Resin composition, adhesive, encapsulation material, cured object, semiconductor device, and electronic component

Abstract

The present invention addresses the problem of providing a resin composition and an adhesive which are curable at least thermally and can be inhibited from suffering bleeding.　Provided is a resin composition comprising (A) a (meth)acrylate compound, (B) a polythiol compound, (C) a curing catalyst, and (D) zeolite particles.

Description

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

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

[0002] Photo- and thermosetting resin compositions are known that can be temporarily fixed by irradiation with light and then fully cured by heating. More specifically, adhesives that are temporarily fixed by ultraviolet (UV) irradiation and then fully cured by heat are used in many fields (e.g., Patent Documents 1 and 2). This type of adhesive is particularly popular for image sensor module applications.

[0003] Patent Document 3 discloses a photo- and thermosetting resin composition that has both excellent photocurability and excellent thermosetting properties, and when light irradiation is performed under conditions that produce unirradiated portions, subsequent heating can completely cure the entire composition including the unirradiated portions to produce a cured product with high adhesive strength, and also has good storage stability.The photo- and thermosetting resin composition includes: (1) a compound having a (meth)acryloyl group; (2) a polyene compound having two or more vinyl groups or allyl groups per molecule; (3) a polythiol compound having two or more thiol groups per molecule; (4) a photoradical generator; (5) a thermal radical generator; and (6) a thermal anionic polymerization initiator.

[0004] JP 2009-51954 A International Publication No. 2005 / 052021 JP 2017-101112 A

[0005] Bleeding is an issue in the assembly process of semiconductor modules. Bleeding is a phenomenon in which unreacted components seep out from the adhesive coating or cured product over time when an adhesive containing a curable resin composition is used to fix or bond components. The exuded components themselves are sometimes called "bleed." When bleed comes into contact with metal wiring on a substrate, it can cause electrical defects, resulting in a problem of reduced reliability and bonding strength of the semiconductor module.

[0006] In particular, when an adhesive containing a photo- and thermosetting resin composition is used in the assembly process of a semiconductor module (e.g., an image sensor module or a camera module), UV irradiation curing involves UV irradiation from the outside of the semiconductor module, which means that the inside of the semiconductor module is not exposed to UV light, and uncured portions of the adhesive may remain. Inner bleeding that occurs from the uncured portions of the adhesive tends to progress during storage at room temperature after UV irradiation and during subsequent thermal curing, increasing the length of the bleeding. Furthermore, depending on the location where the adhesive is applied, it may be shaded by a component, preventing UV irradiation, and therefore curing by thermal curing alone. Even in this case, there is a problem in that bleeding is likely to occur from the applied adhesive portion during storage at room temperature and thermal curing.

[0007] In recent years, there has been a growing demand for smaller and more highly integrated electronic components such as semiconductor chips, and the distance to the wiring parts arranged around the electronic components is becoming shorter. In semiconductor modules equipped with such smaller and more highly integrated electronic components, there is a problem that the bleeding phenomenon increases the risk of contact between the bleeding and the wiring parts.

[0008] Therefore, an object of the present invention is to provide at least a thermosetting resin composition and an adhesive that can suppress the bleeding phenomenon.

[0009] Specific means for solving the above problems are as follows. A first embodiment of the present invention is the following resin composition. (1) A resin composition comprising: (A) a (meth)acrylate compound; (B) a polythiol compound; (C) a curing catalyst; and (D) zeolite particles. (2) The resin composition according to (1) above, wherein the average particle size of the (D) zeolite particles is 1 μm or less. (3) The resin composition according to (1) or (2) above, wherein the content of the (D) zeolite particles is 0.1 mass% or more relative to the total mass of the resin composition. (4) The resin composition according to any one of (1) to (3) above, further comprising (E) a surfactant. (5) The resin composition according to any one of (1) to (4) above, further comprising (F) a rubber component. (6) The resin composition according to any one of (1) to (5) above, further comprising (G) a photoradical initiator.

[0010] A second embodiment of the present invention is an adhesive or sealant as follows: (7) An adhesive or sealant comprising the resin composition according to any one of (1) to (6) above. (8) The adhesive or sealant according to (7) above, which is used for fixing, adhering, or protecting components constituting an image sensor or a camera module.

[0011] A third embodiment of the present invention is the following cured product. (9) A cured product obtained by curing the resin composition according to any one of (1) to (6) above, or the adhesive or sealant according to (7) or (8) above. A fourth embodiment of the present invention is the following semiconductor device or electronic component. (10) A semiconductor device or electronic component comprising the cured product according to (9) above. (11) The semiconductor device or electronic component according to (10) above, which is an image sensor or a camera module.

[0012] According to the first embodiment of the present invention, at least a thermosetting resin composition capable of suppressing the bleeding phenomenon can be obtained. Also, according to the second embodiment of the present invention, at least a thermosetting adhesive or sealant capable of suppressing the bleeding phenomenon can be obtained. Furthermore, according to the third embodiment of the present invention, a cured product in which the bleeding phenomenon is suppressed can be obtained. According to the fourth embodiment of the present invention, a semiconductor device or electronic component excellent in reliability and bonding can be obtained because it contains a cured product in which the bleeding phenomenon is suppressed.

[0013] [Resin Composition] The resin composition according to the first embodiment of the present invention comprises: (A) a (meth)acrylate compound; (B) a polythiol compound; (C) a curing catalyst; and (D) zeolite particles. According to this embodiment, it is possible to obtain at least a thermosetting resin composition capable of suppressing bleeding.

[0014] (A) (Meth)acrylate Compound The resin composition of this embodiment contains (A) a (meth)acrylate compound (hereinafter also referred to as "component (A)"). The (A) (meth)acrylate compound can impart transparency and appropriate hardness to the cured resin composition. The (meth)acrylate compound of component (A) is not particularly limited as long as it contains a (meth)acrylate compound having two or more (meth)acryloyl groups. In consideration of ensuring heat resistance, a compound having two or more (meth)acryloyl groups is preferred, a compound having 2 to 6 (meth)acryloyl groups is more preferred, and a compound having two (meth)acryloyl groups is even more preferred. Furthermore, in order to adjust the viscosity and physical properties of the cured product (such as adhesive strength and flexibility), a compound having one (meth)acryloyl group can also be used in addition to a compound having two (meth)acryloyl groups.

[0015] Examples of the (meth)acrylate compound (A) include diacrylate and / or dimethacrylate of tris(2-hydroxyethyl)isocyanurate; tris(2-hydroxyethyl)isocyanurate triacrylate and / or trimethacrylate; trimethylolpropane triacrylate and / or trimethacrylate, or an oligomer thereof; pentaerythritol triacrylate and / or trimethacrylate, or an oligomer thereof; polyacrylate and / or polymethacrylate of dipentaerythritol; tris(acryloxyethyl)isocyanurate; caprolactone-modified tris(acryloxyethyl)isocyanurate; caprolactone-modified tris(methacryloxyethyl)isocyanurate; polyacrylate and / or polymethacrylate of alkyl-modified dipentaerythritol; caprolactone-modified dipentaerythritol Examples of suitable acrylates include, but are not limited to, polyacrylates and / or polymethacrylates of teflon, ethoxylated bisphenol A diacrylate and / or ethoxylated bisphenol A dimethacrylate, dihydrocyclopentadiethyl acrylate and / or dihydrocyclopentadiethyl methacrylate, polyester acrylate and / or polyester methacrylate, dimethylol-tricyclodecane diacrylate, poly(meth)acrylate of ditrimethylolpropane, polyurethanes having two or more (meth)acryloyl groups per molecule, polyesters having two or more (meth)acryloyl groups per molecule, phenoxyethyl acrylate, isobornyl acrylate, phenoxydiethylene glycol (meth)acrylate, 4-tert-butylcyclohexyl acrylate, and epoxy resin half acrylate. From the viewpoint of reactivity, it is preferable that component (A) is substantially free of methacrylate compounds and is an acrylate compound. As the (meth)acrylate compound (A), any one of the above-mentioned (meth)acrylate compounds may be used alone, or two or more of them may be used in combination.

[0016] From the viewpoint of preparation and dispensability of the resin composition, it is preferable that component (A) has a viscosity of 0.01 to 100 Pa s. In this specification, viscosity refers to a value measured at a measurement temperature of 25°C using a viscometer appropriate for the viscosity range.

[0017] Examples of commercially available products of component (A) include, but are not limited to, polyester acrylate (product name: EBECRYL 810) manufactured by Daicel-Allnex Corporation, ditrimethylolpropane tetraacrylate (product name: EBECRYL 140) manufactured by Daicel-Allnex Corporation, polyester acrylate (product name: M7100) manufactured by Toagosei Co., Ltd., dimethylol-tricyclodecane diacrylate (product name: Light Acrylate DCP-A) manufactured by Kyoeisha Chemical Co., Ltd., and neopentyl glycol-modified trimethylolpropane diacrylate (product name: KAYARAD R-604) manufactured by Nippon Kayaku Co., Ltd. Any one of these may be used as component (A), or two or more may be used in combination.

[0018] From the viewpoint of adhesive strength of the resin composition, the content of component (A) is preferably 10 to 70 mass %, more preferably 20 to 60 mass %, relative to the total mass of the resin composition.

[0019] (B) Polythiol Compound The resin composition of this embodiment contains (B) a polythiol compound (hereinafter also referred to as "component (B)"). The (B) polythiol compound imparts high photocurability to the resin composition. Component (B) is not particularly limited as long as it is bifunctional or higher, i.e., has two or more thiol groups. Component (B) preferably contains a trifunctional or higher thiol compound, and more preferably contains a trifunctional and / or tetrafunctional thiol compound. Trifunctional and tetrafunctional thiol compounds refer to thiol compounds having three and four thiol groups, respectively.

[0020] Examples of polythiol compounds include, but are not limited to, pentaerythritol tetrakis(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, pentaerythritol tetrakis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptobutyrate), and trimethylolethane tris(3-mercaptobutyrate).

[0021] Commercially available products of the component (B) include trimethylolpropane tris(3-mercaptopropionate) (manufactured by SC Organic Chemical Industry Co., Ltd.: TMMP), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate (manufactured by SC Organic Chemical Industry Co., Ltd.: TEMPIC), pentaerythritol tetrakis(3-mercaptopropionate) (manufactured by SC Organic Chemical Industry Co., Ltd.: PEMP), tetraethylene glycol bis(3-mercaptopropionate) (manufactured by SC Organic Chemical Industry Co., Ltd.: EGMP-4), dipentaerythritol hexakis(3-mercapto propionate) (manufactured by SC Organic Chemical Co., Ltd.: 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 (manufactured by Showa Denko K.K.: Karenz MT (registered trademark) NR1), trimethylolpropane tris(3-mercaptobutyrate) (manufactured by Showa Denko K.K.: Karenz MT (registered trademark) TPMB), and the like, but are not limited to these.

[0022] Furthermore, examples of the polythiol compound (B) include glycoluril compounds represented by the following general formula (1):

[0023]

[0024] In general formula (1), R １ , and R ２ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group. n is an integer of 0 to 10.

[0025] Component (B) may also be a compound represented by the following chemical formula (2) or (3).

[0026]

[0027]

[0028] The compounds represented by chemical formula (2) or chemical formula (3) are more preferred compounds as component (B).

[0029] Furthermore, the polythiol compound (B) may be a polythiol compound represented by the general formula (4).

[0030]

[0031] In general formula (4), R ３ , R ４ , R ５ and R ６ are each independently hydrogen or C ｎ H ２ｎ SH (n is 2 to 6). ３ , R ４ , R ５ and R ６ At least one of ｎ H ２ｎSH (n is 2 to 6). In terms of curability, n in the polyfunctional thiol compound of component (B) represented by general formula (4) is preferably 2 to 4. Furthermore, in terms of the balance between the physical properties of the cured product and the curing rate, this polyfunctional thiol compound is more preferably a mercaptopropyl group where n is 3. Component (B) represented by general formula (4) itself has a sufficiently flexible skeleton, making it effective when it is desired to lower the modulus of elasticity of the cured product. By adding component (B) represented by general formula (4), the modulus of elasticity of the cured product can be controlled, thereby increasing the adhesive strength (particularly peel strength) after curing.

[0032] Commercially available products of the component (B) include, but are not limited to, a thiol glycoluril derivative manufactured by Shikoku Chemical Industry Co., Ltd. (product name: TS-G (corresponding to chemical formula (2)), thiol equivalent: 100 g / eq), product name: C3 TS-G (corresponding to chemical formula (3)), thiol equivalent: 114 g / eq), and a thiol compound manufactured by SC Organic Chemical Co., Ltd. (product name: PEPT (corresponding to general formula (4)), thiol equivalent: 124 g / eq).

[0033] Other examples of the component (B) include 1,3,4,6-tetrakis(mercaptomethyl)glycoluril, 1,3,4,6-tetrakis(mercaptomethyl)-3a-methylglycoluril, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a-methylglycoluril, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a-methylglycoluril, 1,3,4,6-tetrakis(mercaptomethyl)-3a,6a-dimethylglycoluril, and 1,3,4,6-tetrakis(2-mercaptoethyl)-3a,6 a-Dimethylglycoluril, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a,6a-dimethylglycoluril, 1,3,4,6-tetrakis(mercaptomethyl)-3a,6a-diphenylglycoluril, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a,6a-diphenylglycoluril, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a,6a-diphenylglycoluril, pentaerythritol tetrapropanethiol, 1,2,3-tris(mercaptomethylthio)propane , 1,2,3-tris(2-mercaptoethylthio)propane, 1,2,3-tris(3-mercaptopropylthio)propane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, tetrakis(mercaptomethylthiomethyl)methane, tetra bis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercaptopropylthiomethyl)methane, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 1,1,5,5-tetrakis(mercaptomethylthio)-3-thiapentane, 1,1,6,6-tetrakis(mercaptomethylthio)-3,4-dithiahexane, 2,2-bis(mercaptomethylthio)ethanethiol, 3-mercaptomethylthio-1,7-dimercapto-2,6-dithiaheptane, 3,6-bis(mercaptomethylthio)-1,9-dimercapto-2,5,8-trithianonane, 3-mercaptomethylthio-1,6-dimercapto-2,5-dithiahexane, 1,1,9,9-tetrakis(mercaptomethylthio)-5-(3,3-bis(mercaptomethylthio)-1-thiapropyl)3,7-dithianonane, tris(2,2-bis(mercaptomethylthio)ethyl)methane, tris(4,4-bis(mercaptomethylthio)-2-thiabutyl)methane, tetrakis(2,2-bis(mercaptomethylthio)ethyl)methane, tetrakis(2,2-bis(mercaptomethylthio)ethyl)methane, bis(mercaptomethylthio)-2-thiabutyl)methane, 3,5,9,11-tetrakis(mercaptomethylthio)-1,13-dimercapto-2,6,8,12-tetrathiatridecane, 3,5,9,11,15,17-hexakis(mercaptomethylthio)-1,19-dimercapto-2,6,8,12,14,18-hexathianonadecane, 9-(2,2-bis(mercaptomethylthio)ethyl)-3,5,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,6,8,10,12,16-hexakis Thiaheptadecane, 3,4,8,9-tetrakis(mercaptomethylthio)-1,11-dimercapto-2,5,7,10-tetrathiaundecane, 3,4,8,9,13,14-hexakis(mercaptomethylthio)-1,16-dimercapto-2,5,7,10,12,15-hexathiahexadecane, 8-[bis(mercaptomethylthio)methyl]-3,4,12,13-tetrakis(mercaptomethylthio)-1,15-dimercapto-2,5,7,9,11,14-hexathiapentadecane, 4,6-bis[3,5-bis(mercaptomethylthio)] 1,1-bis[4-(6-mercaptomethylthio)-1,3-dithianylthio]-1,3-bis(mercaptomethylthio)propane, 1-[4-(6-mercaptomethylthio)-1,3-dithianylthio]-3-[2,2-bis(mercaptomethylthio)ethyl]-7,9-bis(mercaptomethylthio)-2,4,6,10-Tetrathiaundecane, 3-[2-(1,3-dithietanyl)]methyl-7,9-bis(mercaptomethylthio)-1,11-dimercapto-2,4,6,10-tetrathiaundecane, 9-[2-(1,3-dithietanyl)]methyl-3,5,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,6,8,10,12,16-hexathiaheptadecane, 3-[2-(1,3-dithietanyl)]methyl-7,9,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,4,6,10,1 2,16-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)- 4-[3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiaoctyl]-5-mercaptomethylthio-1,3-dithiolane, 2-{bis[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]methyl}-1,3-dithietane, 2-[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexyl thio]mercaptomethylthiomethyl-1,3-dithietane, 2-[3,4,8,9-tetrakis(mercaptomethylthio)-11-mercapto-2,5,7,10-tetrathiaundecylthio]mercaptomethylthiomethyl-1,3-dithietane, 2-[3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiaoctyl]mercaptomethylthiomethyl-1,3-dithietane, 4-{1-[2-(1,3-dithietanyl)]-3-mercapto-2-thiapropylthio}-5-[1,Examples of suitable thiol compounds include, but are not limited to, 2-bis(mercaptomethylthio)-4-mercapto-3-thiabutylthio]-1,3-dithiolane.

[0034] As the component (B), any one of them may be used alone, or two or more of them may be used in combination.

[0035] In this specification, functional group equivalents such as thiol equivalent and (meth)acryloyl equivalent represent the molecular weight of a compound per functional group, and functional group equivalent numbers such as thiol group equivalent number and (meth)acryloyl group equivalent number represent the number of functional groups (equivalent number) per mass (charge amount) of a compound.

[0036] In the resin composition, the ratio of the number of (meth)acryloyl group equivalents of component (A) to the number of thiol group equivalents of component (B) ([number of (meth)acryloyl group equivalents of component (A)] / [number of thiol group equivalents of component (B)]) is preferably 0.25 to 3.0, more preferably 0.4 to 2.0, and even more preferably 0.5 to 1.5. Theoretically, the thiol equivalent of component (B) is the molecular weight of component (B) divided by the number of thiol groups in one molecule. The actual thiol equivalent can be determined, for example, by determining the thiol value by potentiometric measurement. This method is widely known and is disclosed, for example, in paragraph 0079 of JP 2012-153794 A. The thiol group equivalent number of component (B) is the number of thiol groups (equivalent number) per mass (charge amount) of component (B), and is the quotient obtained by dividing the mass (g) of the polyfunctional thiol compound (B) by the thiol equivalent of that thiol compound (when multiple thiol compounds are contained, the sum of such quotients for each thiol compound). Theoretically, the (meth)acryloyl equivalent number of the (A) (meth)acrylate compound is equal to the molecular weight of the (meth)acrylate compound divided by the number of acryloyl groups (or methacryloyl groups) in one molecule. The actual (meth)acryloyl equivalent number can be measured, for example, by NMR. The (meth)acryloyl group equivalent number of component (A) is the number of (meth)acryloyl groups (equivalent number) per mass (charge amount) of component (A), and is the quotient obtained by dividing the mass (g) of the (A) (meth)acrylate compound by the (meth)acryloyl equivalent of that (meth)acrylate compound (if multiple (meth)acrylate compounds are contained, the sum of such quotients for each (meth)acrylate compound). By setting the ratio [(meth)acryloyl group equivalent number of component (A)] / [thiol group equivalent number of component (B)] in the range of 0.25 to 3.0, a certain amount or more of (meth)acryloyl groups and thiol groups react, resulting in sufficient formation of molecular crosslinks and making it easier to demonstrate high adhesive strength.

[0037] (C) Curing Catalyst The resin composition of this embodiment contains a curing catalyst (C) (hereinafter also referred to as "component (C)"). The curing catalyst (C) used in this embodiment is not particularly limited as long as it is a curing catalyst for (meth)acrylate compounds, and known curing catalysts can be used, but it is preferably a latent curing catalyst. The latent curing catalyst of component (C) is a compound that is inactive at room temperature but is activated by heating to function as a curing catalyst. Examples of the latent curing catalyst include imidazole compounds that are solid at room temperature; solid-dispersed amine adduct latent curing catalysts such as reaction products of amine compounds and epoxy compounds (amine-epoxy adducts); and reaction products of amine compounds and isocyanate compounds or urea compounds (urea adducts).

[0038] 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, and 2,4-diamino-6-(2'-methylimidazolyl-(1)')-ethyl-S-triazine. Examples of the methylimidazole include, but are not limited to, dimethylimidazolyl-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, and N,N'-(2-methylimidazolyl-(1)-ethyl)-adiboyldiamide.

[0039] Examples of epoxy compounds used as one of the raw materials for producing a solid dispersion type amine adduct latent curing catalyst (amine-epoxy adduct) include polyglycidyl ethers obtained by reacting epichlorohydrin with polyhydric phenols such as bisphenol A, bisphenol F, catechol, and resorcinol, or polyhydric alcohols such as glycerin and polyethylene glycol; glycidyl ether esters obtained by reacting epichlorohydrin with hydroxycarboxylic acids such as p-hydroxybenzoic acid and β-hydroxynaphthoic acid; phthalic acid, terephthalic acid, and the like; Examples of epoxy compounds include, but are not limited to, polyglycidyl esters obtained by reacting a polycarboxylic acid such as carboxylic acid with epichlorohydrin; glycidylamine compounds obtained by reacting 4,4'-diaminodiphenylmethane or m-aminophenol with epichlorohydrin; and polyfunctional epoxy compounds such as epoxidized phenol novolac resin, epoxidized cresol novolac resin, and epoxidized polyolefin; and monofunctional epoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, and glycidyl methacrylate.

[0040] The amine compound used as another raw material for producing the solid dispersion-type amine adduct latent curing catalyst may be any compound as long as it has one or more active hydrogen atoms in the molecule capable of addition reacting with an epoxy group and at least one functional group selected from a primary amino group, a secondary amino group, and a tertiary amino group in the molecule. Examples of such amine compounds include, but are not limited to, aliphatic amines such as diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, and 4,4'-diamino-dicyclohexylmethane; aromatic amine compounds such as 4,4'-diaminodiphenylmethane and 2-methylaniline; and nitrogen-containing heterocyclic compounds such as 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline, piperidine, and piperazine.

[0041] Among these, compounds having a tertiary amino group in the molecule are particularly useful as raw materials for providing latent curing catalysts with excellent curing acceleration capabilities. Examples of such compounds include amine compounds such as dimethylaminopropylamine, diethylaminopropylamine, di-n-propylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, and N-methylpiperazine, as well as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, and 2-phenylimidazole. primary or secondary amines having a tertiary amino group in the molecule, such as imidazole compounds such as imidazole; 2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol, 1-(2-hydroxy-3-phenoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-ethyl-4 ... 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-butoxypropyl)-2-ethyl-4-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-phenylimidazoline, 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazoline, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol, N-β-hydroxyethylmorpholine, 2-dimethylaminoethanethiol, 2-mercaptopyridine, 2-benzimidazole Examples of the tertiary amino acid include, but are not limited to, alcohols, phenols, thiols, carboxylic acids, and hydrazides having a tertiary amino group in the molecule, such as thiazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 4-mercaptopyridine, N,N-dimethylaminobenzoic acid, N,N-dimethylglycine, nicotinic acid, isonicotinic acid, picolinic acid, N,N-dimethylglycine hydrazide, N,N-dimethylpropionic acid hydrazide, nicotinic acid hydrazide, and isonicotinic acid hydrazide.

[0042] Further, examples of the isocyanate compound used as another manufacturing raw material for the solid dispersion type amine adduct latent curing catalyst include monofunctional isocyanate compounds such as n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, and benzyl isocyanate; polyfunctional isocyanate compounds such as hexamethylene diisocyanate, toluylene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, and bicycloheptane triisocyanate; and terminal isocyanate group-containing compounds obtained by reacting these polyfunctional isocyanate compounds with active hydrogen compounds. Examples of such a terminal isocyanate group-containing compound include, but are not limited to, an addition compound having a terminal isocyanate group obtained by reacting toluylene diisocyanate with trimethylolpropane, and an addition compound having a terminal isocyanate group obtained by reacting toluylene diisocyanate with pentaerythritol.

[0043] Examples of urea compounds include, but are not limited to, urea and thiourea.

[0044] The solid-dispersed latent curing catalyst that can be used in this embodiment is, for example, the above-mentioned combination of two components: (a) an amine compound and an epoxy compound, (b) a combination of three components: these two components and an active hydrogen compound, or (c) a combination of two or three components: an amine compound and an isocyanate compound and / or a urea compound. These can be easily prepared by mixing the components, reacting them at a temperature from room temperature to 200°C, cooling them to solidify them, and then pulverizing them, or by reacting them in a solvent such as methyl ethyl ketone, dioxane, or tetrahydrofuran, removing the solvent, and then pulverizing the solid content.

[0045] Representative examples of commercially available solid dispersion-type latent curing catalysts include amine-epoxy adducts (amine adducts), such as "Amicure PN-23" (product name of Ajinomoto Fine-Techno Co., Ltd.), "Amicure PN-40" (product name of Ajinomoto Fine-Techno Co., Ltd.), "Amicure PN-50" (product name of Ajinomoto Fine-Techno Co., Ltd.), "Hardener X-3661S" (product name of ACR Co., Ltd.), and "Hardener X-3670S" (product name of ACR Co., Ltd.). - CR Corporation product name), "Novacure HX-3742" (Asahi Kasei Corporation product name), "Novacure HX-3721" (Asahi Kasei Corporation product name), "Novacure HXA3922HP" (Asahi Kasei Corporation product name), "Novacure HXA9322HP" (Asahi Kasei Corporation product name), "Novacure HXA5945HP" (Asahi Kasei Corporation product name), "Novacure HXA5911HP" (Asahi Kasei Corporation product name), "Fujicure FXR1121" (T & K TOKA Corporation product name), and the like, and examples of urea-type adducts include "Fujicure FXE-1000" (T & K TOKA Corporation product name), "Fujicure FXR-1030" (T & K TOKA Corporation product name), but are not limited thereto. The component (C) may be used alone or in combination of two or more.

[0046] The content of the curing catalyst (C) is preferably 0.1 to 40 mass %, more preferably 1 to 20 mass %, relative to the total mass of the resin composition, from the viewpoints of the curing rate and pot life of the resin composition.

[0047] (D) Zeolite Particles The resin composition of this embodiment contains (D) zeolite particles (hereinafter also referred to as "component (D)"). This makes it possible to obtain a resin composition that can suppress the bleeding phenomenon. It is believed that the high adsorption properties of zeolite allow components in the system that could cause bleeding to be adsorbed by the zeolite, thereby suppressing the bleeding phenomenon.

[0048] Zeolite is a general term for crystalline aluminosilicates, and its general composition is represented by the following formula (I): Mz + [(SiO ２ ) x (Al ２ O ３)y]z- (I) (In formula (I), M is an ion-exchangeable cation species, and typically represents a monovalent or divalent metal, z is the valence of M, and x and y are any integers.) Preferably, M is a metal atom selected from Groups 1 to 13, and more preferably a hydrogen ion (H ＋ ), lithium ion (Li ＋ ), sodium ions (Na ＋ ), potassium ions (K ＋ ), calcium ions (Ca ２＋ ), magnesium ions (Mg ２＋ ) and barium ions (Ba ２＋ ) and x / y (SiO ２ / Al ２ O ３ The molar ratio is, for example, 1 to 100, preferably 2 to 6. The zeolite represented by the formula (I) may be expressed as a general formula further including a hydrate. ２ / Al ２ O ３ The molar ratio can be measured using X-ray fluorescence analysis (XRF).

[0049] Zeolites have a variety of crystal structures, including, for example, A-type, X-type, LSX-type, beta-type, ZSM-5-type, ferrierite-type, mordenite-type, L-type, and Y-type. In this embodiment, zeolites of any crystal structure can be used, but A-type, X-type, and LSX-type are preferred, A-type and X-type are more preferred, and A-type is even more preferred. Zeolites generally have cations in their crystal structure, and these cations compensate for the negative charge in the crystal structure composed of aluminosilicate, thereby making up for the lack of positive charge. Examples of cations include hydrogen ions, lithium ions, calcium ions, sodium ions, potassium ions, magnesium ions, and barium ions.

[0050] In this embodiment, the zeolite is in a particulate form, and the average particle size of the (D) zeolite particles is preferably 1 μm or less, more preferably 10 nm to 1 μm, and even more preferably 10 nm to 500 nm, from the viewpoint of better bleed suppression. In one aspect, the particle size of the (D) zeolite particles is 10 nm to 250 nm. In this case, the bleed suppression effect is particularly remarkable. In another aspect, the particle size of the (D) zeolite particles is 250 nm to 1 μm. In this case, both the bleed suppression effect and workability can be achieved.

[0051] From the viewpoints of suppressing bleeding and improving the workability of the resin composition, the content of the (D) zeolite particles is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, relative to the total mass of the resin composition. Also, the content is preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 5% by mass or less. In one embodiment, the content is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, and particularly preferably 0.1 to 5% by mass.

[0052] (E) Surfactant The resin composition of this embodiment can further contain (E) a surfactant (hereinafter also referred to as "component (E)"). This can achieve a further bleeding suppression effect. Known surfactants can be used as (E). Preferred surfactants include surfactants having one or more, preferably two or more, hydrophilic groups selected from the group consisting of hydroxyl groups and carbonyl groups in the molecule, and surfactants having two or more hydroxyl groups in the molecule are more preferred. Among such surfactants, surfactants having a hydrophilic portion containing a cyclic structure and / or gemini surfactants are more preferred. When the resin composition contains a surfactant having one or more hydrophilic groups selected from the group consisting of hydroxyl groups and carbonyl groups in the molecule, the surfactant is coordinated at the interface between the resin and the substrate, and the hydrophilic portion (particularly the hydroxyl group or carbonyl group) of the surfactant interacts with the substrate, exerting a pinning effect and further suppressing bleeding.

[0053] The cyclic structure in the surfactant having a hydrophilic portion containing a cyclic structure includes an alicyclic hydrocarbon group such as cyclopentane or cyclohexane, or an alicyclic heterocyclic group such as tetrahydrofuran or tetrahydropyran. This cyclic structure is preferably substituted with one or more, preferably two or more, substituents selected from a hydroxyl group, a carbonyl group, and an ester bond. This cyclic structure is bonded to the hydrophobic portion with or without a spacer group containing a group selected from a hydroxyl group, a carbonyl group, and an ester bond. Examples of such compounds include compounds in which a cyclic structure such as tetrahydrofuran is bonded to a saturated or unsaturated fatty acid. This allows the molecule to contain multiple hydrophilic groups selected from the group consisting of hydroxyl groups and carbonyl groups in a compact region, which is thought to enhance interaction with the substrate and further suppress bleeding.

[0054] A gemini surfactant is a surfactant in which a plurality of, typically two, surfactants each having one hydrophobic chain and one hydrophilic group, i.e., a monomeric surfactant, are bonded via a spacer. In this embodiment, the gemini surfactant can have two or more hydrophilic groups selected from the group consisting of hydroxyl groups and carbonyl groups in the molecule, which is thought to enhance the interaction with the substrate and further suppress bleeding.

[0055] Examples of surfactants having one or more hydrophilic groups selected from the group consisting of hydroxyl groups and carbonyl groups in the molecule include compounds represented by the following general formulas (5) to (7): Compound represented by general formula (5): In formula (5), X is carbon (C) or oxygen (O), and R １ , R ２ , R ３ and R ４ are each independently hydrogen (H), a hydroxyl group (OH), -(CH ２ ) ｎ -OC(=O)-R ５ where R ５ is the hydrocarbon chain of a fatty acid, n is 0 to 3, (CH ２ ) ｎEach hydrogen atom in the R group may be independently replaced with a hydroxyl group; １ , R ２ , R ３ and R ４ At least one of the following is -(CH ２ ) ｎ -OC(=O)-R ５ and R １ , R ２ , R ３ and R ４ At least one of the groups is a hydroxyl group, or (CH ２ ) ｎ The hydrogen of the group is replaced with a hydroxyl group, so that the compound has at least one hydroxyl group. ５ The hydrocarbon chain of the fatty acid in the formula (5) has, for example, 10 to 20 carbon atoms, preferably 11 to 18 carbon atoms, and more preferably 12 to 18 carbon atoms. The hydrocarbon chain of the fatty acid may contain a carbon-carbon double bond, and the number of carbon-carbon double bonds is, for example, 0 to 5, preferably 0 to 3, and more preferably 0 to 2. When a carbon-carbon double bond is contained, both the cis- and trans-isomers are included in the compound of formula (5). Preferably, R １ , R ２ , R ３ and R ４ Two of the groups are hydroxyl groups. ２ ) ｎ The hydrogen of the group is replaced with at least one hydroxyl group. １ , R ２ , R ３ and R ４ Two of the groups are hydroxyl groups, and (CH ２ ) ｎ The hydrogen of the group is replaced with at least one hydroxyl group.

[0056] Specific examples of the compound of general formula (5) include compounds of the following chemical formulas (5a), (5b) and (5c). Compounds of formula (5b) and (5c) are particularly preferred.

[0057] Compound of formula (6): In formula (6), m and n each represent an integer of 0 to 10, and m+n represents an integer of 0 to 20, preferably 2 to 8.

[0058] Compound of formula (7): In formula (7), n is 1 to 20.

[0059] The compounds of formula (5), formula (5a), formula (5b), formula (5c), formula (6), and formula (7) are not limited to the description of structural formulae for convenience, and include all isomers (e.g., geometric isomers, optical isomers based on asymmetric carbons, rotational isomers, stereoisomers, tautomers, and the like) that may arise from the structure of the compounds, as well as mixtures of two or more of these isomers.

[0060] Examples of surfactants having one or more hydrophilic groups selected from the group consisting of hydroxyl groups and carbonyl groups in the molecule include polyoxyethylene octyl ether, polyoxyethylene decyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl (C12-13) ether, polyoxyethylene secondary alkyl (C12-14) ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene myristyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyalkylene alkyl (C11-15) ether, polyoxyalkylene secondary alkyl (C12-14) ether, polyoxyalkylene cetyl ether, polyoxyethylene laurylamine, polyoxyethylene oleylamine, polyoxyethylene polystyrylphenyl ether, polyoxyethylene octyl ether, polyoxyethylene dec ... Polyoxyalkylene polystyrylphenyl ether, polyoxyethylene polystyrylphenyl ether, polyoxyethylene polystyrylphenyl ether condensate, polyoxyethylene cumylphenyl ether, polyoxyethylene naphthyl ether, polyoxyethylene dilaurate, polyoxyethylene laurate, polyoxyethylene diolate, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan oleate, polyoxyethylene sorbitan trioleate, trimethylolpropane tridecanoate polyoxyalkylene butyl ether, polyoxyalkyl oleyl ether, polyoxyethylene polyoxypropylene condensate, trimethylolpropane tris(polyoxyalkylene)ether, polyoxyalkylene diglyceryl ether, but are not limited to these.

[0061] The surfactant (E) may be used alone or in combination of two or more thereof.

[0062] From the viewpoint of suppressing bleeding, the content of the surfactant (E) is preferably 0.1 to 10 mass %, more preferably 0.2 to 7 mass %, and even more preferably 0.3 to 5 mass %, relative to the total mass of the resin composition.

[0063] (F) Rubber Component The resin composition of the present embodiment may further contain (F) a rubber component (hereinafter also referred to as "component (F)"). This can provide an even greater bleeding suppression effect. It is believed that the rubber component acts as a steric hindrance and inhibits the resin flow of the resin composition, thereby further suppressing bleeding.

[0064] The type of rubber component is not particularly limited. Preferred monomers constituting the rubber component include ethylene, propylene, butadiene, styrene, acrylonitrile, acrylic acid esters, methacrylic acid esters, urethane, epoxypropyl methacrylate, divinylbenzene, and various derivatives. The rubber component is a copolymer obtained by polymerizing one or more of these monomers. Specific examples of the rubber component include acrylic rubber, urethane rubber, urethane acrylate rubber, isoprene rubber, butadiene rubber, styrene / isoprene copolymer rubber, styrene / butadiene copolymer rubber, acrylonitrile / butadiene copolymer rubber, saturated rubbers obtained by hydrogenating or partially hydrogenating these diene rubbers, silicone rubber, chloroprene rubber, natural rubber, ethylene / propylene copolymer rubber, ethylene / propylene / diene monomer terpolymer rubber, butyl rubber, chlorosulfonated polyethylene, chlorinated polyethylene, epichlorohydrin rubber, fluororubber, and acrylic / silicone composite rubber. Among these, from the viewpoint of suppressing bleeding, a rubber component made of any one of acrylic rubber, urethane rubber, isoprene rubber, butadiene rubber, acrylonitrile / butadiene copolymer rubber, silicone rubber, and silicone / acrylic composite rubber is more preferable. These rubber components may be crosslinked or uncrosslinked. The crosslinking method for the rubber is selected depending on the type of rubber component, and examples include sulfur crosslinking, peroxide crosslinking, resin crosslinking, amine crosslinking, polyol crosslinking, oxime crosslinking, and metal crosslinking. The (F) rubber component may be solid at 25°C or liquid at 25°C.

[0065] When the (F) rubber component is solid at 25°C, the form of the (F) rubber component is not particularly limited, and examples include granular, powdery, and pellet-like forms. From the viewpoint of dispersibility, the (F) rubber component is preferably granular. The granular rubber component may be rubber particles having a core-shell structure, specifically, rubber particles having the aforementioned rubber component as a core and further having a shell made of a polymer of a radically polymerizable compound coating the outside. When the (F) rubber component is granular, the average particle diameter of the (F) rubber component is preferably 0.01 μm to 20 μm, more preferably 0.02 μm to 10 μm, and even more preferably 0.03 μm to 5 μm. In this specification, the average particle diameter of the rubber particles is the arithmetic (number) average particle diameter, which can be measured using a dynamic light scattering method. For example, rubber particles can be dispersed in an appropriate organic solvent and measured using a particle size distribution analyzer. Furthermore, when the rubber component (F) is solid at 25°C, from the viewpoint of rubber elasticity, the glass transition point of the rubber component is preferably 40°C or lower, more preferably 25°C or lower, and even more preferably 0°C or lower. The glass transition point is preferably -100°C or higher. The glass transition point can be determined by DSC measurement based on JIS K6240.

[0066] When the (F) rubber component is liquid at 25°C, examples of the (F) rubber component include low molecular weight components such as liquid isoprene rubber, carboxy-modified liquid isoprene rubber, liquid butadiene rubber, carboxy-modified liquid butadiene rubber, hydroxyl-modified liquid butadiene rubber, liquid acrylonitrile / butadiene copolymer rubber, liquid styrene / butadiene copolymer rubber, liquid styrene / isoprene copolymer rubber, and liquid silicone rubber. The weight average molecular weight of the low molecular weight component is preferably 5,000 to 80,000, and more preferably 8,000 to 50,000.

[0067] Examples of commercially available rubber components (F) that are solid at 25°C include a butadiene-acrylonitrile-2,3-epoxypropyl methacrylate-divinylbenzene polymer compound (product name: XER81) manufactured by JSR Corporation, and cross-linked urethane rubber beads (product names: C-400T, C-600T, C-800T, and C-1000T; P-400T and P-800T; U-600T; C-600TH; JB-400CB, JB-600T, and JB-800T; CE-400T and CE-800T; AK-800TR; TK-800T, and TK-1000TR) manufactured by Negami Chemical Industrial Co., Ltd., but are not limited thereto. Examples of rubbers that are liquid at 25°C include, but are not limited to, carboxy-terminated butadiene nitrile rubber (product names: CTBN1300 and CTBN1008-SP) manufactured by Ube Industries, Ltd., amine-terminated butadiene nitrile rubber (product name: ATBN1300-16) manufactured by Ube Industries, Ltd., silicone rubber powder (product name: AY42-119) manufactured by Dow Corning Toray Co., Ltd., and epoxidized polybutadiene rubber (product name: Epolead PB3600) manufactured by Daicel Chemical Industries, Ltd. The rubber component (F) may be used alone or in combination of two or more.

[0068] The content of the rubber component (F) in the resin composition is preferably 0.1 to 10 mass %, more preferably 0.2 to 7 mass %, and even more preferably 0.3 to 5 mass %, based on the total mass of the resin composition.

[0069] (G) Photoradical Initiator The resin composition of this embodiment may contain (G) a photoradical initiator (hereinafter also referred to as "component (G)") within a range that does not impair the effects of the present invention. By including the (G) photoradical initiator, UV curing is promoted. Examples of the (G) photoradical initiator include, but are not limited to, alkylphenone-based compounds and acylphosphine oxide-based compounds.

[0070] Examples of alkylphenone compounds include benzyl dimethyl ketals such as 2,2-dimethoxy-1,2-diphenylethan-1-one (commercially available as Omnirad 651 from IGM Resins B.V.); α-aminoalkylphenones such as 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one (commercially available as Omnirad 907 from IGM Resins B.V.); α-hydroxyalkylphenones such as 1-hydroxy-cyclohexyl-phenyl-ketone (commercially available as Omnirad 184 from IGM Resins B.V.); 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one (commercially available as Omnirad 184 from IGM Resins B.V.); 379EG), 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone (commercially available as Omnirad 369, manufactured by IGM Resins BV), and the like.

[0071] Examples of the acylphosphine oxide compound include, but are not limited to, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (commercially available as Omnirad TPO H manufactured by IGM Resins B.V.), bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (commercially available as Omnirad 819 manufactured by IGM Resins B.V.), and the like.

[0072] (G) Examples of the photoradical initiator include, in addition to the above-mentioned photoradical initiators, 2-hydroxy-2-methyl-1-phenylpropan-1-one, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin phenyl ether, and benzyl dimethyl ketone. Examples of suitable benzoxanthone include, but are not limited to, benzoyl, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methylphenyl glyoxylate, benzil, and camphorquinone.

[0073] From the viewpoint of UV curability, the content of the (G) photoradical initiator is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 8 parts by mass, per 100 parts by mass of the (meth)acrylate compound.

[0074] (H) Filler The resin composition of this embodiment may contain (H) filler (hereinafter also referred to as "component (H)") within a range that does not impair the effects of the present invention. By containing (H) filler in the resin composition, the linear expansion coefficient of the cured product obtained by curing the resin composition can be reduced, and thermal cycle resistance can be improved. Furthermore, if the filler has a low elastic modulus, it can alleviate stress generated in the cured product, improving long-term reliability. (H) fillers are broadly classified into inorganic fillers and organic fillers.

[0075] The inorganic filler is not particularly limited as long as it is a granular material formed from an inorganic material and has the effect of lowering the linear expansion coefficient when added. However, in this specification, (D) zeolite particles are excluded from (H) filler (or inorganic filler). As inorganic materials, silica, talc, alumina, aluminum nitride, calcium carbonate, aluminum silicate, magnesium silicate, magnesium carbonate, barium sulfate, barium carbonate, lime sulfate, aluminum hydroxide, calcium silicate, potassium titanate, titanium oxide, zinc oxide, silicon carbide, silicon nitride, boron nitride, etc. can be used. As the inorganic filler, any one type may be used, or two or more types may be used in combination. As the inorganic filler, silica filler is preferably used because it can increase the loading amount. As the silica, amorphous silica is preferred.

[0076] The inorganic filler is preferably one whose surface has been treated with a coupling agent such as a silane coupling agent, which allows the viscosity of the resin composition to fall within an appropriate range.

[0077] Examples of the organic filler include polytetrafluoroethylene (PTFE) filler, silicone filler, acrylic filler, styrene filler, etc. The particulate (F) rubber component is excluded from the (H) filler (or organic filler). The organic filler may be surface-treated. The glass transition temperature of the organic filler is preferably above 40°C.

[0078] The shape of the filler is not particularly limited, and may be any of spherical, flaky, needle-like, irregular, etc.

[0079] In one embodiment, the average particle size of the filler is preferably 5.0 μm or less, more preferably 4.0 μm or less, and even more preferably 3.0 μm or less. In this specification, the average particle size refers to the volume-based median diameter (d ５０ ), or a value calculated as the number average of 50 measurements arbitrarily selected from observation images obtained by a transmission electron microscope (TEM) or a scanning electron microscope (SEM). By setting the average particle size of the filler to the upper limit or less, sedimentation of the filler can be suppressed, and the formation of coarse particles can be suppressed, thereby preventing clogging of the dispenser nozzle. The lower limit of the average particle size of the filler is not particularly limited, but from the viewpoint of the viscosity of the resin composition, it is preferably 0.005 μm or more, and more preferably 0.1 μm or more. In one aspect of this embodiment, the average particle size of the filler (H) is preferably 0.01 μm to 5.0 μm, and more preferably 0.1 μm to 3.0 μm. Fillers with different average particle sizes may be used in combination. For example, a filler having an average particle size of 0.005 μm or more but less than 0.1 μm may be used in combination with a filler having an average particle size of 0.1 μm to 5.0 μm.

[0080] The content of the filler (H) in the resin composition of this embodiment is preferably 0.5 to 80% by mass, more preferably 1 to 70% by mass, and even more preferably 3 to 60% by mass, based on the total mass of the resin composition. By setting the content of the filler (H) within this range, thermal cycle resistance is improved, and the viscosity of the resin composition is set within an appropriate range, improving applicability in dispensers.

[0081] (I) Stabilizer The resin composition of this embodiment may contain (I) a stabilizer (hereinafter also referred to as "component (I)") to the extent that the effects of the present invention are not impaired. The (I) stabilizer is added to increase the stability of the resin composition during storage and to suppress the occurrence of polymerization reactions due to unintended radicals or basic components. Typical examples of the (I) stabilizer include radical polymerization inhibitors and anionic polymerization inhibitors.

[0082] Known radical polymerization inhibitors can be used, and examples thereof include, but are not limited to, N-nitroso-N-phenylhydroxylamine aluminum, triphenylphosphine, p-methoxyphenol, and hydroquinone. Known radical polymerization inhibitors disclosed in JP-A-2010-117545, JP-A-2008-184514, etc. can also be used. Any one of the radical polymerization inhibitors may be used alone, or two or more may be used in combination.

[0083] When a radical polymerization inhibitor is contained, the content of the radical polymerization inhibitor is preferably 0.0001 to 5 mass %, and more preferably 0.001 to 3 mass %, relative to the total mass of the resin composition, from the viewpoint of pot life.

[0084] Known anionic polymerization inhibitors can be used, such as boric acid ester compounds and strong acids. Specific examples of anionic polymerization inhibitors include, but are not limited to, trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, trifluoromethanesulfonic acid, maleic acid, methanesulfonic acid, barbituric acid, difluoroacetic acid, trichloroacetic acid, phosphoric acid, and dichloroacetic acid. Among these, preferred anionic polymerization inhibitors are at least one selected from tri-n-propyl borate, triisopropyl borate, and barbituric acid. Furthermore, known anionic polymerization inhibitors disclosed in JP 2010-117545 A, JP 2008-184514 A, JP 2017-171804 A, and the like can also be used. Any one of the anionic polymerization inhibitors may be used, or two or more may be used in combination.

[0085] When an anionic polymerization inhibitor is contained, the content of the anionic polymerization inhibitor is preferably 0.001 to 5 mass %, more preferably 0.01 to 3 mass %, based on the total mass of the resin composition.

[0086] The resin composition may further contain, as necessary, a solvent, a coupling agent, carbon black, titanium black, an ion trapping agent, a leveling agent, an antioxidant, an antifoaming agent, a thixotropic agent, a viscosity modifier, a flame retardant, and / or other additives, within a range that does not impair the object of this embodiment.

[0087] The resin composition can be obtained, for example, by stirring, melting, mixing, and / or dispersing components (A) to (D), and optionally components (E), (F), (G), (H), and (I), and / or other additives, simultaneously or separately, while optionally applying heat treatment. The apparatus used for mixing, stirring, dispersing, etc. is not particularly limited. Examples of apparatus that can be used include a Raikai mixer, Henschel mixer, three-roll mill, ball mill, planetary mixer, and bead mill equipped with a stirring and heating device. These apparatuses may also be used in appropriate combinations.

[0088] The resin composition thus obtained has photocurability and thermosetting properties, and can be sufficiently cured by heat curing alone. When the resin composition is used in an image sensor module, the heat curing temperature of the resin composition is preferably 60 to 90°C.

[0089] The resin composition of this embodiment can be used, for example, as an adhesive, sealant, or damming agent for fixing, adhering, or protecting components, and as a raw material thereof, and is suitable as a one-component type. Here, the damming agent is formed, for example, around the periphery of a substrate before sealing multiple semiconductor chips or the like on the substrate with a low-viscosity filler or the like. The formation of a dam by this damming agent can prevent the subsequent outflow of the low-viscosity filler that seals the multiple semiconductor chips. Furthermore, adhesives containing the resin composition of this embodiment enable good bonding to engineering plastics, ceramics, and metals.

[0090] [Adhesive or Sealant] An adhesive or sealant according to a second embodiment of the present invention comprises the resin composition of the first embodiment described above. This adhesive or sealant enables good bonding to engineering plastics, ceramics, and metals. The adhesive or sealant of this embodiment is preferably used to fix, bond, or protect components that constitute an image sensor or camera module.

[0091] [Cured Product of Resin Composition, Adhesive, or Sealant] The cured product of the third embodiment of the present invention is a cured product obtained by curing the resin composition of the first embodiment or the adhesive or sealant of the second embodiment described above.

[0092] [Semiconductor Device, Electronic Component] A semiconductor device or electronic component according to a fourth embodiment of the present invention includes the cured product according to the third embodiment. Here, the term "semiconductor device" refers to any device that can function by utilizing semiconductor properties, including electronic components, semiconductor circuits, modules incorporating these, and electronic devices. Examples of semiconductor devices or electronic components include, but are not limited to, HDDs, semiconductor elements, sensor modules such as image sensor modules, camera modules, semiconductor modules, and integrated circuits. In one aspect, the semiconductor device or electronic component may be an image sensor or camera module.

[0093] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following examples, parts and % represent parts by mass and % by mass unless otherwise specified.

[0094] [Examples 1 to 19, Comparative Examples 1 to 4] Resin compositions were prepared by mixing predetermined amounts of each component using a three-roll mill according to the formulations shown in Table 1. In Table 1, the amount of each component is expressed in parts by mass (unit: g). The components used in the examples and comparative examples are as follows.

[0095] (A) (meth)acrylate compound (component (A)) (A-1): Polyester acrylate manufactured by Toagosei Co., Ltd. (product name: M7100, acryloyl equivalent: 188 g / eq) (A-2): Dimethylol-tricyclodecane diacrylate manufactured by Kyoeisha Chemical Co., Ltd. (product name: Light Acrylate DCP-A, acryloyl equivalent: 152 g / eq) (A-3): Neopentyl glycol-modified trimethylolpropane diacrylate manufactured by Nippon Kayaku Co., Ltd. (product name: Kayarad R-604, acryloyl equivalent: 163 g / eq) (B) Polythiol compound (component (B)) (B-1): Pentaerythritol tetrakis(3-mercaptopropionate) manufactured by SC Organic Chemical Co., Ltd. (product name: PEMP, thiol equivalent: 122 g / eq) (B-2): Thiol glycoluril derivative manufactured by Shikoku Chemical Industries, Ltd. (product name: C3 TS-G, thiol equivalent: 114 g / eq) (C) Curing catalyst (component (C)) (C-1): Solid dispersion type latent curing catalyst manufactured by T&K TOKA Corporation (product name: FXR1121) (D) Zeolite particles (component (D)) (D-1): Zeolite particles manufactured by Nakamura Choukou (product name: Zeoal4A 300 nm) (D-2): Zeolite particles manufactured by Nakamura Choukou (product name: Zeoal4A 50 nm) (D') Filler other than zeolite particles (component (D')) (D'-1): Calcium carbonate manufactured by Ube Material Industries, Ltd. (product name: CS3NA) (E) Surfactant (component (E)) (E-1): Sorbitan laurate (product name: D-931) manufactured by Takemoto Oil & Fat Co., Ltd. (F) Rubber (component (F)) (F-1): Butadiene-acrylonitrile-2,3-epoxypropyl methacrylate-divinylbenzene polymer compound (product name: XER81) manufactured by JSR Corporation (G) Photoradical initiator (component (G)) (G-1): α-Aminoalkylphenone manufactured by IGM Resins B.V.1-hydroxy-cyclohexyl-phenyl-ketone (product name: Omnirad 184) (H) Filler (component (H)) (H-1): calcium carbonate manufactured by Ube Material Industries, Ltd. (product name: CS3NA) Note that, although component (D'-1) and component (H-1) are the same component, for convenience, in Comparative Example 2, for comparison with Examples 1 to 3 which contain component (D), they are expressed as (D') filler other than zeolite particles, and in Examples 15 to 19 and Comparative Example 4, they are expressed as (H) filler which may be further contained.

[0096] [Bleeding Evaluation] 1.5 mg of the resin compositions of the Examples and Comparative Examples were potted onto a ceramic substrate that had been plasma-treated with argon (Ar) gas using a dispenser. After potting, the resin compositions were left at room temperature for 5 minutes and then thermally cured at 80°C for 60 minutes. The length of bleeding that occurred on the ceramic substrate from the cured resin composition was measured using a CCD camera (N = 3 pcs × 2 sides). The results are shown in Table 1.

[0097]

[0098]

[0099] It can be seen that the resin compositions of Examples 1 to 3, by including (D) zeolite particles, significantly suppressed the bleeding phenomenon compared to the resin composition of Comparative Example 1, which did not include (D) zeolite particles, and the resin composition of Comparative Example 2, which included a filler other than (D') zeolite particles (calcium carbonate filler) instead of (D) zeolite particles. It can be seen that the resin compositions of Examples 4 to 6, which varied the types and amounts of the (A) (meth)acrylate compound and the (B) polythiol compound, significantly suppressed the bleeding phenomenon compared to the resin composition of Comparative Example 1, which did not include (D) zeolite particles, by including (D) zeolite particles. It can be seen that the resin compositions of Examples 7 to 9, by including (D) zeolite particles and at least one of (E) surfactant and (F) rubber component, significantly suppressed the bleeding phenomenon. In Examples 10 to 14 and Comparative Example 3, which contain a (G) photoradical initiator, the inclusion of (D) zeolite particles (Examples 10 to 14) significantly suppresses the bleeding phenomenon compared to a resin composition that does not contain (D) zeolite particles (Comparative Example 3).In Examples 15 to 19 and Comparative Example 4, which contain a (H) filler, the inclusion of (D) zeolite particles (Examples 15 to 19) significantly suppresses the bleeding phenomenon compared to a resin composition that does not contain (D) zeolite particles (Comparative Example 4).

[0100] The present invention provides a resin composition that is at least thermosetting and capable of suppressing the bleeding phenomenon, and is particularly useful as an adhesive or sealant used for fixing, adhering, or protecting components of miniaturized or highly integrated semiconductor modules.

[0101] The disclosure of Japanese Patent Application No. 2022-048207 (filing date: March 24, 2022) is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. (A) a (meth)acrylate compound, (B) a polythiol compound, (C) a curing catalyst, and (D) Zeolite particles A resin composition comprising:

2. The resin composition according to claim 1, wherein the average particle size of the zeolite particles (D) is 1 μm or less.

3. The resin composition according to claim 1, wherein the content of the (D) zeolite particles is 0.1 mass% or more relative to the total mass of the resin composition.

4. The resin composition according to claim 1 , further comprising (E) a surfactant.

5. The resin composition according to claim 1 , further comprising a rubber component (F).

6. The resin composition according to claim 1 , further comprising (G) a photoradical initiator.

7. An adhesive or sealant comprising the resin composition according to any one of claims 1 to 6.

8. The adhesive or sealant according to claim 7, which is used for fixing, adhering or protecting components that constitute an image sensor or a camera module.

9. A cured product obtained by curing the resin composition according to any one of claims 1 to 6.

10. A semiconductor device or electronic component comprising the cured product according to claim 9.

11. The semiconductor device or electronic component according to claim 10, which is an image sensor or a camera module.