Resin compositions, adhesives, encapsulants, cured products, semiconductor devices and electronic components

Abstract

The objective is to provide a resin composition and adhesive that are at least thermosetting and capable of suppressing the bleed phenomenon. (A) Polymerizable compound having a carbon-carbon double bond, (B) Polythiol compounds, (C) Polymer initiator, and (D) Modified polydimethylsiloxane satisfying at least one of the following features (a) and (b): (a) An organic substituent containing a COOH group or an OH group is bonded to polydimethylsiloxane directly or through a linker; (b) In the 1H NMR spectrum measured in dichloroform, there are signals in the range of 0.3 to -0.3 ppm and 4.4 to 3.2 ppm, and also signals that disappear upon addition of D2O in the range of 13 to 0 ppm. A resin composition comprising is provided.

Description

Technology Field

[0001] The present invention relates to a resin composition, an adhesive or encapsulant comprising the same, a cured product thereof, a semiconductor device and an electronic component comprising the cured product thereof. Background Technology

[0002] Currently, adhesives and encapsulating materials containing curable resin compositions are frequently used for the assembly or mounting of components used in semiconductor devices, such as semiconductor chips, for the purpose of maintaining reliability. As such resin compositions, curable compositions are known that are based on epoxy compounds or (meth)acrylate compounds and use thiol-based compounds as curing agents (e.g., Patent Documents 1 and 2).

[0003] Patent Document 3 discloses a photo- and thermosetting resin composition that combines excellent photocuring and excellent thermosetting properties, and when light irradiation is performed under conditions such as generating a tailings irradiated portion, the entire composition including the tailings irradiated portion can be completely cured to produce a cured product with high adhesive strength and also has good storage stability, comprising (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. Prior art literature

[0004] Japanese Patent Publication No. 2009-51954, International Publication No. 2005 / 052021, Japanese Patent Publication No. 2017-101112

[0005] Bleeding is a challenge in the assembly process of semiconductor modules. Bleeding is a phenomenon in which unreacted components seep out from the adhesive coating or cured material over time when an adhesive containing a curable resin composition is used for fixing or bonding components; the seeped-out components themselves are sometimes referred to as "bleed." There is a challenge in that contact between the bleed and the metal wiring on the substrate can cause electrical defects and reduce the reliability of the semiconductor module. In particular, inner bleed originating from uncured portions of the adhesive tends to progress and lengthen when the adhesive coating is left at room temperature and / or undergoes thermal curing.

[0006] Recently, electronic components such as semiconductor chips are increasingly required to be miniaturized or highly integrated, and the distance to the wiring portion placed around the electronic components is becoming shorter. In semiconductor modules equipped with such miniaturized or highly integrated electronic components, there is a challenge that the risk of contact between the bleed and the wiring portion increases due to the bleed phenomenon.

[0007] Therefore, the present invention aims to provide at least a photocurable or thermosetting resin composition and an adhesive capable of suppressing the bleed phenomenon.

[0008] Specific means for solving the above problem are as follows. Embodiments of the present invention include a resin composition, an adhesive or encapsulant, a cured product, and a semiconductor device or electronic component of the following aspects.

[0009] [1](A) Polymerizable compound having a carbon-carbon double bond,

[0010] (B) Polythiol compounds,

[0011] (C) Polymer initiator, and

[0012] (D) Modified polydimethylsiloxane satisfying at least one of the following features (a) and (b):

[0013] (a) An organic substituent containing a COOH group or an OH group is bonded to polydimethylsiloxane directly or through a linker;

[0014] (b) Measured in dichloroform 1 In the H NMR spectrum, there is a signal in the range of 0.3 to -0.3 ppm and 4.4 to 3.2 ppm, and also a signal that disappears upon D2O addition in the range of 13 to 0 ppm.

[0015] A resin composition comprising

[0016] [2] The resin composition of [1], wherein the polymerizable compound having (A) a carbon-carbon double bond is a (meth)acrylate compound.

[0017] [3] A resin composition of [1] or [2] in which the content of the modified polydimethylsiloxane (D) is 0.01 to 5 mass% with respect to the total mass of the resin composition.

[0018] [4](E) A resin composition of any one of [1] to [3] further comprising a filler.

[0019] [5] An adhesive or encapsulating material comprising any one of the resin compositions [1] to [4] above.

[0020] [6] The adhesive or encapsulating material of [5] used for fixing, bonding, or protecting an optical sensor module or a component constituting the same.

[0021] [7] A cured product in which any one of the resin compositions [1] to [4] above, or the adhesive or encapsulant of [5] or [6] above is cured.

[0022] [8] A semiconductor device or electronic component comprising the cured product of [7] above.

[0023] [9] The semiconductor device or electronic component of [8], which is an optical sensor module.

[0024] According to an embodiment of the present invention, at least a photocurable or thermocurable resin composition capable of suppressing bleed phenomena, an adhesive or encapsulant comprising the same, a cured product obtained by curing the same, and a semiconductor device or electronic component comprising the cured product are provided. Specific details for implementing the invention

[0025] [Resin Composition]

[0026] A resin composition that is an embodiment of the present invention is,

[0027] (A) Polymerizable compound having a carbon-carbon double bond,

[0028] (B) Polythiol compounds,

[0029] (C) Polymer initiator, and

[0030] (D) Modified polydimethylsiloxane satisfying at least one of the following features (a) and (b):

[0031] (a) An organic substituent containing a COOH group or an OH group is bonded to polydimethylsiloxane directly or through a linker;

[0032] (b) Measured in dichloroform 1 In H NMR, it has a signal in the range of 0.3 to -0.3 ppm and 4.4 to 3.2 ppm, and also has a signal that disappears upon D2O addition in the range of 13 to 0 ppm.

[0033] It includes. According to the present embodiment, at least a photocurable or thermosetting resin composition capable of suppressing the bleed phenomenon can be provided.

[0034] (A) Polymerizable compounds having carbon-carbon double bonds

[0035] The resin composition of the present embodiment comprises (A) a polymerizable compound having a carbon-carbon double bond (hereinafter also referred to as "(A) polymerizable compound" or "component (A)"). The polymerizable compound having a carbon-carbon double bond (A) undergoes polymerization through a radical polymerization reaction between the polymerizable compounds (A) or between the polymerizable compound (A) and the polythiol compound (B) described later, or through a crosslinking reaction between the polymerizable compound (A) and the polythiol compound (B) in an anionic polymerization system, thereby imparting curability and adhesion to the resin composition. Examples of the polymerizable compound having a carbon-carbon double bond (A) include (meth)acrylate compounds, maleimide compounds, styrene compounds, polybutadiene compounds, vinyl ether compounds, allyl ether compounds, etc., but are not limited thereto.

[0036] In this specification, a (meth)acrylate compound is a compound having at least one (meth)acryloyl group in its molecule, and examples 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 the present 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 a methacryloyl group and an acryloyl group. Additionally, "(meth)acrylate compound" includes both an acrylate compound and a methacrylate compound.

[0037] 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 its oligomer; pentaerythritol triacrylate and / or trimethacrylate, or its oligomer; polyacrylate and / or polymethacrylate of dipentaerythritol; tris(acryloxyethyl)isocyanurate; caprolactone-modified tris(acryloxyethyl)isocyanurate; caprolactone-modified tris(methacryloxyethyl)isocyanurate; alkyl-modified polyacrylate and / or polymethacrylate of dipentaerythritol; caprolactone-modified Polyacrylates and / or polymethacrylates of dipentaerythritol; ethoxylated bisphenol A diacrylate and / or ethoxylated bisphenol A dimethacrylate; dihydrocyclopentadienyl acrylate and / or dihydrocyclopentadienyl methacrylate, and polyester acrylates and / or polyester methacrylates, poly(meth)acrylates of dimethylol tricyclodecane diacrylate, ditrimethylolpropane, ethoxylated bisphenol A diacrylate, polyurethanes having two or more (meth)acryloyl groups in one molecule, polyfunctional (meth)acrylates such as polyesters having two or more (meth)acryloyl groups in one molecule; phenoxyethyl acrylate, 2-(o-phenylphenoxy)ethyl acrylate, isobornyl acrylate, Examples of monofunctional (meth)acrylates include phenoxydiethylene glycol (meth)acrylate, 4-tert-butylcyclohexyl acrylate, and epoxy resin half-acrylate, but are not limited to these.

[0038] From a reactivity perspective, it is preferable that the (meth)acrylate compound substantially does not contain methacrylate compounds and is an acrylate compound.

[0039] Any one type of (meth)acrylate compound may be used, or two or more types may be used in combination.

[0040] Maleimide compounds include monofunctional maleimide compounds having one maleimide group and polyfunctional maleimide compounds having two or more maleimide groups, and in particular, maleimide compounds having two maleimide groups are sometimes called 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'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6'-bismaleimido-(2,2,4-trimethyl)hexane, bis-(3-ethyl-5-methyl-4-maleimidophenyl)methane, m-phenylenebismaleimide(N,N'-1,3-phenylenebismaleimide), 1,6-bismaleimidohexane, 1,2-bismaleimidoethane(N,N'-ethylenedimaleimide), N,N'-(1, Examples include 2-phenylene)bismaleimide, N,N'-1,4-phenylenedimaleimide, N,N'-(sulfonyldi-p-phenylene)dimaleimide, and N,N'-[3,3'-(1,3-phenylenedioxy)diphenyl]bismaleimide, but are not limited to these. These may be used individually or in combination of two or more types.

[0041] When a low room temperature elastic modulus is required for a cured product of a resin composition, it is preferable that the bismaleimide compound be a bismaleimide compound having a hydrocarbon group derived from a dimer acid. Such a bismaleimide compound is described, for example, in Japanese Patent Publication No. 2015-193725. Commercially available bismaleimide compounds having a hydrocarbon group derived from a dimer acid include, for example, "BMI-689," "BMI-1500," and "BMI-1700," which are liquid at 25°C, or "BMI-3000," which is solid at 25°C (all from Designer Molecules Inc.), but are not limited thereto. These may be used individually or in combination of two or more types.

[0042] Styrene compounds are compounds that have 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, Examples include 6-bis(m-vinylphenyl)hexane, 1-(p-vinylphenyl)-6-(m-vinylphenyl)hexane, and divinylbenzene polymers (oligomers) having vinyl groups in their side chains, but are not limited to these. These may be used individually or in combination of two or more types.

[0043] Examples of polybutadiene compounds include polybutadiene having vinyl groups in its side chains and polybutadiene having 90% or more by weight of 1,2-links in its structure, but are not limited thereto. These may be used individually or in combination of two or more types.

[0044] Vinyl ether compounds are compounds having at least one vinyl ether group (H2C=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 may be used individually or in combination of two or more types.

[0045] Examples of allyl ether compounds include, but are not limited to, allylglycidyl ether, trimethylolpropanediallyl ether, pentaerythritoltriallyl ether, and glycerin monoallyl ether. These may be used individually or in combination of two or more.

[0046] It is preferable that component (A) has a viscosity of 0.01 to 100 Pa·s from the perspective of preparation and administration of the resin composition. In addition, in this specification, viscosity refers to a value measured at a measurement temperature of 25°C using a viscometer suitable for the viscosity range.

[0047] Examples of commercially available products of ingredient (A) include, for instance, Daicel Allnex Co., Ltd. Polyester Acrylate (Product Name: EBECRYL810), Daicel Allnex Co., Ltd. Ditrimethylolpropane Tetraacrylate (Product Name: EBECRYL140), Toa Synthetic Co., Ltd. Polyester Acrylate (Product Name: M7100), Kyoeisha Chemical Co., Ltd. Dimethylol Tricyclodecane Diaacrylate (Product Name: Light Acrylate DCP-A), Nippon Hwayaku Co., Ltd. Neopentyl Glycol Modified Trimethylolpropane Diaacrylate (Product Name: Kayarad R-604), Nisshoku Techno Fine Chemical Co., Ltd. 2-(o-phenylphenoxy)ethyl Acrylate (Product Name: HRD-01), Shinnakamura Chemical Co., Ltd. Ethoxylated Bisphenol A Diaacrylate (Product Name: ABE-300), etc. There are, but are not limited to, these. Ingredient (A) may be any one of these, or two or more may be used in combination.

[0048] The content of component (A) is preferably 10 to 70 mass% with respect to the total mass of the resin composition, and more preferably 20 to 60 mass%, in terms of the adhesive strength of the resin composition.

[0049] (B) Polythiol compounds

[0050] The resin composition of the present embodiment comprises (B) a polythiol compound (hereinafter also referred to as "component (B)"). The polythiol compound (B) imparts high curability to the resin composition. Component (B) is not particularly limited as long as it has two or more functionalities, that is, two or more thiol groups. It is preferable that component (B) comprises a thiol compound having three or more functionalities, and it is more preferable that it comprises a thiol compound having three and / or four functionalities. Furthermore, trifunctional and tetrafunctional thiol compounds are thiol compounds having three and four thiol groups, respectively.

[0051] Polythiol compounds include, for example, 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 Examples include trimethylolethanetris (3-mercaptobutyrate), but are not limited to these.

[0052] Commercial products of the above component (B) include trimethylolpropane tris(3-mercaptopropionate) (SC Organic Chemical Co., Ltd.: TMMP), tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate (SC Organic Chemical Co., Ltd.: TEMPIC), pentaerythritol tetrakis(3-mercaptopropionate) (SC Organic Chemical Co., Ltd.: PEMP), tetraethylene glycol bis(3-mercaptopropionate) (SC Organic Chemical Co., Ltd.: EGMP-4), dipentaerythritol hexakis(3-mercaptopropionate) (SC Organic Chemical Co., Ltd.: DPMP), pentaerythritol tetrakis(3-mercaptobutyrate) (Showa Denko Co., Ltd.: Karens MT (registered trademark) PE1), 1, 3, 5-tris(3-mercaptobutyryloxyethyl)-1, 3, Examples include 5-triazine-2, 4, 6(1H, 3H, 5H)-trione (Showa Denko Co., Ltd.: Carens MT (registered trademark) NR1), trimethylolpropane tris(3-mercaptobutyrate) (Showa Denko Co., Ltd.: Carens MT (registered trademark) TPMB), but are not limited to these.

[0053] In addition, (B) polythiol compounds may include glycoluryl compounds represented by the following general formula (1).

[0054]

[0055] R in general formula (1) 1 , and R 2 Each is independently hydrogen or an alkyl group having 1 to 10 carbon atoms, or a phenyl group. n is an integer from 0 to 10.

[0056] Additionally, component (B) may be a compound represented by the following chemical formula (2) or chemical formula (3).

[0057]

[0058]

[0059] In addition, (B) polythiol compounds include polythiol compounds represented by the general formula (4).

[0060]

[0061] R in general formula (4) 3 , R 4 , R 5 and R 6 Each independently, hydrogen or C n H 2n SH(n is 2 to 6). Also, R 3 , R 4 , R 5 and R 6 At least one of C n H 2n SH (n is 2 to 6). For the polythiol compound of component (B) represented by general formula (4), n is preferably 2 to 4 in terms of curability. Furthermore, for the balance of cured material properties and curing speed, it is more preferable that this polythiol compound be a mercaptopropyl group with n of 3. Since component (B) represented by general formula (4) itself has a sufficiently flexible framework, it is effective when one wants to lower the elastic modulus of the cured material. By adding component (B) represented by general formula (4), the elastic modulus of the cured material can be controlled, thereby increasing the adhesive strength (especially peel strength) after curing.

[0062] Commercial products of the above component (B) include Shikoku Kasei Kogyo thiol glycoluryl derivative (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 SC Organic Chemical thiol compound (product name: PEPT (equivalent to general formula (4), thiol equivalent: 124 g / eq)), but are not limited to these.

[0063] Other examples of the above component (B) include 1,3,4,6-tetrakis(mercaptomethyl)glycoluryl, 1,3,4,6-tetrakis(mercaptomethyl)-3a-methylglycoluryl, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a-methylglycoluryl, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a-methylglycoluryl, 1,3,4,6-tetrakis(mercaptomethyl)-3a,6a-dimethylglycoluryl, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a,6a-dimethylglycoluryl, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a,6a-dimethylglycoluryl, 1,3,3, 4,6-tetrakis(mercaptomethyl)-3a,6a-diphenylglycoluryl, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a,6a-diphenylglycoluryl, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a,6a-diphenylglycoluryl, 3-[2,3-bis(3-sulfanylpropoxy)propoxy]propane-1-thiol, 3-[2,2-bis[(3-mercaptopropoxy)methyl]butoxy]-1-propanethiol, pentaerythritoltetrapropanethiol, 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-dithioctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithioundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithioundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithioundecane, 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-thiopentan, 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-tricyanonan, 3-mercaptomethylthio-1,6-dimercapto-2,5-dithiahexane, 1,1,9,9-tetrakis(mercaptomethylthio)-5-(3,3-bis(mercaptomethylthio)-1-thipropyl)3,7-dicyanonan, tris(2,2-bis(mercaptomethylthio)ethyl)methane, tris(4,4-bis(mercaptomethylthio)-2-thiabyl)methane, tetrakis(2,2-bis(mercaptomethylthio)ethyl)methane, tetrakis(4,4-bis(mercaptomethylthio)-2-thiabyl)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-hexacyanonadecane, 9-(2,2-bis(mercaptomethylthio)ethyl)-3,5,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,6,8,10,12,16-hexathiaheptadecane, 3,4,8,9-tetrakis(mercaptomethylthio)-1,11-dimercapto-2,5,7, 10-tetrathioundecane, 3, 4, 8, 9, 13, 14-hexakis(mercaptomethylthio)-1, 16-dimercapto-2, 5, 7, 10, 12, 15-hexathiahexadecane, 8-[bis(mercaptomethylthio)methyl]-3, 4, 12, 13-tetrakis(mercaptomethylthio)-1, 15-dimercapto-2, 5, 7, 9, 11, 14-hexathiapentadecane, 4, 6-bis[3, 5-bis(mercaptomethylthio)-7-mercapto-2, 6-dithiaheptylthio]-1, 3-dithian, 4-[3, 5-bis(mercaptomethylthio)-7-mercapto-2, 6-dithiaheptylthio]-6-mercaptomethylthio-1,3-dithian, 1,1-bis[4-(6-mercaptomethylthio)-1,3-dithianilthio]-1,3-bis(mercaptomethylthio)propane, 1-[4-(6-mercaptomethylthio)-1,3-dithianilthio]-3-[2,2-bis(mercaptomethylthio)ethyl]-7,9-bis(mercaptomethylthio)-2,4,6,10-tetrathioundecane, 3-[2-(1,3-dithienyl)]methyl-7,9-bis(mercaptomethylthio)-1,11-dimercapto-2,4,6,10-tetrathioundecane, 9-[2-(1,3-dithiethanolil)]methyl-3,5,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,6,8,10,12,16-hexathyaheptadecane, 3-[2-(1,3-dithiethanolil)]methyl-7,9,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,4,6,10,12,16-hexathyaheptadecane, 4,6-bis[4-(6-mercaptomethylthio)-1, 3-Dithianylthio]-6-[4-(6-Mercaptomethylthio)-1,3-Dithianylthio]-1,3-Dithian, 4-[3,4,8,9-Tetrakis(Mercaptomethylthio)-11-Mercapto-2,5,7,10-Tetrathioundecyl]-5-Mercaptomethylthio-1,3-Dithiolan, 4,5-Bis[3,4-Bis(Mercaptomethylthio)-6-Mercapto-2,5-Dithiahexylthio]-1,3-Dithiolan, 4-[3,4-Bis(Mercaptomethylthio)-6-Mercapto-2,5-Dithiahexylthio]-5-Mercaptomethylthio-1,3-Dithiolan, 4-[3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithioctyl]-5-mercaptomethylthio-1,3-dithiolane, 2-{bis[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]methyl}-1,3-dithiethane, 2-[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]mercaptomethylthiomethyl-1,3-dithiethane, 2-[3,4,8,9-tetrakis(mercaptomethylthio)-11-mercapto-2,5,7,10-tetrathioundecylthio]mercaptomethylthiomethyl-1, Examples include 3-dithiethane, 2-[3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithioctyl]mercaptomethylthiomethyl-1,3-dithiethane, 4-{1-[2-(1,3-dithiethanel)]-3-mercapto-2-thipropylthio}-5-[1,2-bis(mercaptomethylthio)-4-mercapto-3-thiabylthio]-1,3-dithiolane, etc.

[0064] As for ingredient (B), any one type may be used, or two or more types may be used in combination.

[0065] In the present embodiment, the content of component (B) in the resin composition is preferably 1 to 70 mass% with respect to the total mass of the resin composition, more preferably 10 to 60 mass%, and even more preferably 20 to 50 mass%.

[0066] Among polythiol compounds, there are polythiol compounds that have a hydrolyzable partial structure, such as an ester bond, in the molecule (i.e., hydrolyzable). From the perspective of 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 with respect to the total mass of component (B), for example, 0 to 90 mass%, for example, 0 to 80 mass%, for example, 0 to 70 mass%, for example, 0 to 60 mass%, for example, 0 to 50 mass%.

[0067] (C) Polymerization initiator

[0068] The resin composition of the present embodiment comprises (C) a polymerization initiator (hereinafter also referred to as "Component (C)"). In this specification, the polymerization initiator (C) comprises (C1) a basic catalyst, (C2) a photobase generator, (C3) a photoradical polymerization initiator, and (C4) a thermal radical polymerization initiator. The polymerization initiator (C) can be appropriately selected depending on the application location or use of the resin composition, or, for example, whether the resin composition is photocurable, thermosetting, or both photo-thermal-setting. For example, any one of (C1) a basic catalyst, (C2) a photobase generator, (C3) a photoradical polymerization initiator, and (C4) a thermal radical polymerization initiator may be used alone, or they may be used in any combination.

[0069] (C1) Basic catalyst

[0070] (C1) Known basic catalysts may be used, but it is preferable that the catalyst be a thermal latent catalyst. A thermal latent catalyst is a compound or material that is inert at room temperature and becomes activated by heating to function as a polymerization catalyst. Examples include amine compounds that are solid at room temperature; amine adduct-type thermal latent polymerization catalysts such as reaction products of amine compounds and epoxy compounds (amine-epoxy adduct system), reaction products of amine compounds and isocyanate compounds or urea compounds (urea-type adduct system); solid-dispersed thermal latent polymerization catalysts such as microcapsule-type thermal latent polymerization catalysts; and inclusion-type thermal latent polymerization catalysts. Amine compounds include aliphatic amines, aromatic amines, and heterocyclic amines.

[0071] Amine compounds that are solid at room temperature include, for example, 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 isocyanuric acid adduct, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, Examples include 1-cyanoethyl-2-methylimidazole-trimellitate, 1-cyanoethyl-2-phenylimidazole-trimellitate, N-(2-methylimidazolyl-1-ethyl)-urea, N, N´-(2-methylimidazolyl-(1)-ethyl)-adipoyldiamide, but are not limited to these.

[0072] An amine compound used as one of the raw materials for manufacturing an amine adduct-based latent curing catalyst may have one or more active hydrogens in its molecule capable of addition reaction with epoxy groups or isocyanate groups, and may also have at least one functional group selected from primary amino groups, secondary amino groups, and tertiary amino groups in its 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´-diaminodicyclohexylmethane; aromatic amine compounds such as 4,4´-diaminodiphenylmethane and 2-methylaniline; and heterocyclic amine compounds containing nitrogen atoms such as 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline, piperidine, and piperazine; but are not limited to these.

[0073] In addition, among these, compounds having a tertiary amino group in their molecule or imidazole derivatives are raw materials that provide potential curing catalysts with excellent curing-promoting ability. Examples of such compounds include amine compounds such as dimethylaminopropylamine, diethylaminopropylamine, di-n-propylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, N-methylpiperazine, etc., or 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, 1-(2-aminoethyl)-2-methylimidazole, etc.; 2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol, 1-(2-hydroxy-3-phenoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-ethyl-4-methylimidazole, 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazole, 1-(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, Examples include alcohols, phenols, thiols, carboxylic acids, and hydrazides having a tertiary amino group or an imidazole backbone within the molecule, such as 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 4-mercaptopyridine, N,N-dimethylaminobenzoic acid, N,N-dimethylglycine, nicotinic acid, isonicotinic acid, picolinic acid, N,N-dimethylglycine hydrazide, N,N-dimethylpropionic acid hydrazide, nicotinic acid hydrazide, isonicotinic acid hydrazide, etc., but are not limited to these.

[0074] Epoxy compounds used as one of the raw materials for manufacturing amine-epoxy adduct-based latent curing catalysts include, for example, polyglycidyl ethers obtained by reacting polyhydric phenols such as bisphenol A, bisphenol F, catechol, and resorcinol, or polyhydric alcohols such as glycerin or polyethylene glycol with epichlorohydrin; glycidyl ether esters obtained by reacting hydroxycarboxylic acids such as p-hydroxyanoic acid and β-hydroxynaphthoic acid with epichlorohydrin; polyglycidyl esters obtained by reacting polycarboxylic acids such as phthalic acid and terephthalic acid with epichlorohydrin; glycidylamine compounds obtained by reacting 4,4'-diaminodiphenylmethane or m-aminophenol with epichlorohydrin; and also multifunctional epoxy compounds such as epoxidized phenol novolak resins, epoxidized cresol novolak resins, and epoxidized polyolefins. Examples include butylglycidyl ether, phenylglycidyl ether, various phenylphenolglycidyl ethers, monofunctional epoxy compounds such as glycidyl methacrylate, but are not limited to these.

[0075] As isocyanate compounds used as one of the raw materials for manufacturing amine-urea type adduct-type latent curing catalysts, examples 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, xylene diisocyanate, paraphenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, and bicycloheptane triisocyanate; and also, terminal isocyanate group-containing compounds obtained by the reaction of these polyfunctional isocyanate compounds with active hydrogen compounds may be used. Examples of such terminal isocyanate group-containing compounds include, but are not limited to, an addition compound having a terminal isocyanate group obtained by the reaction of toluylene diisocyanate with trimethylolpropane, and an addition compound having a terminal isocyanate group obtained by the reaction of toluylene diisocyanate with pentaerythritol.

[0076] Examples of urea compounds used as raw materials for the manufacture of amine-urea type adduct system latent curing catalysts include urea and thiourea, but are not limited to these.

[0077] The amine adduct-based latent curing catalyst is, for example, a combination of (a) two components of an amine compound and an epoxy compound, (b) three components of these two components and an active hydrogen compound, or (c) two or three components of an amine compound and an isocyanate compound and / or urea compound. These can be easily produced by extracting and mixing each component, reacting them at a temperature from room temperature to 200°C, cooling and solidifying them, and then grinding them, or by reacting them in a solvent such as methyl ethyl ketone, dioxane, or tetrahydrofuran, desolvating them, and then grinding the solids.

[0078] A microcapsule-type latent curing catalyst is a curing catalyst having a structure in which a core is an amine compound, or an amine adduct compound obtained by the reaction of an amine compound with an epoxy compound, an isocyanate compound, or a urea compound, and is coated by a shell made of a synthetic resin or an inorganic oxide. Examples of amine compounds include the above-mentioned amine compounds. Since they exhibit suitable latent properties, imidazole derivatives are preferred for the amine compounds. 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 serving as the shell include phenol resin, melamine resin, epoxy resin, urethane resin, and urea resin, and these resins may also be used in combination. Inorganic oxides that serve as shells include silica, alumina, titania, and magnesia.

[0079] Representative examples of commercially available thermal potential curing catalysts include, but are not limited to, the following. As amine-epoxy adduct-based curing catalysts, "Amicure PN-23" (Ajinomoto Fine Techno Co., Ltd. product name), "Amicure PN-40" (Ajinomoto Fine Techno Co., Ltd. product name), "Amicure PN-50" (Ajinomoto Fine Techno Co., Ltd. product name), "Hardener X-3661S" (ACR Co., Ltd. product name), "Hardener X-3670S" (ACR Co., Ltd. product name), "Novacure HX-3742" (Asahi Kasei Co., Ltd. product name), "Novacure HX-3721" (Asahi Kasei Co., Ltd. product name), "Novacure HXA9322HP" (Asahi Kasei Co., Ltd. product name), "Novacure HXA3922HP" (Asahi Kasei Co., Ltd. product name), Examples include "Novacure HXA3932HP" (Asahi Kasei Co., Ltd. product name), "Novacure HXA5945HP" (Asahi Kasei Co., Ltd. product name), "Novacure HXA5911HP" (Asahi Kasei Co., Ltd. product name), and "Novacure HXA9382HP" (Asahi Kasei Co., Ltd. product name), but are not limited to these. The above "Novacure" series is also a microcapsule-type latent curing catalyst. In addition, examples of amine-urea type adduct-based curing catalysts include "Fujicure-FXE-1000" (T&K TOKA Inc. product name), "Fujicure-FXR1020" (T&K TOKA Inc. product name), "Fujicure-FXR-1030" (T&K TOKA Inc. product name), "Fujicure-FXR1121" (T&K TOKA Inc. product name), "Fujicure-FXR1081" (T&K TOKA Inc. product name), "Fujicure-1061" (T&K TOKA Inc. product name), and "Fujicure-1171" (T&K TOKA Inc. product name), but are not limited to these.

[0080] An inclusion-type thermal latent curing catalyst is a curing catalyst having a structure in which guest molecules, such as amine compounds, are trapped at the molecular level within a crystal space formed by a host molecule. An example of a commercially available inclusion-type thermal latent curing catalyst is "NISSOCURE TIC-188" (Nippon Soda Co., Ltd. product name).

[0081] (C1) Any one type of basic catalyst may be used, or two or more types may be used in combination.

[0082] When the resin composition includes a (C1) basic catalyst, the content of the (C1) basic catalyst is preferably 0.1 to 40 mass% with respect to the total mass of the resin composition, and more preferably 1 to 20 mass%, in terms of the curing rate and pot life of the resin composition.

[0083] (C2) Photobase generator

[0084] Photobase generators absorb light and generate bases as active species, thereby promoting the polymerization of anionic polymerizable compounds. Examples of photobase generators include various compounds that generate amines, amidines, guanidines, phosphazenes, carbenes, etc., as bases, but are not limited to these.Specific examples of photobasic generators are, for example, 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-dihydroanthracene 2-yl)ethylcyclohexylcarbamate, 1-(9,10-dioxo-9,10-dihydroanthracene 2-yl)ethyl 1H-imidazole-1-carboxylate, 3, 4, 6, 7, 8, 9-hexahydro-2H-pyrimido[1,2-a]pyrimidine-1-yum2-(3-benzoylphenyl)propanoate, diaminomethaneiminum2-(3-benzoylphenyl)propanoate, (Z)-N-(((bis(dimethylamino)methylene)amino)(isopropylamino)methylene)propane-2-aminum2-(3-benzoylphenyl)propanoate, 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidium n-butyltriphenylborate, (Z)-{[bis(dimethylamino)methyleneidene]amino}-N-cyclohexyl(cyclohexylamino)methanimiumtetrakis(3-fluorophenyl)borate, 1, Examples include, but are not limited to, 2-diisopropyl-3-[bis(dimethylamino)methylene]guanidium 2-(3-benzoylphenyl)propionate, 9-anthrylmethyl 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.

[0085] (C2) Any one type of photobase generator may be used, or two or more types may be used in combination.

[0086] When the resin composition includes (C2) a photobase generator, the content of (C2) a photobase generator in the resin composition is preferably 0.1 to 15 parts by mass and more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the total of (A) polymerizable compounds.

[0087] (C3) Photoradical polymerization initiator

[0088] Photoradical polymerization initiators absorb light and generate radicals as active species, thereby promoting the polymerization of radical polymerizable compounds. Examples of photoradical polymerization initiators include, but are not limited to, alkylphenone compounds, acylphosphine oxide compounds, and oxime compounds.

[0089] Examples of alkylphenone compounds include benzyldimethylketal such as 2,2-dimethoxy-1,2-diphenylethane-1-one (commercially available as IGM Resins BV Omnirad 651); α-aminoalkylphenone such as 2-methyl-2-morpholino(4-thiomethylphenyl)propane-1-one (commercially available as IGM Resins BV Omnirad 907); α-hydroxyalkylphenone such as 1-hydroxy-cyclohexyl-phenyl-ketone (commercially available as IGM Resins BV Omnirad 184); and 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butane-1-one (commercially available as IGM Resins BV Omnirad 379EG). Examples include 2-benzyl-2-(dimethylamino)-4'-mopolinobutyrophenone (commercially available product: Omnirad 369 from IGM Resins BV).

[0090] Examples of acylphosphine oxide compounds include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (commercially available as Omnirad TPO H from IGM Resins BV), bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (commercially available as Omnirad 819 from IGM Resins BV).

[0091] Examples of oxime compounds include 2-(benzoylmino)-1-[4-(phenylthio)phenyl]-1-octanone (commercially available as Irgacure OXE01 sold by BASF Japan, Ltd.), 6-[1-(acetylmino)ethyl]-9-ethyl-9H-carbazole-3-(2-methylphenyl)ketone (commercially available as Irgacure OXE02 sold by BASF Japan, Ltd.), and [8-[[(acetylmino)imino][2-(2,2,3,3-tetrafluoropropoxy)phenyl]methyl]-11-(2-ethylhexyl)-11H-benzo[a]carbazole-5-yl]-(2,4,6-trimethylphenyl)methanone (commercially available as Irgacure OXE03 sold by BASF Japan, Ltd.). Examples of commercially available products include Irgacure OXE04 sold by BASF Japan Co., Ltd.

[0092] (C3) As photoradical polymerization initiators, in addition to the photoradical polymerization initiators described above, for example, 2-hydroxy-2-methyl-1-phenylpropane-1-one, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropane-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, benzyl dimethyl ketal, benzophenone, benzoyl benzoic acid, Examples include methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, benzophenone acrylate, 4-benzoyl-4'-methyldiphenylsulfide, 3,3'-dimethyl-4-methoxybenzophenone, thioxantone, 2-chlorothioxantone, 2-methylthioxantone, 2,4-dimethylthioxantone, isopropylthioxantone, 2,4-dichlorothioxantone, 2,4-diethylthioxantone, 2,4-diisopropylthioxantone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methylphenylglyoxylate, benzyl, camperquinone, etc.

[0093] When the resin composition includes (C3) a photoradical polymerization initiator, the content of (C3) the photoradical polymerization initiator is preferably 0.01 to 10 parts by mass and more preferably 0.1 to 8 parts by mass with respect to photocurability, with respect to 100 parts by mass of (A) polymerizable compound.

[0094] (C4) Thermal radical polymerization initiator

[0095] Thermal radical polymerization initiators generate radicals as active species upon heat, thereby promoting the polymerization of radical polymerizable compounds. The thermal radical polymerization initiators that can be used are not particularly limited, and known materials may be used. Specific examples of thermal radical polymerization initiators include dialkylperoxides such as dicumyl peroxide, t-butylcumyl peroxide, 1,3-bis(2-t-butylperoxyisopropyl)benzene, or 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane; peroxyketals such as 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-amylperoxy)cyclohexane, 2,2-bis(t-butylperoxy)butane, n-butyl 4,4-bis(t-butylperoxy)valerate, or ethyl 3,3-(t-butylperoxy)butyrate; and Examples of alkyl peroxyesters such as t-butylperoxy-2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxymaleate, or t-butylperoxybenzoate may be used, but are not limited thereto. Any one of these may be used as a thermal radical polymerization initiator, or two or more may be used in combination.

[0096] When the resin composition includes a (C4) thermal radical polymerization initiator, the content of the (C4) thermal radical polymerization initiator is preferably 0.01 to 5 mass%, more preferably 0.1 to 3 mass%, with respect to the total mass of the resin composition.

[0097] (D) Modified polydimethylsiloxane

[0098] The resin composition of the present embodiment comprises (D) modified polydimethylsiloxane (hereinafter also referred to as "component (D)"). In the present embodiment, (D) modified polydimethylsiloxane satisfies at least one of the following features (a) and (b).

[0099] (a) Organic substituents containing COOH groups or OH groups are bonded to polydimethylsiloxane directly or through a linker.

[0100] (b) Measured in dichloroform 1 In the H NMR spectrum, there is a signal in the range of 0.3 to -0.3 ppm and 4.4 to 3.2 ppm, and also a signal that disappears upon addition of D2O in the range of 13 to 0 ppm.

[0101] Modified polydimethylsiloxane is, more specifically, formula:

[0102]

[0103] The polydimethylsiloxane has a structure in which an organic substituent is introduced as a modifying group, either directly or through a linker such as an alkyl group or an alkylene group, to the side chain and / or the end of a polydimethylsiloxane main chain composed of dimethylsiloxane repeating units represented by [characteristic]. Here, "an organic substituent is introduced to the side chain of the polydimethylsiloxane main chain" means that a methyl group of a part of the polydimethylsiloxane main chain is substituted with an organic substituent. "An organic substituent is introduced to the end of the polydimethylsiloxane main chain" means that the end of the polydimethylsiloxane main chain (e.g., a methyl group or -OSi(CH3)3) is substituted with an organic substituent. The location of introduction of the modifying group in the modified polydimethylsiloxane may be the side chain, the end (one end or both ends), or both the side chain and the end. Additionally, the modified polydimethylsiloxane includes polydimethylsiloxane with a Gemini structure. The degree of polymerization (number of dimethylsiloxane repeating units) of the modified polydimethylsiloxane is not particularly limited, for example, 3 or more, and preferably 5 or more.

[0104] In the modified polydimethylsiloxane according to the above feature (a), the organic substituent contains a COOH group or an OH group.

[0105] Examples of modified polydimethylsiloxanes in which the above organic substituent includes a COOH group include those commercially available under names such as carboxyl-modified polydimethylsiloxane or carboxyl-modified silicone. Examples of such commercially available products include, but are not limited to, products sold by Shin-Etsu Chemical Co., Ltd., such as X-22-3701E, X-22-162C, and X-22-3710.

[0106] Confirmation of whether the organic substituents of modified polydimethylsiloxane contain a COOH group is determined by Fourier transform infrared spectroscopy (FT-IR) measurements of the modified polydimethylsiloxane, at approximately 1715 cm⁻¹ derived from the C=O stretching vibration of the carboxylic acid. －1 This can also be done by observing the presence or absence of the IR spectrum.

[0107] Examples of modified polydimethylsiloxanes in which the above organic substituent includes an OH group include those commercially available as carbinol-modified polydimethylsiloxane or carbinol-modified silicone. Examples of such commercially available products include, but are not limited to, products sold by Shin-Etsu Chemical Co., Ltd. such as X-22-4039, X-22-4015, KF-6000, KF-6001, KF-6002, KF-6003, X-22-170BX, X-22-170DX.

[0108] Other examples of modified polydimethylsiloxanes in which the above organic substituent includes an OH group include polyether-modified polydimethylsiloxanes or polyether-modified silicones, and also those in which the terminal of the polyether group is an OH group. Examples of such commercially available products include, but are not limited to, products sold by Shin-Etsu Chemical Co., Ltd., such as X-22-4272 and KF-6123. Additionally, such polyether-modified polydimethylsiloxanes or polyether-modified silicones are sometimes named "PEG-(number)Dimethicone" in cosmetic labeling. "PEG-(number)" indicates that n has an average of the corresponding number of PEG chains. "PEG-(number)Dimethicone" is denoted as "PEG-(n)DIMETHICONE" in INCI nomenclature. Examples of this include, but are not limited to, PEG-9 dimethicone (product name: KF-6013), PEG-3 dimethicone (product name sold by Shin-Etsu Chemical Co., Ltd.: KF-6015), PEG-10 dimethicone (product name sold by Shin-Etsu Chemical Co., Ltd.: KF-6017), and PEG-10 dimethicone (product name sold by Shin-Etsu Chemical Co., Ltd.: KF-6043).

[0109] Examples of polyether groups as organic substituents include polyethylene glycol groups and polypropylene glycol groups, and polyethylene glycol groups are preferred.

[0110] Reactive silicones whose hydroxyl values ​​are disclosed in catalogs, etc., can also be presumed to be modified polydimethylsiloxanes in which the organic substituent includes OH groups. The presence of OH groups in the modified polydimethylsiloxane can be confirmed by measuring the hydroxyl value of the modified polydimethylsiloxane. In one embodiment, the modified polydimethylsiloxane has a hydroxyl value of 1 mg KOH / g or more. The measurement of the hydroxyl value can be performed, for example, by a method conforming to JIS K 0070 or by FT-NIR (near-infrared spectroscopy) conforming to JIS K 1557-6.

[0111] Confirmation of whether the organic substituents of modified polydimethylsiloxane contain OH groups is determined by Fourier transform infrared spectroscopy (FT-IR) measurements of the modified polydimethylsiloxane, at approximately 1360 to 1340 cm⁻¹ derived from the angle-shifting vibrations of alcoholic OH. －1 This can also be done by observing the presence or absence of the IR spectrum.

[0112] Depending on the commercially available modified polydimethylsiloxane, the detailed structure of the modifying group may not be disclosed. Additionally, there are products marketed as various additives such as surfactants, surface modifiers, leveling agents, defoaming agents, wetting agents, and dispersants that correspond to modified polydimethylsiloxane, even though they are not explicitly labeled as such or their structure is not disclosed. In such cases, the modified polydimethylsiloxane measured in dichloroform 1 The modified polydimethylsiloxane of the present embodiment corresponds to having a signal in the H NMR spectrum in the range of 0.3 to -0.3 ppm and 4.4 to 3.2 ppm, and also having a signal that disappears upon D2O addition in the range of 13 to 0 ppm (the above feature (b)). The signal observed in the range of 0.3 to -0.3 ppm is a signal originating 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 originating from a hydrogen atom connected to a carbon adjacent to an oxygen atom of an OH group or ether. The signal observed in the range of 13 to 0 ppm and which disappears upon D2O addition can be presumed to be a signal originating from a hydrogen atom of an OH group or NH group.

[0113] The signal lost due to the addition of D2O is typically observed in the range of 13 to 0 ppm. Among these, the signal observed in the range of 3 to 2 ppm and lost due to the addition of D2O can be presumed to be a signal originating from the hydrogen atoms of the OH group.

[0114] Estimation of whether the signal lost due to D2O addition is a signal originating from either the OH group or the NH group hydrogen atom can be performed, for example, by the following method.

[0115] · Fourier Transform Infrared Spectroscopy (FT-IR) Measurement

[0116] The above 1 In addition to H NMR measurements, Fourier transform infrared spectroscopy (FT-IR) measurements of modified polydimethylsiloxane yielded approximately 1360 to 1340 cm⁻¹ derived from the angle-shifting vibrations of alcoholic OH. －1 By observing the presence or absence of the IR spectrum, the signal lost due to the addition of D2O can be estimated to be a signal originating from the hydrogen atoms of the OH group.

[0117] · Measurement of acidity

[0118] The above 1 In addition to H NMR measurement, by measuring the acidity of the modified polydimethylsiloxane, it is possible to estimate whether the signal lost upon the addition of D2O originates from a hydrogen atom of the OH group or the NH group. For example, 100 mg of a sample of modified polydimethylsiloxane is dissolved in 200 μL of isopropyl alcohol, 200 μL of pure water is added and shaken well, and the pH of the liquid is measured. If the pH is between 3 and 7, the signal lost upon the addition of D2O can be estimated to originate from a hydrogen atom of the OH group. If the pH is 8 or higher, indicating basicity, the signal lost upon the addition of D2O can be estimated to originate from a hydrogen atom of the NH group.

[0119] The modified polydimethylsiloxane satisfying the above characteristic (b) is measured in dichloroform 1In the 1H NMR spectrum, a signal may be present 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 hydrogen atoms of the methyl groups in the polypropylene glycol chains acting as polyether modifying groups. In one embodiment, the modified polydimethylsiloxane measured in dichloroform 1 In the H NMR spectrum, it has a signal in the range of 1.25 to 0.95 ppm. In one embodiment, the modified polydimethylsiloxane measured in dichloroform 1 In the H NMR spectrum, there is no signal in the range of 1.25 to 0.95 ppm.

[0120] Examples of modified polydimethylsiloxane satisfying characteristic (b) include KF-945 sold by Shin-Etsu Chemical Co., Ltd., TEGO TWIN 4000 sold by Evonik Japan Co., Ltd., TEGO TWIN 4100, etc.

[0121] In the resin composition of the present embodiment, by including a modified polydimethylsiloxane satisfying at least one of features (a) and (b) of (D), the bleed phenomenon is suppressed not only during thermal curing but also when left at room temperature after coating on a substrate, etc. The reason why the bleed phenomenon is suppressed by the resin composition including (D) modified polydimethylsiloxane is not limited to this, but is thought to be as follows. When a resin composition containing modified polydimethylsiloxane is applied to a substrate, etc., a portion of the modified polydimethylsiloxane migrates to the surface of the coating film of the resin composition due to the surface migration properties of the modified polydimethylsiloxane. The modified polydimethylsiloxane that has migrated to the surface of the coating film migrates very slightly onto a substrate that is not in contact with the resin composition before other unreacted components seep out from the coating film of the resin composition, and the modified groups of the modified polydimethylsiloxane are adsorbed onto the surface of the substrate. Accordingly, it is believed that an adsorption film of modified polydimethylsiloxane is formed on the surface of the substrate, and water and oil repellency attributable to the polydimethylsiloxane portion is exhibited to suppress bleeding. In addition, it is believed that a higher adsorption effect of the modified polydimethylsiloxane on the substrate is obtained by including a COOH group or an OH group as the organic substituent as the modifying group.

[0122] 1 H NMR measurements can be performed using normal conditions. For example, 100 mg of the sample to be measured is dissolved in 500 μl of dichloroform, and a diameter of 5 mm 1 Place the sample in a sample tube for H NMR and perform measurements under the following conditions. After the measurement, add 50 μl of heavy water (D2O) to the sample tube containing the sample and perform measurements again under the same conditions. It can be seen that the signal that disappears after the addition of heavy water is a signal derived from active hydrogen bound to a hydroxyl group or an amino group.

[0123] Measurement frequency: 40 to 600 MHz

[0124] Solvent: Dichloroform

[0125] Measured nuclide: 1 H

[0126] Accumulation count: 4 to 80 times

[0127] Measurement temperature: 15 to 50℃

[0128] (D) Any one type of polyether-modified polydimethylsiloxane may be used, or two or more types may be used in combination.

[0129] (D) The content of modified polydimethylsiloxane is preferably 0.01 mass% or more with respect to the total mass of the resin composition, more preferably 0.1 mass% or more, and more preferably 0.2 mass% or more. Additionally, it is preferably 5 mass% or less, more preferably 4 mass% or less, and more preferably 3 mass% or less. In one embodiment, the content of (D) modified polydimethylsiloxane is preferably 0.01 to 5 mass% with respect to the total mass of the resin composition, more preferably 0.1 to 4 mass%, and more preferably 0.2 to 3 mass%.

[0130] (E) Filler

[0131] The resin composition of the present embodiment may contain (E) a filler (hereinafter also referred to as "component (E)") to a extent that does not impair the effects of the present invention. By including (E) a filler in the resin composition, the coefficient of linear expansion of the cured product obtained by curing the resin composition can be lowered, thereby improving thermal cycle resistance. In addition, if the filler has a low elastic modulus, stress generated in the cured product can be relieved, thereby improving long-term reliability. (E) fillers are broadly classified into inorganic fillers and organic fillers.

[0132] Inorganic fillers are not particularly limited as long as they consist of granular bodies formed from inorganic materials and have the effect of lowering the coefficient of linear expansion upon 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 oxide, zinc oxide, silicon carbide, silicon nitride, boron nitride, etc. Any single type of inorganic filler may be used, or two or more types may be used in combination. As for the inorganic filler, it is preferable to use silica filler because it allows for a large filling amount. Amorphous silica is preferred.

[0133] It is preferable that the surface of the inorganic filler be treated with a coupling agent such as a silane coupling agent. Accordingly, the viscosity of the resin composition can be set within an appropriate range.

[0134] Examples of organic fillers include polytetrafluoroethylene (PTFE) fillers, silicone fillers, acrylic fillers, styrene fillers, etc. Organic fillers may be surface-treated. It is preferable that the glass transition point of the organic filler be greater than 40°C.

[0135] The shape of the filler is not particularly limited and can be spherical, scale-like, needle-like, irregular, etc.

[0136] In some embodiments, the average particle size of the filler is preferably 5.0 μm or less, more preferably 4.0 μm or less, and more preferably 3.0 μm or less. In this specification, the average particle size refers to a volume-based median diameter (d) measured by laser diffraction in accordance with ISO-13320 (2009). 50It refers to a value obtained as the numerical average of 50 measurements arbitrarily selected from observation images acquired by a transmission electron microscope (TEM) or a scanning electron microscope (SEM). By keeping the average particle size of the filler below the upper limit, sedimentation of the filler can be suppressed, and the formation of coarse particles can be suppressed, thereby suppressing clogging of the dispenser nozzle. The lower limit of the average particle size of the filler is not particularly limited, but from the perspective of the viscosity of the resin composition, it is preferable that it be 0.005 μm or more, and more preferable that it be 0.1 μm or more. In any aspect of the present 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 also be used in combination. For example, a filler with an average particle size of 0.005 μm or more and less than 0.1 μm, and a filler with an average particle size of 0.1 μm to 5.0 μm may be used in combination.

[0137] The content of (E) filler in the resin composition of the present embodiment is preferably 0.5 to 80 mass% with respect to the total mass of the resin composition, more preferably 1 to 70 mass%, and even more preferably 3 to 60 mass%. By setting the content of (E) filler to the above range, thermal cycle resistance is improved, and the viscosity of the resin composition is set to an appropriate range, thereby improving applicability in a dispenser.

[0138] (F) Stabilizer

[0139] The resin composition of the present embodiment may include (F) a stabilizer (hereinafter also referred to as "component (F)") to the extent that it does not impair the effects of the present invention. The stabilizer (F) is added to increase the stability of the resin composition during storage and to suppress the occurrence of polymerization reactions caused by unintended radicals or basic components. Typically, radical polymerization inhibitors and anionic polymerization inhibitors may be used as the stabilizer (F).

[0140] Known radical polymerization inhibitors may be used, for example, at least one selected from N-nitroso-N-phenylhydroxylamine aluminum, triphenylphosphine, p-methoxyphenol, and hydroquinone may be used. In addition, known radical polymerization inhibitors disclosed in Japanese Patent Publication No. 2010-117545, Japanese Patent Publication No. 2008-184514, etc. may also be used. Any one type of radical polymerization inhibitor may be used, or two or more types may be used in combination.

[0141] When a radical polymerization inhibitor is included, the content of the radical polymerization inhibitor is preferably 0.0001 to 5 mass% with respect to the total mass of the resin composition in terms of pot life, and more preferably 0.001 to 3 mass%.

[0142] Known substances may be used as anionic polymerization inhibitors, for example, boric acid ester compounds and strong acids may be used. Specific examples of anionic polymerization inhibitors include trimethylborate, triethylborate, tri-n-propylborate, triisopropylborate, trifluoromethanesulfonic acid, maleic acid, methanesulfonic acid, barbituric acid, difluoroacetic acid, trichloroacetic acid, phosphoric acid, dichloroacetic acid, etc. Among these, a preferred anionic polymerization inhibitor is at least one selected from tri-n-propylborate, triisopropylborate, and barbituric acid. Additionally, known substances disclosed in Japanese Patent Publication No. 2010-117545, Japanese Patent Publication No. 2008-184514, Japanese Patent Publication No. 2017-171804, etc. may be used as anionic polymerization inhibitors. Any one type of anionic polymerization inhibitor may be used, or two or more types may be used in combination.

[0143] When an anionic polymerization inhibitor is included, the content of the anionic polymerization inhibitor is preferably 0.001 to 5 mass%, more preferably 0.01 to 3 mass%, with respect to the total mass of the resin composition.

[0144] The resin composition may further contain, as necessary and to the extent that the purpose of the present embodiment is not impaired, coupling agents, carbon black, titanium black, ion trapping agents, leveling agents, antioxidants, defoaming agents, thixotropic agents, viscosity modifiers, flame retardants, and / or other additives. However, in order to prevent a reduction in curing strength, it is preferable that the resin composition substantially does not contain solvents, for example, that the solvent content is 1 mass% or less relative to the total mass of the resin composition. In addition, the amount of volatile organic compounds (VOCs) can be reduced accordingly. Examples of solvents include organic solvents common in the field of curable compositions, such as hydrocarbons (benzene, toluene, xylene, cyclohexane, etc.), non-protonic 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 (cyclopentylmethyl ether, diethyl ether, tetrahydrofuran, dimethoxyethane, etc.), alcohols (methanol, ethanol, propanol, butanol, etc.), terpenes (turpentine oil, terpineol, isobornyl acetate, etc.), and halogenated solvents (dichloromethane, chloroform, etc.).

[0145] A resin composition can be obtained, for example, by stirring, melting, mixing, and / or dispersing components (A) to (D), components (E), components (F), and other additives, either simultaneously or separately, while applying heat treatment as needed. The apparatus for such mixing, stirring, and dispersion is not particularly limited. As such apparatus, a blast furnace, Henschel mixer, three-roll mill, ball mill, planetary mixer, and bead mill equipped with stirring and heating devices may be used. Additionally, these apparatuses may be used in a suitable combination.

[0146] The resin composition obtained in this way is photocurable, thermosetting, or photo-thermosetting, depending on the type of (C) polymerization initiator included in the resin composition. Photocuring of the resin composition is performed, for example, by irradiating the resin composition with UV light. Thermosetting of the resin composition is performed, for example, under conditions of 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 (for example, an optical sensor module or a camera module) that includes a component that degrades under high-temperature conditions. The thermosetting time may be 30 to 120 minutes, for example, depending on other curing conditions. When the resin composition is photo-thermosetting, for example, the resin composition may be pre-cured by curing with light (UV) and then fully cured by curing with heat.

[0147] The resin composition of the present embodiment can be used, for example, as an adhesive, encapsulating agent, damming agent, and raw material for fixing, bonding, or protecting components, and is suitable as a one-component type. Here, the damming agent is formed on the outer periphery of a substrate in advance, for example, before encapsulating a plurality of semiconductor chips, etc., on a substrate with a low-viscosity filler, etc. By forming a dam with this damming agent, the leakage of the low-viscosity filler used to encapsulate the plurality of semiconductor chips can be suppressed. In addition, the adhesive containing the resin composition of the present embodiment enables good bonding to engineering plastics, ceramics, and metals.

[0148] [Adhesive or encapsulating material]

[0149] An adhesive or encapsulant of one embodiment of the present invention comprises the resin composition of the embodiment described above. This adhesive or encapsulant enables good bonding to engineering plastics, ceramics, and metals. The adhesive or encapsulant of this embodiment is preferably used for fixing, bonding, or protecting components constituting an optical sensor module or a camera module.

[0150] [Curing product of resin composition, adhesive, or encapsulant]

[0151] A cured product in another embodiment of the present invention is a cured product obtained by curing the resin composition of the above-described embodiment or the adhesive or encapsulant of the above-described embodiment. Bleeding is suppressed around the substrate to which this cured product is adhered.

[0152] [Semiconductor devices, electronic components]

[0153] A semiconductor device or electronic component of one embodiment of the present invention comprises a hardened product of the above-described embodiment. Here, a semiconductor device refers to any device capable of functioning by utilizing semiconductor characteristics, and includes electronic components, semiconductor circuits, modules containing such components, electronic devices, etc. Examples of semiconductor devices or electronic components include, but are not limited to, HDDs, semiconductor devices, optical sensor modules, camera modules, semiconductor modules, integrated circuits, etc. Examples of optical sensors include, but are not limited to, photodiodes, photo ICs, photomultiplier tubes (PMTs), photocells, image sensors, spectrometers / spectral sensors, infrared sensors, ultraviolet / flame sensors, X-ray sensors, radiation sensors, electron / ion sensors, distance / position sensors, etc.

[0154] Examples

[0155] The present invention will be explained in more detail below through examples and comparative examples, but the present invention is not limited to these examples. Additionally, in the following examples, parts and % represent parts by mass and % by mass, respectively, unless otherwise noted.

[0156] [Preparation of resin composition]

[0157] Resin compositions of the Examples and Comparative Examples were prepared by mixing a predetermined amount 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 indicated in parts by mass (unit: g). The components used in the Examples and Comparative Examples are as follows.

[0158] ·(A) Polymerizable compound having a carbon-carbon double bond (Component (A))

[0159] (A-1): Polyester acrylate (Product name: M7100, Toa Synthetic Co., Ltd., (meth)acryloyl equivalent: 188 g / eq)

[0160] (A-2): Dimethylol tricyclodecane diacrylate (Product name: Light Acrylate DCP-A, Kyoei Chemical Co., Ltd., (meth)acryloyl equivalent: 152 g / eq)

[0161] (A-3): 2-(o-phenylphenoxy)ethyl acrylate (Product name: HRD-01, Nisshoku Techno Fine Chemical Co., Ltd., (meth)acryloyl equivalent: 268 g / eq)

[0162] (A-4): Ethoxylated bisphenol A diacrylate (Product name: ABE-300, Shinnakamura Chemical Co., Ltd., (meth)acryloyl equivalent: 236 g / eq)

[0163] ·(B) Polythiol compound (component (B))

[0164] (B-1): Thiol glycoluryl derivative (Product name: C3 TS-G, Shikoku Kasei Kogyo, thiol equivalent: 114 g / eq)

[0165] (B-2): Thiol glycoluryl derivative (Product name: TS-G, Shikoku Kasei Kogyo, thiol equivalent: 100 g / eq)

[0166] (B-3): Pentaerythritol tetrakis(3-mercaptopropionate) (Product Name: PEMP, SC Organic Chemicals Co., Ltd., Thiol Equivalent: 122 g / eq)

[0167] ·(C) Polymerization initiator (Component (C))

[0168] (C1-1): Amine-epoxy adduct-based latent curing catalyst (Product name: Novacure HXA9322HP, Asahi Kasei Co., Ltd.)

[0169] (C1-2): Amine-urea type adduct-based latent curing catalyst (Product name: Fujicure-FXR-1121, solid at room temperature, T&K TOKA Co., Ltd.)

[0170] (C3-1): 1-hydroxy-cyclohexyl-phenyl-ketone (Product name: Omnirad 184, IGM Resins BV)

[0171] ·(D) Modified polydimethylsiloxane (Component (D))

[0172] ·(D’) Modified polydimethylsiloxane other than component (D) (Component (D’))

[0173] As component (D) and component (D'), the modified polydimethylsiloxanes of Table 1 below were used. Various modified polydimethylsiloxanes in dichloroform 1 The results of H NMR measurement, Fourier transform infrared spectroscopy (FT-IR) measurement, and acidity measurement are shown in Table 1.

[0174] [Table 1]

[0175]

[0176] In Table 1, "Ph" represents a phenyl group and "Me" represents a methyl group.

[0177] ·(E) Filler( Ingredient (E))

[0178] (E-1): Calcium carbonate filler (Product name: CS3NA, Ube Materials Co., Ltd.)

[0179] (E-2): Silica filler (Product name: CAB-O-SIL (registered trademark) TS-720, polydimethylsiloxane surface-treated fumed silica, Cabot Corporation)

[0180] [of modified polydimethylsiloxane 1 [H NMR Measurement]

[0181] 100 mg of a measurement sample of various modified polydimethylsiloxanes was dissolved in 500 μL of dichloroform, and a diameter of 5 mm 1 The sample was placed in a sample tube for H NMR, and measurements were performed under the following conditions. After the measurement, 50 μL of heavy water (D2O) was added to the sample tube containing the sample, and measurements were performed again under the same conditions. Table 1 shows the integrated values ​​of each signal when the value of the chloroform-derived signal from 0.3 to -0.3 ppm was set to 6.

[0182] Measuring device: Oxford instrument Pulsar HF

[0183] Measurement frequency: 60 MHz

[0184] Solvent: Dichloroform

[0185] Measured nuclide: 1 H

[0186] Measured temperature: 37℃

[0187] Accumulated count: 32 times

[0188] Examples of attribution for each signal under the above measurement conditions are as follows.

[0189] 0.3 to ―0.3 ppm: C H 3 -Si, C H 2 -Si (hydrogen atom connected to a carbon atom adjacent to a Si atom)

[0190] 4.4 to 3.2 ppm: -C H 2 -O-, -C=C-C H 2 -O- (a hydrogen atom connected to a carbon atom adjacent to an oxygen atom in an alcohol or ether)

[0191] 1.1 ppm(d, approx. 6 Hz): -CH2-CHC H 3 -O-(hydrogen atom of the methyl group of propylene glycol)

[0192] Under the above measurement conditions, a signal appearing in the range of 9.0 to 0.5 ppm and also disappearing upon D2O addition: OH group or NH group

[0193] [Fourier Transform Infrared Spectroscopy (FT-IR) Measurement of Modified Polydimethylsiloxane]

[0194] Fourier transform infrared spectroscopy (FT-IR) measurements of various modified polydimethylsiloxanes were performed under the following conditions, and the C=O stretching vibration of the carboxylic acid (approx. 1715 cm⁻¹) － 1 The presence or absence of ) and the changing angular vibration of alcoholic OH (approx. 1360 to 1340 cm⁻¹) －1 The presence or absence of ) was checked. The results are shown in Table 1.

[0195] Measuring device: Perkin-Elmer FT-IR Spectrometer Spectrum 3

[0196] Measurement method: ATR method

[0197] [Measurement of Acidity of Modified Polydimethylsiloxane]

[0198] 100 mg of various modified polydimethylsiloxane samples were dissolved in 200 μL of isopropyl alcohol (IPA), 200 μL of pure water was added and the mixture was shaken well. The pH was determined by immersing a pH test strip in the resulting liquid. Macherey Nagel #90204 Universal indicator paper was used. The results are shown in Table 1.

[0199] In the examples and comparative examples, the characteristics of the resin composition were measured as follows.

[0200] [Bleed Assessment]

[0201] 1.5 mg of the resin compositions of the Examples and Comparative Examples were potted onto a ceramic substrate plasma-treated with argon (Ar) gas using a dispenser. Below, the bleed lengths under two conditions were measured using a CCD camera (N = 3 pcs × 2 sides). The results are shown in Tables 2-1 to 2-5. Condition 1: Bleed length on the ceramic substrate after leaving it at room temperature (20°C to 25°C) for 60 minutes following potting. Condition 2: Bleed length on the ceramic substrate after leaving it at room temperature (20°C to 25°C) for 60 minutes following potting, and then heat-curing the resin composition at 80°C for 60 minutes.

[0202] [Table 2-1]

[0203]

[0204] [Table 2-2]

[0205]

[0206] [Table 2-3]

[0207]

[0208] [Table 2-4]

[0209]

[0210] [Table 2-5]

[0211]

[0212] It can be seen that the resin compositions of Examples 1 to 20, which include a modified polydimethylsiloxane satisfying at least one of features (a) and (b) of (D), significantly suppress the bleed phenomenon in either Condition 1 or Condition 2 when compared to the resin compositions of Comparative Examples 1, 6 to 11, which do not include the modified polydimethylsiloxane of (D), and the resin compositions of Comparative Examples 2 to 5, which include the component of (D') or a modified polydimethylsiloxane other than (D).

[0213] Industrial applicability

[0214] The present invention is a resin composition that is at least photocurable or thermosetting capable of suppressing bleed phenomena, and is particularly useful as an adhesive or encapsulant used for fixing, bonding, or protecting components of miniaturized or highly integrated semiconductor modules.

[0215] The disclosure of Japanese Patent Application No. 2023-211994 (filing date: December 15, 2023) is incorporated herein by reference in its entirety.

[0216] All documents, patent applications, and technical specifications described in this specification are incorporated by reference into this specification to the same extent as if each individual document, patent application, and technical specification were incorporated by reference specifically and individually.

Claims

Claim 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 features (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) measured in dichloroform 1 A resin composition comprising, in the H NMR spectrum, having a signal in the range of 0.3 to -0.3 ppm and 4.4 to 3.2 ppm, and also having a signal that disappears upon addition of D2O in the range of 13 to 0 ppm. Claim 2 A resin composition according to claim 1, wherein the polymerizable compound having (A) a carbon-carbon double bond is a (meth)acrylate compound. Claim 3 A resin composition according to claim 1 or 2, wherein the content of the (D) modified polydimethylsiloxane is 0.01 to 5 mass% with respect to the total mass of the resin composition. Claim 4 A resin composition comprising (E) a filler, in any one of claims 1 to 3. Claim 5 An adhesive or encapsulant comprising a resin composition according to any one of claims 1 to 4. Claim 6 In paragraph 5, an adhesive or encapsulant used for fixing, bonding, or protecting an optical sensor module or a component constituting the same. Claim 7 A cured product in which the resin composition of any one of paragraphs 1 to 4, or the adhesive or encapsulant of paragraph 5 or 6, is cured. Claim 8 A semiconductor device or electronic component comprising the cured material of paragraph 7. Claim 9 In paragraph 8, a semiconductor device or electronic component that is an optical sensor module.

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