition is very useful as an adhesive or a sealant suitable for use in the manufacture of semiconductor devices.

[0203] The disclosure of Japanese Patent Application No. 2022-173404 (filing date: October 28, 2022) is incorporated herein by reference in its entirety.

[0204] 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 thiol curing agent A having two or more thiol groups; A main agent B having two or more reactive groups b that can react with thiol groups; an odor masking agent C having one reactive group c that can react with a thiol group; and Thermal latent curing catalyst D, The amount of the thiol curing agent A is 10% to 60% by mass relative to the total mass of the resin composition. The C is a monofunctional compound having, in its molecule, one group including an unsaturated double bond and an electron withdrawing group adjacent thereto.

2. The resin composition according to claim 1, wherein Component C is a monofunctional (meth)acrylate compound having a molecular weight of 100 to 400.

3. The resin composition according to claim 1 or 2, wherein Component B contains a polyfunctional epoxy compound, and the amount of the polyfunctional epoxy compound in the total mass of component B is 51% by mass to 100% by mass.

4. The resin composition according to any one of claims 1 to 3, wherein The ratio of the equivalent number of reactive groups C of component C that can react with thiol groups to the equivalent number of thiol groups of component A, i.e., [equivalent number of reactive groups C of component C that can react with thiol groups] / [equivalent number of thiol groups of component A], is 0.01 to 0.

7.

5. The resin composition according to any one of claims 1 to 4, wherein The ratio of the sum of the equivalent number of reactive groups b reactive with thiol groups of component B and the equivalent number of reactive groups c reactive with thiol groups of component C to the equivalent number of thiol groups of component A, i.e., ([equivalent number of reactive groups b reactive with thiol groups of component B] + [equivalent number of reactive groups c reactive with thiol groups of component C]) / [equivalent number of thiol groups of component A] is 0.5 to 1.

5. 6 . An adhesive or a sealant comprising the resin composition according to claim 1 .

7. A cured product, wherein The resin composition according to any one of claims 1 to 5, or the adhesive or sealant according to claim 6 is cured.

8. A semiconductor device comprising the cured product according to claim 7. 9 . The resin composition according to claim 1 , or the adhesive or sealant according to claim 6 , which is used for curing by heat alone.

10. Use of the resin composition according to any one of claims 1 to 5, or the adhesive or sealant according to claim 6, in curing by heat alone.

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