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

Abstract

To provide a resin composition and an adhesive which can suppress bleeding, at least thermosetting. 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 dimethylpolysiloxane satisfying at least one of the following characteristics (a) and (b): (a) an organic substituent containing a COOH group or an OH group is directly bonded to the dimethylpolysiloxane, or is bonded to the dimethylpolysiloxane through a linking group; (b) a signal disappears in deuterated chloroform 1 In the1H NMR spectrum, signals were present in the ranges of 0.3 to -0.3 ppm and 4.4 to 3.2 ppm, and a signal disappeared due to the addition of D2O in the range of 13 to 0 ppm.

Description

Technical Field

[0001] This invention relates to resinous compositions, adhesives or sealants containing the resinous compositions, cured products thereof, semiconductor devices and electronic components containing the cured products. Background Technology

[0002] Currently, adhesives and sealants containing curable resin compositions are frequently used in the assembly and installation of components used in semiconductor devices, such as semiconductor chips, to maintain reliability. Among such resin compositions are known curable compositions that are primarily composed of epoxy compounds or (meth)acrylate compounds and use thiol compounds as curing agents (e.g., Patent Documents 1 and 2).

[0003] In Patent Document 3, a photo- and thermosetting resin composition was disclosed that has both excellent photocurability and excellent thermosetting properties. When light is applied under conditions where no light is applied, the entire composition, including the un-illuminated area, can be completely cured by subsequent heating to generate a cured product with high adhesive strength and good storage stability. The resin composition includes (1) a compound having a (meth)acryloyl group, (2) a polyene compound having two or more vinyl 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] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2009-51954

[0007] Patent Document 2: International Publication No. 2005 / 052021

[0008] Patent Document 3: Japanese Patent Application Publication No. 2017-101112 Summary of the Invention

[0009] In the assembly of semiconductor modules, overflow has become a problem. Overflow refers to the phenomenon where unreacted components seep out of the adhesive coating or cured product over time when adhesives containing curable resin compositions are used to fix and bond components. Sometimes, the seeping component itself is also referred to as "overflow." Sometimes, overflow can come into contact with metal wiring on the substrate, causing electrical malfunctions and reducing the reliability of the semiconductor module. In particular, internal overflow originating from uncured portions of the adhesive tends to develop further when the adhesive coating is left at room temperature and / or during heat curing, with an increasing overflow length.

[0010] In recent years, electronic components such as semiconductor chips have been increasingly required to be miniaturized or highly integrated, resulting in shorter distances to the wiring sections surrounding these components. In semiconductor modules incorporating such miniaturized or highly integrated electronic components, the risk of leakage contact with the wiring sections increases due to leakage phenomena.

[0011] Therefore, the object of the present invention is to provide a resin composition and adhesive that are at least photocurable or thermocurable and capable of suppressing leakage.

[0012] Specific means for solving the above-mentioned problems are shown below. Embodiments of the present invention include resin compositions, adhesives or sealants, cured products, and semiconductor devices or electronic components in the following manner.

[0013] [1] A resin composition comprising:

[0014] (A) Polymerizable compounds with carbon-carbon double bonds

[0015] (B) Polythiol compounds,

[0016] (C) Polymerization initiator, and

[0017] (D) Modified polydimethylsiloxanes that satisfy at least one of the following characteristics (a) and (b):

[0018] (a) Organic substituents containing COOH or OH groups are directly bonded to polydimethylsiloxane, or are bonded to polydimethylsiloxane through linking groups;

[0019] (b) Detected in deuterated chloroform 1 In the 1H NMR spectrum, there is a signal in the range of 0.3 to -0.3 ppm and 4.4 to 3.2 ppm, and the signal disappears due to the addition of D2O in the range of 13 to 0 ppm.

[0020] [2] According to the resin composition described in [1] above, wherein the polymerizable compound having carbon-carbon double bonds in (A) above is a (meth)acrylate compound.

[0021] [3] According to the resin composition described in [1] or [2] above, wherein the content of the above-mentioned (D) modified polydimethylsiloxane is 0.01 to 5% by mass relative to the total mass of the resin composition.

[0022] [4] The resin composition according to any one of [1] to [3] above further comprises (E) filler.

[0023] [5] An adhesive or sealing material comprising the resin composition described in any one of [1] to [4] above.

[0024] [6] The adhesive or sealing material described in [5] above is used for fixing, bonding or protecting the optical sensor module or the components constituting it.

[0025] [7] A cured product obtained by curing the resin composition described in any one of [1] to [4] above, or the adhesive or sealant described in [5] or [6] above.

[0026] [8] A semiconductor device or electronic component comprising the cured material described in [7] above.

[0027] [9] The semiconductor device or electronic component described in [8] above is an optical sensor module.

[0028] According to embodiments of the present invention, a resin composition, at least photocurable or thermocurable, capable of suppressing leakage, an adhesive or sealant comprising the resin composition, a cured product thereof, and a semiconductor device or electronic component comprising the cured product can be provided. Detailed Implementation

[0029] [Resin Composition]

[0030] As one embodiment of the present invention, the resin composition comprises:

[0031] (A) Polymerizable compounds with carbon-carbon double bonds

[0032] (B) Polythiol compounds,

[0033] (C) Polymerization initiator, and

[0034] (D) Modified polydimethylsiloxanes that satisfy at least one of the following characteristics (a) and (b):

[0035] (a) Organic substituents containing COOH or OH groups are directly bonded to polydimethylsiloxane, or are bonded to polydimethylsiloxane through linking groups;

[0036] (b) Detected in deuterated chloroform 1 In H NMR, there is a signal in the range of 0.3 to -0.3 ppm and 4.4 to 3.2 ppm, and the signal disappears due to the addition of D2O in the range of 13 to 0 ppm.

[0037] According to this embodiment, a resin composition that is at least photocurable or thermocurable can be provided, capable of suppressing leakage.

[0038] (A) Polymerizable compounds with carbon-carbon double bonds

[0039] The resin composition of this embodiment comprises (A) a polymerizable compound having carbon-carbon double bonds (hereinafter also referred to as "(A) polymerizable compound" or "component (A)"). The (A) polymerizable compound having carbon-carbon double bonds polymerizes through free radical polymerization between (A) polymerizable compounds or between (A) polymerizable compounds and (B) polythiol compounds described later, or through crosslinking reaction between (A) polymerizable compounds and (B) polythiol compounds in an anionic polymer system, thereby imparting curability and adhesiveness to the resin composition. Examples of (A) polymerizable compounds having carbon-carbon double bonds include (meth)acrylate compounds, maleimide compounds, styrene compounds, polybutadiene compounds, vinyl ether compounds, allyl ether compounds, etc., but are not limited to these.

[0040] In this specification, the term "(meth)acrylate compound" refers to a compound having at least one (meth)acryloyl group within its molecule. Examples include monofunctional (meth)acrylate compounds having one (meth)acryloyl group and polyfunctional (meth)acrylate compounds 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, "(meth)acryloyl group" includes both methacryloyl and acryloyl groups. Furthermore, "(meth)acrylate compound" includes both acrylate compounds and methacrylate compounds.

[0041] Examples of (meth)acrylate compounds include diacrylates and / or dimethacrylates of tris(2-hydroxyethyl) isocyanurate; triacrylates and / or trimethacrylates of tris(2-hydroxyethyl) isocyanurate; trimethylolpropane triacrylates and / or trimethacrylates, or oligomers thereof; pentaerythritol triacrylates and / or trimethacrylates, or oligomers thereof; dipentaerythritol polyacrylates and / or polymethacrylates; tris(acryloyloxyethyl) isocyanurate; caprolactone-modified tris(acryloyloxyethyl) isocyanurate; caprolactone-modified tris(methacryloyloxyethyl) isocyanurate; alkyl-modified dipentaerythritol polyacrylates and / or polymethacrylates; caprolactone-modified dipentaerythritol polyacrylates and / or polymethacrylates; ethoxylated... Bisphenol A diacrylate and / or ethoxylated bisphenol A dimethacrylate; dihydrocyclopentanediethyl acrylate and / or dihydrocyclopentanediethyl methacrylate, as well as polyester acrylates and / or polyester methacrylates, dihydroxymethyl-tricyclodecane diacrylates, bis(trimethylolpropane)poly(meth)acrylates, ethoxylated bisphenol A diacrylates, polyurethanes having two or more (meth)acryloyl groups in one molecule, polyesters having two or more (meth)acryloyl groups in one molecule, and other polyfunctional (meth)acrylates; phenoxyethyl acrylate, 2-(o-phenylphenoxy)ethyl acrylate, isobornyl acrylate, phenoxydiethylene glycol (meth)acrylate, 4-tert-butylcyclohexyl acrylate, epoxy resin semiacrylate, and other monofunctional (meth)acrylates, but not limited to them.

[0042] From a reactivity point of view, (meth)acrylate compounds are preferably not substantially composed of methacrylate compounds, but rather of acrylate compounds.

[0043] (Meth)acrylate compounds may be used in combination of any one type or two or more types.

[0044] Among maleimide compounds, there exist monofunctional maleimide compounds having one maleimide group and polyfunctional maleimide compounds having two or more maleimide groups. Sometimes, maleimide compounds having two maleimide groups are specifically referred to as bismaleimide compounds. Examples of bismaleimide compounds include N,N'-(4,4'-diphenylmethane)bismaleimide, bisphenol A 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-maleimidephenyl)methane, and m-phenylene bismaleimide. Amines (N,N'-1,3-phenylene bismaleimide), 1,6-bismaleimide hexane, 1,2-bismaleimide ethane (N,N'-ethylene bismaleimide), N,N'-(1,2-phenylene)bismaleimide, N,N'-1,4-phenylene bismaleimide, N,N'-(sulfonyl di-p-phenylene)bismaleimide, N,N'-[3,3'-(1,3-phenylenedioxy)diphenyl]bismaleimide, but not limited to these. They can be used alone or in combination of two or more.

[0045] When a low room-temperature modulus of elasticity 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 a bismaleimide compound is described, for example, in Japanese Patent Application Publication No. 2015-193725. Commercially available bismaleimide compounds having a hydrocarbon group derived from a dimer acid include, for example, those that are liquid at 25°C under the names "BMI-689", "BMI-1500", and "BMI-1700", or solid at 25°C under the name "BMI-3000" (all manufactured by Designer Molecules Inc.), but are not limited to these. They can be used alone or in combination of two or more.

[0046] Styrene compounds are compounds having at least one styrene group (H2C=CH-C6H5-). Examples of styrene compounds include 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-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 divinylphenyl polymers (oligomers) having vinyl groups in their side chains, but are not limited to these. They can be used alone or in combination of two or more.

[0047] Examples of polybutadiene compounds include polybutadiene with vinyl groups in the side chains and polybutadiene with 1,2-bonds comprising more than 90% by weight in the structure, but these are not limited to these. They can be used alone or in combination of two or more.

[0048] Vinyl ether compounds are compounds having at least one vinyl ether group (H₂C=CH-O-). Examples of vinyl ether compounds include ethyl vinyl ether, triethylene glycol divinyl ether, trimethylolpropane trivinyl ether, hydroxybutyl vinyl ether, vinyl ether of 1,4-cyclohexanediethanol, dodecyl vinyl ether, and cyclohexyl vinyl ether, but are not limited to these. They can be used alone or in combination of two or more.

[0049] Examples of allyl ether compounds include allyl glycidyl ether, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, and glycerol monoallyl ether, but are not limited to these. They can be used alone or in combination of two or more.

[0050] From the viewpoint of the preparation and distribution of the resin composition, component (A) is preferably found to have a viscosity of 0.01 to 100 Pa·s. It should be noted that, in this specification, viscosity refers to a value obtained by measuring the viscosity using an appropriate viscometer at a measurement temperature of 25°C, according to the viscosity range.

[0051] Commercially available products that can be used as ingredient (A) include, for example, polyester acrylate (product name: EBECRYL810) manufactured by Daicel Allnex Co., Ltd., bis(trimethylolpropane)tetraacrylate (product name: EBECRYL140) manufactured by Daicel Allnex Co., Ltd., polyester acrylate (product name: M7100) manufactured by Toa Synthetic Co., Ltd., dimethylol-tricyclodecane diacrylate (product name: LIGHT ACRYLATE DCP-A) manufactured by Kyoei 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 Nippon 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. Component (A) may use any one of them, or two or more of them together.

[0052] Regarding the content of component (A), from the viewpoint of the adhesive strength of the resin composition, it is preferably 10 to 70% by mass relative to the total mass of the resin composition, and more preferably 20 to 60% by mass.

[0053] (B) Polythiol compounds

[0054] The resin composition of this embodiment includes (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 difunctional or has two or more thiol groups. Component (B) preferably includes a trifunctional or more thiol compound, and more preferably includes a trifunctional and / or quadrifunctional thiol compound. It should be noted that trifunctional and quadrifunctional thiol compounds refer to thiol compounds having three and four thiol groups, respectively.

[0055] Examples of polythiols include, but are not limited to, pentaerythritol tetra(3-mercaptopropionate), trimethylolpropane tri(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), pentaerythritol tetra(3-mercaptobutyrate), tri-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, pentaerythritol tetra(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 tri(3-mercaptobutyrate), and trimethylolethane tri(3-mercaptobutyrate).

[0056] Commercially available products of the aforementioned component (B) include trimethylolpropane tris(3-mercaptopropionate) (manufactured by SC Organic Chemicals Co., Ltd.: TMMP), tri-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate (manufactured by SC Organic Chemicals Co., Ltd.: TEMPIC), pentaerythritol tetra(3-mercaptopropionate) (manufactured by SC Organic Chemicals Co., Ltd.: PEMP), tetraethylene glycol bis(3-mercaptopropionate) (manufactured by SC Organic Chemicals Co., Ltd.: EGMP-4), dipentaerythritol hexa(3-mercaptopropionate) (manufactured by SC Organic Chemicals Co., Ltd.: DPMP), pentaerythritol tetra(3-mercaptobutyrate) (manufactured by Showa Denko Co., Ltd.: Karenz MT (registered trademark) PE1), and 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by Showa Denko Co., Ltd.: Karenz). MT (registered trademark) NR1), trimethylolpropane tris(3-mercaptobutyrate) (manufactured by Showa Denko Corporation: Karenz MT (registered trademark) TPMB), etc., but not limited to them.

[0057] In addition, as a (B) polythiol compound, a glycourea compound represented by the following general formula (1) can be cited.

[0058] [Chemistry 1]

[0059]

[0060] In general formula (1), R 1 and R 2 Each is independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, or a phenyl group. n is an integer from 0 to 10.

[0061] Alternatively, component (B) may be a compound represented by the following chemical formula (2) or chemical formula (3).

[0062] [Chemistry 2]

[0063]

[0064] [Chemistry 3]

[0065]

[0066] In addition, as (B) polythiols, polythiols represented by general formula (4) can be cited.

[0067] [Chemistry 4]

[0068]

[0069] In general formula (4), R 3 R 4R 5 and R 6 Each is independently hydrogen or C n H 2n SH (n is 2 to 6). In addition, R 3 R 4 R 5 and R 6 At least one of them is C n H 2n SH (n is 2 to 6). Regarding the polythiol compound represented by formula (4), n is preferably 2 to 4 from the viewpoint of curability. Furthermore, regarding this polythiol compound, from the viewpoint of balancing the properties of the cured product with the curing speed, mercaptopropyl with n of 3 is more preferred. Component (B) represented by formula (4) is effective when it is necessary to reduce the elastic modulus of the cured product because it has a sufficiently soft skeleton. By adding component (B) represented by formula (4), the elastic modulus of the cured product can be controlled, thus improving the adhesive strength (especially peel strength) after curing.

[0070] Commercially available products that are components (B) mentioned above include thiol glycourea derivatives produced by Shikoku Chemical Industry (product name: TS-G (equivalent to chemical formula (2), thiol equivalent: 100 g / eq), C3 TS-G (equivalent to chemical formula (3), thiol equivalent: 114 g / eq), and thiol compounds produced by SC Organic Chemicals (product name: PEPT (equivalent to general formula (4), thiol equivalent: 124 g / eq), but are not limited to them.

[0071] Other examples of the aforementioned component (B) include 1,3,4,6-tetra(mercaptomethyl)glycourea, 1,3,4,6-tetra(mercaptomethyl)-3a-methylglycourea, 1,3,4,6-tetra(2-mercaptoethyl)-3a-methylglycourea, 1,3,4,6-tetra(3-mercaptopropyl)-3a-methylglycourea, 1,3,4,6-tetra(mercaptomethyl)-3a,6a-dimethylglycourea, 1,3,4,6-tetra(2-mercaptoethyl)-3a,6a-dimethylglycourea, 1,3,4,6-tetra(3-mercaptopropyl)-3a,6a-dimethylglycourea, 1,3,4,6-tetra(mercaptomethyl)-3a,6a-diphenylglycourea, and 1,3,4,6-tetra(2-mercaptoethyl)-3a... 6a-Diphenylglycourea, 1,3,4,6-Tetra(3-mercaptopropyl)-3a,6a-diphenylglycourea, 3-[2,3-bis(3-thioalkylpropoxy)propoxy]propane-1-thiol, 3-[2,2-bis[(3-mercaptopropyloxy)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, tetra(mercaptomethylthiomethyl)methane, tetra(2-mercaptoethylthiomethyl)methane, tetra(3-mercaptopropylthiomethyl)methane, 1,1,3,3-tetra(mercaptomethylthio)propane, 1,1,2,2-tetra(mercaptomethylthio)ethane, 1,1,5,5-tetra(mercaptomethylthio)-3-thiapentane, 1,1,6,6-tetra(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-mercapto... Methylthio-1,6-dimercapto-2,5-dithiahexane, 1,1,9,9-tetra(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, tetra(2,2-bis( (Mercaptomethylthio)ethyl)methane, tetra(4,4-bis(mercaptomethylthio)-2-thiamethoxy)methane, 3,5,9,11-tetra(mercaptomethylthio)-1,13-dimercapto-2,6,8,12-tetrathiatridecane, 3,5,9,11,15,17-hexa(mercaptomethylthio)-1,19-dimercapto-2,6,8,12,14,18-Hexathionechodecane, 9-(2,2-bis(mercaptomethylthio)ethyl)-3,5,13,15-tetra(mercaptomethylthio)-1,17-dimercapto-2,6,8,10,12,16-hexathionechodecane, 3,4,8,9-tetra(mercaptomethylthio)-1,11-dimercapto-2,5,7,10-tetrathionechodecane, 3,4,8,9,13,14-hexa(mercaptomethylthio)-1,16-dimercapto-2,5,7,10,12,15-hexathionechodecane, 8-[bis(mercaptomethylthio)methyl]-3,4,12,13-tetra(mercaptomethylthio)-1,15-dimercapto-2,5,7,9,11,14-hexathionechodecane, 4,6-bis[3, [5-bis(mercaptomethylthio)-7-mercapto-2,6-dithiaheptylthio]-1,3-dithiaane, 4-[3,5-bis(mercaptomethylthio)-7-mercapto-2,6-dithiaheptylthio]-6-mercaptomethylthio-1,3-dithiaane, 1,1-bis[4-(6-mercaptomethylthio)-1,3-dithiaanethio]-1,3-bis(mercaptomethylthio)propane, 1-[4-(6-mercaptomethylthio)-1,3-dithiaanethio]-3-[2,2-bis(mercaptomethylthio)ethyl]-7,9-bis(mercaptomethylthio)-2,4,6,10-tetrathiaundecane, 3-[2-(1,3-dithiacyclobutyl)]methyl-7,9-bis(mercaptomethylthio)-1,11-dimercapto-2 4,6,10-Tetrathiaheptadecane, 9-[2-(1,3-dithiacyclobutyl)]methyl-3,5,13,15-tetra(mercaptomethylthio)-1,17-dimercapto-2,6,8,10,12,16-hexathiaheptadecane, 3-[2-(1,3-dithiacyclobutyl)]methyl-7,9,13,15-tetra(mercaptomethylthio)-1,17-dimercapto-2,4,6,10,12,16-hexathiaheptadecane, 4,6-bis[4-(6-mercaptomethylthio)-1,3-dithiaalkylthio]-6-[4-(6-mercaptomethylthio)-1,3-dithiaalkylthio]-1,3-dithiadecane, 4-[3,4,8,9-tetra(mercaptomethylthio)-11-mercapto-2 [5,7,10-Tetrathiaundecyl]-5-mercaptomethylthio-1,3-dithiopentane, 4,5-bis[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]-1,3-dithiopentane, 4-[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]-5-mercaptomethylthio-1,3 -Dithiopentane, 4-[3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiaoctyl]-5-mercaptomethylthio-1,3-dithiopentane, 2-{bis[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]methyl}-1,3-dithionecyclobutane, 2-[3,4-Bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]mercaptomethylthiomethyl-1,3-dithiacyclobutane, 2-[3,4,8,9-tetra(mercaptomethylthio)-11-mercapto-2,5,7,10-tetrathiaundecylthio]mercaptomethylthiomethyl-1,3-dithiacyclobutane, 2-[3-bis(mercaptomethylthio)methyl- [5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiaoctyl]mercaptomethylthiomethyl-1,3-dithionecyclobutane, 4-{1-[2-(1,3-dithionecyclobutyl)]-3-mercapto-2-thiapropanethio}-5-[1,2-bis(mercaptomethylthio)-4-mercapto-3-thiabutanethio]-1,3-dithiopentane, etc.

[0072] As component (B), any one of them can be used, or two or more can be used together.

[0073] In this embodiment, the content of component (B) in the resin composition is preferably 1 to 70% by mass relative to the total mass of the resin composition, more preferably 10 to 60% by mass, and even more preferably 20 to 50% by mass.

[0074] Among polythiol compounds, there exist polythiol compounds with hydrolyzable partial structures such as ester bonds in the molecule (i.e., hydrolyzable polythiol compounds). From the viewpoint of the moisture resistance of the cured resin composition, the amount of polythiol compounds with hydrolyzable partial structures such as ester bonds in the molecule is preferably 90% by mass or less relative to the total mass of component (B), for example, 0 to 90% by mass, for example, 0 to 80% by mass, for example, 0 to 70% by mass, for example, 0 to 60% by mass, for example, 0 to 50% by mass.

[0075] (C) Polymerization initiator

[0076] The resin composition of this embodiment includes (C) a polymerization initiator (hereinafter also referred to as "component (C)"). In this specification, the polymerization initiator (C) includes (C1) a basic catalyst, (C2) a photo-alkali-generating agent, (C3) a photo-radical polymerization initiator, and (C4) a thermal radical polymerization initiator. The polymerization initiator (C) can be appropriately selected according to the application site and / or use of the resin composition, or according to, for example, whether the resin composition is photocurable, thermocurable, or both photocurable and thermocurable. For example, the polymerization initiator (C) can be used alone, or any one of (C1) the basic catalyst, (C2) the photo-alkali-generating agent, (C3) the photo-radical polymerization initiator, and (C4) the thermal radical polymerization initiator, or they can be used in any combination.

[0077] (C1) Alkaline catalyst

[0078] (C1) Known basic catalysts can be used as the basic catalyst; however, thermally latent catalysts are preferred. A thermally latent catalyst is a compound or substance that is inactive at room temperature but is activated by heating and functions as a polymerization catalyst. Examples include amine compounds that are solid at room temperature; amine adduct latent polymerization catalysts such as the reaction products of amine compounds and epoxides (amine-epoxide adduct systems), and the reaction products of amine compounds and isocyanate or urea compounds (urea adduct systems); microencapsulated thermally latent polymerization catalysts; and inclusion-type thermally latent polymerization catalysts, etc., which are solid-dispersed thermally latent polymerization catalysts. Amine compounds include aliphatic amines, aromatic amines, and heterocyclic amines.

[0079] 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, and 2,4-diamino-6-(2′-methylimidazolyl-(1)′). -Ethyl-S-triazine isocyanuric acid adduct, 2-methylimidazolium, 2-phenylimidazolium, 2-phenyl-4-methylimidazolium, 1-cyanoethyl-2-phenylimidazolium, 1-cyanoethyl-2-methylimidazolium-trimethoxylate, 1-cyanoethyl-2-phenylimidazolium-trimethoxylate, N-(2-methylimidazolium-1-ethyl)-urea, N,N′-(2-methylimidazolium-(1)-ethyl)-hexamethylenediamine, etc., but not limited to them.

[0080] Amine compounds used as one of the raw materials for manufacturing latent curing catalysts for amine adduct systems only need to have one or more active hydrogen atoms capable of addition reactions with epoxy or isocyanate groups within the molecule, and at least one functional group selected from primary, secondary, and tertiary amines within the molecule. Examples of such amine compounds, in addition to the aforementioned amine compounds that are solid at room temperature, include aliphatic amines such as diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, and 4,4′-diamino-dicyclohexylmethane; aromatic amine compounds such as 4,4′-diaminodiphenylmethane and 2-methylaniline; and heterocyclic amine compounds containing nitrogen atoms such as 2-ethyl-4-methylimidazolium, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline, piperidine, and piperazine; etc., but are not limited to these.

[0081] In addition, compounds, especially those containing tertiary amino groups within the molecule and imidazole derivatives, are raw materials for providing latent curing catalysts with excellent curing-promoting capabilities. Examples of such compounds include amine compounds such as dimethylaminopropylamine, diethylaminopropylamine, di-n-propylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, and N-methylpiperazine; imidazole compounds such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4-methylimidazole, and 1-(2-aminoethyl)-2-methylimidazole; and imidazole compounds such as 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, and 1-(2-... 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazol, 1-(2-hydroxy-3-butoxypropyl)-2-ethyl-4-methylimidazol, 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 Alcohols, phenols, thiols, carboxylic acids, and acyl hydrazides, such as 2-mercaptopyridine, benzimidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 4-mercaptopyridine, N,N-dimethylaminobenzoic acid, N,N-dimethylglycine, nicotinic acid, isonicotinic acid, pyridinecarboxylic acid, N,N-dimethylglycine hydrazide, N,N-dimethylpropionic acid hydrazide, nicotinic acid hydrazide, and isonicotinic acid hydrazide, have a tertiary amino or imidazole skeleton in their molecules, but are not limited to these.

[0082] Epoxy compounds used as raw materials for manufacturing thermally latent curing catalysts for amine-epoxy adduct systems include, but are not limited to, polyglycidyl ethers obtained by reacting polyphenols such as bisphenol A, bisphenol F, catechol, and resorcinol, or polyols such as glycerol and polyethylene glycol with epichlorohydrin; glycidyl ether esters obtained by reacting hydroxycarboxylic acids such as p-hydroxybenzoic acid and β-hydroxynaphthoic acid with epichlorohydrin; polyglycidyl esters obtained by reacting polycarboxylic acids such as phthalic acid and terephthalic acid with epichlorohydrin; glycidyl amine compounds obtained by reacting 4,4′-diaminodiphenylmethane, m-aminophenol, etc., with epichlorohydrin; and polyfunctional epoxy compounds such as epoxidized phenol linear phenolic resins, epoxidized cresol linear phenolic resins, and epoxidized polyolefins, as well as monofunctional epoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, various phenylphenol glycidyl ethers, and glycidyl methacrylate.

[0083] Isocyanate compounds used as raw materials for manufacturing latent curing catalysts for amine-urea adduct systems include, for example, monofunctional isocyanate compounds such as n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, and benzyl isocyanate; polyfunctional isocyanate compounds such as hexamethylene diisocyanate, toluene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4′-diisocyanate, isophorone diisocyanate, phenylenediamine diisocyanate, p-phenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, and dicycloheptane triisocyanate; and compounds containing terminal isocyanate groups obtained by reacting these polyfunctional isocyanate compounds with active hydrogen compounds. Examples of such compounds containing a terminal isocyanate group include addition compounds with a terminal isocyanate group obtained by the reaction of toluene diisocyanate with trimethylolpropane, and addition compounds with a terminal isocyanate group obtained by the reaction of toluene diisocyanate with pentaerythritol, but are not limited to these.

[0084] Urea compounds that can be used as raw materials for manufacturing latent curing catalysts for amine-urea adduct systems include, but are not limited to, urea and thiourea.

[0085] Amine adduct-based thermally latent curing catalysts are, for example, the combination of (a) an amine compound and an epoxy compound as two components, (b) the two components and an active hydrogen compound as three components, or (c) an amine compound and two or three components of an isocyanate compound and / or a urea compound. They can be readily prepared by collecting and mixing the components, reacting them at a temperature from room temperature to 200°C, cooling and curing them, and then pulverizing them; or by reacting them in solvents such as methyl ethyl ketone, dioxane, or tetrahydrofuran, removing the solvent, and then pulverizing the solid components.

[0086] So-called microencapsulated latent curing catalysts are curing catalysts having a structure in which an amine adduct compound obtained by reacting an amine compound with an epoxy compound, an isocyanate compound, or a urea compound serves as the core, and is coated with a shell made of a synthetic resin or an inorganic oxide. Examples of amine compounds include the aforementioned amine compounds. From the perspective of exhibiting suitable latency, imidazole derivatives are preferred as amine compounds. Examples of imidazole derivatives include 2-methylimidazolium, 2-phenylimidazolium, 2-phenyl-4-methylimidazolium, 2-phenyl-4,5-dihydroxymethylimidazolium, and 2-phenyl-4-methyl-5-hydroxymethylimidazolium. Examples of synthetic resins used as the shell include phenolic resins, melamine resins, epoxy resins, polyurethane resins, and urea resins; these resins can also be used in combination. Examples of inorganic oxides used as the shell include silica, alumina, titanium dioxide, and magnesium oxide.

[0087] Examples of commercially available thermally latent curing catalysts include the following products, but are not limited to them. Examples of amine-epoxy adduct curing catalysts include "Amicure PN-23" (Ajinomoto Fine-Techno Co., Ltd.), "Amicure PN-40" (Ajinomoto Fine-Techno Co., Ltd.), "Amicure PN-50" (Ajinomoto Fine-Techno Co., Ltd.), "Hardener X-3661S" (ACR Co., Ltd.), "Hardener X-3670S" (ACR Co., Ltd.), "Novacure HX-3742" (Asahi Kasei Co., Ltd.), "Novacure HX-3721" (Asahi Kasei Co., Ltd.), "Novacure HXA9322HP" (Asahi Kasei Co., Ltd.), "Novacure HXA3922HP" (Asahi Kasei Co., Ltd.), "Novacure HXA3932HP" (Asahi Kasei Co., Ltd.), and "Novacure HXA3932HP". The product names include "HXA5945HP" (Asahi Kasei Corporation), "Novacure HXA5911HP" (Asahi Kasei Corporation), and "Novacure HXA9382HP" (Asahi Kasei Corporation), but are not limited to these. The aforementioned "Novacure" series are also microencapsulated latent solidification catalysts. In addition, examples of amine-urea type adduct curing catalysts include "Fujicure FXE-1000" (T&K TOKA Co., Ltd.), "Fujicure FXR1020" (T&K TOKA Co., Ltd.), "Fujicure FXR-1030" (T&K TOKA Co., Ltd.), "Fujicure FXR1121" (T&K TOKA Co., Ltd.), "Fujicure FXR1081" (T&K TOKA Co., Ltd.), "Fujicure 1061" (T&K TOKA Co., Ltd.), and "Fujicure 1171" (T&K TOKA Co., Ltd.), but they are not limited to these.

[0088] So-called inclusion-type latent curing catalysts are curing catalysts with a structure in which guest molecules such as amine compounds are encapsulated at the molecular level in crystal cavities formed by the host molecules. As a commercially available example of an inclusion-type latent curing catalyst, "NISSOCURE TIC-188" (product name of Nippon Soda Co., Ltd.) can be cited.

[0089] (C1) Any one type of alkaline catalyst can be used, or two or more types can be used in combination.

[0090] When the resin composition contains a (C1) alkaline catalyst, the content of the (C1) alkaline catalyst, from the viewpoint of the curing speed and usable time of the resin composition, is preferably 0.1 to 40% by mass, more preferably 1 to 20% by mass, relative to the total mass of the resin composition.

[0091] (C2) Photoalkali-producing agent

[0092] Photoalkali-producing agents, upon absorbing light, generate a base as an active species, thereby promoting the polymerization of anionic polymerizable compounds. Examples of photoalkali-producing agents include various compounds that produce amines, amidines, guanidines, phosphazenes, and carbenes as bases, but are not limited to these. Specific examples of photoalkali-producing agents 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, and 1-(9,10-dioxo-9,10-dihydroanthracite-2-yl) Ethylcyclohexylcarbamate, 1-(9,10-dioxo-9,10-dihydroanthracene-2-yl)ethyl 1H-imidazol-1-carboxylate, 3,4,6,7,8,9-hexahydro-2H-pyrimidino[1,2-a]pyrimidin-1-onium 2-(3-benzoylphenyl)propionate, diaminomethyleneimineonium 2-(3-benzoylphenyl)propionate, (Z)-N-(((bis(dimethylamino)methylene)amino)(isopropylamino)methylene)propane- 2-Ammonium-2-(3-benzoylphenyl)propionate, 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidine-2-butyltriphenylborate, (Z)-{[bis(dimethylamino)methylethylene]amino}-N-cyclohexyl(cyclohexylamino)methaneimine-2-(3-fluorophenyl)borate, 1,2-diisopropyl-3-[bis(dimethylamino)methylene]guanidine-2-(3-benzoylphenyl)propionate, 9-anthraylmethyl N,N-diethylaminomethyl Salts, (E)-1-piperidinyl-3-(2-hydroxyphenyl)-2-propen-1-one, 2-nitrophenylmethyl4-methacryloyloxypiperidin-1-carboxylate, tetramethylguanidium tetra(3-fluorophenyl)borate, tetramethylguanidium tetra(4-fluorophenyl)borate, salts containing protonated DBU and tetra(3-fluorophenyl)borate anions, salts containing benzylated DBU and tetra(3-fluorophenyl)borate anions, etc., but not limited to these. They can be used alone or in combination of two or more.

[0093] (C2) Any one of the photo-alkali-producing agents can be used, or two or more can be used in combination.

[0094] When the resin composition contains a (C2) photoalkali-generating agent, the content of the (C2) photoalkali-generating agent in the resin composition is preferably 0.1 to 15 parts by mass relative to the total 100 parts by mass of the (A) polymerizable compound, more preferably 0.5 to 10 parts by mass.

[0095] (C3) Photoradical polymerization initiator

[0096] Photoradical polymerization initiators absorb light and generate free radicals, which act as active species, thereby promoting the polymerization of radical polymerizable compounds. Examples of photoradical polymerization initiators include alkyl phenyl ketone compounds, acylphosphine oxide compounds, and oxime compounds, but they are not limited to these.

[0097] Examples of alkyl phenyl ketone compounds include benzoyladium dimethyl ketals such as 2,2-dimethoxy-1,2-diphenylethane-1-one (commercially available as Omnirad 651 manufactured by IGM Resins BV); α-aminoalkyl phenyl ketones such as 2-methyl-2-morpholino(4-methylthiophenyl)-1-propanone (commercially available as Omnirad 907 manufactured by IGM Resins BV); α-hydroxyalkyl phenyl ketones such as 1-hydroxy-cyclohexyl-phenyl-one (commercially available as Omnirad 184 manufactured by IGM Resins BV); and 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholino-4-yl-phenyl)-1-butanone (commercially available as Omnirad 651 manufactured by IGM Resins BV). 379EG), 2-benzyl-2-(dimethylamino)-4'-morpholinophenylbutanone (commercially available as Omnirad 369 manufactured by IGM Resins BV), etc.

[0098] Examples of acylphosphine oxide compounds include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (commercially available as Omnirad TPO H manufactured by IGM Resins BV) and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (commercially available as Omnirad 819 manufactured by IGM Resins BV).

[0099] Examples of oxime compounds include 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone (marketed as Irgacure OXE01 by BASF Japan Co., Ltd.), 6-[1-(acetoxyimino)ethyl]-9-ethyl-9H-carbazole-3-yl(2-methylphenyl)one (marketed as Irgacure OXE02 by BASF Japan Co., Ltd.), [8-[[(acetoxy)imino][2-(2,2,3,3-tetrafluoropropoxy)phenyl]methyl]-11-(2-ethylhexyl)-11H-benzo[a]carbazole-5-yl]-(2,4,6-trimethylphenyl) methyl ketone (marketed as Irgacure OXE03 by BASF Japan Co., Ltd.), and Irgacure (marketed as Irgacure by BASF Japan Co., Ltd.). OXE04, etc.

[0100] In addition to the photoradical polymerization initiators mentioned above, other examples of photoradical polymerization initiators that can be used as (C3) photoradical polymerization initiators include 2-hydroxy-2-methyl-1-phenyl-1-propanone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl-1-propanone, 1-(4-dodecylphenyl)-2-hydroxy-2-methyl-1-propanone, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin n-butyl ether. Ethers, benzoin phenyl ether, benzoyl dimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyl diphenyl sulfide, 3,3'-dimethyl-4-methoxybenzophenone, thioxanone, 2-chlorothioxanone, 2-methylthioxanone, 2,4-dimethylthioxanone, isopropylthioxanone, 2,4-dichlorothioxanone, 2,4-diethylthioxanone, 2,4-diisopropylthioxanone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, methyl benzoylformate, benzoyl, camphorquinone, etc.

[0101] When the resin composition contains a (C3) photoradical polymerization initiator, from the viewpoint of photocurability, the content of the (C3) photoradical polymerization initiator is preferably 0.01 to 10 parts by mass relative to 100 parts by mass of the (A) polymerizable compound, more preferably 0.1 to 8 parts by mass.

[0102] (C4) Thermal free radical polymerization initiator

[0103] Thermal free radical polymerization initiators generate free radicals through heat, which act as active species, thereby promoting the polymerization of free radical polymerizable compounds. There are no particular limitations on the thermal free radical polymerization initiators that can be used; known materials can be employed. Specific examples of thermal free radical polymerization initiators include dialkyl peroxides such as dicumyl peroxide, tert-butyl peroxide, 1,3-bis(2-tert-butylperoxyisopropyl)benzene, or 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane; 1,1-bis(tert-butylperoxy)cyclohexane, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, and 1,1-bis(tert-pentylperoxy)cyclohexane. Ketal peroxides such as hexane, 2,2-bis(tert-butylperoxy)butane, n-butyl 4,4-bis(tert-butylperoxy)valerate, or ethyl 3,3-(tert-butylperoxy)butyrate; and alkyl peroxides such as tert-butyl peroxy-2-ethylhexanoate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, tert-butyl peroxyisobutyrate, tert-butyl peroxymaleate, or tert-butyl peroxybenzoate, but not limited to these. Any one of these peroxides, or two or more, can be used as a thermal free radical polymerization initiator.

[0104] When the resin composition contains a (C4) thermal free radical polymerization initiator, the content of the (C4) thermal free radical polymerization initiator relative to the total mass of the resin composition is preferably 0.01 to 5% by mass, more preferably 0.1 to 3% by mass.

[0105] (D) Modified polydimethylsiloxane

[0106] The resin composition of this embodiment contains (D) modified polydimethylsiloxane (hereinafter also referred to as "component (D)"). In this embodiment, (D) modified polydimethylsiloxane is a compound that satisfies at least one of the following characteristics (a) and (b).

[0107] (a) An organic substituent containing a COOH group or an OH group is directly bonded to polydimethylsiloxane, or is bonded to polydimethylsiloxane through a linking group.

[0108] (b) Detected in deuterated chloroform 1 In the 1H NMR spectrum, there is a signal in the range of 0.3 to -0.3 ppm and 4.4 to 3.2 ppm, and the signal disappears due to the addition of D2O in the range of 13 to 0 ppm.

[0109] More specifically, regarding modified polydimethylsiloxanes, a structure having an organic substituent introduced as a modifying group directly or interleaved with alkyl, alkylene, or other linking groups on the side chains and / or ends of a polydimethylsiloxane backbone composed of repeating dimethylsiloxane units represented by the following formula:

[0110] [Chemistry 5]

[0111]

[0112] Here, "introducing organic substituents into the side chains of the polydimethylsiloxane backbone" means that a portion of the methyl group in the polydimethylsiloxane backbone is replaced with an organic substituent. "Introducing organic substituents into the ends of the polydimethylsiloxane backbone" means that the ends of the polydimethylsiloxane backbone (e.g., methyl groups or -OSi(CH3)3) are replaced with organic substituents. The location of the modifying group in the modified polydimethylsiloxane can be any position on the side chain, at the end (single-terminal or double-terminal), or both. Furthermore, the modified polydimethylsiloxane also includes bimeric polydimethylsiloxanes. The degree of polymerization (the number of repeating units in dimethylsiloxane) of the modified polydimethylsiloxane is not particularly limited, but is, for example, 3 or more, preferably 5 or more.

[0113] In the modified polydimethylsiloxane of feature (a) above, the organic substituent contains a COOH group or an OH group.

[0114] Examples of modified polydimethylsiloxanes containing COOH groups as organic substituents include commercially available products called carboxyl-modified polydimethylsiloxanes or carboxyl-modified silicones. Examples of such commercially available products include those sold by Shin-Etsu Chemical Co., Ltd. under names such as X-22-3701E, X-22-162C, and X-22-3710, but these are not the only examples.

[0115] The presence or absence of the C=O stretching vibration at approximately 1715 cm⁻¹ originating from carboxylic acids can be observed by Fourier transform infrared spectroscopy (FT-IR) of modified polydimethylsiloxane. -1 The IR spectrum was used to confirm whether the organic substituents of the modified polydimethylsiloxane contained COOH groups.

[0116] Examples of modified polydimethylsiloxanes containing OH groups as organic substituents include commercially available products known as methanol-modified polydimethylsiloxanes or methanol-modified silicones. Examples of such commercially available products include those sold by Shin-Etsu Chemical Co., Ltd. under the names X-22-4039, X-22-4015, KF-6000, KF-6001, KF-6002, KF-6003, X-22-170BX, and X-22-170DX, but these are not the only examples.

[0117] Other examples of modified polydimethylsiloxanes containing OH groups as organic substituents include products called polyether-modified polydimethylsiloxanes or polyether-modified silicones, where the polyether group ends in an OH group. Examples of such commercially available products include those sold by Shin-Etsu Chemical Co., Ltd. under names such as X-22-4272 and KF-6123, but these are not limited to these. Furthermore, such polyether-modified polydimethylsiloxanes or polyether-modified silicones are sometimes named "PEG-(n)dimethylsiloxane" in cosmetic ingredient labeling. "PEG-(n)" refers to a PEG chain having n as the average corresponding number. "PEG-(n)dimethylsiloxane" is represented as "PEG-(n)DIMETHICONE" in the INCI nomenclature. Examples of such products include PEG-9 dimethylsiloxane (product name: KF-6013), PEG-3 dimethylsiloxane (product name sold by Shin-Etsu Chemical Industry Co., Ltd.: KF-6015), PEG-10 dimethylsiloxane (product name sold by Shin-Etsu Chemical Industry Co., Ltd.: KF-6017), and PEG-10 dimethylsiloxane (product name sold by Shin-Etsu Chemical Industry Co., Ltd.: KF-6043), but these are not the only ones that can be mentioned.

[0118] Examples of polyether groups used as organic substituents include polyethylene glycol groups and polypropylene glycol groups, with polyethylene glycol groups being preferred.

[0119] Furthermore, for reactive silicones whose hydroxyl values ​​are disclosed in product catalogs, etc., it can be inferred that they are modified polydimethylsiloxanes with OH groups included in the aforementioned organic substituents. The hydroxyl value of the modified polydimethylsiloxane can be determined 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 higher. The determination of the hydroxyl value can be performed, for example, by the method according to JIS K 0070 or by FT-NIR (near-infrared spectroscopy) according to JIS K 1557-6.

[0120] Alternatively, the presence of bending vibrations originating from the alcoholic OH group at approximately 1360–1340 cm⁻¹ can be determined by Fourier transform infrared spectroscopy (FT-IR) of modified polydimethylsiloxane. -1 The IR spectrum was used to confirm whether the organic substituents of the modified polydimethylsiloxane contained OH groups.

[0121] Some commercially available modified polydimethylsiloxanes do not disclose the detailed structure of their modifying groups. Additionally, some products, while sold as surfactants, surface conditioners, leveling agents, defoamers, wetting agents, dispersants, and other additives, do not explicitly declare themselves as modified polydimethylsiloxanes or their structure; however, they are still classified as modified polydimethylsiloxanes. In such cases, if the modified polydimethylsiloxane is measured in deuterated chloroform... 1 If a substance exhibits a signal in the 1H NMR spectrum in the ranges of 0.3 to -0.3 ppm and 4.4 to 3.2 ppm, and a signal that disappears due to the addition of D₂O in the range of 13 to 0 ppm, then the substance belongs to the modified polydimethylsiloxane of this embodiment (characteristic (b) above). The signal observed in the range of 0.3 to -0.3 ppm originates from hydrogen atoms attached to carbon atoms adjacent to Si atoms. The signal observed in the range of 4.4 to 3.2 ppm originates from hydrogen atoms attached to carbon atoms adjacent to oxygen atoms of OH groups or ethers. The signal observed in the range of 13 to 0 ppm and disappearing due to the addition of D₂O can be inferred to originate from hydrogen atoms of OH groups or NH groups.

[0122] The signal that disappears due to the addition of D₂O is usually observed in the range of 13–0 ppm. Among them, the signal that is observed in the range of 3–2 ppm and disappears due to the addition of D₂O can be inferred to be the signal from hydrogen atoms of the OH group.

[0123] To infer whether the signal that disappears due to the addition of D2O originates from the hydrogen atom of the OH or NH group, the following methods can be used, for example.

[0124] Fourier transform infrared spectroscopy (FT-IR) determination

[0125] In the above 1 In addition to H NMR determination, Fourier transform infrared spectroscopy (FT-IR) of modified polydimethylsiloxane can also be used to observe whether there is a bending vibration of approximately 1360–1340 cm⁻¹ originating from the alcoholic OH radical. -1 The IR spectrum was analyzed, leading to the conclusion that the signal that disappeared due to the addition of D2O originated from the hydrogen atoms of the OH group.

[0126] • Determination of acidity

[0127] In the above 1Besides ¹H NMR determination, the acidity of modified polydimethylsiloxane can be used to infer whether the signal disappearing due to the addition of D₂O originates from the hydrogen atoms of the OH or NH groups. For example, 100 mg of the modified polydimethylsiloxane sample is dissolved in 200 μL of isopropanol, 200 μL of pure water is added, and the mixture is shaken thoroughly. The pH of the liquid is then measured. If the pH is between 3 and 7, it can be inferred that the signal disappearing due to the addition of D₂O originates from the hydrogen atoms of the OH groups. If the pH is above 8 (alkaline), it can be inferred that the signal disappearing due to the addition of D₂O originates from the hydrogen atoms of the NH groups.

[0128] The modified polydimethylsiloxane satisfying the above characteristic (b) was determined in deuterated chloroform to have a certain content. 1 The H NMR spectrum shows a signal in the range of 1.25–0.95 ppm. The signal observed in this range originates from the hydrogen atoms of the methyl groups in the polypropylene glycol chain, which serves as the polyether modifying group. In one embodiment, the modified polydimethylsiloxane was determined in deuterated chloroform. 1 The H NMR spectrum showed a signal in the range of 1.25–0.95 ppm. In one embodiment, the modified polydimethylsiloxane was determined in deuterated chloroform. 1 The H NMR spectrum shows no signal in the range of 1.25–0.95 ppm.

[0129] Examples of modified polydimethylsiloxanes that satisfy feature (b) include products sold by Shin-Etsu Chemical Industry Co., Ltd.: KF-945, and products sold by Evonik Japan Co., Ltd.: TEGO TWIN 4000, TEGO TWIN 4100, etc.

[0130] In the resin composition of this embodiment, by including (D) a modified polydimethylsiloxane satisfying at least one of features (a) and (b), overflow can be suppressed not only during thermosetting after coating onto a substrate or the like, but also during storage at room temperature. While not limited to this, the reason for suppressing overflow by including (D) the modified polydimethylsiloxane in the resin composition can be considered as follows: When the resin composition containing the modified polydimethylsiloxane is applied to a substrate or the like, due to the surface transfer properties of the modified polydimethylsiloxane, a portion of the modified polydimethylsiloxane is transferred to the coating surface of the resin composition. Before other unreacted components permeate from the coating of the resin composition, a very small amount of the modified polydimethylsiloxane transferred to the coating surface is transferred to the substrate, which is not in contact with the resin composition, and the modified groups of the modified polydimethylsiloxane are adsorbed onto the substrate surface. Thus, an adsorption film of modified polydimethylsiloxane is formed on the substrate surface. This film exhibits water and oil resistance due to its polydimethylsiloxane moiety, and is therefore believed to inhibit leakage. Furthermore, it is thought that by including COOH or OH groups in the organic substituents used as modifying groups, the adsorption effect of modified polydimethylsiloxane onto the substrate can be further enhanced.

[0131] 1 H NMR measurements can be performed under standard conditions. For example, 100 mg of the sample is dissolved in 500 μl of deuterated chloroform, and a 5 mm diameter filter is added. 1 ¹H NMR was performed in a test tube under the following conditions. After the measurement, 50 μl of heavy water (D₂O) was added to the test tube containing the sample, and the measurement was performed again under the same conditions. It was found that the signal that disappeared after adding heavy water came from the active hydrogen bonded to hydroxyl or amino groups.

[0132] Measurement frequency: 40–600 MHz

[0133] Solvent: Deuterated chloroform

[0134] Determining the nuclear species: 1 H

[0135] Total number of times: 4 to 80

[0136] Measurement temperature: 15~50℃

[0137] (D) Any one of the polyether-modified polydimethylsiloxanes may be used, or two or more may be used in combination.

[0138] The content of (D) modified polydimethylsiloxane relative to the total mass of the resin composition 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. 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 (D) modified polydimethylsiloxane relative to the total mass of the resin composition 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.

[0139] (E) Packing

[0140] The resin composition of this embodiment may contain (E) filler (hereinafter also referred to as "component (E)") to a extent that does not impair the effects of the present invention. By containing (E) filler in the resin composition, the coefficient of linear expansion of the cured product obtained by curing the resin composition can be reduced, and the thermal cycling resistance can be improved. In addition, if the filler is of low elastic modulus, the stress generated in the cured product can be relieved, and the long-term reliability can be improved. (E) filler is generally divided into inorganic filler and organic filler.

[0141] Inorganic fillers are made of granular materials formed from inorganic materials. There are no particular limitations on any inorganic filler that reduces the coefficient of linear expansion through addition. Suitable inorganic materials 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 dioxide, zinc oxide, silicon carbide, silicon nitride, and boron nitride. Any one type of inorganic filler can be used, or two or more can be used in combination. Silica filler is preferred from the perspective of increasing the filler volume. Amorphous silica is preferred.

[0142] The surface of the inorganic filler can be treated with coupling agents such as silane coupling agents. This allows the viscosity of the resin composition to be set within an appropriate range.

[0143] Examples of organic fillers include polytetrafluoroethylene (PTFE) fillers, silicone fillers, acrylic fillers, and styrene fillers. Organic fillers can be surface-treated. The glass transition temperature of organic fillers is preferably higher than 40°C.

[0144] The shape of the filler is not particularly limited and can be any shape, such as spherical, scaly, needle-like, or amorphous.

[0145] 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 term "average particle size" refers to the median diameter (d50) of a volume reference determined by laser diffraction according to ISO-13320 (2009), or the arithmetic mean of 50 measurements arbitrarily selected from observation images obtained using 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 below, filler sedimentation can be suppressed, and the formation of coarse particles can be suppressed, thus suppressing clogging of the nozzle of the sizing machine. The lower limit of the average particle size of the filler is not particularly limited; however, from the viewpoint of the viscosity of the resin composition, it is preferably 0.005 μm or more, more preferably 0.1 μm or more. In one embodiment of this invention, the average particle size of the filler is preferably 0.01 μm to 5.0 μm, more preferably 0.1 μm to 3.0 μm. Fillers with different average particle sizes can also be used in combination. For example, fillers with an average particle size of 0.005 μm or more but less than 0.1 μm and fillers with an average particle size of 0.1 μm to 5.0 μm can be used in combination.

[0146] The content of filler (E) in the resin composition of this embodiment is preferably 0.5 to 80% by mass relative to the total mass of the resin composition, more preferably 1 to 70% by mass, and even more preferably 3 to 60%. By setting the content of filler (E) within the above range, the heat resistance cycling performance is improved, and the viscosity of the resin composition is also set within an appropriate range, thus improving its applicability in a sizing machine.

[0147] (F) Stabilizer

[0148] The resin composition of this embodiment may contain a (F) stabilizer (hereinafter also referred to as "component (F)") without impairing the effects of the present invention. The (F) stabilizer is an additive used to improve the stability of the resin composition during storage, added to inhibit the occurrence of polymerization reactions caused by unintended free radicals or alkaline components. Typically, free radical polymerization inhibitors and anionic polymerization inhibitors can be cited as examples of (F) stabilizers.

[0149] Known substances can be used as free radical polymerization inhibitors, such as at least one selected from N-nitroso-N-phenylhydroxylamine aluminum, triphenylphosphine, p-methoxyphenol, and hydroquinone. Alternatively, known free radical polymerization inhibitors disclosed in Japanese Patent Application Publication No. 2010-117545 and Japanese Patent Application Publication No. 2008-184514 may be used. Any one free radical polymerization inhibitor may be used, or two or more may be used in combination.

[0150] When a free radical polymerization inhibitor is included, the content of the free radical polymerization inhibitor, from the viewpoint of usable time, is preferably 0.0001 to 5% by mass relative to the total mass of the resin composition, more preferably 0.001 to 3% by mass.

[0151] Known substances can be used as anionic polymerization inhibitors, such as borate esters 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. Preferred anionic polymerization inhibitors are at least one selected from tri-n-propyl borate, triisopropyl borate, and barbituric acid. Furthermore, substances disclosed in Japanese Patent Application Publication Nos. 2010-117545, 2008-184514, and 2017-171804 can also be used as anionic polymerization inhibitors. Any one anionic polymerization inhibitor can be used, or two or more can be used in combination.

[0152] When an anionic polymerization inhibitor is included, the content of the anionic polymerization inhibitor relative to the total mass of the resin composition is preferably 0.001 to 5% by mass, more preferably 0.01 to 3% by mass.

[0153] The resin composition may, as needed, contain coupling agents, carbon black, titanium black, ion trapping agents, leveling agents, antioxidants, defoamers, thixotropic agents, viscosity modifiers, flame retardants, and / or other additives, without compromising the purpose of this embodiment. However, from the viewpoint of preventing a decrease in cured strength, the resin composition preferably does not contain solvents substantially, for example, the solvent content is preferably 1% by mass or less relative to the total mass of the resin composition. Furthermore, this reduces the amount of volatile organic compounds (VOCs). Examples of solvents include 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 halogen solvents (dichloromethane, chloroform, etc.), which are commonly used organic solvents in the field of curable compositions.

[0154] Resin compositions can be obtained, for example, by simultaneously or separately stirring, melting, mixing, and / or dispersing components (A) to (D), component (E) and (F) as needed, and other additives, while applying heat treatment as needed. There are no particular limitations on the apparatus used for these mixing, stirring, and dispersing operations. Suitable apparatuses include pounders equipped with stirring and heating devices, Henschel mixers, three-roll mills, ball mills, planetary mixers, and bead mills. Furthermore, these apparatuses can be used in appropriate combinations.

[0155] The resulting resin composition is photocurable, thermocurable, or photo- and thermocurable depending on the type of polymerization initiator (C) contained in the resin composition. Photocuring of the resin composition is performed, for example, by irradiating the resin composition with UV light. Thermocuring of the resin composition is performed, for example, at a temperature of 100°C. Regarding the thermocuring temperature of the resin composition, in the case of manufacturing semiconductor modules (e.g., optical sensor modules, camera modules) containing components in which the resin composition deteriorates under high-temperature conditions, 60–90°C is preferred. The thermocuring time, while depending on other curing conditions, can be, for example, 30–120 minutes. In the case of a photo- and thermocurable resin composition, for example, the resin composition can be pre-cured by light-based (UV) curing and then finally cured by heat-based curing.

[0156] The resin composition of this embodiment can be used, for example, as an adhesive, sealant, damming agent, or raw material for fixing, bonding, or protecting components, and is suitable for formulation into a liquid form. Here, the damming agent is pre-formed on the outer periphery of a substrate before sealing multiple semiconductor chips or the like with a low-viscosity filler. By forming a dam using this damming agent, the outflow of the low-viscosity filler used to seal the multiple semiconductor chips can be suppressed. Furthermore, the adhesive containing the resin composition of this embodiment can achieve good bonding with engineering plastics, ceramics, and metals.

[0157] [Adhesive or sealant]

[0158] The adhesive or sealant, as one embodiment of the present invention, comprises the resin composition of the above-described embodiments. This adhesive or sealant enables good bonding to engineering plastics, ceramics, and metals. The adhesive or sealant of this embodiment is preferably used for fixing, bonding, or protecting components constituting an optical sensor module or camera module.

[0159] [Cure of resin composition, adhesive, or sealant]

[0160] As another embodiment of the present invention, the cured product is a cured product obtained by curing the resin composition of the above-described embodiments or the adhesive or sealant of the above-described embodiments. In the area surrounding the adherend to which this cured product is bonded, seepage is suppressed.

[0161] [Semiconductor devices, electronic components]

[0162] One embodiment of the present invention provides a semiconductor device or electronic component comprising the cured product of the embodiments described above. Here, a semiconductor device refers to an entire device capable of functioning by utilizing the characteristics of semiconductors, including electronic components, semiconductor circuits, modules assembled thereon, electronic devices, etc. Examples of semiconductor devices or electronic components include HDDs, semiconductor elements, optical sensor modules, camera modules, semiconductor modules, integrated circuits, etc., but are not limited to these. Examples of optical sensors include photodiodes, photoelectric integrated circuits, photomultiplier tubes (PMTs), phototubes, image sensors, beam splitters / spectral sensors, infrared sensors, ultraviolet / flame sensors, X-ray sensors, radiation sensors, electron / ion sensors, distance / position sensors, etc., but are not limited to these.

[0163] Example

[0164] The present invention will be further described in detail below using embodiments and comparative examples; however, the present invention is not limited to these embodiments. It should be noted that in the following embodiments, unless otherwise specified, parts and percentages refer to parts by mass and percentage by mass.

[0165] [Preparation of the resin composition]

[0166] The resin compositions of the Examples and Comparative Examples were prepared by mixing the given 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 (in g). The components used in the Examples and Comparative Examples are shown below.

[0167] • (A) Polymerizable compounds having carbon-carbon double bonds (component (A))

[0168] (A-1): Polyester acrylate (Product name: M7100, manufactured by Toa Synthetic Co., Ltd., (meth)acryloyl equivalent: 188g / eq)

[0169] (A-2): Dihydroxymethyl-tricyclodecane diacrylate (Product name: LIGHT ACRYLATE DCP-A, manufactured by Kyoei Chemical Co., Ltd., (meth)acryloyl equivalent: 152g / eq)

[0170] (A-3): 2-(o-phenylphenoxy)ethyl acrylate (Product name: HRD-01, manufactured by TECHNO FINECHEMICAL Co., Ltd., (meth)acryloyl equivalent: 268g / eq)

[0171] (A-4): Ethoxylated bisphenol A diacrylate (Product name: ABE-300, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., (meth)acryloyl equivalent: 236 g / eq)

[0172] • (B) Polythiol compounds (component (B))

[0173] (B-1): Thiol glyurea derivative (product name: C3 TS-G, manufactured by Shikoku Chemical Industry, thiol equivalent: 114 g / eq)

[0174] (B-2): Thiol glycourea derivative (product name: TS-G, manufactured by Shikoku Chemical Industry, thiol equivalent: 100g / eq)

[0175] (B-3): Pentaerythritol tetra(3-mercaptopropionate) (Product name: PEMP, manufactured by SC Organic Chemicals Co., Ltd., thiol equivalent: 122 g / eq)

[0176] • (C) Polymerization initiator (component (C))

[0177] (C1-1): Amine-epoxy adduct system latent curing catalyst (product name: Novacure HXA9322HP, manufactured by Asahi Kasei Corporation)

[0178] (C1-2): Amine-urea type adduct latent curing catalyst (product name: Fujicure FXR-1121, solid at room temperature, manufactured by T&K TOKA Co., Ltd.)

[0179] (C3-1): 1-Hydroxy-cyclohexyl-phenyl-one (Product name: Omnirad 184, manufactured by IGM Resins BV)

[0180] • (D) Modified polydimethylsiloxane (Component (D))

[0181] • Modified polydimethylsiloxane other than component (D) (component (D))

[0182] As components (D) and (D'), the modified polydimethylsiloxanes listed in Table 1 below are used. Various modified polydimethylsiloxanes are reacted in deuterated chloroform. 1 The results of H NMR determination, Fourier transform infrared spectroscopy (FT-IR) determination, and acidity determination are shown in Table 1.

[0183]

[0184] In Table 1, “Ph” represents phenyl and “Me” represents methyl.

[0185] • (E) Filler (Composition (E))

[0186] (E-1): Calcium carbonate filler (Product name: CS3NA, manufactured by Ube Materials Co., Ltd.)

[0187] (E-2): Silica filler (Product name: CAB-O-SIL (registered trademark) TS-720, polydimethylsiloxane surface-treated pyrolysis silica, manufactured by Cabot Corporation)

[0188] [Modified polydimethylsiloxane] 1 [H NMR determination]

[0189] Dissolve 100 mg of the test sample of various modified polydimethylsiloxanes in 500 μL of deuterated chloroform, and add a 5 mm diameter... 1 ¹H NMR was performed in test tubes under the following conditions. After the measurement, 50 μL of heavy water (D₂O) was added to the test tube containing the sample, and the measurement was performed again under the same conditions. The signals from chloroform in the range of 0.3 to -0.3 ppm were integrated, and the integrated values ​​of each signal are shown in Table 1 with the obtained value set to 6.

[0190] Measuring apparatus: Oxford instrument Pulsar HF

[0191] Measurement frequency: 60 MHz

[0192] Solvent: Deuterated chloroform

[0193] Determining the nuclear species: 1 H

[0194] Measurement temperature: 37℃

[0195] Total number of times: 32

[0196] The assignment examples of each signal under the above measurement conditions are shown below.

[0197] 0.3~-0.3ppm: C H3 -Si, C H2 -Si (hydrogen atom attached to the carbon atom adjacent to the Si atom)

[0198] 4.4~3.2ppm: -C H2 -O-、-C=CC H2 -O- (a hydrogen atom attached to a carbon atom adjacent to the oxygen atom of an alcohol or ether)

[0199] 1.1 ppm (d, approx. 6 Hz): -CH2-CHC H3 -O- (hydrogen atom of the methyl group in propylene glycol)

[0200] Under the above measurement conditions, the signals that appear in the range of 9.0–0.5 ppm and disappear upon the addition of D₂O are: OH groups or NH groups.

[0201] [Determination of modified polydimethylsiloxane by Fourier transform infrared spectroscopy (FT-IR)]

[0202] Under the following conditions, Fourier transform infrared spectroscopy (FT-IR) was performed on various modified polydimethylsiloxanes to confirm the C=O stretching vibration of carboxylic acid (approximately 1715 cm⁻¹). -1 The presence or absence of OH and the bending vibration of alcoholic OH (approximately 1360–1340 cm). -1 The presence or absence of ) is shown in Table 1.

[0203] Measurement apparatus: Perkin-Elmer FT-IR Spectrometer Spectrum 3

[0204] Measurement method: ATR method

[0205] [Determination of the acidity of modified polydimethylsiloxane]

[0206] 100 mg of various modified polydimethylsiloxane samples were dissolved in 200 μL of isopropanol (IPA), 200 μL of pure water was added, and the mixture was shaken thoroughly. pH test paper was then immersed in the resulting liquid to determine the pH. Macherey Nagel #90204 general-purpose pH test paper was used. The results are shown in Table 1.

[0207] In the examples and comparative examples, the properties of the resin compositions were determined as follows.

[0208] [Leakage Assessment]

[0209] The resin compositions of the examples and comparative examples, each containing 1.5 mg, were applied to a ceramic substrate treated with argon (Ar) plasma using a dispensing machine. The overflow length (N = 3 pcs × 2 sides) under two conditions was measured using a CCD camera. The results are shown in Tables 2-1 to 2-5. Condition 1: Overflow length on the ceramic substrate after application, placed at room temperature (20°C to 25°C) for 60 minutes. Condition 2: Overflow length on the ceramic substrate after application, placed at room temperature (20°C to 25°C) for 60 minutes, and then thermosetting the resin composition at 80°C for 60 minutes.

[0210]

[0211]

[0212]

[0213]

[0214]

[0215] As can be seen, the resin compositions of Examples 1-20 containing at least one of features (a) and (b) of modified polydimethylsiloxane (D) significantly suppressed the overflow phenomenon under conditions 1 and 2 compared with the resin compositions of Comparative Examples 1, 6-11 that do not contain modified polydimethylsiloxane (D) and the resin compositions of Comparative Examples 2-5 that contain component (D') and modified polydimethylsiloxane other than (D).

[0216] Industrial availability

[0217] The present invention relates to a resin composition, at least photocurable or thermocurable, capable of suppressing leakage, and is particularly useful as an adhesive or sealant used for fixing, bonding or protecting components of miniaturized or highly integrated semiconductor modules.

[0218] The entire contents of the disclosure of Japanese Patent Application No. 2023-211994 (filed on December 15, 2023) are incorporated herein by reference.

[0219] All documents, patent applications and technical standards described in this specification are incorporated herein by reference to the same extent as the specific and individually described documents, patent applications and technical standards are incorporated herein by reference.

Claims

1. A resin composition comprising: (A) Polymerizable compounds with carbon-carbon double bonds (B) Polythiol compounds, (C) Polymerization initiator, and (D) Modified polydimethylsiloxanes that satisfy at least one of the following characteristics (a) and (b): (a) Organic substituents containing COOH or OH groups are directly bonded to polydimethylsiloxane, or are bonded to polydimethylsiloxane through linking groups; (b) Detected in deuterated chloroform 1 In the H NMR spectrum, there is a signal in the range of 0.3ppm to -0.3ppm and 4.4ppm to 3.2ppm, and a signal that disappears due to the addition of D2O in the range of 13ppm to 0ppm.

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

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

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

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

6. The adhesive or sealing material according to claim 5, used for fixing, bonding or protecting an optical sensor module or components thereof.

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

8. A semiconductor device or electronic component comprising the cured material of claim 7.

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

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