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

Abstract

The present invention addresses the problem of providing a resin composition and an adhesive with which a cured material, in which unreacted residues are suppressed after thermal curing following UV curing, can be obtained.　Provided is a resin composition comprising (A) a (meth)acrylate compound, (B) a polyfunctional thiol compound, (C) a photoradical polymerization initiator, and (D) a thermal curing accelerator containing an azabicyclo ring compound having bridgehead nitrogen.

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 resin composition containing (A) an acrylic resin, (B) a thiol compound, and (C) a latent curing accelerator, as a photo- and thermosetting resin composition that has high adhesive strength (particularly, high peel strength) after curing and can suppress a decrease in adhesive strength (particularly, peel strength) after a moisture resistance test after curing.

[0004] JP 2009-51954 A International Publication No. 2005 / 052021 International Publication No. 2018 / 047849

[0005] It has been found that photo- and thermosetting resin compositions or adhesives that are cured in a two-stage curing process, consisting of UV irradiation curing (first stage curing) followed by thermal curing (second stage curing), still have a significant amount of unreacted low-molecular-weight components remaining in the cured product even after the second stage of thermal curing. This is thought to be because, typically, most of the molecules in the region cured by UV irradiation curing in the first stage are immobilized, suppressing molecular motion in the second stage of thermal curing, and requiring more thermal energy for the thermosetting components to react compared to thermal curing alone. These unreacted components (hereinafter also referred to as "residual components") remaining in the cured region can cause problems such as bleed-out and outgassing over time. Furthermore, in some cases, additional heating is required in the third or subsequent stages when assembling the entire module. During this additional heating, the remaining components harden, causing the cured product to shrink, potentially resulting in misalignment or optical axis misalignment.

[0006] Therefore, an object of the present invention is to provide a resin composition and an adhesive that provide a cured product in which unreacted components are unlikely to remain after the second heat curing step that follows the first UV curing step.

[0007] 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 polyfunctional thiol compound; (C) a photoradical polymerization initiator; and (D) a thermal curing accelerator including an azabicyclo ring compound having a bridgehead nitrogen. (2) The resin composition according to (1) above, in which 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 0.25 to 3.0. (3) The resin composition according to (1) or (2) above, in which the (B) polyfunctional thiol compound includes a tri- or higher functional thiol compound. (4) The resin composition according to any of (1) to (3) above, further including (E) an epoxy compound.

[0008] A second embodiment of the present invention is an adhesive or sealant as follows: (5) An adhesive or sealant comprising the resin composition according to any one of (1) to (4) above. (6) The adhesive or sealant according to (5) above, which is used for fixing, adhering, or protecting components constituting an image sensor or a camera module.

[0009] A third embodiment of the present invention is the following cured product. (7) A cured product obtained by curing the resin composition according to any one of (1) to (4) above, or the adhesive or sealant according to (5) or (6) above. A fourth embodiment of the present invention is the following semiconductor device or electronic component. (8) A semiconductor device or electronic component comprising the cured product according to (7) above. (9) The semiconductor device or electronic component according to (8) above, which is an image sensor or a camera module.

[0010] According to a first embodiment of the present invention, a resin composition can be obtained that suppresses the remaining unreacted components after the second thermal curing step following the first UV curing step, suppresses the generation of bleed-out and outgassing, and provides a cured product with high dimensional stability upon additional heating. According to a second embodiment of the present invention, an adhesive or sealant can be obtained that suppresses the remaining unreacted components after the second thermal curing step following the first UV curing step, suppresses the generation of bleed-out and outgassing, and provides a cured product with high dimensional stability upon additional heating. According to a third embodiment of the present invention, a cured product with suppressed bleed-out and outgassing and high dimensional stability upon additional heating can be obtained. According to a fourth embodiment of the present invention, a semiconductor device or electronic component can be obtained that includes a cured product with suppressed bleed-out and outgassing and high dimensional stability upon additional heating.

[0011] [Resin Composition] The resin composition according to a first embodiment of the present invention comprises: (A) a (meth)acrylate compound, (B) a polyfunctional thiol compound, and (C) a photoradical polymerization initiator, and (D) a thermal curing accelerator containing an azabicyclo ring compound having a bridgehead nitrogen atom. According to this embodiment, it is possible to obtain a resin composition that suppresses the remaining of unreacted components after the second thermal curing step following the first UV curing step, suppresses the generation of bleed-out and outgassing, and provides a cured product that has high dimensional stability when subjected to additional heating.

[0012] (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 has one 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.

[0013] 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.

[0014] 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.

[0015] 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 type of component (A) may be used, or two or more types may be used in combination.

[0016] 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.

[0017] (B) Polyfunctional Thiol Compound The resin composition of this embodiment contains (B) a polyfunctional thiol compound (hereinafter also referred to as "component (B)"). The (B) polyfunctional thiol 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.

[0018] Examples of polyfunctional thiol 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).

[0019] 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.

[0020] Furthermore, examples of the polyfunctional thiol compound (B) include glycoluril compounds represented by the following general formula (1).

[0021]

[0022] 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.

[0023] Component (B) may also be a compound represented by the following chemical formula (2) or (3).

[0024]

[0025]

[0026] The compounds represented by chemical formula (2) or chemical formula (3) are more preferred compounds as component (B).

[0027] Furthermore, the polyfunctional thiol compound (B) may be a polyfunctional thiol compound represented by the general formula (4).

[0028]

[0029] 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.

[0030] 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)).

[0031] 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.

[0032] As the component (B), any one of these may be used alone, or two or more of them may be used in combination.

[0033] 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.

[0034] 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.

[0035] (C) Photoradical Polymerization Initiator The resin composition of this embodiment contains (C) a photoradical polymerization initiator (hereinafter also referred to as "component (C)"). By including the (C) photoradical polymerization initiator, UV curing is promoted. Examples of the (C) photoradical polymerization initiator include, but are not limited to, alkylphenone-based compounds and acylphosphine oxide-based compounds.

[0036] 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.

[0037] 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.

[0038] (C) Photoradical polymerization initiators include, in addition to the above-mentioned photoradical polymerization initiators, for example, 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 Examples of the benzoxanthone include, but are not limited to, ketals, 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, camphorquinone, and the like.

[0039] From the viewpoint of the curing rate and pot life of the resin composition, the content of component (C) is preferably 0.01 to 40 mass %, more preferably 0.1 to 20 mass %, relative to the total mass of the resin composition.

[0040] (D) Thermal Curing Accelerator The resin composition of this embodiment contains (D) a thermal curing accelerator containing an azabicyclocyclic compound having a bridgehead nitrogen (hereinafter also referred to as "component (D)"). By including (D) a thermal curing accelerator containing an azabicyclocyclic compound having a head-position nitrogen, it is possible to obtain a resin composition that suppresses the remaining unreacted components after the second-stage thermal curing following the first-stage UV curing, suppresses the generation of bleed-out and outgassing, and provides a cured product with high dimensional stability during additional heating. In this way, the generation of bleed-out and outgassing is suppressed, thereby suppressing contamination of surrounding components. Furthermore, the high dimensional stability during additional heating suppresses misalignment and optical axis misalignment.

[0041] Examples of the azabicyclo ring compound having a bridgehead nitrogen atom contained in the thermal curing accelerator (D) include compounds represented by the following general formula (5). In the general formula (5), Q is CR (where R is a hydrogen atom (H) or a hydrocarbon chain such as an alkyl group), a nitrogen atom (N), or a group represented by the following formula (6): (In formula (6), each single bond of the carbon atom is bonded to X and Y in formula (5), and the single bond of the nitrogen atom is bonded to Z in formula (5)), and X, Y, and Z each independently represent -(CH ２ ) n -(n=0 or 1 or more), and at least two of X, Y and Z have n=1 or more, and the hydrogen atoms on the hydrocarbon chains of Q, X, Y and Z may be substituted with a substituent selected from an optionally substituted alkyl group, a hydroxy group and an amino group, or may be substituted with an oxygen atom (O) to form a carbonyl group together with the carbon atom of the hydrocarbon chain. The substituent of the optionally substituted alkyl group is an alkyl group, a hydroxy group or an amino group.

[0042] In one embodiment, preferred compounds of general formula (5) are those in which Q is CR (wherein R is a hydrogen atom (H) or a hydrocarbon chain such as an alkyl group) or a nitrogen atom (N); X, Y, and Z are each independently -(CH ２ ) n-(n=2 or more, preferably n=2), and the hydrogen atoms on the hydrocarbon chains of Q, X, Y, and Z may be substituted with a substituent selected from an optionally substituted alkyl group, a hydroxy group, and an amino group, or may be substituted with an oxygen atom (O) to form a carbonyl group together with the carbon atoms of the hydrocarbon chain.

[0043] In one embodiment, another preferred compound of general formula (5) is one in which Q is represented by the following formula (6): (in formula (6), each single bond of the carbon atom is bonded to X and Y in formula (5), and the single bond of the nitrogen atom is bonded to Z in formula (5)), and X and Z are each independently -(CH ２ ) n -(n=1 or more, preferably 2 to 6) hydrocarbon chain, and Y is -(CH ２ ) n -(n=0), and the hydrogen atoms on the hydrocarbon chains of Q, X, and Z may be substituted with a substituent selected from an optionally substituted alkyl group, a hydroxy group, and an amino group, or may be substituted with an oxygen atom (O) to form a carbonyl group together with the carbon atoms on the hydrocarbon chain.

[0044] Azabicyclo compounds having a bridgehead nitrogen atom also include compounds containing a moiety represented by general formula (5). A compound containing a moiety represented by general formula (5) refers to a compound in which a compound represented by general formula (5) is bonded or linked to a second moiety via a covalent bond. The second moiety is not particularly limited, and examples thereof include saturated or unsaturated cyclic hydrocarbons, saturated or unsaturated heterocycles, aryls, and heteroaryls.

[0045] Examples of the compound of formula (5) include 1,4-diazabicyclo[2.2.2]octane (DABCO (registered trademark)), 1-azabicyclo[2.2.2]octan-3-ol (trivial name: 3-quinuclidinol), 1,4-diazabicyclo[2.2.2]octane-2-methanol, 1-azabicyclo[2.2.2]octan-3-one (trivial name: 3-quinuclidinone), 1,4-diazabicyclo[2.2.2]octan-2-ol, 1,8-diazabicyclo[5.4.0]-7-undecene (DBU (registered trademark)), and 1,5-diazabicyclo[4.3.0]non-5-ene (DBN (registered trademark)). Component (D) may be used alone or in combination of two or more.

[0046] It has been found that when a heat curing accelerator containing an imidazole compound, which is widely used as a heat curing accelerator for thermosetting resin compositions, is used, the reactivity is sufficient when heat curing is performed alone, but is not high when heat curing is performed after UV curing, and a considerable amount of low-molecular-weight components remain in the cured product. This is thought to be because, typically, most of the molecules in the region cured by the first-stage UV irradiation curing are immobilized, suppressing molecular motion in the second-stage heat curing, and requiring more thermal energy for the thermosetting components to react compared to when heat curing is performed alone. The inventors have found that by using a heat curing accelerator containing (D) an azabicyclocyclic compound having a bridgehead nitrogen atom in this embodiment, the reactivity is high even when heat curing is performed after UV curing, and the remaining unreacted components are suppressed in the cured product after the second-stage heat curing following the first-stage UV curing. The mechanism behind this is not limited, but is presumed to be as follows. In a photo- and heat-curable resin composition or adhesive cured by a two-stage curing process, there are regions where UV curing is incomplete after the first-stage UV irradiation. The thermal curability of the thermosetting functional groups remaining in the incompletely UV-cured region depends on the type of thermal curing accelerator. Azabicyclo compounds with bridgehead nitrogen are highly basic, so they are likely to react in the thermal curing process after UV curing. Saturated azabicyclo compounds with bridgehead nitrogen are particularly preferred because the steric hindrance of the bridgehead nitrogen is minimal. Furthermore, saturated diazabicyclo compounds with bridgehead nitrogen have two bridgehead nitrogens, making them even more preferred due to their high reactivity. On the other hand, commonly used thermal curing accelerators such as imidazole compounds and their derivatives have sufficient curing properties as thermal curing accelerators in the thermal curing process alone, but are less likely to undergo thermal curing reactions after UV curing due to their lower basicity compared to azabicyclo compounds with bridgehead nitrogen.

[0047] The present inventors have also found that the use of a thermal curing accelerator containing (D) an azabicyclocyclic compound having a bridgehead nitrogen enables the resin composition to be thermally cured at lower temperatures. For example, when a thermal curing accelerator containing an imidazole compound is used, the resin composition exhibits excellent low-temperature curing properties, but the curing temperature is limited to approximately 80°C. When a thermal curing accelerator containing (D) an azabicyclocyclic compound having a bridgehead nitrogen is used, the resin composition can be thermally cured at temperatures below 80°C, for example, at temperatures between 50°C and 80°C. The resin composition of this embodiment can also be thermally cured at temperatures above 80°C. When the resin composition is used in the manufacturing process of a semiconductor device or electronic component, particularly an image sensor module, the use of a thermal curing accelerator containing (D) an azabicyclocyclic compound having a bridgehead nitrogen enables the resin composition to be thermally cured at lower temperatures, thereby preventing thermal damage to module components (e.g., lenses, etc.).

[0048] From the viewpoint of curability, the azabicyclo compound having a bridgehead nitrogen contained in the (D) thermal curing accelerator is preferably a saturated azabicyclo compound having a bridgehead nitrogen. Examples of saturated azabicyclo compounds having a bridgehead nitrogen include compounds having a 1,4-diazabicyclooctane skeleton and compounds having a quinuclidine skeleton. From the viewpoint of increasing the reaction probability, compounds having a 1,4-diazabicyclooctane skeleton, which are compounds having two bridgehead nitrogens, are preferred. Specific examples of such compounds include 1,4-diazabicyclo[2.2.2]octane, 1,4-diazabicyclo[2.2.2]octane-2-methanol, 1,4-diazabicyclo[2.2.2]octan-2-ol, and 1,4-diazabicyclo[2.2.2]octane. Furthermore, from the viewpoint of affinity with the resin, compounds having a quinuclidine skeleton, which are compounds having one bridgehead nitrogen, are preferred. Specifically, from the viewpoint of affinity with resins having high polarity, 1-azabicyclo[2.2.2]octan-3-ol is preferred, and from the viewpoint of affinity with resins having low polarity, 1-azabicyclo[2.2.2]octan-3-one is preferred.

[0049] From the viewpoint of the curing rate and pot life of the resin composition, the content of component (D) is preferably 0.01 to 40 mass %, more preferably 0.05 to 20 mass %, relative to the total mass of the resin composition.

[0050] From the viewpoint of latency, the (D) heat curing accelerator may be a heat curing accelerator compound dispersed in an epoxy compound or supported between layers of a layered inorganic compound. A latent heat curing accelerator is an accelerator that is inactive at room temperature and is activated by heating to function as a curing catalyst. A representative example of a commercially available latent heat curing accelerator containing component (D) is "Novacure HXA5945HP" (product name of Asahi Kasei Corporation). The epoxy compound may be the following (E) epoxy compound.

[0051] The resin composition of this embodiment may contain a heat curing accelerator other than component (D) as long as the effects of the present invention are not impaired. Examples include imidazole compounds that are solid at room temperature; solid-dispersion 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).

[0052] Representative examples of commercially available heat curing accelerators other than component (D) 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 ACS Corporation), "Hardener X-3670S" (product name of ACS Corporation), "Novacure HX-3742" (product name of Asahi Kasei Corporation), "Novacure HX-3721" (product name of Asahi Kasei Corporation), "Novacure HXA3922HP" (product name of Asahi Kasei Corporation), "Novacure HXA9322HP" (product name of Asahi Kasei E-materials Co., Ltd.), and "Fujicure FXR-1121" (product name of T&K Corporation). Examples of urea-type adducts include "Fujicure FXE-1000" (product name, T&K TOKA Corporation) and "Fujicure FXR-1030" (product name, T&K TOKA Corporation), but are not limited to these.

[0053] It should be noted that when component (D) and heat curing accelerators other than component (D) are used that are provided in the form of a dispersion in an epoxy compound, the amount of the epoxy compound in which they are dispersed is also included in the amount of component (E) in the resin composition of this embodiment.

[0054] (E) Epoxy Compound The resin composition of this embodiment may further contain (E) an epoxy compound (hereinafter also referred to as "component (E)"). The (E) epoxy compound is not particularly limited as long as it is difunctional or higher, i.e., has two or more epoxy groups, and any conventionally used epoxy resin can be used as component (E). Note that epoxy resin is a general term for thermosetting resins that can be cured by forming a crosslinked network with the epoxy groups present in the molecule, and includes prepolymer compounds before curing. In one aspect of this embodiment, component (E) contains a difunctional epoxy compound.

[0055] Because the epoxy compound cannot undergo a crosslinking reaction upon excitation by the (C) photoradical polymerization initiator, it remains unreacted in the cured region of the resin composition after UV irradiation, and molecular motion is suppressed. This makes it difficult for the epoxy compound to undergo a curing reaction in the second thermal curing stage. The resin composition of this embodiment contains (D) a thermal curing accelerator containing an azabicyclocyclic compound having a bridgehead nitrogen, thereby accelerating the thermal curing of the epoxy compound in a state where molecular motion is suppressed.

[0056] The epoxy compound (E) is roughly classified into an aliphatic epoxy compound and an aromatic epoxy compound. In the present embodiment, the epoxy compound (E) preferably includes an aromatic epoxy compound.

[0057] Examples of aliphatic epoxy compounds include: diepoxy compounds such as (poly)ethylene glycol diglycidyl ether, (poly)propylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, polytetramethylene ether glycol diglycidyl ether, glycerin diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexane diglycidyl ether, and dicyclopentadiene diglycidyl ether; triepoxy compounds such as trimethylolpropane triglycidyl ether and glycerin triglycidyl ether; alicyclic epoxy compounds such as vinyl(3,4-cyclohexene) dioxide and 2-(3,4-epoxycyclohexyl)-5,1-spiro-(3,4-epoxycyclohexyl)-m-dioxane; -glycidylamine type epoxy compounds such as tetraglycidylbis(aminomethyl)cyclohexane; -hydantoin type epoxy compounds such as 1,3-diglycidyl-5-methyl-5-ethylhydantoin; and -epoxy compounds having a silicone skeleton such as 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane, but are not limited to these.

[0058] Among the above examples, "cyclohexane-type diglycidyl ether" refers to a compound having a structure in which two glycidyl groups are each bonded via an ether bond to a divalent saturated hydrocarbon group having one cyclohexane ring as the parent structure. "Dicyclopentadiene-type diglycidyl ether" refers to a compound having a structure in which two glycidyl groups are each bonded via an ether bond to a divalent saturated hydrocarbon group having a dicyclopentadiene skeleton as the parent structure. The aliphatic polyfunctional epoxy compound preferably has an epoxy equivalent of 90 to 450 g / eq. Furthermore, as the cyclohexane-type diglycidyl ether, cyclohexanedimethanol diglycidyl ether is particularly preferred.

[0059] Aromatic epoxy compounds are epoxy compounds having a structure containing an aromatic ring such as a benzene ring. Many of the epoxy resins that have been commonly used so far, such as bisphenol A epoxy resins, are of this type. Examples of aromatic epoxy compounds include, but are not limited to, bisphenol A type epoxy compounds; branched polyfunctional bisphenol A type epoxy compounds such as p-glycidyloxyphenyldimethyltrisbisphenol A diglycidyl ether; bisphenol F type epoxy compounds; novolac type epoxy compounds; tetrabromobisphenol A type epoxy compounds; fluorene type epoxy compounds; biphenyl aralkyl epoxy compounds; diepoxy compounds such as 1,4-phenyldimethanol diglycidyl ether; biphenyl type epoxy compounds such as 3,3',5,5'-tetramethyl-4,4'-diglycidyloxybiphenyl; glycidylamine type epoxy compounds such as diglycidylaniline, diglycidyltoluidine, triglycidyl-p-aminophenol, and tetraglycidyl-m-xylylenediamine; and naphthalene ring-containing epoxy compounds. In this embodiment, from the viewpoint of compatibility with the thiol compound, it is preferable that component (E) contains an aromatic epoxy compound rather than an aliphatic epoxy compound. As the aromatic epoxy compound, bisphenol F type epoxy compounds, bisphenol A type epoxy compounds, and glycidylamine type epoxy compounds are preferred, and among them, those having an epoxy equivalent of 90 to 300 g / eq are more preferred, those having an epoxy equivalent of 110 to 300 g / eq are particularly preferred, and those having an epoxy equivalent of 150 to 220 g / eq are most preferred. The (E) epoxy compound may be used alone or in combination of two or more types.

[0060] When the resin composition contains an epoxy compound (E), in the resin composition, the ratio of the sum of the number of (meth)acryloyl group equivalents of component (A) and the number of epoxy group equivalents of component (E) to the number of thiol group equivalents of component (B) (([number of (meth)acryloyl group equivalents of component (A)] + [number of epoxy group equivalents of component (E)]) / [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.

[0061] Furthermore, when the resin composition contains an epoxy compound (E), the ratio of the number of (meth)acryloyl group equivalents of component (A) to the number of epoxy group equivalents of component (E) ([number of (meth)acryloyl group equivalents of component (A)] / [number of epoxy group equivalents of component (E)]) in the resin composition is preferably 1 to 100, more preferably 2 to 80, even more preferably 3 to 50, particularly preferably 3 to 40, and most preferably 5 to 35.

[0062] Theoretically, the epoxy equivalent of component (E) is the molecular weight of component (E) divided by the number of epoxy groups in one molecule. The actual epoxy equivalent can be determined by the method described in JIS K7236. The epoxy group equivalent of component (E) is the number of epoxy groups (equivalent number) per mass (charge amount) of component (E), and is the quotient obtained by dividing the mass (g) of the epoxy compound in component (E) by the epoxy equivalent of that epoxy compound (when multiple epoxy compounds are contained, the sum of such quotients for each epoxy compound).

[0063] Alternatively, when the resin composition contains an epoxy compound (E), the content thereof is preferably 1.5 to 40 mass%, more preferably 2 to 30 mass%, and even more preferably 3 to 20 mass%, relative to the total mass of the resin composition.

[0064] (F) Filler The resin composition of this embodiment may contain (F) filler (hereinafter also referred to as "component (F)") within a range that does not impair the effects of the present invention. By containing (F) 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. (F) fillers are broadly classified into inorganic fillers and organic fillers.

[0065] The inorganic filler is not particularly limited as long as it is made of granular material formed from an inorganic material and has the effect of lowering the linear expansion coefficient when added. Examples of inorganic materials that can be used include silica, talc, alumina, aluminum nitride, calcium carbonate, aluminum silicate, magnesium silicate, magnesium carbonate, barium sulfate, barium carbonate, lime sulfate, aluminum hydroxide, calcium silicate, potassium titanate, titanium oxide, zinc oxide, silicon carbide, silicon nitride, and boron nitride. Any one of the inorganic fillers may be used alone, or two or more 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.

[0066] 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.

[0067] Examples of the organic filler include polytetrafluoroethylene (PTFE) filler, silicone filler, acrylic filler, styrene filler, etc. The organic filler may be surface-treated.

[0068] The shape of the filler is not particularly limited, and may be any of spherical, flaky, needle-like, irregular, etc.

[0069] 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 refers to 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 (F) is preferably 0.01 μm to 5.0 μm, and more preferably 0.1 μm to 3.0 μm. Fillers with different average particle sizes may be used in combination. For example, a filler having an average particle size of 0.005 μm or more but less than 0.1 μm may be used in combination with a filler having an average particle size of 0.1 μm to 5.0 μm.

[0070] The content of the filler (F) in the resin composition of this embodiment is preferably 0.5 to 80 mass %, more preferably 1 to 70 mass %, based on the total mass of the resin composition. By setting the content of the filler (F) 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.

[0071] (G) Stabilizer The resin composition of this embodiment may contain a (G) stabilizer (hereinafter also referred to as "component (G)") to the extent that the effects of the present invention are not impaired. The (G) 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 (G) stabilizer include radical polymerization inhibitors and anionic polymerization inhibitors.

[0072] 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.

[0073] 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.

[0074] 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.

[0075] 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.

[0076] (H) Thermal Radical Polymerization Initiator The resin composition of this embodiment may contain (H) a thermal radical polymerization initiator (hereinafter also referred to as "component (H)") to the extent that the effects of the present invention are not impaired. By including a thermal radical polymerization initiator in the resin composition, it becomes possible to cure the resin composition by heating for a short period of time. There are no particular limitations on the thermal radical polymerization initiator that can be used. Known materials can be used. Specific examples of thermal radical polymerization initiators include dialkyl peroxides such as dicumyl peroxide, t-butylcumyl peroxide, 1,3-bis(2-t-butylperoxyisopropyl)benzene, or 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-amylperoxy)cyclohexane, 2,2-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-amylperoxy)cyclohexane, 1,1 ...amylperoxy)cyclohexane, 1,1-bis(t-amylperoxy)cyclohexane, 1,1-bis(t-amylperoxy)cyclohexane, 1,1-bis(t-amylperoxy)cyclohexane, 1,1-bis(t Examples of the thermal radical polymerization initiator include, but are not limited to, peroxyketals such as t-butylperoxy)butane, n-butyl 4,4-bis(t-butylperoxy)valerate, or ethyl 3,3-(t-butylperoxy)butyrate, and alkyl peroxyesters such as t-butylperoxy 2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxymaleate, or t-butylperoxybenzoate. As the thermal radical polymerization initiator, a single substance may be used, or two or more substances may be used in combination.

[0077] When the (H) thermal radical polymerization initiator is contained, the content of the (H) thermal radical polymerization initiator is preferably 0.01 to 5 mass%, more preferably 0.1 to 3 mass%, relative to the total mass of the resin composition.

[0078] (I) Other Additives The resin composition may contain, as needed, carbon black, titanium black, silane coupling agents, ion trapping agents, leveling agents, antioxidants, antifoaming agents, or other additives, provided that the properties of the resin composition of this embodiment are not impaired. The resin composition may also contain viscosity modifiers, flame retardants, solvents, and the like. Carbon black and titanium black can be used as light-shielding agents. Titanium black is preferred from the viewpoint of achieving both light-shielding properties and UV curability (curing depth). Examples of titanium black include, but are not limited to, Titanium Black 12S (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Titanium Black 13M (manufactured by Mitsubishi Materials Corporation), Titanium Black 13M-C (manufactured by Mitsubishi Materials Corporation), and Tilack D (manufactured by Ako Kasei Co., Ltd.). Titanium Black 13M is particularly preferred. The types and amounts of each additive are as per usual.

[0079] The method for producing the resin composition of this embodiment is not particularly limited. The resin composition can be obtained, for example, by stirring, melting, mixing, and dispersing components (A) to (D), and optionally components (E), (F), (G), (H), and / or (I) and other additives, simultaneously or separately, while applying heat treatment as necessary. The apparatus used for mixing, stirring, dispersing, etc. is not particularly limited. A Raikai mixer, Henschel mixer, three-roll mill, ball mill, planetary mixer, bead mill, or the like equipped with a stirring device and a heating device can be used. Furthermore, these devices may be used in appropriate combination.

[0080] The resin composition obtained in this manner is photocurable and thermosetting. When used in an image sensor module, the thermosetting temperature of the resin composition is preferably 50 to 120°C, more preferably 50 to 90°C, even more preferably 50 to 80°C, and particularly preferably 50 to 70°C. By including component (D), the resin composition of this embodiment can be thermoset not only at 80°C but also at 60°C during the second thermosetting step after the first UV curing step.

[0081] 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.

[0082] [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.

[0083] [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.

[0084] [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.

[0085] 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.

[0086] [Examples 1 to 15, Comparative Examples 1 and 2] 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.

[0087] (A) (Meth)acrylate Compounds (Component (A)) (A-1): Dimethylol-tricyclodecane diacrylate (trade name: Light Acrylate DCP-A, manufactured by Kyoeisha Chemical Co., Ltd., acryloyl equivalent: 152 g / eq) (A-2): Neopentyl glycol-modified trimethylolpropane diacrylate (trade name: Kayarad R-604, manufactured by Nippon Kayaku Co., Ltd., acryloyl equivalent: 163 g / eq) (A-3): Ditrimethylolpropane tetraacrylate (trade name: EBECRYL 140, manufactured by Daicel-Allnex Corporation, acryloyl equivalent: 117 g / eq)

[0088] (B) Polyfunctional thiol compounds (component (B)) (B-1): pentaerythritol tetrakis(3-mercaptopropionate) (product name: PEMP, manufactured by SC Organic Chemicals, thiol equivalent: 122 g / eq) (B-2): polyfunctional thiol compound of general formula (4) (product name: PEPT, manufactured by SC Organic Chemicals, thiol equivalent: 124 g / eq) (B-3): polyfunctional thiol compound of chemical formula (3) (product name: C3 TS-G, manufactured by SC Organic Chemicals, thiol equivalent: 114 g / eq) (B-4): pentaerythritol tetrakis(3-mercaptobutyrate) (product name: Karenz MT (registered trademark) PE1, manufactured by Showa Denko K.K., thiol equivalent: 136 g / eq)

[0089] (C) Photoradical initiator (component (C)) (C-1): 1-hydroxycyclohexylphenylketone (product name: Omnirad 184, manufactured by IGM Resins) (C-2): 2,4,6-trimethylbenzoyldiphenylphosphine oxide (product name: Omnirad TPO H, manufactured by IGM Resins B.V.)

[0090] (D) Thermal curing accelerator containing an azabicyclo ring compound having a bridgehead nitrogen (component (D)) (D-1): Thermal curing accelerator containing 1,4-diazabicyclo[2.2.2]octane (DABCO (registered trademark)) (product name: Novacure HXA5945HP, manufactured by Asahi Kasei Corporation) (D-2): Thermal curing accelerator containing 1,4-diazabicyclo[2.2.2]octane (DABCO (registered trademark)) (1,4-diazabicyclo[2.2.2]octane itself, obtained from Tokyo Chemical Industry Co., Ltd.) (D-3): Thermal curing accelerator containing 1-azabicyclo[2.2.2]octan-3-ol (common name: 3-quinuclidinol) (1-azabicyclo[2.2.2]octan-3-ol itself, obtained from Tokyo Chemical Industry Co., Ltd.) (D-4): A thermal curing accelerator containing 1,8-diazabicyclo[5.4.0]-7-undecene (DBU (registered trademark)) (1,8-diazabicyclo[5.4.0]-7-undecene itself, obtained from Tokyo Chemical Industry Co., Ltd.)

[0091] (D') Heat curing accelerator other than component (D) (component (D')) (D'-1): Heat curing accelerator containing an imidazole compound (trade name: Novacure HXA3922HP, manufactured by Asahi Kasei E-materials Corporation) (D'-2): Heat curing accelerator containing 2-ethyl-4-methylimidazole (trade name: Curesol 2E4MZ, manufactured by Shikoku Chemicals Corporation)

[0092] Of the heat curing accelerators (D) and (D'), components (D-1) and (D'-1) are provided in the form of a dispersion in which a fine particle curing accelerator compound is dispersed in a mixture of epoxy compounds (bisphenol A epoxy compound and bisphenol F epoxy compound). The parts by mass of components (D-1) and (D'-1) in Table 1 are the parts by mass of the components obtained by subtracting the parts by mass of the epoxy compound mixture from the parts by mass of the dispersion. The epoxy compounds that make up this dispersion are treated as part of component (E), and the epoxy compound in (D-1) is referred to as component (E-1), and the epoxy compound in (D'-1) is referred to as component (E-2). The parts by mass of (E-1) and (E-2) in Table 1 are the parts by mass of the epoxy compounds in components (D-1) and (D'-1).

[0093] Epoxy compounds (component (E)) (E-1) A mixture of bisphenol A epoxy compounds and bisphenol F epoxy compounds (epoxy equivalent: 180 g / eq) (E-2): A mixture of bisphenol A epoxy compounds and bisphenol F epoxy compounds (epoxy equivalent: 180 g / eq) (E-3): A mixture of bisphenol A epoxy compounds and bisphenol F epoxy compounds (product name: EXA-835LV, manufactured by DIC Corporation, epoxy equivalent: 165 g / eq)

[0094] Filler (component (F)) (F-1): Silica filler (product name: SE2300, average particle size 0.6 μm, manufactured by Admatechs Co., Ltd.) (F-2): Calcium carbonate filler (product name: CS4NA, average particle size: <0.5 μm, manufactured by Ube Material Industries, Ltd.) (F-3): Hydrophobic fumed silica (product name: CAB-O-SIL (registered trademark) TS720, manufactured by CABOT Corporation, average particle size: 12 nm) Stabilizer (component (G)) (G-1): Triisopropyl borate (manufactured by Tokyo Chemical Industry Co., Ltd.) (G-2): N-nitroso-N-phenylhydroxylamine aluminum (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0095] In the examples and comparative examples, the properties of the resin compositions and cured products were measured as follows.

[0096] [Residual heat generation amount obtained by DSC (differential scanning calorimetry)] The resin compositions of the examples and comparative examples were degassed in vacuum and exposed to UV irradiation at a dose of 2000 mJ / cm. ２ The resin was UV-cured using a UV lamp (UV wavelength: 365 nm, LED lamp) and then thermally cured in a fan dryer at 80°C for 60 minutes to obtain a cured resin. Five mg of the resulting cured resin was sampled and measured using a DSC under nitrogen conditions, raising the temperature from 30°C to 250°C at a heating rate of 10°C / min to obtain an exothermic curve. If a residual exothermic peak was present, the exothermic peak was integrated to calculate the residual heat value. A residual heat value of 25 J / g or less was determined to indicate that the remaining unreacted components were suppressed and rated as "A," while a residual heat value of more than 25 J / g was determined to indicate that a large amount of unreacted components remained and rated as "F."

[0097] [Evaluation of 60°C curability] The 60°C curability of the prepared resin composition was evaluated by dropping one drop of the resin composition into a sample, and then heating the sample at 60°C for 60 minutes and observing the state of the sample. If the sample was solid and not stringy, it was judged to be sufficiently cured and rated "A." If it was solid but stringy, it was judged to have poorer curability than "A" and rated "B." If the hemispherical sample did not become solid, it was judged to be uncured and rated "F." The results are shown in Table 1.

[0098]

[0099]

[0100]

[0101] The resin compositions of Examples 1 to 15 contained a heat curing accelerator containing (D) an azabicyclocyclic compound having a bridgehead nitrogen, which reduced the amount of unreacted components remaining in the cured product after the second heat curing step following the first UV curing step, and the resin compositions were able to be heat cured at 60°C. On the other hand, in Comparative Examples 1 and 2, in which the resin compositions contained a heat curing accelerator other than component (D), more unreacted components remained in the cured product after the second heat curing step following the first UV curing step, and the resin compositions could not be cured at 60°C.

[0102] [Increase in strength of cured product by additional heating] The resin compositions obtained in Example 1 and Comparative Example 1 were stencil printed on an LCP (LAPEROS (registered trademark) E463i) plate with a size of φ2 mm and a thickness of 125 μm, and a 1.5 mm × 3 mm × 0.5 mm alumina chip was placed on the printed resin composition with the 1.5 mm × 3 mm surface facing downward to prepare a test piece (n = 10). The curing conditions were as follows: a UV LED irradiation device AC475 manufactured by Excelitas Technologies, Inc., was used from the surface (rear surface) opposite to the surface on which the alumina chip was mounted (front surface), with an integrated light dose of 2000 mJ / cm ２ The LCP plate was cured at 80°C for 60 minutes (measured using a Ushio Inc. UIT-250 (connected to a UVD-365 photodetector)), and then heated in a blast oven at 80°C for 60 minutes. An alumina chip on this LCP plate was poked from the side with an Aiko Engineering Co., Ltd. Model 1605HTP strength tester, and the shear strength was calculated from the value at which the alumina chip peeled off, and this value was designated shear strength A. Meanwhile, a similarly prepared test piece was additionally heated in a blast oven at 120°C for 1 hour, and the shear strength was calculated in the same manner, and this value was designated shear strength B. The change in the strength increase rate of the cured product due to additional heating was determined using the following formula. The results are shown in Table 2. Strength increase rate of cured product due to additional heating = shear strength B / shear strength A. A larger strength increase rate due to additional heating indicates that unreacted components in the cured product were cured by the additional heating, i.e., that a larger amount of unreacted components remained in the cured product after thermal curing following UV curing.

[0103]

[0104] [Measurement of Change in Shrinkage Rate Due to Additional Heating] The volumetric shrinkage rates of the resin compositions obtained in Example 1 and Comparative Example 1 were measured by the specific gravity method. Specifically, the liquid specific gravity ρL was calculated using a pycnometer with a liquid specific gravity of approximately 10 mL, and the specific gravity of the cured product ρS was determined by measuring the weight in water and the weight in air. Using these values, the shrinkage rate was calculated according to the following calculation formula (1): Volumetric shrinkage rate (%) = (1 / ρL - 1 / ρS) / (1 / ρL) (1) The resin composition was irradiated with a UV LED irradiation device AC475 manufactured by Excelitas Technologies, with an integrated light dose of 2000 mJ / cm. ２The specific gravity of the cured product was taken as ρS1 when the sample was cured by UV irradiation (measured using a Ushio Inc. UIT-250 (with a UVD-365 receiver connected)) and heated at 80°C for 60 minutes in a blast dryer. A similarly prepared test piece was then additionally heated at 120°C for 1 hour in the blast dryer, and the specific gravity of the cured product was taken as ρS2. Using these values, the change in shrinkage due to additional heating was measured using the following calculation formula (2). The results are shown in Table 3. Change in shrinkage due to additional heating (%) = (1 / ρL - 1 / ρS2) / (1 / ρL) - (1 / ρL - 1 / ρS1) / (1 / ρL) ... (2)

[0105]

[0106] The cured product obtained in Example 1 showed almost no change in shrinkage due to additional heating, while the cured product obtained in Comparative Example 1 showed a 0.2% increase in shrinkage due to additional heating. From this, it is believed that the amount of change over time was smaller in the Examples, and problems such as misalignment were less likely to occur.

[0107] [Measurement of outgassing amount by additional heating] The resin compositions obtained in Example 1 and Comparative Example 1 were subjected to UV irradiation at a dose of 2000 mJ / cm ２ A cured resin was prepared by UV curing using a UV lamp (UV wavelength: 365 nm, LED lamp). 10 mg of the resulting cured resin was sampled and measured using a differential thermogravimetric simultaneous analyzer (TG8120, manufactured by Rigaku Corporation) to measure the outgassing generated during 60 minutes of heating at 80°C under air conditions (outgassing generated during normal curing), and the amount of outgassing generated during additional heating from the initial 60 minutes of heating at 80°C until the temperature reached 120°C (outgassing that may be generated by additional heating). If the outgassing amount was less than 100 ppm, the outgassing resistance was deemed good and rated "A." If the outgassing amount was 100 ppm or greater, the outgassing resistance was deemed poor and rated "F." The results are shown in Table 4.

[0108]

[0109] [Thermal Curability in UV-Insufficient Curing Region] 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 is performed from the outside of the semiconductor module, making it difficult for the UV light to reach the inside of the semiconductor module. This can result in an insufficient UV-curing region where the adhesive is partially UV-cured but not completely UV-cured. It was found that unreacted components remaining in this insufficient UV-curing region do not undergo curing reaction during the next thermal curing, and are particularly likely to remain as residual components. In this evaluation test, the insufficient UV-curing region of the adhesive was reproduced, and the thermosetting property in the insufficient UV-curing region was evaluated. To reproduce the insufficient UV-curing region, the UV irradiation dose was set low. Comparative Example 3 is an example in which component (D-2) in the resin composition of Example 13 was replaced with component (D'-2). The resin compositions of Example 13 and Comparative Example 3 were degassed in a vacuum and subjected to a UV irradiation dose of 40 mJ / cm. ２ The resin was UV-cured using a UV lamp (UV wavelength: 365 nm, LED lamp) and then thermally cured in a fan dryer at 60°C for 60 minutes and 80°C for 60 minutes to obtain a cured resin. Five mg of the resulting cured resin was sampled and measured using a DSC under nitrogen conditions, increasing the temperature from 30°C to 250°C at a rate of 10°C / min to obtain an exothermic curve. If a residual exothermic peak was present, the residual heat generation amount was calculated by integrating the exothermic peak. The results are shown in Table 5.

[0110]

[0111] The cured product of the resin composition obtained in Example 13 had almost no residual heat generation, whereas the cured product of the resin composition obtained in Comparative Example 3 had a large residual heat generation. This confirmed that the examples containing component (D) exhibited high thermosetting properties even in the cured areas where UV curing was incomplete, which reproduced areas that were difficult to expose to UV, and therefore had fewer unreacted components. It is believed that the fewer unreacted components contributes to the suppression of the above-mentioned positional misalignment and outgassing.

[0112] The present invention relates to a resin composition that can be thermally cured at 60°C and in which the amount of unreacted components remaining in the cured product after the second thermal curing step following the first UV curing step is suppressed, and is particularly useful as an adhesive or sealant used for fixing, adhering, or protecting components that constitute an image sensor or camera module.

[0113] The disclosure of Japanese Patent Application No. 2022-030685 (filing date: March 1, 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 polyfunctional thiol compound, (C) a photoradical polymerization initiator, and (D) A thermal curing accelerator containing an azabicyclo ring compound having a bridgehead nitrogen atom A resin composition comprising:

2. 2. The resin composition according to claim 1, wherein 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 0.25 to 3.

0.

3. The resin composition according to claim 1 , wherein the polyfunctional thiol compound (B) comprises a tri- or higher functional thiol compound.

4. The resin composition according to claim 1 , further comprising (E) an epoxy compound.

5. An adhesive or sealant comprising the resin composition according to any one of claims 1 to 4.

6. The adhesive or sealant according to claim 5, which is used for fixing, adhering or protecting components that constitute an image sensor or a camera module.

7. A cured product obtained by curing the resin composition according to any one of claims 1 to 4.

8. A semiconductor device or electronic component comprising the cured product according to claim 7.

9. The semiconductor device or electronic component according to claim 8, which is an image sensor or a camera module.