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

Abstract

The present invention addresses the problem of providing at least a thermosetting resin composition and an adhesive agent that can suppress the bleeding phenomenon. 　Provided is a resin composition comprising (A) a polymerizable compound having a carbon-carbon double bond, (B) a polythiol compound, (C) a polymerization initiator, and (D) a modified polydimethylsiloxane satisfying at least one of features (a) and (b): (a) an organic substituent group including a COOH group or an OH group is bound to a polydimethylsiloxane directly or via a linker; and (b) an 1H NMR spectrum measured in deuterated chloroform has signals in the ranges of 0.3 to -0.3 ppm and 4.4-3.2 ppm, and has a signal that is in the range of 13 to 0 ppm and that disappears through the addition of D2O.

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] Currently, adhesives, sealants, etc. containing curable resin compositions are often used for assembling and mounting components used in semiconductor devices, such as semiconductor chips, in order to maintain reliability, etc. Known examples of such resin compositions include curable compositions containing an epoxy compound or a (meth)acrylate compound as a base compound and a thiol compound as a curing agent (e.g., Patent Documents 1 and 2).

[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 in one molecule; (3) a polythiol compound having two or more thiol groups in one 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 referred to as "bleed." When the bleed comes into contact with metal wiring on the substrate, it can cause electrical defects, resulting in reduced reliability of the semiconductor module. In particular, inner bleed, which occurs from uncured portions of the adhesive, tends to progress when the adhesive coating is left at room temperature and / or during thermal curing, and the bleed length tends to increase.

[0006] 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.

[0007] Therefore, an object of the present invention is to provide at least a photocurable or thermosetting resin composition and adhesive that can suppress the bleeding phenomenon.

[0008] Specific means for solving the above problems are as follows. Embodiments of the present invention include a resin composition, an adhesive or sealant, a cured product, and a semiconductor device or electronic component having the following aspects. [1] (A) a polymerizable compound having a carbon-carbon double bond, (B) a polythiol compound, (C) a polymerization initiator, and (D) a modified polydimethylsiloxane satisfying at least one of the following characteristics (a) and (b): (a) an organic substituent containing a COOH group or an OH group is bonded to the polydimethylsiloxane directly or via a linker; (b) a molecular weight of the modified polydimethylsiloxane measured in deuterated chloroform. １ In the H NMR spectrum, it has signals in the ranges of 0.3 to -0.3 ppm and 4.4 to 3.2 ppm, and D in the range of 13 to 0 ppm. ２A resin composition comprising: a resin having a signal that disappears upon addition of O. [2] The resin composition according to the above [1], wherein the (A) polymerizable compound having a carbon-carbon double bond is a (meth)acrylate compound. [3] The resin composition according to the above [1] or [2], wherein the content of the (D) modified polydimethylsiloxane is 0.01 to 5 mass% relative to the total mass of the resin composition. [4] The resin composition according to any of the above [1] to [3], further comprising (E) a filler. [5] An adhesive or encapsulant comprising the resin composition according to any of the above [1] to [4]. [6] The adhesive or encapsulant according to the above [5], which is used for fixing, adhering, or protecting an optical sensor module or a component constituting the same. [7] A cured product obtained by curing the resin composition according to any of the above [1] to [4], or the adhesive or encapsulant according to the above [5] or [6]. [8] A semiconductor device or electronic component comprising the cured product according to the above [7]. [9] The semiconductor device or electronic component according to the above [8], which is an optical sensor module.

[0009] According to an embodiment of the present invention, there are provided at least a photocurable or thermosetting resin composition capable of suppressing the bleeding phenomenon, an adhesive or sealant containing the same, a cured product obtained by curing the same, and a semiconductor device or electronic component containing the cured product.

[0010] [Resin Composition] A resin composition according to one embodiment of the present invention comprises: (A) a polymerizable compound having a carbon-carbon double bond; (B) a polythiol compound; (C) a polymerization initiator; and (D) a modified polydimethylsiloxane that satisfies at least one of the following characteristics (a) and (b): (a) an organic substituent containing a COOH group or an OH group is bonded to the polydimethylsiloxane directly or via a linker; (b) a molecular weight of the modified polydimethylsiloxane measured in deuterated chloroform is 1000; １ In H NMR, it has signals in the ranges of 0.3 to -0.3 ppm and 4.4 to 3.2 ppm, and D in the range of 13 to 0 ppm. ２ and having a signal that disappears upon addition of O. According to this embodiment, it is possible to provide at least a photocurable or thermosetting resin composition that can suppress the bleeding phenomenon.

[0011] (A) Polymerizable Compound Having a Carbon-Carbon Double Bond The resin composition of this embodiment contains (A) a polymerizable compound having a carbon-carbon double bond (hereinafter also referred to as "(A) polymerizable compound" or "component (A)"). In the (A) polymerizable compound having a carbon-carbon double bond, polymerization proceeds via a radical polymerization reaction between (A) polymerizable compounds or between (A) polymerizable compounds and a (B) polythiol compound described below, or a crosslinking reaction between (A) polymerizable compounds and a (B) polythiol compound in an anionic polymerization system, thereby imparting curability and adhesiveness to the resin composition. Examples of the (A) polymerizable compound having a carbon-carbon double bond include, but are not limited to, (meth)acrylate compounds, maleimide compounds, styrene compounds, polybutadiene compounds, vinyl ether compounds, and allyl ether compounds.

[0012] In this specification, the (meth)acrylate compound refers to a compound having at least one (meth)acryloyl group in the molecule, and examples thereof include a monofunctional (meth)acrylate compound having one (meth)acryloyl group and a polyfunctional (meth)acrylate compound having two or more (meth)acryloyl groups. In this embodiment, the (meth)acrylate compound is preferably a polyfunctional (meth)acrylate compound or a combination of a polyfunctional (meth)acrylate compound and a monofunctional (meth)acrylate compound. In this specification, the term "(meth)acryloyl group" includes both a methacryloyl group and an acryloyl group. Furthermore, the term "(meth)acrylate compound" includes both an acrylate compound and a methacrylate compound.

[0013] Examples of (meth)acrylate compounds include diacrylate and / or dimethacrylate of tris(2-hydroxyethyl)isocyanurate; tris(2-hydroxyethyl)isocyanurate triacrylate and / or trimethacrylate; trimethylolpropane triacrylate and / or trimethacrylate, or oligomers thereof; pentaerythritol triacrylate and / or trimethacrylate, or oligomers thereof; polyacrylate and / or polymethacrylate of dipentaerythritol; tris(acryloxyethyl)isocyanurate; caprolactone-modified tris(acryloxyethyl)isocyanurate; caprolactone-modified tris(methacryloxyethyl)isocyanurate; polyacrylate and / or polymethacrylate of alkyl-modified dipentaerythritol; polyacrylate and / or polymethacrylate of caprolactone-modified dipentaerythritol; ethoxylated bisphenol Examples of suitable (meth)acrylates include, but are not limited to, polyfunctional (meth)acrylates such as 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, ethoxylated bisphenol A diacrylate, polyurethane having two or more (meth)acryloyl groups per molecule, and polyester having two or more (meth)acryloyl groups per molecule; and monofunctional (meth)acrylates such as phenoxyethyl acrylate, 2-(o-phenylphenoxy)ethyl acrylate, isobornyl acrylate, phenoxydiethylene glycol (meth)acrylate, 4-tert-butylcyclohexyl acrylate, and epoxy resin half acrylate. From the viewpoint of reactivity, the (meth)acrylate compound is preferably an acrylate compound that is substantially free of methacrylate compounds. The (meth)acrylate compounds may be used alone or in combination of two or more.

[0014] Maleimide compounds include monofunctional maleimide compounds having one maleimide group and polyfunctional maleimide compounds having two or more maleimide groups. Maleimide compounds having two maleimide groups are sometimes called bismaleimide compounds. Examples of bismaleimide compounds include N,N'-(4,4'-diphenylmethane)bismaleimide and bisphenol A. Examples of suitable bismaleimides include, but are not limited to, diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, bis-(3-ethyl-5-methyl-4-maleimidophenyl)methane, m-phenylene bismaleimide (N,N'-1,3-phenylene bismaleimide), 1,6-bismaleimidehexane, 1,2-bismaleimideethane (N,N'-ethylenedimaleimide), N,N'-(1,2-phenylene)bismaleimide, N,N'-1,4-phenylenedimaleimide, N,N'-(sulfonyldi-p-phenylene)dimaleimide, and N,N'-[3,3'-(1,3-phenylenedioxy)diphenyl]bismaleimide. These may be used alone or in combination of two or more.

[0015] When a low room temperature modulus is required for the cured resin composition, the bismaleimide compound is preferably a bismaleimide compound having a hydrocarbon group derived from a dimer acid. Such bismaleimide compounds are described, for example, in JP 2015-193725 A. Commercially available bismaleimide compounds having a hydrocarbon group derived from a dimer acid include, but are not limited to, products named "BMI-689," "BMI-1500," and "BMI-1700," which are liquid at 25°C, and "BMI-3000," which is solid at 25°C (all manufactured by Designer Molecules Inc.). These compounds may be used alone or in combination of two or more.

[0016] Styrene compounds contain a styrene group (H ２ C=CH-C ６ H ５-) is a compound having at least one Examples of the styrene compound include, but are not limited to, 1,2-bis(p-vinylphenyl)ethane, 1,2-bis(m-vinylphenyl)ethane, 1-(p-vinylphenyl)-2-(m-vinylphenyl)ethane, bis(p-vinylphenyl)methane, bis(m-vinylphenyl)methane, p-vinylphenyl to m-vinylphenylmethane, 1,4-bis(p-vinylphenyl)benzene, 1,4-bis(m-vinylphenyl)benzene, 1-(p-vinylphenyl)-4-(m-vinylphenyl)benzene, 1,3-bis(p-vinylphenyl)benzene, 1,3-bis(m-vinylphenyl)benzene, 1-(p-vinylphenyl)-3-(m-vinylphenyl)benzene, 1,6-bis(p-vinylphenyl)hexane, 1,6-bis(m-vinylphenyl)hexane, 1-(p-vinylphenyl)-6-(m-vinylphenyl)hexane, and divinylbenzene polymers (oligomers) having vinyl groups on the side chains. These may be used alone or in combination of two or more.

[0017] Examples of polybutadiene compounds include, but are not limited to, polybutadiene having vinyl groups in the side chains, polybutadiene having 90% by weight or more of 1,2-bonds in the structure, etc. These may be used alone or in combination of two or more.

[0018] The vinyl ether compound has a vinyl ether group (H ２ C═CH—O—). Examples of vinyl ether compounds include, but are not limited to, ethyl vinyl ether, triethylene glycol divinyl ether, trimethylolpropane trivinyl ether, hydroxybutyl vinyl ether, vinyl ether of 1,4-cyclohexanedimethanol, dodecyl vinyl ether, and cyclohexyl vinyl ether. These compounds may be used alone or in combination of two or more.

[0019] Examples of the allyl ether compound include, but are not limited to, allyl glycidyl ether, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, glycerin monoallyl ether, etc. These may be used alone or in combination of two or more.

[0020] 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.

[0021] Examples of commercially available products of component (A) include polyester acrylate (product name: EBECRYL810) manufactured by Daicel-Allnex Corporation, ditrimethylolpropane tetraacrylate (product name: EBECRYL140) 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., neopentyl glycol-modified trimethylolpropane diacrylate (product name: Kayarad R-604) manufactured by Nippon Kayaku Co., Ltd., 2-(o-phenylphenoxy)ethyl acrylate (product name: HRD-01) manufactured by Nisshoku Techno Fine Chemical Co., Ltd., and ethoxylated bisphenol A diacrylate (product name: ABE-300) manufactured by Shin-Nakamura Chemical Co., Ltd., but are not limited to these. The component (A) may be any one of these, or two or more of them may be used in combination.

[0022] 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.

[0023] (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 curability 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.

[0024] 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).

[0025] 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.

[0026] Furthermore, examples of the polythiol compound (B) include glycoluril compounds represented by the following general formula (1).

[0027]

[0028] 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.

[0029] Component (B) may also be a compound represented by the following chemical formula (2) or (3).

[0030]

[0031]

[0032] Furthermore, the polythiol compound (B) may be a polythiol compound represented by the general formula (4).

[0033]

[0034] 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 ２ｎ SH (n is 2 to 6). In terms of curability, n in the polythiol 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 polythiol compound is more preferably a mercaptopropyl group where n is 3. Component (B) represented by general formula (4) itself has a sufficiently flexible skeleton, so it is effective when it is desired to lower the elastic modulus of the cured product. By adding component (B) represented by general formula (4), the elastic modulus of the cured product can be controlled, thereby increasing the adhesive strength (particularly peel strength) after curing.

[0035] 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), 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).

[0036] 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,6a-diglycoluril. Methyl glycoluril, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a,6a-dimethyl glycoluril, 1,3,4,6-tetrakis(mercaptomethyl)-3a,6a-diphenyl glycoluril, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a,6a-diphenyl glycoluril, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a,6a-diphenyl glycoluril, 3-[2,3-bis(3-sulfanylpropoxy)propoxy]propane-1-thiol, 3-[2,2-bis[(3 -mercaptopropoxy)methyl]butoxy]-1-propanethiol, pentaerythritol tetrapropanethiol, 1,2,3-tris(mercaptomethylthio)propane, 1,2,3-tris(2-mercaptoethylthio)propane, 1,2,3-tris(3-mercaptopropylthio)propane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane Thiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercaptopropylthiomethyl)methane, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 1,1,5,5-tetrakis(mercaptomethylthio)-3-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(4,4-bis(mercaptomethylthio)-2-thiabutyl)methane, 3,5,9,11-tetrakis(mercaptomethylthio)-1,13-dimercapto-2,6,8,12-tetrathiatridecane, 3,5,9,11,15,17-hexakis(mercaptomethylthio)-1,19-dimercapto-2,6,8,12,14,18-hexathianonadecane, 9-(2,2-bis(mercaptomethylthio)ethyl)methane 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)ethyl 1,15-dimercapto-2,5,7,9,11,14-hexathiapentadecane, 4,6-bis[3,5-bis(mercaptomethylthio)-7-mercapto-2,6-dithiaheptylthio]-1,3-dithiane, 4-[3,5-bis(mercaptomethylthio)-7-mercapto-2,6-dithiaheptylthio]-6-mercaptomethylthio-1,3-dithiane, 1,1-bis[4-(6-mercaptomethylthio)-1,3-dithianylthio]-1,3-bis(mercaptomethylthio)propane, 1-[4-(6-mercaptomethylthio)-1,3-dithianylthio]-3-[2,2-bis(mercaptomethylthio)ethyl]-7,9-bis(mercaptomethylthio)-2,4,6,10-tetrathiaundecane, 3-[2-(1,3-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-bis(mercaptomethylthio)-2,4,6,10-tetrathiaundecane thietanyl)]methyl-7,9,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,4,6,10,12,16-hexathiaheptadecane, 4,6-bis[4-(6-mercaptomethylthio)-1,3-dithianylthio]-6-[4-(6-mercaptomethylthio)-1,3-dithianylthio]-1,3-dithiane, 4-[3,4,8,9-tetrakis(mercaptomethylthio)-11-mercapto-2,5,7,10-tetrathiaundecyl]-5-mercaptomethylthio-1,3-dithiolane, 4,5-bis[3,4- Bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]-1,3-dithiolane, 4-[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]-5-mercaptomethylthio-1,3-dithiolane, 4-[3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiaoctyl]-5-mercaptomethylthio-1,3-dithiolane, 2-{bis[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]- thio]methyl}-1,3-dithietane, 2-[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]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-[1,2-bis(mercaptomethylthio)-4-mercapto-3-thiabutylthio]-1,3-dithiolane, etc.

[0037] As the component (B), any one of them may be used alone, or two or more of them may be used in combination.

[0038] In this embodiment, the content of component (B) in the resin composition is preferably 1 to 70 mass%, more preferably 10 to 60 mass%, and even more preferably 20 to 50 mass%, relative to the total mass of the resin composition.

[0039] Among the polythiol compounds, there are polythiol compounds having a hydrolyzable partial structure such as an ester bond in the molecule (i.e., hydrolyzable). From the viewpoint of the moisture resistance of the cured product of the resin composition, the amount of the polythiol compound having a hydrolyzable partial structure such as an ester bond in the molecule is preferably 90 mass% or less, for example, 0 to 90 mass%, for example, 0 to 80 mass%, for example, 0 to 70 mass%, for example, 0 to 60 mass%, or for example, 0 to 50 mass%, relative to the total mass of component (B).

[0040] (C) Polymerization Initiator The resin composition of this embodiment contains a (C) polymerization initiator (hereinafter also referred to as "component (C)"). In this specification, the (C) polymerization initiator includes a (C1) basic catalyst, a (C2) photobase generator, a (C3) photoradical polymerization initiator, and a (C4) thermal radical polymerization initiator. The (C) polymerization initiator can be appropriately selected depending on the application location and use of the resin composition, or, for example, whether the resin composition is photocurable, thermosetting, or photo- and thermosetting. For example, the (C) polymerization initiator may be any one of the (C1) basic catalyst, the (C2) photobase generator, the (C3) photoradical polymerization initiator, and the (C4) thermal radical polymerization initiator, or any combination thereof.

[0041] (C1) Basic Catalyst Although known basic catalysts can be used as the (C1) basic catalyst, a thermally latent catalyst is preferred. A thermally latent catalyst is a compound or substance that is inactive at room temperature but is activated by heating to function as a polymerization catalyst. Examples include amine compounds that are solid at room temperature; amine adduct-based latent polymerization 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); microcapsule-type thermally latent polymerization catalysts; and solid-dispersion-type thermally latent polymerization catalysts such as inclusion-type thermally latent polymerization catalysts. Amine compounds include aliphatic amines, aromatic amines, and heterocyclic amines.

[0042] Examples of amine compounds that are solid at room temperature include dicyandiamide, 2-heptadecylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-undecylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4-benzyl-5-hydroxymethylimidazole, 2,4-diamino-6-(2-methyl-1-imidazolyl-(1))-ethyl-S-triazine, 2,4-diamino-6-(2'-methylimidazolyl-(1)')-ethyl-S-triazine, and 2,4-diamino-6-(2'-methylimidazolyl-(1)')-ethyl-S-triazine. Examples of the alkyl acrylate include, but are not limited to, triazine-isocyanuric acid adduct, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole-trimellitate, 1-cyanoethyl-2-phenylimidazole-trimellitate, N-(2-methylimidazolyl-1-ethyl)-urea, and N,N'-(2-methylimidazolyl-(1)-ethyl)-adiboyldiamide.

[0043] The amine compound used as one of the raw materials for producing the amine adduct latent curing catalyst may be any compound having one or more active hydrogen atoms in the molecule capable of addition reacting with an epoxy group or an isocyanate group, and having 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, in addition to the above-mentioned amine compounds that are solid at room temperature, 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 amine compounds such as 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline, piperidine, and piperazine. However, the present invention is not limited to these.

[0044] Among these, compounds having a tertiary amino group in the molecule and imidazole derivatives are particularly useful as raw materials that provide 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, 2-phenylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and 2-phenyl-4,5-dihydroxymethylimidazole. imidazole compounds such as phenyl-4-methylimidazole and 1-(2-aminoethyl)-2-methylimidazole; 2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol, 1-(2-hydroxy-3-phenoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-ethyl-4-methylimidazole, 1-(2-hydroxy 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, benzimidazole, 2 Examples of the tertiary amino acid include, but are not limited to, alcohols, phenols, thiols, carboxylic acids, and hydrazides having a tertiary amino group or an imidazole skeleton in the molecule, such as N,N-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.

[0045] Examples of epoxy compounds used as one of the raw materials for producing the amine-epoxy adduct thermal latent curing catalyst include, but are not limited to, 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; polyglycidyl esters obtained by reacting epichlorohydrin with polycarboxylic acids such as phthalic acid and terephthalic acid; glycidyl amine compounds obtained by reacting epichlorohydrin with 4,4'-diaminodiphenylmethane or m-aminophenol; and polyfunctional epoxy compounds such as epoxidized phenol novolac resins, epoxidized cresol novolac resins, and epoxidized polyolefins; and monofunctional epoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, various phenylphenol glycidyl ethers, and glycidyl methacrylate.

[0046] Examples of the isocyanate compound used as one of the raw materials for producing the amine-urea 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.

[0047] Examples of urea compounds used as one of the raw materials for producing the amine-urea adduct latent curing catalyst include, but are not limited to, urea and thiourea.

[0048] Amine adduct thermally latent curing catalysts are, for example, a combination of the above-mentioned two components, (a) an amine compound and an epoxy compound, (b) a combination of 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 between room temperature and 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.

[0049] A microcapsule-type latent curing catalyst is a curing catalyst having a core made of an amine compound or an amine adduct compound obtained by reacting an amine compound with an epoxy compound, an isocyanate compound, or a urea compound, and coated with a shell made of a synthetic resin or an inorganic oxide. Examples of the amine compound include the amine compounds described above. Imidazole derivatives are preferred as the amine compound because they exhibit favorable latency. Examples of imidazole derivatives include 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole. Examples of synthetic resins that form the shell include phenolic resins, melamine resins, epoxy resins, urethane resins, and urea resins, and these resins can also be used in combination. Examples of inorganic oxides that form the shell include silica, alumina, titania, and magnesia.

[0050] Representative examples of commercially available thermal latent curing catalysts include, but are not limited to, the following: Amine-epoxy adduct curing catalysts include "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.), "Hardener X-3670S" (product name of ACR Co., Ltd.), "Novacure HX-3742" (product name of Asahi Kasei Corporation), and "Novacure Examples of such catalysts include, but are not limited to, "Novacure HX-3721" (product name of Asahi Kasei Corporation), "Novacure HXA9322HP" (product name of Asahi Kasei Corporation), "Novacure HXA3922HP" (product name of Asahi Kasei Corporation), "Novacure HXA3932HP" (product name of Asahi Kasei Corporation), "Novacure HXA5945HP" (product name of Asahi Kasei Corporation), "Novacure HXA5911HP" (product name of Asahi Kasei Corporation), and "Novacure HXA9382HP" (product name of Asahi Kasei Corporation). The "Novacure" series is also a microcapsule-type latent curing catalyst. Furthermore, examples of the amine-urea adduct curing catalyst include, but are not limited to, "Fujicure FXE-1000" (product name of T&K TOKA Corporation), "Fujicure FXR1020" (product name of T&K TOKA Corporation), "Fujicure FXR-1030" (product name of T&K TOKA Corporation), "Fujicure FXR1121" (product name of T&K TOKA Corporation), "Fujicure FXR1081" (product name of T&K TOKA Corporation), "Fujicure 1061" (product name of T&K TOKA Corporation), and "Fujicure 1171" (product name of T&K TOKA Corporation).

[0051] An inclusion-type thermally latent curing catalyst is a curing catalyst having a structure in which guest molecules such as amine compounds are confined at the molecular level in crystalline spaces formed by host molecules. An example of a commercially available inclusion-type thermally latent curing catalyst is "NISSOCURE TIC-188" (product name of Nippon Soda Co., Ltd.).

[0052] The basic catalyst (C1) may be used alone or in combination of two or more kinds.

[0053] When the resin composition contains the basic catalyst (C1), the content of the basic catalyst (C1) is preferably 0.1 to 40 mass %, and 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.

[0054] (C2) Photobase Generator The photobase generator absorbs light to generate a base as an active species, thereby promoting polymerization of the anionically polymerizable compound. Examples of the photobase generator include, but are not limited to, various compounds that generate a base such as an amine, amidine, guanidine, phosphazene, or carbene.Specific examples of the photobase generator include 2-benzyl-2-(dimethylamino)-1-[4-(morpholino)phenyl]-1-butanone, 2-(dimethylamino)-2-(4-methylbenzyl)-1-(4-morpholinophenyl)butan-1-one, 2-nitrobenzyl 4-hydroxypiperidine-1-carboxylate, 4,5-dimethoxy-2-nitrobenzyl 2,6-dimethylpiperidine-1-carboxylate, 1-(9,10-dioxo-9,10-dihydroanthracen-2-yl)ethyl cyclohexylcarbamate, 1-(9,10-dioxo-9,10-dihydroanthracen-2-yl)ethyl 1H-imidazole-1-carboxylate, 3,4,6,7,8,9-hexahydro-2H-pyrimido[1,2-a]pyrimidine-1- ammonium 2-(3-benzoylphenyl)propanoate, diaminomethaniminium 2-(3-benzoylphenyl)propanoate, (Z)-N-(((bis(dimethylamino)methylene)amino)(isopropylamino)methylene)propan-2-aminium 2-(3-benzoylphenyl)propanoate, 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidinium n-butyltriphenylborate, (Z)-{[bis(dimethylamino)methylidene]amino}-N-cyclohexyl(cyclohexylamino)methaniminium tetrakis(3-fluorophenyl)borate, 1,2-diisopropyl-3-[bis(dimethylamino)methylene]guanidinium 2-(3-benzoylphenyl)propionate, 9-anthrylmethyl Examples of the diastereoisopropyl methyl ester include, but are not limited to, N,N-diethylcarbamate, (E)-1-piperidino-3-(2-hydroxyphenyl)-2-propen-1-one, 2-nitrophenylmethyl 4-methacryloyloxypiperidine-1-carboxylate, tetramethylguanidium tetrakis(3-fluorophenyl)borate, tetramethylguanidium tetrakis(4-fluorophenyl)borate, salts containing protonated DBU and tetrakis(3-fluorophenyl)borate anions, and salts containing benzylated DBU and tetrakis(3-fluorophenyl)borate anions. These may be used alone or in combination of two or more.

[0055] The photobase generator (C2) may be used alone or in combination of two or more thereof.

[0056] When the resin composition contains the photobase generator (C2), the content of the photobase generator (C2) in the resin composition is preferably 0.1 to 15 parts by mass, and more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the total of the polymerizable compounds (A).

[0057] (C3) Photoradical polymerization initiator The photoradical polymerization initiator absorbs light to generate radicals as active species, thereby promoting polymerization of the radically polymerizable compound. Examples of the photoradical polymerization initiator include, but are not limited to, alkylphenone compounds, acylphosphine oxide compounds, and oxime compounds.

[0058] 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.

[0059] Examples of the acylphosphine oxide compound include 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.

[0060] Examples of oxime compounds include 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone (commercially available as Irgacure OXE01 sold by BASF Japan Ltd.), 6-[1-(acetyloxyimino)ethyl]-9-ethyl-9H-carbazol-3-yl(2-methylphenyl)ketone (commercially available as Irgacure OXE02 sold by BASF Japan Ltd.), [8-[[(acetyloxy)imino][2-(2,2,3,3-tetrafluoropropoxy)phenyl]methyl]-11-(2-ethylhexyl)-11H-benzo[a]carbazol-5-yl]-(2,4,6-trimethylphenyl)methanone (commercially available as Irgacure OXE03 sold by BASF Japan Ltd.), OXE03), and commercially available products such as Irgacure OXE04 sold by BASF Japan Ltd.

[0061] Examples of the photoradical polymerization initiator (C3) include, in addition to the above-mentioned photoradical polymerization 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 benzoin methyl ether. benzyl dimethyl ketal, 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, benzyl, and camphorquinone.

[0062] When the resin composition contains the (C3) photoradical polymerization initiator, the content of the (C3) photoradical polymerization initiator is, from the viewpoint of photocurability, preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 8 parts by mass, relative to 100 parts by mass of the (A) polymerizable compound.

[0063] (C4) Thermal Radical Polymerization Initiator A thermal radical polymerization initiator generates radicals as active species by heat, and causes the polymerization of a radically polymerizable compound to proceed. There are no particular limitations on the thermal radical polymerization initiator that can be used, and known materials can be used. Specific examples of the thermal radical polymerization initiator include dialkyl peroxides such as dicumyl peroxide, t-butylcumyl peroxide, 1,3-bis(2-t-butylperoxyisopropyl)benzene, and 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, and 2,2-bis(t-butylperoxy)hexane; 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, any one of them may be used alone, or two or more of them may be used in combination.

[0064] When the resin composition contains the thermal radical polymerization initiator (C4), the content of the thermal radical polymerization initiator (C4) is preferably 0.01 to 5 mass %, more preferably 0.1 to 3 mass %, relative to the total mass of the resin composition.

[0065] (D) Modified Polydimethylsiloxane The resin composition of this embodiment contains (D) modified polydimethylsiloxane (hereinafter also referred to as "component (D)"). In this embodiment, the (D) modified polydimethylsiloxane satisfies at least one of the following characteristics (a) and (b): (a) An organic substituent containing a COOH group or an OH group is bonded to the polydimethylsiloxane directly or via a linker. (b) The viscosity of the modified polydimethylsiloxane measured in deuterated chloroform is １In the H NMR spectrum, it has signals in the ranges of 0.3 to -0.3 ppm and 4.4 to 3.2 ppm, and D in the range of 13 to 0 ppm. ２ The signal disappears upon addition of O.

[0066] More specifically, the modified polydimethylsiloxane is represented by the formula: The polydimethylsiloxane has a structure in which organic substituents have been introduced as modifying groups into the side chains and / or terminals of the polydimethylsiloxane main chain, which is composed of dimethylsiloxane repeating units represented by the formula: directly or via a linker such as an alkyl group or an alkylene group. Here, "an organic substituent has been introduced into the side chain of the polydimethylsiloxane main chain" means that some of the methyl groups in the polydimethylsiloxane main chain have been substituted with organic substituents. "an organic substituent has been introduced into the terminal of the polydimethylsiloxane main chain" means that some of the methyl groups in the polydimethylsiloxane main chain have been substituted with organic substituents. ３ ) ３ ) is substituted with an organic substituent. The position of the modifying group in the modified polydimethylsiloxane may be a side chain, a terminal (one terminal or both terminals), or both a side chain and a terminal. Modified polydimethylsiloxanes also include polydimethylsiloxanes with a gemini structure. The degree of polymerization of the modified polydimethylsiloxane (the number of dimethylsiloxane repeating units) is not particularly limited and is, for example, 3 or more, preferably 5 or more.

[0067] In the modified polydimethylsiloxane according to the above feature (a), the organic substituent contains a COOH group or an OH group.

[0068] Examples of modified polydimethylsiloxanes in which the organic substituent contains a COOH group include those commercially available under the names of carboxyl-modified polydimethylsiloxanes or carboxyl-modified silicones, etc. Examples of such commercially available products include, but are not limited to, product names X-22-3701E, X-22-162C, and X-22-3710 sold by Shin-Etsu Chemical Co., Ltd.

[0069] Whether the organic substituent of the modified polydimethylsiloxane contains a COOH group can be confirmed by measuring the modified polydimethylsiloxane by Fourier transform infrared spectroscopy (FT-IR) and determining whether the COOH group is present at approximately 1715 cm , which is derived from the C═O stretching vibration of carboxylic acid. －１ This can also be done by observing the presence or absence of IR spectrum of

[0070] Examples of modified polydimethylsiloxanes in which the organic substituent contains an OH group include those commercially available as carbinol-modified polydimethylsiloxanes or carbinol-modified silicones, etc. Examples of such commercially available products include, but are not limited to, product names X-22-4039, X-22-4015, KF-6000, KF-6001, KF-6002, KF-6003, X-22-170BX, and X-22-170DX sold by Shin-Etsu Chemical Co., Ltd.

[0071] Other examples of modified polydimethylsiloxanes in which the organic substituent contains an OH group include those called polyether-modified polydimethylsiloxanes or polyether-modified silicones, in which the polyether group terminates in an OH group. Examples of such commercially available products include, but are not limited to, product names X-22-4272 and KF-6123 sold by Shin-Etsu Chemical Co., Ltd. Furthermore, such polyether-modified polydimethylsiloxanes or polyether-modified silicones are sometimes labeled "PEG-(number) dimethicone" in cosmetic product names. "PEG-(number)" means that n has an average of the number of PEG chains. "PEG-(number) dimethicone" is abbreviated as "PEG-(n) DIMETHICONE" in the INCI nomenclature. Examples of such dimethicone include, but are not limited to, PEG-9 dimethicone (product name: KF-6013), PEG-3 dimethicone (product name: KF-6015 sold by Shin-Etsu Chemical Co., Ltd.), PEG-10 dimethicone (product name: KF-6017 sold by Shin-Etsu Chemical Co., Ltd.), and PEG-10 dimethicone (product name: KF-6043 sold by Shin-Etsu Chemical Co., Ltd.). Examples of polyether groups as organic substituents include polyethylene glycol groups and polypropylene glycol groups, with polyethylene glycol groups being preferred.

[0072] Reactive silicones whose hydroxyl value is disclosed in a catalog or the like can also be assumed to be modified polydimethylsiloxanes in which the organic substituent contains OH groups. The hydroxyl value of the modified polydimethylsiloxane may be measured to confirm the presence of OH groups in the modified polydimethylsiloxane. In one embodiment, the modified polydimethylsiloxane has a hydroxyl value of 1 mg KOH / g or more. The hydroxyl value can be measured, for example, by a method conforming to JIS K 0070 or by FT-NIR (near-infrared spectroscopy) conforming to JIS K 1557-6. Whether the organic substituent of the modified polydimethylsiloxane contains OH groups can be confirmed by measuring the modified polydimethylsiloxane by Fourier transform infrared spectroscopy (FT-IR) and detecting a hydroxyl value of approximately 1360 to 1340 cm resulting from the deformation vibration of alcoholic OH. －１This can also be done by observing the presence or absence of IR spectrum of

[0073] In some commercially available modified polydimethylsiloxanes, the detailed structure of the modifying group is not disclosed. Furthermore, there are also various commercially available additives such as surfactants, surface conditioners, leveling agents, antifoaming agents, wetting agents, and dispersants, which are considered modified polydimethylsiloxanes even though they are not explicitly labeled as modified polydimethylsiloxanes or their structure is not disclosed. In such cases, the modified polydimethylsiloxane was measured in deuterated chloroform. １ In the H NMR spectrum, it has signals in the ranges of 0.3 to -0.3 ppm and 4.4 to 3.2 ppm, and D in the range of 13 to 0 ppm. ２ The modified polydimethylsiloxane of this embodiment has a signal that disappears upon addition of O (the above-mentioned feature (b)). The signal observed in the range of 0.3 to -0.3 ppm is a signal derived from a hydrogen atom connected to a carbon atom adjacent to a Si atom. The signal observed in the range of 4.4 to 3.2 ppm is a signal derived from a hydrogen atom connected to a carbon atom adjacent to an oxygen atom of an OH group or an ether. The signal observed in the range of 13 to 0 ppm and derived from D ２ The signals that disappear upon addition of O can be presumed to be signals derived from the hydrogen atoms of OH or NH groups.

[0074] D ２ The signal that disappears upon addition of O is usually observed in the range of 13 to 0 ppm. Among them, the signal that disappears in the range of 3 to 2 ppm and D ２ The signal that disappears upon addition of O can be assumed to be a signal derived from the hydrogen atom of the OH group.

[0075] D ２ It can be estimated whether the signal that disappears upon addition of O is a signal derived from a hydrogen atom of an OH group or an NH group, for example, by the following method: Fourier transform infrared spectroscopy (FT-IR) measurement １ In addition to the H NMR measurement, Fourier transform infrared spectroscopy (FT-IR) measurement of the modified polydimethylsiloxane revealed a peak at approximately 1360 to 1340 cm , which is due to the deformation vibration of alcoholic OH.－１ By observing the presence or absence of IR spectrum of D ２ The signal that disappears upon addition of O can be assumed to be a signal derived from the hydrogen atom of the OH group. １ In addition to the H NMR measurement, the acidity of the modified polydimethylsiloxane was measured. ２ The signal that disappears upon addition of O can be estimated as being derived from either the OH group or the NH group hydrogen atom. For example, 100 mg of a measurement sample of modified polydimethylsiloxane is dissolved in 200 uL of isopropyl alcohol, 200 uL of pure water is added, and the mixture is shaken well, and the pH of the liquid is measured. If the pH is between 3 and 7, D ２ The signal that disappears upon addition of O can be assumed to be a signal derived from the hydrogen atom of the OH group. ２ The signal that disappears upon addition of O can be presumed to be a signal derived from the hydrogen atom of the NH group.

[0076] The modified polydimethylsiloxane satisfying the above characteristic (b) was measured in deuterated chloroform. １ In the H NMR spectrum, the modified polydimethylsiloxane may have a signal in the range of 1.25 to 0.95 ppm. The signal observed in the range of 1.25 to 0.95 ppm is a signal derived from a hydrogen atom of a methyl group in a polypropylene glycol chain as a polyether modifying group. In one embodiment, the modified polydimethylsiloxane has a peak intensity measured in deuterated chloroform. １ In the H NMR spectrum, the modified polydimethylsiloxane has signals in the range of 1.25 to 0.95 ppm. In one embodiment, the modified polydimethylsiloxane is measured in deuterated chloroform. １ In the 1 H NMR spectrum, there are no signals in the range of 1.25 to 0.95 ppm.

[0077] Examples of modified polydimethylsiloxanes that satisfy characteristic (b) include KF-945, a product sold by Shin-Etsu Chemical Co., Ltd., and TEGO TWIN 4000 and TEGO TWIN 4100, both sold by Evonik Japan Co., Ltd.

[0078] In the resin composition of this embodiment, by including (D) a modified polydimethylsiloxane that satisfies at least one of characteristics (a) and (b), bleeding is suppressed not only during thermal curing after application to a substrate or the like, but also when left at room temperature. The reason why bleeding is suppressed by including (D) a modified polydimethylsiloxane in the resin composition is thought to be, but is not limited to, the following: When a resin composition containing a modified polydimethylsiloxane is applied to a substrate or the like, a portion of the modified polydimethylsiloxane migrates to the surface of the resin composition coating due to the surface migration of the modified polydimethylsiloxane. A small amount of the modified polydimethylsiloxane that has migrated to the coating surface migrates to a substrate that is not in contact with the resin composition before other unreacted components leach out of the resin composition coating, and the modified group of the modified polydimethylsiloxane is adsorbed to the substrate surface. This forms an adsorbed film of the modified polydimethylsiloxane on the substrate surface, which is believed to exhibit water and oil repellency due to the polydimethylsiloxane portion, thereby suppressing bleeding. Furthermore, it is believed that the organic substituent as the modifying group contains a COOH group or an OH group, which results in a higher adsorption effect of the modified polydimethylsiloxane onto the substrate.

[0079] １ The H NMR measurement can be carried out under normal conditions. For example, 100 mg of a measurement sample is dissolved in 500 μl of deuterated chloroform, and a 5 mm diameter tube is placed in the tube. １ After the measurement, add 50 μl of heavy water (D ２ O) is added and the measurement is performed again under the same conditions. The signal that disappeared after the addition of heavy water is found to be a signal derived from active hydrogen bonded to a hydroxyl group or an amino group. Measurement frequency: 40-600 MHz Solvent: deuterated chloroform Measurement nuclide: １ H Accumulation number: 4 to 80 times Measurement temperature: 15 to 50°C

[0080] The polyether-modified polydimethylsiloxane (D) may be used alone or in combination of two or more thereof.

[0081] ​The content of the (D) modified polydimethylsiloxane is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.2% by mass or more, relative to the total mass of the resin composition. It is also preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less. In one embodiment, the content of the (D) modified polydimethylsiloxane is preferably 0.01 to 5% by mass, more preferably 0.1 to 4% by mass, and even more preferably 0.2 to 3% by mass, relative to the total mass of the resin composition.

[0082] (E) Filler The resin composition of this embodiment may contain (E) filler (hereinafter also referred to as "component (E)") within a range that does not impair the effects of the present invention. By containing (E) 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. (E) fillers are broadly classified into inorganic fillers and organic fillers.

[0083] 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.

[0084] 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.

[0085] Examples of the organic filler include polytetrafluoroethylene (PTFE) filler, silicone filler, acrylic filler, styrene filler, etc. The organic filler may be surface-treated. The glass transition temperature of the organic filler is preferably higher than 40°C.

[0086] The shape of the filler is not particularly limited, and may be any of spherical, flaky, needle-like, irregular, etc.

[0087] 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 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.

[0088] The content of the filler (E) 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 (E) 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.

[0089] (F) Stabilizer The resin composition of this embodiment may contain (F) a stabilizer (hereinafter also referred to as "component (F)") to the extent that the effects of the present invention are not impaired. The (F) 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 (F) stabilizer include radical polymerization inhibitors and anionic polymerization inhibitors.

[0090] As the radical polymerization inhibitor, known ones can be used, for example, at least one selected from 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.

[0091] 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.

[0092] Known anionic polymerization inhibitors can be used, such as boric acid ester compounds and strong acids. Specific examples of anionic polymerization inhibitors include 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.

[0093] 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.

[0094] The resin composition may further contain, as necessary, 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, as long as the object of this embodiment is not impaired. However, from the viewpoint of preventing a decrease in cured strength, it is preferable that the resin composition is substantially free of solvent, for example, that the solvent content is 1% by mass or less relative to the total mass of the resin composition. This also allows the amount of volatile organic compounds (VOCs) to be reduced. Examples of the solvent include organic solvents commonly used in the field of curable compositions, such as hydrocarbons (benzene, toluene, xylene, cyclohexane, etc.), aprotic polar solvents (N,N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, etc.), nitriles (acetonitrile, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), esters (ethyl acetate, butyl acetate, etc.), ethers (cyclopentyl methyl ether, diethyl ether, tetrahydrofuran, dimethoxyethane, etc.), alcohols (methanol, ethanol, propanol, butanol, etc.), terpenes (turpentine, terpineol, isobornyl acetate, etc.), and halogenated solvents (dichloromethane, chloroform, etc.).

[0095] The resin composition can be obtained, for example, by stirring, melting, mixing, and / or dispersing components (A) to (D), and optionally components (E) and (F), and 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, all equipped with a stirring and heating device. These apparatuses may also be used in appropriate combinations.

[0096] The resin composition thus obtained may be photocurable, thermosetting, or photo- and thermosetting, depending on the type of polymerization initiator (C) contained in the resin composition. Photocuring of the resin composition is carried out, for example, by irradiating the resin composition with UV light. Thermosetting of the resin composition is carried out, for example, at a temperature of 100°C. The thermosetting temperature of the resin composition is preferably 60 to 90°C when the resin composition is used in the manufacture of a semiconductor module (e.g., an optical sensor module or a camera module) containing components that deteriorate under high temperature conditions. The thermosetting time depends on other curing conditions, but may be, for example, 30 to 120 minutes. When the resin composition is photo- and thermosetting, for example, the resin composition can be pre-cured by curing with light (UV), and then fully cured by curing with heat.

[0097] 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, on 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.

[0098] [Adhesive or Sealant] An adhesive or sealant according to one embodiment of the present invention includes the resin composition of the above-described embodiment. This adhesive or sealant provides good bonding to engineering plastics, ceramics, and metals. The adhesive or sealant according to this embodiment is preferably used to fix, bond, or protect components that constitute an optical sensor module or a camera module.

[0099] [Cured Product of Resin Composition, Adhesive, or Sealant] Another embodiment of the present invention is a cured product obtained by curing the resin composition, adhesive, or sealant of the above-described embodiment. Bleeding is suppressed around an adherend to which the cured product is adhered.

[0100] [Semiconductor Device, Electronic Component] A semiconductor device or electronic component according to one embodiment of the present invention includes the cured product according to the above-described 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, optical sensor modules, camera modules, semiconductor modules, and integrated circuits. Examples of optical sensors include, but are not limited to, photodiodes, photo ICs, photomultiplier tubes (PMTs), phototubes, image sensors, spectroscopes / spectroscopic sensors, infrared sensors, ultraviolet / flame sensors, X-ray sensors, radiation sensors, electron / ion sensors, and distance / position sensors.

[0101] 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.

[0102] [Preparation of Resin Compositions] Resin compositions of the Examples and Comparative Examples were prepared by mixing predetermined amounts of each component using a three-roll mill according to the formulations shown in Tables 2-1 to 2-5. In Tables 2-1 to 2-5, 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:

[0103] (A) Polymerizable compound having a carbon-carbon double bond (component (A)) (A-1): Polyester acrylate (product name: M7100, manufactured by Toagosei Co., Ltd., (meth)acryloyl equivalent: 188 g / eq) (A-2): Dimethylol-tricyclodecane diacrylate (product name: Light Acrylate DCP-A, manufactured by Kyoeisha Chemical Co., Ltd., (meth)acryloyl equivalent: 152 g / eq) (A-3): 2-(o-phenylphenoxy)ethyl acrylate (product name: HRD-01, manufactured by Nisshoku Techno Fine Chemical Co., Ltd., (meth)acryloyl equivalent: 268 g / eq) (A-4): Ethoxylated bisphenol A diacrylate (product name: ABE-300, manufactured by Shin-Nakamura Chemical Co., Ltd., (meth)acryloyl equivalent: 236 g / eq) (B) Polythiol Compound (Component (B)) (B-1): Thiol glycoluril derivative (product name: C3 TS-G, manufactured by Shikoku Chemical Industries, thiol equivalent: 114 g / eq) (B-2): Thiol glycoluril derivative (product name: TS-G, manufactured by Shikoku Chemical Industries, thiol equivalent: 100 g / eq) (B-3): Pentaerythritol tetrakis(3-mercaptopropionate) (product name: PEMP, manufactured by SC Organic Chemical Co., Ltd., thiol equivalent: 122 g / eq) (C) Polymerization Initiator (Component (C)) (C1-1): Amine-epoxy adduct latent curing catalyst (product name: Novacure HXA9322HP, manufactured by Asahi Kasei Corporation) (C1-2): Amine-urea adduct latent curing catalyst (product name: Fujicure FXR-1121, solid at room temperature, manufactured by T&K TOKA Corporation) (C3-1): 1-hydroxy-cyclohexyl-phenyl-ketone (product name: Omnirad 184, manufactured by IGM Resins B.V.)

[0104] (D) Modified polydimethylsiloxane (component (D)) (D') Modified polydimethylsiloxane other than component (D) (component (D')) The modified polydimethylsiloxanes shown in Table 1 below were used as components (D) and (D'). １ The results of the 1 H NMR measurement, Fourier transform infrared spectroscopy (FT-IR) measurement, and acidity measurement are shown in Table 1.

[0105]

[0106] In Table 1, "Ph" represents a phenyl group and "Me" represents a methyl group.

[0107] (E) Filler (Component (E)) (E-1): Calcium carbonate filler (product name: CS3NA, manufactured by Ube Material Industries, Ltd.) (E-2): Silica filler (product name: CAB-O-SIL (registered trademark) TS-720, polydimethylsiloxane surface-treated fumed silica, manufactured by Cabot Corporation)

[0108] [Modified polydimethylsiloxane １ 1H NMR Measurement] 100 mg of a measurement sample of various modified polydimethylsiloxanes was dissolved in 500 μL of deuterated chloroform, and １ The sample was placed in a H NMR sample tube and measured under the following conditions. After the measurement, 50 μL of heavy water (D ２ O) was added and measurement was carried out again under the same conditions. The integral value of each signal is shown in Table 1, assuming that the integral value of the signal from 0.3 to -0.3 ppm derived from chloroform is 6. Measurement equipment: Oxford instrument Pulsar HF Measurement frequency: 60 MHz Solvent: deuterated chloroform Measurement nuclide: １ H Measurement temperature: 37°C Number of measurements: 32

[0109] The assignment of each signal under the above measurement conditions is as follows: 0.3 to −0.3 ppm: CH ３ -Si, CH ２ -Si (hydrogen atom connected to a carbon atom adjacent to a Si atom) 4.4 to 3.2 ppm: -CH ２ -O-, -C=C-CH ２ -O- (hydrogen atom connected to the carbon atom adjacent to the oxygen atom of an alcohol or ether) 1.1 ppm (d, approximately 6 Hz): -CH ２ -CHCH ３ -O-, (hydrogen atom of methyl group of propylene glycol) Under the above measurement conditions, it appears in the range of 9.0 to 0.5 ppm, and D ２ Signals that disappear upon addition of O: OH group or NH group

[0110] [Fourier transform infrared spectroscopy (FT-IR) measurement of modified polydimethylsiloxanes] Fourier transform infrared spectroscopy (FT-IR) measurement of various modified polydimethylsiloxanes was carried out under the following conditions, and the C═O stretching vibration of carboxylic acid (approximately 1715 cm －１ ) and the presence or absence of alcoholic OH bending vibration (approximately 1360-1340 cm －１ The presence or absence of ) was confirmed. The results are shown in Table 1. Measuring device: Perkin-Elmer FT-IR Spectrometer Spectrum 3 Measuring method: ATR method

[0111] [Measurement of Acidity of Modified Polydimethylsiloxanes] 100 mg of each modified polydimethylsiloxane sample was dissolved in 200 μL of isopropyl alcohol (IPA), 200 μL of pure water was added, and the mixture was shaken well. pH test paper was immersed in the resulting liquid and the pH was determined. Macherey Nagel #90204 Universal indicator paper was used as the pH test paper. The results are shown in Table 1.

[0112] In the examples and comparative examples, the properties of the resin compositions were measured as follows.

[0113] [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. The bleed length under two conditions was measured using a CCD camera (N = 3 pcs x 2 sides). The results are shown in Tables 2-1 to 2-5. Condition 1: The bleed length on the ceramic substrate after potting and leaving it at room temperature (20°C to 25°C) for 60 minutes. Condition 2: The bleed length on the ceramic substrate after potting and leaving it at room temperature (20°C to 25°C) for 60 minutes, and then thermally curing the resin composition at 80°C for 60 minutes.

[0114]

[0115]

[0116]

[0117]

[0118]

[0119] It can be seen that the resin compositions of Examples 1 to 20 containing a modified polydimethylsiloxane (D) that satisfies at least one of characteristics (a) and (b) exhibited significantly reduced bleeding under both Condition 1 and Condition 2, compared to the resin compositions of Comparative Examples 1 and 6 to 11 that did not contain the modified polydimethylsiloxane (D) and the resin compositions of Comparative Examples 2 to 5 that contained a modified polydimethylsiloxane other than component (D') or (D).

[0120] The present invention relates to a resin composition that is at least photocurable or thermosetting and can suppress 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.

[0121] The disclosure of Japanese Patent Application No. 2023-211994 (filing date: December 15, 2023) is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards mentioned 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 polymerizable compound having a carbon-carbon double bond; (B) a polythiol compound; (C) a polymerization initiator; and (D) a modified polydimethylsiloxane that satisfies at least one of the following characteristics (a) and (b): (a) an organic substituent containing a COOH group or an OH group is bonded to the polydimethylsiloxane directly or via a linker; (b) the molecular weight of the modified polydimethylsiloxane is measured in deuterated chloroform. １ In the H NMR spectrum, it has signals in the ranges of 0.3 to -0.3 ppm and 4.4 to 3.2 ppm, and D ２ A resin composition comprising:

2. The resin composition according to claim 1, wherein the polymerizable compound having a carbon-carbon double bond (A) is a (meth)acrylate compound.

3. The resin composition according to claim 1 or 2, wherein the content of the modified polydimethylsiloxane (D) is 0.01 to 5 mass % based on the total mass of the resin composition.

4. The resin composition according to any one of claims 1 to 3, further comprising (E) a filler.

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 an optical sensor module or a component that constitutes the optical sensor module.

7. A cured product obtained by curing the resin composition according to any one of claims 1 to 4, or the adhesive or sealant according to claim 5 or 6.

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

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

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